3.1 plant description - information and library...

C a n c a p a p a y a Liim.

3.1 PLANT DESCRIPTION

3.L1 Family: Caricaceae

3.1.2 Synonym: Bengali-P<^^(?, pappaâ; Gn]nti-Papi^, popaijm\ Umdi-Pêeta:,Kmniidz-Parafi^mra; kappatiga pappaâm Marathi-P<^<^<?;Tm^~?appali,pappa^\ Tth^-Boppaji.

3.1.3 Distfibution: Papaya has never been found wild, but it is probable that it originated m southern Mexico and Costa Rica. It is closely related to Caricapeltata Hook, and Am., occurring in diis area, and may have arisen by hybridization. The tree has gained importance as a plantation crop in Australia, Hawai, Philippines, India, Sri Lanka, South Africa and a number of other countries in tropical America and Soutli-eastern Asia. Papaya was introduced into India in the 16 '’ century and was naturalised quickly. It is quick in growing and heavy yielding crop and is grown both commercially and in home gardens. Six species o f Carica, namely Cpaptâ, C m i m c a t p a C . p u b m b s , C caul^ra, C. monokaT>tsi. and C goudotiana Solms-Laubach have been utilized for so for breeding. According to their crossabilily these species can be arranged in three groups: (1) Q monoica, C. cauhfkra, C. microcarpa and C pubesms. These four species can be crossed readily with each other, producing viable seeds, (2) C papaya and {2>) C jpudoiiana. Crosses between group (1) and (2) do not form mature seeds, but in most cases the immature embryos can be cultivated. Crosses between C papaya m d C. goudotiam always give negative results. These species appear to be important from the viewpoint of breeding disease resistant strains. Although regarded as a cross^

poUitiaring species, papaya can be self-pollinating without loss of vigour (Anonymous, 1992).

3.1.4 Motphology-. A fast groMnng, short-lived, single-stemmed small tree, 2-10 m in height with straight, cylindrical, soft hollow grey trutik roughed by the presence of large leaf and inflorescence scars. Leaves alternate, crowded at the apex of die trunk forming a crown, long petioled, widely patent, glabrous, more or less deeply palmified, flowers fragrant, trimorphous, usually unisexual dioecious, male flowers large, solitary or in few flowered racemes, with' a short thick rachiss; fruit a large berry, varying widely in size, elongate to globose with a large central cavity; seeds black, tuberculous and enclosed in a transparent aril (Anonymous, 1992).

3.1.5 Medicinal Pfoperties: The ripe fruit is tasty; astringent, digestive, carminative, diuretic; cures inflammations, enlargement of tlie spleen; removes urinary concretions; relieves obesity; used in haemoptysis, bleeding piles, wounds of the urinary tracts; usefiil in ringworm, sldn diseases, psoriasis. The milky juice of the unripe fruit is considered anthelmintic and principally effectual in the expulsion of lumbrid. The seeds are also claimed to be vermifuge; but they are mosdy used as an emmenagogue. It is a popular belief diat tfiey may cause abortion. In the Gold Coast, the roots are said to cure yaws, and also piles. The dry leaves when placed in water form yellowish red liquor, which is drunk to cure stomach problems. A decoction of the leaves is given as purgative to horses. They ate given as thirst quencher and they forra a component part of a drink used in fever. Papaine, a digestive enzyme, valued in the medicine and in the preparation of chewing gums, is obtained from the white, thin latex or juice (Kirtikar & Basu, 2000).

