Citrus Plant

5
Flavonoids and Citrus Quality
RUSSELL L. ROUSEFF
Florida Department of Citrus, Institute of Food and Agricultural Sciences,

Agricultural Research and Education Center, P.O. Box 1088,
Lake Alfred, FL 33850
Downloaded by CORNELL UNIV on September 1, 2016 | http://pubs.acs.org
Publication Date: December 15, 1980 | doi: 10.1021/bk-1980-0143.ch005
Flavonoids are one of the most widely distributed and di

verse chemical groups i n the plant kingdom. While flavonoids can
be found i n nature in many organisms, from bacteria to higher
plants, they are most prevalent i n the higher plants. They have
been found i n the roots, stems, flowers, pollen, fruit, seeds,
wood and bark.
In terms of chemical structure, flavonoids are C compounds 15
arranged C -C -C with the central group usually linked with oxy

6 3 6
gen and numbered as shown below:
These compounds are differentiated primarily by the oxida

tion state of the central three carbon atom u n i t . Thus, as shown
in Figure 1, some compounds are c l a s s i f i e d as flavones, flava-
nones, flavonols, anthocyanins, etc. (The A and Β rings have
been l e f t off for clarity). A secondary means of differentiating
flavonoids i s by the position and numbers of attached hydroxy,
methoxy or sugar units. In c i t r u s , flavonoids usually occur as
glycosides, although the polymethoxylated flavones are a notable
exception.
Metabolically flavonoids can be thought of as a combination
of two d i s t i n c t u n i t s : 1) the C5 fragment o f the A r i n g and 2)
the C3-C6 fragment o f the Β r i n g . However, w h i l e s i g n i f i c a n t
progress has been made i n the areas o f b i o l o g i c a l o r i g i n s and
i n t e r r e l a t i o n s h i p s o f f l a v o n o i d compounds the exact b i o l o g i c a l
f u n c t i o n o f these compounds remains a mystery.
Q u a l i t y i n any food product i s u s u a l l y defined i n terms o f a
0-8412-0595-7/80/47-143-083$06.50/0
© 1980 American Chemical Society
Nagy and Attaway; Citrus Nutrition and Quality

ACS Symposium Series; American Chemical Society: Washington, DC, 1980.
84 CITRUS NUTRITION AND QUALITY
II FLAVONOLS
C-OH
C —
CH-
XHOH C-OH
FLAVANONOLS FLAVONES ANTHOCYANINS
LEUCOANTHOCYANINS FLAVANONES
Figure 1. Flavonoid structures and nomenclature as determined by the central

C group (A and Β rings have been left off)
3

5. ROUSEFF Flavonoids and Citrus Quality 85
number of f a c t o r s . These f a c t o r s are u s u a l l y evaluated by the

human senses, namely, s i g h t , t a s t e , touch and s m e l l . The primary
sense i n e v a l u a t i n g a food item i s t a s t e , although other senses,
such as s i g h t and s m e l l , can i n f l u e n c e the perception of t a s t e .
Flavonoids play a major r o l e i n the determination o f c i t r u s q u a l
i t y p r i m a r i l y due to the t a s t e of flavanone neohesperiodosides.
Flavonoids do not play a s i g n i f i c a n t r o l e i n the v i s u a l d e t e r
mination o f f r u i t or j u i c e q u a l i t y . Although many f l a v o n o i d s i n
the p l a n t kingdom are h i g h l y c o l o r e d , most c i t r u s f l a v o n o i d s are
c o l o r l e s s . The compounds r e s p o n s i b l e f o r the deep y e l l o w s and
oranges i n c i t r u s are c a r o t e n o i d s . Flavonoids play a s i g n i f i c a n t
r o l e i n human n u t r i t i o n but s i n c e t h i s area i s the s u b j e c t of
chapter 3, the present d i s c u s s i o n w i l l be l i m i t e d to how f l a
vonoids a f f e c t c i t r u s q u a l i t y .
P h y s i c a l and Chemical C h a r a c t e r i s t i c s
Chemical and p h y s i c a l p r o p e r t i e s of i n d i v i d u a l c i t r u s f l a
vonoids and f l a v o n o i d s i n general have been discussed i n other
reviews U-5.). In the f l a v o n o i d molecule the A and Β r i n g s are
s t a b l e and r e l a t i v e l y u n r e a c t i v e . The c e n t r a l C3 group i s the
most r e a c t i v e p o r t i o n o f the molecule, e s p e c i a l l y i f l i n k e d w i t h
oxygen to form a h e t e r o c y c l i c r i n g . The dihydropyrone r i n g of
flavanones i s very r e a c t i v e and r e a d i l y undergoes r i n g opening
r e a c t i o n s w i t h base or a c e t i c anhydride ( 3 ) . However, f l a v o n o i d s
are g e n e r a l l y s t a b l e under normal processing or storage c o n d i
t i o n s . Flavonoid p h y s i c a l p r o p e r t i e s , such as UV absorption
spectrum and s o l u b i l i t y are h i g h l y dependent on the bonding and
arrangement of the atoms i n the C group. S i g n i f i c a n t s h i f t s are
3
observed i n the absorption maxima from the UV spectra of f l a v o

noids -when r i n g opening o r complexing reagents are i n t r o d u c e d .
Thus, much s t r u c t u r a l i n f o r m a t i o n can be i n f e r r e d from the spec
t r a l changes of these compounds ( 6 ) . There i s l i t t l e enzymatic
a c t i v i t y to a l t e r the f l a v o n o i d composition during storage as the
f r e s h l y e x t r a c t e d j u i c e i s p a s t e u r i z e d to i n a c t i v a t e most enzymes.
H e s p e r i d i n S o l u b i l i t y . H e s p e r i d i n , a t a s t e l e s s flavanone
g l y c o s i d e , i s the l e a s t s o l u b l e of a l l c i t r u s f l a v o n o i d s . It is
found i n p r a c t i c a l l y every v a r i e t y of c i t r u s (5) and i s the major
f l a v o n o i d i n sweet oranges and lemons. In f r u T t or l e a v e s ,
h e s p e r i d i n i s found as a s o l u b l e complex which can be e x t r a c t e d
w i t h water or a l c o h o l ( 5 ) . During j u i c e e x t r a c t i o n , the complex
i s destroyed and hesperTdin s l o w l y p r e c i p i t a t e s as f i n e , w h i t e ,
needle-shaped c r y s t a l s . Once i n the s o l i d form, h e s p e r i d i n can
be r e d i s s o l v e d i n formamide, p y r i d i n e or i n d i l u t e a l k a l i .
Hesperidin c r y s t a l s are found i n f r o s t damaged oranges (8)
where c e l l s have been d i s r u p t e d due to the formation of i c e
c r y s t a l s . I t o c c a s i o n a l l y p r e c i p i t a t e s out o f concentrated
orange j u i c e products during storage and i s o f t e n found as a

t h i n c r u s t on the surfaces of f a l l i n g f i l m evaporators used i n

the production of f r o z e n orange concentrate (9). Hesperidin
c r y s t a l s have a l s o been found to coat the surface of j u i c e ex
t r a c t o r s . This c r u s t reduces the r a t e o f evaporator heat ex
change which adds to the energy costs and slows the r a t e of con
c e n t r a t e p r o d u c t i o n . I f the evaporator surfaces are not cleaned
p e r i o d i c a l l y , h e s p e r i d i n c r y s t a l s w i l l f l a k e o f f i n t o the con
centrated j u i c e . J u i c e c o n t a i n i n g excessive amounts of hesper
i d i n c r y s t a l s i s downgraded (10). Shown i n Figure 2 are a c c e p t
able and unacceptable amounts of h e s p e r i d i n c r y s t a l s from 710 ml
of r e c o n s t i t u t e d orange j u i c e . I t should be pointed out t h a t the
presence of h e s p e r i d i n c r y s t a l s i n a c i t r u s product i s a v i s u a l
d e f e c t and does not a f f e c t the f l a v o r of the product.
Naringin S o l u b i l i t y . N a r i n g i n , the major f l a v o n o i d i n grape-

