Maillard Technology as Applied to Meat and Savory Flavors - ACS

Chapter 38

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Maillard Technology as Applied to Meat and Savory Flavors Lawrence L. Buckholz, Jr. International Flavors and Fragrances, Dayton, NJ 08810

The purpose of pyrolytically treating certain foods is to promote flavor changes that increase their overall palatability. A knowledge of the composition of flavor volatiles produced by heating foods would therefore be most desirable. The Maillard reaction is responsible for these changes and it is involved with food processing in three quite different ways: 1) The development of flavors in traditional roasting, baking and cooking processes. 2) The rational use of "reaction flavor" technology to manufacture engineered foods and processed flavors. 3) Efforts to inhibit undesirable browning, such as that of whey in cheese powders. The development of cooked meat flavors for new "fast" food, frozen entree, and microwave applications is strongly impacted by the Maillard reaction. This review discusses the use of Maillard technοlogy to generate meat and savory flavors, with emphasis on flavor chemistry, precursors, volatiles, and recent flavor improvements. MAN HAS B E E N INVOLVED WITH MAILLARD REACTION T E C H N O L O G Y FROM T H E DAWN O F T I M E WHEN H E F I R S T U S E D F I R E TO COOK H I S F O O D . T H E CHANGES THAT OCCURRED DURING THE C O O K I N G OF MEAT WERE T H E R E S U L T O F NON ENZYMATIC BROWNING. T H E FLAVOR PRODUCED WAS T H E R E S U L T O F SUGARA M I N O A C I D R E A C T I O N S , S T R E C K E R D E G R A D A T I O N , A N D FAT O X I D A T I O N ; T H U S , W I T H O U T H I S A W A R E N E S S , MAN WAS U S I N G T H E BROWNING R E A C T I O N TO R E N D E R MEAT T E N D E R , F L A V O R F U L A N D P A L A T A B L E . MANY

BLAND

TRANSFORMED HEAT-TREATED CHOCOLATE, UNDERGO

AND

EVEN UNPLEASANT

I N T O SOME OF FOODS BREAD,

C O M P R I S I N G SUCH COFFEE,

M A I L L A R D BROWNING

GENERATED

FROM T H E

ROASTED

SUBSTANCES ARE BY ROASTING

TASTES

CEREALS,

ENORMOUS

AND

FEW P R I M A R Y R E A C T A N T S APPLICATIONS

HAVE

(AMINO

B E E N WELL

A C I D S AND S U G A R S ) . STUDIED,

(1).

AROMAS A S

AND TOASTED FLAVOR

L A R G E NUMBER OF P O S S I B L E P E R M U T A T I O N S

TIVELY

ABOUT

MEATS,

FOOD

FLAVORS

DIFFERENT

REACTIONS.

FLAVOR

UNDERSTOOD

TASTING

T H E MOST D E S I R A B L E

MUCH

NUTS

VARIETY

IS

AMONG R E L A WHILE

ITS

R E M A I N S TO

B A S I C P R I N C I P L E S GOVERNING MAILLARD CHEMISTRY

0097-6156/89/0409-0406$06.00A) ο 1989 American Chemical Society Parliment et al.; Thermal Generation of Aromas ACS Symposium Series; American Chemical Society: Washington, DC, 1989.

BE

(2).

38.

