Ascorbic Acid Technology in Agricultural, Pharmaceutical, Food, and

20 Ascorbic A c i d Technology i n Agricultural, Pharmaceutical, Food, and Industrial

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Applications J. CHRISTOPHER BAUERNFEIND Gainesville, FL 32605

Ascorbic acid, as well as its salts and esters, has many useful applications. In plants L-ascorbic acid has been reported to promote germination of seeds, growth of plants, and growth of roots on cuttings. Spraying of plants such as lettuce, celery, spinach, petunias, and roses with ascorbic acid or sodium ascorbate solutions enabled those plants to better withstand damage from ozone and smog exposure. Spraying tree or bush fruits with ascorbic acid solution syn chronizes maturation and causes fruit to fall more easily in mechanical harvesting. In some instances ascorbic acid application has been cited to improve the defense mechnism of plants to attack by disease agents. Fish require a dietary source of vitamin C, without which they grow poorly and develop fracture dislocations of the spine, distortions of cartilage, and other deficiency signs. In some instances, ruminants and monogastric animals appear to benefit from administration of L-ascorbic acid under stress. Animals with viral disease, such as canine or feline distemper, have responded to treatment with high levels of ascorbic acid. Solid and liquid forms constitute a substan tial pharmaceutical market for manufactured ascorbic acid. Tableting techniques have been devised to prepare a wide array of swallowable or chewable tablets with an assured vitamin C content after manufacture and prolonged storage. L-Ascorbic acid may be added to foods or food ingredients as a nutrient to fortify natural or fabricated foods having little or no vitamin C, to restore losses, and to standardize a given class of food products with a preselected quantity of 0065-2393/82/0200-0395$26.75/0 © 1982 American Chemical Society In Ascorbic Acid: Chemistry, Metabolism, and Uses; Seib, P., et al.; Advances in Chemistry; American Chemical Society: Washington, DC, 1982.

396

ASCORBIC

the vitamin.

ACID

Factors that must be considered with appro-

priate technology before adding ascorbic acid are the following: (i) cost of the specific food; (ii) convenience (iii) relationship of the food in question

of use;

to normal food

selection or to replacement or supplemental food products; (iv) stability of the vitamin in the food during slielf life and home preparation;

(v) public

health considerations;

and

(vi) special food needs, such as infant, geriatric, and mili-


tary. In addition to serving as an added nutrient in food, L-ascorbic acid is often used as a processing aid or as a preservative in certain foods or food ingredients. include preventing

enzymatic

Examples

browning of cut fruit, scav-

enging oxygen in beer, fruit, or vegetable products, inhibiting oxidative rancidity in frozen fish, stabilizing the color and flavor in cured meats, maturing of wheat flour and improving of dough, and acting as a reducing agent in wine. An extensive list of patents and scientific papers exists on proposed industrial uses of ascorbic

acid.

The greatest

interest appears to be in the synthetic polymer industry, in photoprocessing,

and in metal technology.

Miscellaneous

uses have been proposed in cosmetics, tobacco, fibers, preservation

of

blood, preservation

of

cut

plants,

cleaning

agents, and in assay reagents.

p p r o x i m a t e l y 50 years a g o L - a s c o r b i c a c i d h a d its b e g i n n i n g as a 1

x

p u r e c h e m i c a l c o m p o u n d . I n t h e 1928-1931 p e r i o d S z e n t - G y o r g y i

(1,2)

e x t r a c t e d f r o m a d r e n a l g l a n d s , c a b b a g e , oranges, a n d p a p r i k a , a

substance h e n a m e d h e x u r o n i c a c i d .

I n 1932 W a u g h a n d K i n g

(3,4)

reported hexuronic a c i d was identical w i t h v i t a m i n C that they isolated f r o m l e m o n s a n d oranges.

Subsequently Svirbely and Szent-Gyorgyi

( 5 - 8 ) i n 1932-1933 d e m o n s t r a t e d a n t i s c o r b u t i c a c t i v i t y f o r the substance. T h e s t r u c t u r a l f o r m u l a ( F i g u r e 1) w a s d e t e r m i n e d i n 1933 b y s e v e r a l investigators

(9-12).

CH OH 2

Figure I .

CH OH 2

Structural formulas of L-ascorbic acid (reductant) (right) and L-denydroascorbic acid (oxidant) (left).

In Ascorbic Acid: Chemistry, Metabolism, and Uses; Seib, P., et al.; Advances in Chemistry; American Chemical Society: Washington, DC, 1982.

20.

397

Ascorbic Acid Technology

BAUERNFEIND

L - A s c o r b i c a c i d w a s s y n t h e s i z e d i n 1933 b y R e i c h s t e i n a n d c o w o r k e r s (13)

i n S w i t z e r l a n d a n d also i n d e p e n d e n t l y

by Ault

et a l . (14)

in

E n g l a n d . I n d u s t r i a l synthesis l a r g e l y f o l l o w s t h e L - s o r b o s e process ( F i g ure 2)

of

starting

Reichstein.

with

Continuous improvements

D-glucose have

feasible process.

made

i n the various

this a p p r o a c h

the

steps

commercially

C o m m e r c i a l p r o d u c t i o n has b e e n c o n t i n u o u s since 1933

a n d is c u r r e n t l y p r a c t i c e d i n several c o u n t r i e s . I n one l a r g e f a c t o r y a b o u t 30 tons of p u r e L - a s c o r b i c a c i d is p r o d u c e d d a i l y , a n a m o u n t e q u i v a l e n t


to t h a t c o n t a i n e d i n 1 / 2 b i l l i o n (500,000,000) large oranges.

Today, an

i n c r e a s i n g tonnage of this v e r s a t i l e substance is p r o d u c e d a n n u a l l y a n d a v e r y w i d e r a n g e of a p p l i c a t i o n s has b e e n f o u n d for i t i n t h e

food

i n d u s t r y . It o c c u p i e s a n e s t a b l i s h e d p o s i t i o n as a n essential n u t r i e n t a n d as a p h a r m a c e u t i c a l agent i n h u m a n n u t r i t i o n (915) use as a n a d d i t i v e to a n i m a l feeds is g r o w i n g .

and medicine.

Its

Applications on plants

a n d c r o p s as w e l l as i n v a r i o u s i n d u s t r i e s h a v e b e e n i n d i c a t e d . L - A s c o r b i c acid, a six-carbon, water-soluble, white, crystalline c o m p o u n d is v i t a m i n C ( t h e a n t i s c o r b u t i c v i t a m i n ) a n d has also b e e n c a l l e d L - x y Z o - a s c o r b i c a c i d , h e x u r o n i c a c i d , or c e v i t a m i c a c i d . L - A s c o r b i c a c i d ( C H 0 ) resembles the sugars i n s t r u c t u r e a n d reacts l i k e sugars u n d e r 6

8

6

some c h e m i c a l c o n d i t i o n s . T h e u n u s u a l p r o p e r t i e s of t h e m o l e c u l e

(mol.

w t . 176.13) are d u e to t h e e n e - d i o l g r o u p i n g . O t h e r p r o p e r t i e s a r e : m e l t i n g p o i n t of 1 9 0 ° - 1 9 2 ° C w i t h d e c o m p o s i t i o n ; p K i of 4.17 a n d a p K

2

[«]

D

2 0

+

23° i n w a t e r ; a

of 11.57. I t is a m o d e r a t e l y s t r o n g r e d u c i n g a g e n t

a n d is sufficiently a c i d i c to f o r m n e u t r a l salts w i t h bases.

L-Ascorbic acid

( 1 g ) dissolves i n a b o u t 3 m L of w a t e r , or 50 m L of a b s o l u t e e t h a n o l , or 100 m L of g l y c e r o l .

T h e p H of a 1 0 % a q u e o u s s o l u t i o n is

2.1-2.5;

f o r a 1 0 % a q u e o u s s o l u t i o n of s o d i u m ascorbate i t is 7.4—7.9. D e s c r i p t i o n , i d e n t i f i c a t i o n , specifications, a n d tests of L - a s c o r b i c a c i d a n d s o d i u m L - a s c o r b a t e are g i v e n i n the U . S . P h a r m a c o p o e i a

(15)

the F o o d

palmitoyl

Chemicals

Codex

(16).

Similar

information

on

L - a s c o r b i c a c i d ( a s c o r b y l p a l m i t a t e ) is c o n t a i n e d i n t h e C o d e x .

and

Sodium

ascorbate is t w i c e as s o l u b l e i n w a t e r as a s c o r b i c a c i d . A s c o r b y l p a l m i tate is s o l u b l e i n e t h a n o l ( 2 5 ° C ) p r o p y l e n e g l y c o l , or d e c a g l y c e r o l ( 2 5 ° C ) at 0 . 0 1 - 0 . 1 %

at 1 2 . 5 % , i n h o t octaoleate

(80°C)

glycerin,

to 1 0 % , i n vegetable

oils

a n d i n w a t e r ( 7 0 ° C ) at 0 . 2 % .

C r y s t a l structures of L - a s c o r b i c a c i d v a r y i n g f r o m coarse to u l t r a f i n e p o w d e r constitute t h e m a j o r c o m m e r c i a l p r o d u c t forms of t h e c o m p o u n d , f o l l o w e d b y s p e c i a l c o a t e d a n d g r a n u l a t e d forms. also p r o d u c e d

i n granular and powder

other forms s u c h as c a l c i u m ascorbate

forms.

S o d i u m L - a s c o r b a t e is Limited production

and ascorbyl palmitate

of

depend

o n d e m a n d of these p r o d u c t s i n s p e c i a l t y use a p p l i c a t i o n s . H u n d r e d s of d e r i v a t i v e s of L - a s c o r b i c a c i d h a v e b e e n r e p o r t e d i n t h e l i t e r a t u r e , some of w h i c h are as f o l l o w s : m e t a l c o m p l e x e s or salts of


398

ASCORBIC

2

2

2

CO I HOCH I HCOH I HO 2.5 cm in May 1979 from Young Pecan Trees Treated with Dikegulac on October 4, 1978 in Three Georgia Orchards New


Dosage (g Active/L)

Control (no s p r a y ) 1.07 1.60 2.14

Living

Law Orchard* (Tifton)

Shoots/Terminal

Shoot

a

Garrison Orchard (Ray City)

Rigdon Orchard (Tifton)

5.3 a

3.8 a

5.8 a

6.4 a 5.6 a 6.8 a

5.3 b 6.1c 6.0 be

8.4 b 8.9 b 9.5 b

M e a n separation b y D u n c a n ' s m u l t i p l e range test, 5% l e v e l . C u l t i v a r s i n the L a w orchard were " C h e r o k e e " and " C h i c k a s a w " . T h e R i g d o n orchard was " D e s i r a b l e " and the G a r r i s o n orchard was " S t u a r t " . Source: R e p r o d u c e d , w i t h permission, f r o m R e f . 112. C o p y r i g h t 1980, A m e r i c a n Society for H o r t i c u l t u r a l Science. a

6

Animal Applications A s stated b y C h a t t e r j e e et a l . (116,918),

the a b i l i t y to

L - a s c o r b i c a c i d is absent i n insects, invertebrates, a n d t h e t i c c a p a c i t y started p h y l o g e n e t i c a l l y

synthesize

fish.

The biosyn

i n the k i d n e y of

amphibians,

r e m a i n e d i n t h a t of reptiles, b e c a m e t r a n s f e r r e d to the l i v e r of m a m m a l s , a n d finally d i s a p p e a r e d f r o m the g u i n e a p i g , some flying m a m m a l s , t h e m o n k e y , a n d h u m a n s . T h e o v e r a l l p a t t e r n of a s c o r b i c a c i d synthesis b y different species of a n i m a l s is c o r r e l a t e d to t h e i r p h y l o g e n y ( F i g u r e 3 ) . T r a d i t i o n a l l y , f a r m a n i m a l s d o not r e q u i r e a s c o r b i c a c i d i n t h e i r diets since this v i t a m i n is p r o d u c e d w i t h i n t h e i r bodies.

H o w e v e r , i t has l o n g

b e e n t h o u g h t t h a t the c a p a c i t y of the e n z y m e system i n v o l v e d c o u l d b e o v e r t a x e d or i m p a i r e d u n d e r stress c o n d i t i o n s s u c h as h i g h t e m p e r a t u r e a n d disease.

It is also c o n c e i v a b l e

t h a t i n b r e e d i n g a n i m a l s for h i g h

planes of p r o d u c t i v i t y , the rate of synthesis c o u l d b e i n a d e q u a t e .

De

p e n d i n g u p o n c i r c u m s t a n c e s a n d species, s u p p l e m e n t a r y L - a s c o r b i c a c i d i n the d i e t of some a n i m a l s has h a d a b e n e f i c i a l effect. Fish.

F i s h f a r m i n g or a q u a c u l t u r e , as i t is m o r e l i k e l y t o b e c a l l e d

t o d a y , has b e e n a t i m e - h o n o r e d p r a c t i c e g o i n g b a c k o v e r a t h o u s a n d years.

U n t i l m o r e r e c e n t l y , fish f a r m i n g w a s p r a c t i c e d o n a s m a l l scale

basis as m o r e or less a c o m p l e m e n t to other a g r i c u l t u r a l or m a r i n e p u r suits.

L i t t l e or n o t e c h n o l o g y

w a s i n v o l v e d ; b r e e d i n g stock w a s i n t r o

d u c e d i n t o a s u i t a b l e p o n d or f e n c e d off estuary, a n d n a t u r e p e r f o r m e d t h e rest. H a r v e s t i n g was d o n e b y h o o k i n g , n e t t i n g , or d r a i n i n g . W i t h i n t h e past t w o decades a n e w a p p r o a c h w a s i n t r o d u c e d , n a m e l y the l a r g e scale, e n v i r o n m e n t a l l y c o n t r o l l e d , r e s e a r c h - g u i d e d a q u a c u l t u r e w i t h a n expectancy

of l a r g e v o l u m e p r o d u c t i o n of h u m a n f o o d .

Growing


fish


20.

BAUERNFEIND

407


BIRDS

H I G H E R OROffft)

Figure 3. Schematic of ascorbic acid synthesizing abilities of various species of animals in relation to their phytogeny. (Reproduced, with permission, from Ref. 918. Copyright 1973, American Association for the Advancement of Science.)


408

ASCORBIC

ACID

confined i n tanks w i t h water temperature, acidity, a n d salinity controlled, f e d a r t i f i c i a l l y f o r m u l a t e d diets, a n d t r e a t e d w i t h p r o p h y l a c t i c

drugs

a n d p e s t i c i d e s b r o u g h t f o r t h p r o b l e m s absent i n t h e o l d s t y l e p r a c t i c e s . A s e a r l y as 1933, M c C a y a n d T u n i s o n (117) h a d n o t e d t h a t b r o o k t r o u t f e d f o r m a l i n - p r e s e r v e d m e a t d e v e l o p e d lordosis a n d scoliosis

(Fig

u r e 4 ) , b u t t h e c a u s a t i v e agent w a s u n k n o w n u n t i l t h e m i d - s i x t i e s w h e n K i t a m u r a et a l . ( 1 1 8 ) , N a k a g a w a (119), a n d P o s t o n (120) d e m o n s t r a t e d t h a t these d i s t o r t i o n s of t h e v e r t e b r a l c o l u m n w e r e t h e s y m p t o m s of a


d i e t a r y d e f i c i e n c y of L - a s c o r b i c a c i d ( v i t a m i n C ) . O t h e r d e f i c i e n c y s y m p toms a r e f r a c t u r e d i s l o c a t i o n of t h e s p i n e , b i z a r r e d i s t o r t i o n of c a r t i l a g e , impaired

collagen

formation,

depigmented

areas,

poor

growth, a n d

m o r t a l i t y . T h e d e f i c i e n c y is c o m m o n l y r e f e r r e d t o as t h e " b r o k e n b a c k " syndrome.

A s c o r b i c a c i d deficient t r o u t h a v e a l o w h e m a t o c r i t a n d h i g h

p l a s m a levels of t r i g l y c e r i d e s a n d c h o l e s t e r o l

(121).

B y 1972 i t w a s

k n o w n (122) t h a t s a l m o n , t r o u t , c h a r , c a r p , a q u a r i u m fish, a n d p r o b a b l y many

more

k i n d s of

fish

d e v e l o p specific

avitaminosis C

symptoms

( F i g u r e 4 ) w h e n d e n i e d d i e t a r y sources of a s c o r b i c a c i d . H i l t o n (123) r e p o r t e d t h a t t h e r a i n b o w t r o u t has v i r t u a l l y n o a b i l i t y t o s y n t h e s i z e a s c o r b i c a c i d . W h i l e c l i n i c a l aspects a r e d r a m a t i c , t h e s u b c l i n i c a l m a n i festations of t h e d e f i c i e n c y m a y p l a y a n e v e n m o r e i m p o r t a n t r o l e i n resistance t o b a c t e r i a l or v i r a l infections a n d the r e p a i r of tissue d a m a g e d

Figure 4. Ascorbic acid deficiency in fish. Coho salmon fed diet devoid of ascorbic acid and showing spinal curvatures typical of scoliosis (upper). Normal coho fed complete test diet containing 100 mg vitamin C/100 g dry ration (middle). Coho on same diet as upper fish and showing spinal curvature typical of lordosis (bottom). (Reproduced, with permission, from Ref. 130. Copyright 1969, American Fisheries Society.)


20.

BAUERNFEIND


b y p a r a s i t i c i n v a s i o n o r b y p h y s i c a l means.

409

B l a c k d e a t h is r e g a r d e d as

a n a s c o r b i c a c i d d e f i c i e n c y disease i n p e n a e i d s h r i m p ( 1 2 4 ) .

I n large-

scale a q u a c u l t u r a l field p r a c t i c e , v i t a m i n C deficiency w a s one of t h e u n a p p r e c i a t e d d i e t a r y aspects d u r i n g t h e late sixties a n d t h e seventies. C h a n n e l catfish f r o m i n t e n s i v e c u l t u r e s r a i s e d b y l o c a l fish f a r m e r s a n d showing skeletal deformities stimulated L o v e l l

( 1 2 5 ) i n 1973 t o

d e m o n s t r a t e e x p e r i m e n t a l l y t h a t these s y m p t o m s w e r e t h e result of a deficiency

of L - a s c o r b i c a c i d .

I n addition to the physical deformities,


w e i g h t gains of t h e g r o w i n g fish a n d f e e d c o n v e r s i o n w e r e

adversely

i n f l u e n c e d . W i l s o n a n d P o e (126) i n t h e same y e a r i n d u c e d the s c o r b u t i c c o n d i t i o n i n c h a n n e l catfish r e a r e d i n floating cages. T h e L - a s c o r b i c a c i d r e q u i r e m e n t w a s d e t e r m i n e d t o b e a b o u t 50 m g / k g of d i e t

(127,128).

W h i l e i n t h e past catfish a p p a r e n t l y w e r e a b l e t o o b t a i n a significant a m o u n t of a s c o r b i c a c i d f r o m organisms s u c h as insects, l a r v a e , a n d a l g a e w h e n r a i s e d i n e a r t h e n p o n d s , L o v e l l a n d L i m ( 1 2 9 ) i n 1978 s h o w e d that additional ascorbic a c i d was beneficial. Ascorbic a c i d supplemented diets a r e n e e d e d

f o r t r o u t (118-121, 130,131,132),

salmon

(119,130,

132), c a r p (133), a n d eels (134). A t t e m p t s h a v e b e e n m a d e to d e v e l o p m o r e stable forms of v i t a m i n C f o r fish feeds. (135)

A s c o r b a t e - 2 - s u l f a t e has b e e n p r o p o s e d

as a stable f o r m

of v i t a m i n C . A s a d i e t a r y c o m p o n e n t i t has b e e n r e p o r t e d to c u r e

scorbutic

signs i n s a l m o n o i d

fish

(136), to p r e v e n t

s c u r v y i n catfish

(137) b u t n o t t o possess a n t i s c o r b u t i c a c t i v i t y f o r e i t h e r t h e g u i n e a p i g (138) o r t h e rhesus m o n k e y

(139).

A n interesting pesticide-ascorbic

a c i d i n t e r a c t i o n i n fish h a s b e e n

s t u d i e d b y M a y e r a n d c o w o r k e r s (140-143).

S e v e r a l species of fish w e r e

c o n t i n u o u s l y e x p o s e d t o t o x a p h e n e o n diets w i t h a n d w i t h o u t

ascorbic

a c i d . T h e t o x a p h e n e r e d u c e d t h e a s c o r b i c a c i d content of t h e v e r t e b r a e b u t n o t of the l i v e r , l e a d i n g the investigators t o b e l i e v e t h a t this r e d u c t i o n u n f a v o r a b l y affects c o l l a g e n f o r m a t i o n . D i e t s c o n t a i n i n g t h e h i g h e r levels of L - a s c o r b i c a c i d r e d u c e d t o x a p h e n e residues a n d i n c r e a s e d t h e t o l e r a n c e t o t h e c h r o n i c effect of t o x a p h e n e o n g r o w t h , b o n e

development,

a n d s k i n lesions. Poultry.

M o r e t h a n 100 papers h a v e b e e n p u b l i s h e d o n t h e v a l u e

of s u p p l e m e n t i n g diets of f a r m a n i m a l s w i t h L - a s c o r b i c a c i d . T h e o v e r a l l results a r e at times c o n t r o v e r s i a l . E n h a n c e m e n t of p o u l t r y g r o w t h h a s b e e n r e p o r t e d b y s e v e r a l w o r k e r s u s i n g p u r i f i e d (144,145) a n d p r a c t i c a l (146,147,148)

rations a n d n o t b y others (149), t h e g e n e r a l i n t e r p r e t a

t i o n b e i n g t h a t t h e a s c o r b i c a c i d does n o t f u n c t i o n d i r e c t l y b u t i n d i r e c t l y , i n v o l v i n g a p r o t e c t i v e a c t i o n o r i m p r o v e d u t i l i z a t i o n of nutrients.

other

A d d e d d i e t a r y a s c o r b i c a c i d has b e e n r e p o r t e d t o s t i m u l a t e

synthesis o r l i b e r a t i o n of f o l i c a c i d b y i n t e s t i n a l b a c t e r i a , t o a i d i n its c o n v e r s i o n to f o l a c i n (146,150,151,152),

to reinforce antibiotics i n h i g h


410

ASCORBIC

energy feeds a n d t o i m p r o v e i r o n a b s o r p t i o n .

ACID

H i g h environmental tem

peratures r e d u c e t h e thickness ( 1 5 3 ) of eggshells of hens, thus l o w e r i n g the b r e a k i n g s t r e n g t h of t h e eggs ( 1 5 4 ) as w e l l as l o w e r i n g , e g g p r o d u c tion.

H i g h concentrations

of a s c o r b i c a c i d a r e f o u n d n o r m a l l y i n t h e

b i r d ' s tissues, e s p e c i a l l y i n t h e k i d n e y s a n d adrenals, gonads, a n d i n t h e bursa (155).

N e a r significant c o r r e l a t i o n has b e e n f o u n d b e t w e e n t h e

a s c o r b i c a c i d content of t h e a d r e n a l g l a n d a n d e g g p r o d u c t i o n i n t h e d u c k (156).

T h o r t o n a n d D e e b (157) noted that w h i l e ascorbic

acid


synthesis i n t h e k i d n e y s of l a y i n g hens w a s sufficient f o r p h y s i o l o g i c a l needs at n o r m a l e n v i r o n m e n t a l temperatures, i t w a s n o t w h e n t e m p e r a tures w e r e i n c r e a s e d f r o m 2 1 ° t o 31 ° C as b l o o d a s c o r b i c decreased.

N e s t o r et a l . ( 1 5 8 ) d e m o n s t r a t e d

a c i d levels

that ascorbic

acid (330

m g / k g ) a d d e d to t h e r a t i o n p r e v e n t e d a d e c l i n e i n b l o o d ascorbic levels that o c c u r r e d i n t u r k e y s c o n s u m i n g t h e u n s u p p l e m e n t e d

acid

ration

during w a r m weather ( 3 0 ° C ) . I n a trial during hot weather ( 3 5 - 4 0 ° C ) , P e r e k a n d K e n d l e r (159) o b t a i n e d significant i m p r o v e m e n t in egg production

a n d eggshell

weight when

ascorbic

m g / k g ) w a s a d d e d to t h e r a t i o n of L e g h o r n l a y i n g hens.

(Table V )

acid

(25-400

A subsequent

r e p o r t o n a s c o r b i c a c i d a p p l i c a t i o n ( 2 5 - 4 0 0 m g / k g ) b y t h e same w o r k e r s (160) c o n f i r m e d increases i n e g g p r o d u c t i o n ( 1 1 - 2 4 % ) , b u t e g g w e i g h t differences w e r e e q u i v o c a l .

S u p p l e m e n t a t i o n of diets w i t h a s c o r b i c a c i d

c o u n t e r a c t i n g h i g h e n v i r o n m e n t a l temperatures f o r p o u l t r y w e r e c l a i m e d b y A h m a d et a l . (161) a n d P a s u a l et a l . (162).

Under practical condi

tions of t h e r m a l stress ( 2 2 . 8 - 3 6 . 9 ° C ) a n d h u m i d i t y some benefit i n e g g p r o d u c t i o n has b e e n n o t e d f o l l o w i n g t h e f e e d i n g of a s p i r i n a n d a s c o r b i c acid

(163). S i n c e there is a n a b n o r m a l i t y of c a l c i u m m e t a b o l i s m i n s c u r v y , i t has

b e e n reasoned that s u p p l e m e n t a r y a s c o r b i c a c i d i n t h e h e n r a t i o n m i g h t h e l p t o resolve t h e p r o b l e m of t h i n e g g s h e l l d u r i n g s u m m e r heat.

Some

reports s h o w i m p r o v e d s h e l l soundness d u r i n g h i g h e n v i r o n m e n t a l t e m p e r a t u r e s ; others d o n o t . A c c o r d i n g t o T h o r t o n (164,165) a n d T h o r t o n

Table V .

Effect of Feeding L - A s c o r b i c A c i d to Hens Ascorbic Acid in Feed

Criteria

0

25

75

C u l l i n g a n d m o r t a l i t y (% of groups) E g g production (total eggs/hen) F e e d efficiency (average g / e g g ) E g g weights (average g/egg) E g g s h e l l w e i g h t (average % of whole egg)

31.5 80.0 232.2 60.1 9.05

7.4 102.7 210.4 60.9 9.87

20.3 90.6 206.7 61.3 9.25

(mg/kg)

400 12.9 103.5 202.8 62.7 9.47

Source: Reproduced, with permission, from Ref. 159. Copyright 1962, Poultry Science Association.


20.

