Maillard Technology: Manufacturing Applications in Food Products

14 Maillard Technology: Manufacturing Applications in Food Products J A M E S P. D A N E H Y and B E R N A R D

WOLNAK

Downloaded by CORNELL UNIV on August 23, 2016 | http://pubs.acs.org Publication Date: April 29, 1983 | doi: 10.1021/bk-1983-0215.ch014

Bernard Wolnak and Associates, Chicago, IL

60601

Just about forty years ago the United States Army Quartermaster Corps was having serious problems with the deterioration of certain stored foods, attributable to non-enzymatic browning reactions. The Corps approached the Corn Products Refining Company (now CPC International) and requested them to undertake research directed toward alleviating their problems. The late Ward Pigman, a carbohydrate chemist, and myself, in charge of the research on proteins, had never heard of the Maillard reaction. Nevertheless, we accepted their invitation, and the result was the first English language review of Maillard chemistry (1), published thirty-one years ago in Advances in Food Research. Maillard reactions can be involved in the manufacture of foods in at least three quite different ways. First, there is the unconscious role played in the development of flavor* in such traditional processes as the roasting of coffee and cacao beans, the baking of breads and cakes, and the cooking of meats. Second, there is the deliberate use of Maillard technology in the production of artificial (or engineered) foods and flavors. Third, there are the efforts to inhibit undesirable results of Maillard reactions in food processing today. The Role of Browning in Specific Food Systems Many bland, or even downright unpleasant-tasting, substances are transformed into some of the most desirable flavors and popular foods by roasting. Thus, those foods, representing such different tastes and aromas as chocolate, bread, roast beef, coffee, and toasted nuts have in common the fact that they are products of the Maillard browning

* Aromas (or odors) are the signals perceived by the olfactory organs, tastes are the signals perceived by the lingual organs, and flavors are the simultaneous perceptions of the other two.

0097-6156/83/0215-0303$06.00/0 © 1983 American Chemical Society

Waller and Feather; The Maillard Reaction in Foods and Nutrition ACS Symposium Series; American Chemical Society: Washington, DC, 1983.

304

MAILLARD REACTIONS

reaction. T h e e n o r m o u s v a r i e t y in flavor is due a l m o s t e n t i r e l y to the l a r g e n u m b e r o f p e r m u t a t i o n s f r o m the i n t e r a c t i o n s o f a r e l a t i v e l y f e w p r i m a r y r e a c t a n t s , and to the i m p o r t a n c e o f b a l a n c e b e t w e e n the c o m ponents f i n a l l y p r e s e n t . T h e r e p r o d u c i b i l i t y o b t a i n e d in these seemingly c h a o t i c , and c e r t a i n l y r a n d o m , s y s t e m s is as r e m a r k a b l e as the sensitive d i s c r i m i n a t i o n o f the m a m m a l i a n o l f a c t o r y - g u s t a t o r y s y s t e m .


D u r i n g the last f o r t y y e a r s a g r e a t d e a l has b e e n l e a r n e d , both by m o d e l s t u d i e s and by the a p p l i c a t i o n o f s o p h i s t i c a t e d a n a l y t i c a l methods to f o o d s , about the c h e m i s t r y w h i c h a c c o u n t s for these f l a v o r s . T o date, h o w e v e r , t h e r e is l i t t l e or no e v i d e n c e t h a t the i n - d e p t h c h e m i c a l inform a t i o n has had any i m p a c t on the p r o c e s s e s by w h i c h a u t h e n t i c , "natu r a l " foods a r e m a n u f a c t u r e d . H o w e v e r , d u r i n g these s a m e four d e c a d e s about a hundred p a t e n t s have b e e n g r a n t e d w o r l d w i d e for p r o c e s s e s and p r o d u c t s based on M a i l lard browning technology. S i n c e C h e m i c a l A b s t r a c t s has the p o l i c y o f a b s t r a c t i n g o n l y the first issued o f s e v e r a l e q u i v a l e n t p a t e n t s , and l i s t ing the l a t e r ones in a p a t e n t c o n c o r d a n c e , we h a v e c o u n t e d o n l y those p a t e n t s a b s t r a c t e d in C h e m i c a l A b s t r a c t s . We h a v e , h o w e v e r , used a v a r i e t y o f s e a r c h and r e t r i e v a l m e t h o d s and b e l i e v e t h a t our b i b l i o g r a phy o n M a i l l a r d p a t e n t s is s u b s t a n t i v e l y c o m p l e t e . G i v a u d a n (2) has s t a t e d t h a t o v e r the last t w e n t y y e a r s , about a t h o u s a n d p a t e n t s i n this f i e l d h a v e been g r a n t e d to v a r i o u s flavor c o m p a n i e s . E v e n a l l o w i n g for the i n c l u s i o n o f a l l e q u i v a l e n t p a t e n t s in this s u m , it is d i f f i c u l t to b e l i e v e t h a t this n u m b e r c o u l d be r e a c h e d . We have f o u n d 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 w h i c h s p e c i f y m i x i n g one or m o r e a m i n o a c i d s w i t h one or m o r e c a r b o n y l c o m p o u n d s and h e a t i n g , w i t h s o m e or a l l o f the o p e r a t i n g c o n d i t i o n s g i v e n : temperature, t i m e , water content, p H , innumerable additives. It was pointed out p r e v i o u s l y t h a t slight c h a n g e s in i n i t i a l c o m p o s i t i o n and r e a c t i o n c o n d i t i o n s p r o d u c e s i g n i f i c a n t c h a n g e s in the flavor and a r o m a o f the reaction products. But not one o f these p a t e n t s g i v e s a r i g i d , controlled specification. T h e wide r a n g e s o f o p e r a t i n g c o n d i t i o n s and the numerous a l t e r n a t i v e s o f f e r e d p r o d u c e s u c h a c o m p l e t e o v e r l a p b e t w e e n these p a t e n t s t h a t not e v e n a k n o w l e d g e a b l e c h e m i s t and a w i l y l a w y e r c o u l d d i s t i n g u i s h one f r o m the o t h e r . What v a l u e might these p a t e n t s h a v e ? P r o b a b l y v e r y l i t t l e , both f r o m the s t a n d p o i n t o f the h o l d e r s o f t h e p a t e n t s , and f r o m the s t a n d point o f those who might hope to l e a r n by s t u d y i n g t h e m . We have a l r e a d y e m p h a s i z e d the r e d u n d a n c y o f the " s t a n d a r d " p a t tents. N o t o n l y do t h e y a l l s a y s u b s t a n t i a l l y the s a m e t h i n g , but t h e y a p p e a r to c o n t a i n l i t t l e , if a n y t h i n g , t h a t was not f u l l y d i s c l o s e d in the m o d e l s t u d i e s w h i c h have been discussed e a r l i e r in this s y m p o s i u m . We b e l i e v e t h a t it is d o u b t f u l i f the v a l i d i t y o f a n y one o f t h e m c o u l d be upheld in c o u r t in view o f the p r i o r art p u b l i s h e d in journals. Further, we do not b e l i e v e t h a t a h o l d e r o f one o f these e x i s t i n g p a t e n t s c o u l d sue s u c c e s s f u l l y for i n f r i n g e m e n t , for t w o quite d i f f e r e n t r e a s o n s . First, in v i e w o f the e x t r e m e c o m p l e x i t y o f the c o m p o s i t i o n o f the r e a c t i o n p r o d u c t s , it would be i m p o s s i b l e to d e t e r m i n e , by e x a m i n i n g t h e m , how t h e y were m a d e . S e c o n d , in v i e w o f the r e d u n d a n c y o f the p a t e n t s t h e m s e l v e s , t h e r e would be no way to d e t e r m i n e whose p a t e n t was being infringed.


14.