f r u i t and pummel ο, has been observed (11) to c r y s t a l i z e i n canned

f r u i t or j u i c e during storage. This problem was found p r i m a r i l y
when s l i g h t l y immature f r u i t was used. Since n a r i n g i n concen
t r a t i o n s are highest i n immature f r u i t and g e n e r a l l y decrease as
the f r u i t matures, the e a s i e s t way to prevent t h i s p r e c i p i t a t i o n
problem i s to use mature f r u i t . Another means of reducing the
n a r i n g i n content i s to reduce or e l i m i n a t e from the f i n a l product
those p o r t i o n s of the f r u i t c o n t a i n i n g high n a r i n g i n c o n c e n t r a
t i o n s , i . e . , the albedo and segment membrane.
Methods of Analysis
The establishment of p r e c i s e o b j e c t i v e measurements f o r

c i t r u s q u a l i t y has been hindered by the l a c k of good a n a l y t i c a l
methods and the l a c k of consensus on a common d e f i n i t i o n of
q u a l i t y . The e v a l u a t i o n of b i t t e r n e s s i s a prime example.
I d e a l l y the method should be r a p i d , s p e c i f i c , accurate and i n
expensive. U n f o r t u n a t e l y , no method has been developed t h a t
s a t i s f i e s a l l f o u r c r i t e r i a . Compromises and t r a d e - o f f s must be
made.
One of the e a r l i e s t methods to measure the b i t t e r n a r i n g i n
and other flavanones i n g r a p e f r u i t j u i c e was developed by W. B.
Davis i n 1947 (12!). This t e s t i s based on the r e a c t i o n of d i l u t e
a l k a l i w i t h flavanones to form the corresponding y e l l o w chalcones.
The flavanone c o n c e n t r a t i o n i s then determined by measuring the
absorbance of the chalcones a t 427 nm. Davis pointed out t h a t
the procedure was not s p e c i f i c f o r any flavanone but could be
used to determine the p r i n c i p l e flavanones i n c i t r u s j u i c e , i . e . ,
n a r i n g i n i n g r a p e f r u i t j u i c e and h e s p e r i d i n i n orange j u i c e .
He suggested t h a t the method might a l s o be s u i t a b l e f o r the
determination of flavones and f l a v o n o l s . This method i s s t i l l
widely used to measure n a r i n g i n i n g r a p e f r u i t j u i c e ; a l b e i t i t
i s not s p e c i f i c f o r n a r i n g i n , i t i s a s i m p l e , r a p i d and inexpen
s i v e method of a n a l y s i s . However, s i n c e g r a p e f r u i t contains
both b i t t e r and n o n b i t t e r flavanone g l y c o s i d e s , Davis values are
only a crude approximation of b i t t e r n e s s .

ROUSEFF Flavonoids and Citrus Quality
SCORING GUIDE
FOR HESPERIDIN
FROZEN CONCENTRATED ORANGE JUICE
AND CONCENTRATED ORANGE FOR MFG.
UNACCEPTABLE ACCEPTABLE
Figure 2. USD A visual aids used ίο determine acceptable and unacceptable

amounts of hesperidin crystals in orange juice

Other c o l o r i m e t r i c methods have been developed to determine

f l a v o n o i d b i t t e r n e s s i n c i t r u s products (1^3, 1^, 15^ jJ6). The
b a s i c approach i n v o l v e s the a d d i t i o n of a reducing agent, such as
sodium borohydride or magnesium, to j u i c e f o l l o w e d by the a d d i t i o n
of HC1 to form a c h a r a c t e r i s t i c c o l o r . A g a i n , the c o l o r i s due
to both b i t t e r and n o n b i t t e r flavanone g l y c o s i d e s i n a d d i t i o n to
the t a s t e l e s s flavanone aglycones. An o l d e r and even l e s s
s p e c i f i c method i s the f e r r i c c h l o r i d e method (17^, 18) f o r
n a r i n g i n . U n f o r t u n a t e l y , t h i s method r e a c t s w i t h many f l a v o n o i d s ,
both b i t t e r and n o n b i t t e r , as w e l l as c i t r i c a c i d and other hy-
droxy compounds present i n the j u i c e .
D i r e c t u l t r a v i o l e t s p e c t r o p h o t o m e t r y methods have been
developed to measure n a r i n g i n i n g r a p e f r u i t (19) and h e s p e r i d i n
i n orange j u i c e (20, 21). While these methods are r a p i d , they
are a l s o n o n s p e c i f i c f o r f l a v o n o i d b i t t e r n e s s .
Chromatographic methods were developed to separate a few of

the c i t r u s f l a v o n o i d s from the complex mixture of c i t r u s f l a v o n -
o i d s . The e a r l y paper chromatographic methods f o r flavanones
(22, 23) were d i f f i c u l t to quanti t a t e because of band broadening
and uneven s o l v e n t development. Several t h i n l a y e r chromato-
graphic (TLC) methods were developed to separate the b i t t e r from
the n o n b i t t e r flavanone g l y c o s i d e s (24^, 2!5, 26, 27).
G a s - l i q u i d chromatography (GLC) has not been employed f o r
the a n a l y s i s of flavanone g l y c o s i d e s because they are n o n - v o l -
a t i l e and t h e r m a l l y u n s t a b l e . One GLC method (28) has been de-
veloped f o r the a n a l y s i s of the flavanone aglycones. However,
the method i s extremely time consuming i n t h a t the samples must
be e x t r a c t e d , hydrolyzed and d e r i v a t i z e d before a n a l y s i s .
Furthermore, the procedure cannot d i s t i n g u i s h between b i t t e r and
nonbitter flavonoids.
S w i f t (28) developed a TLC-spectrophotometric a n a l y s i s of
f i v e methoxylated flavones from orange p e e l . Since the a n a l y s i s
c o n s i s t e d of two s t a g e s , one f o r s e p a r a t i o n and the l a s t f o r
q u a n t i t a t i o n , the a n a l y s i s was r a t h e r time consuming and a l s o
s u b j e c t to some p o s i t i v e e r r o r s due to incomplete sample sep-
a r a t i o n . Tatum et a K (29) developed several d i r e c t TLC methods
f o r methoxylated and hydroxylated f l a v o n e s , coumarins and
psoralens i n c i t r u s . Maier and M e t z l e r (30) developed a semi-
q u a n t i t a t i v e , two-dimensional TLC procedure to determine a number
of c i t r u s f l a v a n o n e s , f l a v a n o l s , f l a v o n e s , coumarins and psoralen
aglycones. High performance l i q u i d chromatographic methods
(HPLC) have been developed f o r the separation of n a r i n g i n from
n a r i r u t i n (3l_, 32) i n c i t r u s j u i c e s . A method to determine the
major methoxylated flavones i n c i t r u s has been developed (33).
Gradient e l u t i o n HPLC has been employed to separate a wide
v a r i e t y of c i t r u s flavanone g l y c o s i d e s , coumarins and psoralens
(34). Thus, w i t h the recent improvements i n methodology, i t i s
now p o s s i b l e to evaluate the r e l a t i v e c o n t r i b u t i o n of i n d i v i d u a l
c i t r u s f l a v o n o i d s because the c o n c e n t r a t i o n of each can now be
r a p i d l y and a c c u r a t e l y measured.

C i t r u s Flavonoids as Q u a l i t y Factors
Flavonoids have no odor or mouth f e e l and, i n g e n e r a l , do

not c o n t r i b u t e s i g n i f i c a n t l y to the c o l o r of most c i t r u s j u i c e s .
T h e i r primary e f f e c t on c i t r u s q u a l i t y i s due to the b i t t e r t a s t e
of c e r t a i n flavanone g l y c o s i d e s . Thus, q u a n t i t a t i v e d e s c r i p t i o n s
of d e s i r a b l e c i t r u s q u a l i t i e s are u s u a l l y based on the absence
or maximum c o n c e n t r a t i o n l i m i t s f o r these compounds.
B i t t e r n e s s i s a g e n e r a l l y u n d e s i r a b l e f l a v o r component and
i s u s u a l l y d e t r i m e n t a l to the q u a l i t y of c i t r u s products. Any
b i t t e r n e s s i n orange or tangerine products reduces t h e i r q u a l i t y ,
whereas, a l i t t l e b i t t e r n e s s i s a c t u a l l y d e s i r a b l e f o r g r a p e f r u i t
products. However, i t has been shown (35) t h a t as the concen-
t r a t i o n of b i t t e r m a t e r i a l s i n c r e a s e , f l a v o r scores and o v e r a l l
product a c c e p t a b i l i t y decrease. Thus, excessive b i t t e r n e s s i s
u s u a l l y considered o b j e c t i o n a b l e and the F l o r i d a Department of

