Bioregulation of Pigment Biosynthesis by Onium Compounds - ACS

9 Bioregulation of Pigment Biosynthesis by Onium Compounds

Downloaded by UNIV OF LIVERPOOL on November 26, 2015 | http://pubs.acs.org Publication Date: February 11, 1982 | doi: 10.1021/bk-1982-0181.ch009

H. Y O K O Y A M A , W. J. HSU, S. POLING, and Ε. H A Y M A N U.S. Department of Agriculture, Agricultural Research Service, Fruit and Vegetable Chemistry Laboratory, Pasadena, C A 91106 A l a r g e number of onium compounds r e g u l a t e carotenoid pigment b i o s y n t h e s i s i n plant t i s s u e s . They stimulate carotenoid b i o s y n t h e t i c pathways w i t h no apparent h e r b i c i d a l activity. A sub s t a n t i a l amount of information on s t r u c t u r e -activity r e l a t i o n s h i p s f o r b i o r e g u l a t i o n of carotenoids i n higher p l a n t s has been developed. Both the t r a n s - and cis- b i o s y n t h e t i c systems can be r e g u l a t e d . The carotenoid p a t t e r n observed i s determined e s s e n t i a l l y by the nature of onium compounds employed. For example, 2-diethylaminoethyl-4-methylphenylether caused a l a r g e accumula t i o n of all trans-lycopene (ψ,ψ-carotene), whereas 2-diethylaminoethylhexanoate induced the formation of ß-carotene (ß,ß-carotene). The compound N -methyl,N-hexylbenzylamine stimulated the formation of c i s - c a r o t e n e s .

Regulation of the b i o s y n t h e s i s of the carotenoids was demonstrated i n the e a r l y 1950 s when i t was shown that 3-ionone stimulated carotenogenesis i n the fungus Phycomyces blakesleeanus Ql> 2l9 3) without i t s e l f being incorporated i n t o the carotene molecules (4). A s i m i l a r s t i m u l a t o r y e f f e c t of 3-ionone was observed on carotene production i n h e t e r o t h a l l i c c u l t u r e s of Phycomyces blakesleeanus (_5) . In Β lake s l e a t r i s p o r a . an e f f e c t somewhat s i m i l a r to that observed with 3-ionone was seen with t r i s p o r i c acid (6). T r i s p o r i c a c i d only stimulated caroteno genesis i n the (-) s t r a i n (7). Both 3-ionone and t r i s p o r i c a c i d do not appear to a f f e c t carotene b i o s y n t h e s i s i n higher p l a n t s (8). Ninet et a l . (9) i n v e s t i g a t e d the b i o s y n t h e s i s of c a r o tenoids by 15. t r i s p o r a i n the presence of v a r i o u s nitrogenous compounds. P y r i d i n e , i m i d a z o l e , and some of t h e i r d e r i v a t i v e s were found to stimulate the s y n t h e s i s of trans-lycopene ( ψ , ψ c a r o t e n e ) , whereas i s o n i c o t i n o y l h y d r a z i n e , s u c c i n i m i d e , f

This chapter not subject to U.S. copyright. Published 1982 American Chemical Society. In Biochemical Responses Induced by Herbicides; Moreland, D., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 1982.


154

BIOCHEMICAL RESPONSES INDUCED BY HERBICIDES

and 4-hydroxypyridine enhanced 3-carotene (3,3~carotene) syn thesis. In 1969, Knypl (10) found that an onium compound, chlormequat [(2-chloroethyl)-trimethylammonium c h l o r i d e ] , caused a l l trans-lycopene accumulation i n detached pumpkin (Curcubita pepo) cotyledons. However, no such response was observed when chlormequat was a p p l i e d to other p l a n t t i s s u e s (11). A major step forward was observed i n 1970 with the d i s c o v e r y that another onium compound, 2-(4-chlorophenylthio)-triethylammonium c h l o r i d e (CPTA), can cause the accumulation of lycopene i n a wide a r r a y of p l a n t t i s s u e s and microorganisms (11). Since the d i s c o v e r y o f CPTA, r e s e a r c h on onium compounds has generated a s u b s t a n t i a l amount of i n f o r m a t i o n r e l a t i v e to the s t r u c t u r e - a c t i v i t y r e l a t i o n s h i p s f o r b i o r e g u l a t i o n of c a r o t e n o i d pigments i n higher p l a n t s and microorganisms. Both the t r a n s and c j i s - b i o s y n t h e t i c pathways can be r e g u l a t e d . The c a r o t e n o i d p a t t e r n observed i s determined e s s e n t i a l l y by the nature of the onium compounds employed. All-trans

Carotenes

General Formula. carotenogenic system, formula:

In the r e g u l a t i o n o f the t r a n s the onium compounds have the s p e c i a l