3.2 CHEMICAL CONSTITUENTS AND BIOLOGICAL ACTIVITIESAnalysis of the unripe and ripe fruit gave the following values, respectively: moisture-92.0, 90.8; ptoteins-0.7, 0.6; fat-0.2, 0.1; fiber-0.9, 0.8; carbohydrates- 5.7, 7.2; energy-27, 32 K cal; and minerals-0.5, 0.5 g/100 g; calcium-28, 17; phosphorus-40, 13; iron-0.9, 0.5; vitamin C-12, 57; thiamine-0.01, 0.04; riboflavin-0.01, 0.25; niacin-0.1, 0.2 mg/lOOg; and carotene-0.666}xg/100g. The vitamin C content of fruit varies from place to place. The essential amino acid composition of ripe fruit is as follows: lysine-6.4; tryptophan-2.08; and mediioniae-0.48g/16 g. The papaya juice mainly contain «-butyric acid, »- hexanoic and »-octanoic acids. Analysis of the pulp Upid showed the following acid composition; mytstic-7.2; palmatic-24,9; stearic-1.6; linoleic-4.2; Unolenic- 19.2; and as-vaccenic and oleic-22.4%. Analysis of the seed gave: inoisture-71,89; protein-8.4; carbohydi:ates-9.44; and ash-1.47%. The seed yields fatty oils (9.5%) having die following characteristics: sp gr^s-0.9130, n'*°-1.4627; saponification value-193.4; iodine value-74.77; and unsaponification matter-2 .11%. The oil has following fatty acid composition: lauric,-0.13; myristic-0.l6; palmitiG-15.13; stearic-3.61; arachidic-0.87; behenic-0.22; oleic-71.60; linoleic-7.,68; and linolenic- 0.6%. The defatted seed contains: crude p r o t e i n - 40.0; atude fibeif-48.9; ^ d ash- 6.86%; caldum-1.66; magnesiuin-0.64; phosphorus-0.84; potassium-0.33; and

Chapter 3 papaya

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sulphur-0.46%, presence of manganese, iron and copper is also reported. Papaya root contains caiposide and an enzyme myrosin (Anonymous, 1992).

Benzyl-p-D-glucoside, 2-phenylethyl-P-D-glucoside, 4-hydioxyphenyl*2-ethyl-p-D- glucoside and four isomeric malonated benzyl-P-D-glucosides were isolated frotn C. papaya fcuit pulp by liquid chromatography. Identifications were performed after permethylation by comparison o f HRGC, HRGC-MS and HRGC-FTIR data with those o f synthesized reference compounds (Schwab and Schreier, 1988).

Echeverri et al., 1997 isolated a new phytoalexin from papaya fruit slices treated widi copper salts; its structure was established as 3', 5'-dimethoxy-4'-hydroxy-(2- hydroxy) acetophenone. This compound exhibited high antifungal activity against Colktotrichum gloesporioides, a pathogenic fungus of papaya.

Five species o f the family Caricaceae were examined for glucosinolates like C. papaya L., diey all contained benzylglucosinolate as the sole thioglucoside (Gmelin and Kjaer, 1970).

Oxygenated terpenoids derived from linalodl, a major constituent of papaya fruit volatiles, were studied by HRGC and HRGC-MS. Using a sample preparation technique suitable for the separation and enrichment of polar compounds, the two diastereoisomers of 6, 7-epoxy-linalool, 2, 6-diniiethyl-octa-l, 7-diene-3, 6- diol, 2 , 6-dimethyl-octa-3, 7-diene-2, 6-dioI, (B)- and (2)-2, 6-dimethyl-octa-2, 7- diene-1, 6-diol and 2, 6-dimethyl-oct-7-ene-2, 3, 6-triol were identified. Additionally, each of four diastereoisometic epoxy-linalool oxides in theirfuranoid and pyranoid forms were detected for the first time as natural plantconstituents (Winterhalter 1986).

Kermanshai et aL, 2001 extracted C papaya seeds in an aqueous buffer or inorganic solvents, fractionated by chromatography on silica and aliquots tested for anthelmintic activity by viability assays using Caenorhabditis ekgans, 'Bot all preparations and fractions tested, anthelmintic activity and benzyl isothiocyanate content correlated positively. Aqueous extracts prepared iSroiii heat-treated seeds had no anthelmintic activity or benzyl isothiocyanate content although both appeared authentic when liese extracts were incubated with a myrosinase- containing fraction prepared from papaya seeds. A 10 hr incubation of crude seed extracts at room temperature led to a decrease in anthelmintic activity and fractionated samples showed a lower benzyl isothiocyanate content relative to non-incubated controls. Benzyl thiocyanate, benzyl cyanide, and benzonitrile were not detected in any preparations and cyaiiogetiic glucosides, which were present, could not account for die anthelmintic activity detected. ITius, it was proposed that benzyl isothiocyanate was the predonoinant or sole anthelmintic agent in papaya seed extracts regardless of how seeds were extracted.