DANEHY AND WOLNAK

Maillard

Technology: Applications

305

In o r d e r to get r e p r o d u c i b l e r e s u l t s , it is e s s e n t i a l to e x e r c i s e the most p r e c i s e c o n t r o l at e v e r y stage o f the r e a c t i o n p r o c e s s . T h e basis for this is not p r o v i d e d b y a n y o f the p a t e n t s , w h i c h c h a r a c t e r i s t i c a l l y g i v e broad r a n g e s . M a i l l a r d r e a c t i o n p r o d u c t s are b e i n g m a n u f a c t u r e d c o m m e r c i a l l y t o d a y by d e t a i l e d , p r o p r i e t a r y p r o c e s s e s w h i c h are not g i v e n by a n y patent. It is w o r t h w h i l e to r e v i e w what has been l e a r n e d about t w o s t u d i e d food s y s t e m s , for upon this s c i e n t i f i c base c e r t a i n u s e f u l , f i c i a l f l a v o r s and f o o d p r o d u c t s have been d e v e l o p e d .


C h o c o l a t e and

wellarti-

Cocoa

One o f the w o r l d ' s most p o p u l a r f l a v o r s is d e t e r m i n e d by a p h y s i c a l - c h e m i c a l c o m p o s i t i o n w h i c h s t a r t s w i t h the seeds o f the p l a n t , T h e o b r o m a c a c a o , and c o n t i n u e s w i t h an e m p i r i c a l p r o c e s s d i s c o v e r e d and p e r f e c t e d by t h e A z t e c s , or by an e a r l i e r s o c i e t y f r o m whom the A z t e c s r e c e i v e d it. T w o e n t i r e l y s e p a r a t e s t a g e s are e s s e n t i a l for the d e v e l o p m e n t o f this f l a v o r : T h e f e r m e n t a t i o n o f the beans (seeds) in t h e i r mucilaginous pulp e n c l o s u r e when the p o d is o p e n e d , and the r o a s t i n g o f the d r i e d , f e r m e n t e d beans. It has l o n g been known t h a t n e i t h e r a r o m a nor aroma p r e c u r s o r s are present in u n f e r m e n t e d c a c a o beans w h i c h , when r o a s t e d , d e v e l o p an odor r e m i n i s c e n t o f broad beans (3). S u b s t a n t i a l l y the only sugar present in u n f e r m e n t e d beans is s u c r o s e , but a m i x t u r e o f fructose and g l u c o s e a c c o u n t s for m o s t o f the sugar in f e r m e n t e d beans (4,5). A l s o , in g o i n g f r o m u n f e r m e n t e d to f e r m e n t e d beans, the c o n c e n t r a t i o n o f f r e e a m i n o a c i d s i n c r e a s e s b e t w e e n t h r e e - and f o u r - f o l d (6). T h a t s u m m a r y is based on the r e p o r t s o f a w e l l - c o n c e i v e d and c a r e f u l l y e x e c u t e d r e s e a r c h p r o g r a m c a r r i e d out by R o h a n . M o h r et a l . (7) e x t e n d e d these studies and was able to d r a w a d d i t i o n a l c o n c l u s i o n s . F i r s t , without e x c e p t i o n , f r e e a m i n o a c i d s are m u c h m o r e s e n s i t i v e to d e s t r u c t i o n in this s y s t e m t h a n the p e p t i d e - b o u n d a m i n o a c i d s . Second, d i f f e r e n c e s in the s t a b i l i t y o f a m i n o a c i d s under these c o n d i t i o n s are not g r e a t — f r o m 25% loss for i s o l e u c i n e to 68.5% f o r l y s i n e , o v e r a r e l a t i v e l y short p e r i o d o f t i m e . In this s y s t e m the r e d u c i n g sugars must be the l i m i t i n g f a c t o r , s i n c e the g l u c o s e and f r u c t o s e are c o m p l e t e l y d e s t r o y e d or r e m o v e d . T h i r d , n e i t h e r c y s t i n e nor c y s t e i n e are r e p o r t e d to be p r e s e n t , and the o n l y o t h e r s u l f u r - c o n t a i n i n g a m i n o a c i d , m e t h i o n i n e , is present at a m u c h l o w e r c o n c e n t r a t i o n t h a n any o t h e r a m i n o acid. C l e a r l y , as we s h a l l see l a t e r , c o c o a would p r o b a b l y have a c o n s i d e r a b l y d i f f e r e n t f l a v o r i f c y s t e i n e o r c y s t i n e were p r e s e n t in t h e f e r m e n t e d beans. R o h a n had suggested t h a t the o p e r a t i v e r e a c t i o n in the d e v e l o p m e n t o f c h o c o l a t e a r o m a m i g h t be a S t r e c k e r d e g r a d a t i o n o f the amino acid fraction. B a i l e y et a l . (8) d e m o n s t r a t e d q u a n t i t a t i v e l y t h a t t h r e e a l d e h y d e s , which c o u l d be r e l a t e d to l e u c i n e , v a l i n e , and a l a n i n e , w e r e p r o m i n e n t in the v o l a t i l e s f r o m a t y p i c a l s a m p l e o f r o a s t e d , ground c a c a o beans.



306

MAILLARD REACTIONS

O b v i o u s l y , h o w e v e r , while a s y n t h e t i c m i x t u r e c o r r e s p o n d i n g to the a b o v e would be f r a g r a n t , it would c e r t a i n l y not suggest the a r o m a o f c o c o a , based o n the work r e p o r t e d by m a n y o t h e r s . W h a t , t h e n is the c h e m i c a l basis for the a r o m a and f l a v o r w h i c h are c h a r a c t e r i s t i c o f c o c o a and c h o c o l a t e p r o d u c t s ? D u r i n g the p e r i o d o f 1964-1976 m o r e than a d o z e n r e p o r t s a d d r e s s e d t h e m s e l v e s to this p r o b l e m . They r a n g e d f r o m the h e r c u l e a n labors o f the F i r m e n i c h g r o u p , w h i c h c a r r i e d out a c l a s s i c a l f r a c t i o n a t i o n o f 750 k i l o g r a m s o f A r r i b a (Venezuelan) c o c o a , w h i c h c o n f i r m e d the p r e s e n c e o f 43 c o m p o u n d s p r e v i o u s l y r e p o r t e d by o t h e r s and i d e n t i f i e d 29 c o m p o u n d s not p r e v i o u s l y reported(9), to the p o w e r f u l l y i n s t r u m e n t e d i n v e s t i g a t i o n s w h i c h , to d a t e , have c l a i m ed the i d e n t i f i c a t i o n o f m o r e t h a n t h r e e hundred c o n s t i t u e n t s o f c o c o a volatiles. T h e c u m u l a t i v e r e s u l t o f a l l this e f f o r t is the r e a s o n a b l y sure e s t a b l i s h m e n t that at l e a s t 350 d i f f e r e n t kinds o f o r g a n i c molecules a r e p r e s e n t in c o c o a v o l a t i l e s in at least d e t e c t a b l e a m o u n t s and t h a t a g o o d l y , though i n d e t e r m i n a b l e , n u m b e r o f t h e m are f i n a l p r o d u c t s o f the Maillard reactions. F e w , i f a n y , o f these m o l e c u l e s would be o d o r l e s s . But how t h e y c o m b i n e , in i n t e n s i t y and s p e c i f i c i t y , to p r o d u c e the i n s t a n t l y r e c o g n i z a b l e a r o m a and f l a v o r o f c h o c o l a t e is s t i l l unknown. In v i e w o f the f a c t t h a t h o l d i n g l a r g e n u m b e r s o f o r g a n i c c o m pounds o f d i v e r s e f u n c t i o n a l i t y in a h o m o g e n e o u s s y s t e m at r o o m t e m p e r a t u r e , m u c h less at about 1 0 0 ° , is c o n d u c i v e to c h e m i c a l r e a c t i o n , we should c o n s i d e r at least two o t h e r reasons for the l a c k o f s u c c e s s in a t t e m p t s to r e c o n s t i t u t e the a r o m a o f c o c o a . F i r s t , s o m e o f the c o m p o u n d s w h i c h c o n t r i b u t e to the a r o m a o f c o c o a m a y have d e c o m p o s e d and are no l o n g e r p r e s e n t in the e x t r a c t a n a l y z e d . Second, some o f the c o m p o u n d s i d e n t i f i e d in the e x t r a c t m a y be a r t i f a c t s , not actually p r e s e n t in the c o c o a , but s y n t h e s i z e d d u r i n g the e x t r a c t i o n and w o r k i n g up p r o c e s s . The c o c o a and c h o c o l a t e c o n s u m e d by the A m e r i c a n m a r k e t are p r o d u c e d by a r e l a t i v e l y s m a l l n u m b e r o f A m e r i c a n and D u t c h m a n u f a c t u r e r s who s t a r t w i t h the d r i e d , f e r m e n t e d beans. Current manuf a c t u r i n g p r a c t i c e uses i m p r o v e d m a c h i n e design and e x t e n d e d automatic c o n t r o l in a c c o r d w i t h m o d e r n p r i n c i p l e s o f c h e m i c a l e n g i n e e r i n g , but it is based s o l i d l y on the t r a d i t i o n a l p r o c e s s , l i t t l e m o d i f i e d d u r i n g the last century. T h e r e is no e v i d e n c e that any o f the m a n u f a c t u r e r s o f c o c o a and c h o c o l a t e have a d a p t e d a n y p a r t o f the M a i l l a r d t e c h n o l o g y t o their manufacturing processes. T h e r e a r e at least two reasons for t h i s . First, the s t a n d a r d p r o c e s s e s , as a p p l i e d to beans o f good q u a l i t y , p r o d u c e excellent products. S e c o n d , while the work just r e v i e w e d has g i v e n us a r a t h e r c l e a r outline as to how c h o c o l a t e a r o m a is d e v e l o p e d in the r o a s t i n g o f f e r m e n t e d b e a n s , the r e s e a r c h work has not yet b e e n d o n e , or r e p o r t e d , t h a t would s e r v e as a basis for i m p r o v i n g the i n d u s t r i a l p r o c e s s i n g o f c a c a o beans. H o w e v e r , t h e r e are t w o r e l a t e d classes o f p r o d u c t s w h i c h do d e p e n d , m o r e or l e s s , on M a i l l a r d t e c h n o l o g y : c h o c o l a t e f l a v o r s , and c o c o a s u b s t i t u t e s (or e x t e n d e r s , as t h e y are m o r e r e a l i s t i c a l l y c a l l e d ) . F o r those foods and b e v e r a g e s w h i c h r e q u i r e a c h o c o l a t e f l a v o r , w i t h o u t the a d d e d bulk o f c o c o a or t h e fat o f c h o c o l a t e , the f l a v o r