BAUERNFEIND

411


a n d M o r e n g (166), a s c o r b i c a c i d ( 2 2 m g / k g ) a d d e d t o t h e f e e d w a s of v a l u e d u r i n g t h e h o t s u m m e r m o n t h s ( 2 9 ° C ) f o r t h e m a i n t e n a n c e of e g g s h e l l s t r e n g t h a n d thickness. I t w a s b e l i e v e d t h a t t h e a d d e d a s c o r b i c a c i d i n the feed increased feed consumption a n d oxygen consumption i n hens d u r i n g h o t w e a t h e r a n d t h a t a s c o r b i c a c i d counters t h e n o r m a l d e c l i n e i n t h y r o i d a c t i v i t y d u r i n g the h o t s u m m e r m o n t h s (167). A n o t h e r e x p l a n a t i o n offered f o r t h e h i g h t e m p e r a t u r e effect is a p o s s i b l e d e f o r m a t i o n i n t h e s t r u c t u r e of t h e i n n e r layers of t h e s h e l l u p o n w h i c h c a l c i u m Downloaded by UCSF LIB CKM RSCS MGMT on November 18, 2014 | http://pubs.acs.org Publication Date: June 1, 1982 | doi: 10.1021/ba-1982-0200.ch020

is d e p o s i t e d d u r i n g t h e e g g l a y i n g process as w e l l as t h e m i c r o s t r u c t u r e of the outer s h e l l (168,169).

A s n o t e d b y L y l e a n d M o r e n g (153), u n d e r

i n c r e a s e d t e m p e r a t u r e s , t h e a d d i t i o n of a s c o r b i c a c i d ( 4 4 m g / k g ) t o t h e d i e t p r e v e n t e d the b o d y t e m p e r a t u r e increase a n d the associated decrease i n e g g s h e l l t h i c k n e s s . S u l l i v a n a n d c o w o r k e r s (170,171) a n d E l - B o u s h y a n d c o w o r k e r s (168,172,173)

p u b l i s h e d c o n f i r m a t o r y results i n d i c a t i n g

significant i m p r o v e m e n t i n e g g q u a l i t y u n d e r h i g h e n v i r o n m e n t a l t e m peratures.

F o r example

(168),

the shell percentage

of t h e e g g w a s

significantly i m p r o v e d w h e n ascorbic a c i d ( 5 0 m g / k g ) was incorporated into the diet under a hot environmental temperature ( F i g u r e 5 ) . I n this r e p o r t , t h e a s c o r b i c a c i d a d d e d to t h e f e e d w a s s h o w n t o b e present. Changes

1 control

in shell

percentage

2 3 acclima. acclima. tization 1 tization 2

4 transition

5 stress

6 7 Months vitamin C vitaminC addition 1 addition 2 Experimental periods

Figure 5. Changes in eggshell percentage during the course of environmental temperature changes and vitamin C additions. Key: control, cold; O , treated, cold; A , control, hot; •, treated, hot; , vitamin C addition. (Reproduced, with permission, from Ref. 168. Copyright 1966, H. Veenman ir Zonen NV.)


412

ASCORBIC

ACID

K i v i m a e (174) o b t a i n e d i m p r o v e m e n t i n t h e q u a l i t y of t h e e g g s h e l l w i t h supplementary dietary ascorbic acid (100 m g / k g ) .

O t h e r w o r k e r s (160,

175-185) h a v e n o t b e e n a b l e t o s h o w i m p r o v e m e n t i n s h e l l t h i c k n e s s of eggs p r o d u c e d u n d e r t h e stress of h i g h t e m p e r a t u r e e n v i r o n m e n t s . Some

c r i t i c s c o n t e n d t h a t past e x p e r i m e n t a l studies d i d n o t i n v o l v e

c u r r e n t l y u s e d , h i g h - p r o d u c i n g genetic strains of p o u l t r y a n d t h e better f o r m u l a t e d rations c u r r e n t l y i n c o m m e r c i a l use. A g e n e r a l c r i t i c i s m l e v e l e d at m a n y of t h e studies o n a s c o r b i c a c i d a d d i t i o n t o t h e d i e t is


t h a t s t a b i l i t y d a t a a r e n o t r e p o r t e d a n d , d u e to t h e w e l l - k n o w n l a b i l i t y of the c o m p o u n d , i t m a y n o t h a v e b e e n a l w a y s present i n t h e f e e d a t t h e t i m e of c o n s u m p t i o n as d e c l a r e d . A n o t h e r i n d e x of e g g q u a l i t y , n a m e l y t h e t h i c k n e s s or v i s c o s i t y of the a l b u m e n s u r r o u n d i n g t h e y o l k , m e a s u r e d i n H a u g h u n i t s , w a s f o u n d to b e s u p e r i o r b y M o s t e r t (186), H e r r i c k a n d N o c k e l s (187), a n d C h e n a n d N o c k e l s (188) w i t h a s c o r b i c a c i d s u p p l e m e n t a t i o n of t h e hen's d i e t , b u t R a u c h ( 1 8 9 ) r e p o r t e d n o effect. S t i m u l a t e d spermatogenesis i n c o c k erels w a s i n d i c a t e d b y t h e e a r l y observations of W a w r z y n i a k (190) a n d Zanelli

(191).

T h e s e observations w e r e c o n f i r m e d b y t h e studies o f

Perek a n d Snapir (192).

W h e n ascorbic a c i d (100-200 m g / k g ) w a s

f e d i n t h e d i e t over some m o n t h s , t h e d a t a s h o w e d a significant i n c r e a s e of s p e r m a t o z o a n p r o d u c t i o n f o r the t r e a t e d groups over the c o n t r o l g r o u p . A n o t h e r t y p e of stress, " l a y i n g cage f a t i g u e , " w h e r e i n t h e l a y i n g h e n h a s difficulty i n s t a n d i n g o n t h e w i r e floor, has r e s p o n d e d t o a d m i n i s t r a t i o n of a s c o r b i c a c i d b y injections ( 1 0 0 m g ) a c c o r d i n g t o P o l s t e r (193). T h e r o l e of v i t a m i n C i n t h e p h y s i o l o g y a n d n u t r i t i o n of p o u l t r y h a s b e e n r e v i e w e d b y T a g w e r k e r (194). Swine.

I t is g e n e r a l l y a c c e p t e d that pigs d o n o t n e e d a s u p p l e m e n

t a r y s u p p l y of L - a s c o r b i c a c i d i n t h e i r r a t i o n u n d e r field o r p e n confine ment management practices.

Some f e e d i n g trials w h e r e a d d e d

ascorbic

a c i d w a s tested r e s u l t e d i n n e g a t i v e r e p o r t i n g s u c h as those of B a r b e r et a l . ( 1 9 5 ) , B o w l a n d (196), a n d T r a v n i c e k et a l . (197). I n others s u c h as C r o m w e l l et a l . ( 1 9 8 ) a v a r i a b l e g r o w t h response w a s r e p o r t e d a n d D v o r a k (199) r e p o r t e d e q u i v o c a l d a t a . B r o w n et a l . (200) f e d g r o w i n g pigs supplementary ascorbic a c i d (0-1000 m g p e r head d a i l y ) i n feed w i t h different levels of energy ( 1 4 0 - 3 4 0 k c a l X k g W °

7 5

per head d a i l y ) .

Increases i n g r o w t h o b s e r v e d w e r e i n a n i n c r e a s i n g o r d e r w i t h i n c r e a s i n g ascorbic

acid intake a n d a decreasing increment w i t h the rising

e n e r g y i n t a k e . B u r n s i d e (201) r e p o r t e d some g a i n i n f e e d efficiency w i t h a s c o r b i c a c i d ( 1 0 0 m g / k g ) , a n d V a l d m a u i s (202) a n d A n d r e s e n (203) d e m o n s t r a t e d i n c r e a s e d v i a b i l i t y i n b a b y p i g s . O t h e r s suggested L - a s c o r b i c a c i d as a s u p p l e m e n t f o r p i g l e t feeds (204) o r as p r o t e c t i o n a g a i n s t stress c o n d i t i o n s (205). iron availability:

T h e state of a s c o r b i c a c i d a d e q u a c y

Dvorak

(206) r e p o r t e d i r o n d e f i c i e n c y

influences

anemic

pigs

to h a v e l o w e r e d p l a s m a levels of a s c o r b i c a c i d , a n d G i p p et a l . (207)


20.

observed

413


BAUERNFEIND

i n c r e a s e d p l a s m a v a l u e s of i r o n w h e n a s c o r b i c a c i d

(0.5%)

w a s a d d e d to f e e d of the p i g l e t s . Ruminants.

T r e a t m e n t of r u m i n a n t s w i t h L - a s c o r b i c a c i d has m e r i t

i n u n u s u a l c i r c u m s t a n c e s r a t h e r t h a n a n y t y p e of r o u t i n e p r a c t i c e since these species synthesize t h e i r r e q u i r e m e n t s i n t h e i r n o r m a l l i f e

cycle

p a t t e r n . T h e d i g e s t i v e system of t h e y o u n g c a l f or l a m b f u n c t i o n s s i m i l a r l y to t h a t of m o n o g a s t r i c a n i m a l s f o r t h e e a r l y w e e k s of l i f e u n t i l t h e r u m i n a t i n g process is i n i t i a t e d .


Phillips a n d coworkers sin recommended

of t h e U n i v e r s i t y of W i s c o n

(208,209,210)

L-ascorbic a c i d (250 m g ) , v i t a m i n A (5000 I U ) , a n d

n i a c i n ( 5 0 m g ) as a d a i l y s u p p l e m e n t f o r t h e first 1 0 - 2 1 days of l i f e f o r the c a l f as p r o p h y l a x i s a n d c o n t r o l of e a r l y c a l f h o o d diseases.

Subsequent

reports b y N o r t o n et a l . (211) a n d N e v i n s et a l . (212) d i d n o t c o n f i r m the d e c l a r e d

benefits

of s u p p l e m e n t a r y

v i t a m i n feedings.

I n 1944 a

strange e c z e m a t o i d disease of calves w i t h c o n c o m i t a n t v e r y l o w p l a s m a a s c o r b i c a c i d values o c c u r r i n g o n d a i r y f a r m s i n M i c h i g a n w a s r e p o r t e d b y C o l e et a l . (213). T h e c o n d i t i o n r e s p o n d e d to a s c o r b i c a c i d t h e r a p y . B e t w e e n 1951 a n d 1961 a b o u t 4 % of t h e y o u n g calves i n a S c o t t i s h l a r g e h e r d of F r i e s i a n cattle w e r e n o t e d w i t h a n i n h e r i t e d d e r m a t o l o g i c a l c o n d i t i o n a n d other disorders w i t h l o w l i v e r , b l o o d a n d u r i n e a s c o r b i c a c i d values.

Calves treated w i t h ascorbic

acid produced

sponse (214) a n d r e l a p s e d after t h e r a p y Olson a n d Tammeus

a spectacular r e

ceased.

( 2 1 5 ) r e p o r t e d a s y n d r o m e of s u b p e r i o s t e a l

h e m o r r h a g e s , progressive stiffness, a n d e v e n t u a l i m m o b i l i t y i n a h e r d of H e r e f o r d cattle that r e s p o n d e d t o L - a s c o r b i c a c i d t r e a t m e n t b u t r e l a p s e d w h e n t r e a t m e n t ceased.

M i c h i g a n w o r k e r s (216) also o b s e r v e d a s c u r v y

like condition, a dermatitis, l o w hemoglobin

a n d ascorbic

acid

blood

v a l u e s , a n d d e a t h ( 3 5 a n i m a l s ) i n a h e r d of S h o r t h o r n cattle. S o m e decades a g o i t h a d b e e n f o u n d t h a t a s c o r b i c a c i d injections i m p r o v e d a large percentage

of sterile o r p a r t i a l l y sterile b u l l s

(217).

I n very h i g h p r o d u c i n g m i l k cows, w h i c h have difficulty b e c o m i n g

preg

n a n t , c e r t a i n breeders h a v e f o u n d , b y p r a c t i c a l experience, t h a t a s c o r b i c a c i d injected intravenously (2 g ) a n d intramuscularly ( 2 g ) before breed i n g w i t h t h e b u l l o n t h e same d a y or t h e f o l l o w i n g d a y i m p r o v e s c e p t i o n , e v e n t h o u g h , i n l a r g e h e r d s , i t is a b u r d e n s o m e P h i l l i p s et a l . (218), as e a r l y as 1941, i n observations " h a r d t o settle" c o w s , i n d i c a t e d that c e r t a i n cases

con

procedure.

a n d trials w i t h

(Table

V I ) were

a m e n a b l e t o a s c o r b i c a c i d t h e r a p y (0.5 g i n t r a v e n o u s l y a n d 2 g s u b c u taneously).

T h e vitamin A adequacy

of these a n i m a l s is n o t r e p o r t e d

a n d , hence, c o u l d b e a n i n f l u e n c i n g factor as i n v i t a m i n A synthesis of v i t a m i n C is d e c r e a s e d Disease Therapy.

deficiency,

(219).

I n a c t i v a t i o n of viruses b y L - a s c o r b i c a c i d w a s

r e p o r t e d i n 1935 t o o c c u r r a t h e r q u i c k l y u n d e r i n v i t r o c o n d i t i o n s

(220)

a n d s o m e w h a t l a t e r b y J u n g e b l u t (221) w i t h l i m i t e d c o n f i r m a t i o n in v i v o .


414

ASCORBIC


Table V I .

D a t a Showing the Effect of A s c o r b i c

Cow

Before Treatment (Number of Times Bred)

Type of Case

427

4

r e g u l a r e s t r u m — f a i l e d to settle

455

7

s k i p s 1 or 2 periods after service

437

6


17

8


16

9


29

4


33

5


1W

6


9W

5


4W

4


1450

many

u t e r u s — n o tone

1479

many

u t e r u s — n o tone

B

4

65

many

cystic ovary

404

many

cystic ovary

662

7

cystic ovary

D

many

ACID


Source: Reproduced, with permission, from Ref. 218. Copyright 1941, American Dairy Science Association. I n t h e c h i c k e n , t h e presence of i n c r e a s e d a s c o r b i c a c i d i n t a k e h a s b e e n r e p o r t e d t o l o w e r t h e response

to a T - i n d e p e n d e n t

antigen,

Brucella

abortus, a n d t o raise t h e response i n a d u l t s ( 2 2 2 ) , a n d t o i n h i b i t r e p l i c a t i o n a n d i n e f f e c t i v i t y of t h e a v i a n R N A t u m o r v i r u s ( 2 2 3 ) . reports b y others

(224r-230) s h o w e d

Subsequent

e n c o u r a g i n g results f o r a s c o r b i c

a c i d t r e a t m e n t i n t h e i n a c t i v a t i o n or a l l e v i a t i o n of c e r t a i n v i r a l a n d b a c t e r i a l diseases. N u n g e s t e r a n d A m e s ( 2 3 1 ) n o t e d t h a t a c t i v i t y o f p h a g o cytes w a s s i g n i f i c a n t l y i n c r e a s e d w i t h h i g h e r a s c o r b i c a c i d c o n c e n t r a tions i n t h e a m b i e n t m e d i u m .

I n 1971 a b i o c h e m i c a l m e c h a n i s m o f

a c t i o n i n p h a g o c y t o s i s w a s offered b y D e C h a t e l e t et a l . (232,919) i n volving L-ascorbic acid.


20.

BAUERNFEIND

415


A c i d T h e r a p y u p o n H a r d to Settle C o w s


After Treatment Services

Result

Method of Treating

1

pregnancy

injections 8 weeks before b r e e d i n g — w e e k l y , subcutaneous

pregnancy

6 i n j e c t i o n s over 5 weeks, b e g i n n i n g w i t h b r e e d i n g

pregnancy

6 injections over 30 d a y s p r i o r t o b r e e d i n g

pregnancy

i n t r a v e n o u s a n d subcutaneous i n j e c t i o n a t t i m e of heat

pregnancy

4 doses over 10 d a y s after b r e e d i n g

pregnancy


pregnancy


pregnancy

3 doses over 12 d a y s before b r e e d i n g

pregnancy


pregnancy


many

no help

subcutaneous a n d i n t r a v e n o u s

many

no help

subcutaneous a n d i n t r a v e n o u s

3

?

subcutaneous

many

no help

subcutaneous

many

no help

subcutaneous

several

no help

subcutaneous subcutaneous a n d i n t r a v e n o u s dosage too low

In

1967

Belfield

(233)

introduced a therapeutic program

L - a s c o r b i c a c i d i n the t r e a t m e n t against d i s t e m p e r of canines

using

(2000mg

i n t r a v e n o u s l y d a i l y ) a n d of felines (cats a n d t o y b r e e d s of dogs, 1000 mg)

w i t h s u p p o r t i v e t h e r a p y w i t h a r e s u l t a n t h i g h d e g r e e of

success.

C o n f i r m a t i o n o f the t r e a t m e n t w a s r e p o r t e d b y E d w a r d s (234)

i n the

t r e a t m e n t of cats w i t h f e l i n e r h i n o t r a c h e i t i s a n d b y B r a n d t ( 2 3 5 )

i n the

t r e a t m e n t of f e l i n e d i s t e m p e r a n d p n e u m o n i t i s i n cats. successful w i t h dogs. L e v e q u e (236)

B r a n d t w a s less

t r e a t e d dogs ( 6 7 a n i m a l s ) o v e r a

22-month p e r i o d w i t h canine distemper w i t h ascorbic a c i d a n d raised h i s r e c o v e r y rate of a n i m a l s to 7 2 % ( T a b l e V I I ) f r o m 5 - 1 0 % experienced.

W a r d (237)

previously

i n d i c a t e d t h a t h e h a d success i n a s c o r b i c a c i d


416

ASCORBIC

ACID

Table VII. Recovery Rates Among Dogs Treated with Ascorbic A c i d for Canine Distemper Complex Number Treated

Number Recovered

Recovery Rate (%)

A l l dogs t r e a t e d

67

48

71.6

Cases showing C N S disturbance

16

7

43.8

4

3

75.0

T y p i c a l cases w i t h c o n v u l s i o n s

12

4

33.3

Cases without C N S disturbance

51

41

80.4

T y p i c a l cases w i t h c o n v u l s i o n s a n d g i v e n 3 or fewer doses of ascorbic a c i d

7

1

14.3

T y p i c a l cases w i t h c o n v u l s i o n s a n d g i v e n more t h a n 3 doses of ascorbic acid

5

3

60.0

T y p i c a l cases w i t h o u t c o n v u l s i o n s a n d g i v e n more t h a n 3 doses of ascorbic acid

14

11

78.6

Patient Group


A t y p i c a l cases w i t h C N S d i s t u r b a n c e but no c o n v u l s i o n s

Source: Reproduced, with permission, from Ref. 236. Copyright 1969, Veterinary Medicine Publishing Company.

t r e a t m e n t of c a n i n e a n d f e l i n e d i s t e m p e r over a p e r i o d of years.

Other

v i r a l diseases s u c h as v i r a l e n c e p h a l i t i s ( 2 3 8 ) , for w h i c h there is a l a c k of effective t h e r a p y , m a y r e s p o n d to t r e a t m e n t w i t h h i g h levels of a s c o r b i c acid. Administration Methods.

I n a d m i n i s t e r i n g L - a s c o r b i c a c i d to a n i

m a l s , there are several feasible routes, d e p e n d i n g

o n the size of

the

a n i m a l a n d its c h a r a c t e r i s t i c s . F o r s m a l l a n i m a l s s u c h as c h i c k e n s , i t is p o s s i b l e to a d d the L - a s c o r b i c a c i d to t h e a u t o m a t i c w a t e r s u p p l y , p r o v i d i n g d i s s o l v e d trace m i n e r a l s s u c h as c o p p e r a n d i r o n c a n b e a v o i d e d or m i n i m i z e d , for e x a m p l e b y i n c o r p o r a t i o n of a c h e l a t i n g agent w i t h t h e a s c o r b i c a c i d . T h i s route w o u l d o n l y b e c o n s i d e r e d for a short p e r i o d or as a n e m e r g e n c y measure since s t a b i l i t y of aqueous solutions e x p o s e d to a i r is poor.

F o r l a r g e a n i m a l s , p a r e n t e r a l a d m i n i s t r a t i o n is t h e m o s t

r a p i d a n d effective

r o u t e for short p e r i o d s of n e e d .

F o r longer term

a d m i n i s t r a t i o n t h e f e e d r o u t e is p r e f e r r e d , a s s u m i n g a d e q u a t e

stability

exists for the t i m e p e r i o d of i n t e n d e d use. H i g h m o i s t u r e content i n feeds or exposure of f e e d to h i g h h u m i d i t y , h i g h t e m p e r a t u r e storage is d e t r i m e n t a l to a d d e d a s c o r b i c a c i d . P e l l e t i n g of f e e d , w h i c h i n c l u d e s exposure to steam or h o t w a t e r a n d s u b s e q u e n t storage, also destroys ( 3 0 - 6 0 % )

a s c o r b i c a c i d . A t t e m p t s to o v e r c o m e


20.

BAUERNFEIND


All

t h i s d e s t r u c t i v e a c t i o n i n c l u d e t h e use of c o a t e d a s c o r b i c a c i d p r o d u c t f o r m s a n d t h e a p p l i c a t i o n of a s c o r b i c a c i d to t h e p e l l e t f e e d f o l l o w i n g t h e p e l l e t i z i n g process. L - A s c o r b i c a c i d c o a t e d w i t h e t h y l c e l l u l o s e ( 4 % ) a n d finely p o w d e r e d a s c o r b i c a c i d u n i f o r m l y b l e n d e d i n t o a w a r m e d i b l e h y d r o g e n a t e d fat ( 5 0 % )

and immediately sprayed i n chilled air into

s m a l l b e a d l e t f o r m are t w o m e t h o d s

that have improved stability i n

a n i m a l feeds ( T a b l e V I I I ) . E v e n w i t h these p r o d u c t s , a n excess o v e r c l a i m values must be added.


If s o l i d fat is a n i n g r e d i e n t of t h e f e e d as a n e n e r g y source, p r a c t i c a l w a y of a d d i n g a s c o r b i c a c i d is to u n i f o r m l y s u s p e n d t h e powdered

product into the liquified hydrogenated

one finely

fat a n d s p r a y

the

s u s p e n s i o n onto t h e c o o l e d p e l l e t e d f e e d i n a t u m b l e r or o n a m o v i n g belt conveyor.

A n d r e w s a n d D a v i s (239)

f e a s i b l e for p e l l e t e d fish f e e d .

r e p o r t e d this m e t h o d to

be

H e a t - e x p a n d e d c o m m e r c i a l catfish f e e d

( 3 2 % p r o t e i n ) w a s s p r a y e d w i t h a w a r m fat suspension of a s c o r b i c a c i d to 2, 5, a n d 1 0 % fat c o a t i n g o n the feed. A f t e r d r y i n g , t h e w a t e r s t a b i l i t y ( w a t e r l e a c h i n g of a s c o r b i c a c i d ) of t h e p r o d u c t w a s e v a l u a t e d

(Table

I X ) as fish f e e d is n o r m a l l y cast o n w a t e r f o r fish c o n s u m p t i o n . A p r o b l e m arose as h o w to a d d L - a s c o r b i c a c i d to b a k e d

monkey

b i s c u i t s since b a k i n g is q u i t e d e s t r u c t i v e to a s c o r b i c a c i d . A f t e r some trial work it was discovered that ascorbic a c i d ( 1 0 - 2 0 % ) i n concentrated

Table VIII.

Ascorbic A c i d Stability in Unpelleted Feed Storage Condition 3 Weeks/45°C 100% Humidity

(% Retention Ascorbic Acid)

Type Product Ascorbic acid, crystalline E t h o c e l coated, A A F a t ( 5 0 % ) beadlets, A A

Table IX.

90 197 379

0 0 78-84

40-80 84-87 91-99

Retention of Ascorbic Acid° in Fabricated Fish Feeds

i ' A 'J T 7 Ascorbic Acid Level mg/kg Diet A

6 Weeks/45°C Room Humidity

Ascorbic Acid (%) Remaining in Feed Particles Alter Water Exposure 1 Minute

5 Minutes

10 Minutes

96 86 83

74 67 67

50 42 36

° Ascorbic acid in a warm fat suspension sprayed on feed after pelleting. Source: Reproduced, with permission, from Ref. 239. Copyright 1979, Miller Publishing Company.


418

ASCORBIC

ACID

sucrose s y r u p ( 5 0 - 6 0 % ) c o u l d b e b r u s h e d , s p r a y e d , o r d r o p p e d o n t o the b i s c u i t s after b a k i n g w i t h f a i r l y g o o d s t a b i l i t y p e r f o r m a n c e .

Ascorbic

a c i d is q u i t e stable i n h i g h sugar c o m p o s i t i o n s u c h as c a n d y , a d d e d a t the last stage of p r o c e s s i n g b e c a u s e of t h e dense n a t u r e of t h e h i g h sucrose p r o d u c t s a n d r e l a t i v e f r e e d o m f r o m

oxygen.

I n m i s c e l l a n e o u s a n i m a l a p p l i c a t i o n s r e l a t i n g to t h e

Miscellaneous.

use of a s c o r b i c a c i d , i n t e r a c t i o n s w i t h t o x i c levels of m i n e r a l s h a v e b e e n observed.

H i l l (240) f o u n d i n c r e a s e d d i e t a r y a s c o r b i c a c i d i n c h i c k e n s


w a s specific i n c o u n t e r a c t i n g m e t a l t o x i c i t y i n cases of s e l e n i u m a n d v a n a d i u m . T h i s w a s also n o t e d b y B e r g et a l . (241).

C a d m i u m toxicity

i n t h e r a t (242) a n d i n Japanese q u a i l (243,244) has b e e n r e v e r s e d o r counteracted.

Ascorbic acid (500 m g / k g )

given intraperitoneally before

or s i m u l t a n e o u s l y w i t h a n o r a l dose of p a r a q u a t a l t e r e d t h e a c t i v i t y of p a r a q u a t i n d i c a t i n g a s c o r b i c a c i d to b e a n effective

detoxifying

agent

(245). K a l l i s t r a t o s a n d F a s s k e (246) n o t e d i n h i b i t i o n of b e n z o [ a ] p y r e n e carcinogenesis i n rats w i t h a s c o r b i c a c i d t r e a t m e n t . T h e r e is a d e c r e a s e d l e v e l of a s c o r b i c a c i d i n l u n g tissue of m i c e f o l l o w i n g exposure t o o z o n e , a n d K r a t z i n g a n d W i l l i s (247) p r o p o s e t h a t one f u n c t i o n of tissue ascor b i c a c i d m a y b e a n e x t r a c e l l u l a r a n t i o x i d a n t i n t h e l u n g s . U s e of ascor b i c a c i d a n d m i n e r a l s u p p l e m e n t s i n t h e detoxification of n a r c o t i c a d d i c t s (248,920)

has b e e n

discussed.

W h i l e not a practical approach, the

i n j e c t i o n of y o u n g c h i c k e n s w i t h s o d i u m ascorbate has b e e n r e p o r t e d to h e a l bruises at a faster rate t h a n i n n o n t r e a t e d a n i m a l s (249).

