1

An Introduction to Pectins: Structure and Properties

James N. BeMiller

Department of Chemistry and Biochemistry, Southern Illinois University at Carbondale,

Carbondale, IL 62901

Pectin, a polysaccharide, is composed primarily of

Downloaded by 189.229.145.72 on January 6, 2017 | http://pubs.acs.org

essentially linear polymers of D-galactopyranosyl

Publication Date: June 5, 1986 | doi: 10.1021/bk-1986-0310.ch001

uronic acid units joined in-D(1->4)glycosidic

linkages; the polymer chains are esterified to
various degrees with methanol. This regular
structure is interrupted, however, with
L-rhamnopyranosyl units and with side chains
containing other neutral sugars. The polymer chains
may also be partially acetylated. The most
important physical property of pectin is its ability
to form spreadable gels. Gel formation results when
the polymer chains interact over a portion of their
length to form a three-dimensional network. This
aggregation of chains occurs through hydrogen
bonding, divalent cation crossbridging, and/or
hydrophobic interactions.

Terminology

I n 1944, d e f i n i t i o n s f o r p e c t i n s were e s t a b l i s h e d by t h e Committee

f o r t h e R e v i s i o n o f t h e Nomenclature o f P e c t i c Substances O ) ; b u t
s i n c e t h e n , t e r m i n o l o g y has changed somewhat, and m o d i f i e d
d e f i n i t i o n s have been used. A t t h i s t i m e , t h e r e a r e no
u n i v e r s a l l y agreed upon and a c c e p t e d d e f i n i t i o n s . The d e f i n i t i o n s
presented here a r e t h o s e g e n e r a l l y i n c u r r e n t commercial use (2).
P e c t i c acids are galacturonoglycans [poly(a-D-
g a l a c t o p y r a n o s y l u r o n i c a c i d s ) ] w i t h o u t , o r w i t h oTTly a n e g l i g i b l e
c o n t e n t o f , methyl e s t e r groups. P e c t i c a c i d s may have v a r y i n g
degrees o f n e u t r a l i z a t i o n . S a l t s o f p e c t i c a c i d s a r e c a l l e d
pectates.
P e c t i n i c acids are galacturonoglycans with various, but
g r e a t e r t h a n n e g l i g i b l e , c o n t e n t s o f m e t h y l e s t e r groups.
P e c t i n i c a c i d s may have v a r y i n g degrees o f n e u t r a l i z a t i o n . S a l t s
of p e c t i n i c a c i d s a r e c a l l e d p e c t i n a t e s .

0097-6156/ 86/0310-0002$06.00/0
1986 American Chemical Society

Fishman and Jen; Chemistry and Function of Pectins

ACS Symposium Series; American Chemical Society: Washington, DC, 1986.
 1. BEMILLER Pectins: Structure and Properties 3

P e c t i n s a r e m i x t u r e s o f p o l y s a c c h a r i d e s t h a t o r i g i n a t e from
p l a n t s , c o n t a i n p e c t i n i c a c i d s as major components, a r e water
s o l u b l e , and a r e a b l e t o form g e l s under s u i t a b l e c o n d i t i o n s (See
s e c t i o n on P h y s i c a l P r o p e r t i e s ) .
I n t h i s c h a p t e r , as i s f r e q u e n t l y done, t h e term p e c t i n w i l l
be used i n a g e n e r i c sense t o d e s i g n a t e t h o s e w a t e r - s o l u b l e
g a l a c t u r o n o g l y c a n s o f v a r y i n g methyl e s t e r c o n t e n t and degree o f
n e u t r a l i z a t i o n t h a t a r e capable o f f o r m i n g g e l s under s u i t a b l e
c o n d i t i o n s (See s e c t i o n on P h y s i c a l P r o p e r t i e s ) , i . e . , o t h e r
p o l y s a c c h a r i d e s t h a t may be p r e s e n t i n commercial m i x t u r e s w i l l be
ignored.
P e c t i n s a r e s u b d i v i d e d a c c o r d i n g t o t h e i r degree o f
e s t e r i f i c a t i o n (DE), a d e s i g n a t i o n o f t h e p e r c e n t o f c a r b o x y l
groups e s t e r i f i e d w i t h methanol. P e c t i n s w i t h DE > 50? a r e
high-methoxyl p e c t i n s ( H M - p e c t i n s ) ; t h o s e w i t h DE < 50? a r e
Downloaded by 189.229.145.72 on January 6, 2017 | http://pubs.acs.org

low-methoxyl p e c t i n s ( L M - p e c t i n s ) .
Publication Date: June 5, 1986 | doi: 10.1021/bk-1986-0310.ch001

The degree of a m i d a t i o n (DA) i n d i c a t e s t h e p e r c e n t o f

c a r b o x y l groups i n t h e amide form (See s e c t i o n on Chemical
Properties).

Structure

For a more d e t a i l e d d i s c u s s i o n o f t h e c h e m i c a l s t r u c t u r e o f
p e c t i n s , see r e f e r e n c e 3.
P e c t i n , a s t r u c t u r a l , c e l l - w a l l polysaccharide of a l l higher
p l a n t s , l i k e most o t h e r p o l y s a c c h a r i d e s , i s b o t h p o l y m o l e c u l a r and
p o l y d i s p e r s e , i . e . , i t i s heterogeneous w i t h r e s p e c t t o b o t h
c h e m i c a l s t r u c t u r e and m o l e c u l a r weight (jjO. From m o l e c u l e t o
m o l e c u l e , i n any sample o f p e c t i n , b o t h t h e number and percentage
of i n d i v i d u a l monomeric u n i t t y p e s w i l l v a r y , and t h e average
c o m p o s i t i o n and d i s t r i b u t i o n o f m o l e c u l a r w e i g h t s can v a r y w i t h
the s o u r c e , t h e c o n d i t i o n s used f o r i s o l a t i o n , and any subsequent
t r e a t m e n t s . Because both parameters determine p h y s i c a l
p r o p e r t i e s , v a r i o u s f u n c t i o n a l t y p e s o f p e c t i n can be produced by
c o n t r o l l i n g t h e s o u r c e , i s o l a t i o n p r o c e d u r e , and subsequent
treatment(s)
P e c t i n i s p r i m a r i l y a polymer o f D - g a l a c t u r o n i c a c i d . The
p r i n c i p a l and key f e a t u r e o f a l l p e c t i n m o l e c u l e s i s a l i n e a r
chain of (1+4)-linked a-D-galactopyranosyluronic a c i d u n i t s ,
making i t an a-D-galacturonan [ a p o l y ( a - D - g a l a c t o p y r a n o s y l u r o n i c
a c i d ) or an a - D - g a l a c t u r o n o g l y c a n ] . ~"
I n a l l n a t u r a l p e c t i n s , some o f t h e c a r b o x y l groups a r e i n
the methyl e s t e r form. Depending on t h e i s o l a t i o n c o n d i t i o n s , t h e
r e m a i n i n g f r e e c a r b o x y l i c a c i d groups may be p a r t l y o r f u l l y
n e u t r a l i z e d , i . e . , p a r t l y o r f u l l y p r e s e n t as sodium, potassium o r
ammonium c a r b o x y l a t e groups. The r a t i o o f e s t e r i f i e d
D-galacturonic acid units t o t o t a l D-galacturonic a c i d units i s
"Sailed t h e degree o f e s t e r i f i c a t i o n " " ( D E ) and s t r o n g l y i n f l u e n c e s
the s o l u b i l i t y , g e l f o r m i n g a b i l i t y , c o n d i t i o n s r e q u i r e d f o r
g e l a t i o n , g e l l i n g temperature, and g e l p r o p e r t i e s o f t h e
preparation.
I n p e c t i n from some s o u r c e s , some o f t h e u n i t s occur as 0-2
o r 0-3 a c e t a t e s . Such e s t e r i f i c a t i o n hampers g e l a t i o n , so much so
t h a t complete i n h i b i t i o n o f g e l a t i o n o c c u r s when one out o f e i g h t