14.

DANEHY AND WOLNAK

Maillard

Technology:

Applications

307


houses p r o v i d e s y n t h e t i c a p p r o x i m a t i o n s , e x t r a c t s o f c o c o a , or m i x t u r e s thereof. T h e f l a v o r i s t is an a r t i s t , s k i l l f u l in the b l e n d i n g o f e s s e n t i a l o i l s and pure o r g a n i c c o m p o u n d s . M o r e r e c e n t l y , d e l i b e r a t e use has been made o f the p r o d u c t s o f M a i l l a r d r e a c t i o n s b e t w e e n s e l e c t e d i n g r e d i e n t s , but o p e r a t i v e d e t a i l s are r e t a i n e d as highly c o n f i d e n t i a l i n formation. While s o m e a r t has been r e c o r d e d in p a t e n t s , these d a t a u s u a l l y list s p e c i f i c o r g a n i c c o m p o u n d s , and f r e q u e n t l y m e t h o d s for their synthesis. G e n e r a l l y , these p a t e n t s a r e o f v e r y d o u b t f u l v a l u e . C o c o a e x t e n d e r s or s u b s t i t u t e s , as p r o d u c t s w h i c h purport to be s e r i o u s c o n t e n d e r s for a f r a c t i o n o f the c o c o a m a r k e t , a r e a r e l a t i v e l y new p h e n o m e n o n . So l o n g as c o c o a was p l e n t i f u l , c h e a p , and of superior q u a l i t y a c o c o a s u b s t i t u t e m a d e no sense. But the s t e a d y i n c r e a s i n g o f p r i c e s and t i g h t e n i n g o f supplies o f c o c o a in v i e w o f r i s i n g w o r l d wide d e m a n d p r o v i d e d the i n c e n t i v e for s o m e c o m p a n i e s to u n d e r t a k e limited development of c o c o a substitutes. It was no c o i n c i d e n c e that t h e i r a p p e a r a n c e on the m a r k e t in e a r l y 1977 m a t c h e d the p e a k i n g p r i c e s o f b o t h c a c a o beans a n d c o c o a . T h e s e c o c o a s u b s t i t u t e s are o f t w o kinds. F i r s t , t h e y consist o f o t h e r w i s e u n p r o c e s s e d bulking agents w i t h added f l a v o r and c o l o r . The b u l k i n g agents e m p l o y e d are s o y b e a n f l o u r , m o d i f i e d f o o d s t a r c h e s , d e x t r i n s , or m i x t u r e s t h e r e o f . T h e y are d e f i n i t e l y o f f e r e d as e x t e n d e r s ; none o f the m a n u f a c t u r e r s r e c o m m e n d t h a t t h e y be used as a t o t a l r e p l a c e m e n t for c o c o a . M a n u f a c t u r e r s i n c l u d e C a r g i l l , Inc., M i n n e a p o l i s , M i n n e s o t a ( C o c o a - M a x ) , M c C o r m i c k & C o m p a n y , Inc., H u n t V a l l e y , M a r y l a n d , ( M c C o r m i c k C o c o a E x t e n d e r s ) , and N a t i o n a l S t a r c h & C h e m i c a l C o r p . , Bridge water, New J e r s e y ( N - L i v e n Cocoa). A . E . Staley Mfg. C o . , D e c a t u r , Illinois, e n t e r e d the f i e l d but q u i c k l y d r o p p e d o u t . T h e s e c o n d kind o f c o m m e r c i a l c o c o a s u b s t i t u t e c o n s i s t s o f roasted food p r o d u c t s . C l e a r l y , w h e t h e r intentionally or n e t , t h e y e m p l o y M a i l l a r d t e c h n o l o g y in the s a m e way in w h i c h it is e m p l o y e d in producing c o c o a and c o f f e e . T h e i n g r e d i e n t s d i s c l o s u r e s suggest t h a t no e f f o r t has b e e n m a d e to m o d i f y or to e n h a n c e the f l a v o r s by the a d d i t i o n o f amino a c i d s or o f s p e c i a l sugars ( x y l o s e , for e x a m p l e ) . A t l e a s t t h r e e o f these p r o d u c t s are w o r t h m e n t i o n i n g . T h e c a r o b , or l o c u s t b e a n , t r e e , C e r a t o n i a s i l i q u a L . , is indigenous to M e d i t e r r a n e a n shores. It p r o d u c e s f l a t pods, known as St. J o h n ' s b r e a d , eight to t w e l v e i n c h e s l o n g , f r o m w h i c h the seeds are r e m o v e d and processed to yield locust bean g u m . T h e d e s e e d e d pods a r e d r i e d , b r o k e n , and sold as " k i b b l e " , w h i c h c a n be r o a s t e d and ground to p r o vide a nutrient flavoring agent. T h e c o l o r range and a r o m a s a t t a i n a b l e by v a r y i n g the t i m e s and t e m p e r a t u r e o f r o a s t i n g , the p o w d e r y b u l k , c o m p l e t e c o m p a t i b i l i t y w i t h c o c o a , its G R A S s t a t u s , and its p r i c e ( ~ $ 0 . 6 0 / l b . ) g i v e it an i n i t i a l a d v a n t a g e as a c o c o a e x t e n d e r . But it c e r t a i n l y d o e s n ' t t a s t e l i k e cocoa, a l t h o u g h it is s w e e t and has a r a t h e r p l e a s a n t t a s t e . It has been a v a i l a b l e for a l o n g t i m e c o m m e r c i a l l y . Indeed, its h u m a n use p r o b a b l y a n t e d a t e s that o f c o c o a , and c e r t a i n l y does i n Europe. Its s t a t u s as a c o c o a e x t e n d e r arises s i m p l y f r o m t e m p o r a r y e c o n o m i c conditions.