BUCKHOLZ


Historical

Maillard Technology Applied to Meat and Savory Flavors

Perspective

The e a r l i e s t r e p o r t e d s c i e n t i f i c s t u d i e s of the M a i l l a r d r e a c t i o n were i n i t i a t e d by L o u i s C a m i l l e M a i l l a r d ( 1 ) . In a misguided attempt to determine the b i o l o g i c a l s y n t h e s i s o f p r o t e i n s , he heated concentrated s o l u t i o n s of D-glucose and amino a c i d s . What he observed was a g r a d u a l d a r k e n i n g and f r o t h i n g , w i t h the development o f odors r e m i n i s c e n t of the b a k i n g of bread or the r o a s t i n g o f a n i m a l or v e g e t a b l e p r o d u c t s . T h i s work a t t r a c t e d s u f f i c i e n t a t t e n t i o n to persuade many o t h e r s to c o n t i n u e the s t u d y o f what has come to be c a l l e d the M a i l l a r d r e a c t i o n . On November 27, 1911 M a i l l a r d f i r s t r e p o r t e d a c o n d e n s a t i o n o f amino a c i d s by the use o f g l y c e r o l . I n a l a t e r r e p o r t he c i t e d a paper on m a l t i n g by L i n g ( 3 ) , who noted the e f f e c t s o f k i l n i n g o r heat d r y i n g a t 120°C to 150^C. Others performed f u r t h e r e x p e r i m e n t s f o l l o w i n g M a i l l a r d ' s methods; i n 1912 Lintner reported obtaining d a r k r e a c t i o n p r o d u c t s which were r e s p o n s i b l e f o r f l a v o r and aroma (4). Four y e a r s l a t e r , P i c t e t d e s c r i b e d the f o r m a t i o n of p y r a z i n e and i s o q u i n o l i n e bases from the a c i d h y d r o l y s i s of c a s e i n i n the presence of formaldehyde ( 5 ) . A d d i t i o n a l h i s t o r i c a l d e t a i l s o f the M a i l l a r d r e a c t i o n are a v a i l a b l e ( 6 ) . Both the volume o f the p u b l i s h e d work and the r e c o g n i t i o n o f its p o t e n t i a l importance to the food i n d u s t r y l e d to the f i r s t g e n e r a l r e v i e w o f the s u b j e c t i n 1951 by Danehy ( 7 ) . Only two y e a r s l a t e r a second r e v i e w , l i m i t e d l a r g e l y to a c o n s i d e r a t i o n o f model systems and m e c h a n i s t i c i n t e r p r e t a t i o n s was p u b l i s h e d by Hodge (8). I n i t , he c o n c l u d e d t h a t " . . . t h e c o n t r o l of browning r e a c t i o n s to produce o n l y wanted f l a v o r s and odors i s an i n t r i g u i n g p o s s i b i l i t y , ...but p r o g r e s s toward t h i s g o a l can be made o n l y as the r e a c t i o n mechanisms are b e t t e r u n d e r s t o o d . " More r e c e n t l y , t h r e e intern a t i o n a l symposia have been devoted to the M a i l l a r d r e a c t i o n ( 9 - 1 1 ) . C h e m i s t r y o f the M a i l l a r d R e a c t i o n The M a i l l a r d r e a c t i o n i s a c t u a l l y a complex group o f hundreds o f p o s s i b l e r e a c t i o n s . The initial r e a c t i o n sequence i s s i m i l a r to t h a t f o r c a r a m e l i z a t i o n , except t h a t the sugars t h e r m a l l y condense w i t h amino a c i d s , p e p t i d e s , and p r o t e i n s . C o n d e n s a t i o n i s f o l l o w e d by e n o l i z a t i o n and d e h y d r a t i o n . Two of the s e v e r a l branches o f the M a i l l a r d r e a c t i o n are shown i n F i g u r e 1 ( 1 2 ) . The major pathway leads from the 1,2-eneaminol o f the Amadori compound to 5-hydroxymethyl-l,2-furaldehyde. The amino a c i d may be r e t a i n e d i n some m o l e c u l e s o f t h i s pathway. The minor branch b e g i n s w i t h the 2,3e n e d i o l of the Amadori compound; the amino compounds can then condense w i t h the a c y c l i c c a r b o n y l forms of s u g a r s . Amino a c i d s , peptides, and p r o t e i n s o f f e r b a s i c amino groups when the pH o f the a d j a c e n t medium r i s e s above the i s o e l e c t r i c p o i n t o f the amino compound. The i n i t i a l r a t e of browning of a r e d u c i n g sugar w i t h a given amino compound i s d i r e c t l y r e l a t e d to the r a t e a t w h i c h the s u g a r ' s r i n g opens to a r e d u c i b l e form. Pentoses and 2-deoxy-Dr i b o s e r e a c t f a s t e r then 2-deoxy hexoses, which i n t u r n r e a c t f a s t e r than hexoses. Among the hexoses, browning r a t e s d e c r e a s e i n the order: D - g a l a c t o s e > D-mannose > D-glucose. The g e n e r a l p r o p e r t i e s and c h a r a c t e r i s t i c s o f the M a i l l a r d r e a c t i o n a r e summarized i n T a b l e I (13).