Fishman and Jen; Chemistry and Function of Pectins

ACS Symposium Series; American Chemical Society: Washington, DC, 1986.
 4 CHEMISTRY AND FUNCTION OF PECTINS

D - g a l a c t o p y r a n o s y l u r o n i c a c i d u n i t s are m o n o e s t e r i f i e d w i t h a c e t i c
a c i d at 0-2 or 0 - 3 . The presence of a c e t y l groups, t h e r e f o r e ,
makes c e r t a i n p o t e n t i a l s o u r c e s of commercial p e c t i n , e.g., sugar
beet ( 5 ) , s u n f l o w e r , and p o t a t o , l e s s d e s i r a b l e .
N e u t r a l s u g a r s , p r i m a r i l y L-rhamnose, are a l s o p r e s e n t .
However, t h e r e i s disagreement over t h e i r d i s t r i b u t i o n i n the
l i n e a r c h a i n . One group of workers (6) r e p o r t e d t h a t , i n c i t r u s ,
a p p l e , and s u n f l o w e r p e c t i n s , L-rhamnopyranosyl u n i t s are more or
l e s s e v e n l y i n s e r t e d i n t o t h e g a l a c t u r o n a n c h a i n i n the f o l l o w i n g
manner: 0-a-D-GalpA-(1+2)-0-L-Rhap-(1+4)-0-a-D-GalpA. The
c o n f i g u r a t i o n " " o f the L-rhamnopyranosyl l i n k a g e " i s unknown, but
c a l c u l a t i o n s have shown t h a t i t s h o u l d be b e t a i n o r d e r t o p r o v i d e
the n e c e s s a r y degree of k i n k i n g i n the s t r u c t u r e (6) (See s e c t i o n
on P h y s i c a l P r o p e r t i e s ) .
Another group (7) r e p o r t e d t h a t the L-rhamnopyranosyl u n i t s
Downloaded by 189.229.145.72 on January 6, 2017 | http://pubs.acs.org

are q u i t e unevenly d i s t r i b u t e d w i t h i n t h e ~ g a l a c t u r o n a n backbone.

Publication Date: June 5, 1986 | doi: 10.1021/bk-1986-0310.ch001

These workers r e p o r t (8) t h a t a p p l e p e c t i n c o n s i s t s of "smooth"

regions [poly(a-D-galactopyranosyluronic a c i d ) r e g i o n s ] and
" h a i r y " r e g i o n s . " A c c o r d i n g to them, the l a t t e r r e g i o n s c o n s i s t of
rhamnogalacturonan sequences t h a t c o n t a i n h i g h l y branched
a r a b i n o g a l a c t a n s i d e c h a i n s and g a l a c t u r o n a n sequences w i t h s h o r t
s i d e c h a i n s composed of D - x y l o s e . The same may a l s o be t r u e of
sugar beet p e c t i n ( 5 ) .
The d a t a of the former group (9) a l s o i n d i c a t e s t h a t , however
the L-rhamnopyranosyl u n i t s o c c u r i n the c h a i n , the l e n g t h of the
p o l y T a - D - g a l a c t o p y r a n o s y l u r o n i c a c i d ) sequences between
L-rhamriopyranose i n t e r r u p t i o n s (whether s i n g l e u n i t s or b l o c k s of
u n i t s ) i s r a t h e r c o n s t a n t and t h a t the sequences are about 25
u n i t s l o n g i n each p e c t i n ( c i t r u s , a p p l e , s u n f l o w e r ) s t u d i e d .
The t o t a l c o n t e n t of n e u t r a l sugars v a r i e s w i t h t h e s o u r c e ,
the e x t r a c t i o n c o n d i t i o n s , and subsequent t r e a t m e n t s .
F e r u l i c a c i d i s e s t e r i f i e d t o the n e u t r a l sugar s i d e c h a i n s
of p e c t i n from s p i n a c h (j_0) and sugar beet (5,11).

Conformation

G e l s are formed when polymer m o l e c u l e s i n t e r a c t over a p o r t i o n of

t h e i r l e n g t h t o form a network t h a t e n t r a p s s o l v e n t and s o l u t e
m o l e c u l e s . The j u n c t i o n zones t h a t r e s u l t from t h e s e c h a i n
i n t e r a c t i o n s must be of l i m i t e d s i z e . I f they are too l a r g e , a
p r e c i p i t a t e , r a t h e r than a g e l , r e s u l t s . The i n s e r t e d
L-rhamnopyranosyl u n i t s may p r o v i d e the n e c e s s a r y i r r e g u l a r i t i e s
T k i n k s ) i n the s t r u c t u r e and l i m i t the s i z e of the j u n c t i o n zones.
The presence of " h a i r y " r e g i o n s may a l s o be a f a c t o r t h a t l i m i t s
the e x t e n t of c h a i n a s s o c i a t i o n . As w i l l be d i s c u s s e d f u r t h e r i n
the s e c t i o n on P h y s i c a l P r o p e r t i e s , j u n c t i o n zones are formed
between r e g u l a r , unbranched p e c t i n c h a i n s when the n e g a t i v e
charges on the c a r b o x y l a t e groups are removed ( a d d i t i o n of a c i d ) ,
h y d r a t i o n of the m o l e c u l e s i s reduced ( a d d i t i o n of a c o s o l u t e ) ,
and/or polymer c h a i n s are b r i d g e d by d i v a l e n t c a t i o n s ( c a l c i u m
i ons),
A n a l y s i s of p r o t o n n.m.r. s p e c t r a and m a t h e m a t i c a l model
b u i l d i n g suggests that i n d i v i d u a l a-D-galactopyranosyluronic a c i d
u n i t s have the ^C<| c o n f o r m a t i o n (6),~ Sodium and c a l c i u m p e c t a t e s ,