C

2H

5 x

N-CH -R 2

C H ^ 2

5

In g e n e r a l , the Ν,Ν-dimethyl analogs are l e s s e f f e c t i v e than the Ν,Ν-diethyl compounds i n promoting c a r o t e n o i d formation. The magnitude of the s t i m u l a t i o n , but not the general p a t t e r n of c a r o t e n o i d response, depends on R (12). The nature of R can cause m o d i f i c a t i o n s i n the amount o f the i n d i v i d u a l c a r o t e n o i d s . Thus, when R l a c k s an aromatic r i n g , t h e r e appears to be l e s s i n h i b i t i o n o f the c y c l a s e ( s ) ; consequently, more c y c l i c c a r o tenoids accumulate. Examples are g i v e n i n Tables I - I I I . A l l of the compounds tested caused lycopene accumulation i n Marsh grape f r u i t (Citrus paradisi). The untreated f r u i t had the normal l i g h t y e l l o w c o l o r . A f t e r treatment, the c o l o r of the flavedo ranged from l i g h t orange to an i n t e n s e r e d . The flavedo of a l l t r e a t e d f r u i t showed lycopene accumulation (Tables I, I I , and III). Lycopene was not detected i n the untreated f r u i t s and i t i s not normally present i n mature g r a p e f r u i t (13). The b i o l o g i c a l a c t i v i t y was a l s o c o r r e l a t e d with the l o g a r i t h m of the 1-octanol/water p a r t i t i o n c o e f f i c i e n t ( l o g P ) . D i e t h y l a l k y l a m i n e s . Treatments w i t h d i f f e r e n t d i e t h y l a l k y l amines (Table I) gave a f a i r l y c o n s i s t e n t response p a t t e r n as the length o f the a l k y l group was i n c r e a s e d . The amount of any given carotene remained about the same or increased s l i g h t l y w i t h

In Biochemical Responses Induced by Herbicides; Moreland, D., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 1982.


9.

Bioregulation

YOKOYAMA ET AL.

Table I.

Phytofluene ζ-Carotene Neurosporene Lycopene γ-Carotene α-Carotene 3-Carotene

37.3 2.25 1.72

Total Log Ρ

43.9

0.37 0.54 1.72

(C H5) N(CH2)4CH3 (C2H5)2N(CH2) CH (C H5)2N(CH ) CH3 2

2

5

2

155

Biosynthesis

E f f e c t of t r i a l k y l a m i n e s on carotene content of the flavedo of Marsh seedless g r a p e f r u i t (pg/g dry w t ) . Postharvest treatment of f r u i t s , and method of i s o l a t i o n and i d e n t i f i c a t i o n o f pigments are described i n r e f e r e n c e 12. A p o r t i o n of ground flavedo was d r i e d i n vacuo a t 65 C to o b t a i n the dry wt. z~\ . t Control

*1. 2. 3.

of Pigment

2

3

4. 5.

Compound* ^

7

;

^

38.6 2.47 1.28 1.01 0.30 1.04 1.41

29.0 3.13 1.37 6.99 0.96 1.02 1.20

39.5 27.8 28.3 17.8 4.32 - 14.6 2.94 5.16 1.38 115 59.0 143 3.21 2.59 1.17 2.11 2.07 1.26 6.75 4.73 1.35

46.1 2.94

43.7 3.44

96.8 197.7 189.5 4.94 4.44 3.94

(C2H )2N(CH ) CH (C H ) N(CH )8CH 5

2

5

2

2

2

7

3

3

6



156


Table I I . E f f e c t of diethylaminoalkylbenzenes on carotene content of f l a v e d o o f Marsh seedless g r a p e f r u i t (pg/g d r y wt). See c a p t i o n o f Table I f o r e x p e r i mental d e t a i l s . Control


23.1 1.13 0.71

Total Log Ρ

26.5

*1. 2. 3.

0.57 0.95

(C2H5) NCH2C H (C H ) N(CH ) C H (C H ) N(CH ) C H 2

2

5

2

2

5

6

2

2

2

4. 5.

5

2

6

3

5

6

C o m

—j

2

d

P°™ *

^

25.3 1.38 0.83 8.62 0.55 0.77 0.56

29.3 37.9 38.7 86.2 1.38 6.77 27.5 53.8 0.83 1.11 7.16 12.0 8.62 188 104 153 0.55 1.07 0.59 1.67 0.77 0.61 2.19 0.76 0.56 0.95 t r a c e 0.68

37.8 3.07

37.8 236 180 308 3.07 4.07 4.57 5.07

(C H ) N(CH ) C H (C H ) N(CH ) C H 2

5

2

2

4

6

5

2

5

2

2

5

6

5

5



*1. 2. 3.

