Seventy Years of the Maillard Reaction - American Chemical Society

this reaction. In a later report Maillard (4) cited a paper (5) by Arthur ... contained C 58.85, H 4.92, Ν 4.35, and 0 31.88%; thus the empirical ...
0 downloads 0 Views 1MB Size
1

S e v e n t y Y e a r s of t h e

Maillard

Reaction

Downloaded by 171.113.221.145 on October 13, 2015 | http://pubs.acs.org Publication Date: April 29, 1983 | doi: 10.1021/bk-1983-0215.ch001

SIN'ITIRO KAWAMURA Kagawa-ken Meizen Junior College, Kameoka 1-10, Takamatu, 760 Japan

A historical review with107 references. Life and work of Louis-Camille Maillard (Feb. 4, 1878 May 12, 1936) are described. The first use of the index term Maillard reaction in Chemical Abstracts was in 1950. German scientists with early interest in this reaction were Lintner (1912) and Ruckdeschel (1914). Several aspects of this reaction are reviewed with emphasis on the work of Japanese scientists. About the Year 1912 Ten years ago Kawamura (_1) published a brief historical review on this reaction in memory of the sixtieth anniversay of its first report by Louis-Camille Maillard (2). The first Maillard paper was presented on January 8, 1912, by Armand Emile Justin Gautier (1837-1920) in a session of the Academy of Sciences in Paris. Six weeks earlier (November 27, 1911) a remarkable study was reported by Maillard Ο ) on the condensation of amino acids by use of glycerol. The method of peptide synthesis by Emil Hermann Fischer (1835-1919) was known to him. However, Maillard searched for milder conditions. Thus he wished to condense amino acids by use of glycerol as a condensing agent. He thus obtained cycloglycylglycine and pentaglycylglycine. Maillard (2^) then used sugars instead of glycerol to investigate the formation of polypeptides by the reaction of amino acids with alcohols. It was found that the aldehyde group (of an aldose) had more intense effect on amino acids than did the hydroxyl groups. This led to the discovery of this reaction. In a later report Maillard (4) cited a paper (5) by Arthur Robert Ling (1861-1937). Ling, lecturer on brewing and malting at the Sir John Cass Institute, presented a paper on 0097-6156/83/0215-0003$06.00/0 © 1983 American Chemical Society In The Maillard Reaction in Foods and Nutrition; Waller, G., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 1983.

4

MAILLARD REACTIONS

m a l t i n g at the meeting h e l d at the C r i t e r i o n R e s t a u r a n t , P i c c a d i l l y , L o n d o n , on May 11, 1908. He n o t e d a r e m a r k a b l e e f f e c t of k i l n i n g or heat d r y i n g . "At t h e s e c o n d s t a g e o f k i l n i n g when t h e range o f t e m p e r a t u r e i s f r o m 120 t o 150°C, t h i s m e l l o w i n g by a u t o d i g e s t i o n i s continued Flavouring and c o l o u r i n g m a t t e r s a r e produced....When t h e s e amino-compounds p r o d u c e d f r o m p r o t e i n s a r e h e a t e d a t 120-140 C w i t h s u g a r s s u c h as o r d i n a r y g l u c o s e o r m a l t o s e , w h i c h a r e produced at t h i s stage of p r o c e s s , c o m b i n a t i o n o c c u r s . The p r e c i s e n a t u r e o f t h e compounds p r o d u c e d i s unknown t o me, but t h e y a r e p r o b a b l y g l u c o s a m i n e - l i k e b o d i e s . " He f u r t h e r d e s c r i b e d the r e a c t i o n of h e a t i n g g l u c o s e w i t h a s p a r a g i n e , which produced darkening i n c o l o r . C a r l Joseph Ludwig L i n t n e r (1855-1926), l e a d e r of the S c i e n t i f i c S t a t i o n f o r Brewing ( W i s s e n s c h a f t l i c h e S t a t i o n fuer B r a u e r e i ) i n M u n i c h was s t u d y i n g t h e f o r m a t i o n o f m a l t aroma. He gave a l e c t u r e ( 6 ) a t t h e 3 6 t h M e e t i n g o f t h e S t a t i o n i n November, 1912. As soon as he knew o f t h e r e p o r t o f M a i l l a r d (2^), he made some e x p e r i m e n t s by t h e p r o c e s s o f M a i l l a r d ( n a c h dem Vorgange v o n M a i l l a r d ) . He o b t a i n e d d a r k r e a c t i o n p r o d u c t s w h i c h were r e s p o n s i b l e a l s o f o r f l a v o r and aroma ( c f . 7). Ame P i c t e t (1857-1937) o f t h e U n i v e r s i t y o f Geneva r e p o r t e d t h e f o r m a t i o n o f p y r i d i n e and i s o q u i n o l i n e b a s e s f r o m a c i d h y d r o l y z a t e of c a s e i n i n the presence of formaldehyde i n 1916 ( 8 ) . M a i l l a r d ( 9 ) c l a i m e d p r i o r i t y o v e r him i n d i s c o v e r i n g t h e c o n d e n s a t i o n o f amino a c i d s w i t h a l d e h y d e s o r s u g a r s t o y i e l d p y r i d i n e b a s e s by c i t i n g h i s own p a p e r ( 1 0 ) . We s h o u l d n o t e t h a t W o r l d War I went on f r o m J u l y 1914 t o November 1918; S w i s s s c i e n t i s t s c o u l d c o n t i n u e r e s e a r c h , whereas F r e n c h ones c o u l d n o t do so e a s i l y . 1

1

Downloaded by 171.113.221.145 on October 13, 2015 | http://pubs.acs.org Publication Date: April 29, 1983 | doi: 10.1021/bk-1983-0215.ch001

q

L i f e and Work o f M a i l l a r d

(1878-1936)

L o u i s - C a m i l l e M a i l l a r d was b o r n on F e b r u a r y 4, 1878 i n P o n t - a - M o u s s o n (Meuthe e t M o s e l l e ) (48.55°N , 6.03°E). He went to Nancy, where he o b t a i n e d t h e d e g r e e s o f M. S c . i n 1897 and Dr. Med. i n 1903. T h e r e a f t e r he worked i n t h e C h e m i c a l D i v i s i o n o f t h e S c h o o l o f M e d i c i n e , U n i v e r s i t y o f Nancy. In 1914 he moved t o P a r i s and t h e young d o c t o r worked as head o f a b i o l o g i c a l group i n t h e C h e m i c a l L a b o r a t o r y , U n i v e r s i t y o f Paris (7). In 1911 h i s f i r s t r e p o r t (3») on p e p t i d e s y n t h e s i s was p r e s e n t e d and i n 1912 h i s f i r s t r e p o r t ( 2 ) on t h e s u g a r - a m i n o a c i d r e a c t i o n was p u b l i s h e d . He c o m p l e t e d a book (1_1) i n 1913. A f t e r W o r l d War I i n 1919 he was a p p o i n t e d p r o f e s s o r o f b i o l o g i c a l and m e d i c a l c h e m i s t r y a t t h e U n i v e r s i t y o f A l g i e r s . In t h e same y e a r he became a c o r r e s p o n d i n g member o f t h e D i v i s i o n o f Pharmacy, Academy of M e d i c i n e . In May 1936 he was i n v i t e d t o P a r i s f o r a l e c t u r e . On

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

1.