Fishman and Jen; Chemistry and Function of Pectins

ACS Symposium Series; American Chemical Society: Washington, DC, 1986.
 1. BEMILLER Pectins: Structure and Properties 5

p e c t i c a c i d , and p e c t i n i c a c i d a l l occur i n t h e s o l i d s t a t e
( f i b e r s ) as r i g h t - h a n d e d (3-|) h e l i c e s w i t h a t h r e e - f o l d screw a x i s
( t r i s a c c h a r i d e r e p e a t ) (12-15). I n s o l i d p e c t i n i c a c i d , the
polymer m o l e c u l e s pack so t h a t the c h a i n s a r e p a r a l l e l t o each
o t h e r ; the p e c t a t e s pack as c o r r u g a t e d s h e e t s o f a n t i p a r a l l e l
c h a i n s 0J4,JJ5).
I t i s f u r t h e r s u g g e s t e d t h a t j u n c t i o n zones i n p e c t i n i c a c i d
(HM-pectin p l u s s u c r o s e ) g e l s are formed by a columnar s t a c k i n g of
m e t h y l e s t e r groups t o form c y l i n d r i c a l h y d r o p h o b i c a r e a s p a r a l l e l
t o the h e l i x a x e s . Two models f o r the f o r m a t i o n o f j u n c t i o n zones
i n c a l c i u m p e c t a t e (LM-pectin) g e l s have been proposed. One
s u g g e s t s an a g g r e g a t i o n of c h a i n s by a c r o s s l i n k i n g of c a r b o x y l a t e
anions w i t h c a l c i u m i o n s t o form a s t r u c t u r e s i m i l a r t o t h a t o f
the c o r r u g a t e d s h e e t s of a n t i p a r a l l e l h e l i c e s (3~6 c h a i n s i n an
average j u n c t i o n zone) found i n s o l i d c a l c i u m p e c t a t e 0 5 ) . The
Downloaded by 189.229.145.72 on January 6, 2017 | http://pubs.acs.org

o t h e r i s the "egg box" model used t o d e s c r i b e the f o r m a t i o n of

Publication Date: June 5, 1986 | doi: 10.1021/bk-1986-0310.ch001

c a l c i u m a l g i n a t e g e l s 0 _ 6 , V 7 ) . T h i s model i s proposed because of

the c l o s e s i m i l a r i t y between (1->4)-linked poly(-D-galacto-
p y r a n o s y l u r o n i c a c i d ) segments o f p e c t i c a c i d and~"(1 -MJ-linked
p o l y ( a - L - g u l o - p y r a n o s y l u r o n i c a c i d ) segments o f a l g i n i c a c i d s ,
segments t h a t a r e m i r r o r images e x c e p t f o r the c o n f i g u r a t i o n at
C-3. From c i r c u l a r d i c h r o i s m and e q u i l i b r i u m d i a l y s i s s t u d i e s , i t
has been c o n c l u d e d t h a t i n t e r c h a i n a s s o c i a t i o n of h y d r a t e d
p e c t i n i c a c i d m o l e c u l e s , i n the presence o f swamping l e v e l s o f
monovalent c o u n t e r i o n s , i s l i m i t e d t o the f o r m a t i o n of dimers o f
c h a i n s o f 2y h e l i c a l symmetry w i t h s p e c i f i c s i t e - b i n d i n g of
c a l c i u m i o n s a l o n g one f a c e of each p a r t i c i p a t i n g c h a i n ( 1 8 , 1 9 ;
see a l s o r e f e r e n c e 20). 2 +
When C a i s the s o l e or p r i n c i p a l
c o u n t e r i o n , t h e s e dimers f u r t h e r aggregate w i t h o u t rearrangement,
2 +
l e a d i n g t o an a p p r o x i m a t e d o u b l i n g o f the amount o f C a bound
c o o p e r a t i v e l y (J_8,J_9). Based on a v a i l a b l e i n f o r m a t i o n , the
U n i l e v e r R e s e a r c h group (J_9) has concluded t h a t d r y i n g of a
c a l c i u m p e c t i n a t e g e l e f f e c t s a p o l y m o r p h i c phase t r a n s i t i o n i n
which a s s o c i a t e d , r e g u l a r , b u c k l e d c h a i n s w i t h t w o - f o l d symmetry
("egg box") as found i n L - g u l u r o n o g l y c a n c h a i n segments a r e
c o n v e r t e d i n t o a s s o c i a t e d c h a i n s w i t h t h r e e - f o l d symmetry as found
i n s o l i d s t a t e c a l c i u m p e c t i n a t e (12-15). I t s h o u l d be n o t e d t h a t
the a x i a l - a x i a l l i n k a g e s i n a c h a i n o f a l d o h e x o p y r a n o s y l u n i t s
l i n k e d 1+4 g i v e s a b u c k l e d c o n f o r m a t i o n n a t u r a l l y ( F i g u r e 1) and
t h a t t h e g e l s t r u c t u r e ( s ) i s ( a r e ) as yet not w e l l u n d e r s t o o d .