308

MAILLARD REACTIONS

V C R (Viobin C o c o a R e p l a c e r ) is " . . . . p r e s s u r e - r o a s t e d d e f a t t e d wheat g e r m , ground to a fine powder w h i c h is s i m i l a r in c o l o r and t e x t u r e to p r o c e s s e d c o c o a s . . . T h e t o a s t i n g p r o c e s s d e v e l o p s a r o m a and t a s t e charact e r i s t i c s t h a t c o m p l e m e n t . . . c o c o a . . . " Such a r o m a as it has, and it would not be m i s t a k e n f o r c o c o a , c a n be a t t r i b u t e d to M a i l l a r d r e a c t i o n s t a k ing p l a c e d u r i n g t o a s t i n g . It is m a n u f a c t u r e d and sold by the V i o b i n C o r p o r a t i o n , M o n t i c e l l o , Illinois. F o r a l m o s t four y e a r s C o o r s F o o d P r o d u c t s C o m p a n y , G o l d e n , C o l o r a d o , has t r i e d to p e r f e c t a p r o d u c t ( C o c o m o s t ) c o n s i s t i n g o f 100% b r e w e r s y e a s t " , though p r o c e s s e d , o f c o u r s e . S a m p l e s were r e l e a s e d on a v e r y l i m i t e d basis f o r a short p e r i o d o f t i m e in m i d - 1 9 7 8 to f o o d m a n u f a c t u r e r s , and s o m e f a v o r a b l e , but p r e m a t u r e , p u b l i c i t y a p p e a r e d in n a t i o n a l m a g a z i n e s w h i c h c a t e r to the food i n d u s t r y . The process (prop r i e t a r y ) w h i c h p r o d u c e s the a l l e g e d c o c o a - l i k e f l a v o r is c o m p l e x and d i f f i c u l t to c o n t r o l . C o c o m o s t has not yet a p p e a r e d on the m a r k e t , nor are s a m p l e s a g a i n a v a i l a b l e . TT


1

T h e f a t e o f c o c o a s u b s t i t u t e s is e n t i r e l y d e p e n d e n t on two quite independent f a c t o r s : q u a l i t y , and the p r i c e o f c o c o a . It is at l e a s t c o n c e i v a b l e t h a t a s u b s t i t u t e c o u l d be d e v e l o p e d t h a t would be e q u a l to cocoa. If its p r i c e w e r e right we would have a r e a l c o c o a r e p l a c e r . But to d a t e the p r o d u c t s a r e , at b e s t , a c c e p t a b l e a d u l t e r a n t s , based on l i m i t e d d e v e l o p m e n t , and no r e a l r e s e a r c h work. N o r is the p r i c e s i t u a t i o n f a v o r a b l e to c o c o a s u b s t i t u t e s . S w i f t l y f a l l i n g p r i c e s and a c c u m u l a t i n g s t o c k s for c o c o a f r o m m i d - 1 9 7 7 to e a r l y 1980 are m o r e o f an o v e r r e a c t i o n than anyone p r e d i c t e d . B a s e d on the i n f o r m a t i o n p r e s e n t l y a v a i l a b l e , the o u t l o o k for c o c o a s u b s t i t u t e s is not f a v o r a b l e . Meat Flavors, Natural

and

Artificial

M e a t is the m u s c u l a r tissue o f the c o m m o n d o m e s t i c a n i m a l s , c o n s i d e r e d and used as food f o r h u m a n c o n s u m p t i o n . M e a t is at l e a s t a t h r e e - p h a s e s y s t e m c o n s i s t i n g o f (1) a h y d r o p h i l i c , but w a t e r - i n s o l u b l e , f i b r o u s p r o t e i n n e t w o r k , (2) a h y d r o p h o b i c fat deposit held t o g e t h e r by m e m b r a n e s , and (3) an aqueous s o l u t i o n c o n t a i n i n g m a n y s o l u b l e , low m o l e c u l a r weight c o m p o u n d s . R a w m e a t has v e r y l i t t l e a r o m a at r o o m t e m p e r a t u r e a l t h o u g h it is u s u a l l y possible to d i s t i n g u i s h b e e f , p o r k , l a m b , and c h i c k e n by sniffing. T h e t a s t e o f raw m e a t , w h i c h is not at a l l p a l a t a b l e to most h u m a n beings, c a n be d e s c r i b e d as s o m e w h a t s a l t y a n d m e t a l l i c . Raw meat must be c o o k e d in s o m e f a s h i o n in o r d e r to d e v e l o p a n y o r g a n o l e p t i c a l l y a c c e p t a b l e odor and f l a v o r . C l e a r l y , t h e n , the u n h e a t e d tissues must c o n t a i n p r e c u r s o r s w h i c h undergo t h e r m a l l y i n d u c e d c h e m i c a l r e a c t i o n ; these r e a c t i o n s p r o d u c e both v o l a t i l e c o m p o u n d s w i t h d e s i r a b l e a r o m a s and n o n v o l a t i l e c o m p o u n d s w h i c h i n f l u e n c e the t a s t e ; the c o m b i n a t i o n of these t w o c a t e g o r i e s d e t e r m i n e s the f l a v o r . A s we p r o c e e d , s t r i k i n g a n a l o g i e s b e t w e e n the d e v e l o p m e n t o f f l a v o r s in the c o o k i n g o f m e a t and in the f o o d s y s t e m we have a l r e a d y d i s c u s s e d ( c o c o a and c h o c o l a t e ) will become apparent. In a s e r i e s o f i n v e s t i g a t i o n s (10-19) it was d e f i n i t e l y e s t a b l i s h e d that the e x t r a c t i o n o f m i n c e d , l e a n m e a t (beef, p o r k , and lamb) w i t h


14.

DANEHY AND WOLNAK

Maillard

Technology:

Applications

309


c o l d w a t e r gave solutions w h i c h c o n t a i n e d s a l t , l a c t i c a c i d , glycoproteins, i n o s i n i c a c i d , t a u r i n e , g l u t a m i n e , a s p a r a g i n e , g l u c o s e , and s o m e a m i n o acids. A g i n g , p a r t i c u l a r l y in the c a s e o f b e e f , is i m p o r t a n t in the d e v e l o p m e n t o f the various f l a v o r p r e c u r s o r s ( Γ 7 ) . T h u s , g l y c o g e n u n d e r goes g l y c o l y s i s t o l a c t i c a c i d a l m o s t c o m p l e t e l y w i t h i n 24 hours a f t e r slaughter. P a r t i a l a u t o l y s i s o f the p r o t e i n s and n u c l e i c a c i d s g i v e s a n a s s o r t m e n t o f p e p t i d e s and a m i n o a c i d s f r o m the f o r m e r , and a mixture o f i n o s i n i c a c i d a n d its f r a g m e n t s (inosine, h y p o x a n t h i n e , r i b o s e - 5 - p h o s p h a t e , and ribose) f r o m the l a t t e r . When the f i l t e r e d , aqueous e x t r a c t o f ground b e e f is h e a t e d , a s e q u e n c e o f a r o m a s is d e v e l o p e d , beginning w i t h a f a i n t , b l o o d - l i k e a r o m a in the b a r e l y w a r m s o l u t i o n , passing through a phase in the b o i l i n g s o l u t i o n w h i c h g i v e s o f f the a r o m a o f b o i l e d b e e f , and t e r m i n a t i n g in the h o t , d r i e d , brown r e s i d u e ( 1 0 0 - 1 5 0 ° ) w i t h an a r o m a r e s e m b l i n g broil ed steak. When this o r i g i n a l , f i l t e r e d , aqueous e x t r a c t was s u b j e c t e d to d i a l y s i s against w a t e r in c e l l u l o s i c sausage c a s i n g s , and the l o w m o l e c u l a r - w e i g h t f r a c t i o n t h a t passed t h r o u g h the m e m b r a n e was l y o p h i l i z e d to a white powder and t h e n p y r o l y z e d , it underwent the typical M a i l l a r d b r o w n i n g to p r o d u c e a s t r o n g a r o m a o f b r o i l e d m e a t . This a r o m a was s u b s t a n t i a l l y the s a m e , whether the o r i g i n a l l e a n m e a t was b e e f or pork. T h i s m a y result f r o m t h e f a c t that the a m i n o a c i d c o n t e n t s o f b e e f , p o r k , and l a m b are s e m i q u a n t i t a t i v e l y r a t h e r s i m i l a r . It a p p e a r s , t h e n , that t h e r e is a g e n e r a l , m e a t y a r o m a , c o m m o n to c o o k e d b e e f , p o r k , and l a m b (and p r o b a b l y p o u l t r y ) , a t t r i b u t a b l e to the p y r o l y s i s o f the m i x t u r e o f low m o l e c u l a r weight n i t r o g e n o u s and c a r b o n y l c o m p o u n d s e x t r a c t e d f r o m the l e a n m e a t by c o l d w a t e r . But the a r o m a s o f r o a s t b e e f , r o a s t p o r k , roast l a m b , and r o a s t c h i c k e n are unmistakably different. T h e c h e m i c a l c o m p o s i t i o n o f the m u s c u l a r fat d e p o s i t s o f these a n i m a l s d i f f e r a p p r e c i a b l y , and it is to these l i p i d c o m p o n e n t s that we must l o o k to a c c o u n t for the s p e c i f i c f l a v o r differ ences. H e a t i n g the c a r e f u l l y s e p a r a t e d f a t alone d o e s not g i v e a meaty a r o m a at a l l , m u c h less an a n i m a l - s p e c i f i c one. It is the subsequent r e a c t i o n s o f p y r o l y s i s p r o d u c t s o f nonlipid c o m p o n e n t s t h a t g i v e the c h a r a c t e r i s t i c a r o m a s and f l a v o r s o f r o a s t e d m e a t s (20). S i n c e it is p r e c i s e l y at the s u r f a c e o f r o a s t i n g m e a t that w a t e r c o n c e n t r a t i o n s are l o w e s t and t e m p e r a t u r e s are h i g h e s t , it is at the m e a t s u r f a c e that the f l a v o r and c o l o r g e n e r a t i n g a c t i v i t y d u r i n g roast ing is m o s t p r o m i n e n t . T h i s s i t u a t i o n is analogous to the f o r m a t i o n o f c r u s t and a r o m a in bread and o t h e r baked c e r e a l p r o d u c t s . The same f a c t s also a c c o u n t f o r the s i g n i f i c a n t d i f f e r e n c e b e t w e e n r o a s t e d and boiled meats. P a r a l l e l i n g the studies o f the v o l a t i l e p r o d u c t s o f r o a s t e d c a c a o beans and o f b a k e d c e r e a l p r o d u c t s , and using the s a m e t e c h n i q u e s , a g r e a t d e a l o f e f f o r t has gone into the d e t e r m i n a t i o n o f the c o m p o u n d s present in the v o l a t i l e f r a c t i o n s o f c o o k e d m e a t . M o s t o f these have b e e n c o n c e r n e d o n l y w i t h b e e f , e i t h e r r o a s t e d or b o i l e d , but c h i c k e n has also r e c e i v e d a p p r e c i a b l e a t t e n t i o n (21). Several lists of compounds i s o l a t e d f r o m the v o l a t i l e s o f c o o k e d b e e f have been published (22-24), both c u m u l a t i v e and n e w l y i s o l a t e d o n e s . T h e t o t a l s for c h i c k e n (as o f 1972) and for b e e f (as o f 1977) are m o r e than two hundred e a c h . It



310

MAILLARD REACTIONS

must be e m p h a s i z e d again t h a t these are q u a l i t a t i v e i d e n t i f i c a t i o n s , not quantitative accountings. T h e s e c u m u l a t i v e tables f o r c o o k e d m e a t v o l a t i l e s are v e r y d i f f i c u l t to d i s t i n g u i s h f r o m those published s o m e w h a t e a r l i e r f o r c o c o a volatiles. Indeed, the l a r g e r c u m u l a t i v e t a b l e s r e s e m b l e s o m e w h a t a b r i d g e d v e r s i o n s o f the A l d r i c h and E a s t m a n K o d a k c a t a l o g s o f o r g a n i c chemicals. M e a n i n g f u l c o m p a r i s o n s are h i n d e r e d by t w o q u i t e d i f f e r e n t facts. F i r s t , there is u s u a l l y no hint as to the f r a c t i o n o f the m e a t , or e v e n the f r a c t i o n o f the v o l a t i l e s , that is c o m p r i s e d by a g i v e n c o m pound. S e c o n d , we are p r o b a b l y g e t t i n g a g r e a t d e a l o f noise w i t h the signals: that i s , t h e r e must be m a n y c o m p o u n d s w h i c h , e v e n though t h e y have o d o r s , would not be m i s s e d , i f t h e y w e r e absent. We s i m p l y c a n n o t b e l i e v e that m o r e than 200 c o m p o u n d s a r e r e q u i r e d to p r o d u c e any one o f the d i s t i n c t i v e r o a s t e d food a r o m a s . But the h u m a n nose has no d i f f i c u l t y in d i s t i n g u i s h i n g c h o c o l a t e f r o m r o a s t b e e f , and the f l a v o r c h e m i s t is t r y i n g to c a t c h up w i t h this degree of discrimination. C h a n g and P e t e r s o n have s u g g e s t e d t h a t l a c t o n e s , a c y c l i c s u l f u r c o m p o u n d s , n o n a r o m a t i c h e t e r o c y c l i c c o m p o u n d s c o n t a i n i n g r i n g S, N , or Ο a t o m s , and a r o m a t i c h e t e r o c y c l i c c o m p o u n d s c o n t a i n i n g r i n g S, Ν o r Ο a t o m s m a y be i m p o r t a n t c o n t r i b u t o r s to m e a t f l a v o r , e v e n though none o f t h e m , a l o n e , s m e l l a n y t h i n g l i k e c o o k e d m e a t . Wilson and K a t z i d e n t i f i e d 46 s u l f u r - c o n t a i n i n g c o m p o u n d s f r o m the v o l a t i l e s o f l e a n beef p r e s s u r e - c o o k e d w i t h w a t e r at 1 6 3 ° and 1 8 2 ° . M o s t o f these compounds were t h i o p h e n e or t h i a z o l e d e r i v a t i v e s , but a c y c l i c t h i o l s , m e t h y l sulfide, and four d i s u l f i d e s w e r e also p r e s e n t . A l s o , as we s h a l l see l a t e r , s u l fur c o m p o u n d s ( e s p e c i a l l y c y s t e i n e ) p l a y a k e y r o l e in m a n u f a c t u r i n g a r t i f i c i a l meat flavors. T o n s b e e k et a l . (25,26) have i s o l a t e d 4 - h y d r o x y 5 - m e t h y l - 2 , 3 - d i h y d r o f u r a n - 3 - o n e and 4 - h y d r o x y - 2 , 5 - d i m e t h y l - 2 , 3 - d i h y d r o f u r a n - 3 - o n e , p a r t i c u l a r l y pungent c o m p o u n d s , f r o m c o o k e d beef. Pyra z i n e s a r e a p a r t i c u l a r l y i m p o r t a n t class o f f l a v o r c o m p o u n d s , but it was not u n t i l 1971 t h a t t h e i r p r e s e n c e in b e e f v o l a t i l e s was r e p o r t e d (27), and by 1973 a t o t a l o f 33 o f t h e m had been i d e n t i f i e d (28). Recently, F l a m e n t et a l . (28) i d e n t i f i e d s e v e r a l p y r r o l o [ l , 2 - a ] p y r a z i n e s . D e s p i t e the l a r g e a m o u n t o f q u a l i t a t i v e , if not q u a n t i t a t i v e , d a t a on the c h e m i c a l c o m p o s i t i o n o f the v o l a t i l e s f r o m c o o k e d m e a t , no one has yet c l a i m e d a n y t h i n g l i k e a d u p l i c a t i o n o f a m e a t a r o m a by the c o m b i n a t i o n o f the pure c h e m i c a l s i d e n t i f i e d in m e a t a r o m a s . Once m o r e , the p a r a l l e l w i t h c o c o a and baked p r o d u c t s is s t r i k i n g . J u s t one e x a m p l e points up the e l u s i v e r e l a t i o n s h i p b e t w e e n c h e m i c a l c o m p o u n d s and food f l a v o r s . H y d r o g e n s u l f i d e has the odor w h i c h does c h a r a c t e r i z e r o t t e n e g g s , yet it a p p e a r s to be a n e c e s s a r y c o m p o n e n t o f m e a t aromas. Its odor t h r e s h o l d is 10 parts per b i l l i o n (ppb), but its c o n c e n t r a t i o n in f r e s h l y c o o k e d c h i c k e n is 20 to 100 t i m e s g r e a t e r . It is g e n e r a l l y a g r e e d t h a t the a r o m a o f a food is the sensed p e r c e p t i o n o f an e x t r e m e l y c o m p l e x i n t e r a c t i o n o f m a n y c o m p o n e n t s , but one r e a d s b e t w e e n t h e lines the d i s a p p o i n t m e n t o f s o m e who r e p o r t new c o m p o u n d s and note that t h e y do not have a m e a t l i k e a r o m a . C h a n g and Peterson (24) suggest the j u s t i f i a b l e f e a r that s o m e c o m p o n e n t s m a y have been d e c o m p o s e d or m i s s e d , but t h e i r hope that a unique c o m p o n e n t m a y still