KAWAMURA

Seventy Years of the Maillard Reaction

May 12, 1936, he d i e d s u d d e n l y d u r i n g a m e e t i n g , where he was a judge of the c o m p e t i t i o n f o r f e l l o w s h i p ( 1 2 ) . T h e r e a r e a t l e a s t 6 p a p e r s o f M a i l l a r d (_3> 13-17) on p e p t i d e s y n t h e s i s and a t l e a s t 8 (2^, 4, 9, 10, 18-21) on t h e sugar-amino a c i d r e a c t i o n . T h i s r e a c t i o n , r e p o r t e d b r i e f l y i n 1912 (_2) , was d e s c r i b e d i n d e t a i l l a t e r ( 2 0 ) . The e v o l u t i o n o f c a r b o n d i o x i d e d u r i n g the r e a c t i o n was a t t r i b u t e d t o t h e c a r b o x y l group o f t h e amino a c i d a f t e r very c a r e f u l q u a n t i t a t i v e experiments. The m e l a n o i d i n p r e p a r e d f r o m g l u c o s e and g l y c i n e was s o l u b l e i n t h e e a r l y s t a g e and t h e n became i n s o l u b l e i n t h e l a t e r stage of h e a t i n g . The i n s o l u b l e m e l a n o i d i n he o b t a i n e d c o n t a i n e d C 58.85, H 4.92, Ν 4.35, and 0 3 1 . 8 8 % ; t h u s t h e e m p i r i c a l f o r m u l a was ^ β ΐ 5 β · He p r o c e e d e d t o c a r r y o u t t h e r e a c t i o n s o f v a r i o u s amino a c i d s w i t h g l u c o s e a t 100°C, and r e a c t i o n s o f g l y c i n e w i t h v a r i o u s s u g a r s ( a r a b i n o s e , x y l o s e , g l u c o s e , mannose, g a l a c t o s e , f r u c t o s e , m a l t o s e , l a c t o s e , and s u c r o s e ) a t 100°C. I n t h e f i r s t e x p e r i m e n t s t h e a c t i v i t y i n t h i s r e a c t i o n was i n t h e order (highest f i r s t ) : a l a n i n e , v a l i n e , g l y c i n e , glutamic a c i d , l e u c i n e , s a r c o s i n e , and t y r o s i n e . T h i s i s n e a r l y t h e same as the o r d e r g i v e n more r e c e n t l y by K a t o (22^). I n l a t e r e x p e r i m e n t s M a i l l a r d ( 2 0 ) showed t h a t s u c r o s e , a n o n r e d u c i n g s u g a r , gave no b r o w n i n g upon s h o r t h e a t i n g w i t h g l y c i n e , b u t t h e m i x t u r e showed t h e b e g i n n i n g o f a d a r k e n i n g r e a c t i o n a f t e r 3 h r o f h e a t i n g , w h i c h was a t t r i b u t e d t o h y d r o l y s i s o f s u c r o s e . P e n t o s e s , e s p e c i a l l y x y l o s e , gave h i g h e r v e l o c i t y i n t h i s r e a c t i o n than hexoses. Being a b i o c h e m i s t , M a i l l a r d (20) s t u d i e d the r e a c t i o n of g l y c i n e w i t h x y l o s e o r g l u c o s e a t 40° and t h e n a t 34°C, i n o r d e r t o know t h e p o s s i b i l i t y o f t h e change i n v i v o . The l a s t c h a p t e r o f t h e same r e p o r t ( 2 0 ) d e a l s w i t h r e a c t i o n o f g l y c y l g l y c i n e w i t h x y l o s e a t 75, 40, and 34°C, and t h r e e c o m m e r c i a l p e p t o n e p r e p a r a t i o n s w i t h x y l o s e a t 110°C. The l a t t e r c o m b i n a t i o n s d a r k e n e d a f t e r 45 t o 90 m i n . The l a s t r e p o r t o f M a i l l a r d (2_1) i s r a t h e r a r e v i e w i n n a t u r e , w i t h more t h a n 50 r e f e r e n c e s . The c h e m i c a l n a t u r e s n o t o n l y o f humus i n s o i l b u t a l s o o f m i n e r a l f u e l ( c o a l ) and b r o w n i n g i n f o o d m a t e r i a l were d i s c u s s e d , e s p e c i a l l y i n r e l a t i o n t o t h e p r e s e n c e o f n i t r o g e n i n browned p r o d u c t s , w h i c h was i n f e r r e d t o be d e r i v e d f r o m amino a c i d s ( a n d r e l a t e d n i t r o g e n o u s m a t e r i a l s ) used f o r s y n t h e t i c " m e l a n o i d i n s " . Thus M a i l l a r d w o r k e d e n e r g e t i c a l l y on t h i s r e a c t i o n f r o m 1911 t h r o u g h 1917 w i t h n o t a b l e r e s u l t s .

Downloaded by 171.113.221.145 on October 13, 2015 | http://pubs.acs.org Publication Date: April 29, 1983 | doi: 10.1021/bk-1983-0215.ch001

(

Naming t h e " M a i l l a r d

Η

Ν Ο

Reaction"

R e y n o l d s (2J3, 24) and S t r a h l m a n n (_7) have c i t e d E l l i s (1959) (2_5) and Heyns and P a u l s e n ( 1 9 6 0 ) ( 2 6 ) as t h e f i r s t t o c a l l t h i s browning the M a i l l a r d r e a c t i o n . I t i s c e r t a i n l y t r u e

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

5

MAILLARD REACTIONS

6

t h a t t h e y p u b l i s h e d r e v i e w a r t i c l e s w i t h t h e s e words i n t h e title. However, I wondered i f any o t h e r w o r k e r u s e d t h e t e r m Maillard reaction earlier. E x a m i n a t i o n of the s u b j e c t indexes of Chemical A b s t r a c t s (CA) r e s t r i c t e d t o t h e terms b r o w n i n g and M a i l l a r d r e a c t i o n gave t h e r e s u l t s shown i n T a b l e I . Table I .

Downloaded by 171.113.221.145 on October 13, 2015 | http://pubs.acs.org Publication Date: April 29, 1983 | doi: 10.1021/bk-1983-0215.ch001

Vols.

(Years)

" B r o w n i n g " and " M a i l l a r d r e a c t i o n " as Terms i n CA ( a ) Browning

(b)

Maillard

1-10 (1907-16) C o l o r , change o f 11-20 (1917-26) 21-30 (1927-36) D i s c o l o r a t i o n * 31-40 (1937-46) 41-50 (1947-56) ( o f f o o d s ) 18 browning 169 51-55 (1957-61) π *** 56-65 (1962-66) 66-75 (1967-71) 120 3 40 76-85 (1972-76) Browning'J U ^ U J U ^ . 1 5 1

(a) (b) * **

Index

reaction.

No

Yes

13 32 52 77 157

Number o f a b s t r a c t s u n d e r each i n d e x t e r m shown. Browning or s u b s t i t u t e index term. (See a l s o C o l o r ( s ) ; C o l o r i n g ; S t a i n i n g ; Y e l l o w i n g . ) (See a l s o " b r o w n i n g " under D i s c o l o r a t i o n . )