Physical Properties

P e c t i n s are s o l u b l e i n pure w a t e r , but they a r e i n s o l u b l e i n

aqueous s o l u t i o n s i n w h i c h they would g e l a t the same t e m p e r a t u r e
i f d i s s o l v e d a t a h i g h e r t e m p e r a t u r e . Monovalent c a t i o n ( a l k a l i
m e t a l ) s a l t s of p e c t i n i c and p e c t i c a c i d s a r e u s u a l l y s o l u b l e i n
water; d i - and t r i v a l e n t c a t i o n s a l t s are weakly s o l u b l e or
insoluble.
A l t h o u g h p e c t i n s a r e not employed as t h i c k e n i n g a g e n t s ,
p e c t i n s o l u t i o n s e x h i b i t the non-Newtonian, p s e u d o p l a s t i c b e h a v i o r
c h a r a c t e r i s t i c o f most p o l y s a c c h a r i d e s . As w i t h s o l u b i l i t y , the
v i s c o s i t y of a p e c t i n s o l u t i o n i s r e l a t e d t o t h e m o l e c u l a r w e i g h t ,
DE, and c o n c e n t r a t i o n o f the p r e p a r a t i o n and the pH and p r e s e n c e

Fishman and Jen; Chemistry and Function of Pectins

ACS Symposium Series; American Chemical Society: Washington, DC, 1986.
 6 CHEMISTRY A N D FUNCTION OF PECTINS
Downloaded by 189.229.145.72 on January 6, 2017 | http://pubs.acs.org
Publication Date: June 5, 1986 | doi: 10.1021/bk-1986-0310.ch001

F i g u r e 1. Alkaline d e p o l y m e r i z a t i o n o f a sequence of a p e c t i n i c
a c i d o f DE 25.

Fishman and Jen; Chemistry and Function of Pectins

ACS Symposium Series; American Chemical Society: Washington, DC, 1986.
 1. BE M I L L E R Pectins: Structure and Properties 1

of c o u n t e r i o n s i n the s o l u t i o n . For example, a d d i t i o n of

monovalent c a t i o n s e f f e c t s a r e d u c t i o n i n v i s c o s i t y , the degree of
which i s g r e a t e r w i t h d e c r e a s i n g DE. A d d i t i o n of s a l t s o f d i - and
t r i v a l e n t c a t i o n s has an o p p o s i t e e f f e c t ( 2 0 ) . I n g e n e r a l ,
v i s c o s i t y , s o l u b i l i t y , and g e l a t i o n a r e r e l a t e d , i . e . , f a c t o r s
t h a t i n c r e a s e g e l s t r e n g t h , f o r example, w i l l i n c r e a s e the
tendency t o g e l , decrease s o l u b i l i t y , and i n c r e a s e v i s c o s i t y , and
vice versa.
These p h y s i c a l p r o p e r t i e s o f p e c t i n s are a f u n c t i o n o f t h e i r
s t r u c t u r e which i s t h a t of a l i n e a r p o l y a n i o n ( p o l y c a r b o x y l a t e ) .
As s u c h , monovalent c a t i o n s a l t s o f p e c t i n s are h i g h l y i o n i z e d i n
s o l u t i o n , and the d i s t r i b u t i o n of i o n i c charges a l o n g the m o l e c u l e
tends t o keep i t i n an extended form by r e a s o n o f coulombic
r e p u l s i o n ( 2). F u r t h e r m o r e , t h i s same columbic r e p u l s i o n between
the c a r b o x y l a t e anions p r e v e n t s a g g r e g a t i o n o f the polymer c h a i n s .
Downloaded by 189.229.145.72 on January 6, 2017 | http://pubs.acs.org

(The number of n e g a t i v e charges i s , of c o u r s e , determined by the

Publication Date: June 5, 1986 | doi: 10.1021/bk-1986-0310.ch001

DE.) I n a d d i t i o n , each p o l y s a c c h a r i d e c h a i n , and e s p e c i a l l y each

c a r b o x y l a t e group, w i l l be h i g h l y h y d r a t e d . S o l u t i o n s of
monovalent s a l t s of p e c t i n s e x h i b i t s t a b l e v i s c o s i t y because each
polymer c h a i n i s h y d r a t e d , extended, and independent.
Because the commercial importance of p e c t i n i s p r e d o m i n a t e l y
the r e s u l t of i t s unique a b i l i t y t o form s p r e a d a b l e g e l s i n the
presence of a d e h y d r a t i n g agent (sugar) a t a pH a t or near 3 o r i n
the presence of c a l c i u m i o n (jams, j e l l i e s , and marmalades made
from f r u i t j u i c e s o r whole f r u i t ) , t h a t i s the p r o p e r t y most o f t e n
s t u d i e d and f o c u s e d upon. F a c t o r s t h a t determine whether g e l a t i o n
can occur and t h a t i n f l u e n c e g e l c h a r a c t e r i s t i c s are pH,
c o n c e n t r a t i o n o f c o s o l u t e s ( s u g a r s ) , c o n c e n t r a t i o n and type of
c a t i o n s , t e m p e r a t u r e , and p e c t i n c o n c e n t r a t i o n . The ways i n w h i c h
these f a c t o r s i n f l u e n c e g e l a t i o n a r e dependent upon the f o l l o w i n g
m o l e c u l a r p r o p e r t i e s of the s p e c i f i c p e c t i n : m o l e c u l a r weight
(Jp, degree o f e s t e r i f i c a t i o n (DE), degree of a m i d a t i o n (DA),
presence of a c e t a t e e s t e r s , and h e t e r o g e n e i t y . A l l these
parameters are i n t e r d e p e n d e n t . I n g e n e r a l , under s i m i l a r
c o n d i t i o n s , the degree of g e l a t i o n , the g e l l i n g t e m p e r a t u r e , and
the g e l s t r e n g t h a r e g e n e r a l l y p r o p o r t i o n a l t o each o t h e r and each
p r o p e r t y i s g e n e r a l l y p r o p o r t i o n a l t o the m o l e c u l a r weight and
i n v e r s e l y p r o p o r t i o n a l t o the DE.
As the pH i s l o w e r e d , i . e . , as the hydrogen i o n c o n c e n t r a t i o n
of the s o l u t i o n i s i n c r e a s e d , i o n i z a t i o n o f the c a r b o x y l a t e groups
i s r e p r e s s e d , i . e . , the h i g h l y h y d r a t e d c a r b o x y l a t e groups a r e
c o n v e r t e d i n t o o n l y s l i g h t l y h y d r a t e d c a r b o x y l i c a c i d groups. As
a r e s u l t of l o s i n g some of t h e i r c h a r g e , the p o l y s a c c h a r i d e
m o l e c u l e s no l o n g e r r e p e l each o t h e r over t h e i r e n t i r e l e n g t h ; and
as a r e s u l t o f l o s i n g some of the water o f h y d r a t i o n , they can
a s s o c i a t e over a p o r t i o n of t h e i r l e n g t h t o form a g e l . Apparent
pK v a l u e s (pH a t 50% d i s s o c i a t i o n ) v a r y w i t h the DE of the p e c t i n
(22); a 65% DE p e c t i n has an apparent pK of 3.55, w h i l e a 0 DE
p e c t i c a c i d has an apparent pK of 4.10. However, p e c t i n s w i t h
i n c r e a s i n g l y g r e a t e r degrees of m e t h y l a t i o n w i l l g e l a t somewhat
h i g h e r pH, undoubtedly because they have fewer c a r b o x y l a t e a n i o n s
at any g i v e n pH (See l a t e r p a r a g r a p h ) . pH a f f e c t s g e l t e x t u r e
more t h a n g e l s t r e n g t h .