14.

DANEHY AND WOLNAK

Maillard

Technology:

Applications

311

be found w h i c h alone or in c o m b i n a t i o n w i l l have a c h a r a c t e r i s t i c b e e f a r o m a , is less j u s t i f i a b l e . The k e y i n v o l v e m e n t o f o r g a n i c s u l f u r c o m p o u n d s in the d e v e l o p ment o f m e a t l i k e f l a v o r s was a n n o u n c e d s i m u l t a n e o u s l y in 1960 by s e v eral investigators. In what was the e a r l i e s t paper to d e s c r i b e deliberate a t t e m p t s to p r o d u c e a r o m a s u s e f u l in foods v i a M a i l l a r d r e a c t i o n s , K i e l y et a l . (30) n o t e d that both c y s t e i n e and c y s t i n e g a v e m e a t y odors when h e a t e d with r e d u c i n g sugars. M a y et a l . r e c e i v e d s e v e r a l e q u i v a l e n t p a t e n t s (31-35) in w h i c h t h e y c l a i m e d t h a t h e a t i n g c y s t e i n e or c y s t i n e w i t h f u r a n , or s u b s t i t u t e d f u r a n s , p e n t o s e s , or g l y c e r a l d e h y d e g a v e a meatlike flavor. It is p r e c i s e l y to 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 that the g r e a t m a j o r i t y o f p a t e n t s based on the M a i l l a r d r e a c t i o n h a v e been d i r e c t e d . Mos o f t h e m i n d i c a t e c y s t e i n e o r c y s t i n e as the e s s e n t i a l s u l f u r - c o n t a i n ing c o m p o u n d . O t h e r p a t e n t s c l a i m a l t e r n a t i v e s o u r c e s for s u l f u r , e . g . , d e r i v a t i v e s of m e r c a p t o a c e t a l d e h y d e (36), m e r c a p t o a l k y l a m i n e s (37), S a c e t y l m e r c a p t o s u c c i n i c a c i d (38), 2 - t h i e n v l t e t r a s u l f i d e (39), "a s u l f i d e " (40), and h y d r o g e n s u l f i d e (heated w i t h aqueous x y l o s e without any amino acid) (41). T w o p a t e n t s (42-43) c l a i m the c o n t r i b u t i o n to m e a t l i k e f l a v o r s made by t h i a m i n e when it is present in the s t a n d a r d p y r o l y t i c m i x t u r e . A r n o l d et a l . (44) have r e p o r t e d on the v o l a t i l e f l a v o r c o m p o u n d s p r o d u c e d by the t h e r m a l d e g r a d a t i o n o f t h i a m i n e a l o n e . It is g e n e r a l l y a g r e e d t h a t the p r e s e n c e o f m e t h i o n i n e , the o t h e r s u l f u r - c o n t a i n i n g a m i no a c i d in the f l a v o r - d e v e l o p i n g m i x t u r e , p r o d u c e s n e g a t i v e a n d / o r u n desirable results. H o w e v e r , one patent (45) s p e c i f i e s m e t h i o n i n e in a s t a n d a r d M a i l l a r d p r o c e d u r e , and no c y s t e i n e . S h i b a m o t o a n d R u s s e l l (46) h e a t e d an aqueous g l u c o s e - a m m o n i a h y d r o g e n s u l f i d e s o l u t i o n at 1 0 0 ° for t w o hours. O f the 34 major c o m ponents i d e n t i f i e d , 2 - m e t h y l t h i o p h e n e a c c o u n t e d f o r 24.9% o f the a r e a o f the c h r o m a t o g r a p h i c p e a k s e t h y l s u l f i d e , t h i o p h e n e , f u r f u r a l , a n d 2a c e t y l f u r a n e a c h a c c o u n t e d for 1 0 - 1 1 % , a n d m e t h y l s u l f i d e and 2 , 5 - d i m e t h y l t h i o p h e n e , 7% e a c h . T h e r e a c t i o n m i x t u r e as a whole was deemed by s e n s o r y p a n e l e v a l u a t i o n to have a c o o k e d b e e f o d o r . O n c e m o r e , a l t h o u g h the d i s t r i b u t i o n s are e x p r e s s e d q u a n t i t a t i v e l y , t h e r e is no i n f o r m a t i o n on t h e y i e l d s o f these i n t e r e s t i n g c o m p o u n d s m a d e f r o m g l u c o s e , a m m o n i a , and h y d r o g e n s u l f i d e . Earlier, however, in t h e i r studies o f c a r b o h y d r a t e s - a m m o n i a s y s t e m s (47-49), S h i b a m o t o and R u s s e l l found that the a m o u n t s o f t o t a l p y r a z i n e s p r o d u c e d , based on the s u g a r s , w e r e in the r a n g e o f 1-2%. Wilson's r e v i e w o f t h e r m a l l y p r o d u c e d i m i t a t i o n m e a t f l a v o r s is w e l l w o r t h c o n s u l t i n g (50). T o what e x t e n t has M a i l l a r d t e c h n o l o g y been e x p l o i t e d in the p r o duction of artificial meat flavors? It is d i f f i c u l t to o b t a i n a quantitative answer to that q u e s t i o n s i n c e e i t h e r the f l a v o r s are p r o d u c e d as p r o p r i e t a r y p r o d u c t s and sold to f o o d m a n u f a c t u r e r s , w i t h no way o f a c c o u n t ing f o r the s i z e o f the m a r k e t without a c c e s s to p r i v a t e r e c o r d s , o r else the f l a v o r s are p r o d u c e d in-house by the food m a n u f a c t u r e r s and put in t h e i r s h e l f i t e m s , w i t h e v e n less o f a n o p p o r t u n i t y to d e t e r m i n e the a m o u n t s p r o d u c e d .