The contraceptive evaluation and to^cological effects of die aqueous extract of the seeds of C. papcQa'vci adult male rabbits have be^tepw^^2000. Thirty adult male rabbits were divided itito five groups of Six atiiojals each; Group I, control; Groups II-V were adniiiiistered ordly with aqueous extract of

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the seeds of C. papcâ at doses of 20, 50, 75 and 100 mg/kg per day for 150 days, respectively. The body weight, reproductive organs weight, semen analysis, semen biochemistry, toxicological profiles and the fertility status have been recorded. The aqueous extract failed to exhibit contraceptive effects at any of the dose regimens tested, contrary to the observations made in the previous studies. Unaltered toxicological profiles indicated that the drug was free of side effects. The results suggest that the failure of contraceptive effects may be due to species specificity; relative resistance of die animals to the drug or lack of potency of the extract due to factors generally affects biological activity of the plant preparations.

Mature seeds of C papcâ have less in-vitro anti-amoebic action when compared to metronidazole as reference product (Tona etal, 1998).

Experiments were conducted to investigate the abortifacient potential of aqueous extract of C. papaya seeds in female Sprague-Dawley rats. Oral doses of 100 and 800 mg/kg body weight were administered once a day on days 1-10 post-coitum. No significant differences in total body weight were found in foetuses exposed to these regimes. However, in the group treated with 100 mg/kg body weight, there was a significant increase (p<0.05) in the implantation sites and foetal weight was significandy decreased (p<0.05) compared to the controls. No dead or malformed foetuses were found. However, in the group treated with 800 mg/kg body weight, there was obvious vaginal bleeding but no treatment related increase in implantation sites compared with control. There was however, complete resorption of about 30% of die foetuses. The surviving foetuses were stunted when compared witii the control but were witliout any external malformations. The results of the present investigations lead to the dear conclusion that low dose aqueous crude extract of C. papcâ seeds does not adversely affect prenatal development. The altered toxicological profile indicates that die abortifacient property is a high dose side effect. The results indicate that C papaj/a toxicity can adversely affect the foetus (Oderinde, 2002).

The contraceptive effects of benzene chromatographic fraction of tlie chloroform extract of the seeds of C pcâja have been reported in male albino rats at the dose regimens 5 and 10 mg/animal/day; oral for 150 days. The body weight, weight of testis, epididymis, seminal vesicle and ventral prostate remained unaltered during the entire course of the investigation. Total suppression of cauda epididymal sperm motility coincided with a decrease in sperm count, viability and an increase in per cent abnormal spermatozoa during-60-150 days observation period. Minor changes in the germ cell proliferations in the testis and vacuolization and pyknotic nuclei in the few epithelial cells of the cauda epididymis were observed. Histology and biochemical composition of testis and accessory sex organs, haematology and serum clinical biochemistry and serum testosterone levels remained unchanged throughout the course o f the investigation. Test for estrogenicity indicated mild estrogenicity. Monthly fertility test showed negative fertiHty. All the altered pâmeters returned to normal level following 60 days withdrawal of the treatment. The results suggest that the benzene chromatographic fraction of the chloroform extract of the seeds of C.

Chapter 3 c. papaya

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papaya exerts antifertility effects in rats without adverse toxicity and that tlie effects may be directly rendered on the spermatozoa (Pathak et aL, 2000).

The chloroform extract of C pcâya seeds, 50 mg/kg/day, was administered orally for 360 days to adult male langur monkeys {Pmbyiis entellus) to establish the antifertility effect. The sperm characteristics by light and electron microscopy, die sperm functional tests, Ae semen biochemistry, the serum testosterone level, the Leydig cell function, and the histology and ultrastructure of testis were determined to evaluate the antifertility activity and the blood biochemistry and hematology, to evaluate the toxicology. The extract gradually decreased the sperm concentration since days 30-60 of treatment widi a total inliibition of sperm motility, a decrease in sperm viability and increase in sperm abnormality. Azoospermia was observed after day 90 of treatment and continued during the whole treatment period. Treatment withdrawal resulted in a gradual recovery in these parameters and 150 days later they reverted to nearly the pretreatment values. Morphological observation of the ejaculated sperm by light and scanning electron microscopy showed deleterious changes, particularly on the mid-piece. Sperm functional tests, sperm mitochondrial activity index, acrosome intactness test and hypo-osmotic swelling test scored in the infertile range during treatment and returned to the fertile values 150 days after drug withdrawal. Histology of the testis revealed shrunken tubules, germ cell atrophy and normal Leydig cells. Ultrastructure of the testis showed vacuolization in die c5rtoplasm of Sertoli cells and germ cells. Loss of cytoplasmic organelles were evident in spermatocytes and spermatids. Round spermatids showed loss of Golgi bodies, peripheral mitochondria and vacuolated cytoplasm, indicating maturational arrest. Leydig cell functional test indicated a mild inhibition of steroidogenic function. Haematology and serum biochemistry study disclosed no significant toxicological effect and l±ie serum testosterone level was not affected. C. pcêâ seed extract may selectively act on the developing germ cells, possibly mediated via Sertoli cells, leading to azoospermia (Lohiya etal., 2002).