***Browning r e a c t i o n . See M a i l l a r d r e a c t i o n ; see " b r o w n i n g " under D i s c o l o r a t i o n . D i s c o l o r a t i o n , b r o w n i n g . — See a l s o M a i l l a r d r e a c t i o n . * * * * S t u d i e s o f b r o w n i n g o f f o o d and r e l a t e d m a t e r i a l s were indexed at t h i s heading. Thus CA a l r e a d y u s e d t h e i n d e x t e r m M a i l l a r d r e a c t i o n i n t h e 5 t h C o l l e c t i v e I n d e x ( 1 9 4 7 - 5 6 ) , p r i o r t o 1959. There was no i n d e x t e r m M a i l l a r d r e a c t i o n up t o v o l . 43 (1949) o f CA. The e a r l i e s t c i t a t i o n s by t h a t t e r m a r e t o t h e 6 p a p e r s (27-32) i n CA 44 (1950) and 46-48 ( 1 9 5 2 - 5 4 ) . J o h n B. Thompson (21) worked a t t h e T r a c e M e t a l R e s e a r c h L a b o r a t o r i e s i n C h i c a g o , w h i l e Andre P a t r o n (28) was employed a t t h e I n s t i t u t e o f C o l o n i a l F r u i t s and C i t r u s e s ( I n s t i t u t e de F r u i t s e t Agrumes C o l o n i a u x ) i n P a r i s , and p r e p a r e d a r e v i e w ( 3 3 ) c o n t a i n i n g t h e words M a i l l a r d r e a c t i o n i n t h e t i t l e . R. G e o f f r o y (29) o f t h e F r e n c h C o l l e g e o f M i l l i n g ( E c o l e Française de M e u n e r i e ) i n P a r i s a l s o p u b l i s h e d a b r i e f r e v i e w on t h e M a i l l a r d r e a c t i o n i n the c e r e a l i n d u s t r y . H. L. A. T a r r (30) o f P a c i f i c F i s h e r i e s S t a t i o n , V a n c o u v e r , B r i t i s h C o l u m b i a , as w e l l as Hans Wegner (3_2) o f t h e R e s e a r c h I n s t i t u t e o f S t a r c h F a b r i c a t i o n ( F o r s c h u n g s i n s t i t u t der S t a e r k e f a b r i k a t i o n ) i n B e r l i n , a l s o used t h i s term i n the t i t l e s of r e s e a r c h papers.

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

Downloaded by 171.113.221.145 on October 13, 2015 | http://pubs.acs.org Publication Date: April 29, 1983 | doi: 10.1021/bk-1983-0215.ch001

1.

KAWAMURA

Seventy Years of

the

Maillard Reaction

7

P. de Lange (31) o f t h e C e n t r a l I n s t i t u t e o f Food R e s e a r c h (Centr. I n s t . Voedingonderzoek), U t r e c h t , Netherlands reviewed t h e mechanism o f t h e M a i l l a r d r e a c t i o n , though h i s t i t l e d i d n o t show t h e t e r m . Thus, I once c o n s i d e r e d Thompson ( 1 9 5 0 ) and P a t r o n (1950) to be t h e f i r s t namers o f t h e M a i l l a r d r e a c t i o n . However, B a r n e s and Kaufman (34) o f G e n e r a l Foods C o r p o r a t i o n , Hoboken, N J , p u b l i s h e d a r e v i e w i n 1947, t h r e e y e a r s e a r l i e r , o f w h i c h t h e a b s t r a c t i n CA b e g i n s t h u s : " M a i l l a r d o r b r o w n i n g r e a c t i o n i n f o o d s t u f f s i s a t t r i b u t e d t o a r e a c t i o n between s u g a r s and p r o t e i n s o r o t h e r amino b o d i e s , " and t h e r e v i e w i t s e l f r e p e a t e d l y r e f e r s to the M a i l l a r d r e a c t i o n . L a t e r I found t h a t P a t r o n (33) c i t e d a p a p e r by S e a v e r and K e r t e s z (1946) (35) w i t h t h i s term i n the t i t l e . However, t h i s t y p e o f s e a r c h p r o v e d n o t r e l i a b l e . In r e a d i n g t h e a b s t r a c t o f a p a p e r by W i l l y R u c k d e s c h e l (36) o f the L a b o r a t o r y of Fermentation Chemistry, Royal T e c h n i c a l C o l l e g e ( K o e n i g l i c h e Technische Hochschule) at Munich I found t h e words M a i l l a r d ' s r e a c t i o n i n CA more t h a n t h r e e t i m e s . The o r i g i n a l p a p e r by R u c k d e s c h e l (1914) (36) c o n t a i n e d t h e words " d i e R e a k t i o n M a i l l a r d s " f i r s t and t h e n t h e words " d i e M a i l l a r d s c h e R e a k t i o n " f o u r t i m e s . Hence, he may be c a l l e d one of t h e f i r s t namers o f t h i s r e a c t i o n . I t i s t r u e t h a t M a i l l a r d h i m s e l f w r o t e o f t e n "my r e a c t i o n " (ma r e a c t i o n ) . I t i s a v e r y s i m p l e but c l e a r c o n c l u s i o n t h a t t h e f i r s t namer o f t h e M a i l l a r d r e a c t i o n was t h e o r i g i n a l a u t h o r M a i l l a r d h i m s e l f ! I b e l i e v e t h a t no one w o u l d p r o t e s t t h i s d e d u c t i o n . As has a l r e a d y been n o t e d , i n 1912 L i n t n e r ( 6 ) u s e d t h e p h r a s e "by t h e p r o c e s s o f M a i l l a r d " . I t i s of i n t e r e s t t o f i n d two German s c i e n t i s t s , L i n t n e r and Ruckdeschel, c o n c e r n i n g themselves w i t h a r e a c t i o n then r e c e n t l y d i s c o v e r e d by a F r e n c h s c i e n t i s t , e s p e c i a l l y s i n c e W o r l d War I began i n J u l y , 1914. Chemistry of the M a i l l a r d R e a c t i o n Among c h e m i c a l r e v i e w s (22-26, 37-42) t h e p a p e r o f Hodge ( 3 8 ) c o n t a i n i n g t h e famous scheme i s e s p e c i a l l y n o t a b l e . The scheme was c o n s i d e r e d p r a c t i c a l l y u s e f u l and e f f e c t i v e even a f t e r 25 y e a r s ( 4 2 ) . The c o n d e n s a t i o n o f an amino a c i d w i t h an a l d o s e t o f o r m a S c h i f f base was f i r s t r e c o g n i z e d by M a i l l a r d (20). The r e s u l t i n g N - s u b s t i t u t e d a l d o s y l a m i n e i s c o n v e r t e d t o a d e o x y k e t o s y l a m i n e by t h e A m a d o r i r e a r r a n g e m e n t . ( I n the r e a c t i o n o f an amino a c i d w i t h a k e t o s e a d e o x y a l d o s y l a m i n e i s formed by t h e Heyns r e a r r a n g e m e n t ( 2 4 ) ) . The t h r e e pathways o f Hodge (_38) s h o u l d be augmented t o f i v e (41 ). Condensation products of t r i o s e reductone w i t h g l y c i n e , l e u c i n e , m e t h i o n i n e , and p h e n y l a l a n i n e have been c h a r a c t e r i z e d (43). H a s h i b a , ejt a l . (44) i s o l a t e d s i x A m a d o r i compounds f r o m

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

MAILLARD REACTIONS

soy sauce and o t h e r brewed p r o d u c t s . Very r e c e n t l y Hashiba (45) compared t h e i n t e n s i t y o f b r o w n i n g c a u s e d by h e a t i n g s u g a r s w i t h g l y c i n e a t 120°C f o r 5 m i n . I t was i n t h e o r d e r (highest f i r s t ) : ribose, glucuronic acid, xylose, arabinose, g a l a c t u r o n i c a c i d , g a l a c t o s e , mannose, g l u c o s e , and l a c t o s e . R e d u c i n g power and t h e amount o f g l y c i n e consumed were p r o p o r t i o n a l t o t h e i n t e n s i t y of b r o w n i n g , but t h e amount o f A m a d o r i compounds a c c u m u l a t e d i n t h e r e a c t i o n m i x t u r e c o u l d n o t be c o r r e l a t e d w i t h t h e s e . The c o r r e s p o n d i n g A m a d o r i compounds were a l s o compared f o r b r o w n i n g i n t e n s i t y . A general route I

Downloaded by 171.113.221.145 on October 13, 2015 | http://pubs.acs.org Publication Date: April 29, 1983 | doi: 10.1021/bk-1983-0215.ch001