C i t r u s has enacted r e g u l a t i o n s which l i m i t the amount of n a r i n g i n
which may be present during the e a r l y weeks of the season (36).
I t i s d i f f i c u l t to q u a n t i t a t i v e l y d e f i n e g r a p e f r u i t q u a l i t y i n
terms of b i t t e r n e s s because i n d i v i d u a l t a s t e thresholds and
b i t t e r n e s s preferences vary markedly. Guadagni et^ al_. (37) found
t h a t 7% of a 27 member t a s t e panel could d e t e c t as l i t t l e as 1.5
ppm n a r i n g i n i n water. Y e t , another 7% of t h a t same panel could
not d i s t i n g u i s h a 50 ppm n a r i n g i n s o l u t i o n from water alone.
This represents over a 30-Fold d i f f e r e n c e i n t a s t e t h r e s h o l d s .
F e l l e r s (38) used a l a r g e population of g r a p e f r u i t j u i c e
users to evaluate n a r i n g i n b i t t e r n e s s preference l e v e l s . Some of
h i s data i s shown i n Table I. Using a low n a r i n g i n j u i c e he
added various amounts of n a r i n g i n to d i f f e r e n t l o t s of the same
j u i c e . The t a s t e r s were not t o l d the j u i c e s contained d i f f e r e n t
b i t t e r n e s s l e v e l s but were asked to evaluate each j u i c e on a s i x
p o i n t s c a l e from poor = 1 to e x c e l l e n t = 6 . As expected f l a v o r
scores f e l l as the n a r i n g i n content of the j u i c e i n c r e a s e d .
Correspondingly, the percentage of the panel t h a t thought the
j u i c e was too b i t t e r increased w i t h i n c r e a s i n g n a r i n g i n concen-
t r a t i o n . However, the s u r p r i s i n g r e s u l t o f t h i s study was t h a t
at 1900 ppm n a r i n g i n (an e x c e s s i v e l y b i t t e r j u i c e ) , 12% of the
t a s t e r s d i d not t h i n k the j u i c e was b i t t e r enough. These r e s u l t s
show the tremendous range i n i n d i v i d u a l b i t t e r n e s s response, as
w e l l as i n s e n s i t i v i t y .
Taste and S t r u c t u r e of C i t r u s Flavonoids
I n t e r e s t i n g l y , flavanone g l y c o s i d e s e x i s t as s t r u c t u r a l
isomers of which one w i l l be i n t e n s e l y b i t t e r w h i l e the other i s
t a s t e l e s s . The flavanone p o r t i o n of the b i t t e r molecule i s
t a s t e l e s s , w h i l e the g l y c o s i d e p o r t i o n i s t a s t e l e s s or s l i g h t l y
sweet ( 1 ) . B i t t e r n e s s i s observed only when the sugars and the

Table I. E v a l u a t i o n of n a r i n g i n b i t t e r n e s s as a f a c t o r i n
preference of F l o r i d a g r a p e f r u i t j u i c e
Nan* ngin cone, (ppm)

300 700 1100 1500 1900
Mean r a t i n g 3.7 3.6 3.4 3.4 3.3
Bitterness
Too b i t t e r 17 a
31 33 46 51
Just right 59 55 55 44 37
Not enough
bitterness 24 14 17 10 12
Don't know
(Number of
respondents) (201) (198) (198) (197) (197)
α
Percentage of t a s t e r s
Source: (38)
flavanone aglycone are l i n k e d i n a s p e c i f i c f a s h i o n . These com
pounds have been thoroughly studied to determine the r e l a t i o n s h i p
between t a s t e and s t r u c t u r e and has been thoroughly reviewed by
Horowitz ( U 37). While no s i n g l e s t r u c t u r a l f e a t u r e has been
a s s o c i a t e d witiï b i t t e r n e s s , the l i n k a g e of the sugars rhamnose
and glucose i s very important. Linked from C - l i n the rhamnose
to the C-2 i n g l u c o s e , the r e s u l t i n g d i s a c c h a r i d e i s c a l l e d
neohesperidose (2-0-(rhamnopyranosyl) glucopyranose). I f the
e s s e n t i a l l y t a s t e l e s s neohesperidose (40) i s l i n k e d to a f l a -
vanone through the 7-hydroxy p o s i t i o n , the r e s u l t i n g flavanone
g l y c o s i d e w i l l be i n t e n s e l y b i t t e r . However, i f the same sugars
are l i n k e d C - l to C-6 to form 6-0-(rhamnopyranosyl) glucopyranose
( r u t i n o s e ) and l i n k e d i n the same way to the i d e n t i c a l flavanone
aglycone, the r e s u l t i n g molecule i s t a s t e l e s s . The d i f f e r e n t
rhamnose-glucose l i n k a g e s are i l l u s t r a t e d i n Figure 3 f o r the
b i t t e r n a r i n g i n and i t s n o n b i t t e r isomer, n a r i r u t i n .
A l l c i t r u s flavanone neohesperidosides are b i t t e r and a l l
flavanone r u t i n o s i d e s are t a s t e l e s s Since the neohesper-
iodose sugar plays such an important r o l e i n flavanone b i t t e r n e s s
one might expect other f l a v o n o i d s w i t h a neohesperiodose attached
at the 7 p o s i t i o n to be e q u a l l y b i t t e r . F o r t u n a t e l y , t h i s i s not
the case, f o r even s u b t l e changes i n the flavanone molecule can
destroy i t s b i t t e r n e s s . As shown i n Figure 4 i f the b i t t e r
neohesperidin i s converted to neodiosmin (the corresponding
f l a v o n e ) the r e s u l t i n g compound i s t a s t e l e s s (41). Similar
r e s u l t s have been observed f o r other flavanone neohesperidosides
( 1 ) . No c i t r u s f l a v o n e g l y c o s i d e has been found to be b i t t e r .
Furthermore, i f the rhamnose p o r t i o n of the neohesperidoside i s
removed from n a r i n g i n , the r e s u l t i n g g l u c o s i d e (prunin) i s s t i l l
b i t t e r , but a t a much reduced i n t e n s i t y (See Table I I ) . While

OH OH 0
NARIRUTIN (naringenin 7-β-rutinoside)
Figure 3. Structural isomers of naringenin illustrating the two possible configura

tions of the sugars attached at the 7 position. Naringin is bitter whereas narirutin
is tasteless.
OH 0
Neodiosmin (tasteless)
Figure 4. Minor structural changes to the aglycone portion of the molecule can
destroy bitterness. Adding a single double bond between Carbons 2 and 3 will
convert bitter flavanone neohesperidosides to tasteless flavone neohesperidosides.

a l l flavanone neohesperidosides are b i t t e r , some are more b i t t e r

than o t h e r s . Thus, as shown i n Table I I , n a r i n g i n and p o n c i r i n
are two of the most b i t t e r flavone g l y c o s i d e s found i n c i t r u s .
Each i s about o n e - f i f t h as b i t t e r as quinine d i h y d r o c h l o r i d e .
Neohesperidin and n e o e r i o c i t r i n are only one-tenth as b i t t e r as
the other two flavanone g l y c o s i d e s . Thus, i t appears the number
and p o s i t i o n of r i n g s u b s t i t u t i o n s a f f e c t s the degree of b i t t e r -
ness of the o v e r a l l molecule.
Table II. R e l a t i v e B i t t e r n e s s of C i t r u s Flavonoid Aglycones

and Glycosides
*
Compound Taste Relative Bitterness
Hesperetin a
SI. sweet
Eriodictoyl 3
No t a s t e —
Naringenin? No t a s t e —
Hesperidin No t a s t e —
Neohesperidin 0
Bitter 2
Narirutin No t a s t e —
Naringin 0
Bitter 20
Didymin b
No t a s t e —
Poncirin . Bitter 20
Eriocitrin No t a s t e —
Neoeriocitrin 0
Bitter 2
Prunin Bitter 6
On a molar b a s i s w i t h q u i n i n e d i h y d r o c h l o r i d e taken as 100
b Aglycones
Rutinosides
. Neohesperidosides
Glucoside
Source: ( 1 , 39)
Hagen e t a K (42) determined the r e l a t i v e amounts of a l l the