Volatile compounds were isolated from fresh papaya fruit by simultaneous steam distillation solvent extraction according to Likens-Nickerson. Compounds were identified by capillary GC-MS and sensorily characterized by sniffing GC. One hundred and sixty-six compounds were identified in die aroma conc., of which 77 were identified for the first time as papaya volatiles. Among the identified compounds, methyl butanoate, ethyl butanoate, 3-methyl-1-butanol and 1- butanol were found to be the major components. The esters of lower fatty acids were considered to contribute much to the typical papaya flavor (Pino et al., 2003).

The effect of ripening on the chemical composition of C papaya var. Ripening was characterized sensorily, as well as dirough physical and chemical analyses. Volatile compounds were isolated by a simultaneous distiUation/solvent extraction taethod. Butanol, 3-methylbutanol, benzyl alcohol and a-terpineol showed maximum concentration in the third maturation stage, in correspondence with fruit ripeness (Almora 2004).

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C. papaya seeds extracted widi 80% edianol caused concentration-dependent tocolfsis of uterine strips isoJated from gravid and non-gravid rats. Previous workers have reported benzyl isodaiocyanate as the main bioactive and anthelmintic compound in different extracts of papaya seeds. Using election impact ionization methods, the presence of these compounds in the ethanolic extract was also shown in this study (Adebiyi et ai, 2003).

Many orange-colored fruits contain P-cryptoxanthin in its non-esterified as well as its esterified form. Information concerning the absorption of P-ciyptoxanthin, especially widi regard to the metabolism of its fatty acid esters, is rather scarce. A study assessed the plasma concentration reached after consumption of a single dose of native P-cryptoxanthin esters from C papaya or non-esterified P- cryptoxanthin in equal total amounts. In a randomized, single-blind crossover study, twelve subjects were served a portion of yoghurt containing esterified or non-esterified P-cryptoxanthin (1-33 m ^ together with a balanced breakfast. Between the two intervention days, there was a 2-week depletion period. After a fasting blood sample had been taken, further samples were taken from the subjects at 3, 6 , 9, 12 and 24 hr. The concentcation of non-esterified p- cryptoxanthin in the whole plasma was determined by HPLC; P-cryptoxanthin identification was confirmed by liquid chromatography-atmospheric pressure chemical ionization-MS analyses. Irrespective of the consumed diet, the plasma P-cryptoxandiin concentration increased significantly (p=0.05) and peaked after 6-12 hr. The concentration curves, as weU as the areas under the curves, were not distinguishable according to two-sided F and t tests (p=0.05). Standardization of P-ctyptoxanthin concentration to plasma triacylglycerol and cholesterol had no impact on die results. Thus, the present study indicates comparable bioavailability of both non-esterified P-cryptoxanthin and mixtures o f p- cryptoxanthin esters. The results support the existence of an effective enzymic cleavage system accepting various p-cryptoxanthin esters (Breithaupt et al, 2003).

Carpine was extracted from C pi^aya Itaves and found to have antitumor activity in mtro against mousee lymphoid leukemia L1210, lymphocytic leukemia P388, and Ehrlich ascites tumor cells (Luz etal., 1972),

Three thiol proteinases, namely papain (important digesting enzyme), chymopapain and proteinase omega were purified to homogeneity from the latex of C papaya L. During the purification procedure, the thiol function of the cysteinyl residues were protected either as mixed disulfides with cysteamine or 2- tWopyridone or as S-sulphenylthiosulfate derivative or after blocking wilii p- chloromercuribenzoic add. In marked contrast widi earlier publications, chymopapain also was found to be a monothiol proteinase as papain arid proteinase omega. The active sites of chymopapain and proteinase omega could not be distinguished from tiiat of papain neither by die analysis o f the pH dependence of kcat/Km nor by the examination of the pH dependence of the fluorescence emission spectra (Dubois 1998).