Pharmaceutical

Applications

L - A s c o r b i c a c i d ( v i t a m i n C ) is a n a c t i v e i n g r e d i e n t i n a v a r i e t y of p h a r m a c e u t i c a l dosage forms s u c h a s : h i g h - p o t e n c y m u l t i v i t a m i n s u p p l e ment;

high-potency

multivitamin supplement w i t h iron;

high-potency

multivitamin supplement w i t h minerals; vitamin B complex; v i t a m i n B c o m p l e x w i t h v i t a m i n E ; p e d i a t r i c d r o p s ; tablets of a r a n g e of p o t e n c i e s ; i n j e c t a b l e s ; a n d s y r u p s a n d elixirs. A n a l t e r n a t i v e list of p h a r m a c e u t i c a l dosage forms c o n t a i n i n g a s c o r b i c a c i d w o u l d b e : tablets w i t h a w i d e r a n g e of potencies, d r o p s ( e s p e c i a l l y f o r p e d i a t r i c u s e ) , injectables, s y r u p s a n d elixirs, effervescent tablets, a n d m u l t i v i t a m i n p r e p a r a t i o n s . M a n y v i t a m i n s a r e q u i t e stable u n d e r n o r m a l p r o c e s s i n g tions a n d present l i t t l e o r n o s t a b i l i t y p r o b l e m s ceutical products.

in

finished

condi

pharma

These include biotin, niacin, niacinamide, pyridoxine,

r i b o f l a v i n , a n d a - t o c o p h e r y l acetate.

O t h e r s t h a t c a n present

problems

are a s c o r b i c a c i d , c a l c i f e r o l , c a l c i u m p a n t o t h e n a t e , c y a n o c o b a l a m i n , f o l a c i n , a n d r e t i n y l esters.

Overages

above label c l a i m are customarily

a d d e d t o v i t a m i n f o r m u l a t i o n s as a means of m a i n t a i n i n g t h e c l a i m e d l e v e l of e a c h v i t a m i n f o r t h e e x p e c t e d shelf l i f e of t h e p r o d u c t s . T h e p e r c e n t o v e r a g e f o r a p a r t i c u l a r v i t a m i n s u c h as L - a s c o r b i c a c i d w i l l v a r y


20.

419


BAUERNFEIND

a c c o r d i n g t o its p e r f o r m a n c e p a t t e r n . I n g e n e r a l , p r o b l e m s of i n s t a b i l i t y of v i t a m i n s are m u c h m o r e acute i n m u l t i v i t a m i n l i q u i d s t h a n i n s i n g l e v i t a m i n f o r m u l a t i o n s or i n s o l i d dosage forms. L - A s c o r b i c a c i d tablets constitute one of t h e

Solid Dosage Forms.

m a j o r uses i n p h a r m a c e u t i c a l a p p l i c a t i o n s . T a b l e t s m a y b e of t h e c o a t e d or u n c o a t e d t y p e , i n v a r i o u s potencies a n d sizes, a n d also s w a l l o w a b l e o r chewable.

These

s o l i d dosage forms

are p r e p a r e d

either b y

c o m p r e s s i o n or s l u g g i n g , b y w e t g r a n u l a t i o n , or b y d i r e c t

double

compression.


I n t h e u s u a l process of t a b l e t p r e p a r a t i o n a s c o r b i c a c i d i n p o w d e r

or

fine g r a n u l a r f o r m together w i t h s u i t a b l e d i l u e n t s of lactose, sucrose, o r s t a r c h w i t h l u b r i c a n t is s l u g g e d a n d r e d u c e d t o g r a n u l e s , t h e n

recom-

p r e s s e d i n t o tablets of t h e d e s i r e d size. A n alternate m e t h o d consists of m a k i n g a m o i s t paste of lactose, s t a r c h , a n d sucrose, w h i c h is screened, d r i e d , a n d r e d u c e d t o granules, t h e n m i x e d w i t h a s c o r b i c a c i d i n coarse crystalline form

a n d lubricant a n d compressed

i n t o tablets.

Special

L - a s c o r b i c a c i d a p p l i c a t i o n forms are a v a i l a b l e that p e r m i t d i r e c t c o m pression i n t o t a b l e t f o r m .

C h e w a b l e tablets c o n t a i n s o d i u m ascorbate i n

a d d i t i o n t o a s c o r b i c a c i d a n d flavoring agents t o p r o v i d e a m o r e p l e a s a n t taste. A n o t h e r s p e c i a l t y p e of s o l i d dosage f o r m is t h e effervescent t a b l e t , u s u a l l y of h i g h e r p o t e n c y

( 0 . 5 - 2 . 0 g ) t h a t is c o n s u m e d

when

added

w a t e r converts t h e t a b l e t to a l i q u i d p r e p a r a t i o n . T h e r e are a n u m b e r of scientific papers facture

(250-257)

(258-266), bility

a n d patents d e t a i l i n g t h e f o r m u l a t i o n a n d m a n u of s o l i d a s c o r b i c

a c i d dosage f o r m s , t h e i r s t a b i l i t y

i n v i t r o release of n u t r i e n t s (267,268,269),

(270-275).

Data (Table

X ) collected

a n d bioavaila

on commercial

ascorbic

a c i d tablets stored at r o o m t e m p e r a t u r e ( 2 5 ° C ) d e m o n s t r a t e f u l l l a b e l p o t e n c y over a shelf l i f e p e r i o d of m a n y years.

U n d e r n o r m a l storage

c o n d i t i o n s , c o m m e r c i a l t y p e a s c o r b i c a c i d tablets are stable f o r over 5 years

( > 9 5 % potency

products

retention).

(dehydroascorbic

T h e a m o u n t of three

acid, diketogulonic

breakdown

acid, a n d oxalic

acid)

f o r m e d u n d e r v a r i o u s storage c o n d i t i o n s constitutes a s m a l l p e r c e n t a g e of t h e a s c o r b i c a c i d content a n d poses n o d i e t a r y h a z a r d (276).

I n the

a p p l i c a t i o n of sugar c o a t i n g to m u l t i v i t a m i n tablets, c a r e f u l t e c h n i q u e is r e q u i r e d t o p r e v e n t excessive p e n e t r a t i o n of m o i s t u r e i n t o t h e t a b l e t core, w h i c h c a n l e a d to h i g h losses of v i t a m i n s sensitive to m o i s t u r e a n d p H influences. L i q u i d Dosage Forms.

I n d r y f o r m a n d at v e r y l o w m o i s t u r e c o n

tent, L - a s c o r b i c a c i d is v e r y stable, b u t i n s o l u t i o n e x p o s e d t o a i r o r o x y g e n i t is subject to o x i d a t i o n a c c e l e r a t e d b y d i s s o l v e d t r a c e m i n e r a l s ( c o p p e r a n d i r o n ) a n d l i g h t exposure.

L - A s c o r b i c a c i d is a r e d u c i n g

agent a n d is subject t o o x i d a t i v e d e c o m p o s i t i o n

i n solution. T h i s pro

ceeds first to d e h y d r o a s c o r b i c a c i d , w h i c h has f u l l v i t a m i n C a c t i v i t y , b u t continues t o d i k e t o g u l o n i c a c i d a n d v a r i o u s other b r e a k d o w n

products.

T h e d e g r a d a t i o n reactions are c o m p l e x a n d v a r y w i t h a e r o b i c o r a n a e r o b i c


420

ASCORBIC

Table X .

ACID

S t a b i l i t y of


Analysis of Ascorbic Acid, 100-mg Tablets, After Long-Term Storage at 25°C Lot Number

Storage Time (months)

V-418 KRK-202-66I KRK-202-65-III KRK-202-65-IV KRK-202-66-II DMS-289-II L o t 2082 L o t 2964B L o t 002-0B097A

103 103 103 103 103 90 120 240 96

Assay (% of claim)'

Initial Assay of claim) 103 107 110 110 111 102

99 104 106 106 105 104 111 101 98

— — —

* Assay by iodoraetric and 2,6-dichloroindophenol titrations.

situations, the n a t u r e of the f o r m u l a t i o n , a n d the t y p e of stress to w h i c h p h a r m a c e u t i c a l solutions are subjected. p H dependent.

A s c o r b i c a c i d d e g r a d a t i o n is also

U n d e r a e r o b i c c o n d i t i o n s , the rate of o x i d a t i o n

shows

m a x i m a at p H 5, c o r r e s p o n d i n g to r e a c t i o n w i t h 1 e q u i v a l e n t of

base,

a n d at p H 11.5, c o r r e s p o n d i n g to r e a c t i o n w i t h 2 e q u i v a l e n t s of

base.

A p H - l o g rate profile ( p H r a n g e of 3.5-7.2) for rate of a e r o b i c o x i d a t i o n of aqueous

a s c o r b i c a c i d solutions ( 6 7 ° C ) w a s d e t e r m i n e d b y

and Hajratwala (277). and Yacomeni solutions

(278)

A

first-order

degradation was observed.

Blaug Rogers

also s t u d i e d the effect of p H o n a s c o r b i c

acid

(25°C).

Under

anaerobic

c o n d i t i o n s , the

dependency

of

the s t a b i l i t y of

a s c o r b i c a c i d i n aqueous solutions o n p H is r e l a t i v e l y l o w , b u t t h e r e is a m a x i m u m rate of d e g r a d a t i o n , w h i c h is e q u a l to the p K ^ i of a c i d , at a p H of a b o u t 4.1.

ascorbic

S t a b i l i t y of a s c o r b i c a c i d i n m u l t i v i t a m i n

d r o p s has b e e n s t u d i e d at v a r i o u s p H levels. M a x i m u m losses o c c u r i n the p H range of 3.3 to 4.5 a n d s m a l l e r losses are f o u n d at h i g h e r p H ( u p to 5.5).

F i g u r e 6 shows s t a b i l i t y d a t a f o r a s c o r b i c a c i d i n m u l t i v i t a

m i n e l i x i r p r e p a r a t i o n s for teaspoon dosage for storage at 4 5 ° C . of s u c h solutions has a m o r e p r o n o u n c e d drops.

The p H

effect t h a n i n m u l t i v i t a m i n

Losses at p H 3.5 are as h i g h as 4 0 % i n 6 weeks at 4 5 ° C .

Rate

studies o n the a n a e r o b i c d e g r a d a t i o n of a s c o r b i c a c i d as i n f l u e n c e d b y m e t a l ions, F i n h o l t et a l . (279,280), h a v e i n d i c a t e d the i n v o l v e m e n t of s a l t - a c i d a n d metal complex formations. D u r i n g the past t w o decades a s c o r b i c a c i d free r a d i c a l s h a v e b e c o m e recognized

a n d their kinetics studied

(281-287)

i n the oxidation

of

a s c o r b i c a c i d . I n t e r a c t i o n s b e t w e e n c e r t a i n of the v i t a m i n s or i n g r e d i e n t s


20.

BAUERNFEIND

421


Vitamin C Tablets Analysis of Ascorbic After Long-Term

Acid, 100-mg Tablets, Storage at 25°C

Diketogulonic


Acid

4 3 4 4 6

Oxalic

(%)

Acid (%)

1.0 2.0 1.0 1.0 2.0 0.5

0.5 0.5 0.5 0.5 1.0 0.5 0.2 0.4

S o u r c e : R e p r o d u c e d , w i t h permission, from R e f . 276. Pharmaceutical Association.

Dehydroascorbic Acid

(%)

0.5 0.2 0.2 0.4 2.4 0.3 0.4 2.3 1.3 C o p y r i g h t 1976, A m e r i c a n

are of great interest to the p h a r m a c e u t i c a l c h e m i s t b o t h f r o m the t h e o r e t i c a l a n d the p r a c t i c a l v i e w p o i n t s . 1.

H a n d , G u t h r i e , a n d S h a r p (288) r e p o r t e d t h a t r i b o f l a v i n catalyzes the p h o t o c h e m i c a l o x i d a t i o n of a s c o r b i c a c i d t h a t occurs i n t h e presence of o x y g e n o n exposure to l i g h t . C o n v e r s e l y , a s c o r b i c a c i d exerts a r e d u c i n g effect o n r i b o flavin, w h i c h is v e r y l i k e l y i n v o l v e d i n the f o r m a t i o n of c h l o r o f l a v i n i n B - c o m p l e x solutions c o n t a i n i n g a s c o r b i c acid.

2.

A y e l l o w c o m p l e x of 1 m o l e c u l e of n i a c i n a m i d e w i t h 1 m o l e c u l e of a s c o r b i c a c i d also forms r e a d i l y i n s o l u t i o n b y w h a t appears to b e a charge-transfer r e a c t i o n . T h e c o m p l e x has b e e n p r e p a r e d i n s o l i d f o r m . I t has b e e n c l a i m e d that the p r e f o r m i n g of this c o m p l e x presents difficulties w i t h t h i c k e n i n g a n d h a r d e n i n g of m i x t u r e s e m p l o y e d i n soft g e l a t i n capsules. G u t t m a n a n d B r o o k e ( 2 8 9 ) f o u n d the extent of association b e t w e e n n i a c i n a m i d e a n d a s c o r b i c a c i d to b e p H d e p e n d e n t w i t h m a x i m u m a d s o r b a n c e at p H 3.8.

3.

I n a c i d m e d i u m the f o l i c a c i d m o l e c u l e is c l e a v e d b y r e d u c i n g agents s u c h as a s c o r b i c a c i d . T h i s r e a c t i o n occurs i n t w o stages: ( i ) cleavage to the p t e r i d i n e m o i e t y p l u s p - a m i n o b e n z o y l g l u t a m i c a c i d , a n d ( i i ) d e s t r u c t i o n of t h e free a m i n o g r o u p of the p - a m i n o b e n z o y l g l u t a m i c a c i d . T h e d e c o m p o s i t i o n of f o l i c a c i d is m o r e r a p i d at p H 3 t h a n at p H 6.5.

4.

S t a b i l i z a t i o n of v i t a m i n B solutions i n the presence of t h i a m i n e , n i a c i n a m i d e , a n d a s c o r b i c a c i d has b e e n the s u b ject of a n u m b e r of patents. N e w m a r k (290) has d e s c r i b e d i 2



Figure 6.

Ascorbic acid in multivitamin preparations for teaspoon dosage. Left, 3 weeks/45°C ucts); right, 6 weeks/45°C (4 products).


(5 prod-

o > o 8

M

W W

o o

>

to to

20.

423


BAUERNFEIND

the effective s t a b i l i z a t i o n of B i i n s u c h solutions b y v a r i ous i r o n c o m p o u n d s a n d salts.


2

5.

A s c o r b i c a c i d w i l l destroy m a n y of t h e F D & C a z o colors i n s o l u t i o n , so stable colorants m u s t b e chosen.

6.

T h e d e c o m p o s i t i o n of a s c o r b i c a c i d is c a t a l y z e d b y trace m e t a l ions i n s o l u t i o n , h e n c e t h e a d d i t i o n of s e q u e s t e r i n g agents s u c h as E D T A a n d its salts has b e e n s h o w n t o e n h a n c e t h e s t a b i l i t y of a s c o r b i c a c i d (291,292,293).

A r e v i e w of s u c h i n t e r a c t i o n s w a s p u b l i s h e d b y S c h e i n d l i n ( 2 9 4 ) i n 1958.

P o r i k h a n d L o f g r e n ( 2 9 5 ) d e m o n s t r a t e d i n c r e a s e d s t a b i l i t y of

a s c o r b i c a c i d , c o n f i r m e d b y K a t o (296), w h e n g l y c e r i n a n d / o r p r o p y l e n e g l y c o l t y p e p r o d u c t s w e r e s u b s t i t u t e d f o r p a r t of t h e w a t e r i n a n o r a l multivitamin findings

liquid.

B a u d e l i n a n d Tuschhoff

(297)

reported

similar

o n a s c o r b i c a c i d a n d , i n a d d i t i o n , f o u n d t h a t e t h a n o l o r sugars

s u c h as sucrose, c o r n s y r u p , a n d dextrose also p r o v i d e a s t a b i l i z i n g effect o n a s c o r b i c a c i d . P a u s t a n d C o l i a z z i ( 2 9 8 ) a n d F a b r i z i et a l . ( 2 9 9 ) f o u n d t h a t t h e first-order rate constants f o r o x i d a t i v e d e c o m p o s i t i o n of a s c o r b i c a c i d decrease as a f u n c t i o n of p o l y s o r b a t e 80 c o n c e n t r a t i o n u p t o 3 0 % at 3 0 ° C .

Similar

findings

w e r e o b s e r v e d b y N i x o n a n d C h a w l a (300)

w i t h p o l y s o r b a t e 20. O t h e r reports (301-309) d e a l w i t h factors i n f l u e n c i n g f o r m u l a t i o n a n d s t a b i l i t y of l i q u i d dosage forms of a s c o r b i c a c i d . Sterile a q u e o u s solutions p r e p a r e d w i t h h i g h p u r i t y a s c o r b i c a c i d and

pyrogen-free distilled water i n glass-lined equipment under absolute

sanitary operations a n d filled i n t o a m p u l e s a r e necessary f o r i n j e c t a b l e solutions f o r p a r e n t e r a l use i n h u m a n s a n d a n i m a l s . F o r a l l i n j e c t a b l e p r o d u c t s , i t is i m p o r t a n t t o select c o n t a i n e r , stopper, p r e s e r v a t i v e , a n d other i n g r e d i e n t s t h a t are c o m p a t i b l e . T h e f o r m u l a t o r of l i q u i d m u l t i v i t a m i n p h a r m a c e u t i c a l p r o d u c t s s u c h as b a b y d r o p s , s y r u p s , elixirs, a n d injectables encounters n u m e r o u s p r o b lems i n a t t e m p t i n g to d e v e l o p p r o d u c t s h a v i n g a d e q u a t e p h y s i c a l a n d c h e m i c a l s t a b i l i t y as w e l l as s u i t a b l e taste, o d o r , color, a n d f r e e d o m f r o m b a c t e r i a l c o n t a m i n a t i o n . M a n y of these p r o b l e m s arise f r o m t h e d i f f e r i n g s o l u b i l i t y a n d s t a b i l i t y c h a r a c t e r i s t i c s of t h e i n d i v i d u a l v i t a m i n s , p a r t i c u l a r l y as these relate t o t h e p H of t h e solutions a n d p o t e n t i a l i n t e r a c t i o n s . D e s p i t e these n u m e r o u s p r o b l e m s , v a r i o u s w a y s h a v e b e e n d e v i s e d f o r producing multivitamin combinations i n liquid form containing L-ascorbic a c i d that have acceptable stability characteristics. Successful

develop

m e n t of s u c h p r o d u c t s r e q u i r e s a k n o w l e d g e o f : ( i ) t h e f u n d a m e n t a l aspects of t h e p h y s i c a l a n d c h e m i c a l p r o p e r t i e s of t h e v i t a m i n

forms

a v a i l a b l e ; ( i i ) t h e use of a d e q u a t e t e c h n i q u e s of m a n u f a c t u r e ; a n d ( h i ) t h e e m p l o y m e n t of s u i t a b l e overages b a s e d o n c r i t i c a l s t a b i l i t y studies.


424

ASCORBIC

ACID

Food Applications L - A s c o r b i c a c i d m a y b e a d d e d to foods or f o o d i n g r e d i e n t s as a n u t r i e n t to f o r t i f y n a t u r a l foods h a v i n g l i t t l e or n o v i t a m i n C , to restore losses, to s t a n d a r d i z e a g i v e n class of f o o d p r o d u c t s to h a v i n g a p r e selected q u a n t i t y , a n d to e n d o w or e n r i c h s y n t h e t i c foods w i t h n u t r i t i o n a l value.

T h e t e r m n u t r i f i c a t i o n is u s e d to c o v e r a l l t h e a b o v e situations

f o r a d d i n g a n u t r i e n t to a f o o d p r o d u c t .

T o n u t r i f y a f o o d o r to m a k e

it a n u t r i f i e d f o o d i m p l i e s a n act to m a k e the f o o d m o r e n u t r i t i o u s .


Adding

m i c r o n u t r i e n t s s u c h as v i t a m i n s , m i n e r a l s , a m i n o

acids,

and

v i t a m i n A a c t i v e c a r o t e n o i d colorants to a f o o d at l o w cost for n u t r i t i o n a l i m p r o v e m e n t is not a n e w c o n c e p t . I o d i n e w a s a d d e d to salt i n t h e 19th c e n t u r y i n S o u t h A m e r i c a . N u t r i f i c a t i o n is a most r a p i d , most e c o n o m i c a l , most

flexible, a n d most

socially acceptable

method

of

changing

the

n u t r i e n t i n t a k e of a g i v e n p o p u l a t i o n (310). N e w t e c h n o l o g i c a l a d v a n c e s e n a b l e the f o o d p r o c e s s i n g i n d u s t r y t o m a r k e t m a n y m o r e f o o d p r o d u c t s t h a n decades past. F a c t o r s t h a t m u s t be considered i n conjunction w i t h appropriate technology before a d d e d a s c o r b i c a c i d is c o n s i d e r e d a r e : cost of the specific f o o d ; c o n v e n i e n c e

of

use; r e l a t i o n s h i p of the n u t r i e n t to the u s u a l f o o d selection p a t t e r n o r other r e p l a c e m e n t or s u p p l e m e n t a l f o o d p r o d u c t s ; s t a b i l i t y of the n u t r i ent i n the f o o d d u r i n g m a r k e t shelf l i f e a n d h o m e p r e p a r a t i o n ; s p e c i a l f o o d needs,

for

e x a m p l e , i n f a n t , g e r i a t r i c , or m i l i t a r y ; p u b l i c h e a l t h

considerations. L - A s c o r b i c a c i d is also a d d e d to f o o d i n essentially a n o n - n u t r i e n t c a p a c i t y s u c h as a p r e s e r v a t i v e or o x y g e n acceptor, as a n a c i d u l a n t , as a s t a b i l i z e r of c u r e d m e a t color, or as a flour i m p r o v e r .

B e c a u s e of t h e

e n e - d i o l g r o u p , i t has a m a r k e d i n h i b i t o r y influence o n the o x i d a t i o n r e d u c t i o n reactions r e s p o n s i b l e for u n d e s i r a b l e color, development.

flavor,

and

odor

Its m e c h a n i s m of a c t i o n is d e p e n d e n t u p o n the c h a r a c t e r

istics of the f o o d or f o o d i n g r e d i e n t , the associated e n v i r o n m e n t s , t h e p r o c e s s i n g t e c h n o l o g y , a n d the storage e x p e c t a n c y of the p r o d u c t . T h e food processing industry can obtain L-ascorbic a c i d a n d sodium ascorbate c o m m e r c i a l l y i n a v a r i e t y of m e s h sizes to meet the r e q u i r e ments of v a r i o u s k i n d s of f o o d p r o d u c t s .

These crystalline compounds

are stable f o r years w h e n s t o r e d u n d e r c o o l , d r y c o n d i t i o n s i n containers.

closed

E s t e r s of a s c o r b i c a c i d s u c h as a s c o r b y l p a l m i t a t e are also

available. A d d i t i o n Methods.

T h e f o u r b a s i c technologies d e v e l o p e d for a d d

i n g a s c o r b i c a c i d to foods a r e : 1.

Tablets or wafers. C o m p r e s s e d s o l u b l e discs c o n t a i n i n g inert, e d i b l e carriers a n d sufficient a s c o r b i c a c i d to m e e t the ascorbic a c i d regulatory a n d (or) processing require ments of a g i v e n q u a n t i t y of f o o d . T h e t a b l e t a d d e d t o


20.

BAUERNFEIND

425



the c o n t a i n e r p r i o r t o filling a n d s e a l i n g of l i q u i d foods dissolves i m m e d i a t e l y , o r m a y b e d i s s o l v e d a n d a d d e d t o s e m i s o l i d foods o r d r y foods at a late stage of f o o d preparation. 2.

Dry premixes. A u n i f o r m m i x t u r e of a k n o w n a m o u n t of a s c o r b i c a c i d a n d a d r y c a r r i e r , u s u a l l y a constituent of t h e f o o d . T h e p r e m i x b l e n d e d w i t h a p r e s c r i b e d q u a n t i t y of d r y f o o d p r o d u c t gives a greater assurance of p r o d u c t u n i f o r m i t y since t h e q u a n t i t y of t h e p u r e v i t a m i n m a y b e small.

3.

Liquid sprays. S p r a y s of a s c o r b i c a c i d solutions o r s u s p e n sions t h a t m a y b e c o n s i d e r e d l i q u i d p r e m i x e s . T h e sprays are d i r e c t e d onto t h e surface of a f o o d o r i n j e c t e d i n t o l i q u i d f o o d p r o d u c t s t o c i r c u m v e n t difficult o r c o n t i n u o u s p r o c e s s i n g c o n d i t i o n s . F o r e x a m p l e , toasted ready-to-eat cereals a r e f o r t i f i e d b y s p r a y i n g a s o l u t i o n onto flakes s t i l l w a r m f r o m t h e t o a s t i n g process.

4.

Pure compound. C r y s t a l l i n e a s c o r b i c a c i d , s o d i u m ascor bate o r s p e c i a l c o a t e d p r o d u c t forms a r e w i d e l y a d d e d d i r e c t l y to f o o d o r p r e d e t e r m i n e d q u a n t i t i e s often i n t h e f o r m of p r e w e i g h e d packets f o r c o n v e n i e n c e . A d d i t i o n is a c c o m p a n i e d b y m i x i n g t o ensure u n i f o r m i t y .

H u n d r e d s , i f n o t t h o u s a n d s , of reports h a v e b e e n p u b l i s h e d o n t h e a p p l i c a t i o n of a s c o r b i c a c i d t o f o o d p r o d u c t s f o r either n u t r i t i o n a l objec tives o r i m p r o v e m e n t i n f o o d q u a l i t y . B a u e r n f e i n d r e v i e w e d t h e use of a s c o r b i c a c i d (311,312) i n p r o c e s s i n g f o o d i n 1953 ( 4 0 6 references) a n d a g a i n i n 1970 ( 5 2 0 r e f e r e n c e s ) ; other r e v i e w s (313-332) o n f o o d a p p l i cations of a s c o r b i c a c i d h a v e a p p e a r e d p r i o r t o a n d f o l l o w i n g these dates. T h e s t a b i l i t y of a s c o r b i c a c i d is i n f l u e n c e d b y a t m o s p h e r i c

oxygen,

water activity, oxidative enzymes, pasteurization methods, metal con t a m i n a t i o n , a n d s u l f u r d i o x i d e content. T h e d e g r a d a t i o n of a s c o r b i c a c i d i n foods h a s b e e n w i d e l y s t u d i e d . I t is c o m p l e x

i n nature a n d depends

presence of other substances.

o n specific c o n d i t i o n s a n d t h e

W h i l e d e g r a d a t i o n is n o t a t o p i c of this

r e v i e w a f e w f o o d r e l a t e d references a r e i n c l u d e d as a n i n t r o d u c t i o n t o t h e l i t e r a t u r e o n this subject.