Sugar + amino a c i d

II A m a d o r i compd

brown p i g m e n t

has been p o s t u l a t e d f o r t h e M a i l l a r d r e a c t i o n by K a t o (40)· It was t h e p u r p o s e o f H a s h i b a ' s s t u d y t o f i n d w h e t h e r d i f f e r e n c e s i n b r o w n i n g a r e due t o d i f f e r e n c e s i n r e a c t i o n v e l o c i t y i n s t e p I o r I I . However, t h e r e s u l t s were not c l e a r - c u t . He c o n s i d e r e d t h a t t h e d i f f e r e n c e o f b r o w n i n g among s u g a r s depended on t h e r a t e o f s t e p I o r a c o m b i n a t i o n o f r a t e s o f b o t h s t e p s I and I I , a c c o r d i n g t o t h e s u g a r u s e d . N a m i k i and H a y a s h i (46) r e c e n t l y summarized t h e i r t h e o r y o f f o r m a t i o n o f i n t e r m e d i a t e f r e e r a d i c a l s , Ν, Ν'-disubstituted p y r a z i n e c a t i o n r a d i c a l s , i n an e a r l y s t a g e o f t h e M a i l l a r d r e a c t i o n ( c f . 47). M e l a n o i d i n s ( 3 6 , 48-50) a r e d i f f e r e n t f r o m m e l a n i n s , h u m i n s , and c a r a m e l s , but s i m i l a r t o humus (3_7 ), a c c o r d i n g t o M a i l l a r d ( 4 , 11, 1 9 - 2 1 ) . K a t o and T s u c h i d a (51) s t u d i e d the p o s s i b l e c h e m i c a l s t r u c t u r e of m e l a n o i d i n s . N u t r i t i o n a l Aspects

of the M a i l l a r d

Reaction

Some r e v i e w s ( 4 ^ , 52-54) a r e a v a i l a b l e . The p o s i t i v e a s p e c t s a r e f o u n d i n t h e p r o d u c t i o n o f d e s i r a b l e f l a v o r s and aromas. F u j i m a k i and K u r a t a (5_5) l i s t e d a l d e h y d e s and p y r a z i n e s , v o l a t i l e compounds p r o d u c e d by h e a t i n g amino a c i d s w i t h c a r b o n y l compounds, i s o v a l e r a l d e h y d e p r o d u c e d by r e a c t i o n o f l e u c i n e w i t h c a r b o n y l compounds ( a l d e h y d e s , 3 - d e o x y g l u c o s o n e , x y l o s e , and g l u c o s e ) , and v o l a t i l e compounds p r o d u c e d by r e a c t i o n o f c y s t e i n e w i t h p y r u v a l d e h y d e . A recent r e v i e w (5_6) c i t e d 127 r e f e r e n c e s i n c l u d i n g about 30 J a p a n e s e ones. To s t u d y t h e e f f e c t o f t h e M a i l l a r d r e a c t i o n on n u t r i t i v e v a l u e o f p r o t e i n , P a t t o n , e_t a l . (57) h e a t e d p u r i f i e d c a s e i n and soybean g l o b u l i n i n 5% g l u c o s e s o l u t i o n f o r 24 h r s a t 96.5°C, and f o u n d s i g n i f i c a n t l o s s e s o f l y s i n e , a r g i n i n e , t r y p t o p h a n , and h i s t i d i n e ( 5 2 ) . Kawamura, e_t a _ l . (58) r e p o r t e d t h a t t h e n o n r e d u c i n g sugar l e v e l , a v a i l a b l e l y s i n e , and w h i t e n e s s d e c r e a s e d i n p a r a l l e l w i t h h e a t i n g t i m e o f d e f a t t e d soybean f l a k e s a t 100 o r 120°C. C o n c e n t r a t i o n s of the t h r e e o l i g o s a c c h a r i d e s ( s u c r o s e ,

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

KAWAMURA

Seventy Years of

the

Maillard Reaction

9

r a f f i n o s e , and s t a c h y o s e ) t e n d e d t o d e c r e a s e . These n o n r e d u c i n g s u g a r s were presumed t o u n d e r g o h y d r o l y s i s upon h e a t i n g , and r e d u c i n g s u g a r s formed ( f r u c t o s e , g l u c o s e , and g a l a c t o s e ) were r e s p o n s i b l e f o r t h e M a i l l a r d r e a c t i o n . S t u d i e s w i t h N - n o n d i a l y z a b l e m e l a n o i d i n showed t h a t 76% of t h e d i e t a r y m e l a n o i d i n was e x c r e t e d i n r a t s ' f e c e s ( 5 9 ) . The o r a l a d m i n i s t r a t i o n 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 c a u s e d an i n c r e a s e i n t h e g r o w t h o f b o t h a e r o b i c and a n a e r o b i c l a c t o b a c i l l i i n the m i c r o f l o r a of r a t s ( 6 0 ) . 1 5

Downloaded by 171.113.221.145 on October 13, 2015 | http://pubs.acs.org Publication Date: April 29, 1983 | doi: 10.1021/bk-1983-0215.ch001

M u t a g e n i c i t y of M a i l l a r d R e a c t i o n Products I n a d v a n c e d s t a g e s o f t h e M a i l l a r d r e a c t i o n some mutagens m i g h t be f o r m e d . F o r e x a m p l e , mutagens a p p e a r e d when g r o u n d b e e f hamburgers were c o o k e d o v e r 200°C ( c f . 41)· Reductive i n t e r m e d i a t e s i s o l a t e d from b r o w n i n g m i x t u r e s o f t r i o s e r e d u c t o n e w i t h g u a n i n e and i t s d e r i v a t i v e s a l s o showed mutagenicity (61). Japanese workers i n the N a t i o n a l Cancer Center Research I n s t i t u t e p u b l i s h e d r e v i e w s c o n c e r n i n g mutagens i n h e a t e d f o o d s (62-64). P y r o l y z a t e s o f p r o t e i n s , p e p t i d e s , and amino a c i d s , e s p e c i a l l y t r y p t o p h a n and g l u t a m i c a c i d , showed m u t a g e n i c i t y (65-69). C o f f e e p r e p a r e d i n t h e u s u a l way f o r d r i n k i n g c o n t a i n e d some m u t a g e n i c s u b s t a n c e ( s ) ( 7 0 ) . B l a c k t e a and g r e e n t e a were a l s o m u t a g e n i c . However, t h e s e f a v o r i t e b e v e r a g e s were n o t c a r c i n o g e n i c ( 6 4 ) . N i n e h e t e r o c y c l i c amines were i s o l a t e d as m u t a g e n i c compounds f r o m p y r o l y z a t e s ( 6 3 ) : two p y r i d o i n d o l e s , f o u r p y r i d o i m i d a z o l e s , two i m i d a z o q u i n o l i n e s , and 2 - a m i n o - 5 - p h e n y l p y r i d i n e . None o f them have been i s o l a t e d as p r o d u c t s o f t h e M a i l l a r d r e a c t i o n . Moreover, m u t a g e n i c i t y a p p e a r e d o n l y above 400°, and even more s t r o n g l y a t 500-600°C as t h e p y r o l y s i s t e m p e r a t u r e . L e e , e_t a _ l . (_71) c a r r i e d out l o n g - t e r m (up t o 12 months) f e e d i n g e x p e r i m e n t s o f browned egg a l b u m i n w i t h r a t s . Several changes were f o u n d , b u t no m u t a g e n i c r e s p o n s e was o b s e r v e d . The

M a i l l a r d Reaction i n Vivo

A s i m p l e s k e t c h i s g i v e n a l o n g t h e l i n e s o f two r e c e n t r e v i e w s (^2> 73_). B o r s o o k , e t a l . (74) o b s e r v e d t h e o c c u r r e n c e of A m a d o r i compounds i n v i v o , w h i c h were c o n f i r m e d by Heyns and P a u l s e n (75) t o be 1-deoxy-l-N-aminoacy1-D-fructose derivatives. F e e n e y , e t a _ l . (76) i n c u b a t e d g l u c o s e w i t h egg w h i t e a t 37°C f o r a few days and o b s e r v e d t h e d i s a p p e a r a n c e o f glucose. H o l m q u i s t and S c h r o e d e r (JJ) f i r s t showed t h a t t h e N - t e r m i n a l v a l i n e of H b - A - l - c was b l o c k e d and s u b s e q u e n t r e s e a r c h e r s showed t h e o c c u r r e n c e o f A m a d o r i r e a r r a n g e m e n t o f an a l d o s y l a m i n e , N - ( 1 - d e o x y g l u c o s y l ) v a l i n e . Rahbar (78) d i s c o v e r e d an i n c r e a s e i n t h e m i n o r h e m o g l o b i n component, Hb-A-l-c, i n the blood of d i a b e t i c p a t i e n t s .