flavanone g l y c o s i d e s i n Texas g r a p e f r u i t . T h e i r r e s u l t s are
shown i n Table I I I . Naringin i s the dominant f l a v o n o i d i n grape-
f r u i t and i s p r i m a r i l y r e s p o n s i b l e f o r the immediate b i t t e r t a s t e
i n g r a p e f r u i t . The e q u a l l y b i t t e r p o n c i r i n and the much l e s s
b i t t e r neohesperidin are present i n r e l a t i v e l y small amounts and
do not c o n t r i b u t e s i g n i f i c a n t l y to o v e r a l l b i t t e r n e s s .
While there are no b i t t e r flavone g l y c o s i d e s i n c i t r u s ,
there are some h i g h l y methoxylated f l a v o n e aglycones t h a t are
r e p o r t e d l y b i t t e r . S w i f t (28) i d e n t i f i e d s i n e n s e t i n , n o b i l e t i n ,
t e t r a - O - m e t h y s c u t e l l e r e i n , 3, 5, 6, 7, 8, 3 ' , 4 heptamethoxy-
1
flavone and t a n g e r e t i n from the b i t t e r f r a c t i o n of orange peel

j u i c e . He l a t e r determined the i n d i v i d u a l and c o l l e c t i v e t a s t e
thresholds of these flavones and compared ,them to the c o n c e n t r a -
t i o n s found i n commercial orange j u i c e (43). Orange j u i c e w i t h
an added t o t a l of 24 ppm of these flavones could not be d i f f e r -
e n t i a t e d from the orange j u i c e alone. Since the maximum t o t a l

c o n c e n t r a t i o n found i n orange j u i c e over several years was 7 ppm,

he concluded t h a t these flavones were not important c o n t r i b u t o r s
to the f l a v o r o f orange j u i c e .
Table I I I . Flavanone Glycosides i n Texas Canned G r a p e f r u i t J u i c e
Compound Concentration (ug/ml)

Naringin 306
Naringin r u t i n o s i d e 124
Neohesperidin 10.5
Hesperidin 9.9
Poncirin 17.0
Isosakuranetin r u t i n o s i d e 5.3
Source: (42)
Flavonoid B i t t e r n e s s Suppressors
A l l known c i t r u s f l a v o n e g l y c o s i d e s are odorless and gen-

e r a l l y t a s t e l e s s y e t they appear to have an important f u n c t i o n i n
reducing the perceived b i t t e r n e s s of flavanone neohesperidosides
and l i m o n o i d s . Horowitz (1_) was the f i r s t to i d e n t i f y the b i t t e r -
ness suppressing f u n c t i o n of these compounds. He found t h a t
r h o i f o l i n , the f l a v o n e e q u i v a l e n t o f the b i t t e r n a r i n g i n , could
p a r t i a l l y suppress the b i t t e r n e s s o f n a r i n g i n . Thus, higher
n a r i n g i n concentrations were necessary before b i t t e r n e s s could be
d e t e c t e d , i f the s o l u t i o n contained l a r g e amounts o f r h o i f o l i n .
Guadagni e t al_. (41) found neodiosmin, the t a s t e l e s s f l a v o n e
analog o f b i t t e r neohesperidin, to be a very e f f e c t i v e b i t t e r n e s s
suppressor. As l i t t l e as 10 ppm i n water increased the b i t t e r -
ness t h r e s h o l d o f n a r i n g i n and l i m o n i n , a nonflavonoid b i t t e r
compound, 3.5-and 4 . 0 - f o l d , r e s p e c t i v e l y . Neodiosmin was a l s o
e f f e c t i v e i n reducing preceived b i t t e r n e s s o f l i m o n i n i n orange
juice.
I t was speculated t h a t these f l a v o n e neohesperidosides are
so s i m i l a r i n s t r u c t u r e t h a t they compete w i t h flavanone neo-
hesperidosides f o r s i t e s on the b i t t e r n e s s receptors i n the mouth.
This e x p l a n a t i o n assumed t h a t these flavones could be adsorbed a t
t a s t e s i t e s without producing an a p p r e c i a b l e t a s t e response of
t h e i r own. U n f o r t u n a t e l y , n e i t h e r o f these b i t t e r n e s s suppressors
has been found to occur n a t u r a l l y i n the sweet orange (C_. s i n e n -
s i s ) although Nakabayashi (44) found r h o i f o l i n i n the sour orange
"(CT aurantium). Dunlap and Wender (45) reported f i n d i n g r h o -
i T o l i n i n g r a p e f r u i t e x t r a c t s but no attempt was made to d e t e r -
mine i t s c o n c e n t r a t i o n i n j u i c e . Neodiosmin has y e t to be found
i n g r a p e f r u i t . Thus, i t remains to be shown i f these compounds
play any r o l e i n the natural r e d u c t i o n o f n a r i n g i n b i t t e r n e s s as
g r a p e f r u i t matures.

Chalcones and Dihydrochalcones. Chalcones and d i h y d r o -

chalcones are i n t e n s e l y sweet compounds (39) t h a t are e f f e c t i v e
i n r a i s i n g the t h r e s h o l d a t which the b i t t e r n e s s of n a r i n g i n and
limonin i s perceived (46). As i l l u s t r a t e d i n Figure 5, chalcones
are e a s i l y formed from flavanone g l y c o s i d e s by the a d d i t i o n of
a l k a l i and dihydrochalcones are formed from hydrogenated c h a l -
cones. L i k e the flavanone neohesperidosides, the chalcones and
dihydrochalcones vary i n the i n t e n s i t y of t h e i r t a s t e response.
Dihydrochalcones are sweeter than chalcones and of the d i h y d r o -
chalcones, neohesperidin dihydrochalcone (NHD) i s the sweetest
(39). I t has been estimated t h a t NHD i s 1,500 times sweeter than
sucrose on an equal weight b a s i s . Thus, i t has been proposed t h a t
NHD be added to e x c e s s i v e l y b i t t e r j u i c e to reduce the perceived
b i t t e r n e s s and i n c r e a s e the q u a l i t y of the j u i c e (47). A 1969
F l o r i d a Department of C i t r u s Market Research Report i n d i c a t e d
f a v o r a b l e s a l e s and consumer acceptance of a r t i f i c i a l l y sweetened

g r a p e f r u i t j u i c e . F e l l e r s (47) found the average t a s t e t h r e s h o l d
of NHD i n s i n g l e - s t r e n g t h g r a p e f r u i t j u i c e to be about 8 ppm.
Neohesperidin dihydrochalcone l e v e l s between 8-12 ppm produced a
s i g n i f i c a n t sweetening of the g r a p e f r u i t j u i c e w i t h only a s l i g h t
but acceptable a f t e r t a s t e . Higher l e v e l s of neohesperidin d i -
hydrochal cone produced j u i c e s t h a t were e x c e s s i v e l y and unaccept-
ably sweet. Thus, NHD employed i n the proper amounts could be
used to upgrade the f l a v o r of e a r l y season g r a p e f r u i t j u i c e or
r e p l a c e a s i g n i f i c a n t amount of sucrose used i n covering syrups
i n canned or f r o z e n g r a p e f r u i t s e c t i o n s .
Chalcones have been proposed (48) as a precursor t h a t i s
e n z y m a t i c a l l y c y c l i z e d to form flavanone g l y c o s i d e s . The enzyme
r e s p o n s i b l e f o r t h i s s t e r e o s p e c i f i c r i n g c l o s u r e disappears o r
i s i n a c t i v a t e d as the f r u i t matures ( 5 ) . However, no chalcones
have been i s o l a t e d from c i t r u s . T h e r e f o r e , i f chalcones are a
p a r t of the metabolic pathway t h a t leads to the formation of
flavanone g l y c o s i d e s they probably e x i s t as short l i v e d , unstable
i n t e r m e d i a t e s . I t appears u n l i k e l y t h a t these compounds play a
s i g n i f i c a n t r o l e in m i t i g a t i n g bitterness at t h e i r natural l e v e l s .
Taxonomic S i g n i f i c a n c e of Flavonoids
In terms of i t s f l a v o n o i d c o m p o s i t i o n , c i t r u s i s unique
w i t h i n the p l a n t kingdom. Some c i t r u s f l a v a n o i d s are found no-
where e l s e . Furthermore, the r e l a t i v e f l a v o n o i d composition
v a r i e s w i t h each v a r i e t y . Thus, the f l a v o n o i d composition of
c i t r u s j u i c e s has been proposed (2) as a measure of j u i c e authen-
ticity.
In most of the p l a n t kingdom, flavanones occur only i n small
amounts compared to other f l a v o n o i d s , y e t they are the predom-
inant f l a v o n o i d i n c i t r u s . C i t r u s flavanones u s u a l l y occur as
g l y c o s i d e s , whereas i n other p l a n t s , flavanones are seldom found
i n the g l y c o s i d e form (1). Four types of glycosides have been
found i n c i t r u s . They are O-glucosides, C - g l y c o s i d e s , r u t i n o s i d e s
and neohesperidosides. Kefford (2) was one of the f i r s t i n v e s t i -
gators to recognize t h a t flavanone composition could be used to