A s c o r b i c a c i d has t h e a b i l i t y t o scavenge

s u p e r o x i d e a n d h y d r o x y l r a d i c a l s as w e l l as singlet o x y g e n (333).

In a

1975 r e p o r t o n t h e d e s t r u c t i o n of a s c o r b i c a c i d as a f u n c t i o n of w a t e r a c t i v i t y b y L e e a n d L a b u z a ( 3 3 4 ) , t h e h a l f - l i f e of a s c o r b i c a c i d ( F i g u r e 7)

is w e l l i l l u s t r a t e d as a f u n c t i o n of m o i s t u r e content.

Degradation

compounds formed b y heating ascorbic a c i d i n solution were identified b y T a t u m et a l . ( 3 3 5 ) a n d K a m i y a (337)

(336).

Thompson and Fennema

o b s e r v e d differences i n t h e effect of f r e e z i n g o n t h e rate of o x i

d a t i o n of a s c o r b i c a c i d i n foods as c o m p a r e d w i t h d i l u t e s i m p l e solutions. T i m b e r l a k e (338) f o u n d t h e o x i d a t i o n of a s c o r b i c a c i d i n t h e presence of metals w a s significant a n d c o u l d b e i n f l u e n c e d b y m e t a l c h e l a t i n g



426

ASCORBIC A C I D

MOISTURE CONTENT (g H 0/IOOg SOLIDS) 2

Figure 7. Half-life for ascorbic acid as a function of moisture content. Key: %, DM; O, DH. (Reproduced, with permission, from Ref. 334. Copyright 1975, Institute of Food Technologists.) agents i n b l a c k c u r r a n t juice. I n t h e last d e c a d e m o r e a t t e n t i o n h a s b e e n g i v e n t o k i n e t i c s of q u a l i t y d e g r a d a t i o n i n c l u d i n g a s c o r b i c a c i d o x i d a t i o n i n food products

or model

systems.

E x a m p l e s are m o i s t u r e - s e n s i t i v e

p r o d u c t s (339), a s c o r b i c a c i d o x i d a t i o n i n i n f a n t f o r m u l a d u r i n g storage (340), a s c o r b i c a c i d s t a b i l i t y of t o m a t o j u i c e as f u n c t i o n s of t e m p e r a t u r e , p H , a n d m e t a l c a t a l y s t (341), t h e d e g r a d a t i o n of a s c o r b i c

acid i n a

d e h y d r a t e d f o o d system (342), a n d t h e o x y g e n effect o n t h e d e g r a d a t i o n of a s c o r b i c a c i d i n a d e h y d r a t e d f o o d system ( 3 4 3 ) . T h e p o i n t i n t h e f o o d m a n u f a c t u r i n g process a t w h i c h a s c o r b i c a c i d is i n t r o d u c e d is i m p o r t a n t . I d e a l l y , i t is a d d e d as close t o t h e t e r m i n a l process stage as p o s s i b l e , w h e n c o n d i t i o n s a l l o w . T o m a x i m i z e t h e sta b i l i t y a n d efficacy of a s c o r b i c a c i d a d d e d t o foodstuffs, precautions are recommended

the following

f o r p r a c t i c a l success a c c o r d i n g t o K l a e u i

(317): 1.

D i r e c t contact of t h e f o o d p r o d u c t o r its i n g r e d i e n t s w i t h brass, b r o n z e , m o n e l , steel, a n d i r o n m u s t b e a v o i d e d .


20.

BAUERNFEIND

2.

T h e e q u i p m e n t u s e d s h o u l d b e of stainless steel, a l u m i n u m , e n a m e l , glass, c h i n a , or a p p r o v e d p l a s t i c . W h e r e v e r possible, deaeration should precede processing, w h i c h s h o u l d b e c a r r i e d out u n d e r i n e r t gas o r i n a vacuum. D u r i n g mixing, emulsification, homogenization, a n d the l i k e , o x y g e n or a i r s h o u l d n o t b e i n t r o d u c e d i n t o t h e product. W h e r e possible, food product should be protected f r o m l i g h t a n d other r a d i a n t energy. C o n t a i n e r s s h o u l d b e filled to m a x i m u m c a p a c i t y , t h a t i s , t h e h e a d s p a c e s h o u l d b e k e p t as s m a l l as p o s s i b l e . A f t e r h e a t p r o c e s s i n g of sealed containers, r a p i d c o o l i n g s h o u l d f o l l o w a n d the p r o d u c t s s h o u l d be s t o r e d at c o o l temperatures.

3.

4.

5.


427


6. 7.

8.

If p r a c t i c a b l e , s e q u e s t e r i n g agents s u c h as citrates, E D T A , or cysteine m a y b e a d d e d .

phosphates,

9.

A l l a u t o x i d i z a b l e i n g r e d i e n t s , s u c h as flavoring oils, a d d e d to the f o o d p r o d u c t s h o u l d h a v e a l o w p e r o x i d e v a l u e .

10.

W h e n e v e r feasible, a s h o r t - t i m e heat t r e a t m e n t of f r e s h f o o d p r o d u c t s s h o u l d b e e m p l o y e d to i n a c t i v a t e e n z y m e s before a d d i n g ascorbic acid.

11.

W h e r e feasible, m i c r o o r g a n i s m s m a y b e r e m o v e d b y fil t r a t i o n or i n a c t i v a t e d b y heat t r e a t m e n t a n d , i f p o s s i b l e , p r o c e s s i n g m a y b e c o n t i n u e d u n d e r aseptic c o n d i t i o n s .

12.

P r e f e r a b l y , some a s c o r b i c a c i d s h o u l d b e present p r i o r to b o t t l i n g or c a n n i n g ( 1 m L of r e s i d u a l a i r reacts, t h e o r e t i c a l l y , w i t h 3.3 m g of a s c o r b i c a c i d ) .

L - A s c o r b i c a c i d is f o u n d i n a l l l i v i n g tissues, b o t h a n i m a l a n d p l a n t m a t t e r , a n d as s u c h has b e e n c o n s u m e d b y h u m a n s for t h o u s a n d s

of

years, thus g i v i n g e n c o u r a g e m e n t t h a t the c o m p o u n d is p h y s i o l o g i c a l l y a c c e p t a b l e a n d safe.

F u r t h e r m o r e , extensive t e s t i n g of L - a s c o r b i c a c i d

p r e p a r e d b y c h e m i c a l synthesis confirms its r e l a t i v e safety.

Large-scale

m a n u f a c t u r e , c o u p l e d w i t h h i g h standards of p u r i t y a n d r e l a t i v e l y l o w cost, makes a p p l i c a t i o n to f o o d p r o d u c t s e c o n o m i c a l l y feasible. Use as a Nutrient. complete

P r o c e s s i n g n e v e r makes a f o o d p r o d u c t

more

than the o r i g i n a l fresh product nor can it compensate

for

nature's i d i o s y n c r a s i e s i n c o n t e n t of o r i g i n a l n u t r i e n t s . H o w e v e r ,

the

p r e s e r v a t i o n , p r o c e s s i n g , a n d storage of f o o d are necessary to p r o v i d e p a l a t a b i l i t y , safety to h e a l t h , v a r i e t y of selection, a n d p r o v i s i o n for f u t u r e use. I n t h e p r o d u c t i o n , h a n d l i n g , p r e s e r v i n g , p r o c e s s i n g , a n d storage of f o o d , some n u t r i e n t s are lost or s i g n i f i c a n t l y l o w e r e d . N o t o n l y does t h e n u t r i e n t content v a r y i n the n a t u r a l w h o l e - p l a n t f o o d — b e c a u s e of v a r i e t y , c l i m a t e , h a r v e s t i n g m e t h o d s , s t o r a g e — b u t p r o c e s s i n g ( b e c a u s e of e x p o sure to heat, o x y g e n , metals, a n d so f o r t h , a n d f o o d - f r a c t i o n a t i o n

proc

esses ) modifies t h e n u t r i e n t content. O n e n u t r i e n t e s p e c i a l l y sensitive to


428

ASCORBIC

ACID

some of the factors m e n t i o n e d is L - a s c o r b i c a c i d . F u r t h e r m o r e , n o t o n l y are the t r a d i t i o n a l n a t u r a l a n d p r o c e s s e d but

also n e w

"convenience,"

" d i e t e t i c or l o w - c a l o r i e " foods. foods.

or r e f i n e d foods s o l d

"semblance,"

"fabricated,"

today,

"novel,"

and

S o m e of these p r o d u c t s s i m u l a t e k n o w n

O t h e r s h a v e n o p a s t c o u n t e r p a r t a n d m a y h a v e l o w levels

of

m i c r o n u t r i e n t s s u c h as L - a s c o r b i c a c i d , w h i c h c a n b e c o r r e c t e d b y n u t r i fication.

M a n y countries ( 3 4 4 ) h a v e e s t a b l i s h e d a r e c o m m e n d e d

daily

a l l o w a n c e or i n t a k e of a s c o r b i c a c i d f o r h u m a n s ( T a b l e X I ) .


FRUIT

L - A s c o r b i c a c i d has b e e n associated w i t h

BEVERAGE PRODUCTS.

f r u i t a n d f r u i t juices since 1 7 5 3 w h e n C a p t a i n James L i n d , p h y s i c i a n t o t h e B r i t i s h F l e e t , d e m o n s t r a t e d the successful t r e a t m e n t of s c u r v y i n c o r p o r a t i n g c i t r u s juices i n t h e d i e t . consumption

has u n d e r g o n e

a

T h e p a t t e r n of f r u i t

gradual change

d e c l i n e of w h o l e f r e s h f r u i t a n d v e g e t a b l e

over

the

consumption

years. is

by

products The

correlated

w i t h i n c r e a s e d use of f r o z e n or c a n n e d f r u i t s , vegetables, a n d juices a n d , m o r e r e c e n t l y , r e c o n s t i t u t e d f r u i t - f l a v o r e d beverages.

F r u i t a n d vege

t a b l e p r o d u c t s are the p r i m a r y sources of L - a s c o r b i c a c i d i n this d i e t . A p p l e , g r a p e , p i n e a p p l e , p r u n e , a n d c r a n b e r r y juices a n d p e a c h

and

a p r i c o t nectars c o n t a i n l i t t l e or n o a s c o r b i c a c i d unless n u t r i f i e d . O t h e r juices m a y b e v a r i a b l e sources.

F r u i t juices l o w i n a s c o r b i c a c i d a r e

u s e d i n t e r c h a n g e a b l y w i t h those of h i g h a s c o r b i c a c i d content.

Table X I .

International Dietary Allowances

Country Australia Canada Columbia Finland East Germany West Germany INCAP India Indonesia Japan Malaysia Netherlands Philippines Thailand Turkey United Kingdom U n i t e d States*

Adult Male 30 30 50 30 70 75 55 ( 5 0 ) ' 50 60 60 (50)• 30 50 75 ( 7 0 ) ' 30 50 30 60

It is t h e

for Vitamin C

Pregnancy

Lactation

60 40 65 50 100 100 60 50 90 60 60 75 100 50 70 60 80

60 50 65 90 100 120 60 80 90 90 60 75 150 50 80 60 100

Note: Values are given in milligrams per day. ° Female. * NRC-1980 allowance. Source. Reproduced, with permission, from Ref. 844- Copyright 1975, Common Agricultural Bureaux.


20.

BAUERNFEIND

429


c o n t e n t i o n of some g r o u p s t h a t i t is d e s i r a b l e t o n u t r i f y those juices t o m a k e t h e m m o r e c o m p a r a b l e w i t h t h e l a t t e r f r o m a s t a n d p o i n t of n u t r i t i v e v a l u e , h e n c e , l e a v i n g c h o i c e of s e l e c t i o n b a s e d o n flavor preferences. A s c o r b i c a c i d levels of 3 0 - 6 0 m g / 1 0 0 - 2 0 0 m L a r e m e a n i n g f u l c o n centrations.

F o r example, D e l M o n t e (345) began a d d i n g L-ascorbic

a c i d t o t o m a t o j u i c e ( 6 0 m g / 1 8 0 m L ) o n a c o m m e r c i a l basis i n 1974. T h i s c o n f o r m s t o U . S . F D A r e g u l a t i o n s . T h e effect of p r o c e s s i n g v a r i a b l e s a n d p r o d u c t storage i n a s c o r b i c n u t r i f i e d t o m a t o j u i c e has b e e n s t u d i e d


b y F l i n n (346) a n d b y P o p e a n d G o u l d ( 3 4 7 ) . I n a d d i t i o n t o t h e s t r a i g h t f r u i t juices, different b e v e r a g e - b a s e d

products have

been

s t u d i e d as

a s c o r b i c a c i d n u t r i f i e d foods; s u c h p r o d u c t s i n c l u d e a c h o c o l a t e - f l a v o r e d p o w d e r (348), a w h e y - s o y drink m i x (349), malt lemonades (350), a n d f r u i t j u i c e c a r b o n a t e d beverages (351,352).

L - A s c o r b i c a c i d s t a b i l i t y , its

i n f l u e n c e o n q u a l i t y d u r i n g storage, a n d its influence o n p r o c e s s i n g f r u i t juices a n d beverages r e m a i n a subject of a c t i v e s t u d y

(353-359).

T h e a c i d - t y p e f r u i t a n d v e g e t a b l e juices a r e g o o d carriers of a s c o r b i c a c i d , t h u s p r o v i d i n g a r e l a t i v e l y stable e n v i r o n m e n t .

G r e s s w e l l (322)

a n d others i n t h e past (311, 312,318) h a v e r e v i e w e d t h e use of L - a s c o r b i c a c i d i n beverages a n d f r u i t juices. I n a d d i n g a s c o r b i c a c i d t o juices a n d beverages,

a decision must be made about the nutrient level to b e

c l a i m e d for the product i n the market place plus that expected to b e d e s t r o y e d i n p r o c e s s i n g a n d d u r i n g shelf l i f e . It m u s t b e r e c o g n i z e d t h a t o x i d a t i v e e n z y m e s ( a s c o r b i c a c i d oxidase, p e r o x i d a s e s ) exist i n f r u i t a n d n e e d t o b e h e a t i n a c t i v a t e d . R e m o v a l of o x y g e n

or a i r b y v a c u u m

d e a e r a t i o n a n d r e p l a c e m e n t b y n i t r o g e n or c a r b o n d i o x i d e o r

flushing

h e a d s p a c e w i t h i n e r t gas w i l l r e d u c e a s c o r b i c a c i d d e s t r u c t i o n . I n some instances t h e a d d i t i o n of glucose oxidase a n d catalase is u s e f u l i n r e m o v i n g dissolved a n d headspace oxygen, w h i c h minimizes required ascorbic a c i d a d d i t i o n . U s e of m i n i m u m a m o u n t s of s u l f u r d i o x i d e (insufficient to cause

flavor

changes)

c a n b e h e l p f u l i n some p r o d u c t s f o r b e t t e r

ascorbic a c i d retention values. E x p o s u r e of a s c o r b i c a c i d n u t r i f i e d juices a n d beverages t o d i r e c t sunlight, d e p e n d i n g o n the l i q u i d formulation, c a n accelerate destruction of a s c o r b i c a c i d a n d b r i n g a b o u t flavor changes.

If the product w i l l be

e x p o s e d , c h o i c e of p a c k a g i n g m a y m i n i m i z e l i g h t influences.

Oxygen

p e r m e a b i l i t y of p a c k a g i n g m a t e r i a l s h o u l d n o t b e o v e r l o o k e d .

In any

n e w p r o d u c t t o b e n u t r i f i e d , p i l o t - s i z e p r o d u c t i o n batches ( T a b l e X I I ) s h o u l d b e r u n w i t h t h e best selected v a r i a n t s a n d storage d a t a o b t a i n e d b e f o r e c o m m e r c i a l p r o d u c t i o n is c o m m e n c e d .

A d d e d L-ascorbic acid i n

d r y , f r u i t - f l a v o r e d p o w d e r e d p r o d u c t s t o b e r e c o n s t i t u t e d is q u i t e stable i f m o i s t u r e levels a r e k e p t l o w a n d i f t h e y a r e p a c k e d i n l a m i n a t e d , moisture-resistant packets. I t has b e e n r e c o g n i z e d t h a t t h e e l d e r l y (360) d o n o t a l w a y s c o n s u m e sufficient L - a s c o r b i c a c i d d u e , i n p a r t , t o l a c k of s e l e c t i o n of a p p r o p r i a t e


430

ASCORBIC

Table X I I .

ACID

S t a b i l i t y of A d d e d After Processing


Product A p p l e juice A p p l e juice A p p l e juice A p p l e juice A p p l e juice A p p l e juice A p p l e juice A p p l e juice Apple cherry A p p l e orange A p p l e orange A p p l e orange Applesauce A p r i c o t nectar A p r i c o t nectar A p r i c o t nectar A p r i c o t pineapple Apricot drink Apricot drink A p r i c o t orange Cereals, d r y Cereals, dry Cereals, d r y C o c o a powders C o c o a powders C o c o a powders C o c o a powders C o c o a powders C r a n b e r r y juice C r a n b e r r y juice C r a n b e r r y juice C r a n b e r r y juice C r a n b e r r y orange Cranberry apricot F r u i t punch F r u i t punch

Ascorbic Acid

Vitamin C

30 m g / 4 fl oz 30 m g / 4 fl oz 30 m g / 1 0 fl oz 30 m g / 4 fl oz 30 m g / 8 fl oz 35 m g / 1 0 0 m L 30 m g / 4 fl oz 30 m g / 4 fl oz 30 m g / 4 fl oz 30 m g / 4 fl oz 40 m g / 1 0 0 m L 40 m g / 1 0 0 m L 30 m g / 1 0 0 g 30 m g / 4 fl oz 30 m g / 4 fl oz 30 m g / 4 fl oz 30 m g / 4 fl oz 30 m g / 6 fl oz 30 m g / 4 fl oz 30 m g / 4 fl oz 10 m g / o z 10 m g / o z 10 m g / o z 25 m g / 1 0 0 g 120 m g / l b 75 m g / 2 0 g 15 m g / 0 . 7 5 oz 15 m g / o z 30 m g / 4 fl oz 30 m g / 4 fl oz 30 m g / 4 fl oz 30 m g / 6 fl oz 30 m g / 6 fl oz 30 m g / 6 fl oz 30 m g / 8 fl oz 30 m g / 1 0 fl oz

40 38 38 38 35 35 38 42 53 66 62 61 69 57 35 39 69 47 49 47 10.3 11.4 10.5 34 180 78 14.1 18 39 60 42 38 59 38 44 67

44 41 49 43 47 41 45 49 54

c a n , 1 2 oz c a n , 1 2 oz c a n , 1 2 oz

30 m g / 1 2 fl oz 30 m g / 1 2 fl oz 30 m g / 1 2 fl oz

42 44 40

46 46 50

p a c k a g e , 3 oz envelope

30 m g / 3 oz 30 m g / 4 fl oz

82 78

87 79

Packaging glass, 1 q t glass, 1 q t glass, 1 q t glass, 1 q t glass, 24 oz c a n , 2 0 oz c a n , 1 8 oz glass, 1 q t glass, 1 q t glass, 4 oz glass, a m b e r can can, 1 lb c a n , 4 oz c a n , 1 8 oz

—

can, 4 oz can, 6 oz c a n , 1 2 oz c a n , 1 2 oz box, l i n e r box, l i n e r box, l i n e r envelope f o i l bags box, 1 lb can, 0.5 lb package glass, 16 oz glass, 16 oz glass, 16 oz glass, 16 oz glass, 1 q t glass, 1 q t c a n , 4 6 oz glass, 0.5 g a l

Goal

a

—

63 62 74 59 40

—

70 48 53 49

— — —

48 214 80

— —

39 61 49 41 61 49 48 68

F r u i t c a r b o n a t e d beverages grape orange root beer F r u i t p o w d e r mixes orange orange


20.

BAUERNFEIND

Ascorbic A c i d i n Food

Products Storage, 70-75°F

(23°C)

6 Months Ascorbic Acid 31 29


Vitamin C 6

— 33

31 35 31 28 35 56 (85) 46 49 59 61 31 37 (95) 53 40 48 43 8.3 (80)

—8.0

12 Months

40 ( 8 0 ) 33 (80)

— 29

(76)

34 166 76 13.0 (92) 15.8 (88) 30 51 -7 33 47 35 31 54

431


(77) 34 (72)

— 33

(73) 30 (61) 44 (81)

— 48 53 62 62 46

— 56

(76) (85) (84) (100) (100)

(80) 46 (95) 49 (92) 43 (88) 9.7 12.5 10.7 45 (94) 194 (90) 87 (100) 14.0

— 35

Ascorbic Acid

Vitamin C

— — 25 — 28

— — 37 — 32

26 26 25 31 54 (82) 37 39 56 45 29 32 (82) 52 29 37

31 26 31 34

—7.2

—9.9

(70) 9.9 (87) 7.0 (67) 28 137 77 11.4 (81) 16.5 (91)

— 40 48 56 50 32

(76) (68) (76) (58) (63) (63) (64) (77) (76) (84) (80)

— 59

(84) 40 (83) 41 (77)

10.3 9.1 39 (81) 171 (80) 82 (100) 12.9

— — — 38

(90) (94) (80) (86) (87) (82) (73) (85)

— — 32

— 38 — —

— 40 — —

30 30 31

35 (76) 35 (76) 41 (82)

26 22 28

28 (61) 25 (54) 32 (64)

75 71

80 (92) 77 (97)

73 68

79 (91) 76 (96)

57 39 35 53 40 35 58

32

(78) 34 (83) (82)

Continued on next page.


432

ASCORBIC

ACID

Table

XII.

After Processing


Product F r u i t p o w d e r mixes orange orange lemon fruit gelatin fruit gelatin F r u i t lollipops lemon pineapple G r a p e juice C ' Grape drink Grape drink Grape drink Grape drink Grape drink Grape drink Grapefruit juice G r a p e f r u i t juice Grapefruit juice Grapefruit juice Grapefruit juice G r a p e f r u i t juice C° Lemonade drink

Goal

Packaging glass, 7 oz c a n , 4 oz glass, 7 oz c a n , 2 4 oz c a n , 2 4 oz

136 m g / o z 75 m g / 4 fl oz 60 m g / 2 5 g 15 m g / 3 oz 15 m g / 4 oz

c a n , 6 oz can c a n , 12 oz c a n , 46 oz. can,1 qt glass, 0.5 g a l glass, 0.5 g a l glass, 17 oz c a n , 1 8 oz c a n , 18 oz c a n , 1 8 oz c a n , 6 oz c a n , 6 oz c a n , 4 6 oz

30 30 15 30 30 30 30 30 30 30 30 30 30 30 30 30

L o w - c a l o r i e d r i n k powders vanilla c a n , 8 oz chocolate c a n , 8 oz

mg/pop mg/pop m g / 1 oz m g / 8 fl oz m g / 6 fl oz m g / 6 fl oz m g / 6 fl oz m g / 8 fl oz m g / 8 fl oz m g / 4 fl oz m g / 4 fl oz m g / 4 fl oz m g / 4 fl oz m g / 4 fl oz m g / 4 fl oz m g / 8 fl oz

136 144 75 17.5 63 29 30 13 31 44 43 36 26 30 68 56 63 57 74 44* 76 d

Vitamin C a

—

122

—

18.2 68

— —

14* 33 48 46 40 35 41 71 58 69 57 76 47 78 d

188 180

100 m g / q t 100 m g / q t

148 140

50 m g / c a n 50 m g / c a n

54 99 94 57 63 136 157 184

63 79 200 188 200

47 33 67 28 53 40 37 79

50 39 88 28 56 44 44 82

M i l k products liquid formula liquid formula evaporated m i l k dry formula dry formula dry m i l k , whole dry m i l k , whole dry m i l k , whole

c a n , 13 oz c a n , 1 3 oz c a n , 13 oz c a n / g gas can/g vacuum can, air can, air c a n , gas

60 m g / 1 1 2 g 60 m g / 1 1 2 g 100 m g / l b 100 m g / l b 100 m g / l b

Orange Orange Orange Orange Orange Orange Orange Orange

c a n , 4 6 oz c a n , 1 2 oz c a n , 1 2 oz glass, 1 q t glass, 1 q t glass, 1 q t c a n , 46 oz glass, 0.5 g a l

30 30 60 15 30 30 30 30

drink drink drink drink drink drink drink drink

Ascorbic Acid

m g / 8 fl oz m g / 6 fl oz m g / 1 2 fl oz m g / 4 fl oz m g / 8 fl oz m g / 8 fl oz m g / 8 fl oz m g / 1 0 fl oz


56

— —

20.

BAUERNFEIND

433


Continued Storage, 70-75°F


6 Months Ascorbic Acid Vitamin C 139 (100) 144 71 (95) 16.8 62 — — 12" 31 33 37 35 23 28 _ 48 56 50 (88) 68 43" 69

— 121 (99) — 17.9 (98) 68 (100) — — 14" (100) 34 (100) 39 (81) 39 (85) 41 (100) 27 (80) 31 (76) — 51 (88) 61 (90) — 69 (90) 4 8 " (100) 77 (99)

(23°C)

12 Months Ascorbic Acid Vitamin C 166 (85) 106 71 (95) 15.5 61 30 (100) 30 (100) 11" 18 — 26 24 — — 51 46 53 49 60 — 60

— 119 (97) — 16.6 (91) 66 (97) — — 1 2 " (86) 31 (94) — 32 (70) 26 (65) — — 52 (73) 48 (83) 57 (83) 4 9 (86) 63 (83) — 67 (86)

141 136

168 (90) 160 (90)

100 129

121 (64) 143 (80)

27 49 (50) 62 (64) — — 147 115 184 37 27 62 25 50 36 31 71

34 — — — — 195 158 189 41 30 81 27 54 40 37 73

— 49(50) — 58 63 138 133 188 — — — 16 32 31 27 66

— — — 61 76 168 122 186 — — — 23 46 33 34 68

(60)

(98) (84) (95) (82) (77) (92) (99) (96) (91) (84) (89)

(97) (96) (84) (65) (93)

(82) (82) (75) (77) (83)

Continued on next page.