Oiapter 3 C papaya

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Chapter 3 C papaya

Chemical ConstituentsReported from C. papaya

o

o

R "'0

OR

Mftlonated-p-D-glucoside (I, II, 111) I=R-maloiiyI, R ’, R", R’”=H II=R, R”, R'**=H, R'=Malonyl III=R, R’, R'”=H» R'»=Malonyl IV=R, R', R"=H, R'"=Malonyl

Benzylis othiocyanate

4-lydro3ypheByl>2-etlig^I-P-D-gIucosi<

Malonated benzyl-p-D-glucoside

Benzyl-P -D-glucos e

78

S— C,H„05

Chapter 3 pap^yQ

O H H2CHSC6N-—OSO,r

Benzylglucosinolate

3.3 EXPERIMENTAL

3.3.1 Materials And Methods

3.3.1.1 General: Mps were uncorrected: Perfit melting point apparatus; IR: Bio- Rad FTIR Spectrophotometer KBr; UV; Lambda Bio 20 Spectrophotometer, MeOH; ^H-NMR (300 MHz): DPX 300, Bruker Spectrospin, CDCI3 and DMSO- «Ir; 13C-NMR (300 MHz); DPX 300, Bruker Spectrospin, CDCI3 and DMSO-fl ? -with TMS as an internal standard; MS: ESIMS JEOL-JMS-DX 303; CC: Silica gel (Qualigens), 60-120 mesh; TLC: Silica gel G (QuaUgens). Spots were visualized by exposure to iodine vapours, UV radiation and by spraying with eerie ammonium sulphate and perchloric acid.

3.3.1.2 Collection of material: C. papaya seeds were procured from the Khari Baoli market of Delhi and was identified by Dr. M.P. Sharma, Department of Botany, Jamia Hamdard. New Delhi. A voucher specimen is deposited in the herbarium of die Phytochemistry Research Laboratory, Faculty of Pharmacy.

3.3.3.3 Extraction and Isolation: The dried drug (2 kg) was coarsely powdered, defatted with petroleum ether and then exhaustively extracted with ethanol (95%). The combined extracts were then concentrated on a water bath and dried under reduced pressure to get 75 g (3.75% yield) of dark brown mass. The viscous dark brown mass was dissolved in litde quantity of methanol and adsorbed on siUca gel (60-120 mesh) for the preparation of slurry. It was dried, packed and chromatographed over silica gel column packed in petroleum ether. The colvimn was eluted with petroleum ether, chloroform and methanol successively in the order of increasing polarity to isolate following compounds:

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Caricadilinolenide (CP-1)Elution of column with petroleum ether-CHCU (1:3) (ffaction No. 1-50) affotded light brown waxy mass of CP-1, recrystaUised from CHCb, 125 mg (0.00625% yield).Rp 0.80 (CHCI3).UV (MeOH); 251 nm (log s 4.8).IR Vmax(KBf): 2926, 2851, 1740, 1725, 1720, 1462, 1377, 1239, 1164, 1097, 794, 774, 732 cm-i.iH NMR (CDCI3): 5 5.35 (2H, m, H-9', H-10'), 5.33 (4H, m, H-9", H-10", H- 9'", H-10'"), 4.28 (4H, m, H -12", H-13”, H-12”', H-13'"), 4.32 (IH, d,/=4.2 Hz, H2-la), 4.28 (IH, d,/=4.2 Hz, Ha-lb), 4.17 (IH, d j= 5 .7 Hz, H2-3a), 4.13 (IH, d, 7=5.7 Hz, H2-3b), 3.66 (IH, m, H-2), 2.34 (2H, brs, Hz-Z'), 2.31 (2H, bts, H 2-2"), 2.28 (2H, bfs, H2-2 ”'), 2.01 (4H, brs, H2-II" , H a-ll'"), 1-98 (4H, brs, H2-8 ', H 2- 11'), 1.61 (4H, brs, H2-8", H2-8'"), 1.59 (4H, brs, H2-I4 '', H2- I4 '"), 1.30 (34 H, brs, HxCHa), 1.25 (20H, brs, IOXCH2), 0.89 (3H, t,/=5.7 Hz, Me-16'), 0.88 (3H, t,/™6.6 Hz, Me-18"), 0.85 (3H, tj= 6 .6 Hz, Me-18'").+ve ion ESI MS m /^ . 852 |M]^ (CssHgcOg).