Parliment et al.; Thermal Generation of Aromas ACS Symposium Series; American Chemical Society: Washington, DC, 1989.

407


compound

Amadori

I I

CHOH

CHOH

c=o

H2Ç-NC

Enediol

— •

-Amine CHOH

c=o

I _

CH 2 I C—OH

CH 1 CHOH

II —

2

^

+H 0

j c=o

C-OH 2

Methyl adicarbonyl intermediate

CHOH

C=0

CH 3

intermediate

3Deexyhexosene

CHOH

1 CH 2

HC=0

H Ç =
d i d an e x t e n s i v e study o f the M a i l l a r d r e a c t i o n and meat f l a v o r . Many d e s i r a b l e meat f l a v o r v o l a t i l e s a r e s y n t h e s i z e d by h e a t i n g w a t e r - s o l u b l e p r e c u r s o r s such as amino a c i d s and carbohydrates. These latter constituents interact t o form i n t e r m e d i a t e s which a r e c o n v e r t e d to meat f l a v o r compounds by o x i d a t i o n , d e c a r b o x y l a t i o n , c o n d e n s a t i o n , and c y l i z a t i o n . 0-, N-, and S-heterocyclics including f u r a n s , furanones, pyrazines, thiophenes, thiazoles, thiazolines, and cyclic polysulfides c o n t r i b u t e s i g n i f i c a n t l y to the o v e r a l l d e s i r a b l e aroma i m p r e s s i o n o f meat. The M a i l l a r d r e a c t i o n i s important to the f o r m a t i o n of S t r e c k e r a l d e h y d e s , hydrogen s u l f i d e and ammonia. There a r e two approaches to meat f l a v o r a n a l y s i s : one is concerned w i t h the i s o l a t i o n and i d e n t i f i c a t i o n o f v o l a t i l e f l a v o r components, and the o t h e r i n v o l v e s i d e n t i f i c a t i o n o f non v o l a t i l e flavor precursors. Non-volatile Precursors. Water-soluble meat f l a v o r precursors encompass a number o f d i f f e r e n t o r g a n i c c l a s s e s o f compounds i n c l u d i n g n u c l e i c a c i d s , n u c l e o t i d e s , n u c l e o s i d e s , p e p t i d e s , amino a c i d s , f r e e s u g a r s , sugar amines, g l y c o g e n , and amines (20-30). The influence of h e a t i n g on the d i a l y z a b l e low m o l e c u l a r weight c o n s t i t u e n t s (amino a c i d s , c a r b o h y d r a t e s , n u c l e o t i d e s , n u c l e o s i d e s ) i n beef, pork and lamb was s t u d i e d (25-29). The predominant amines i n the d i a l y z a b l e d i f f u s a t e were a l a n i n e , a n s e r i n e - c a r n o s i n e , and t a u r i n e , and these decreased c o n s i d e r a b l y d u r i n g h e a t i n g . Other amino a c i d s d e c r e a s i n g d u r i n g h e a t i n g i n c l u d e d m e t h y l h i s t i d i n e , i s o l e u c i n e , l e u c i n e , methionine, cystine, serine, lysine, glycine and glutamic acid. Glucose, f r u c t o s e , and e s p e c i a l l y r i b o s e and ribose-5-phosphate r e a d i l y decomposed d u r i n g h e a t i n g a t 100 C f o r one hour ( 3 0 ) . e

V o l a t i l e Precursors. I n v e s t i g a t i o n s i n v o l v i n g model systems f o r meat aromas have been reviewed (31-34). More than 600 v o l a t i l e s have been i d e n t i f i e d from meat o r s i m u l a t e d meat p r e c u r s o r s .



38.

BUCKHOLZ

HC=0

•


HC=H—CH2COOM I

HINCNJCOOH

•M

HC=0

HC=0

H,0 X

"V"

6 0 2

HC

HC=0

I

• HCHO •

C0

COOH

OH NH

/HHî

2

HC 2

I OH

C00H

-2H 0 2

-ÎL,

HC

Figure 2. Strecker degradation reactions and products. (Reprinted with permission from ref. 13. Copyright 1976 Marcel Dekker.)