DIHY PR 0 CHALCONE
Figure 5. Conversion of bitter flavanone neohesperidosides to the corresponding

intensely sweet chalcones and dihydrochalcones

d i s t i n g u i s h d i f f e r e n t v a r i e t i e s of c i t r u s . He c l a s s i f i e d sweet
oranges, mandarins, lemons and c i t r o n s together because hesper
i d i n was the predominant flavanone i n each. Since the p r i n c i p a l
f l a v o n o i d i n g r a p e f r u i t and pummelo was n a r i n g i n , Kefford put
these c u l t i v a r s i n a separate group. Horowitz [1) observed t h a t
the f l a v o n o i d g l y c o s i d e s of many v a r i e t i e s of c i t r u s occurred
e i t h e r a l l i n the r u t i n o s i d e or neohesperidoside forms. He thus
proposed t h a t a l l c i t r u s could be d i v i d e d according to t h e i r
g l y c o s i d e form.
Albach and Redman (49) confirmed t h i s method of c l a s s i f i c a
t i o n w i t h t h e i r flavanone survey of 41 c i t r u s c u l t i v a r s and 49
hybrids from Texas. They found t h a t the r e l a t i v e amounts of
flavanones w i t h i n d i f f e r e n t c u l t i v a r s of the same species were
f a i r l y constant. Some of t h e i r r e s u l t s are shown i n Table IV.
Most of the commercial c i t r u s c u l t i v a r s c o n t a i n only the non
b i t t e r r u t i n o s i d e s , whereas the sour orange and pummelo (C.

grandis) have only b i t t e r flavanone neohesperidosides. Working
w i t h hybrids of known parentage, they found i f one v a r i e t y con
t a i n i n g only flavanone r u t i n o s i d e s i s crossed w i t h another con
t a i n i n g only neohesperidosides, the r e s u l t i n g h y b r i d contained
both types of flavanone g l y c o s i d e s . An example of t h i s i s shown
i n Table IV f o r the cross between s i n e n s i s χ Poncirus t r i -
f o l i a t a . Thus, i t i s suspected t h a t the Meyers lemon (C. limon)
and the g r a p e f r u i t are hybrids r a t h e r than pure v a r i e t i e s because
they c o n t a i n both flavanone r u t i n o s i d e s and neohesperidosides.
Kamiya e t al^. (50) d i v i d e d c i t r u s i n t o 12 groups based on
the number and kind of flavanone g l y c o s i d e s found. With t h i s
c l a s s i f i c a t i o n system, they were able to d i s t i n g u i s h between
n u c e l l a r and z y g o t i c seedlings using both leaves and f r u i t . Of
the 94 hybrids examined, 53 c u l t i v a r s were judged as t r u e hy
b r i d s . The remaining c u l t i v a r s were not c l a s s i f i e d as t r u e hy
b r i d s because t h e i r flavanone g l y c o s i d e p a t t e r n was not s u f f i
c i e n t l y d i f f e r e n t from the female parent.
Ta turn e t al_. (29) used the presence of v a r i o u s methoxylated
flavones from l e a f e x t r a c t s to d i s t i n g u i s h between n u c e l l a r and
z y g o t i c s e e d l i n g s . They a l s o i d e n t i f i e d the predominant f l a
vanone g l y c o s i d e and three u n i d e n t i f i e d coumarins i n t h e i r
samples. Ting e t ^ a l . (51) showed t h a t there were q u a n t i t a t i v e
as w e l l as q u a l i t a t i v e cfifferences i n the methoxylated f l a v o n e
content from the j u i c e s of d i f f e r e n t c i t r u s v a r i e t i e s . They
f u r t h e r showed t h a t c e r t a i n blends of j u i c e s could be d i s t i n
guished based on the amounts of methoxylated flavones found.
Both d i r e c t l y and i n d i r e c t l y , f l a v o n o i d composition a f f e c t s
the q u a l i t y of i n d i v i d u a l c i t r u s c u l t i v a r s and h y b r i d s . Some
c u l t i v a r s , such as the sour orange, are d i r e c t l y a f f e c t e d by the
presence of b i t t e r neohesperidosides to the p o i n t they are un
p a l a t a b l e . The q u a l i t y of other c u l t i v a r s may be i n d i r e c t l y
a f f e c t e d due to the presence of b i t t e r n e s s suppressing f l a v o n e
neohesperidosides. C e r t a i n h y b r i d s , such as the Κ e a r l y , a l s o
c o n t a i n b i t t e r flavanone g l y c o s i d e s a t l e v e l s which reduce i t s
a c c e p t a b i l i t y . T h e r e f o r e , the knowledge of the r e l a t i v e type and

Table IV. Thin Layer Chromatographic Survey of Flavanones

i n C i t r u s Taxa
Relative fluorescence i n t e n s i t y 3
7-Rutinosides o f : 7-Neohesperidosides of:
_l. 3" 3 3 —J» Φ 3" 3

3
CO -s Φ
CO -s Φ -s
-s ο CO -S -s Ο CO
__ι. —ι· CO O "O -J.
—1. CO ο Ί3 Q- φ 3
& QL Φ 3 3 0)
ca _l. -s CO C Q —- —J* -s C Q
Φ Φ — o φ Φ
Φ — ο Π)
3 3 -s ,r+ rp 3
3 -s ,c+ c-p
—ι. Οί —j. -J.
—1.
3
np <<
ο
__ι.
3 3 3 ^O< 3 3
1IC
Φ
-P*
-P* C-P
_J.
I
11 1
1 3
C Q
CO
C
_ O
ο
ο
Ο
Ο o
co
CO
CO
_J.
-J. _ι.
Q .
CL
Q_
Π) Φ
Φ
C i t r u s Taxa
C i t r u s s i n e n s i s (7) 4 2 - 10 1
C. r e t i c u l a t o r (4) 4 2 - 10 -
V. a u r a n t i f o l i a 10 -
C. limon " L i s b o n " 2 - 10 10 -
_
"Meyer" 1 - - 10 -
? "Ponderosa" 1 - - Ι 3 - - 10
-1
Ο. grandis - - - 10
- --
C. aurantium (3)
C. p a r a d i s i (2)
-
4 1 -
- -
T 1
10
10
-2 - 10
T
-
1
Poncirus t r i f o l i a t a - - - 10 10
- -
Hybrids
C. p a r a d i s i χ C. r e t i c u l a t a
"Minneola" Tangelo 4 2 - 10
"Orlando" 3 1 - 10
C. s i n e n s i s χ Poncirus trifoliata
"Rustic" citrange 4 5 10 8
"Troyer" 4 10 10 2
The flavanone w i t h the highest f l u o r e s c e n c e i n t e n s i t y was
given a value o f 10; Τ = t r a c e ; - = not d e t e c t e d .
( ) number of v a r i e t i e s t e s t e d
Source: (49)

concentrations of f l a v o n o i d s i n p o t e n t i a l parentage w i l l be im-

portant to p l a n t breeders i n developing hybrids of d e s i r e d
flavor.
E f f e c t s of F r u i t M a t u r i t y , Rootstocks and H o r t i c u l t u r a l V a r i a b l e s
I t i s g e n e r a l l y held t h a t the amount of f l a v o n o i d s i n whole

f r u i t increase only during the very e a r l y stages of f r u i t develop-
ment. There i s l i t t l e change i n the absolute amount of c i t r u s
f l a v o n o i d s during most of the l i f e t i m e of the f r u i t . Kesterson
and Hendrickson (7) found t h a t the t o t a l amount of n a r i n g i n (as
measured by the Davis Test) i n several c u l t i v a r s of g r a p e f r u i t
remained constant once the f r u i t reached 2.3 inches i n diameter.
However, as shown i n Figure 6, the c o n c e n t r a t i o n of n a r i n g i n
decreased c o n t i n u a l l y because i t was being d i l u t e d due to i n -
c r e a s i n g f r u i t s i z e . They (52) reported s i m i l a r r e s u l t s w i t h