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

MAILLARD REACTIONS

T a n z e r (7_9) o b s e r v e d the p r e s e n c e of t h e r e d u c e d f o r m of t h e A m a d o r i compounds formed w i t h h y d r o x y l y s i n e and reducing s u g a r s i n aged c o n n e c t i v e t i s s u e s . M e s t e r , e_t a l _ . (80) s u g g e s t e d the f o r m a t i o n of A m a d o r i compounds i n the b l o o d f r o m g l u c o s e and l y s i n e - r i c h p r o t e i n o r s e r o t o n i n e . C e r a m i , eit 3^.(81) showed t h a t i n d i a b e t e s m e l l i t u s s t r u c t u r a l p r o t e i n s of t h e l e n s m i g h t be a f f e c t e d by h i g h g l u c o s e c o n c e n t r a t i o n t o induce c a t a r a c t through Amadori-type r e a c t i o n . It is likely t h a t t h i s k i n d of s t u d y has not been made by J a p a n e s e w o r k e r s .

Downloaded by 171.113.221.145 on October 13, 2015 | http://pubs.acs.org Publication Date: April 29, 1983 | doi: 10.1021/bk-1983-0215.ch001

M a i l l a r d Reaction i n R e l a t i o n to L i p i d s L i p i d s upon a u t o x i d a t i o n p r o d u c e c a r b o n y l compounds, w h i c h r e a c t w i t h amino compounds t o f o r m brown h i g h - m o l e c u l a r products. T h i s t y p e of b r o w n i n g has r e c e n t l y been r e v i e w e d by P o k o r n y (82^). A c c o r d i n g t o him the f i r s t p a p e r on the s u b j e c t was p u b l i s h e d by S t a n s b y ( 8 3 ) . F u j i m o t o , e t a l . (84-89) s t u d i e d t h i s r e a c t i o n w i t h some f i s h and r e p o r t e d t h a t most brown p i g m e n t of f i s h m u s c l e was s o l u b l e i n b e n z e n e - m e t h a n o l . Thus i n t h i s c a s e o x i d i z e d l i p i d - p r o t e i n i n t e r a c t i o n s a r e more i m p o r t a n t t h a n the r e a c t i o n between amino a c i d s and r i b o s e . In f i s h m u s c l e the b r o w n i n g due t o o x i d i z e d l i p i d s i s a c c o m p a n i e d by the M a i l l a r d r e a c t i o n between amino a c i d s and r i b o s e . In t h i s c o n n e c t i o n i t i s i n t e r e s t i n g t o n o t e an e a r l i e r g a p e r by T a r r ( 3 0 ) , who r e p o r t e d t h a t upon h e a t i n g 1 h r a t 120 C h a l i b u t browned s l i g h t l y whereas l i n g c o d d a r k e n e d m a r k e d l y and t h a t f r e e r i b o s e was d e t e c t e d i n the l a t t e r f i s h m u s c 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 have a n t i o x i d a n t a c t i v i t y ( 9 0 , 91). F r a n z k e and I w a i n s k y (92) f i r s t r e p o r t e d t h i s a c t i v i t y of melanoidins. P a t t o n (93) n o t e d the c o n t r i b u t i o n of the M a i l l a r d r e a c t i o n i n p r e v e n t i n g d r y m i l k powder f r o m o x i d a t i o n . G r i f f i t h and J o h n s o n (94) showed t h a t the p r o d u c t s from r e a c t i o n of g l u c o s e and g l y c i n e e x h i b i t e d a n t i o x i d a t i v e p r o p e r t i e s i n model s y s t e m w i t h l a r d . The a n t i o x i d a t i v e p r o p e r t i e s were a t t r i b u t e d t o r e d u c t o n e s and t h i s was p r o v e d by E v a n s , et_ a l . ( 9 5 ) . Z i p s e r and W a t t s (£6) r e p o r t e d t h a t s t e r i l i z a t i o n o f meat p r o d u c e d a n t i o x i d a t i v e compounds by t h e Maillard reaction. Y a m a g u c h i , e_t a_l. (91) as w e l l as K i r i g a y a , e t a l . (98) made e x t e n s i v e s t u d i e s c o n c e r n i n g t h i s p r o b l e m . E i c h n e r (90) s t u d i e d i n t e r m e d i a t e r e d u c t o n e - l i k e compounds as antioxidants. Y a m a g u c h i , e t a l . (99) f r a c t i o n a t e d the r e a c t i o n p r o d u c t s o b t a i n e d by h e a t i n g D - x y l o s e and g l y c i n e and f o u n d s t r o n g a n t i o x i d a t i v e a c t i v i t y i n some m e l a n o i d i n f r a c t i o n s . Studies

on

Soy

Sauce

Soy sauce i s u s e d e v e r y day by J a p a n e s e p e o p l e . It is a f e r m e n t e d p r o d u c t made f r o m steamed s o y b e a n s , p a r c h e d w h e a t , and s a l t . I t has a s p e c i a l l y p l e a s a n t f l a v o r and a deep but attractive color. I t i s now known t h a t the c o l o r of f r e s h soy

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

KAWAMURA

Seventy Years of the Maillard Reaction

11

Downloaded by 171.113.221.145 on October 13, 2015 | http://pubs.acs.org Publication Date: April 29, 1983 | doi: 10.1021/bk-1983-0215.ch001

sauce i s formed c h i e f l y by the ordinary M a i l l a r d r e a c t i o n , whereas the undesirable dark c o l o r of soy sauce stored i n contact with atmospheric oxygen i s produced not only by the advanced M a i l l a r d r e a c t i o n but a l s o and more pronouncedly by o x i d a t i v e browning r e a c t i o n . The pigments of soy sauce, f i r s t studied by Kurono and Katsume (100), are melanoidins, which were reported by Omata, et a l . (101) to be produced from the r e a c t i o n of sugars and amino a c i d s . Kato, e_t a_l. ( 102) found 3-deoxyglucosone as an intermediate i n browning of soy sauce ( c f . 103). Oxidative browning (104,105) was again reviewed (44) with emphasis on the browning of Amadori compounds and i n t e r a c t i o n between melanoidins and i r o n . Studies on Dried Milk

Products

One of the e a r l i e r reviews (31) concerned the M a i l l a r d r e a c t i o n i n d r i e d milk during storage. Spray-dried whey has considerable amounts of lactose and p r o t e i n r i c h i n l y s i n e . T h e o r e t i c a l treatment of the problem i n whey powder was the object of recent studies by Labuza and Saltmarch (106, 107). When the whey powders are stored at a^ (water a c t i v i t y ) 0.33, 0.44, and 0.65, p r o t e i n q u a l i t y loss and browning extent were greatest not at 0.65 but at 0.44, where amorphous lactose began to s h i f t to the alpha-monohydrate c r y s t a l l i n e form with a release of water which mobilized reactants f o r the M a i l l a r d r e a c t i o n (106). This type of research was continued with s p e c i a l reference to temperature c o n d i t i o n s . The temperatures used were f a i r l y constant at 25, 35, and 45°C or f l u c t u a t i n g between 2 5 ° and 45 °C with a l t e r n a t i n g 5-day periods at each temperature. Experiments were c a r r i e d out f o r 100-200 days. Temperature h i s t o r y , however, d i d not s i g n i f i c a n t l y change r e a c t i o n mechanisms (107). Acknowledgments Thanks are due to Prof. George R. Waller for h i s kind cooperation. Professor Hiromichi Kato of the U n i v e r s i t y of Tokyo and Professor Mitsuo Namiki of Nagoya U n i v e r s i t y provided information on many valuable references. The author i s g r a t e f u l to them and several other colleagues. Literature cited Chem. Abstr.) 1. 2.