MAILLARD REACTIONS

312

G i v a u d a n , in the J a n u a r y , 1979, issue o f t h e i r house o r g a n (2), gives an a p p r e c i a t i v e n o n t e c h n i c a l i n t r o d u c t i o n to the s u b j e c t w h i c h c o n c l u d e s w i t h this passage:


" M u c h o f our work in t h i s f i e l d has b e e n d e v o t e d t o the s e a r c h for m o r e s u i t a b l e n a t u r a l i n t e r m e d i a t e s as s t a r t i n g m a t e r i a l s . T h e s e had to be p r e t r e a t e d p r i o r to t h e i r use in b r o w n i n g r e actions. T h e l a t e s t d e v e l o p m e n t in this f i e l d is the utilization o f f u l l y n a t u r a l s t a r t i n g m a t e r i a l s w h i c h p e r m i t to r e p r o d u c e t r a d i t i o n a l l y known food f l a v o r s o f g r e a t e s t p e r f e c t i o n . " . . . n o n e n z y m a t i c b r o w n i n g w i l l c o n t i n u e to be an i m p o r t a n t p r o c e s s for the m a n u f a c t u r e o f f l a v o r s . . . E s p e c i a l l y the c o m b i n a t i o n o f e n z y m a t i c and n o n e n z y m a t i c r e a c t i o n s w i l l p l a y an i m p o r t a n t r o l e in r e p r o d u c i n g the e x q u i s i t e f l a v o r s o f r o a s t e d foods". A t l e a s t s i n c e 1969, P f i z e r C h e m i c a l s D i v i s i o n has b e e n m a n u f a c t u r i n g and m a r k e t i n g i m i t a t i o n b e e f and c h i c k e n f l a v o r s under the trademarked name, C O R R A L . T h e i r b r o c h u r e ( d a t a s h e e t N o . 638) l e a v e s no doubt as to what the C O R R A L p r o d u c t s a r e . T h e i n g r e d i e n t s used to m a k e C O R R A L B e e f paste a r e : hydrolyzed vegetable protein, monosodium glutamate, sucrose, vegetable fat, L-arabinose, disodium inosinate, c y s t e i n e h y d r o c h l o r i d e , ^ - a l a n i n e , and g l y c i n e h y d r o c h l o r i d e . It is unders t o o d t h a t t h e s e i n g r e d i e n t s h a v e been h e a t e d in aqueous s o l u t i o n , and t h e n the m i x t u r e l a r g e l y d e h y d r a t e d . T h e i n g r e d i e n t s in C O R R A L chicken p a s t e a r e : Hydrolyzed vegetable protein, monosodium glutamate, sucrose, vegetable fat, cysteine hydrochloride, dextrose, L-arabinose, g l y c i n e h y d r o c h l o r i d e , d i s o d i u m i n o s i n a t e , and d i s o d i u m g u a n y l a t e . It w i l l be n o t e d t h a t the s o m e w h a t d i f f e r e n t s e q u e n c e s in the two f o r m u l a t i o n s , as w e l l as t w o a d d i t i o n a l i n g r e d i e n t s in the s e c o n d , a c c o u n t , at l e a s t in p a r t , for the d i f f e r e n t f l a v o r s . C o n d i t i o n s o f t i m e , temperature, and w a t e r c o n t e n t o f the r e a c t i o n m i x t u r e must also i n f l u e n c e the final results. Representative of F I D C O s aggressively advertised S P E C T R A i m i t a t i o n m e a t f l a v o r s is F I D C O S P E C T R A B N - 1 0 ( N e s t l e ' C o . ) , whose s p e c i f i c a t i o n s show that it c o n t a i n s 34% s o d i u m c h l o r i d e and 54% o r ganic solids, including 33% protein. R e a l i s t i c a l l y , t h a t " p r o t e i n " is a l most c e r t a i n l y 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 (HVP). T h i s p r o d u c t also c o n t a i n s " n a t u r a l and a r t i f i c i a l f l a v o r s , m o n o s o d i u m g l u t a m a t e , b e e f f a t , s o d i u m i n o s i n a t e , s o d i u m g u a n y l a t e , and c a r a m e l c o l o r " . It is r e c o m m e n d e d t h a t it m a k e up 20% by weight o f a d e h y d r a t e d b e e f soup base. In a l l l i k e l i h o o d M a i l l a r d r e a c t i o n p r o d u c t s a r e i n c l u d e d under " a r t i f i c i a l f l a v o r s " , and m a y also be present as part o f the p r o c e s s i n g o f the H V P w i t h r e d u c i n g sugars. C o n s i d e r i n g the s i z e and m a r k e t i n g r e s o u r c e s o f the c o m p a n y , S P E C T R A f l a v o r s p r o b a b l y m a k e up an i m p o r t a n t p a r t o f this m a r k e t . M A G G P s d e h y d r a t e d soup m i x e s , m o r e i m p o r t a n t in Europe than in the U n i t e d S t a t e s , are c l o s e l y r e l a t e d p r o d u c t s o f a n o t h e r d i v i sion o f Nestled r


14.

DANEHY AND WOLNAK

Maillard

Technology:

Applications

313

K n o x Ingredients T e c h n o l o g y ( K I T ) , s u c c e s s o r t o K n o x G e l a t i n e , a w h o l l y owned s u b s i d i a r y o f T h o m a s J . L i p t o n , I n c . , is a major p r o d u c e r o f H V P ' s , and o f a line o f " T a s t e m a k e r N a t u r a l a n d A r t i f i c i a l Flavorings" based on t h e m . R e c e n t press r e l e a s e s b y K I T a r e q u i t e e x p l i c i t about the r o l e o f M a i l l a r d r e a c t i o n p r o d u c t s in t h e m o r e s o p h i s t i c a t e d versions o f these f l a v o r i n g a g e n t s .


T h e E d l o n g C o r p o r a t i o n , E l k G r o v e V i l l a g e , I l l i n o i s , is d e f i n i t e l y a c t i v e i n this f i e l d . T h e y are particularly interested in the production o f p r e c u r s o r s b y f e r m e n t a t i o n w h i c h m a y undergo M a i l l a r d r e a c t i o n s in the c u s t o m e r ' s p r o d u c t d u r i n g c o o k i n g . T h e y have just brought out a " N a t u r a l B u t t e r F l a v o r # 1 - 4 0 0 6 " f o r use i n G r a n o l a - t y p e i t e m s . In addition to t h e f l a v o r w h i c h it d e v e l o p s , it p r o d u c e s a p l e a s i n g yellow-brown r a t h e r t h a n t h e g r a y - b r o w n c o l o r o f t e n c h a r a c t e r i s t i c o f G r a n o l a products. W m . M . B e l l C o . , M e l r o s e P a r k , Illinois, is o n e o f the c o m p a n i e s a c t i v e in this t e c h n o l o g y . They incorporate Maillard reaction products into a v a r i e t y o f f l a v o r s , i n c l u d i n g c h o c o l a t e . B o r d e n Industrial F o o d P r o d u c t s , N o r t h b r o o k , Illinois, m a n u f a c t u r e W y l e r Soups and Wyler B r a n d C B - M f l a v o r c o n c e n t r a t e s . O n e o f the l a t t e r , for e x a m p l e , #78-62 B e e f F l a v o r , c o n t a i n s : hydrolyzed vegetable protein, dextrose, sucrose, vegetable o i l , salt, monosodium g l u t a m a t e , d i s o d i u m i n o s i n a t e , d i s o d i u m g u a n y l a t e , o n i o n p o w d e r , and g a r l i c p o w d e r . T h e y a r e s i m i l a r t o , but not i d e n t i c a l w i t h , P f i z e r ' s C O R R A L , w h i c h also c o n t a i n s a r a b i n o s e , c y s t e i n e , - a l a n i n e , and g l y c i n e . Wyler B r a n d #78-50 C h i c k e n F l a v o r also c o n t a i n s s o m e c h i c k e n . C h e m i c a l M a r k e t i n g R e p o r t e r f o r J u n e 25, 1 9 7 9 , c a r r i e d a n a d v e r t i s e m e n t o f H y d r o c a l , S . A . , G e n e v a , S w i t z e r l a n d , w h i c h a n n o u n c e d the a v a i l a b i l i t y o f "unique new M a i l l a r d f l a v o r s " , m a n u f a c t u r e d by F r u t a r o m , L t d . , H a i f a , Israel. T h e o w n e r o f this o p e r a t i o n is R o b e r t A r i e s , the A m e r i c a n c h e m i c a l e n g i n e e r who b e c a m e e x p a t r i a t e in about 1955, a n d who r e t u r n e d t o t h e U n i t e d S t a t e s in 1979. A l e x F r i e s & B r o . , Inc. C i n c i n n a t i , O h i o , m a k e m e a t , c h e e s e , a n d c h o c o l a t e f l a v o r s based o n M a i l l a r d t e c h n o l o g y . T h e y have no i n f o r m a t i o n t o r e l e a s e on these p r o d u c t s other t h a n that i n t h e i r g e n e r a l b r o chure. F r i t z s c h e - D o d g e & O l c o t t , Inc., N e w Y o r k C i t y , i n c o r p o r a t e s M a i l l a r d r e a c t i o n r o d u c t s on a r a t h e r b r o a d s c a l e into t h e i r m e a t , chocolate, bread, and malt flavors. While t h e a d v e r t i s e m e n t s o f H a a r m a n n & R e i m e r , S p r i n g f i e l d , N e w J e r s e y , e m p h a s i z e the n a t u r a l a p p r o a c h , a s p o k e m a n a g r e e d t h a t t h e y use M a i l l a r d t e c h n o l o g y , e s p e c i a l l y in t h e p r o d u c t i o n o f m e a t f l a v o r s .