h e s p e r i d i n i n oranges. Huet"T53) and Goren (54) conducted
monthly measurements on the f l a v o n o i d contents of V a l e n c i a and
Shamouti oranges grown i n Morocco and I s r a e l , r e s p e c t i v e l y . They
a l s o found t h a t the absolute whole f r u i t f l a v o n o i d content changed
very l i t t l e once the f r u i t reached a c r i t i c a l s i z e e a r l y i n i t s
development.
While there i s general agreement as to the whole f r u i t f l a -
vonoid content of c i t r u s , there i s c o n s i d e r a b l e disagreement as
to what, i f any, changes occur i n j u i c e f l a v o n o i d concentrations
as the f r u i t matures. Many i n v e s t i g a t o r s {7_ 52, 53^, 54) r e p o r t
9
f i n d i n g no s i g n i f i c a n t change i n f l a v o n o i d content u n t i l a f t e r the

f r u i t i s past i t s peak m a t u r i t y . These s t u d i e s employed a v a r i e t y
of e x t r a c t i o n techniques on most of the common orange and grape-
f r u i t c u l t i v a r s t h a t were grown i n d i f f e r e n t regions of the w o r l d .
Each used e i t h e r the Davis t e s t or the d i r e c t UV method to d e t e r -
mine f l a v o n o i d s .
An a l t e r n a t e view i s t h a t j u i c e f l a v o n o i d c o n c e n t r a t i o n de-
creases c o n t i n u a l l y during m a t u r a t i o n . Lime e t al_. (55) using
the Davis Test found f l a v o n o i d c o n c e n t r a t i o n i n Texas Ruby Red
g r a p e f r u i t to decrease c o n t i n u a l l y during the growing season.
Hagen e t al_. (25) used a t h i n l a y e r chromatographic-fluorometric
method to measure the c o n c e n t r a t i o n s of each of the s i x major
flavanone g l y c o s i d e s present i n Texas Ruby Red g r a p e f r u i t . They
a l s o measured t o t a l g l y c o s i d e s using the Davis T e s t . Since both
they and Lime e t a l . (55) used the same v a r i e t y of g r a p e f r u i t
grown a t the s a m e T o c a t t o n , t h e i r r e s u l t s are compared i n Figure
7. In both s t u d i e s t o t a l g l y c o s i d e s decreased r a p i d l y during the
e a r l y p a r t of the season and then g r a d u a l l y diminished as the
f r u i t continued to mature. However, the d i f f e r e n c e s i n the Davis
v a l u e s , shown as curves A and D, f o r these s t u d i e s are too great
to be explained by seasonal v a r i a t i o n . Comparing these values
w i t h another r e p o r t (7) on the same c u l t i v a r and method of a n a l -
y s i s i t was found t h a t the values of Hagen e t al_. (25) were
unusually high. Since Hagen and co-workers separatidf the j u i c e

A M J J A S O N D J F MA
MONTH OF H A R V E S T
Figure 6. Effect of fruit maturity on: (A) fruit size; (B) weight of naringin per
fruit; and (C) the % of naringin in each fruit (Ί)

Figure 7. Maturity effects on naringin and other flavanone glycosides in juice

sacs of Texas Ruby Red grapefruit; (A) "naringin" by Davis value; (B) total
flavanone glycosides by TLC; (C) naringin by TLC (25); and (D) naringin by
Davis value (55)

v e s i c l e s from the c e n t r a l c o r e , segment membrane and albedo be-

f o r e e x t r a c t i n g , there should be no contamination from these high
f l a v o n o i d sources. Rouseff and Dougherty (56) found a s m a l l , but
c o n s i s t e n t , decrease of n a r i n g i n i n F l o r i d a g r a p e f r u i t j u i c e as
the f r u i t matured. They a l s o found t h a t the major drop i n f l a -
vonoid content as w e l l as n a r i n g i n , occurred a f t e r the f r u i t
passed peak m a t u r i t y . However, t h i s was observed only when e x -
perimental c o n d i t i o n s were t i g h t l y c o n t r o l l e d , i . e . , when a
l a r g e number (120) o f c a r e f u l l y s i z e d f r u i t from the same bloom
were e x t r a c t e d i n e x a c t l y the same manner throughout the season.
Numberous f a c t o r s , such as f r u i t s i z e , h o r t i c u l t u r a l c o n -
d i t i o n s and the age o f the t r e e (57) a l l a f f e c t the f l a v o n o i d
content o f the j u i c e . The l a r g e r the f r u i t , the lower the f l a -
vonoid content. Rootstock e f f e c t s are most evident e a r l y i n the
season (53) w i t h only s l i g h t d i f f e r e n c e s found a t the end of the
season. H o r t i c u l t u r a l p r a c t i c e s such as spraying immature grape-

f r u i t w i t h lead arsenate sprays f o r e a r l y m a t u r i t y s i g n i f i c a n t l y
increases the f l a v o n o i d content (58). The a p p l i c a t i o n o f a growth
r e g u l a t o r , such as g i b b e r e l i n , t o T h a m o u t i oranges reduced t h e i r
h e s p e r i d i n content (59).
C l i m a t i c d i f f e r e n c e s w i l l a l t e r the f l a v o n o i d content o f
c i t r u s . Rouse e t _]_. (60) and Maraulja e__al_. (61) found the
h e s p e r i d i n contents i n F l o r i d a oranges t o be higher i n c o l d e r
seasons. In a s i n g l e season, Dougherty and F i s h e r (62) found the
n a r i n g i n c o n c e n t r a t i o n of g r a p e f r u i t to increase d r a m a t i c a l l y
a f t e r a f r e e z e . Conversely, Herzog and Monselise (63) found the
n a r i n g i n content o f g r a p e f r u i t grown i n warm a r i d regions t o be
lower than t h a t from c o o l e r , humid areas. Thus, c o o l e r temper-
atures appear t o f a v o r increases i n f l a v o n o i d c o n c e n t r a t i o n s .
E f f e c t s o f Processing on J u i c e B i t t e r n e s s
Flavonoids are not evenly d i s t r i b u t e d w i t h i n c i t r u s f r u i t .

Flavanone g l y c o s i d e s are concentrated p r i m a r i l y i n the albedo,
(the i n n e r , w h i t e , spongy p o r t i o n o f the peel) w i t h lower concen-
t r a t i o n s i n the c e n t r a l core and segment membranes. J u i c e c o n -
t a i n s the l e a s t amount o f flavanone g l y c o s i d e s (7_, 52, 53). Since
these f l a v o n o i d s r e a d i l y d i s s o l v e i n the j u i c e , a d d i t i o n a l amounts
of flavanone g l y c o s i d e s from other f r u i t parts may d i f f u s e i n t o
the j u i c e during e x t r a c t i o n . In the production o f orange j u i c e ,
a higher f l a v o n o i d content i s o f l i t t l e concern s i n c e most o f
t h i s m a t e r i a l w i l l be t a s t e l e s s h e s p e r i d i n , the predominant
f l a v o n o i d i n sweet oranges. However, i n g r a p e f r u i t j u i c e , the
a d d i t i o n a l f l a v o n o i d content w i l l g e n e r a l l y produce a l e s s d e -
s i r a b l e product because the p r i n c i p l e f l a v o n o i d g l y c o s i d e i s the
b i t t e r n a r i n g i n . Thus, the t e c h n o l o g i c a l challenge i n the p r o -
d u c t i o n o f good g r a p e f r u i t j u i c e i s t o minimize the amount of
n a r i n g i n incorporated i n t o the j u i c e from other f r u i t p a r t s .
E x t r a c t o r designs t h a t minimize squeeze pressure and j u i c e
c o n t a c t time w i t h the albedo w i l l produce g r a p e f r u i t j u i c e s w i t h

lower n a r i n g i n l e v e l s . Designs which i n c o r p o r a t e a p r e f i n i s h e r