Total Log Ρ

5

6

2

2

2

49.9

0.27 0.35 1.35

44.9 2.74 0.33

C H OCH2CH2N(C H5)2 £-CH3~C H40CH CH N(C2H5)2 2-C2H5-C6H4OCH2CH2N(C2H5)2

6


Control

7

6

4

6

2

2

2

2

· £-iso-C H -C H OCH2CH N(C2H5)2 5. - t e r t - C 4 H 9 - C H 4 0 C H C H N ( C H 5 ) 3

2

245 4.05 323 3.55

79.5 3.05

255 4.25

£

95.6 4.65 303 4.35

44.9 13.7 0.93 182 2.13 0.38 0.82

50.9 19.0 0.84 249 2.48 0.41 0.40

48.1 5.45 0.91 22.2 1.01 0.57 1.26

42.6 10.1 1.21 199 1.90 0.23 0.39

4

33.7 4.57 0.63 54.4 1.04 0.63 0.58 51.1 20.6 1.62 226 2.74 0.40 0.70

Compound* Τ

ô

;

See c a p t i o n

on carotene

(ug/g dry w t ) .

CPTA

content o f flavedo o f Marsh seedless g r a p e f r u i t of Table I f o r experimental d e t a i l s .

Table I I I . E f f e c t of CPTA and analogs of diethylaminoethylphenylether



158


d i e t h y l p e n t y l a m i n e and diethylhexylamine, whereas d i e t h y l h e p t y l amine caused a l a r g e r accumulation, D i e t h y l o c t y l a m i n e and d i e t h y l nonylamine caused very l a r g e i n c r e a s e s i n t o t a l carotenoid con t e n t . Lycopene accounted f o r most of the i n c r e a s e i n the t o t a l carotene content but the intermediates, ζ-carotene (7,8,7',8'tetrahydro-i//,ij;-carotene) and neurosporene (7,8-dihydro^,φcarotene) a l s o increased a p p r e c i a b l y . Of s i g n i f i c a n c e are the 3.5 and 4.6-fold increases i n the c y c l i c carotenes, γ-, α- and 3-carotene ( i . e . , 3,ψ-, 3,ε- and 3,3-carotene) caused by d i e t h y l o c t y 1 amine and diethylnonylamine, r e s p e c t i v e l y . The i n c r e a s e i n c y c l i c carotenes i s much l a r g e r than that caused by r e g u l a t o r s t h a t con tained an aromatic r i n g . B u t y l d i e t h y l a m i n e has a l s o been observed to cause the development of red c o l o r i n g r a p e f r u i t , but only with higher c o n c e n t r a t i o n s and longer treatment p e r i o d s . The higher members of t h i s s e r i e s , d i e t h y l d e c y l a m i n e , diethylundecylamine, and diethyldodecylamine caused i n c r e a s i n g p e e l i n j u r y as the length of the a l k y l chain i n c r e a s e d . The l a s t two damaged the peel whenever they were a p p l i e d . The c o l o r of the p e e l next to the damaged areas showed c o l o r enhancement, but to a l e s s e n i n g degree as the a l k y l c h a i n was lengthened. Diethylaminoalkylbenzene. The responses of f r u i t t r e a t e d w i t h compounds l i s t e d i n Table I I were s i m i l a r to that of f r u i t treated with d i e t h y l a l k y l a m i n e s (Table I ) . There was a much l a r g e r i n c r e a s e i n ζ-carotene and neurosporene f o r diethylaminobutylbenzene and diethylaminopentylbenzene, whereas the i n c r e a s e i n c y c l i c carotenes was modest. For the d i e t h y l a l k y l a m i n e s , l y c o pene increased to a very h i g h l e v e l and then dropped f o r the l a s t number o f the s e r i e s (Table I ) . The drop i n lycopene accumulation was observed w i t h diethylaminobutylbenzene, but the amount of lyco pene increased with diethylaminopentylbenzene, although remaining l e s s than the maximum f o r t h i s s e r i e s ' o f b i o r e g u l a t o r s . The very l a r g e i n c r e a s e i n phytofluene (15 cis-7,8,11,12,7 ,8'-hexahydroψ,ψ-carotene), as w e l l as ζ-carotene, caused by diethylaminopentylbenzene r e s u l t e d i n a g r e a t e r i n c r e a s e i n the t o t a l carotene content. Whether t h i s was caused, i n p a r t , by some s i d e e f f e c t of the extensive p e e l damage or e n t i r e l y by the compound i s not c e r t a i n . A s i m i l a r e f f e c t had been observed p r e v i o u s l y (14) a f t e r treatment w i t h [γ-(diethylamino)-propoxy]-benzene and [

Bioregulation of Pigment Biosynthesis by Onium Compounds - ACS

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