434

ASCORBIC

ACID

Table X I I . After

Processing

Ascorbic


Goal

Packaging

Product

Orange drink C° Orange drink C Orange drink C Pineapple juice Pineapple juice Pineapple juice Pineapple juice Pineapple juice Pineapple juice C Pineapple grapefruit Pineapple grapefruit Pineapple grapefruit Pineapple orange Pineapple orange Pineapple orange Potato flakes Potato flakes Potato flakes c

0

c

Soybean products liquid formula dry powder Tomato juice Tomato juice Tomato juice Tomato juice Tomato juice Tomato juice Vegetable juice Vegetable juice Vegetable juice

can, can, can, can, can, can, can,

6 oz 6 oz 6 oz 11 oz 18 oz 46 oz 46 oz

can, can, can, can, can, can, can, can can, can,

6 oz 12 oz 46 oz 46 oz 46 oz 46 oz 12 oz air gas

can, 13 oz can, l i b can, 18 oz can, 46 oz can, 18 oz can, 46 oz glass jar can, 46 oz can, 46 oz can 6 oz glass jar

Acid

Vitamin C a

30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 60 60 60

m g / 4 fl oz m g / 4 fl oz m g / 8 fl oz m g / 4 fl oz m g / 4 fl oz m g / 4 fl oz m g / 4 fl oz m g / 4 fl oz m g / 4 fl oz m g / 6 fl oz m g / 6 fl oz m g / 8 fl oz m g / 8 fl oz m g / 6 fl oz m g / 6 fl oz m g / 3 oz mg/100 g mg/100 g

53 68 39 47 44 43 39 69 79' 40 59 39 36 43 42 48 51 70

57* 71 51 48 44 47 39

50 60 30 30 30 30 30 30 30 30 30

mg/can m g / 4 oz mg/100 m L mg/100 m L m g / 4 fl oz m g / 4 fl oz m g / 6 fl oz m g / 6 fl oz m g / 6 fl oz m g / 4 fl oz m g / 4 fl oz

45 62 52 39 40 41 55 72 53 36 45

—

d

d

d

d

d

—

88 42 60 40 37 45 49 59 65 79

d

62 54

—

41 44 59 75 58 42

—

° Vitamin C equals ascorbic acid plus dehydroascorbic acid. Values in parentheses are percent retention during storage. Concentrate. 0°F. Source: Reproduced, with permission, from Ref. 312. Copyright 1970, Academic Press, Incorporated. b

c

d


20.

BAUERNFEIND

435


Continued Storage, 70-75°F

(23°C) 12 Months

6 Months


Ascorbic Acid 55" 62" 40" 43 38 42 36 63 (91) 78" 35 50 36 32 38 36 30 40 68 47 49 45 35 37 41 51 57 40 32 42

Vitamin C 57"(100) 6 6 " (94) 47"(92) 43 (90) 45 (100) 42 (89) 36 (92) 82"(93) 39 (93) 54 (90) 38 (95) 32 (82) 41 (91) 41 (84) 43 (73) 60 (92) 71 (90)

(100) 60 (97) 45 (83) (90) (93) 50 56 63 43 34 (93)

(100) (95) (84) (74) (81)

Ascorbic Acid

Vitamin C

61" 41" 38 (81) 35 35

65"(91) 4 6 " (90) 36 (82) 35 (74)

55 (80)

38

4 3 (95) 48 44 27 (70) 34 32 39 45 32 29 41 (91)

46 (92)

61 44 30 37 35 47 48 38 29

(98) (81) (93) (80) (80) (64) (66) (69)


436

ASCORBIC

f o o d s b e c a u s e of d e n t i t i o n p r o b l e m s .

ACID

F r u i t purees s u c h as a p p l e sauce

(361) h a v e b e e n o v e r l o o k e d p r o d u c t s .

L i k e d b y t h e e l d e r l y as a b r e a k

fast f r u i t , as a d i n n e r dessert, as a t o p p i n g f o r i c e c r e a m , these w o u l d b e one w a y of g e t t i n g m o r e a s c o r b i c a c i d t o t h e e l d e r l y i f t h e y w e r e n u t r i fied.

Ascorbic acid ( T a b l e X I I ) c a n feasibly a n d economically be a d d e d

to a p p l e

sauce.

C a n c e l et a l . (362)

reported

favorable

retention of

L - a s c o r b i c a c i d a d d e d t o c i t r o n slices p a c k e d i n s y r u p a n d to c i t r o n b a r s . A C I D - F E R M E N T E D


of

A c i d f e r m e n t a t i o n is a v e r y a n c i e n t a r t

PRODUCTS.

p r e s e r v i n g a n d s t o r i n g foods s u c h as c a b b a g e a n d p i c k l e s

retaining their nutritive value.

while

A l t h o u g h cabbage has been k n o w n for

centuries as a v a l u a b l e a n t i s c o r b u t i c v e g e t a b l e , s a u e r k r a u t m a n u f a c t u r i n g , p a c k a g i n g , a n d storage c a n affect a s c o r b i c a c i d levels. D u r i n g a c t i v e a c i d f e r m e n t a t i o n , there is l i t t l e loss, b u t i n t a n k storage a n d t h e c a n n i n g process losses of v i t a m i n C c a n occur.

I n a s t u d y of 217 samples of

c a n n e d k r a u t , v a r i a t i o n s of 1 - 2 5 m g / 1 0 0

g were found.

T h e canned

p r o d u c t c o u l d b e m o d i f i e d to c o n t a i n a g i v e n a m o u n t of a d d e d acid, p r o d u c i n g a more u n i f o r m product POTATO

PRODUCTS.

ascorbic

(363).

I n some countries, potatoes c o n t r i b u t e a n a p p r e

c i a b l e p r o p o r t i o n of t h e d a i l y L - a s c o r b i c a c i d needs.

D u r i n g t h e last

d e c a d e a n d f o r e s h a d o w i n g t h e t r e n d i n t h e d e c a d e a h e a d , m o r e of t h e annual potato

c r o p is b e i n g c o n v e r t e d

to processed

potato

products,

particularly i n the developed countries. Average ascorbic a c i d values for varieties of potatoes t h a t a r e c o m m e r c i a l l y i m p o r t a n t r a n g e f r o m

about

10 t o 33 m g p e r 100 g of t h e f r e s h l y d u g t u b e r s , w i t h a n o v e r a l l v a l u e of 26 m g . Losses d u r i n g storage a p p r o x i m a t e o n e - f o u r t h of t h e a s c o r b i c a c i d c o n t e n t after 1 m o n t h , o n e - h a l f after 3 m o n t h s a n d t h r e e - f o u r t h s after 9 m o n t h s (364). A f u r t h e r d e g r a d a t i o n of a b o u t 4 0 % occurs d u r i n g w a s h i n g a n d c o o k i n g , a loss t h a t m a y increase i f t h e c o o k e d p r o d u c t is h e l d o n steamtables

before serving.

ascorbic a c i d has been observed

F o r f r e n c h fries, a loss of 6 5 % A n ever-increasing

(365).

percentage

of t h e p o t a t o c r o p is p r o c e s s e d i n t o p r o d u c t s s u c h as d e h y d r a t e d flakes,

granules, chips

o r crisps, a n d f r o z e n

sticks.

potato

D e h y d r a t i o n of

potatoes t o flakes, g r a n u l e s , o r slices i n d u c e s losses of 3 0 - 8 9 %

of t h e

natural

i n the

ascorbic

acid

L - a s c o r b i c a c i d content

content

(365-373).

of t h e p o t a t o

Interest

a n d potato

continues

products

(365-377)

w i t h a t t e n t i o n g i v e n t o assay m e t h o d s t h a t s p e c i f i c a l l y m e a s u r e a c i d i n processed potato products

ascorbic

(365).

C o n c e r n has b e e n s h o w n f o r t h e r e s t o r a t i o n of L - a s c o r b i c a c i d losses i n p o t a t o p r o d u c t s o r its a d d i t i o n f o r p r o d u c t i m p r o v e m e n t 367,371,372,373,378).

(317,366,

R e s t o r a t i o n m a y n o t b e a s i m p l e process, d e

p e n d i n g o n t h e specific p r o d u c t .

M e c h a n i c a l m i x i n g of t h e p o t a t o p r o d

u c t , g r a n u l e s , o r flakes w i t h c r y s t a l l i n e L - a s c o r b i c a c i d w i l l n o t y i e l d a u n i f o r m product, a n d mechanical m i x i n g breaks d o w n the potato particle.


20.

437


BAUERNFEIND

P o w d e r e d ascorbic a c i d suspended i n an antioxidant-treated, saturated v e g e t a b l e o i l m a y b e s p r a y e d o n t h e d r i e d flakes, i f t h e p h y s i c a l a p p e a r a n c e of

the n u t r i f i e d p r o d u c t

is n o t

influenced.

W i t h potato

chips,

a s c o r b i c a c i d c a n b e a d d e d i n a salt p r e m i x . A d d i t i o n of a s c o r b i c a c i d t o the l i q u i d p o t a t o m a s h m a y b e p r a c t i c a l i f significant r e c y c l i n g of t h e h e a t e d p r o d u c t t h r o u g h the d r y i n g process is n o t excessive.

I n one s t u d y

( 3 6 7 ) , a s c o r b i c a c i d has b e e n a d d e d to c o o k e d p o t a t o m a s h , w h i c h w a s t h e n d r u m - d r i e d i n t o flakes, p a c k a g e d Downloaded by UCSF LIB CKM RSCS MGMT on November 18, 2014 | http://pubs.acs.org Publication Date: June 1, 1982 | doi: 10.1021/ba-1982-0200.ch020

n i t r o g e n gas. 70 ° F

i n t o cans, a n d sealed i n a i r o r

Storage r e t e n t i o n values i n t h e p r o d u c t after 7 m o n t h s at

approximated

nitrogen-packed.

75%

for a i r - p a c k e d containers

I n another

m a n u f a c t u r i n g of

potato

study

flakes

and 9 0 %

for

the

(372), extrusion variables i n the

were

noted

to s i g n i f i c a n t l y a l t e r

the

a s c o r b i c a c i d l e v e l of the e x t r u d e d p r o d u c t ( T a b l e X I I I ) . Klaeui

(317)

i n d i c a t e s some success has b e e n a t t a i n e d i f s u l f u r

d i o x i d e at levels w i t h i n l e g a l l i m i t s a n d a s m a l l a m o u n t of s o d i u m p y r o p h o s p h a t e a c t i n g as a sequestrant are a d d e d w i t h a s c o r b i c a c i d to p o t a t o Table XIII. Percent Vitamin C Retention in Potato Flakes Influenced by Extrusion Variables in Their Production Extrusion lemperature (°C)

J

RPM

/

t

S

(

r

e

w

g

/

1

g

c

r

e

as

w

Small Die

Large Die

Small Die

Large Die

135

40 80 120 160 200

94.3 90.1 85.2 81.9 80.7

96.5 95.1 91.9 86.8 82.9

90.2 84.7 80.5 80.1 76.1

91.5 90.2 85.8 82.8 79.4

149

40 80 120 160 200

90.4 82.5 80.6 77.1 76.5

92.4 91.0 87.3 82.5 80.6

87.2 80.1 75.2 70.7 64.2

90.5 86.2 83.3 74.0 70.1

163

40 80 120 160 200

88.9 83.5 77.6 70.2 63.5

91.1 88.2 80.3 75.6 72.1

83.1 80.8 75.2 68.3 60.2

87.2 83.3 76.2 72.4 67.9

177

40 80 120 160 200

87.2 81.5 67.4 50.7 46.2

90.2 89.4 73.2 60.0 53.7

83.0 77.2 65.1 48.3 42.6

85.0 80.8 68.9 52.4 44.5

Source: Reproduced, with permission, from Ref. 872. Copyright, 1978, ForsterVerlag AG.


438

ASCORBIC

ACID

m a s h , t o a i d i n g o o d a s c o r b i c a c i d r e t e n t i o n a n d u n i f o r m i t y of c o l o r . U s i n g s o d i u m ascorbate ( 4 0 0 fig/g)

a n d ascorbyl palmitate (300 /*g/g)

i n p l a c e of a s c o r b i c a c i d p r o v i d e d a n t i o x i d a n t v a l u e a n d i m p r o v e d t e x t u r e d u r i n g t h e r e c o n s t i t u t i o n of t h e d r y p r o d u c t i n a d d i t i o n t o i m p r o v e d v i t a m i n v a l u e . I f n i t r o g e n p a c k i n g is n o t u s e d t o d e l a y d e t e r i o r a t i o n i n d r y p o t a t o p r o d u c t s d u r i n g p a c k a g i n g a n d storage, a n t i o x i d a n t s m a y b e incorporated

to retard oxidative

rancidity.

M o i s t u r e content

of t h e

p r o d u c t s h o u l d b e k e p t as l o w as is t e c h n i c a l l y f e a s i b l e ( p r e f e r a b l y


than

less

6-8%). PRODUCTS.

C E R E A L - G R A I N

Cereal

grain products

contribute i m

m e a s u r a b l y t o t h e h u m a n d i e t a r y state (379, 380) a r o u n d the w o r l d . H o w ever, b a k e d goods s u c h as b r e a d , b u n s , a n d rolls a r e n o t g o o d carriers for a d d e d ascorbic a c i d w h e n the expectancy c l a i m is to b e m a d e .

of a specific

nutritional

A s c o r b i c a c i d f u n c t i o n s as a w h e a t flour i m p r o v e r ,

d e c o m p o s i n g t o a l a r g e extent i n its i m p r o v i n g a c t i o n d u r i n g t h e b a k i n g process; therefore l i t t l e r e m a i n s t o m e e t a c l a i m e d a s c o r b i c a c i d v a l u e i n the b a k e d p r o d u c t .

I f situations d e v e l o p w h e r e b y i t is d e s i r a b l e t o h a v e

a s c o r b i c a c i d i n a b a k e d i t e m , i t s h o u l d b e a p r o d u c t of t h e fast heat t y p e s u c h as d o n u t s (381) o r a c a k e o r c o o k i e f o r m u l a t i o n w h e r e a s c o r b i c a c i d is p u t i n a c r e a m filling o r i n a n i c i n g (382).

added

Stable deriva

tives ( 3 8 3 , 384) of a s c o r b i c a c i d t h a t w i l l s u r v i v e t h e b a k i n g process a r e known

b u t have

not been

demonstrated

as b i o l o g i c a l l y a v a i l a b l e t o

humans. A b l e n d of c o r n , soy, a n d m i l k i n a d r y m e a l n u t r i f i e d w i t h m i n e r a l a n d v i t a m i n s , t e r m e d C S M , has b e e n d e s i g n e d as a n u t r i t i o u s f o o d f o r human

consumption.

O n e of t h e a d d e d

Vojnovich a n d Pfeifer ( 3 8 5 ) conducted

v i t a m i n s is L - a s c o r b i c a c i d .

some trials w i t h a s c o r b i c

n u t r i f i e d C S M a n d p r e c o o k e d d r y i n f a n t cereals.

acid

Stability data revealed

t h a t d e s t r u c t i o n of t h e a d d e d a s c o r b i c a c i d w a s a first-order r e a c t i o n a n d that moisture content

w a s a c r i t i c a l issue i n a s c o r b i c

acid retention

( F i g u r e 8 ) . N o t more than 9 % moisture was shown to provide storage r e t e n t i o n v a l u e s .

good

E t h y l cellulose coated ascorbic a c i d was pre

f e r r e d over r e g u l a r c r y s t a l l i n e a s c o r b i c a c i d i n this c e r e a l p r o d u c t a p p l i cation. dry

L i n k o (386) n o t e d s t a b i l i t y of a s c o r b i c a c i d a d d e d t o F i n n i s h

r o l l e d oats w a s excellent

d u r i n g storage

cooking ( 9 2 % , 5 m i n boil i n water).

(88-96%)

and during

I n the U . S . , vitamins have

been

a d d e d t o d r y b r e a k f a s t cereals (387,388,389)

f o r some t i m e , a n d t e c h

nologies f o r a d d i n g t h e m h a v e b e e n d e v e l o p e d .

T h e effects of p r o c e s s i n g

a n d storage of cereals w i t h a d d e d m i c r o n u t r i e n t s , i n c l u d i n g L - a s c o r b i c a c i d , w e r e i n v e s t i g a t e d b y A n d e r s o n et a l . (390), a n d a s l i g h t loss a t 4 0 ° C w a s e x p e r i e n c e d f o r a s c o r b i c a c i d i n some cereals b u t n o t i n others. T h e l o w m o i s t u r e c o n t e n t of this class of p r o d u c t s a n d use of m o i s t u r e resistant p a c k a g i n g m a k e t h e m a g o o d c a r r i e r . K l a e u i (314)

conducted


20.

BAUERNFEIND

439


—

^^CC^TI

26 C , 8.0% H 0 f

2

— 37°C , 8 0% H 0 2

H0 2

4 5 ° C . 8.0% H 0 2

^26 C . 11.8% H 0 Downloaded by UCSF LIB CKM RSCS MGMT on November 18, 2014 | http://pubs.acs.org Publication Date: June 1, 1982 | doi: 10.1021/ba-1982-0200.ch020

2

^37C.

10.4% H 0 2

3

2 4 5 Stotage. Months Figure 8. Storage of CSM containing brand a: effect of moisture content and temperature on retention of ascorbic acid. (Reproduced, with permission, from Ref. 385. Copyright 1970, American Association of Cereal Chemists, Incorporated.)

a s t u d y i n c l u d i n g a s c o r b i c a c i d , s o d i u m ascorbate, a n d a s c o r b y l p a l m i t a t e i n v a r i o u s m i x t u r e s t h a t illustrates t h e s i g n i f i c a n t i n f l u e n c e of t h e t y p e o f carrier o n stability performances ( T a b l e X I V ) .

G a g e (391) has exam

i n e d snack foods i n c l u d i n g those t h a t m a y b e s u i t a b l e f o r n u t r i f i c a t i o n w i t h ascorbic acid. IRON UTILIZATION.

I r o n deficiency, a m a j o r cause o f a n e m i a i n

h u m a n s , is a w o r l d - w i d e p r o b l e m

(392,893,394)

a n d t h e search f o r


440

ASCORBIC

ACID

Table X I V . Stability of Various Vitamin C Forms in Some Edible Carriers ( A f t e r 1 Year Storage in Closed Bottles)


Vitamin

Vitamin

Tem-

Added

perature

Wheat Starch

C-Retention

in Percent Skimmed Milk Powder

Wheat Flour

of Initial

Glucose Monohydrate

Value Glucose Anhydrous

Ascorbic acid

R T

97.8

71.2

83.7

68.5

70.7 70.2

76.8 74.2

97.2

45°C

Sodium ascorbate

R T 45°C

97.5 81.4

70.4 70.2

81.3 72.1

84.5 74.5

94.8 74.2

Ascorbyl palmitate

95.8 85.4

69.3 43.4

86.0

90.1

45°C

81.8

55.3

85.9 80.4

12.0%

12.5%

R T

W a t e r content of carrier material

75.8

0.1%

9.1%

3.5%

Source: Reproduced, with permission, from Ref. 31^. Copyright 1 9 7 4 , Applied Science Publishers Limited. effective s u p p l e m e n t s

(392,394) is a n e v e r e n d i n g o n e . O n e p r e v a i l i n g

approach gaining momentum

( 3 9 2 ) is t o i m p r o v e t h e b i o l o g i c a l a v a i l a

b i l i t y of e x i s t i n g d i e t a r y i r o n s u p p l i e s o r a d d e d i r o n b y also i n c o r p o r a t i n g some f a c i l i t a t i n g substance i n t h e d i e t s u c h as L - a s c o r b i c a c i d

(395-404).

C e r e a l g r a i n meals

(396,397),

sugar (399,407,408),

( 3 9 5 , 3 9 8 ) , soy b e a n

meal

( 3 9 5 ) , salt

M S G , coffee, t e a , a n d m i l k

(401-404)

are some

p o t e n t i a l f o o d c a r r i e r s . I n instances, b o t h a n i r o n s o u r c e a n d a s c o r b i c a c i d are added.

S o m e investigators b e l i e v e t h a t i n h i g h c e r e a l

ascorbic a c i d m a y be needed. dependent.

A s l i t t l e as 2 5 m g , as a m e a l i n t a k e , m a y b e significant (400),

b u t intakes of 1 0 0 m g o r m o r e d a i l y m a y b e t h e g o a l sought. been proposed prospect sodium

as a n i r o n c a r r i e r (405,406) w o u l d prevent

Coffee has

a n d L e e (409) raises t h e

of i n s t a n t coffee as a c a r r i e r f o r L - a s c o r b i c ascorbate

whitener.

diets

T h e e n h a n c i n g b y a s c o r b i c a c i d is d o s e -

acid.

c u r d l i n g of a d d e d

T h e use of

cream

o r coffee

Beverages n u t r i f i e d w i t h a d d e d a s c o r b i c a c i d a n d c o n t a i n i n g

i r o n a r e c l a i m e d t o b e s t a b i l i z e d b y t h e a d d i t i o n of cysteine

according

to M o r s e a n d H a m m e s ( 4 1 0 ) . I N F A N T

MILKS.

T h e effect o f p r e p a r a t i o n , t e c h n o l o g y ,

a n d storage

c o n d i t i o n s of a s c o r b i c a c i d n u t r i f i e d e v a p o r a t e d m i l k i n f a n t f o r m u l a t i o n s has b e e n s t u d i e d b y s e v e r a l investigators (411,412,413) has b e e n r e v i e w e d b y others.

a n d i n the past

It is e c o n o m i c a l l y a n d n u t r i t i o n a l l y s o u n d

t o n u t r i f y e v a p o r a t e d m i l k w i t h 5 0 - 1 0 0 m g of a s c o r b i c a c i d p e r 1 3 fl o z (384.5 m L ) , for future reconstitution to a quart or liter, i n vacuum-sealed c o n t a i n e r s a c c o r d i n g t o P e n n s y l v a n i a State U n i v e r s i t y researchers. T h e s o d i u m salt is p r e f e r r e d t o a v o i d a p o t e n t i a l d e s t a b i l i z a t i o n effect o n t h e


20.


BAUERNFEIND

m i l k p r o t e i n s d u r i n g the s t e r i l i z a t i o n process.

441

W h e n 50 a n d 100 m g w a s

a d d e d , 35 a n d 71 m g of a s c o r b i c a c i d p e r l i t e r , r e s p e c t i v e l y , w e r e present o n a r e c o n s t i t u t e d basis after p r o c e s s i n g a n d 12 m o n t h s ' storage at r o o m temperature ( 2 5 ° C ) .

I n the U . S . e v a p o r a t e d m i l k - b a s e i n f a n t foods are

m a r k e t e d c o n t a i n i n g 50 m g of a d d e d a s c o r b i c a c i d p e r 13-fl-oz c a n , w h i c h is d i l u t e d to a q u a r t b e f o r e c o n s u m p t i o n .

Some dry-formulated infant


foods are l i k e w i s e f o r t i f i e d w i t h a s c o r b i c a c i d . D r y , l o w - c a l o r i e d i e t foods i n t e n d e d for t h e o l d e r a d u l t m a r k e t also c o n t a i n a d d e d a s c o r b i c

acid;

these p r o d u c t s are to be r e c o n s t i t u t e d i n w a t e r or m i l k b e f o r e use.

Many

cereals a n d m i l k p o w d e r s for infants are r o u t i n e l y n u t r i f i e d w i t h one of t h e v a r i o u s a c c e p t a b l e forms of i r o n . T h e b i o a v a i l a b i l i t y of s u c h i r o n is s t r i k i n g l y i m p r o v e d w h e n a s c o r b i c a c i d is also present ( 4 1 4 ) . A r a t i o b y w e i g h t of at least 1:5 i r o n to a s c o r b i c a c i d is H e a d a n d H a n s e n (415)

recommended.

a d d e d L - a s c o r b i c a c i d (42.3

mg/L)

to

w h o l e , chocolate, a n d l o w fat ( 1 % ) fluid m i l k s to increase t h e a s c o r b i c a c i d i n t a k e of s c h o o l c h i l d r e n .

T h r e e m i l k treatments w e r e

examined

( C ) p a s t e u r i z e d m i l k , ( E ) p a s t e u r i z a t i o n ( 7 4 ° C f o r 16 s) after a s c o r b i c a c i d a d d i t i o n , a n d ( F ) a s c o r b i c a c i d a d d i t i o n after p a s t e u r i z a t i o n . S t o r age ( 4 ° C )

r e t e n t i o n of a s c o r b i c a c i d ( F i g u r e 9 ) w a s g o o d , a n d t h e taste

reactions of c h i l d r e n w e r e f a v o r a b l e . a n d A n d e r s o n et a l . (417)

P r e v i o u s l y W e i n s t e i n et a l .

(416)

h a d reported on ascorbic a c i d nutrified fluid

m i l k to w h i c h a s c o r b i c a c i d w a s a d d e d at 50 a n d 200 m g / L , r e s p e c t i v e l y . Infant milks nutrified w i t h ascorbic a c i d were investigated b y C a m e r o n (418)

d u r i n g t h e p r e p a r a t o r y p r o c e d u r e s p r i o r to i n f a n t f e e d i n g . Use as a Processing A i d .

I n a d d i t i o n to s e r v i n g as a n a d d e d n u t r i

ent i n f o o d , L - a s c o r b i c a c i d has the u n u s u a l p r o p e r t y , b e c a u s e of

its

s t r u c t u r e a n d c h e m i c a l n a t u r e , to act as a p r o c e s s i n g a i d for c e r t a i n foods or food ingredients. usually foregoing

I n this r o l e i t is a d d e d for a n i n t e n d e d

nutritional considerations

purpose,

since m u c h of t h e

added

a s c o r b i c a c i d u n d e r g o e s d e g r a d a t i o n to p r o t e c t the q u a l i t y of t h e f o o d product.

O n l y s m a l l a m o u n t s i n some a p p l i c a t i o n s m a y r e m a i n of u n -

reacted ascorbic

acid.

E x a m p l e s of its i m p r o v i n g agent r o l e a r e :

an

o x y g e n s c a v e n g i n g agent i n b o t t l e d a n d c a n n e d f o o d p r o d u c t s ; a n i n h i b i t o r of o x i d a t i v e r a n c i d i t y i n f r o z e n fish; a s t a b i l i z e r of c o l o r a n d flavor i n c u r e d meats; a m a t u r i n g agent for

flour;

an oxygen

acceptor i n beer

p r o d u c t i o n ; a n d a r e d u c i n g agent i n w i n e . FRUIT

A N D

VEGETABLES.

F r u i t s can be

d i v i d e d into two

classes:

those t h a t s h o w d i s c o l o r a t i o n o n c u t t i n g or i n j u r y , s u c h as t h e a p p l e , a p r i c o t , b a n a n a , c h e r r y , n e c t a r i n e , p e a c h , a n d p e a r ; a n d others t h a t d o not, s u c h as c i t r u s f r u i t .

F o r this t y p e of d i s c o l o r a t i o n or b r o w n i n g t o

o c c u r i n c u t f r u i t , three c o m p o n e n t s — s u b s t r a t e , are b r o u g h t together.

oxygen, a n d

enzymes—

I f one of the three is r e m o v e d or p r e v e n t e d f r o m

r e a c t i n g , b r o w n i n g does not t a k e p l a c e .