to separate segment membrane, c e n t r a l core and seeds from the
pulp and j u i c e immediately a f t e r e x t r a c t i o n w i l l a l s o help to r e -
duce j u i c e n a r i n g i n c o n c e n t r a t i o n s . I t has been shown (52) t h a t
n a r i n g i n concentrations could be reduced by l i m i t i n g the amount
of pulp incorporated i n t o the j u i c e . J u i c e n a r i n g i n l e v e l s were
reduced by as much as 20% when the pulp was immediately separated
from the j u i c e a f t e r e x t r a c t i o n . The usual methods of pulp sepa-
r a t i o n , however, produce j u i c e s w i t h 10% l e s s n a r i n g i n but w i t h
no s i g n i f i c a n t improvement i n q u a l i t y .
E x t r a c t i o n and f i n i s h e r pressures can g r e a t l y i n f l u e n c e the
f l a v o n o i d content of c i t r u s j u i c e s . G e n e r a l l y , as the f r u i t i s
squeezed harder more j u i c e i s recovered. However, excessive ex-
t r a c t o r pressures produce j u i c e of a lower q u a l i t y (35). As
shown i n Figure 8, g r a p e f r u i t flavanone g l y c o s i d e concentrations
increase w i t h i n c r e a s i n g e x t r a c t o r pressures. In the e a r l y

p o r t i o n of the season almost twice as much n a r i n g i n was obtained
under hard squeeze c o n d i t i o n s than was obtained w i t h the s o f t
squeeze. The e f f e c t of f i n i s h e r pressure i s not as c l e a r , and i s
dependent on the composition o f the raw j u i c e which, i n t u r n , i s
dependent on the type of e x t r a c t o r used.
Attaway e t a l . (64) found t h a t e x t r a c t o r pressure was p r o -
p o r t i o n a l to t o t i T flavanone g l y c o s i d e values i n several v a r i e t i e s
of orange j u i c e . In a l a t e r survey of commercial orange j u i c e
(65) i t was found t h a t there was a s i g n i f i c a n t c o r r e l a t i o n between
t o t a l flavanone g l y c o s i d e s (Davis Values) and f l a v o r score. Since
the flavanone g l y c o s i d e s i n commercial orange j u i c e are the t a s t e -
l e s s r u t i n o s i d e s , the r e l a t i o n s h i p observed i s probably due to
small amount of the b i t t e r l i m o n o i d , l i m o n i n , whose c o n c e n t r a t i o n
a l s o increases w i t h i n c r e a s i n g e x t r a c t o r pressure.
At one time i t was thought t h a t methoxylated flavones were
found only i n the o i l glands of the f l a v e d o (2). However, l a t e r
i n v e s t i g a t o r s (33) using more s e n s i t i v e techniques found t h a t they
are d i s t r i b u t e d throughout the f r u i t . Rouseff and Ting (66) r e -
ported t h a t of the f i v e major methoxylated flavones i n V a l e n c i a
oranges, 96% were found i n the f l a v e d o and during e x t r a c t i o n very
l i t t l e was incorporated i n t o the j u i c e from other f r u i t p a r t s .
Thus, the type of e x t r a c t o r , e x t r a c t o r pressure, j u i c e pulp
contact time as w e l l as u l t i m a t e j u i c e pulp content w i l l a l l a l t e r
the amount of flavanone g l y c o s i d e s found i n the j u i c e .
I t should be pointed out t h a t i f e x t r a c t i o n c o n d i t i o n s are c a r e -
f u l l y c o n t r o l l e d , the q u a l i t y of the j u i c e w i l l be maintained. No
degree of manipulation of e x t r a c t i o n c o n d i t i o n s can y i e l d a good
q u a l i t y j u i c e i f poor q u a l i t y f r u i t i s used. The important r o l e
that f r u i t v a r i e t y and m a t u r i t y play i n determining the q u a l i t y of
the f i n a l product cannot be overemphasized.
Enzyme D e b i t t e r i n g . One of the more promising ways to reduce

n a r i n g i n b i t t e r n e s s i s to use enzymes to convert the b i t t e r f l a -
vone neohesperidoside i n t o a l e s s b i t t e r g l u c o s i d e or n o n - b i t t e r

aglycone. This can be accomplished by t r e a t i n g the j u i c e w i t h a

naringinase enzyme. The advantage of using enzymes i s t h a t they
are s p e c i f i c , i . e . , under m i l d c o n d i t i o n s they w i l l s e l e c t i v e l y
a l t e r n a r i n g i n or other s i m i l i a r compounds w h i l e , a t the same
t i m e , leave the m a j o r i t y of j u i c e components unchanged. The
j u i c e w i l l be d e b i t t e r e d and the g r a p e f r u i t f l a v o r and c h a r a c t e r
w i l l remain i n t a c t . Other methods of d e s t r o y i n g n a r i n g i n b i t -
t e r n e s s , such as chemical h y d r o l y s i s , would a l s o destroy the
f l a v o r and most of the n u t r i e n t s .
One e a r l y i n v e s t i g a t i o n (67) found t h a t a f t e r t r e a t i n g grape-
f r u i t j u i c e w i t h r e l a t i v e l y higïï c o n c e n t r a t i o n s of p e c t i n o l to
f a c i l i t a t e f i l t e r i n g , j u i c e b i t t e r n e s s and n a r i n g i n values de-
creased. P e c t i n o l i s a commercial p e c t i c enzyme of fungal o r i g i n .
I t was l a t e r found (68) t h a t the enzyme r e s p o n s i b l e f o r j u i c e de-
b i t t e r i n g was an i m p u r i t y i n the p e c t i c enzyme. The d e b i t t e r i n g
enzyme was found to c o n s i s t of a oc- rhamnosidase and a/! - g l u -

cosidase i n about equal proportions (68, 69). Theoc- rhamno-
sidase w i l l cleave rhamnose from n a r i n g i n to produce prunin
(naringenin 7 - g l u c o s i d e ) . This g l u c o s i d e i s about o n e - t h i r d as
b i t t e r as n a r i n g i n (1). β - glucosidase w i l l hydrolyze glucose
from prunin to form the t a s t e l e s s aglycone, n a r i n g e n i n . These
r e a c t i o n s can be w r i t t e n as f o l l o w s :
oc- rhamnosidase
naringin — • prunin + rhamnose
J& - glucosidase
> naringenin + glucose.

Naringinase s o l u t i o n s were found to r a p i d l y convert n a r i n g i n
to n a r i n g e n i n . The same process d i d not occur when naringinase
was added to j u i c e . Due to the n a t u r a l l e v e l s of glucose i n
j u i c e , the r e a c t i o n r a t e of the second step was decreased by over
60% (68). Thus, prunin accumulated as an i n t e r m e d i a t e product and
was s l o w l y converted to n a r i n g e n i n . The i n h i b i t i o n of glucose on
the second r e a c t i o n r a t e could be e l i m i n a t e d i f the enzyme,
e m u l s i n , was a l s o added to n a r i n g i n a s e . However, s a t i s f a c t o r y
d e b i t t e r i n g was achieved w i t h n a r i n g i n a s e a l o n e , and complete
h y d r o l y s i s to naringenin was not r e q u i r e d (68).
I n v e s t i g a t i o n s on p o s s i b l e commercial use of enzymes to r e
move n a r i n g i n b i t t e r n e s s were c a r r i e d out f o r j u i c e (70, 7 1 ) , con
c e n t r a t e C71), and f r u i t s e c t i o n s (72). Those i n v e s t i g a t i o n s
showed t h a t i t was t e c h n i c a l l y p o s s i b l e to use enzymes to reduce
n a r i n g i n b i t t e r n e s s on a commercial s c a l e . However, due to e n
zyme expense, most of the i n d u s t r y has found i t more c o s t e f f e c
t i v e to use more mature ( l e s s b i t t e r ) f r u i t r a t h e r than employ
d e b i t t e r i n g enzymes.
The Japanese have been very a c t i v e i n the use of enzymes to
reduce n a r i n g i n b i t t e r n e s s . This i s due i n p a r t to the presence
of n a r i n g i n i n Natsudaidai orange, an important c u l t i v a r i n
Japan. They were one of the f i r s t to i n v e s t i g a t e the commercial

1000.
Ε
χ ι ι ι ι ι ι 1 1 lJ
I 15 I 15 I 15 I 15 I 15
SEPTEMBER OCTOBER NOVEMBER DECEMBER JANUARY
Figure 8. Effect of extractor pressure on totalflavanoneglycoside concentration

for Florida grapefruit at different stages of maturity (35) ((Φ) hard squeeze; (O)
soft squeeze)
Table V. E f f e c t o f Enzyme Treatment on N a r i n g i n Content and B i t -

terness P e r c e p t i o n i n G r a p e f r u i t Juice.(79)
Juice Circulation Naringin Bitterness