2

411


oldoheiose

+

α-Amino

Acid

1

R

C-OH

1

-QH^

(t)

CH(OH

H-C-OH

ÇH H-C-OH

H

C-OH

CH

\

0

NH-CH-CI R

-CQ 2

+

(Π)

CHjOH

(1)

CHjOH

-C-OH

II

C-OH

C-OH H-C-OH "

• H.O

ÇH

C-OH

Η

CH C-OH ι CH

NH, CH

H=CH ι

R

Amino Acid

t

American Chemical Society.)

m

n

+ R-CHO

-

mi

C-OH CH,OH

II

C-OH

ÇH,

C=0

2

NH« ι * CH ι

ft

" '7

CH,OH

-C-OH

CHO

Pigments

o

B f0

(ΙΠI

rΎ

| 101 CH

5

CHj

+ ommo acetone

CHj

C=0

CM,

NH,

Reductones - ° - ' "

Figure 3. Mechanism for formation of pyrazines. (Reprinted from ref. 17. Copyright 1967

(!)

CH^OH

CH OH

2

H-C-OH

H—C-OH

H-C-OH

H-i-OH

H-C-OH

H-C-OH

CH

1

H- C-OH

•H^

R

H - N - C H - -COOH

H-C-OH

H— N - C H - COOH

a, 0-unsoturoted

M- C - O H ""a-dicorfconyl ~~~ CH OH m)

H-C-OH

I *

CH.

I

c=o

H-C=0 I



38.

BUCKHOLZ


Further e v i d e n c e o f the importance o f the M a i l l a r d r e a c t i o n i n the formation o f v o l a t i l e f l a v o r a n t s from meat p r e c u r s o r s i s g l e a n e d by examining i n g r e d i e n t s i n r e a c t i o n mixtures p a t e n t e d as synthetic meat constituents. C h i n g ( 3 1 ) , examined 128 p a t e n t s o f meat f l a v o r and found t h a t 55 s p e c i f i e d use o f both amino a c i d s and s u g a r s . Cysteine, c y s t i n e , and g l u t a m i c a c i d were used i n 39 such m i x t u r e s . Over 80 p a t e n t s d e s c r i b e meat f l a v o r " r e a c t i o n p r o d u c t s " ( 3 2 ) . Meat aroma i s not the r e s u l t o f one c h e m i c a l c o n s t i t u e n t but the sum o f the s e n s o r y e f f e c t s o f many o f these v o l a t i l e s . Over 90% of the volume o f v o l a t i l e c o n s t i t u e n t s from f r e s h l y r o a s t e d beef i s from l i p i d , but 40% o f the v o l a t i l e s from the aqueous f r a c t i o n a r e thought to be heterocyclic compounds. Heterocyclic compounds c o n t r i b u t e s i g n i f i c a n t l y to the o v e r a l l aroma i m p r e s s i o n o f meat. Although some i n v e s t i g a t o r s b e l i e v e that dihydrofuranone i s derived from ribose-5-phosphate through a dephosphorylationdehydration mechanism, o t h e r s b e l i e v e i t can be formed by a t y p i c a l Maillard r e a c t i o n between amines and s u g a r s , i n which the Amadori products d e h y d r a t e and e l i m i n a t e to amines. Both r o u t e s a r e l i k e l y to o c c u r .

Furans and Furanones E l e v e n f u r a n s and seven furanones have been i d e n t i f i e d from r e a c t i o n mixtures c o n t a i n i n g p r e c u r s o r s r e s p o n s i b l e f o r beef f l a v o r (31). Furfural derivatives were o b t a i n e d by heating water-extractable components from beef and s i m p l e amino a c i d - s u g a r mixtures. Furanones can be formed by Amadori compound pathways: Hexoses produce 5 - m e t h y l f u f u r a l s and 4-hydroxy-2,5-dimethyl-3-(2H)-furanone, while pentoses' y i e l d furfural and 4-hydroxy-5-methyl-3-(2H)furanone. The l a t t e r compound was s y n t h e s i z e d by h e a t i n g amines with x y l o s e , r i b o s e , ribose-5-phosphate, or g l u c o n i c a c i d (35,36). Furans t h a t do not c o n t a i n s u l f u r are u s u a l l y nutty, f r u i t y , and caramel-like i n odor. The furanones d e s c r i b e d above have b u r n t p i n e a p p l e and sweet r o a s t e d n o t e s .