Fishman and Jen; Chemistry and Function of Pectins

ACS Symposium Series; American Chemical Society: Washington, DC, 1986.
 8 CHEMISTRY AND FUNCTION OF PECTINS

I t i s g e n e r a l l y regarded t h a t g e l s form when p e c t i n

m o l e c u l e s , n o r m a l l y s t r o n g l y h y d r a t e d by water m o l e c u l e s , l o s e
some water o f h y d r a t i o n owing t o c o m p e t i t i v e h y d r a t i o n o f c o s o l u t e
molecules. Reduced h y d r a t i o n r e s u l t s i n g r e a t e r c o n t a c t between
p e c t i n c h a i n s , f o r m i n g j u n c t i o n zones ( p r i m a r i l y by means o f
hydrogen bonding) and r e s u l t i n g i n a network o f polymer c h a i n s
t h a t e n t r a p s water and s o l u t e m o l e c u l e s (^3). I n most jams,
j e l l i e s , and marmalades, t h e c o s o l u t e i s sugar ( s u c r o s e ) .
HM-pectins w i l l g e l o n l y i n t h e presence o f l a r g e c o n c e n t r a t i o n s
(at l e a s t 55% w/w) o f sugar. L M - p e c t i n w i l l g e l i n t h e absence o f
sugar ( i f a d i v a l e n t c a t i o n i s p r e s e n t ) , but i n c r e a s i n g t h e
s o l u b l e s o l i d s w i l l r a i s e t h e g e l l i n g temperature and g e l
strength.
L M - p e c t i n w i l l g e l o n l y i n t h e presence o f d i v a l e n t c a t i o n s .
Increasing the concentration of d i v a l e n t c a t i o n s (only calcium i o n
Downloaded by 189.229.145.72 on January 6, 2017 | http://pubs.acs.org

i s used i n food a p p l i c a t i o n s ) i n c r e a s e s t h e g e l l i n g temperature

Publication Date: June 5, 1986 | doi: 10.1021/bk-1986-0310.ch001

and g e l s t r e n g t h . D i v a l e n t c a t i o n s a r e unnecessary f o r t h e
f o r m a t i o n o f a HM-pectin g e l because o f t h e low number o f
c a r b o x y l a t e groups t h a t need t o be b r i d g e d and because o f t h e
f o r m a t i o n o f h y d r o p h o b i c a r e a s p a r a l l e l t o t h e h e l i x axes by a
columnar s t a c k i n g o f methyl e s t e r groups ( 1 5 ) .
Any system c o n t a i n i n g p e c t i n a t p o t e n t i a l g e l l i n g c o n d i t i o n s
( i . e . , n e c e s s a r y c o n c e n t r a t i o n o f an a p p r o p r i a t e p e c t i n , pH,
c o n c e n t r a t i o n o f c o s o l u t e s , and c o n c e n t r a t i o n of d i v a l e n t c a t i o n s )
must be prepared a t a temperature above t h e g e l l i n g t e m p e r a t u r e .
Then, as t h e hot p e c t i n s o l u t i o n i s c o o l e d , t h e thermal energy o f
the m o l e c u l e s d e c r e a s e s and t h e i r tendency t o form j u n c t i o n zones
upon c o l l i s i o n i n c r e a s e s . The temperature a t which g e l a t i o n
o c c u r s i s t h e g e l l i n g t e m p e r a t u r e . Gels made w i t h L M - p e c t i n form
r a p i d l y ; those made w i t h HM-pectin form s l o w l y . L M - p e c t i n g e l s
are t h e r m o r e v e r s i b l e ; HM-pectin g e l s a r e n o t .
The c o n c e n t r a t i o n o f p e c t i n r e q u i r e d f o r g e l f o r m a t i o n i s
i n v e r s e l y r e l a t e d to the concentration of s o l u b l e s o l i d s , f o r i n
general, i n c r e a s i n g the concentration of c o s o l u t e s , i . e . ,
d e c r e a s i n g the water a c t i v i t y , i n c r e a s e s t h e s i z e and number o f
j u n c t i o n zones. When o t h e r f a c t o r s a r e h e l d c o n s t a n t , i n c r e a s i n g
the c o n c e n t r a t i o n o f p e c t i n i n c r e a s e s t h e g e l s t r e n g t h because i t
i n c r e a s e s t h e number o f j u n c t i o n zones.
At c o n s t a n t pH, g e l s t r e n g t h o f HM-pectin g e l s i n c r e a s e s w i t h
i n c r e a s i n g DE, as does t h e r a t e o f g e l a t i o n . As t h e DE o f a
HM-pectin i s l o w e r e d , a lower pH i s r e q u i r e d f o r g e l a t i o n . A g a i n ,
t h i s can be e x p l a i n e d by t h e f a c t t h a t , as t h e DE i s l o w e r e d , even
though t h e pH r e q u i r e d t o produce a g i v e n percentage o f c a r b o x y l
groups i n t h e c a r b o x y l i c a c i d form i n c r e a s e s owing t o an i n c r e a s e
i n apparent pK (22), t h e a b s o l u t e number o f c o n t i g u o u s c a r b o x y l a t e
groups t h a t must be c o n v e r t e d i n t o u n i o n i z e d c a r b o x y l i c a c i d
groups b e f o r e c h a i n a s s o c i a t i o n can occur a l s o i n c r e a s e s . Thus,
as t h e DE o f a HM-pectin i s l o w e r e d , a g r e a t e r and g r e a t e r
percentage of c a r b o x y l a t e groups must be c o n v e r t e d i n t o f r e e
c a r b o x y l i c a c i d groups t o e f f e c t g e l a t i o n .
Among the commercial L M - p e c t i n s , those w i t h t h e l o w e s t DE
v a l u e s have t h e h i g h e s t g e l l i n g temperatures and t h e g r e a t e s t
requirement f o r d i v a l e n t c a t i o n s ( f o r c r o s s b r i d g i n g ) .