Sample volume (mL) time (min) content (ug/mL) rating* 3
Control — — 285 3.8

l a
1500 100-30 240 3.6
2a 1500 180-134 195 3.3
3 a
500 120 122 3.2
4 a
500 125-150 95 2.9
a = blended samples of 2-6 batches o f j u i c e .
b = average b i t t e r n e s s scores from 20 member t a s t e p a n e l , where
1 = no b i t t e r n e s s , 2 = j u s t p e r c e p t i b l e , 3 = d e f i n i t e l y
p e r c e p t i b l e , 4 = moderately i n t e n s e , 5 = very intense and
6 = extremely i n t e n s e .
Journal of Food Science

a p p l i c a t i o n o f naringinase (73) and have done e x t e n s i v e s t u d i e s

to f i n d inexpensive sources f o r t h i s enzyme (74·, 75). The most
s u c c e s s f u l approaches have been to soak the peeled f r u i t i n
enzyme s o l u t i o n s f o r up to 16 hour before processing (76) o r
adding naringinase preparations w i t h low pectinase a c t i v i t y along
w i t h the f r u i t as i t i s being canned (77). Roe and Brummer (78)
s u c c e s s f u l l y i n f u s e d naringinase i n t o whole shaved g r a p e f r u i t
(flavedo removed). This reduced the b i t t e r n e s s o f the albedo to
the p o i n t t h a t i t was as e q u a l l y e d i b l e as the f r u i t segments.
In a d d i t i o n , the process increased the n u t r i t i o n a l and d i e t a r y
f i b e r content o f the f i n a l product.
Cost has not been the only problem i n employing enzymes t o
reduce n a r i n g i n b i t t e r n e s s . The other problem was the u n d e s i r -
able l o s s o f cloud due to pectinase i m p u r i t i e s i n the naringinases
employed (70). However, both problems have been reduced i n a

promising new procedure. Olson e t a K (79) have s u c c e s s f u l l y

immobilized naringinase i n a hollow f i b e r r e a c t o r to reduce
n a r i n g i n b i t t e r n e s s . Enzyme a c t i v i t y was not a f f e c t e d even a f t e r
g r a p e f r u i t j u i c e was pumped through the hollow f i b e r r e a c t o r f o r
up to three days. Thus, much more j u i c e can be t r e a t e d w i t h the
same amount o f enzyme and the cost per u n i t o f j u i c e was reduced.
Pectinase i m p u r i t i e s d i d not cause a l o s s o f j u i c e cloud because
the high molecular weight p e c t i n s could not d i f f u s e through the
hollow f i b e r membrane t o come i n c o n t a c t w i t h the enzyme. As
i l l u s t r a t e d i n Table V, they could reduce j u i c e n a r i n g i n l e v e l s
by c o n t r o l l i n g the amount and the c i r c u l a t i o n time o f the j u i c e .
N a r i n g i n c o n c e n t r a t i o n was reduced from 285 to 95 ppm w i t h a
corresponding r e d u c t i o n i n the b i t t e r n e s s r a t i n g . This i s a
promising approach to the problem o f j u i c e n a r i n g i n b i t t e r n e s s ,
however, the process s t i l l remains t o be evaluated under p i l o t
plant conditions.
Enzymes have a l s o been developed to reduce o r e l i m i n a t e
problems a s s o c i a t e d w i t h h e s p e r i d i n s i n s o l u b i l i t y . Since hes-
1
p e r i d i n problems are v i s u a l problems, enzymes have been used t o

convert the i n s o l u b l e h e s p e r i d i n t o the more s o l u b l e g l y c o s i d e .
The a d d i t i o n o f these enzymes has g r e a t l y reduced the t u r b i d i t y
i n canned mandarin s e c t i o n s due to h e s p e r i d i n c r y s t a l formation
during storage (80).

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RECEIVED July 7, 1980.


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5

Flavonoids and Citrus Quality

Florida Department of Citrus, Institute of Food and Agricultural Sciences,

Flavonoids are one of the most widely distributed and di­

arranged C -C -C with the central group usually linked with oxy­

gen and numbered as shown below:

These compounds are differentiated primarily by the oxida­

Nagy and Attaway; Citrus Nutrition and Quality

FLAVANONOLS FLAVONES ANTHOCYANINS

Figure 1. Flavonoid structures and nomenclature as determined by the central

Nagy and Attaway; Citrus Nutrition and Quality

number of f a c t o r s . These f a c t o r s are u s u a l l y evaluated by the

observed i n the absorption maxima from the UV spectra of f l a v o ­

Nagy and Attaway; Citrus Nutrition and Quality

t h i n c r u s t on the surfaces of f a l l i n g f i l m evaporators used i n

Naringin S o l u b i l i t y . N a r i n g i n , the major f l a v o n o i d i n grape-

f r u i t and pummel ο, has been observed (11) to c r y s t a l i z e i n canned

The establishment of p r e c i s e o b j e c t i v e measurements f o r

Nagy and Attaway; Citrus Nutrition and Quality

Figure 2. USD A visual aids used ίο determine acceptable and unacceptable

Nagy and Attaway; Citrus Nutrition and Quality

Other c o l o r i m e t r i c methods have been developed to determine

Chromatographic methods were developed to separate a few of

Nagy and Attaway; Citrus Nutrition and Quality

Flavonoids have no odor or mouth f e e l and, i n g e n e r a l , do

u s u a l l y considered o b j e c t i o n a b l e and the F l o r i d a Department of

Taste and S t r u c t u r e of C i t r u s Flavonoids

Nagy and Attaway; Citrus Nutrition and Quality

Nan* ngin cone, (ppm)

Nagy and Attaway; Citrus Nutrition and Quality

Figure 3. Structural isomers of naringenin illustrating the two possible configura­

Nagy and Attaway; Citrus Nutrition and Quality

a l l flavanone neohesperidosides are b i t t e r , some are more b i t t e r

Table II. R e l a t i v e B i t t e r n e s s of C i t r u s Flavonoid Aglycones

Hagen e t a K (42) determined the r e l a t i v e amounts of a l l the

flavone and t a n g e r e t i n from the b i t t e r f r a c t i o n of orange peel

Nagy and Attaway; Citrus Nutrition and Quality

c o n c e n t r a t i o n found i n orange j u i c e over several years was 7 ppm,

Table I I I . Flavanone Glycosides i n Texas Canned G r a p e f r u i t J u i c e

Compound Concentration (ug/ml)

A l l known c i t r u s f l a v o n e g l y c o s i d e s are odorless and gen-

Nagy and Attaway; Citrus Nutrition and Quality

Chalcones and Dihydrochalcones. Chalcones and d i h y d r o -

f a v o r a b l e s a l e s and consumer acceptance of a r t i f i c i a l l y sweetened

Nagy and Attaway; Citrus Nutrition and Quality

Figure 5. Conversion of bitter flavanone neohesperidosides to the corresponding

Nagy and Attaway; Citrus Nutrition and Quality

b i t t e r r u t i n o s i d e s , whereas the sour orange and pummelo (C.

Nagy and Attaway; Citrus Nutrition and Quality

Table IV. Thin Layer Chromatographic Survey of Flavanones

7-Rutinosides o f : 7-Neohesperidosides of:

_l. 3" 3 3 —J» Φ 3" 3

Nagy and Attaway; Citrus Nutrition and Quality

concentrations of f l a v o n o i d s i n p o t e n t i a l parentage w i l l be im-

I t i s g e n e r a l l y held t h a t the amount of f l a v o n o i d s i n whole

c r e a s i n g f r u i t s i z e . They (52) reported s i m i l a r r e s u l t s w i t h

f i n d i n g no s i g n i f i c a n t change i n f l a v o n o i d content u n t i l a f t e r the

Nagy and Attaway; Citrus Nutrition and Quality

Nagy and Attaway; Citrus Nutrition and Quality

Figure 7. Maturity effects on naringin and other flavanone glycosides in juice

Nagy and Attaway; Citrus Nutrition and Quality

v e s i c l e s from the c e n t r a l c o r e , segment membrane and albedo be-

season. H o r t i c u l t u r a l p r a c t i c e s such as spraying immature grape-

Flavonoids are one of the most widely distributed and di

arranged C -C -C with the central group usually linked with oxy

These compounds are differentiated primarily by the oxida

observed i n the absorption maxima from the UV spectra of f l a v o

Figure 3. Structural isomers of naringenin illustrating the two possible configura