1

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

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

Waller and Feather; The Maillard Reaction in Foods and Nutrition

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,
1 1
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 q

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 .

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

Waller and Feather; The Maillard Reaction in Foods and Nutrition

ACS Symposium Series; American Chemical Society: Washington, DC, 1983.
1. KAWAMURA Seventy Years of the Maillard Reaction 5

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
( Η Ν Ο
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 .

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

Waller and Feather; The Maillard Reaction in Foods and Nutrition

ACS Symposium Series; American Chemical Society: Washington, DC, 1983.
6 MAILLARD REACTIONS

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 . " 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 Index

Terms i n CA ( a )

Vols. (Years) Browning (b) Maillard reaction.

1-10 (1907-16) C o l o r , change o f No

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 Yes 13
51-55 (1957-61) browning 169 32
56-65 (1962-66) π *** 1 5 1 52
66-75 (1967-71) 120 77
76-85 (1972-76) Browning'J U ^ U J U ^ . 3 40 157

(a) 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.

(b) 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.

Waller and Feather; The Maillard Reaction in Foods and Nutrition

ACS Symposium Series; American Chemical Society: Washington, DC, 1983.
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

Waller and Feather; The Maillard Reaction in Foods and Nutrition

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 II
Sugar + amino a c i d 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 ,

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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 .
1 5
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 ) .

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 .

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 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 .

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

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KAWAMURA Seventy Years of the Maillard Reaction 11

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 (The titles of articles are included. CA:

Chem. Abstr.)

1. 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.
2. 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.
3. 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

Waller and Feather; The Maillard Reaction in Foods and Nutrition

ACS Symposium Series; American Chemical Society: Washington, DC, 1983.
12 MAILLARD REACTIONS

polypeptides. C. R. Hebd. Seances Acad. S c i . 1911, 153,

1078-80.
4. 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.
5. L i n g , A. R. M a l t i n g . J . I n s t . Brew. 1908, 14, 494-521.
6. L i n t n e r , C. J . Ueber Farbe- und Aromabildung im Darrmalz.
Z. Gesamte Brauwes. 1912, 35, 545-8, 553-6.
7. 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.
8. 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.
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.
10. 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.
11. 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.
12. 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.
13. 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.
14. 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.
15. 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.
16. 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.
17. 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.
18. 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.
19. 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.

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ACS Symposium Series; American Chemical Society: Washington, DC, 1983.
1. KAWAMURA Seventy Years of the Maillard Reaction 13

20. Maillard, L.-C. Syntheses des matieres humiques par

action des acides amines sur les sucres reducteurs. Ann.
Chim. (Paris), 1916, (9) 5, 258-317.
21. Maillard, L.-C. Identité des matieres humiques de
synthese avec les matieres humiques naturelles. Ann.
Chim. (Paris) 1917, (9) 7, 113-52.
22. 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.
23. Reynolds, T. H. Chemistry of nonenzymic browning. I. The
reaction between aldoses and amines. Adv. Food Res. 1963,
12, 1-52.
24. Reynolds, T. H. Chemistry of nonenzymic browning. II.
Adv. Food Res. 1965, 14, 167-283.
25. Ellis, G. P. The Maillard reaction. Adv. Carbohydr. Chem.
1959, 14, 63-134.
26. Heyns, K.; Paulsen, H. Ueber die chemische Grundlagen der
Maillard-Reaktion. Wiss. Veroeff. Deutsch. Ges. Ernaehr.
1960, 5, 15-42.
27. Thompson, J . B. A browning reaction involving
copper-proteins. "Symposium on Copper Metabolism;" Johns
Hopkins Press, 1950, pp. 141-53; CA 47, 11269f.
28. 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.
29. Geoffrey, R. The Maillard reaction in the cereal
industry. Bull. Anc. Eleves Ec. Fr. Meun. 1953, (138),
260; CA 48, 7807a.
30. Tarr, H. L. A. Ribose and the Maillard reaction in fish
muscle. Nature 1953, 171, 344-5; CA 47, 5973i.
31. Lange, P. de. Decrease of solubility and nutritive value
of milk powder during storage. Conserva 1954, 2, 322-5;
CA 48, 7808a.
32. Wegner, H. The Maillard reaction and yellowing of starch
sirup. Staerke 1954, 6, 5-10; CA 48, 6150d.
33. 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.
34. Barnes, H. K.; Kaufman, C. W. Industrial aspects of
browning reaction. Ind. Eng. Chem. 1947, 39, 1167-70.
35. Seaver, J . L . ; Kertesz, Ζ. I. "Browning (Maillard)
reaction" in heated solutions of uronic acids. J . Am.
Chem. Soc. 1946, 68, 2178-9.
36. Ruckdeschel, W. Ueber Melanoidine und ihr Vorkommen in
Darrmalz. Z. Gesamte Brauwes. 1914, 37, 430-2, 437-40.
37. 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.