CaricadiarchidoUde (CP-2)Elution of column with CHCU (fraction No. 51-80) afforded Eght brown waxy mass of CP-2, recrystallised from CHCls-acetone (1:1) (67-83), 210 mg (0.0105% yield).Rp 0.75 (CHCI3).UV A,max (MeOH): 242 nm (log 8 4.1).IR Vma« (KBr): 2921, 2815, 1735, 1721, 1715, 1599, 1461, 1410, 1290, 796, 732 cm-^m NM R (CDCI3): 8 5.34 (2H, m, H-9', H-10'), 4.28 (2H, m, H 2-I), 4.17 (2H, m, H2-3), 3.66 (IH, m, H-2), 2.37 (3H, d,/=7.5 Hz, Ha-2'a, H2-2a", Hz-2a"'), 2.32 (3H, d, 7=7.5 Hz, H2-2 'b, H2-2"b, 2"'b), 2.01 (2H, m, H2-8 '), 1.63 (2H, m, H2- 11'), 1.30 (22H, brs, llxCHz), 1.25 (68H, brs, 34 x CH2), 0.88 (3H, t, 7=6.6 Hz, Me-18'), 0.85 (3H, t, 7=6.6 Hz, Me-20"), 0.81(3H, t,7=6.2 Hz, Me-20'").ESI MS m A . 944 |M]+ (CeiHneOe).

Caricadistearide (CP-3)Elution of colvimn with CHCls-MeOH (49:1) (fraction No. 90-110) afforded brown sticky mass o f CP-3, recrystallised from CHCI3, 390mg (0.0195% yield).Rf: 0.70 (CHCl3:MeOH; 9.5;0.5).UV Xnm (MeOH): 249 nm (log 8 2.9).IR Vmax (KBf): 2982,2855,1730,1725,1640,1270,1075, 795 cm"*. m NM R (CDCI3): 5 6.89 (IH, m, H-10'), 6.85 (IH, m, H-12'), 5.34 (2H, m, H- 9', H-13'), 4.30 (IH, d, 7= 6.6 Hz, H2-la), 4.26 (IH, d, 7=6.6 Hz, H2-lb), 3.94 (IH, m, H-2), 3.78 (2H, m, H2-3), 2.78 (2H, m, H2- i r ) , 2.34 (IH, d j= 9 Hz, Ha- 2'a), 2.31 (IH, d,7=9 Hz, H2-2 'b). 2.27 (2H, brs, H2-2 "), 2.01 (2H, brs, H2-2 '"),1.B3 (2H, m, H 2-8'), 1.64 (2H, m, H2-I4'), 1.59 (4H, brs, 2 x CHa), 1.25 (72H, brs,

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36 X CFI2), 0.97 (3H, t,J=5A Hz, Me-18'), 0.96 (3H, tj= 6 .0 , Me-18”), 0.87 (3H, t J = 6.1 Hz, Me-18'”).+ve ESI MS m /2: 886 (CsyHjoeOc).

Caricaphenyl triol (CP-4)Elution of column with CHCU-MeOH (49:1) (ftaction No. 111-118) afforded cream coloured amorphous powder of CP-4, recrystallised from chloroform 350 mg (0.0175% yield).Re 0.70 {Toloune:ethyl acetate:foimic acid; 5:4.5:0.5) m.p.: 218-220°CUV Xmax (MeOH): 281 nm (log e 6.2).IR Vmax (KBf): 3415, 2940, 2824,1640,1513, 1210, 950, 792 cm-i. iH NM R (DMSO-fik): 8 10.37 (IH, brs, D2O Exchangeable, OH), 7.79 (IH, d, 7=8.4 Hz, H-3), 6.82 (IH, d,/=8.4 Hz, H-4), 3.38 (IH, brs, OH), 2.26 (3H, brs, Me-7).^C NM R (DMSO-Jtf): 167.24 (C-1), 161.64 (C-2), 121.44 (C-3), 115.16 (C-4), 131.57 (C-5), 161.64 (C-6), 29.04 (C-7).+ve ESI MS m /z: 140 CyHsOa.