Fishman and Jen; Chemistry and Function of Pectins

ACS Symposium Series; American Chemical Society: Washington, DC, 1986.
 1. MIL L R Pectins: Structure and Properties 9

Ami d a t i o n r e s u l t s i n a h i g h e r g e l l i n g temperature and a

decreased need f o r a d i v a l e n t c a t i o n .
The d i s t r i b u t i o n of c a r b o x y l / c a r b o x y l a t e groups a l s o a f f e c t s
g e l a t i o n . P e c t i n s w i t h b l o c k s of m e t h y l e s t e r and c a r b o x y l groups
(as opposed t o a random d i s t r i b u t i o n ) g e n e r a l l y produce weaker
g e l s and have a g r e a t e r r e q u i r e m e n t f o r d i v a l e n t c a t i o n s .

Chemical P r o p e r t i e s

D i s s o l v e d p e c t i n s undergo d e e s t e r i f i c a t i o n and d e p o l y m e r i z a t i o n i n
aqueous systems. The pH of g r e a t e s t s t a b i l i t y i s about 4. A t pH
v a l u e s b o t h above and below 4, d e e s t e r i f i c a t i o n and
d e p o l y m e r i z a t i o n occur c o n c u r r e n t l y , w i t h the r a t e of
d e e s t e r i f i c a t i o n b e i n g g r e a t e r t h a n the r a t e o f d e p o l y m e r i z a t i o n .
The presence of s o l u t e s , which l o w e r s water a c t i v i t y , reduces the
Downloaded by 189.229.145.72 on January 6, 2017 | http://pubs.acs.org

r a t e s of both r e a c t i o n s .
Publication Date: June 5, 1986 | doi: 10.1021/bk-1986-0310.ch001

D e e s t e r i f i c a t i o n o c c u r s by normal a c i d - and b a s e - c a t a l y z e d
mechanisms of e s t e r h y d r o l y s i s . D e p o l y m e r i z a t i o n a t low pH v a l u e s
o c c u r s by means of a c i d - c a t a l y z e d h y d r o l y s i s of g l y c o s i d i c bonds
(24). A c i d - c a t a l y z e d h y d r o l y s i s occurs p r e f e r e n t i a l l y at the
L-rhamnopyranosyl g l y c o s i d i c bonds. H y d r o l y s i s of these l i n k a g e s
produces g a l a c t u r o n o g l y c a n c h a i n s w i t h a degree of p o l y m e r i z a t i o n
of about 25 (6,9). S i d e c h a i n s , p a r t i c u l a r l y those c o n t a i n i n g
L - a r a b i n o f u r a n o s y l u n i t s , s h o u l d a l s o be p r e f e r e n t i a l l y removed by
" h y d r o l y s i s because of the i n h e r e n t s t a b i l i t y t o a c i d - c a t a l y z e d
h y d r o l y s i s of g l y c u r o n o s y l g l y c o s i d i c bonds and the i n h e r e n t
l a b i l i t y of f u r a n o s y l g l y c o s i d i c bonds (24). However, i f the s i d e
c h a i n s are a t t a c h e d t o rhamnogalacturonan sequences (8), i t s h o u l d
not be p o s s i b l e t o c o n v e r t " h a i r y " r e g i o n s t o "smooth" r e g i o n s by
treatment w i t h a c i d because the l a b i l i t y of the L-rhamnopyranosyl
bonds would r e s u l t i n c o n c u r r e n t d e p o l y m e r i z a t i o n of the main
chain.
At pH v a l u e s o f 5-6 p e c t i n s o l u t i o n s are s t a b l e o n l y a t room
t e m p e r a t u r e . As the temperature i s r a i s e d , p e c t i n c h a i n s c l e a v e
by a b e t a - e l i m i n a t i o n r e a c t i o n (25~39) ( F i g u r e 1), a r e a c t i o n
which i s s t i m u l a t e d by o r g a n i c anions (40). D e e s t e r i f i c a t i o n of
p e c t i n proceeds s i m u l t a n e o u s l y w i t h the b e t a - e l i m i n a t i o n
d e p o l y m e r i z a t i o n r e a c t i o n , which o c c u r s o n l y a t monosaccharide
u n i t s t h a t are e s t e r i f i e d . A t pH v a l u e s above 6, d e e s t e r i f i c a t i o n
and d e p o l y m e r i z a t i o n a r e r a p i d r e a c t i o n s even at room t e m p e r a t u r e ,
the r a t e o f each r e a c t i o n i n c r e a s i n g w i t h i n c r e a s i n g pH.
H y d r o x y l - g r o u p r e a c t i o n s , such as e t h e r i f i c a t i o n , a c e t a l a t i o n
(4j_), e s t e r i f i c a t i o n (42-51 ), and o x i d a t i o n , can be done i n the
same manner as they are on o t h e r p o l y s a c c h a r i d e s . Esterifications
(47) o f c a r b o x y l groups and i n t e r a c t i o n s w i t h c a t i o n s , i n c l u d i n g
p o l y c a t i o n s such as p r o t e i n s below t h e i r i s o e l e c t r i c pH, o c c u r a s
they do w i t h o t h e r g l y c u r o n o g l y c a n s . R e d u c t i o n o f c a r b o x y l groups
t o hydroxyraethyl groups has been done w i t h diborane (52, see a l s o
53) and by b o r o h y d r i d e treatment o f methyl and h y d r o x y e t h y l e s t e r s
(54). R e d u c t i o n of c a r b o x y l groups which have been a c t i v a t e d w i t h
a w a t e r - s o l u b l e c a r b o d i i m i d e s h o u l d be s t r a i g h t f o r w a r d (55,56).
When ammonia (57-61) i s used t o p r e p a r e L M - p e c t i n from
HM-pectin, some o f the methyl c a r b o x y l a t e groups a r e c o n v e r t e d
i n t o carboxaraide groups, p r o d u c i n g "amidated p e c t i n " . The