Waller and Feather; The Maillard Reaction in Foods and Nutrition

ACS Symposium Series; American Chemical Society: Washington, DC, 1983.
14 MAILLARD REACTIONS

38. Hodge, J . E. Chemistry of browning reactions in model

systems. J . Agric. Food Chem. 1953, 1, 928-43.
39. Feeney, R. E . ; Blankenhorn, G.; Dixon, H. B. F.
Carbonyl-amine reactions in protein chemistry. Adv.
Protein Chem. 1975, 29, 135-203.
40. Kato, H. Studies on nonenzymic browning of foods. Nippon
Nogei Kagaku Kaishi 1968, 42, R9-15.
41. Mauron, J . The Maillard reaction in food; a critical
review from the nutritional standpoint. Prog. Food Nutr.
Sci. 1981, 5, 5-35.
42. Nursten, H. E. Recent developments in studies of the
Maillard reaction. Food Chem. 1981, 6, 263-77.
43. 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.
44. Hashiba, H.; Okuhara, Α.; Iguchi, N. Oxygen-dependent
browning of soy sauce and some brewed products. Prog.
Food Nutr. Sci. 1981, 5, 93-113.
45. Hashiba, H. The browning reaction of Amadori compounds
derived from various sugars. Agric. Biol. Chem. 1982, 47,
547-8.
46. 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.
47. 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.
48. Zikes, H. Ueber Melanoidine. Allg. Z. Bierbrau. Malzfabr.
1915, 43, 57-8.
49. 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.
50. Luers, H. The melanoidins. Brew. Dig. 1949, 24 (10),
41-4, 48; CA 44, 794a.
51. Kato, H.; Tsuchida, H. Estimation of melanoidin structure
by hydrolysis and oxidation. Prog. Food Nutr. Sci. 1981,
5, 147-56.
52. Patton, A. R. Present status of heat-processing damage to
protein foods. Nutr. Rev. 1950, 8, 193-6.
53. Adrian, J . Nutritional and physioloical consequences of
the Maillard reaction. World Rev. Nutr. Diet. 1974, 19,
71-122.
54. Dworschak, E. Nonenzymatic browning and its effect on
protein nutrition. CRC Crit. Rev. Food Sci. Nutr. 1980,
12, 1-40.
55. Fujimaki, M.; Kurata, T. Aroma of heated foods. Kagaku To
Seibutsu 1971, 9, 85-96.
56. Mabrouk, A. F. Flavor of browning reaction products.

Waller and Feather; The Maillard Reaction in Foods and Nutrition

ACS Symposium Series; American Chemical Society: Washington, DC, 1983.
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.

Waller and Feather; The Maillard Reaction in Foods and Nutrition

ACS Symposium Series; American Chemical Society: Washington, DC, 1983.
16 MAILLARD REACTIONS

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.

Waller and Feather; The Maillard Reaction in Foods and Nutrition

ACS Symposium Series; American Chemical Society: Washington, DC, 1983.
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

Waller and Feather; The Maillard Reaction in Foods and Nutrition

ACS Symposium Series; American Chemical Society: Washington, DC, 1983.
 MAILLARD REACTIONS

and their formation in amino-acid seasonings. Hakko

Kogaku Zasshi 1956, 34, 166-72.
102. 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.
103. Okuhara, A. Browning of soy sauce. Kagaku To Seibutsu
1972, 10, 383-90.
104. Motai, H. Nonenzymatic oxidative browning: Polymerization
of melanoidins. Kagaku To Seibutsu 1975, 13, 292-4.
105. Hashiba, H. Oxidative browning of soy sauce.
Contribution of Amadori compounds. Kagaku To Seibutsu
1977, 15, 156-8.
106. 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.
107. 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

Waller and Feather; The Maillard Reaction in Foods and Nutrition

ACS Symposium Series; American Chemical Society: Washington, DC, 1983.