Sulfur Compounds Thiophenes and Furanthiols. Thiophenes are extremely important contributors to cooked meat f l a v o r and a r e r e s p o n s i b l e f o r m i l d sulfurous aromas. The s u l f u r i n t h i o p h e n e s may be d e r i v e d from amino a c i d s ( c y s t e i n e , c y s t i n e , m e t h i o n i n e ) o r from t h i a m i n e . Over 36 thiophene derivatives have been found during various i n v e s t i g a t i o n s o f meat o r meat c o n s t i t u e n t s ( 3 2 ) . Probably the most important r e a c t a n t i n the formation of volatile meat flavor compounds i s hydrogen s u l f i d e . I t can be formed as a S t r e c k e r d e g r a d a t i o n product o f c y s t e i n e i n the p r e s e n c e of a diketone (37). S e v e r a l S - s u b s t i t u t e d f u r a n s have been i d e n t i f i e d from M a i l l a r d reaction m i x t u r e s which p o s s e s s meaty aromas i n c l u d i n g 3-mercapto2 - m e t h y l f u r a n and 3-mercapto-2,5-dimethyl furan (38). Thiazoles and Thiazolines. T h i a z o l e s and t h i a z o l i n e s p r o v i d e n u t t y , roasted n o t e s to meat flavors. These compounds can be formed by combining a d i k e t o n e , such as 2,3-butanedione ( d i a c e t y l ) , with acetaldehyde, hydrogen sulfide, and ammonia (39). 2-Acetyl-2-


413

414

THERMAL GENERATION OF AROMAS

thiazoline i s postulated t o be formed by S t r e c k e r d e g r e d a t i o n o f c y s t e i n e f o l l o w e d by o x i d a t i v e c y c l i z a t i o n ( 4 0 ) . Other thiazoles have been i s o l a t e d from meat o r meat c o n s t i t u e n t s which have undergone M a i l l a r d - t y p e r e a c t i o n s ( 4 1 ) .


Polysulfide Heterocyclics. Polysulfur heterocyclics, including thialdine (5,6-dihydro-2,4,5-trimethyl-1,3,5- d i t h i a z i n e ) and t r i t h i o a c e t o n e ( 2 , 2 , 4 , 4 , 6 , 6 - h e x a m e t h y l - l , 3 , 5 - t r i t h i a n e ) , have been identified i n meat f l a v o r e x t r a c t s ( 4 1 ) . The formation of these compounds i s shown i n F i g u r e 4. 1-(Methylthio)ethanethiol. T h i s component was i d e n t i f i e d i n the headspace v o l a t i l e s o f beef b r o t h as a r e s u l t o f S t r e c k e r degrada t i o n ( 4 2 ) . A l t h o u g h i t has a r o a s t e d o n i o n - l i k e odor, t h i s compound i s a s i g n i f i c a n t c o n t r i b u t o r t o beef f l a v o r . Pyrazines The i d e n t i f i c a t i o n o f 49 p y r a z i n e s i n heated beef and o t h e r meats has been e x t e n s i v e l y reviewed (32, 4 3 ) . S e v e r a l mechanisms have been proposed f o r p y r a z i n e f o r m a t i o n by the M a i l l a r d r e a c t i o n . D i c a r b o n y l compounds can i n i t i a t e S t r e c k e r d e g r a d a t i o n o f amino acids to y i e l d α-amino k e t o n e s , which i n t u r n can undergo c o n d e n s a t i o n s and o x i d i z a t i o n s t o form s u b s t i t u t e d p y r a z i n e s ( 1 3 ) . Sugar-Amino A c i d Model Systems A thorough s t u d y o f the aromas produced from over 400 model M a i l l a r d r e a c t i o n systems was performed ( 4 4 ) . Combinations o f 21 amino a c i d s and 8 s u g a r s were e v a l u a t e d under d i f f e r e n t c o n d i t i o n s o f tempera t u r e and h u m i d i t y . T a b l e I I l i s t s beefy o r meaty aromas produced from t h e r m a l i n t e r a c t i o n s between g l u c o s e and e i g h t amino a c i d s .