3.

(The

titles

of

articles

are included.

CA:

Kawamura, S. S i x t y years of the M a i l l a r d Reaction. Shokuhin Kaihatsu 1972, 7 (12), 64-5. M a i l l a r d , L.-C. A c t i o n des acides amines sur l e s sucres: Formation des melanoidines par voie methodique. C. R. Hebd. Seances Acad. S c i . 1912, 154, 66-8. M a i l l a r d , L.-C. Condensation des acides amines en presence de l a g l y c e r i n e ; C y c l o g l y c y l g l y c i n e et

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

12

MAILLARD REACTIONS

4.

5. 6.

Downloaded by 171.113.221.145 on October 13, 2015 | http://pubs.acs.org Publication Date: April 29, 1983 | doi: 10.1021/bk-1983-0215.ch001

7.

8.

9.

10.

11.

12. 13.

14.

15.

16.

17.

18.

19.

polypeptides. C. R. Hebd. Seances Acad. S c i . 1911, 153, 1078-80. M a i l l a r d , L.-C. Formation d'humus et de combustibles mineraux sans i n t e r v e n t i o n de l'oxygene atmospherique, des microorganismes, des hautes temperatures, ou des f o r t e s p r e s s i o n s . C. R. Hebd. Seances Acad. S c i . 1912, 155, 1554-6. L i n g , A. R. M a l t i n g . J . I n s t . Brew. 1908, 14, 494-521. L i n t n e r , C. J . Ueber Farbe- und Aromabildung im Darrmalz. Z. Gesamte Brauwes. 1912, 35, 545-8, 553-6. Strahlmann, H. Louis Camille M a i l l a r d (1878-1936) und die nach ihm benannte Braeunungsreaktion. Alimenta 1978, 17 (5), 144, 146. P i c t e t , Α.; Chou, T. Q. La formation des bases pyridiques et isoquinoleiques a p a r t i r de l a caseine. C. R. Hebd. Seances Acad. S c i . 1916, 162, 127-9. M a i l l a r d , L.-C. Sur l a formation des bases pyridiques a p a r t i r des albuminoides. C. R. Hebd. Seances Acad. Sci. 1916, 162, 757-8. M a i l l a r d , L.-C. Origines des bases c y c l i q u e s du goudron de h o u i l l e . C. R. Hebd. Seances Acad. S c i . 1913, 157, 850-2. M a i l l a r d , L.-C. "Genese de Matieres Proteiques et des Matieres Humiques"; Masson et C i e : P a r i s , 1913; CA 8, 1594. Achard, Ch. Deces de M. Louis M a i l l a r d . C. R. Hebd. Soc. B i o l . 1963, 122, 347-8. M a i l l a r d , L.-C. Synthese des peptides i n f e r i e u r s par une methode nouvelle et d i r e c t e , v o i s i n e des r e a c t i o n b i o l o g i q u e . C. R. Hebd. Seances Mem. Soc. B i o l . 1911, 71, 546-9. M a i l l a r d , L.-C. Synthese des polypeptides par a c t i o n de l a g l y c e r i n e sur l e g l y c o c o l l e . Ann. Chim. ( P a r i s ) , 1914, (9) 1, 519-78. M a i l l a r d , L. C. Synthese des polypeptides par a c t i o n de l a g l y c e r i n e sur l e g l y c o c o l l e : Etude dynamique. Ann. Chim. ( P a r i s ) , 1914, (9) 2, 210-68. M a i l l a r d , L.-C. Les c y c l o - g l y c y l - g l y c i n e s : Synthese d i r e c t e par a c t i o n de l a g l y c e r i n e sur l e s acides amines. Ann. Chim. ( P a r i s ) , 1915, (9) 3, 48-120. M a i l l a r d , L.-C. Synthese des c y c l o - g l y c y 1 - g l y c i n e mixtes par a c t i o n de l a g l y c e r i n e sur l e s melanges d'acides α-amines. Ann. Chim. ( P a r i s ) , 1915, (9) 3, 225-52. M a i l l a r d , L.-C. Reaction generale des acides amines sur les sucres: Ses consequences b i o l o g i q u e s . C. R. Hebd. Seances Mem. Soc. Biol., 1912, 72, 559-601. M a i l l a r d , L.-C. Formation des matieres humiques par a c t i o n de polypeptides sur l e s sucres. C. R. Hebd. Seances Acad. S c i . 1913, 156, 1159-60.

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

1. KAWAMURA 20. 21. 22.

Downloaded by 171.113.221.145 on October 13, 2015 | http://pubs.acs.org Publication Date: April 29, 1983 | doi: 10.1021/bk-1983-0215.ch001

23. 24. 25. 26. 27. 28. 29. 30. 31. 32. 33. 34. 35. 36. 37.

Seventy Years of the Maillard Reaction

13

Maillard, L.-C. Syntheses des matieres humiques par action des acides amines sur les sucres reducteurs. Ann. Chim. (Paris), 1916, (9) 5, 258-317. Maillard, L.-C. Identité des matieres humiques de synthese avec les matieres humiques naturelles. Ann. Chim. (Paris) 1917, (9) 7, 113-52. Kato, H. Chemistry of nonenzymatic browning phenomena. "Shokuhin no Henshoku to Sono Kagaku (Food Discoloration and Its Chemistry)"; Nakabayashi, T., Kimura, S.; and Kato, H., Eds.; Korin Shoin: Tokyo, 1967; pp. 223-89. Reynolds, T. H. Chemistry of nonenzymic browning. I. The reaction between aldoses and amines. Adv. Food Res. 1963, 12, 1-52. Reynolds, T. H. Chemistry of nonenzymic browning. II. Adv. Food Res. 1965, 14, 167-283. Ellis, G. P. The Maillard reaction. Adv. Carbohydr. Chem. 1959, 14, 63-134. Heyns, K.; Paulsen, H. Ueber die chemische Grundlagen der Maillard-Reaktion. Wiss. Veroeff. Deutsch. Ges. Ernaehr. 1960, 5, 15-42. Thompson, J . B. A browning reaction involving copper-proteins. "Symposium on Copper Metabolism;" Johns Hopkins Press, 1950, pp. 141-53; CA 47, 11269f. Patron, A. Recherches sur le brunissement nonenzymatique des fruits et des produits de fruits en conserve. Fruits Outre Mer 1950, 5, 201-7; CA 44, 10204d. Geoffrey, R. The Maillard reaction in the cereal industry. Bull. Anc. Eleves Ec. Fr. Meun. 1953, (138), 260; CA 48, 7807a. Tarr, H. L. A. Ribose and the Maillard reaction in fish muscle. Nature 1953, 171, 344-5; CA 47, 5973i. Lange, P. de. Decrease of solubility and nutritive value of milk powder during storage. Conserva 1954, 2, 322-5; CA 48, 7808a. Wegner, H. The Maillard reaction and yellowing of starch sirup. Staerke 1954, 6, 5-10; CA 48, 6150d. Patron, A. La "Reaction de Maillard" et le brunissement non-enzymatique dans les industries alimentaires. Ind. Agric. Aliment. 1951, 68, 251-6; CA 46, 4687f. Barnes, H. K.; Kaufman, C. W. Industrial aspects of browning reaction. Ind. Eng. Chem. 1947, 39, 1167-70. Seaver, J . L . ; Kertesz, Ζ. I. "Browning (Maillard) reaction" in heated solutions of uronic acids. J . Am. Chem. Soc. 1946, 68, 2178-9. Ruckdeschel, W. Ueber Melanoidine und ihr Vorkommen in Darrmalz. Z. Gesamte Brauwes. 1914, 37, 430-2, 437-40. Danehy, J . P.; Pigman, W. W. Reactions between sugars and nitrogenous compounds and their relationship to certain food problems. Adv. Food Res. 1951, 3, 241-90.