H e a t i n g w o u l d destroy


the

442

ASCORBIC

ACID

9 Or-

eo -


70 -

01 0

i

i

i

i

4

8

12

i

i

i i

16 20 DAYS OF STORAGE

i

i

i

24

28

32

i 36

Figure 9. Ascorbic acid changes during storage of whole milk ( ), chocolate-flavored whole milk (•---), and 1% fat milk (' ' ') with three treatments ( A , C , O , E; F). (Reproduced, with permission, from Ref. 415. Copyright 1979, American Dairy Science Association.) e n z y m e b u t w o u l d result i n a c o o k e d f r u i t flavor a n d a texture c h a n g e . F r u i t tissues t h a t d i s c o l o r h a v e a c o m b i n a t i o n of l o w c o n c e n t r a t i o n of a s c o r b i c a c i d a n d h i g h l y a c t i v e phenolases, a c t i n g o n o r t h o p h e n o l i c strates t o f o r m t h e c o l o r e d o r t h e q u i n o n e c o m p o u n d s .

sub

L-Ascorbic acid

inhibits the phenolase action or the enzymatic b r o w n i n g sequence b y reducing orthoquinone

products

respective orthophenols.

of t h e e n z y m e

reaction back to the

I f t h e a s c o r b i c a c i d content b e c o m e s e x h a u s t e d ,

b r o w n i n g a g a i n c o m m e n c e s . U s e of a s c o r b i c a c i d i n this a p p l i c a t i o n has b e e n p r e v i o u s l y r e v i e w e d (311,312,321,323,332,

419).

S e l e c t e d g r a d e d f r u i t is p e e l e d a n d s l i c e d o r d i c e d , a n d

sugar i s

a d d e d e i t h e r as sugar s y r u p c o n t a i n i n g a s c o r b i c a c i d o r d r y s u g a r p r e v i ously blended w i t h crystalline ascorbic compactly

a c i d , after w h i c h t h e f r u i t is

p a c k a g e d , q u i c k l y f r o z e n , a n d h e l d i n a f r o z e n state u n t i l

t h a w e d b y the consumer.

T h e a d d i t i o n of 3 0 0 - 5 0 0 m g of L - a s c o r b i c a c i d


20.

443


BAUERNFEIND

p e r k g of f r u i t s u g a r p a c k is a d e q u a t e f o r t h e p r o t e c t i o n of t h e p a c k d u r i n g p r o c e s s i n g , storage, a n d t h a w i n g . W h i l e a h i g h p e r c e n t a g e of a s c o r b i c a c i d is c o n v e r t e d to t h e r e v e r s i b l e o x i d a t i o n p r o d u c t , d e h y d r o a s c o r b i c a c i d ( 4 2 0 ) , d u r i n g t h e t h a w i n g of t h e f r u i t ( T a b l e X V ) , t h e latter is f u l l y b i o l o g i c a l l y a c t i v e ( 9 1 5 ) a n d is also c o n s i d e r e d as v i t a m i n C.

S i n c e fresh a p p l e tissue contains e x t r a c e l l u l a r o x y g e n , slices m u s t b e

c u t t h i n l y ( 6 m m ) or a v a c u u m s y r u p step m u s t b e u s e d o n c o n v e n t i o n a l slices t o get a s c o r b i c a c i d p e n e t r a t i o n (421).

Certain additives w i t h


a s c o r b i c a c i d s u c h as N a C l (421), cysteine (422), s u l f u r d i o x i d e

(423),

a n d c i t r i c a c i d (424) h a v e b e e n d e c l a r e d to h a v e some m e r i t . I n a s t u d y of s l i c e d a p p l e t r e a t m e n t b e f o r e f r e e z i n g , P o n t i n g a n d J a c k s o n (425) f a v o r e d s o a k i n g slices i n a 2 0 - 3 0 %

sugar solution containing 0 . 2 - 1 %

ascorbic acid, 0 . 2 - 4 % calcium, a n d 0 . 0 2 % sulfur dioxide, f o l l o w i n g b y r a p i d freezing. T h e a s c o r b i c a c i d t r e a t m e n t process has b e e n u s e d f o r h o l d i n g c u t f r u i t at r e f r i g e r a t e d t e m p e r a t u r e s (426, 427,428, 432, 434), f o r f r u i t t o b e f r o z e n (426, 429, 430), a n d i n some instances t o reverse i n i t i a l b r o w n i n g of c u t f r u i t (431).

H e a t o n et a l . (427) r e p o r t e d s l i c e d peaches t r e a t e d

w i t h ascorbic a c i d (0.15% ) a n d sodium benzoate (0.066% for m i c r o b i a l c o n t r o l ) t o h o l d u p w e l l stored f o r 12 m o n t h s at 0 ° C .

E i d and Holfelder

(432) i m m e r s e d ( 2 0 s ) p e e l e d , c o r e d apples i n a s c o r b i c a c i d solutions ( 5 - 1 5 % ) a n d s t o r e d ( 9 d ) t h e m at c o o l t e m p e r a t u r e s ( 4 - 6 ° C ) p a c k a g e d i n p o l y e t h y l e n e bags, w i t h some v a r i a t i o n i n p e r f o r m a n c e b a s e d o n a p p l e variety.

T h e a s c o r b i c a c i d d i p p i n g a p p r o a c h has also b e e n u s e d (433)

p r i o r t o d r y i n g a p p l e slices.

O t h e r reports d e a l i n g w i t h a s c o r b i c a c i d

a p p l i c a t i o n i n v o l v e p i n e a p p l e s ( 4 3 4 ) , a v o c a d o p u r e e (435), pears (436), s t r a w b e r r i e s (437), a n d a p r i c o t j u i c e (438). Table X V .

Vitamin C Content of Thawed Frozen Sliced Peaches Packed with Sugar S y r u p 0

Pack Number

Percent Sugar in Syrup

1 2 3 4 5

65 65 65 35 35

Added Ascorbic Acid

0 150 200 0 150

Assayed Immediately After Thawing

Assayed After Holding 24 Hours at 22°C (72°F) Thawed

Ascorbic Acid Content

Ascorbic Acid Content

9 140 178 4 36

Total Vitamin C Content

11 146 188 7 141

Total Vitamin C Content

2 76 88 1 79

9 154 190 11 156

° Hale Haven, yellow-fleshed, freestone sliced peaches (3 parts) packed in sugar syrup (1 part by weight). Source: Reproduced, with permission, from Ref. J$0. Copyright 1946, A V I P u b lishing Company.


444

ASCORBIC

ACID

I n h e a t p r o c e s s i n g , t h e oxidases ( a s c o r b i c a c i d oxidase, p o l y p h e n o l oxidase, p e r o x i d a s e )

n a t u r a l l y present i n t h e p r o d u c t

e i t h e r d u r i n g t h e b l a n c h i n g stage o r s e a l e d containers.

finally

C o l o r a n d flavor changes

are destroyed,

d u r i n g s t e r i l i z a t i o n of t h e of f r u i t s a n d vegetables

d u r i n g h e a t p r o c e s s i n g a n d storage, i n p a r t , r e s u l t f r o m o x i d a t i o n b y oxygen w i t h i n the product a n d headspace. helps to protect

aromatic components

u n d e r g o i n g flavor a n d c o l o r changes.

T h e a d d i t i o n of a s c o r b i c a c i d a n d phenolic

substrates

from

C o m b i n e d w i t h deaerating,

filling,


a n d s c a l i n g t e c h n i q u e s , a s c o r b i c a c i d a d d i t i o n efficiently h e l p s t o create a n d m a i n t a i n a n a n a e r o b i c a t m o s p h e r e w i t h i n t h e c o n t a i n e r . I n t h e past this g e n e r a l subject has b e e n

reviewed

(311,319,323,419,439)

i n v o l v e s heat p r o c e s s e d f r u i t s a n d vegetables.

as i t

A s a n e x a m p l e of o n e of

t h e e a r l i e r trials (440), a d d e d a s c o r b i c a c i d a p p r e c i a b l y i m p r o v e d t h e a p p e a r a n c e a n d flavor of h o m e - c a n n e d s l i c e d a p p l i e s ( T a b l e X V I ) . I n a s u b s e q u e n t s t u d y b y H o p e (441) t h e a d d i t i o n of a s c o r b i c a c i d ( 5 0 0 - 6 0 0 m g / k g of f r u i t ) t o a p p l e h a l v e s ( c a n n e d w i t h o u t d e a e r a t i o n , t h e h e a d space c o n t a i n i n g 1 0 - 1 2 v o l u m e s p e r c e n t o x y g e n ) c o n t r o l l e d b r o w n i n g , reduced headspace oxygen, protected the container from corrosion, pro t e c t e d flavor, a n d i n c r e a s e d t h e r e s i d u a l a s c o r b i c a c i d content. A l i g h t c o l o r e d p e a r j u i c e w a s p r e p a r e d b y t h e use of a s c o r b i c a c i d to r e t a r d b r o w n i n g w h i l e t h e p u l p o r j u i c e w a s h e a t e d to i n a c t i v a t e t h e p o l y p h e n o l oxidase

(442).

B i r c h et a l . (319)

have examined

flavor

changes d u r i n g f r u i t j u i c e p r o c e s s i n g b o t h f r o m a m e c h a n i s m c o n c e p t and from practical and deoxygenation flavor."

finding.

T h e y conclude that ascorbic a c i d a d d i t i o n

p r i o r to p a s t e u r i z a t i o n helps to r e d u c e

"processed

T h e a m o u n t of a s c o r b i c a c i d r e q u i r e d t o e l i m i n a t e flavor c h a n g e

Table X V I .

Effect of Added Ascorbic A c i d on Canned Sliced Apples 0

After Canning Pack Number

Added Ascorbic Acid*

Ascorbic Acid

Total Vitamin C

After 6 Months' Storage at 21>°C (75°F) Ascorbic Acid

Total Vitamin C

Appearance of Pack

5 22 74

5 15 33 82

dark throughout slightly dark normal normal

mg/pt Jar 1 2 3 4

0 67 135 200

0.1 15 57 118

3 18 59 118

° Mcintosh apples peeled and sliced, cooked 3 to 4 min to soften, hot-packed with 50% syrup in Ball Ideal pint jars, 5/16-in. headspace, processed 10 min in boiling water. Ascorbic acid added in aqueous solution before sealing jar. Source: Reproduced, with permission, from Ref. 440. Copyright 1947, Ogden Publishing Company. b


20.

445


BAUERNFEIND

is p r o p o r t i o n a l t o t h e glucose c o n c e n t r a t i o n .

These workers

find

that

g r a p e f r u i t , l e m o n , a n d orange j u i c e a p p e a r t o c o n t a i n sufficient a s c o r b i c a c i d t o exert t h e necessary

p r o t e c t i v e effect.

A p p l e , pineapple, a n d

tomato juice m a y require ascorbic a c i d addition. A d d e d ascorbic a c i d m a y also i m p r o v e j u i c e color, b u t this d e p e n d s p r o c e s s i n g m e t h o d s s t u d i e d (443-448).

on the product a n d

B a s e d u p o n p r a c t i c a l experience

a n d s u p p o r t e d b y t h e o r y , a sufficient l e v e l of a s c o r b i c a c i d m u s t b e present, i f t h e p r o d u c t is subject t o o x i d a t i v e d e t e r i o r a t i o n , t o s u r v i v e Downloaded by UCSF LIB CKM RSCS MGMT on November 18, 2014 | http://pubs.acs.org Publication Date: June 1, 1982 | doi: 10.1021/ba-1982-0200.ch020

p r o c e s s i n g , storage, a n d h o m e p r e p a r a t i o n f o r c o n s u m p t i o n as a n a i d t o m a i n t e n a n c e of p r o d u c t characteristics. E v e n w i t h o x y g e n e x h a u s t i o n , subsequent loss of a s c o r b i c a c i d m a y o c c u r d u e to a n a e r o b i c d e c o m p o sition

(449).

Ascorbic acid w i l l not prevent the non-oxidative

type

b r o w n i n g (sugars a n d nitrogeneous c o m p o u n d s ) a n d m a y e v e n p r o m o t e this t y p e of r e a c t i o n . I n a n y n e w c o m m e r c i a l p r o d u c t i o n v e n t u r e , p i l o t scale studies ( T a b l e X I I ) a r e a d v i s a b l e t o d e t e r m i n e results b a s e d o n t h e specific project d e t a i l t o b e e n c o u n t e r e d .

A s i n f r u i t juices a n d c a n n e d

f r u i t , s i m i l a r b e n e f i c i a l effects c a n result w h e n a s c o r b i c a c i d is u s e d as a p r o c e s s i n g a i d f o r c e r t a i n vegetables, f o r e x a m p l e , olives i n b r i n e ( 4 5 0 ) , s a u e r k r a u t i n b r i n e (311), p i c k l e d c a u l i f l o w e r (456), c a n n e d ( 4 5 7 ) o r g l a s s - p a c k e d ( 4 5 1 ) a n d freeze

d r i e d ( 4 5 2 ) carrots, m u s h r o o m s

454,455), h o r s e r a d i s h p o w d e r (458), a n d c o l e s l a w FISH.

ponent

Fish

fillets,

steaks, a n d some shellfish h a v i n g a f a t t y

u n d e r g o i n g o x i d a t i v e r a n c i d i t y i n f r o z e n storage

f r o m a s c o r b i c a c i d a p p l i c a t i o n (311,312). 461) w e r e

(453,

(459). com

m a y benefit

T a r r a n d coworkers

t h e e a r l y i n v e s t i g a t i v e t e a m t h a t r e s e a r c h e d this

(460,

subject.

A s c o r b i c a c i d ( 0 . 5 - 3 . 0 % ) m a y b e a p p l i e d b y either a d i p p i n g o r a s p r a y i n g t e c h n i q u e . T o ensure a n even a n d a sufficiently t h i c k c o a t i n g , t h i c k e n i n g agents m a y b e a d d e d t o t h e s o l u t i o n . T h e f r o z e n

storage

shelf l i f e of t h e fish m a y b e e x t e n d e d several m o n t h s b y t h e a s c o r b i c a c i d treatment. A s a n e x a m p l e , n e w l y c a u g h t h e r r i n g w e r e filleted, d i p p e d i n a s o l u t i o n o f a s c o r b i c a c i d ( 0 . 5 % ) w i t h a t h i c k e n i n g agent, p a c k e d i n a w a x e d c a r d b o a r d b o x , f r o z e n ( — 4 0 ° C ) , a n d stored ( — 2 0 ° C ) . w e r e t h a w e d m o n t h l y a n d e v a l u a t e d (462).

Samples

U n t r e a t e d samples b e c a m e

r a n c i d after 2 m o n t h s of storage, w h e r e a s t r e a t e d samples r e m a i n e d p a l a t a b l e f o r 11 m o n t h s j u d g e d b y taste p a n e l ( F i g u r e 10) a n d T B A values ( F i g u r e 1 1 ) . J a d h a v a n d M a g a r (463) a p p l i e d a n a s c o r b i c a c i d glaze, w h i c h delayed the yellow discoloration a n d allied organoleptic

changes, t o

f r o z e n w h i t e p o m f r e t , s u r m a i , a n d m a c k e r e l fish. U s e of phosphates i n c o m b i n a t i o n w i t h ascorbate esters has b e e n d e c l a r e d t o i m p r o v e the c o l o r and

flavor

of fish p r o d u c t s

(464).

Shellfish

(465,466,467)

including

prawns a n d breaded shrimp, have been ascorbic a c i d treated, the latter in combination w i t h citric acid.

F o r m a t i o n of d i m e t h y l n i t r o s a m i n e i n

A l a s k a n p o l l a c k r o e (468) w a s i n h i b i t e d w h e n a s c o r b i c a c i d w a s i n -


446

ASCORBIC

ACID


Taste score

Storage

time-months

Figure 10. Results from organoleptic evaluation of untreated herring samples (M) and samples treated with ascorbic acid (O) after different times of storage. (Reproduced, with permission, from Ref. 462. Copyright 1961, Institute of Food Technolgists.) eluded w i t h a nitrite treatment.

Alaskan pollack muscle treated w i t h

a s c o r b i c a c i d w a s i n v e s t i g a t e d b y Y o s h n a k a et a l . (469). M o l e d i n a et a l . (470), w o r k i n g w i t h m e c h a n i c a l l y d e b o n e d

flounder

meat, o b s e r v e d a n

i m p r o v e m e n t i n c o l o r a n d flavor ( F i g u r e 12) w h e n t r e a t e d w i t h a c o m b i n a t i o n of a s c o r b i c a c i d ( 0 . 5 % ) , c i t r i c a c i d ( 0 . 5 % ) , N a E D T A ( 0 . 2 % ) 2

a n d phosphates

( K E N A , 0.2%).

A n u m b e r of p a p e r s (468-A74)

have

r e c e n t l y d i s c u s s e d t h e p r o c e s s i n g of m u l l e t i n c l u d i n g a s c o r b i c a c i d a p p l i c a t i o n . T h e t r e a t m e n t appears m o r e effective f o r fish i n t h e r o u n d a n d i n fillets t h e n i n m i n c e d tissue. MEAT.

F o r p r e s e r v a t i o n purposes, m e a t has b e e n c u r e d w i t h a d d e d

salt ( N a C l ) a n d nitrates ( s a l t p e t e r ) since a n c i e n t times. W i t h t h e r e c o g n i t i o n t h a t n i t r a t e w a s r e d u c e d b y m i c r o b i a l a c t i o n , a b o u t 60 years a g o , a d d e d n i t r i t e b e g a n to r e p l a c e n i t r a t e . T h e t y p i c a l r e d c o l o r of c u r e d m e a t results f r o m t h e r e a c t i o n of n i t r i c o x i d e w i t h m y o g l o b i n t o f o r m nitrogen monoxide

myoglobin,

more

frequently

r e f e r r e d t o as n i t r o -

s o m y o g l o b i n , a n d w i t h heat, n i t r o s o m y o c h r o m e . F o r n e a r l y 3 0 years (327,475,478) fixation,

flavor,

i t has been k n o w n that

color

a n d odor were greatly i m p r o v e d w h e n ascorbic a c i d was

i n c l u d e d i n t h e f o r m u l a t i o n of c o o k e d , n i t r i t e d , g r o u n d p o r k a n d t h a t f r a n k f u r t e r s c o n t a i n i n g ascorbate

h a d a more

products

desirable a n d


20.

447


BAUERNFEIND


TBA

O

1

O

1

2

1

400 > 400 28.5 4.3 2.4

Source: Reproduced, with permission, from Ref. 641. Copyright 1973, Verlag Hans Huber.


460

ASCORBIC

Table X X I I I .

Comparative Antioxidant

ACID

Activity"

Days to Reach 20meq/kg PV

b

Concentration


Antioxidant

Chicken Fat

(%)

None DL-a-Tocopherol DL-a-Tocopherol DL-a-Tocopherol DL-a-Tocopherol DL-a-Tocopherol DL-a-Tocopherol DL-y-Tocopherol DL-y-Tocopherol DL-y-Tocopherol Butylated hydroxyanisole DL-a-Tocopherol Ascorbyl palmitate DL-y-Tocopherol Ascorbyl palmitate Ascorbyl palmitate

Beef Fat 10 24

0.02 0.05 0.2 0.02 0.05 0.2 0.02 0.05 0.2 0.02

8 13 13 10 13 13 11 29 40 46 20

3 15 15 15 15 15 15 37 58 61 28

0.02 each

28

28

38

0.02 each 0.02

53 10

67 9

70 12

° Schaal oven, thin layer, 45°C. * Peroxide value. Source: Reproduced, with permission, from Ref. Oil Chemists Society.

T h e development

Pork Fat

6J+2.

— — — — — 40

— — 36

Copyright 1974, American

is i n f l u e n c e d , a m o n g o t h e r t h i n g s , b y o x y g e n

of t h e m i l k , o x i d a t i v e e n z y m e

activity, oxidation-reduction

exposure of t h e m i l k to l i g h t , presence of d i s s o l v e d c o p p e r ,

content

potential, tocopherol

content, a n d a s c o r b i c a c i d content of t h e m i l k . W h e n m i l k is t a k e n f r o m t h e c o w it c o n t a i n s l i t t l e or n o o x y g e n ; h o w e v e r , w h e n i t comes i n c o n tact w i t h the a i r i t absorbs m o r e o x y g e n .

Freshly d r a w n cows' milk may

c o n t a i n as m u c h as 30 m g of a s c o r b i c a c i d i n the r e d u c e d f o r m p e r l i t e r or p e r q u a r t . C u s t o m a r y h a n d l i n g m e t h o d s , p a s t e u r i z a t i o n , a n d t h e l o n g t i m e i n t e r v a l necessary for s h i p m e n t , storage, a n d d e l i v e r y b e t w e e n m i l k i n g a n d c o n s u m p t i o n c a n destroy 7 0 - 8 0 % o r i g i n a l l y present. delays

flavor

of t h e n a t u r a l a s c o r b i c a c i d

K e e p i n g milk deaerated

and from

light

exposure

changes.

T h e p r a c t i c a l use of a d d e d a s c o r b i c a c i d has p r o v e d to b e of benefit to t h e d a i r y i n d u s t r y (311, 321).

T h e a m o u n t s of a s c o r b i c a c i d or s o d i u m

ascorbate u s e d v a r y b e t w e e n t w e n t y a n d s e v e r a l h u n d r e d m i l l i g r a m s p e r l i t e r , 3 0 - 5 0 m g u s u a l l y b e i n g sufficient for f r e s h fluid m i l k . i n t h e results of

some w o r k e r s

Discrepancies

a t t e m p t i n g to e l u c i d a t e t h e v a l u e

of

a s c o r b i c a c i d i n the d e v e l o p m e n t of off-flavor m a y b e d u e to t h e i r e x a m i n a t i o n of a n i n c o m p l e t e system of o x i d a t i v e reactions.

I t has b e e n


dem-

20.

461


BAUERNFEIND

Table X X I V .

O x i d a t i o n of

Soybean O i l Days to Reach 72 meq/kg PV


Antioxidant None 0.01% A P 0.02% A P 0.05% A P 0.2% A P 0.02% B H A 0.02% B H T 0.02% T D P A 0.01% P G 0.02% P G 0.02% N D G A 0.02% T B H Q 0.02% Ascorbic A c i d 0.2% Ascorbic A c i d 0.01% A P + 0.01% P G 0.01 % A P + 0.01 % T D P A 0.01 % A P + 0.01 % B H A 0.01% A P + 0.01% B H T 0.01 % A P + 0.01 % N D G A 0.01% A P + 0.01% Tocopherol A P at 0 . 0 5 % , P G , T D P A a t 0 . 0 1 % A P at 0.05%, B H A , T D P A at 0.01% A P a t 0 . 0 5 % , B H A , P G at 0 . 0 1 % A P at 0 . 0 5 % , B H T , T D P A a t 0 . 0 1 %

7 16 19 21 25 9 10 15 20 20 21 26 12 17 27 21 18 17 28 16 42 30 31 31

"Heated at 45°C. A P = ascorbyl palmitate, B H A = butylated hydroxyanisole, B H T = butylated hydroxytoluene, T D P A = thiodipropionic acid, P G = propyl gallate, N D G A = nordihydroguaiaretic acid, T B H Q = 2-ter£-butylhydroquinone. Source: Reproduced, with permission, from Ref. 642. Copyright 1974, American Oil Chemists Society. b

o n s t r a t e d t h a t the t o c o p h e r o l

content of m i l k also p l a y s a r o l e i n t h e

o x i d a t i v e processes. R e p o r t s c l a i m a s y n e r g i s t i c effect of t o c o p h e r o l

and

a s c o r b i c a c i d to b e b e n e f i c i a l i n p r e v e n t i n g o x i d a t i v e off-flavor i n d a i r y products.

T h e a - t o c o p h e r o l c o n t e n t of c o w s m i l k , as r e c e n t l y

reviewed

( 6 4 7 ) , varies w i t h season a n d f e e d i n g p r a c t i c e s , r a n g i n g f r o m 4 - 3 0 ju,g/g fat.

Tocopherol

removes

the

is i n the fat a n d r e m o v a l of fat f r o m m i l k

tocopherol.

Hence,

both

tocopherol

and

obviously

ascorbic

acid

should be considered equally important i n m i l k a n d dairy product

flavor

s t a b i l i z a t i o n . T h e s e observations c o n f i r m t h e d a t a o n b u t t e r r e p o r t e d i n a n y e a r l i e r section. L i t e r a t u r e reports since the 1970 r e v i e w interest i n s t a b i l i z a t i o n of d a i r y p r o d u c t s

(312)

c o n t i n u e to

show

s u c h as use of a s c o r b i c

a n d t o c o p h e r o l i n c o n t r o l l i n g o x i d i z e d flavor i n s t e r i l i z e d c r e a m


acid

(648).

462

ASCORBIC

ACID

U s e of a d d e d a s c o r b i c a c i d d e l a y e d flavor d e v e l o p m e n t i n p a c k a g e d m i l k concentrates ( 6 4 9 ) , i n m i l k f a t ( 6 5 0 ) , i n goat m i l k c u r d ( 6 5 1 ) , i n b u t t e r f r o m buffalo m i l k

(652), i n y-irradiated skim-milk powder

(653), i n

l o w - f a t d a i r y spreads ( 6 5 4 ) , a n d i n k h o a p r o d u c t s ( 6 5 5 ) . E x p e r i e n c e i n y o g u r t , cheese, a n d i c e c r e a m has b e e n p r e v i o u s l y r e v i e w e d

(311,312).

F o r n e a r l y 3 0 years a d d e d a s c o r b i c a c i d has b e e n

recognized

BEER.

(312,656,657,658)

i n beer processing

as a n o x y g e n

scavenger,

thus

p r e v e n t i n g changes i n flavor a n d color, r e d u c i n g c h i l l a n d o x i d a t i o n h a z e ,


a n d , t h e r e b y , e x t e n d i n g shelf l i f e . T o a c h i e v e o p t i m u m s t a b i l i t y i n beer, d i s s o l v e d a n d c o n t a i n e r h e a d s p a c e a i r s h o u l d b e k e p t as l o w as p o s s i b l e , a n d levels of trace metals s h o u l d b e k e p t as l o w as p o s s i b l e .

I t has b e e n

o b s e r v e d that t h e a m o u n t of ascorbic a c i d r e q u i r e d to t a k e u p 1 m L of o x y g e n f r o m b o t t l e d b e e r varies b e t w e e n 8 a n d 15 m g . T h e a m o u n t of a d d e d a s c o r b i c a c i d f o u n d to b e effective u n d e r most p r a c t i c a l c o n d i t i o n s is 2 0 - 4 0 m g / L , 2 - 4 g / h L , 2.4-4.8 g / b a r r e l , o r 0.54-1.08 l b / 1 0 0 b a r r e l s . M o r e m a y b e h e l p f u l o n l y w h e n there is p o o r a i r c o n t r o l . W h e r e b r e w s h a v e b e e n p r e v i o u s l y t r e a t e d w i t h sulfites t h a t h a v e c o n t r i b u t e d t o a s p e c i a l taste c h a r a c t e r , i t is n o t necessary t o r e m o v e a l l t h e sulfite w h e n ascorbates a r e a d d e d since ascorbates a r e c o m p a t i b l e w i t h sulfite. A s c o r b i c a c i d m a y b e a d d e d as a f r e s h l y p r e p a r e d s o l u t i o n a t a n y b r e w i n g stage after f e r m e n t a t i o n i n r o o m t e m p e r a t u r e w a t e r o r b e e r [100 g p e r 1 (or more) L ] . A proportioning device c a n be used to introduce the a s c o r b i c a c i d s o l u t i o n w h i l e t h e b e e r is t r a n s f e r r e d d u r i n g

processing

for u n i f o r m d i s t r i b u t i o n w i t h o u t i n c o r p o r a t i o n of a i r . R e p o r t s c o n t i n u e i n t h e 1970s o n t h e a s c o r b i c a c i d t r e a t m e n t of b e e r (658-669).