Table I I .

Amino A c i d

G e n e r a t i o n o f "Meaty, B e e f y " Aromas i n Heated M i x t u r e s o f Amino A c i d s w i t h G l u c o s e With G l u c o s e Temperature (°C) 100 140 180 220

Asn Cys Cys Glu Gly He Ser Thr

· 9

· ·

· ·

·

T o t a l Meaty Aromas: Source: Adapted from

3 R e f . 44.

Alone Temperature (°C) 100 140 180 220

• • • • • • • • • • • · • • • · 7


BUCKHOLZ


38.


OH

0 H

3

(3X)

H C-Ç-SH

C

3

H*

H

2,4, (3x)

ι

NH,

HS

(2x)

TRIMETHYLTRITHIANE

2

SH

ι

6~

1 , 3 , 5 -

CH3-CH -S-S-S-CH -CH 2

2

H 5, 6 -

DIHYDRO-

2,4,6

—TRIMETHYL —

1,3,5

— DITHIAZINE

3

4

SH

CH -CH -S-S-CH -CH

4 [·]

S

C H

3

- C H

2

2

2

- S - S - S - S - C H

2

3

- C H

3

DIETHYLTETRASULFIOE

3 , 5 -

DIMETHYL

I ,2, 4-

—

TRITHIOLANE

Figure 4. Formation of important meat aroma polysulfide heterocyclics by heating acetaldehyde and hydrogen sulfide. (Reprinted from ref. 39. Copyright 1976 American Chemical Society.)


415


416

The s e n s o r y p r o p e r t i e s of n e a r l y 450 v o l a t i l e M a i l l a r d r e a c t i o n p r o d u c t s and r e l a t e d compounds have been compiled (45)· The r e v i e w i n c l u d e s q u a n t i t a t i v e aroma and f l a v o r d e s c r i p t i o n s , as w e l l as sensory t h r e s h o l d v a l u e s f o r d i f f e r e n t media, c l a s s i f i e d a c c o r d i n g to c h e m i c a l s t r u c t u r e .