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

14

MAILLARD REACTIONS

38. 39. 40. 41. 42.

Downloaded by 171.113.221.145 on October 13, 2015 | http://pubs.acs.org Publication Date: April 29, 1983 | doi: 10.1021/bk-1983-0215.ch001

43.

44. 45. 46. 47. 48. 49.

50. 51. 52. 53. 54. 55. 56.

Hodge, J . E. Chemistry of browning reactions in model systems. J . Agric. Food Chem. 1953, 1, 928-43. Feeney, R. E . ; Blankenhorn, G.; Dixon, H. B. F. Carbonyl-amine reactions in protein chemistry. Adv. Protein Chem. 1975, 29, 135-203. Kato, H. Studies on nonenzymic browning of foods. Nippon Nogei Kagaku Kaishi 1968, 42, R9-15. Mauron, J . The Maillard reaction in food; a critical review from the nutritional standpoint. Prog. Food Nutr. Sci. 1981, 5, 5-35. Nursten, H. E. Recent developments in studies of the Maillard reaction. Food Chem. 1981, 6, 263-77. Omura, H.; Inoue, Y.; Eto, M.; Tsen, Y.-K.; Shinohara, K. Reaction products of triose reductone with some amino acids. Kyushu Daigaku Nogakubu Gakugei Zasshi 1974, 29, 61-70. Hashiba, H.; Okuhara, Α.; Iguchi, N. Oxygen-dependent browning of soy sauce and some brewed products. Prog. Food Nutr. Sci. 1981, 5, 93-113. Hashiba, H. The browning reaction of Amadori compounds derived from various sugars. Agric. Biol. Chem. 1982, 47, 547-8. Namiki, M.; Hayashi, T. Formation of novel free radical products in an early stage of Maillard reaction. Prog. Food Nutr. Sci. 1981, 5, 81-91. Hayashi, T.; Namiki, M. On the mechanism of free radical formation during browning reaction of sugars with amino compounds. Agric. Biol. Chem. 1981, 45, 933-9. Zikes, H. Ueber Melanoidine. Allg. Z. Bierbrau. Malzfabr. 1915, 43, 57-8. Sattler, L . ; Zerban, F. W. Unfermentable reducing substances in molasses — volatile decomposition products of sugars and their role in melanoidin formation. Ind. Eng. Chem. 1949, 41, 1401-6. Luers, H. The melanoidins. Brew. Dig. 1949, 24 (10), 41-4, 48; CA 44, 794a. Kato, H.; Tsuchida, H. Estimation of melanoidin structure by hydrolysis and oxidation. Prog. Food Nutr. Sci. 1981, 5, 147-56. Patton, A. R. Present status of heat-processing damage to protein foods. Nutr. Rev. 1950, 8, 193-6. Adrian, J . Nutritional and physioloical consequences of the Maillard reaction. World Rev. Nutr. Diet. 1974, 19, 71-122. Dworschak, E. Nonenzymatic browning and its effect on protein nutrition. CRC Crit. Rev. Food Sci. Nutr. 1980, 12, 1-40. Fujimaki, M.; Kurata, T. Aroma of heated foods. Kagaku To Seibutsu 1971, 9, 85-96. Mabrouk, A. F. Flavor of browning reaction products.

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

Downloaded by 171.113.221.145 on October 13, 2015 | http://pubs.acs.org Publication Date: April 29, 1983 | doi: 10.1021/bk-1983-0215.ch001

KAWAMURA

Seventy Years of the Maillard Reaction

15

"Food Taste Chemistry"; Boudreau, J . C., Ed.; ACS Symp. Ser. 1979, 115, 205-45. 57. Patton, A. R.; H i l l , E. G.; Foreman, Ε. M. Effect of browning on the essential amino acid content of soy glubulin. Science 1948, 108, 659-60; through ref. 52. 58. Kawamura, S.; Kasai, T.; Honda, A. Changes of sugars and decrease in available lysine on autoclaving defatted soybean flakes. Eiyo To Shokuryo 1968, 20, 478-81. 59. Homma, S.; Fujimaki, M. Growth response of rats fed a diet containing nondialyzable melanoidin. Prog. Food Nutr. Sci. 1981, 5, 209-16. 60. Horikoshi, H.; Ohmura, Α.; Gomyo, T.; Kuwabara, Y.; Ueda, S. Effects of browning products on the intestinal microflora of the rat. Prog. Food Nutr. Sci. 1981, 5, 223-8. 61. Shinohara, K.; Lee, J.-H.; Tanaka, M.; Murakami, H.; Omura, H. Mutagenicity of intermediates produced in the early stage of browning reaction of triose reductone with nucleic acid related compounds on bacterial tests. Agric. Biol. Chem. 1980, 44, 1737-43. 62. Sugimura, T.; Nagao, M. Mutagenic factors in cooked foods. CRC Crit. Rev. Toxicol. 1979, 7, 189-209. 63. Sugimura, T.; Nagao, M.; Wakabayashi, K. Mutagenic heterocyclic amines in cooked food. Environ. Carcinog. Sel. Methods Anal. 1981, 4, 251-67. 64. Nagao, M. Mutagens in ordinary foods. Hen'igen To Dokusei 1981, 4 (5), 20-31. 65. Nagao, M.; Honda, M.; Seino, Y.; Yahagi, T.; Kawachi, T.; Sugimura, T. Mutagenicities of protein pyrolyzates. Cancer Lett. 1977, 2, 335-40. 66. Matsumoto, T.; Yoshida, D.; Mizusaki, S.; Okamoto, H. Mutagenic activity of amino acid pyrolyzates in Salmonella typhimurium TA 96. Mutat. Res. 1977, 48, 279-86. 67. Matsumoto, T.; Yoshida, D.; Mizusaki, S.; Okamoto, H. Mutagenicities of the pyrolyzates of peptides and proteins. Mutat. Res. 1978, 56, 281-8. 68. Matsukura, H.; Kawachi, T.; Horino, K.; Ohgaki, H.; Sugimura, T.; Takayama, S. Carcinogenicity in mice of mutagenic compounds from a tryptophan pyrolyzate. Science 1981, 213, 346-7. 69. Tsuda, N.; Nagao, M.; Hirayama, T.; Sugimura, T. Nitrite converts 2-amino-α-carboline, an indirect mutagen, into 2-hydroxy-α-carboline, a non-mutagen, and 2-hydroxy-3-nitroso-α-carboline, a direct mutagen. Mutat. Res. 1981, 83, 61-8. 70. Nagao, M.; Takahashi, Y.; Yamanaka, H.; Sugimura, T. Mutagens in coffee and tea. Mutat. Res. 1979, 68, 101-6. 71. Lee, T.-C.; Kimiagar, H.; Pintauro, S. J.; Chichester, C. O. Physiological and safety aspects of Maillard browning of foods. Prog. Food Nutr. Sci. 1981, 5, 243-56.

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

16

MAILLARD REACTIONS

Downloaded by 171.113.221.145 on October 13, 2015 | http://pubs.acs.org Publication Date: April 29, 1983 | doi: 10.1021/bk-1983-0215.ch001

72.