U s e of ascorbic a c i d w i t h sulfites shows f a v o r a b l e results o n

b e e r q u a l i t y as d e s c r i b e d b y S c r i b a n a n d S t i e n n e (662) a n d M a s t o r et a l . (669).

A n a l y s e s of i m p o r t e d b e e r i n d i c a t e a d d i t i o n of ascorbates

i f n o t so l a b e l e d ( 6 6 5 ) .

even

Kormornicka (667) reported 3 g / h L addition

of a s c o r b i c a c i d e x t e n d e d b e e r q u a l i t y 89 d a y s ; 5 g / h L , 108 d a y s . B a e t s l e (666), o n a n i n d u s t r i a l scale, f o u n d 2 g / h L p r e s e r v e d c o l o r a n d flavor of b e e r d u r i n g storage f o r 66 d a y s . WINE.

I n 1948 F r a n z y (670) p u b l i s h e d his observations, i n process

i n g of grapes i n t o sweet w i n e s , o n a d d e d L - a s c o r b i c a c i d ( 1 0 0 m g / L ) as a r e p l a c e m e n t c o m p o u n d

for sulfurous a c i d i n protecting the color

of w i n e f r o m o x i d a t i v e changes a n d p r o m o t i n g f r e s h a r o m a .

About a

decade later ascorbic

to be a

acid became quite widely understood

valuable processing a i d i n w i n e production: flavor;

(a) t o preserve taste a n d

(b) t o p r o m o t e c l a r i t y b y p r e v e n t i n g f e r r i c p h o s p h a t e p r e c i p i t a t i o n

or b y c l a r i f y i n g t u r b i d w i n e s ; (c) to r e m o v e excess s u l f u r d i o x i d e s ; a n d (d)

to reduce

t h e a m o u n t of r e q u i r e d s u l f u r o u s a c i d w h e n

ascorbic

s u l f u r o u s a c i d a p p l i c a t i o n is c h o s e n i n w i n e t r e a t m e n t . T o d a y t h e use of a s c o r b i c a c i d a l o n e o r c o m b i n e d w i t h s u l f u r o u s a c i d t r e a t m e n t is l e g a l l y p e r m i t t e d or tolerated i n m a n y countries.

Reviews, wherein


ascorbic

20.

463


BAUERNFEIND

a c i d a p p l i c a t i o n t o w i n e a r e d i s c u s s e d , c a n b e c o n s u l t e d f o r past p u b l i cations o n this subject

(312,321,671,672, 673, 921).

T h e q u a n t i t y of L - a s c o r b i c a c i d n a t u r a l l y present i n grapes is r e l a t i v e l y l o w a n d is m o s t l y d e s t r o y e d d u r i n g f e r m e n t a t i o n . M o r e f r e q u e n t l y than not ascorbic together

a c i d a n d sulfurous a c i d

advantages.


are used unique

S u l f u r d i o x i d e has a n t i s e p t i c , f u n g i c i d a l , a n t i d i a s t a s e , a n d

antioxidant properties. potentiates

(sulfur dioxide)

since b o t h c o m p o u n d s c o n t r i b u t e

(671,674,675-678)

A s c o r b i c a c i d is a stronger r e d u c i n g agent a n d

t h e l o w r e d u c i n g c a p a c i t y of s u l f u r d i o x i d e a n d , t h e r e b y ,

makes i t p o s s i b l e t o m i n i m i z e t h e c o n c e n t r a t i o n of this necessary b u t headache-related

s u l f u r a d d i t i v e (673,674).

A l o w v a l u e of t h e r e d o x

p o t e n t i a l i n w i n e is m o r e f a v o r a b l e f o r f u l l

flavor

development,

and it

w o u l d t a k e a p r o l o n g e d t i m e to a c h i e v e this w i t h o u t a s c o r b i c a c i d (672). I n Swiss p r a c t i c e , i t has b e e n f o u n d t h a t 5 0 - 1 0 0 m g / L of a s c o r b i c a c i d i n w i n e c o n t a i n i n g 1 5 - 2 0 m g S O ^ / L , w h e n a d d e d a t t h e stage w h e n t h e wine was ready for bottling, generally resulted i n a fruitier bouquet a n d lighter color

(673).

Peynaud

(679),

i n r e p o r t i n g o n 3 years use of

a s c o r b i c a c i d i n w i n e , suggests a d d i t i o n b e m a d e i m m e d i a t e l y b e f o r e o r after a e r a t i o n or, best, just b e f o r e b o t t l i n g . M a x i m u m a d d i t i o n a l l o w e d i n F r a n c e is 10 g / 1 0 0 L ; i n I t a l y , 12 g / 1 0 0 L . M o r e recent studies c o n f i r m t h e v a l u e of a d d e d w i n e f o r i m p r o v e m e n t of q u a l i t y (680-683),

ascorbic

i n champagne

acid i n

production

(684), i n c o n v e r t i n g o r d i n a r y w i n e i n t o s h e r r y w i n e (685), i n e l i m i n a t i n g the n e e d f o r heat s t e r i l i z a t i o n of s u l f u r d i o x i d e (686), a n d i n t h e p r o d u c t i o n of h o t b o t t l e d M o s e l l e w i n e (687).

R e p o r t s o n c o m b i n e d use of

a s c o r b i c a c i d a n d s u l f u r d i o x i d e i n d i c a t e its c o n t i n u e d p r a c t i c a l s i g n i f i cance

(688-691).

COLORS.

T h e m a j o r i t y of t h e F D A certified f o o d colors

display

i n s t a b i l i t y ( 6 9 2 ) w h e n b r o u g h t i n t o contact w i t h r e d u c i n g agents, h e n c e these a z o a n d t r i p h e n y l m e t h a n e colorants m a y f a d e o r b e c o m e colorless b y t h e r e d u c i n g a c t i o n of a s c o r b i c a c i d (692-695).

D e c o l o r i z a t i o n of

these c o a l t a r dyes c a n o c c u r i n c a r b o n a t e d a n d s t i l l beverages i n t h e p r e s e n c e of a s c o r b i c a c i d (696) d e p e n d i n g o n : (a) t h e specific r e a c t i o n t o r e d u c i n g agents;

(b)

t h e a m o u n t of a s c o r b i c

acid

color's added;

(c) t h e o x y g e n a n d d i s s o l v e d m e t a l content; a n d (d) t h e exposure of t h e b o t t l e d beverages t o s u n l i g h t . S o m e c o n t r o l over this aspect c a n b e exer c i s e d b y r e d u c i n g m e t a l content w i t h t h e use of E T D A a n d l i m i t e d e x p o sure of b o t t l e d p r o d u c t s to l i g h t , s u c h as w i t h t h e use of cans or o p a q u e containers ( 6 9 2 ) . A n o t h e r p o s s i b i l i t y t o a v o i d c o l o r f a d i n g is t h e use of nonabsorbable, are r e p o r t e d

p o l y m e r i c c o a l t a r dyes as c o l o r a d d i t i v e s since to be more

stable

t o r e d u c i n g agents

(697)

these

than the

unbound dye. A n t h o c y a n i n s (698,699,700)

a r e s o m e w h a t m o r e stable t o a s c o r b i c

a c i d , b u t beverages n a t u r a l l y c o l o r e d w i t h a n t h o c y a n i n s o r w i t h


added

464

ASCORBIC

ACID

a n t h o c y a n i n s s h o u l d s t i l l b e d e a e r a t e d t o b r i n g o x y g e n levels t o a m i n i m u m (701). S t a r r a n d F r a n c i s h a v e i n v e s t i g a t e d t h e i n f l u e n c i n g f a c t o r s , o x y g e n (702) a n d trace m i n e r a l s ( 7 0 3 ) , o n t h e a n t h o c y a n i n - a s c o r b i c a c i d i n t e r r e l a t i o n s h i p . T h e effect of heat, l i g h t , a n d storage c o n d i t i o n s observed

b y S e g a l a n d D i m a (704)

o n five f r u i t juices

with

were added

a s c o r b i c a c i d . I k a w a ( 7 0 5 ) , i n h i s i n v e s t i g a t i o n of t h e n a t u r a l colors a n d t h e influence of a n t i o x i d a n t s , r e p o r t e d t h a t a s c o r b i c a c i d ( 5 0 - 1 0 0 m g / 100 g ) s t a b i l i z e d b e t a n i n e , a n d h a d n o effect o n c a n t h a x a n t h i n , c o c h i n e a l ,


l a c c a i c , a n d p a p r i k a . O t h e r reports c o n f i r m t h e b e t a n i n e

observation

(706,707,708). T h e naturally occurring carotenoids,

some of w h i c h a r e c o m m e r

c i a l l y a v a i l a b l e i n p u r e f o r m , a r e n o t o n l y resistant t o c o l o r f a d i n g b u t are s t a b i l i z e d b y a s c o r b i c a c i d (709,710,711).

T h e added

carotenoid

f o o d colors a r e stable w h e n r e t o r t e d w i t h p r o t e i n m a t e r i a l a n d a r e s t a b l e w h e n c o m b i n e d w i t h r e d u c i n g agents.

A d d e d ^-carotene e m u l s i o n s p r o

v i d e t h e o r a n g e j u i c e c o l o r h u e ; /?-apocarotenal, t h e d e e p o r a n g e h u e associated w i t h orange beverages.

color

B y p r e l i m i n a r y trials, t h e b e v e r

age m a n u f a c t u r e r c a n choose a n a d d e d c o l o r source, a m o n g t h e colors d i s c u s s e d a n d associated c o n d i t i o n s , t h a t w i l l a l l o w p r o p e r

color h u e

a n d s t a b i l i t y of L - a s c o r b i c a c i d i n t h e l i q u i d p r o d u c t . D r i e d coffee extracts are s t a b i l i z e d i f a d d e d ascor

MISCELLANEOUS.

b i c a c i d is i n c o r p o r a t e d

d u r i n g their processing

Ascorbic

(712,713).

a c i d has also b e e n s t u d i e d i n t h e t e a f e r m e n t a t i o n process (714). C o n fectionaries (715-721)

c a n be a good vehicle for ascorbic acid, p a r t i c u

l a r l y , h a r d c a n d y (311) b e c a u s e of t h e p r e s e n c e of f r u i t acids a n d l o w o x y g e n p e r m e a b i l i t y . A l s o , a s c o r b i c a c i d has b e e n a d d e d successfully t o caramels

(312,721),

chocolates

(312), m a r r o n glaces

and ice

(715),

c a n d i e s (716). A s y n t h e t i c c a v i a r has b e e n d e v e l o p e d a n d p a t e n t e d , t h e f o r m u l a t i o n of w h i c h c a l l s f o r a d d e d a s c o r b i c a c i d Patents have

also b e e n

obtained

o n ascorbic

p r i n c i p l e f o r t h e r e m o v a l of c h l o r i n e f r o m palatable for drinking

(723,724,725).

(722). a c i d as t h e a c t i v e

water, m a k i n g the water

T h e a d d i t i o n of a s c o r b i c

acid

(1 g ) a n d sodium bicarbonate (0.5 g ) to chlorinated water (15 L ) w i l l r e s u l t i n a p a l a t a b l e w a t e r a c c o r d i n g t o a U . S . p a t e n t (723).

City tap

water treated w i t h

t o cause

chlorine-ammonia

(726)

was observed

h e m o l y t i c a n e m i a i n p a t i e n t s i n d i a l y s i s u n i t s of a h o s p i t a l . C o n f i r m a t i o n of this c o n d i t i o n w a s o b t a i n e d i n i n v i t r o tests i n w h i c h t h e s u s p e c t e d water damaged r e d blood

cells.

A s c o r b i c a c i d a d d i t i o n to t h e t r e a t e d

water reduced the anemia p r o b l e m i n the patients i n subsequent

time

periods. L - A s c o r b i c a c i d is n o t n o r m a l l y c o n s i d e r e d

a bacteriostat, y e t i n

aqueous solution at the higher concentrations used i n the aqueous phase of a s c o r b i c a c i d t r e a t e d f o o d s , i t appears t h a t i t c a n c o n f e r some l i m i t e d antimicrobial activity.

Arafa and Chen

(727),

increased

refrigerated


20.

shelf l i f e of

465


BAUERNFEIND

cut-up broiler parts previously d i p p e d

i n ascorbic

acid

s o l u t i o n over w a t e r d i p p e d controls w i t h o u t adverse effects i n t h e c o n sumed product.

Svorcova

(728), investigating ascorbic acid, potassium

sorbate, a n d p H levels i n c a r b o n a t e d beverages, n o t e d some influence of a s c o r b i c a c i d f o r c o n t r o l of n o n s p o r e - f o r m i n g b a c t e r i a . O t h e r instances h a v e b e e n c i t e d for l i m i t e d a n t i m i c r o b i a l a c t i v i t y (729-732) of

ascorbic

acid. Legal Aspects.

T h e use of a s c r o b i c a c i d as a n u t r i e n t or as a f o o d


p r o c e s s i n g a i d is subject to g o v e r n m e n t T h e status of a s c o r b i c

regulation i n many

countries.

a c i d a d d i t i o n i n e a c h instance of d e s i r e d

use

s h o u l d b e d e t e r m i n e d b y c o n s u l t i n g the p e r t i n e n t r e g u l a t i o n s o r p e r t i n e n t g o v e r n m e n t a l a g e n c y of the c o u n t r y . A s c o r b i c a c i d is " g e n e r a l l y r e g a r d e d as safe,"

U N I T E D STATES.

T H E

G R A S , f o r use i n f o o d as a n u t r i e n t or f o o d p r o c e s s i n g a i d p r o v i d e d t h a t a s t a n d a r d has not b e e n e s t a b l i s h e d b y t h e F o o d a n d D r u g A d m i n i s t r a t i o n f o r t h e f o o d w h e r e i n t h e use of a s c o r b i c a c i d is e x c l u d e d or p e r m i t t e d w i t h i n t h e l i m i t a t i o n s specified b y t h e s t a n d a r d . U n d e r G R A S c o n d i t i o n s , t h e q u a n t i t y a d d e d "does n o t e x c e e d t h e a m o u n t r e a s o n a b l y r e q u i r e d to a c c o m p l i s h its i n t e n d e d p h y s i c a l , n u t r i t i o n a l , or other t e c h n i c a l effect o n f o o d , " a n d the q u a n t i t y of

ascorbic

a c i d " b e c o m e s a c o m p o n e n t of f o o d as a r e s u l t of its use i n the m a n u f a c t u r i n g , p r o c e s s i n g , or p a c k a g i n g of f o o d , a n d w h i c h is n o t i n t e n d e d to a c c o m p l i s h a n y p h y s i c a l or other t e c h n i c a l effect o n the f o o d itself, s h a l l b e r e d u c e d to t h e extent r e a s o n a b l y p o s s i b l e " ; a n d t h e a s c o r b i c a c i d "is of a p p r o p r i a t e f o o d g r a d e a n d is p r e p a r e d a n d h a n d l e d as a f o o d i n g r e d i e n t " ; a n d t h e i n c l u s i o n of a s c o r b i c a c i d " i n t h e list of n u t r i e n t s does not constitute a finding o n t h e p a r t of t h e D e p a r t m e n t t h a t ' a s c o r b i c acid* is u s e f u l as a s u p p l e m e n t to t h e d i e t for h u m a n s . " W h e n a s t a n d a r d for a f o o d p r o d u c t has b e e n e s t a b l i s h e d w h e r e i n t h e use of a s c o r b i c a c i d is p e r m i t t e d , t h e s t a n d a r d s h o u l d b e

consulted

to ensure that the l a b e l i n g of t h e f o o d p r o d u c t conforms w i t h the l a b e l i n g specifications of t h e s t a n d a r d . I n a d d i t i o n to t h e r e g u l a t i o n s e s t a b l i s h e d b y t h e F o o d a n d D r u g A d m i n i s t r a t i o n , t h e U n i t e d States D e p a r t m e n t of A g r i c u l t u r e has p r o m u l g a t e d r e g u l a t i o n s p e r t a i n i n g to the use of

ascorbic

acid in

meat

p r o c e s s i n g a n d t h e A l c o h o l a n d T o b a c c o T a x D i v i s i o n of t h e U n i t e d States D e p a r t m e n t of the T r e a s u r y has e s t a b l i s h e d a r e g u l a t i o n p e r t a i n i n g to t h e use of a s c o r b i c a c i d i n w i n e . these r e g u l a t o r y agencies X X V I , and X X V I I .

T h e r e are also F e d e r a l a n d M i l i t a r y

i n t h e U n i t e d States for XXVIII). O T H E R

T h e standards e s t a b l i s h e d

by

as t h e y exist are d e s c r i b e d i n T a b l e s X X V , food procured

by

Specifications

F e d e r a l agencies

(Table

Regulations change a n d must be monitored frequently. COUNTRIES.

M a n y countries h a v e r e g u l a t i o n s c o n c e r n i n g t h e

a d d i t i o n of L - a s c o r b i c a c i d to foods, some of w h i c h are g e n e r a l a n d others


466

ASCORBIC

ACID

Table X X V . U.S. Standards or Regulations of Foods to Which Ascorbic A c i d M a y Be A d d e d 0


Food

Purpose of Ascorbic Acid

Quantity

Permitted

A r t i f i c i a l l y sweetened fruit jelly

preservative

not more t h a n 0 . 1 % b y w e i g h t of finished food

A r t i f i c i a l l y sweetened f r u i t preserves a n d j a m s

preservative

not m o r e t h a n 0 . 1 % b y w e i g h t of f i n i s h e d food

C a n n e d applesauce

preservative, nutrient

not more t h a n 150 p p m , a n a m o u n t to p r o v i d e 60 m g / 4 oz (113 g)

C a n n e d apricots

preservative

a n a m o u n t no greater t h a n necessary to preserve color

Canned artichokes ( p a c k e d i n glass)

preservative

not m o r e t h a n 32 m g / 1 0 0 g of finished food

preservative

a m o u n t no greater t h a n necessary to preserve color

C a n n e d f r u i t nectars

preservative, nutrient

not more t h a n 150 p p m , a m o u n t s to p r o v i d e n o t less t h a n 30 m g or m o r e t h a n 60 m g / 4 fl oz

Canned mushrooms

preservative

n o t more t h a n 37.5 m g / o z of d r a i n e d w e i g h t of mushrooms

C a n n e d peaches

preservative

a m o u n t n o t greater t h a n necessary to preserve color

C a n n e d pineapple juice

nutrient

a m o u n t s to p r o v i d e n o t less t h a n 30 m g or more t h a n 60 m g / 4 fl oz

Canned pineapple grape fruit juice d r i n k

nutrient

a m o u n t s t o p r o v i d e n o t less t h a n 30 m g or more t h a n 60 m g / 4 fl oz

C a n n e d prune juice

nutrient

a m o u n t s to p r o v i d e n o t less t h a n 30 m g or more t h a n 60 m g / 4 fl oz

C r a n b e r r y juice cocktail

nutrient

a m o u n t s to p r o v i d e not less t h a n 30 m g or more t h a n 60 m g / 4 fl oz

F l o u r (white, whole wheat, plain)

dough conditioner

not to exceed 200 p p m

Canned fruit cocktail

F r o z e n r a w breaded s h r i m p p r e s e r v a t i v e

sufficient to r e t a r d d e v e l o p ment of d a r k spots


20.

Table X X V .

Continued


Food


467


BAUERNFEIND

Quantity Permitted

Ice c r e a m (the f r u i t therein)

acidulant

such q u a n t i t y as seasons t h e finished p r o d u c t a n d meets the s t a n d a r d s for ice c r e a m

Margarine

preservative

ascorbyl palmitate a n d / o r a s c o r b y l stearate 0 . 0 2 %

N o n f r u i t w a t e r ices

acidulant

s u c h q u a n t i t y as seasons the finished p r o d u c t

T o m a t o juice

nutrient

a m o u n t to p r o v i d e 10 m g / f l oz ( t o t a l v i t a m i n C )

W a t e r ices (the f r u i t therein)

acidulant

such q u a n t i t y as seasons the finished p r o d u c t

F o o d s for w h i c h s t a n d a r d s are established a n d i n w h i c h p r e s e r v a t i v e s m a y be o p t i o n a l ingredients a r e :

nonspecified

dry whole m i l k dry cream breads, r o l l s , buns

dough c o n d i t i o n e r s not referred to i n s t a n d a r d i f the t o t a l q u a n t i t i e s are not m o r e t h a n 0.5 p a r t for each 100 p a r t s b y w e i g h t of flour used

frozen r a w breaded shrimp

a n t i o x i d a n t p r e s e r v a t i v e — m a y be used t o r e t a r d d e v e l o p m e n t of r a n c i d i t y of the f a t content

° Compiled by D. M . Pinkert. Consult regulations for current status and inter pretation. v e r y specific. It w o u l d take a n u m b e r of pages to d e t a i l s u c h i n f o r m a t i o n for e a c h f o o d p r o d u c t for e a c h c o u n t r y h a v i n g r e g u l a t i o n s . F o r e x a m p l e , i n c o n s i d e r i n g a s c o r b i c a c i d as a flour i m p r o v e r , the l e v e l of p e r m i s s i b l e a d d i t i o n ranges f r o m 50 m g to 10 g / k g of flour ( T a b l e X X I X ) . C e r t a i n countries s u c h as A u s t r a l i a , C a n a d a , C h i l e , H o l l a n d , J a p a n , K e n y a , N e w U n i t e d States, U r u g u a y , a n d Z a m b i a p e r m i t

both

L - a s c o r b i c a c i d a n d b r o m a t e as flour i m p r o v e r w h i l e a n u m b e r of

Zealand,

Sweden,

other

countries o n l y a l l o w L - a s c o r b i c a c i d . I n t h e E C C c o u n t r i e s p e r m i s s i b l e L - a s c o r b i c a c i d levels f o r t e c h n i c a l a p p l i c a t i o n to f o o d v a r y f r o m

100

m g / k g to 2 g / k g of f o o d p r o d u c t . T H E

JOINT

FAO/WHO

Joint F A O / W H O was

C O D E X

ALIMENTARIUS

Codex Alimentarius Commission

COMMISSION.

(the

e s t a b l i s h e d to i m p l e m e n t t h e J o i n t F A O / W H O

Program.

Membership

of

the

C o m m i s s i o n comprises

The

Commission)

Food

Standards

those

Member

N a t i o n s a n d A s s o c i a t e M e m b e r s of F A O a n d / o r W H O t h a t h a v e n o t i f i e d


468

ASCORBIC

Table X X V I .

U.S. Regulations on Ascorbic A c i d Addition to Meat

Food Ascorbic acid i n : cured p o r k a n d beef cuts, c u r e d comminuted meat food p r o d u c t


ACID

Purpose

Quantity Permitted

t o accelerate color f i x i n g

70 oz per 100 g a l p i c k l e a t 1 0 % p u m p l e v e l ; 0.75 oz per 100 l b m e a t or m e a t b y p r o d u c t ; 1 0 % s o l u t i o n to surfaces of cured cuts p r i o r to p a c k a g i n g (the use of such s o l u t i o n s h a l l not r e s u l t i n the a d d i t i o n of a s i g n i f i c a n t a m o u n t of m o i s t u r e to t h e product)

S o d i u m ascorbate to accelerate i n : cured p o r k a n d color f i x i n g beef cuts, cured comminuted meat food p r o d u c t

87.5 oz per 100 g a l p i c k l e a t 1 0 % p u m p l e v e l ; 0.88 oz per 100 l b m e a t or m e a t b y p r o d u c t ; 1 0 % s o l u t i o n to surfaces of cured cuts p r i o r to p a c k a g i n g (the use of such s o l u t i o n s h a l l n o t r e s u l t i n the a d d i t i o n of a s i g n i f i c a n t a m o u n t of m o i s t u r e t o the product)

Table X X V I I . U.S. Regulations on Ascorbic A c i d Addition to Alcoholic Beverages Alcohol and Tobacco Tax Div., U.S. Dept. of Treasury Regulations Food


Wine

to p r e v e n t d a r k e n i n g of color a n d d e t e r i o r a t i o n of flavor, a n d o v e r oxidation

w i t h i n l i m i t a t i o n s w h i c h do not a l t e r the class or t y p e of the w i n e (use need not be d e c l a r e d on the l a b e l )

Beer

antioxidant and bio logical stabilization

to be used o n l y b y agreement between U . S . D e p t . of T r e a s u r y a n d the brewer

Quantity Permitted

the O r g a n i z a t i o n s of t h e i r w i s h to b e c o n s i d e r e d as M e m b e r s . B y F e b r u a r y 1979, 117 countries h a d b e c o m e M e m b e r s of the C o m m i s s i o n . O t h e r countries p a r t i c i p a t i n g i n the w o r k of the C o m m i s s i o n or its s u b s i d i a r y b o d i e s i n a n observer c a p a c i t y are e x p e c t e d to b e c o m e M e m b e r s i n t h e near future. T h e p u r p o s e of the J o i n t F A O / W H O F o o d S t a n d a r d s P r o g r a m is t o e l a b o r a t e i n t e r n a t i o n a l standards for foods a i m e d at p r o t e c t i n g t h e h e a l t h of t h e c o n s u m e r , to ensure f a i r p r a c t i c e s i n the f o o d t r a d e , a n d to f a c i l i tate i n t e r n a t i o n a l t r a d e . I n a d d i t i o n to c o m p o s i t i o n a l c r i t e r i a a n d l a b e l i n g , f o o d s t a n d a r d s i n c o r p o r a t e p r o v i s i o n s i n respect to f o o d


hygiene,

20.

469


BAUERNFEIND

Table X X V I I I . A r m e d Forces Regulations on Ascorbic A c i d Addition to F o o d a



Food

Quantity

Permitted

B e v e r a g e base powders p r e pared from dehydrated f r u i t juices ( T y p e I I )

nutrient

2 0 - 3 0 m g / 1 2 fl oz of recon stituted powder

C o c o a beverage p o w d e r

nutrient

N o t less t h a n 25 m g / o z b y weight

Coffee, i n s t a n t , T y p e I

nutrient

N o t less t h a n 15 m g / 2 . 5 g

D e h y d r a t e d w h i t e potatoes

nutrient

N o t less t h a n 50 m g / o z of dehydrated product

M i l k , non-fat dry (Type II, Style B)

nutrient

20 m g / o z

Peanut butter, v i t a m i n fortified

nutrient

37.5 m g / 1 . 5 oz of p r o d u c t

8

Compiled by N. E . Harris.

f o o d a d d i t i v e s , p e s t i c i d e residues, other c o n t a m i n a n t s , a n d m e t h o d s

of

analysis a n d s a m p l i n g . L - A s c o r b i c a c i d a n d certain derivatives ( T a b l e X X X ) have d e s i g n a t e d t o x i c o l o g i c a l l y as c a t e g o r y A ( 1 ) C A C / F A L 5-1979.