P a t e n t Review While the m a j o r i t y o f M a i l l a r d technology p a t e n t s d e a l w i t h the p r o d u c t i o n o f m e a t - l i k e f l a v o r s ( 1 ) , i t i s a p p r o p r i a t e t o comment on the s i g n i f i c a n c e o f " r e a c t i o n f l a v o r " p a t e n t s . D u r i n g the p a s t 30 y e a r s , s e v e r a l hundred p a t e n t s have been g r a n t e d worldwide f o r p r o c e s s e s and r e a c t i o n p r o d u c t s based on non-enzymatic browning technology. Less than 100 o f these a r e i n c l u d e d i n C h e m i c a l Abstracts, since subsequent patents are listed in patent concordance. There appears t o be about 45 " s t a n d a r d p a t e n t s " , i . e . p a t e n t s which s p e c i f y m i x i n g one o r more amino a c i d s w i t h one o r more carbonyl compounds, f o l l o w e d by p r o c e s s i n g over a range o f temperatures. No s i n g l e patent p r o v i d e s a r i g i d specification. These p a t e n t s have l i t t l e i n s t r u c t i v e o r commercial v a l u e because the extreme c o m p l e x i t y o f the r e a c t i o n product c o m p o s i t i o n would make i t i m p o s s i b l e to determine by e x a m i n a t i o n how they were made. Secondly, i n view o f the redundancy o f the p a t e n t s , i t would be overwhelmingly d i f f i c u l t to determine patent i n f r i n g e m e n t . N e v e r t h e l e s s , the patent l i t e r a t u r e can p r o v i d e i n s i g h t s to the use and importance o f M a i l l a r d t e c h n o l o g y . The key involvement o f o r g a n i c s u l f u r compounds w i t h the development o f m e a t - l i k e f l a v o r s was announced s i m u l t a n e o u s l y i n 1960 by s e v e r a l i n v e s t i g a t o r s ( 4 6 ) . The e a r l i e s t paper to d e s c r i b e attempts to produce aromas usefuï~in foods v i a M a i l l a r d r e a c t i o n s noted t h a t both c y s t e i n e and cystine gave meaty aromas when heated w i t h r e d u c i n g sugars ( 4 7 ) . Heating c y s t e i n e o r c y s t i n e w i t h f u r a n , s u b s t i t u t e d f u r a n s , pentoses o r g l y c e r a l d e h y d e was c l a i m e d to g i v e a m e a t - l i k e f l a v o r (48-52). Most of the o r i g i n a l p a t e n t s r e f e r r i n g to meat flavors u t i l i z i n g Maillard t e c h n o l o g y were c l a i m e d by U n i l e v e r (48-52; 56,57). More r e c e n t p a t e n t s a r e i n v o l v e d w i t h the p r o d u c t i o n o f m e a t - l i k e f l a v o r s . While a m a j o r i t y o f p a t e n t s a r e concerned w i t h c y s t e i n e , c y s t i n e , o r m e t h i o n i n e as the s u l f u r s o u r c e , o t h e r s c l a i m a l t e r n a t i v e s such as mercaptoacetaldehyde, mercaptoalkamines, e t c . S e v e r a l p a t e n t s (53,54), d e c l a r e the c o n t r i b u t i o n t o m e a t - l i k e f l a v o r s produced from t h i a m i n e i n the M a i l l a r d r e a c t i o n . Altern a t e l y , a t e c h n i c a l r e p o r t d e s c r i b e s the v o l a t i l e f l a v o r compounds produced by the t h e r m a l d e g r a d a t i o n of t h i a m i n e a l o n e ( 5 5 ) . M a i l l a r d - r e a c t i o n f l a v o r s have been manufactured f o r y e a r s by v a r i o u s food and f l a v o r companies. P r i n c i p a l companies utilizing Maillard t e c h n o l o g y to c u r r e n t l y develop f l a v o r s a r e P f i z e r , F i d c o , A l e x F r i e s , F r i t z s c h e Dodge & O l c o t t , Dragoco, Haarman & Reimer, Quest, F r i e s & F r i e s , and I n t e r n a t i o n a l F l a v o r s and F r a g r a n c e s . Givaudan has pursued new n a t u r a l raw m a t e r i a l s to use f o r g e n e r a t i o n of M a i l l a r d f l a v o r s ( 5 8 ) . F o l l o w i n g i s a d i s c u s s i o n o f the more r e c e n t p a t e n t s c o n c e r n i n g m e a t - l i k e aroma and f l a v o r i n g agents. Meaty f l a v o r s a r e developed by h e a t i n g r e d u c i n g sugars w i t h c y s t e i n e o r c y s t i n e ( 5 9 ) . Removing cooker j u i c e from f i s h and p r o c e s s i n g i t by M a i l l a r d r e a c t i o n s t o



38.