314

MAILLARD REACTIONS

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.

Danehy, J.P.; Pigman, W.W. Adv. Food Res. 1951, 3, 241-290. Anonymous. The Givaudan Flavourist, International Edition. January, 1979, 3, one page. Rohan, T.A. J. Sci. Food Agric. 1963, 14, 799-805. Rohan, T.A. J. Food Sci. 1964, 29, 456-459. Reineccius, G.Α.; Andersen, D.A.; Kavanaugh, T.D.; Keeney, P.G. J. Agric. Food Chem. 1972, 20, 199-202. Rohan, T.A.; Stewart, T. J. Food Sci. 1965, 30, 416-419. Mohr, W.; Roehrle, M.; Severin, Th. Fette, Seifen, Anstrichm. 1971, 515-521. Bailey, S.D.; Mitchell, D.G.: Bazinet, M.L.; Weurman, C. J. Food Sci. 1962, 27, 165-70. Dietrich, P.; Lederer, E.; Winter, M.; Stoll, M. Helv. Chim. Acta 1964, 47, 1581-90. Hornstein, I.; Crowe, P.F. J. Agric. Food Chem. 1960, 8, 494-498. Wood, T. J. Sci. Food Agric. 1961, 12, 61-9. Macy, Jr., R.L.; Naumann, H.D.; Bailey, M.E. J. Food Sci. 1964, 29, 136-41. Macy, Jr., R.L.; Naumann, H.D.; Bailey, M.E. J. Food Sci. 1964, 29, 142-148. Wasserman, A.E.; Gray, N. J. Food Sci. 1965, 30, 801-807. Landmann, W.A.; Batzer, O.F. J. Agric. Food Chem. 1966, 14, 210-214. Zaika, L.L.; Wasserman, A.E.; Monk, Jr., C.A.; Salay, J. J. Food Sci. 1968, 33, 53-58. Wasserman, A.E. J. Agric. Food Chem. 1972, 20, 737-741. Wasserman, A.E.; Spinelli, A.M. J. Food Sci. 1970, 35, 328-332. Jarboe, J.K.; Malbrouk, A.F. J. Agric. Food Chem. 1974, 22, 787791. Wasserman, A.E.; Spinelli, A.M. J. Agric. Food Chem. 1972, 20, 171-174. Wilson, R.A.; Katz, I. J. Agric. Food Chem. 1972, 20, 741-747. Herz, K.O.; Chang, S.S. Adv. Food Res. 1970, 18, 1-83. MacLeod, G.; Coppock, B.M. J. Agric. Food Chem. 1976, 24, 835843. Chang, S.S.; Peterson, R.J. J. Food Sci. 1977, 42, 298-305. Tonsbeek, C.H.T.; Plancken, A.J.; Weerdof, T. J. Agric. Food Chem. 1968, 16, 1016-1021. Tonsbeek, C.H.T.; Koenders, E.B.; van der Zijden, A.S.M.; Losekoot, J.A. J. Agric. Food Chem. 1969, 17, 397-400. Flament, I.; Ohloff, G. Helv. Chim. Acta 1971, 54, 1911-1913. Mussinan, C.J.; Wilson, R.A.; Katz, I. J. Agric. Food Chem. 1973, 21, 871-872. Flament, I.; Sonnay P.; Ohloff, G. Helv. Chim. Acta 1977, 60, 1872-1873. Kiely, P.J.; Nowlin, A.C.; Moriarty, J.H. Cereal Sci. Today 1960, 5, 273-274.


14.

31. 32. 33. 34. 35. 36.


37. 38. 39. 40. 41. 42. 43. 44. 45. 46. 47. 48. 49. 50.

DANEHY AND WOLNAK

Maillard Technology: Applications

315

May, C.G. (Lever Bros. Company) U.S. Pat. 2,934,435 (April 26, 1960). May, C.G.; Morton, I.D. (Lever Bros. Company) U.S. Pat. 2,934, 436 (April 26, 1960). Morton, I.D.; Akroyd, P.; May, C.G. (Lever Bros. Company) U.S. Pat. 2,934,437 (April 26, 1960). May, C.G.; Akroyd, P. (Unilever N.V.) German Pat. 1,058,824 (June 4, 1959. May, C.G.; Akroyd, P. (Lever Bros. Company) U.S. Pat. 2,918,376 (1959). Broderick, J.J.; Linteris, L.L. (Lever Bros. Company) U.S. Pat. 2, 955,041 (October 4, 1960). Ohwa, T. (Lever Bros. Company) Japanese Pat. 72 50387 (December 18, 1972). Mosher, A . J . (Maggi, AG) French Pat. 2,178,924 (December 21, 1973). Katz, I.; Evers, W.J.; Giacino, C. (International Flavors & Fragrances) (December 19, 1972). U.S. Pat. 3,706,577. Heyland, S.; Cerise, L. (Nestle, S. A.) German Pat. 2,837,513 (April 5, 1979). Gunther, R. (Fritzsche, Dodge & Olcott, Inc.) U.S. Pat. 3,642,497 (February 15, 1972). International Flavors & Fragrances. Neth. Appl. 6,603,722 (September 23, 1966). International Flavors & Fragrances. Neth. Appl. 6,609,520 (January 9, 1967). Arnold, R.G.; Libbey, L.M.; Lindsay, R.C. J. Agric. Food Chem. 1969, 17, 390-392. van Pottelsberghe de la Potterie, P.J. (Maggi, AG) German Pat. 2,149,682 (April 13, 1972). Shibamoto, T.; Russell, G.F. J. Agric. Food Chem. 1976, 24, 843-846. Shibamoto, T.; Bernhard, R.A. J. Agric. Food Chem. 1976, 24, 847-852. Shibamoto, T.; Bernhard, R.A. Agric. Biol. Chem. 1977, 41, 143153. Shibamoto, T.; Bernhard, R.A. J . Agric. Food Chem. 1977, 25, 609-614. Wilson, R.A. J. Agric. Food Chem. 1975, 23, 1032-1037.

RECEIVED November 2, 1982


Maillard Technology: Manufacturing Applications in Food Products

Recommend Documents