Category A (1)

been

i n the release d e s i g n a t e d

a d d i t i v e s are those t h a t h a v e b e e n

fully cleared b y the Joint F A O / W H O E x p e r t C o m m i t t e e on F o o d A d d i tives a n d e i t h e r h a v e b e e n g i v e n a n " a c c e p t a b l e d a i l y i n t a k e " ( A D I )

or

h a v e n o t b e e n l i m i t e d t o x i c o l o g i c a l l y . A p p r o v e d uses of L - a s c o r b i c a c i d h a v e b e e n i n d i c a t e d , m a x i m u m levels ( M L ) h a v e b e e n s h o w n , a n d g o o d m a n u f a c t u r i n g p r a c t i c e ( G M P ) has b e e n e s t a b l i s h e d . A D I is expressed as m i l l i g r a m s p e r k i l o g r a m b o d y w e i g h t ; M L is expressed as w e i g h t p e r k i l o g r a m of p r o d u c t .

G M P refers to the l i m i t a t i o n of f o o d a d d i t i v e i n

s p e c i f i e d foods. I t means t h a t t h e a d d i t i v e i n q u e s t i o n is s e l f - l i m i t i n g i n f o o d for t e c h n o l o g i c a l , o r g a n o l e p t i c , or other reasons a n d t h a t , therefore, t h e a d d i t i v e n e e d n o t b e subject to l e g a l m a x i m u m l i m i t s . I t also means t h a t the f o o d a d d i t i v e m u s t b e u s e d a c c o r d i n g to g o o d m a n u f a c t u r i n g p r a c t i c e , a n d i n a c c o r d a n c e w i t h the G e n e r a l P r i n c i p l e s for the U s e of F o o d Additives.

Industrial Applications A n extensive list of patents a n d scientific p a p e r s exists o n p r o p o s e d uses of a s c o r b i c a c i d i n v a r i o u s i n d u s t r i e s ; h o w e v e r , t h e a m o u n t of c o m -


470

A S C O R B I C ACED

Table X X I X . Legal Status of L-Ascorbic A c i d as a Flour Improver


Country

Maximum

Australia Austria Belgium Brazil Canada Chile Cyprus Denmark England Finland France Germany Greece Holland Italy Japan Kenya N e w Zealand Norway Portugal South A f r i c a Spain Sweden Switzerland Uruguay U n i t e d States Zambia

Level Permitted

GMP 200 m g / k g 50 m g / k g 2 g/kg 200 m g / k g 20-50 m g / k g 75 m g / k g 200 m g / k g GMP 200 m g / k g 500 m g / k g GMP° GMP° 50 m g / k g 200 m g / k g GMP 200 m g / k g GMP° GMP 8-10 g / k g 200 m g / k g 200 m g / k g GMP° GMP 20 m g / k g 200 m g / k g 200 m g / k g a

a

b

a

a

a

° G M P = Good Manufacturing Practice. May only be added by the baker. b

p o u n d u s e d i n the i n d u s t r i a l a p p l i c a t i o n s is s m a l l r e l a t i v e to p h a r m a ceutical and food applications.

W h i l e ascorbic a c i d m a y be

declared

to b e f u n c t i o n a l w i t h m e r i t o r i o u s advantages, there is a s t r o n g p r e f e r e n c e to f i n d a n d use m o r e e c o n o m i c a l c h e m i c a l aids, e v e n t h o u g h t h e y m a y n o t b e q u i t e as effective.

T h e greatest a c t i v i t y i n p u r s u i n g uses appears t o

b e f o r p o l y m e r i z a t i o n reactions i n the plastics i n d u s t r y , for uses i n p r i n t i n g inks, i n photoprocessing, i n metal technology, a n d i n miscellaneous areas, i n c l u d i n g cosmetics, t o b a c c o , fibers, a n a l y t i c a l assays, p r e s e r v a t i o n of b l o o d , p r e s e r v a t i o n of c u t p l a n t s , a n d c l e a n i n g agents. Polymerization

Reactions.

Polymerization

reactions

take

place

u n d e r h i g h a n d l o w t e m p e r a t u r e s . W h e r e a n aqueous p h a s e exists s u c h as i n e m u l s i o n s , or i f a p o l a r solvent is i n v o l v e d , a s c o r b i c a c i d is s o l u b i l i z e d a n d m a y h a v e m e r i t , b e c a u s e of its r e d u c i n g p o w e r , i n f a c i l i t a t i n g t h e p o l y m e r i z a t i o n w i t h a t e m p e r a t u r e a d v a n t a g e , a rate of better control, or a superior e n d product.


reaction,

20.

471


BAUERNFEIND

Table X X X .

Antioxidants and Antioxidant

Synergists


NumAdditive

Evaluation

and Maximum

Limit

ber

List

.230

A(l)

ascorbic a c i d (Syn: L ascorbic acid)

A D I : 0 - 1 5 m g / k g b o d y w e i g h t , s u m of ascorbic a c i d a n d ascorbates f r o m a l l sources ( R e f . : T o x . 29, 30, 3 2 ; Spec. 47 T e c h n . EfT. 28) C o d e x S p e c i f i c a t i o n : A L I N O R M 76/41

.231

A(l)

ascorbate, potassium

A D I : 0 - 1 5 m g / k g b o d y w e i g h t , s u m of ascorbic a c i d a n d ascorbates f r o m a l l sources ( R e f . : T o x . 29, 30, 3 2 ; Spec. 1; T e c h n . EfT. 28)

.232

A(l)

ascorbate, sodium

A D I : 0 - 1 5 m g / k g b o d y w e i g h t , s u m of ascorbic a c i d a n d ascorbates f r o m a l l sources ( R e f . : T o x . 29, 30, 3 2 ; Spec. 47 T e c h n . E f f . 28) C o d e x S p e c i f i c a t i o n : A L I N O R M 76/41

Approved

Uses of .230 in:

Evaluation

Canned tropical fruit salad C a n n e d peaches C a n n e d applesauce E d i b l e f u n g i a n d fungus products A p r i c o t , peach a n d pear n e c t a r s Apple juice Q u i c k frozen s t r a w b e r r i e s C a n n e d mushrooms C a n n e d asparagus Concentrated apple j u i c e T a b l e olives Q u i c k frozen peaches Canned fruit cocktail J a m s a n d jellies B l a c k currant j a m Citrus marmalade Grape juice C o n c e n t r a t e d grape j u i c e Sweetened concentrated L a b r u s c a t y p e grape j u i c e Q u i c k frozen s h r i m p s a n d p r a w n s 0

0

0

0

0

0

Approved

ML: ML: ML: ML: ML: ML: ML: ML: ML: ML: ML: ML: ML: ML: ML: ML: ML: ML:

and Maximum

Limit

700 m g / k g 550 m g / k g 150 m g / k g limited by G M P limited by G M P limited by G M P limited by G M P limited by G M P limited by G M P limited by G M P 200 m g / k g 750 m g / k g limited by G M P 500 m g / k g 750 m g / k g 500 m g / k g 400 m g / k g 400 m g / k g

M L : 400 m g / k g M L : limited by G M P

Uses of .230 and .232 in:

C a n n e d corned beef Luncheon meat C o o k e d cured chopped m e a t C o o k e d cured p o r k shoulder C o o k e d cured h a m C a n n e d b a b y foods C e r e a l - b a s e d processed foods infants and children

I / \ /

M L : 500 m g / k g , expressed as the a c i d M L : 500 m g / k g , s i n g l y o r i n c o m b i n a t i o n w i t h isoascorbic a c i d , i s o ascorbate, expressed as ascorbic acid M L : limited by G M P

for M L : limited by G M P Continued on next page.


472

ASCORBIC

Table X X X .


Approved uses of .231 and .232 in: Q u i c k frozen lobsters Q u i c k frozen fillets of ocean p e r c h Q u i c k frozen fillets o f c o d a n d haddock Q u i c k frozen fillets of flat fish Q u i c k frozen fillets of h a k e Number

List

Additive

.236

A(l)

.237

A(l)

ascorbyl palmitate , , ascorbyl stearate

ACID

Continued

M L : 1 g / k g , expressed as the a c i d M L : 1 g / k g , expressed as t h e a c i d M L : 1 g / k g , expressed as t h e a c i d M L : 1 g / k g , expressed as the a c i d M L : 1 g / k g , expressed as the a c i d

Evaluation

and Maximum

Limit

\ A D I : 0-1.25 m g / k g body weight, singly I or i n c o m b i n a t i o n ( R e f . : T o x . 2 9 , 3 0 ; ) Spec. 4 7 ; T e c h n . EfT. 28) C o d e x S p e c i f i I . A L I N O R M 76/41 c

a

t

i

Approved Uses of .236 in: Infant formula C a n n e d b a b y foods C e r e a l - b a s e d processed foods for infants and children

o

n

M L : limited by G M P M L : limited by G M P M L : limited by G M P

Approved Uses of .236 and .237 in: E d i b l e fats a n d oils

M L : 200 m g / k g , s i n g l y o r i n c o m b i nation

Margarine

M L : 200 m g / k g , s i n g l y o r i n c o m b i nation

° Preserved exclusively by physical means. In products intended for vending machines only. b

I n v i n y l c o m p o u n d p o l y m e r i z a t i o n of v i n y l acetate, a l c o h o l , b r o m i d e , c h l o r i d e , or c a r b o n a t e , a s c o r b i c a c i d c a n b e a c o m p o n e n t of t h e p o l y m e r i z a t i o n m i x t u r e (733-749).

Activators for the polymerization have

b e e n a c r i f l a v i n e ( 7 3 4 ) , other p h o t o s e n s i t i v e d y e c o m p o u n d s hydrogen

peroxides

(740,741,742),

(737,738),

potassium peroxydisulfate

ferrous sulfate, a n d a c y l s u l f o n y l p e r o x i d e s

(747).

(743),

Nagabhooshanam

a n d S a n t a p p a (748) r e p o r t e d o n d y e s e n s i t i z e d p h o t o p o l y m e r i z a t i o n o f v i n y l m o n o m e r s i n t h e presence of a s c o r b i c a c i d - s o d i u m h y d r o g e n o r t h o phosphate complex.

A n o t h e r c o m b i n a t i o n is v i n y l c h l o r i d e w i t h

cyclo-

h e x a n e s u l f o n y l a c e t y l p e r o x i d e w i t h a s c o r b i c a c i d , i r o n sulfate, a n d a n a l c o h o l ( 7 4 9 ) . U s e of l o w t e m p e r a t u r e c o n d i t i o n s i n e m u l s i o n p o l y m e r i z a t i o n , w i t h a s c o r b i c a c i d , is m e n t i o n e d (750,751).

C l a r i t y of c o l o r is

i m p o r t a n t a n d i m p a c t - r e s i s t a n t , clear, m o l d a b l e p o l y v i n y l c h l o r i d e c a n b e p r e p a r e d w i t h a s c o r b i c a c i d as a n a c i d c a t a l y s t (752) i n t h e f o r m u lation.


20.


BAUERNFEIND

473

S i m i l a r reports h a v e a p p e a r e d i n t h e t e c h n o l o g y acrylic monomers

s u c h as a c r y l o n i t r i l e (753-759)

of p o l y m e r i z i n g

or acrylamide

(760-

763). K o r o l e v et a l . (764) h a v e u s e d a s c o r b i c a c i d as a r e d u c i n g agent i n t h e m i x t u r e t o increase t h e p o l y m e r i z a t i o n rate. p o l y m e r i z a t i o n i n t h e presence c o n t a i n i n g a s c o r b i c a c i d (765).

T h e k i n e t i c s of

of o x y g e n has b e e n s t u d i e d i n systems R e c e n t patents (766,767)

have

been

i s s u e d w i t h a s c o r b i c a c i d i n t h e d i s p e r s i o n of a c r y l i c aqueous resins. A t h i r d t y p e of p o l y m e r s is p o l y m e r i z e d m e t h y l m e t h a c r y l a t e o r Downloaded by UCSF LIB CKM RSCS MGMT on November 18, 2014 | http://pubs.acs.org Publication Date: June 1, 1982 | doi: 10.1021/ba-1982-0200.ch020

m e t h a c r y l a m i d e (768-773).

S t r u b e l l (768) has c a r r i e d o u t p o l y m e r i z a

t i o n of m e t h y l m e t h a c r y l a t e w i t h a n a s c o r b i c system.

I n a n aqueous

acid-benzoyl

peroxide

p o l y m e r i z a t i o n of m e t h y l m e t h a c r y l a t e ,

Misra

a n d G u p t a (770) u s e d the r e d o x system of p o t a s s i u m p e r o x y d i s u l f a t e a n d a s c o r b i c a c i d . A s i m i l a r system w a s r e p o r t e d b y P a t t n a i k et a l . ( 7 7 3 ) . A s c o r b i c a c i d is d e c l a r e d t o f u n c t i o n as a n a n t i o x i d a n t f o r p o l y e t h y l e n e (774), f o r l i g h t - s e n s i t i v e p o l y m e r mass ( 7 7 5 ) , f o r clear t h e r m o p l a s t i c s (776), a n d f o r colorless s y n t h e t i c r u b b e r (777).

I t is l i s t e d as

a n accelerator f o r c u r i n g a n a e r o b i c resins (778) a n d f o r h a r d e n i n g p r o c esses of u n s a t u r a t e d p o l y e s t e r resins (779—783). A s c o r b i c a c i d is a n a d d i t i v e w i t h s y n e r g i s t i c effect u p o n other c o m p o u n d s

i n stabilized pre

mixes f o r p o l y u r e t h a n e f o a m (784) a n d as a s t a b i l i z e r f o r polyesters t o b e u s e d as a n l u b r i c a n t a d d i t i v e s or p l a s t i c i z e r s (785).

Ascorbic acid

triggers p o l y m e r i z i n g r e s i n - f o r m i n g m a t e r i a l s u s e d i n w e l l b o r e as d r i l l i n g fluids (786) a n d i n fire-resistant p o l y m e r c o m p o s i t i o n s Ferrocene-containing polymers a n d their photooxidation-reduction t i o n (788,789),

holes (787). reac

a n d synthesis a n d reactions of p o r p h y r i n a n d m e t a l l o -

p o r p h y r i n p o l y m e r s ( 7 9 0 ) are other systems f o r u t i l i t y of a s c o r b i c a c i d . I n plastics a n d p o l y m e r i z a t i o n reactions there appears t o b e m u c h art w i t h i n t h e s y s t e m s — w h a t m a y w o r k i n o n e case or w h a t m a y b e a p l u s feature i n o n e m a y b e u n d e s i r a b l e i n another.

Trials must be r u n

to substantiate w h e r e a n d h o w m u c h of t h e m o r e expensive

ascorbic

a c i d has m e r i t over e c o n o m i c a l i n o r g a n i c a n d o r g a n i c substitutes. A s c o r b i c a c i d m a y h a v e a better o p p o r t u n i t y w h e r e color, o d o r , or safety a r e important i n the e n d product. Photographic Developing and Printing.

T h e association of ascor

b i c a c i d a n d d e r i v a t i v e s w i t h t h e p h o t o g r a p h i c i n d u s t r y is n o t a n e w r e l a t i o n s h i p ; i t goes b a c k over 4 5 years w h e n a s c o r b i c a c i d w a s first p r o d u c e d c o m m e r c i a l l y b y c h e m i c a l synthesis. D u r i n g this

four-decade

p e r i o d m a n y patents h a v e b e e n i s s u e d a r o u n d t h e w o r l d . Some w i l l b e m e n t i o n e d i n this r e v i e w . material development,

Basically, i n the technology

of film emulsions a n d i n film developers white photography.

of p h o t o g r a p h i c

a s c o r b i c a c i d has b e e n c o n s i d e r e d a

component

both i n color a n d black a n d

I t has b e e n s t u d i e d as a n i n v e s t i g a t i o n a l m a t e r i a l ,

a n d w h i l e m e r i t m a y b e s h o w n f o r its i m a g e q u a l i t y o r f o r f u n c t i o n a l


474

ASCORBIC

ACID

q u a l i t i e s i n t h e d e v e l o p i n g s o l u t i o n , its i n s t a b i l i t y , r a p i d i t y of e x h a u s t i o n i n a c t i o n , o r h i g h e r cost a r e d i s a d v a n t a g e o u s

considerations

that keep

its usage i n this i n d u s t r i a l a p p l i c a t i o n at a l o w e r l e v e l t h a n its p o t e n t i a l . A s c o r b i c a c i d has b e e n d e c l a r e d as a u s e f u l o p t i o n a l i n g r e d i e n t i n d e v e l o p e r c o m p o s i t i o n s (791-799).

Ascorbic acid c a n be used

without

sulfite a d d i t i o n a n d i t has n o solvent effect o n s i l v e r h a l i d e s ( 7 9 3 ) . Its a d d i t i o n increases t h e a c t i v i t y of c e r t a i n d e v e l o p e r c o m p o n e n t s

(800)

a n d m a y s t a b i l i z e the i m a g e (801-804) o r i n t e n s i f y i t ( 8 0 5 ) . I n a B e l g i a n


p a t e n t (806) b o t h L - a s c o r b i c a c i d a n d a 2 , 3 - d i p h e n y l - L - a s c o r b i c

acid are

c i t e d as a d d i t i v e s . F o r d e v e l o p e r s f u n c t i o n i n g at a n a l k a l i n e p H , a s c o r b i c a c i d b o r a t e (807) w a s d e c l a r e d t o b e stable w h i l e a c t i n g as a r e d u c i n g agent.

A s c o r b i c a c i d is u s e f u l i n b l e a c h i n g processes (808,809,810):

in

the b l e a c h i n g of p h o t o g r a p h s o b t a i n e d b y t h e s i l v e r salt d i f f u s i o n process (808), i n b l e a c h - f i x b a t h d e s i l v e r i n g (809), a n d as a c o l o r

photography

b l e a c h i n g agent (810). T h e k i n e t i c s of d e v e l o p m e n t a n d silver f o r m a t i o n h a v e b e e n i n v e s t i g a t e d b y W i l l i s et a l . (811) a n d P o n t i u s et a l . (812). Applications for ascorbic acid have been considered tography

where

i n color pho

i t m a y b e a c o m p o n e n t of t h e d e v e l o p e r f o r s p e c i a l

p u r p o s e s u c h as t o r e d u c e f r o t h (813,814), o r i n i m a g e s t a b i l i z a t i o n i n color photographic

m a t e r i a l (815,816).

in

processes

image

emulsions

transfer

Ascorbic acid may be involved

(817,818),

direct

positive

photographic

(819), one-step d i f f u s i o n processes (820) i n a

photographic

p r o d u c t i n c o r p o r a t i n g a d e v e l o p e r y i e l d i n g images b y s i m p l e

treatment

w i t h w a t e r (821), o r as a b i n d e r f o r p h o t o g r a p h i c m a t e r i a l s (822). I n t h e p r e p a r a t i o n of l i t h o g r a p h i c m a t e r i a l s a n d i n t h e l i t h o g r a p h i c process, a s c o r b i c a c i d m a y b e u s e f u l .

T h e production

of l i t h o g r a p h i c

masters is i m p r o v e d b y i n c l u s i o n of a s c o r b i c a c i d i n t h e h a r d e n e r a n d r e c e i v i n g sheet (823) a n d , i n g e n e r a l , i n p r o c e s s i n g

silver halide litho

g r a p h i c m a t e r i a l s (824).

A s c o r b i c a c i d has b e e n c o n s i d e r e d

investigations

as a c o m p o n e n t of t h e d e v e l o p e r s u s e d i n

lithography.

(825-828)

i n several

I n offset p r i n t i n g plates b y c o l l o i d transfer (829), a s c o r b i c

acid a n d l-phenyl-3-pyrazolidinone

are used

as n o n h a r d e n i n g

agents.

I n k w i t h h i g h p o w e r to a b s o r b l i g h t (830) is benefited b y a s c o r b i c a c i d a d d i t i o n . O t h e r a p p l i c a t i o n s i n v o l v e l i g h t - s e n s i t i v e c o p y m a t e r i a l (831), h e a t - d e v e l o p a b l e i m a g i n g systems (832,833), p o w d e r l e s s e t c h i n g a n d various recording a n d print-out papers T h e r e is a m e t a l aspect of p h o t o g r a p h y be i n v o l v e d .

(834),

(835-838). where ascorbic acid m a y

S e v e r a l patents c l a i m a s c o r b i c a c i d u s e f u l as a sequestering

or c h e l a t i n g a g e n t (839,840), g r a p h i c m a t e r i a l (841,842).

or, t o p r e v e n t

i r o n s p o t t i n g of p h o t o

I t is i n c l u d e d i n a t w o - s t a g e c o p p e r d e v e l

o p m e n t of a s i l v e r latent i m a g e i n s e m i c o n d u c t o r

photographic

layers

(843), a n d i n a s t u d y of silver-free p h y s i c a l d e v e l o p m e n t process b y electrochemical

m e t h o d s , a s c o r b i c a c i d acts as a p h y s i c a l d e v e l o p e r i n


20.

BAUERNFEIND

the

form

lesions)

475


of c u p r i a s c o r b i c

acid

(844).

Chromate

dermatitis

(hand

is a n o c c u p a t i o n a l h e a l t h p r o b l e m i n t h e p r i n t i n g a n d l i t h o

g r a p h i c i n d u s t r i e s . A p r e v e n t i v e r e g i m e n ( 8 4 5 ) i n v o l v i n g use of a 1 0 % ascorbic

a c i d s o l u t i o n is b e n e f i c i a l i n p r e v e n t i n g o r c o n t r o l l i n g t h e

occurrence. Metal Technology.

T h e p a t e n t a n d scientific l i t e r a t u r e reveals some

p o t e n t i a l uses f o r a s c o r b i c a c i d i n m e t a l l i c r e d u c t i o n s , c o a t i n g tions, e l e c t r o p l a t i n g processes, a n d o x i d a t i o n c o n t r o l .

composi

Metal ion and


m e t a l c o m p l e x c a t a l y z e d reactions (846) a n d t h e s t r u c t u r e of ascorbate complexes

of metals (847) h a v e b e e n i n v e s t i g a t e d .

T h e kinetics a n d

m e c h a n i s m of t h e r e d u c t i o n of p l a t i n u m ( 8 4 8 ) , v a n a d i u m ( 8 4 9 ) , c e r i u m ( 8 5 0 ) , m o l y b d e n u m ( 8 5 1 ) , g o l d ( 8 5 2 ) , a n d s i l v e r (853,854) b y a s c o r b i c a c i d h a v e b e e n e x a m i n e d . O t h e r topics of a s c o r b i c a c i d i n v o l v e m e n t a r e p r o v i d i n g resistance t o m e t a l surfaces (855, 8 5 6 ) , m e t a l l i z i n g n o n m e t a l l i c substrates (857), o x i d a t i o n - r e s i s t a n t c o a t i n g f o r c o p p e r a n d c o p p e r alloys (858), c o p p e r p l a t i n g (859), n i c k e l p l a t i n g (860,861), of n i c k e l a l l o y films (862-865),

electrodeposition

of z i n c alloys (866,867),

of t i n a l l o y s

(868), e l e c t r o d e p o s i t i o n of a l u m i n u m (869,870), a n d a c t i v a t i o n of z i n c p h o s p h a t e c o m p o s i t i o n s f o r steel (871). R u s t r e m o v e r c o m p o s i t i o n (872) for steels, rust i n h i b i t i n g uses (873,874), a n d r u s t p r o o f i n g agents

(875)

f o r ferrous a n d nonferrous metals a n d alloys a r e other c i t e d a p p l i c a t i o n s .

Miscellaneous

Applications

A s c o r b i c a c i d a n d d e r i v a t i v e s are c i t e d as p o t e n t i a l i n g r e d i e n t s i n c o s m e t i c f o r m u l a t i o n s (876-879). Specific uses i n v o l v e cosmetic c o m p o sitions f o r t h e r m a l d i s p e n s i n g

(880),

d e n t i f r i c e tablets

(881),

bath

p r e p a r a t i o n s (882), deodorants a n d m o u t h w a s h e s (883-886), s k i n p r e p a rations s u c h as s k i n l i g h t e n i n g p r e p a r a t i o n s (887) o r p r o t e c t i v e

creams

(888-890).

T h e m o r e a c t i v e areas h a v e b e e n h a i r a n d scalp p r e p a r a t i o n s

(891,892),

h a i r setting c o m p o s i t i o n s

(893), h a i r b l e a c h i n g

programs

(894, 895), a n d h a i r d y e i n g p r e p a r a t i o n s (896, 897, 898). A s c o r b i c a c i d has b e e n d e c l a r e d u s e f u l i n i n t r a v a g i n a l c o n t r a c e p tives i n r e d u c i n g s p e r m m o t i l i t y (899,900).

T h e p r e s e r v a t i o n of h u m a n

b l o o d b y t h e a d d i t i o n of s o d i u m ascorbate ( 9 0 1 ) has b e e n f o u n d t o h a v e some m e r i t . T h e usefulness of a s c o r b i c a c i d i n the t r e a t m e n t of i n d u s t r i a l c h e m i c a l t o x i c i t y (902,903), i n t h e p r e s e r v a t i o n of c u t - b l o o m s i n w a t e r (904,905), i n w a t e r t r e a t m e n t of the f e r r u g i n o u s t y p e (906), i n i n h i b i t i n g c o r r o s i o n (907), i n t r e a t m e n t f o r t h e p r o d u c t i o n of d u r a b l e creases i n c l o t h (908), a n d i n b r i g h t e n e d y a r n s w i t h h i g h l i g h t fastness ( 9 0 9 ) is mentioned.

Adhesive compositions

(910) a n d s p e c i a l cleansers

912) a r e other p o t e n t i a l a p p l i c a t i o n s .


(911,

476

ASCORBIC

ACID

T h e p u r g i n g o f n i t r o g e n oxides f r o m exhaust gases (913) a n d treat m e n t of s m o k i n g m a t e r i a l s (914) w i t h ascorbates a r e o f interest, p a r t i c u l a r l y t h e latter, w h e r e i n a l o w e r p r o d u c t i o n of p o t e n t i a l l y

carcinogenic

nitrosated compounds m a y result i f the application were to b e p u t into effect. A n extensive l i t e r a t u r e exists o n t h e use o f a s c o r b i c a c i d i n c h e m i c a l a n a l y t i c a l assays.


Literature Cited 1. 2. 3. 4. 5. 6. 7. 8. 9. 10. 11. 12. 13. 14. 15. 16. 17. 18. 19. 20. 21. 22. 23. 24. 25. 26. 27. 28. 29. 30. 31.

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Received for review April 16, 1981. Accepted June 27, 1981.


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