BUCKHOLZ


remove f i s h y odors i s c l a i m e d to p r o v i d e meat f l a v o r (60)· Meat f l a v o r i s r e p o r t e d by h e a t i n g hydrogen s u l f i d e p r e c u r s o r s w i t h an e d i b l e p r o t e i n a c e o u s m a t e r i a l (such as soy p r o t e i n ) i n an aqueous medium ( 6 1 ) . For microwave c o o k i n g a p p l i c a t i o n s , a browning agent comprised o f a h y d r o l y z e d p r o t e i n ( c o l l a g e n o r g e l a t i n ) i n the presence o f a r e d u c i n g sugar was produced ( 6 2 ) . A g l a z e f o r r e f r i g e r a t e d dough a p p l i c a t i o n s t h a t r a p i d l y browns i n the microwave oven has been developed i n the a u t h o r ' s l a b o r a t o r y ( 6 3 ) . Many i n d i v i d u a l f l a v o r c h e m i c a l s which were i s o l a t e d and identified from M a i l l a r d " s i d e r e a c t i o n s " have been r e p o r t e d i n the patent l i t e r a t u r e . I t i s e v i d e n t from these p a t e n t s t h a t much work has been done to g l e a n s p e c i f i c f l a v o r chemicals from the c o m p l e x i t i e s o f the M a i l l a r d r e a c t i o n . 3-Furyl a l k y l sulfide, d i s u l f i d e , and β-chalcogenalkyl s u l f i d e d e r i v a t i v e s a r e c l a i m e d to p r o v i d e b l o o d y , meaty, and r o a s t e d notes to beef b r o t h and beef p r o d u c t s (64-66). 3 - M e t h y l c y c l o p e n t - 2 - e n - l - o n e was d e c l a r e d f o r i t s flavor enhancement o f beef b o u i l l o n ( 6 7 ) . Firmenich claimed 2,6-dimethyl-2-octenal and i t s analogs as p o s s e s s i n g meat flavor qualities ( 6 8 ) . A method to produce d i s u l f i d e s f o r a p p l i c a t i o n to meat and s a v o r y f l a v o r s was patented ( 6 9 ) . Meaty and sauteed onion-like flavors a r e imparted by 2-(o-mercaptoalkyl)-3-thiazoline when added to foods (70). A synthesis of 4-hydroxy-5-methyl-2,3-dihydrofuran-3-one was d e s c r i b e d , which i s c l a i m e d to p r o v i d e meaty o r beefy f l a v o r ( 7 1 ) . 2 - ( 2 , 6 - D i m e t h y l - l , 5 - h e p t a d i e n y l ) - l , 3 - d i t h i o l a n e s possess h y d r o l y z e d v e g e t a b l e p r o t e i n - l i k e o r cooked l i v e r aroma and flavor. Methyl (methylthioalkyl)-l,3-dithiolanes produce v e g e t a b l e - l i k e , sweet m e a t - l i k e , t u r k e y , c h i c k e n , and p o r k - l i k e aromas and flavors. At the proper c o n c e n t r a t i o n , bready notes can a l s o be a c h i e v e d . Furyl and p h e n y l m e r c a p t a l s a r e used to enhance r o a s t e d n u t , r o a s t e d meat, beef b r o t h , b l a c k pepper, o n i o n , f i n e herbs omelet, and cooked o n i o n omelet foods. 4,5-Dimethyl-2-(2-methylthioethyl)-l,3-oxathiolane p r o v i d e s beef b r o t h , o n i o n , g a r l i c , b l o o d y , and mushroom notes to foods and snacks. D i a l k y l t h i o a l k e n e s and derivatives produce v e g e t a b l e p r o t e i n - l i k e and beany nuances. T h i o a l k a n o i c a c i d e s t e r s o f p h e n y l a l k a n o l s produce f l o r a l , r o a s t e d n u t t y , r o a s t e d p e a n u t t y , sesame, coconut macaroon, y e a s t y , and h y d r o l y z e d v e g e t a b l e p r o t e i n l i k e nuances. o-Dioxybenzaldehyde d i m e t h y l m e r c a p t a l s produce beef e x t r a c t , o n i o n y , cabbage-type aroma and f l a v o r i n s p e c i f i e d food a p p l i c a t i o n s (72-78). CONCLUSION

Modern M a i l l a r d r e a c t i o n technology i s c r i t i c a l to today's food i n d u s t r y . The development o f convenience foods and q u i c k l y - p r e p a r e d meals r e q u i r e s the use o f n a t u r a l f l a v o r enhancements to overcome the s e n s o r y gaps when compared w i t h " t r a d i t i o n a l " c o o k i n g methods: the b a s t i n g of r o a s t s , the simmering of soups, g r a v i e s , meats, e t c . M a i l l a r d t e c h n o l o g y can be used to p r o v i d e the f l a v o r , browning, and room aroma t h a t would be l a c k i n g i n q u i c k , c o n v e n i e n t l y prepared f o o d s . As more i s l e a r n e d about non-enzymatic browning and s p e c i f i c f l a v o r c h e m i s t r i e s , the a b i l i t y to m a i n t a i n o r g e n e r a t e d e s i r e d f l a v o r s and aromas w i l l i n c r e a s e , r e g a r d l e s s of food a p p l i c a t i o n .


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1989


Maillard Technology as Applied to Meat and Savory Flavors - ACS

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