Fishman and Jen; Chemistry and Function of Pectins

ACS Symposium Series; American Chemical Society: Washington, DC, 1986.
 10 CHEMISTRY A N D FUNCTION O F PECTINS

presence o f amide groups i n an L M - p e c t i n makes t h e m o l e c u l e s l e s s

h y d r o p h i l i c , i n c r e a s i n g t h e i r tendency t o form g e l s , and l e s s
s e n s i t i v e t o c a l c i u m i o n s . I n g e n e r a l , t h e g e l l i n g temperature
i n c r e a s e s w i t h i n c r e a s i n g DA. P e c t i n amides can a l s o be made by
r e a c t i o n o f p e c t i n s w i t h p r i m a r y and secondary a l k y l a m i n e s
(62-64).
There a r e s e v e r a l types o f enzymes t h a t a c t on p e c t i n
molecules. Those enzymes produced by t h e h i g h e r p l a n t s t h e m s e l v e s
play a s i g n i f i c a n t r o l e i n t h e processes r e s u l t i n g i n t e x t u r a l
changes i n f r u i t s and v e g e t a b l e s d u r i n g r i p e n i n g , s t o r a g e , and
p r o c e s s i n g ( 6 5 - 6 7 ) . F u n g a l enzyme p r e p a r a t i o n s a r e used by t h e
f r u i t j u i c e i n d u s t r y t o improve t h e c l a r i t y o f j u i c e s and t h e
y i e l d from p r e s s i n g ( 6 6 - 6 7 ) . C o n t r o l o f t h e i r a c t i o n i s important
to the production o f p e c t i n .
P e c t i n e s t e r a s e s c a t a l y z e h y d r o l y s i s o f t h e m e t h y l e s t e r group
Downloaded by 189.229.145.72 on January 6, 2017 | http://pubs.acs.org

(68). Because many p e c t i n e s t e r a s e s a c t p r e f e r e n t i a l l y on a m e t h y l

Publication Date: June 5, 1986 | doi: 10.1021/bk-1986-0310.ch001

-D-galactopyranosyluronate u n i t a d j a c e n t t o an n o n e s t e r i f i e d
-TJ-galactopyranosyluronic a c i d u n i t , t h e y produce p e c t i n s t h a t
c o n t a i n b l o c k s , r a t h e r than a random d i s t r i b u t i o n , o f c a r b o x y l
groups ( 6 8 ) and t h a t a r e g e n e r a l l y u n d e s i r a b l e f o r commercial u s e .
Some f u n g a l p e c t i n e s t e r a s e s , however, produce L M - p e c t i n s t h a t a r e
s i m i l a r t o p e c t i n s d e e s t e r i f i e d w i t h a c i d s o r bases w i t h r e s p e c t
t o g e l l i n g a b i l i t y (69) and s e n s i t i v i t y t o c a l c i u m i o n s ( 7 0 ) .
S e v e r a l t y p e s o f l y a s e s o r t r a n s e l i m i n a s e s a r e known ( 6 8 ) .
A l l c a t a l y z e d e p o l y m e r i z a t i o n by a b e t a - e l i m i n a t i o n r e a c t i o n l i k e
that which occurs during base-catalyzed depolymerization. Pectin
l y a s e s , a l l o f which a r e endo-enzyraes, c a t a l y z e b e t a - e l i m i n a t i o n s
at e s t e r i f i e d D - g a l a c t u r o n i c a c i d u n i t s (See F i g u r e 1) ( 6 8 ) .
-
Pectate l y a s e s c a t a l y z e beta-eliminations at n o n e s t e r i f i e d
D - g a l a c t u r o n i c a c i d u n i t s . B o t h exo- and endo-pectate l y a s e s a r e
liown (68).
P o l y g a l a c t u r o n a s e s d e p o l y m e r i z e p e c t i n s by c a t a l y z i n g
h y d r o l y s i s o f g l y c o s i d i c bonds ( 6 8 , 7 J . ) . The f a c t t h a t t h e r a t e o f
d e p o l y m e r i z a t i o n i s i n v e r s e l y p r o p o r t i o n a l t o t h e DE s u g g e s t s a
requirement f o r a n o n e s t e r i f i e d D-galacturonic a c i d u n i t .
Exo-polygalacturonases r e l e a s e mono- o r d i s a c c h a r i d e s from
n o n r e d u c i n g t e r m i n i ; e n d o - p o l y g a l a c t u r o n a s e s a t t a c k randomly ( 6 8 ) .

Literature Cited
1. Kertesz, . I.; Baker, G. I.; Joseph, G. H.; Mottern, H. H.;
Olsen, A. G. Chem. Eng. News 1944, 22, 105.
2. Pedersen, J. "Pectin", in "Industrial Gums"; Academic Press:
Orlando, 3rd ed., 1986.
3. Stephen, A. M. "Other Plant Polysaccharides", in "The
Polysaccharides"; Academic Press: New York, Vol. 2, 1983.
4. Fishman, M. L.; Pepper, L.; Damert, W. C.; Barford, R. A.
This Volume.
5. Rombouts, F. M. This Volume.
6. Rees, D. .; Wight, A. W. J. Chem. Soc. 1971, 1366.
7. de Vries, J. .; Rombouts, F. M.; Voragen, A. G. J.; Pilnik,
W. Carbohydr. Polym. 1982, 2, 25.
8. de Vries, J. .; Voragen, A. G. J.; Rombouts, F. M.; Pilnik,
W. This Volume.

Fishman and Jen; Chemistry and Function of Pectins

ACS Symposium Series; American Chemical Society: Washington, DC, 1986.
 I. BeMILLER Pectins: Structure and Properties 11

9. Powell, D. A.; Morris, E. R.; Gidley, M. J.; Rees, D. A. J.

Mol. Biol. 1982, 155, 517.
10. Fry, S. C. Planta 1983, 157, 111.
11. Rombouts, F. M.; Pilnik, W. Proc. Intern. Workshop Plant
Polysaccharides, Structure Function, Nantes, France, 9-11
July 1984, p. 19.
12. Palmer, K. J.; Hartzog, M. B. J. Am. Chem. Soc. 1945, 67,
2122.
13. Sathyanarayana, . K.; Rao, V. S. R. Curr. Sci. 42, 1973,
773.
14. Walkinshaw, M. D.; Arnott, S. J. Mol. Biol. 1981, 153,
1055.
15. Walkinshaw, M. D.; Arnott, S. J. Mol. Biol. 1981, 153,
1075.
16. Grant, G. T.; Morris, E. R.; Rees, D. .; Smith, P. J. C.;
Thorn, D. FEBS Lett. 1973, 32, 195.
Downloaded by 189.229.145.72 on January 6, 2017 | http://pubs.acs.org
Publication Date: June 5, 1986 | doi: 10.1021/bk-1986-0310.ch001