Mester, L . ; Szabados, L . ; Mester, K.; Yadav, H. Maillard type carbonyl-amine reactions in vivo and their physiological effects. Prog. Food Nutr. Sci. 1981, 5, 295-314. 73. Monnier, V. U.; Stevens, V. J.; Cerami, A. Maillard reactions involving protein and carbohydrates in vivo: relevance to diabetes mellitus and aging. Prog. Food Nutr. Sci. 1981, 5, 315-27. 74. Borsook, H.; Abrams, Α.; Lowy, P. H. Fructose-amino acids in liver: stimuli of amino acid incorporation in vitro. J. Biol. Chem. 1955, 215, 111-24; through ref. 72. 75. Heyns, K.; Paulsen, H. Ueber 'Fructose-Aminosaeuren' und 'Glucose-Aminosaeuren' in Leberextracten. Liebigs Ann. Chem. 1959, 622, 160-74; through ref. 72. 76. Feeney, R. E . ; Clary, J . J.; Clark, J . R. A reaction between egg white proteins in incubated eggs. Nature (London) 1964, 201, 192-3; through ref. 73. 77. Holmquist, W. R.; Schroeder, W. A. A new N-terminal blocking group involving a Schiff base in hemoglobin A-1-c. Biochemistry 1966, 5, 2489-503; through ref. 72. 78. Rahbar, S. An abnormal hemoglobin in red cells of diabetes. Clin. Chim. Acta 1968, 22, 296-8; through ref. 73. 79. Tanzer, M. L. Cross-linking of collagen. Science 1973, 180, 561-6; through ref. 72. 80. Mester, L . ; Kraska, B.; Crisba, J.; Mester, M. Sugar-amine interactions in the blood clotting system and their effects on haemostasis. Proc. Vth Int. Congr. Thromb. Haemostasis 1975, Paris; Int. Soc. Thromb. Haemostasis; through ref. 72. 81. Cerami, Α.; Stevens, V. J.; Monnier, V. M. Role of nonenzymatic glycosylation in the development of the sequelae of Diabetes Mellitus. Metabolism 1979, 28, 431-7; through ref. 72. 82. Pokorny, C. Browning from lipid-protein interactions. Prog. Food Nutr. Sci. 1981, 5, 421-8. 83. Stansby, M. E. Oxidative deterioration in fish and fishery products. I. Introduction. Commer. Fish. Rev. 1957, 19, 24-6; through ref. 82. 84. Fujimoto, K.; Maruyama, M.; Kaneda, T. Brown discoloration of fish products. I. Factors affecting the discoloration. Nippon Suisan Gakkaishi 1968, 34, 519-23. 85. Fujimoto, K. Lipid oxidation and oxidized oil stain of aquatic products. Nippon Suisan Gakkaishi 1970, 36, 850-3, 871-2. 86. Fujimoto, K.; Abe, I.; Kaneda, T. Brown discoloration of fish products. II. Effect of several aldehydes, especially azelaaldehydic acid, in the autoxidized oil on discoloration. Nippon Suisan Gakkaishi 1971, 37, 40-3.

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

Downloaded by 171.113.221.145 on October 13, 2015 | http://pubs.acs.org Publication Date: April 29, 1983 | doi: 10.1021/bk-1983-0215.ch001

1. KAWAMURA

Seventy Years of the Maillard Reaction

17

87. Fujimoto, K.; Saito, J.; Kaneda, T. Brown discoloration of fish products. III. Effect of ribose on the browning reaction derived from autoxidized o i l . Nippon Suisan Gakkaishi 1971, 37, 44-7. 88. Fujimoto, K.; Kandea, T. Brown discoloration of fish products. IV. Nitrogen content of the browning substance. Nippon Suisan Gakkaishi 1973, 39, 179-83. 89. Fujimoto, K.; Kaneda, T. Brown discoloration of fish products. V. Reaction mechanisms in the early stage. Nippon Suisan Gakkaishi 1973, 39, 185-90. 90. Eichner, K. Antioxidative effects of Maillard reaction intermediates. Prog. Food Nutr. Sci. 1981, 5, 441-51. 91. Lingnert, H.; Eriksson, C. E. Antioxidative effect of Maillard reaction products. Prog. Food Nutr. Sci. 1981, 5, 453-66. 92. Franzke, C.; Iwainsky, H. Zur antioxydativen Wirksamkeit der Melanoidine. Dtsch. Lebensm.-Rundsch. 1954, 50, 251-4; through ref. 91. 93. Patton, S. Browning and associated changes in milk and its products: a review. J . Dairy Sci. 1955, 38, 457-478; through ref. 90. 94. Griffith, T.; Johnson, J . A. Relation of the browning reaction to storage stability of sugar cookies. Cereal Chem. 1957, 34, 159-69; through ref. 90. 95. Evans, C. D.; Moser, Η. Α.; Cooney, P. M.; Hodge, J . E. Amino-hexose-reductones as antioxidants. I. Vegetable oils. J . Am. Oil Chem. Soc. 1958, 35, 84-8; through ref. 90. 96. Zipser, M. W.; Watts, Β. M. Lipid oxidation in heat sterilized beef. Food Technol. 1961, 15, 445-7. 97. Yamaguchi, N.; Yokoo, Y.; Fujimaki, M. Studies on antioxidative activities of amino compounds on fats and oils. III. Antioxidative activities of soybean protein hydrolyzates and synergistic effect of hydrolyzate on tocopherol. Nippon Shokuhin Kogyo Gakkaishi 1975, 22, 431-5. 98. Kirigawa, N.; Kato, H.; Fujimaki, M. Studies on antioxidant activity of nonenzymic browning reaction products. III. Fractionation of browning reaction solution between ammonia and D-glucose and antioxidant activity of the resulting fractions. Nippon Nogei Kagaku Kaishi 1971, 45, 292-8. 99. Yamaguchi, N.; Koyama, Y.; Fujimaki, M. Fractionation of antioxidative activity of browning reaction products between D-xylose and glycine. Prog. Food Nutr. Sci. 1981, 5, 429-39. 100. Kurono, K.; Katsume, E. Chemical composition of the pigment of soy sauce. Nippon Nogei Kagaku Kaishi 1927, 3, 594-613. 101. Omata, S.; Ueno, T.; Nakagawa, Y. The pigment components

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

MAILLARD REACTIONS

102.

103. 104.

Downloaded by 171.113.221.145 on October 13, 2015 | http://pubs.acs.org Publication Date: April 29, 1983 | doi: 10.1021/bk-1983-0215.ch001

105. 106.

107.

and their formation in amino-acid seasonings. Hakko Kogaku Zasshi 1956, 34, 166-72. Kato, H.; Yamada, Y.; Izaka, K.; Sakurai, Y. Studies on browning mechanisms of soybean products. I. Separation and identification of 3-deoxyglucosone occurring in soy sauce and miso. Nippon Nogei Kagaku Kaishi 1961, 35, 412-14. Okuhara, A. Browning of soy sauce. Kagaku To Seibutsu 1972, 10, 383-90. Motai, H. Nonenzymatic oxidative browning: Polymerization of melanoidins. Kagaku To Seibutsu 1975, 13, 292-4. Hashiba, H. Oxidative browning of soy sauce. Contribution of Amadori compounds. Kagaku To Seibutsu 1977, 15, 156-8. Saltmarch, R.; Vagnini-Ferrari, M.; Labuza, T. P. Theoretical basis and application of kinetics to browning in spray-dried whey food systems. Prog. Food Nutr. Sci. 1981, 5, 331-44. Labuza, T. P.; Saltmarch, R. Kinetics of browning and protein quality loss in whey powders during steady state and non-steady state storage conditions. J . Food Sci. 1982, 47, 92-6, 113.

RECEIVED January 14, 1983

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