17. Morris, E. R.; Rees, D. .; Thorn, D.; Boyd, J. Carbohydr.

Res. 1978, 66, 145.
18. Gidley, M. J . ; Morris, E. R.; Murray, E. J.; Powell, D. .;
Rees, D. A. J. Chem. Soc. Chem. Commun. 1979, 990.
19. Morris, E. R.; Powell, D. .; Gidley, M. J . ; Rees, D. A. J.
Mol. Biol. 1982, 155, 507.
20. Thibault, J. F.; Rinaudo, M. This Volume.
21. Paoletti, S. This Volume.
22. Plaschina, I. G.; Braudo, . E.; Tolstoguzov, V. .
Carbohydr. Res. 1978, 60, 1.
23. Crandall P. G. This Volume.
24. BeMiller, J. N. Advan. Carbohydr. Chem. 1967, 22, 25.
25. Schneider, G.; Fritschi, U. Ber. 1936, 69, 2537.
26. Hinton, C. L. Food Invest., Special Rep. 1939, No. 48;
4
Chem. Abstr. 1940, 34, 1090 .
27. Bulmer, H. P., and Co., Ltd.; Garrick, P. Brit. Patent
625 675, 1949; Chem. Abstr. 1950, 44, 245e.
28. Vollmert, B. Angew. Chem. 1949, 61, 329.
29. Vollmert, B. Angew. Chem. 1950, 5, 110.
30. Kenner, J. Chem. Ind. (London) 1955, 727.
31. BeMiller, J. N.; Whistler, R. L. Advan. Carbohydr. Chem.
1958, 13, 289.
32. Neukom, H.; Deuel, H. Chem. Ind. (London) 1958, 683.
33. Albersheim, P. Biochem. Biophys. Res. Commun. 1959, 1, 253.
34. Krachanov, Khr. G.; Dimitrov, D. Nauchni Tr., Visshiya Inst.
Khranitelna Vkusova Prom.-Plovdiv 1965, 12, 301; Chem. Abstr.
1966, 64, 16194c.
35. Albersheim, P.; Neukom, H.; Deuel, H. Arch. Biochem.
Biophys. 1960, 90, 46.
36. Launer, H.; Tomimatsu, Y. J. Org. Chem. 1961, 26, 541.
37. Neukom, H. Peut. Lebensm.-Rundschau 1965, 61, 35; Chem.
Abstr. 1965, 62, l6548d.
38. Kiss, J. Advan. Carbohydr. Chem. Biochem. 1974, 29, 229.
39. Van Buren, J. P. This Volume.
40. Keijbets, M. J. H.; Pilnik, W. Carbohydr. Res. 1974, 33,
359.
41. Deuel, H. Helv. Chim. Acta 1947, 30, 1269.

Fishman and Jen; Chemistry and Function of Pectins

ACS Symposium Series; American Chemical Society: Washington, DC, 1986.
 12 CHEMISTRY AND FUNCTION OF PECTINS
42. Bock, H.; Simmerl, J . ; Josten, M. J. Prakt. Chem. 1941,
158, 8.
43. Carson, J. F.; Maclay, W. D. J. Am. Chem. Soc. 1945, 67,
787.
44. Speiser, R.; Eddy, C. R. J. Am. Chem. Soc. 1946, 68, 287.
45. Carson, J. F.; Maclay, W. D. J. Am. Chem. Soc. 1946, 68,
1015.
46. Deuel, H. Helv. Chim. Acta 1947, 30, 1269.
47. Deuel, H. Helv. Chim. Acta 1947, 30, 1523.
48. Lampitt, L. H.; Money, R. W.; Uric, .; Judge, . E. J. Soc.
Chem. Ind. 1948, 67, 101.
49. Schlubach, H. H.; Hoffman-Walbeck, H. P. Makromol. Chem.
1949, 4, 5.
50. Cannav, .; Chiarlo, . Med, sper. 1955, 26, 114; Chem.
Abstr. 1956, 50, 8911f.
Downloaded by 189.229.145.72 on January 6, 2017 | http://pubs.acs.org
Publication Date: June 5, 1986 | doi: 10.1021/bk-1986-0310.ch001

51. Alburn, . E.; Seifter, J. U. S. Patent 2 729 633, 1956;

Chem. Abstr. 1956, 50, 8144b.
52. Smith, F.; Stephen, A. M. Tetrahedron Lett. 1960, 7, 17.
53. Aspinall, G. O.; Fanshawe, R. S. J. Chem. Soc. 1961, 4215.
54. Aspinall, G. O.; Canas-Rodrigues, A. J. Chem. Soc. 1958,
4020.
55. Taylor, R. L.; Conrad, . E. Biochemistry 1972, 11, 1383.
56. Taylor, R. L.; Shively, J. E.; Conrad, . E. Methods
Carbohydr. Chem. 1976, 7, 149.
57. Kieser, A. H.; Bryant, . F. Food Technol. 1949, 3, 85.
58. Mitchell, W. A. Food Technol. 1950, 4, 135.
59. Sohns, J . ; Denzler, .; Deuel, H. Helv. Chim. Acta 1954,
37, 2153.
60. Sohns, J . ; Deuel, h. J. Polym. Sci. 1954, 12, 551.
61. Dargel, D.; Hock, A. Arch. Tierernaehr. 1967, 17, 197;
Chem. Abstr. 1967, 67, 82346n.
62. Carson, J. F. J. Am. Chem. Soc. 1946, 68, 2723.
63. Carson, J. F. U. S. Patent 2 520 123, 1950; Chem. Abstr.
1950, 44, 10733c.
64. Deuel, H.; Neukom, H. Nature 1947, 159, 882.
65. Van Buren, J. P. J. Texture Stud. 1979, 10, 1.
66. McFeeters, R. F. This Volume.
67. Voragen, A. G. J.; Schols, . .; Siliha, . A. I.; Pilnik, W.
This Volume.
68. Rexov-Benkov, L., Markovi, O. Advan. Carbohydr. Chem.
Biochem. 1976, 33, 323.
69. Ishii, S.; Kino, K.; Sugiyama, S.; Sugimoto, H. J. Food Sci.
1979, 44, 611.
70. Kohn, R.; Markovic, O.; Machov, . Coll. Czech. Chem.
Commun. 1983, 48, 790.
71. Pressey, R.; Russell, R. B. This Volume.
RECEIVED December 20, 1985

Fishman and Jen; Chemistry and Function of Pectins

ACS Symposium Series; American Chemical Society: Washington, DC, 1986.