Caricaoleiolide phosphate (CP-5)Elution of column with CHCIj-MeOH (97:3) (fraction No. 118-130) afforded brown waxy mass o f CP-5, recrystaUised from methanol, 670 mg (0.0335% yield). Rf: 0.60 (Toluene:ethyl acetate:formic acid; 5:4:1).UV (MeOH): 249 nm (log s 4.1).IR Vroax (KBf): 3424, 2924, 2853, 1725, 1640, 1442, 1380, 1261, 1075, 795, 773 cm-^m NM R (CDCI3): 5 5.27 (IH, m, H-9'), 5.00 (IH, m, H-10'), 4.20 (2H, brs, H2- 3), 4.00 (2H, brs, H 2-I), 3.69 (IH, m, H-2), 2.28 (IH, d,/=12.9 Hz, H 2-2 'a), 2.23 (IH, d ,/= 12.9 Hz, H2-2 'b), 2.13 (2H, m, H2-8 '), 1.94 (2H, m, Ha-ll'), 1-57 (2H, m, CHa), 1.49 (2H, m, GHz), 1.40 (2H, m, CHa), 1.18 (16H, brs, BxCHa), 0.75 (3H, t,/=6.1 Hz, Me-IBO-

NM R (CDCI3): 5 132.11 (C-9'), 129.23 (C-10'), 128.26 (C-1'), 66.77 (C-2), 61.55 (C-1), 60.01 (C-3), 43.48 (CH2). 42.83 (CH2), 40.82 (CH2), 39.86 (CH2),39.59 (CH2), 37.25 (CH2), 33.68 (CH2), 31.35 (CH2), 29.12 (CH2), 26.63 (CH2),25.01 (2xCH2), 24.39 (CH2), 22.11 (CH2), 13.63 (me-18').+ve ESI M S /n A 436 [M]+(C21H41O7P).

Carpaine (CP-6)Elution of column with CHCls-MeOH (24:1) (fraction No. 131-145) afforded colourless mass of CP-6 , recrystallised from methanol, 450 mg (0.0225% yield).Rfi 0.41 (Tolueneiediylacetateracetic Acid; 5:4:1). m,p.: 118-120®C.UVA,max (MeOH): 241 nm (loge 5.6).[oc]d20:+23.6° ( c - 1.01 in EtOH)-IR Vmax(KBr): 2919,2860,1725,1526,1450,1180, 773 cm-i.

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m NMR (DMSO-di^): 5 4.64 (IH, m, H-3), 4.30 (IH, m, H-3'), 3.89 (2H, m, H-6, H-6'), 3.12 (2H, m, H-2, H-2'), 2.51 (4H, brs, H2-8, H2-8'), 1.48 (4H, brs, H2-4, H2-4 '), 1.43 (4H, bi-s, H 2-5, H2-5'), 1.23 (24H, brs, 12 x CH2), 0.87 (6H, brs, Me-7, Me-7').13C NMR (CDCb): 8 77.41 (C-1'), 76.99 (C-1"), 71.23 (C-2), 63.13 (C-1), 61.17 (C-3), 31.90 (CH2), 29.67 (25xCH2), 25.50 (CH2), 22.67 (CH2), 14.09 (Me-16, Me- 16")+ v e ESI MS m /z: 4 7 8 pVI]+ ( C 28H 50N 2O 4+).

Caricadipalmitate (CP-7)Eludon of column with CHCh-MeOH (24:1) (fraction No. 146-151) afforded buff white amorphous powder of CP-7, recrystalHsed from methanol, 450 mg (0.0225% yield).Rf 0.55 (Toiueiie:etlaylacetate:acetic Acid; 5:4:1). m.p.: 170-172°CUV (MeOH): 213 nm (log e 3.2).IR v«»x(KBf): 3417,2919, 2834,1725,1637,1554,1402, 1017, 771 cm-i.

NMR (CDCI3): 8 4.87 (IH, m, H-2), 4.57 (IH, brs, Ha-la), 4.36 (IH, brs, H2- Ib). 3.96 (IH, brs, H2-3a), 3.81 (IH, brs, H2-3b), 2.73 (2H, brs, CH2-2 '), 1.57 (2H, brs, CH2-2"), 1.25 (52H, brs, 26XCH2), 0.87 (6H, brs, 2XCH3).13C NMR (CDCI3); 5 77.41 (C-1'), 76.99 (C-1"), 71.23 (C-2), 63.13 (C-1), 61.17 (C-3), 31.90 (CH2), 29.67 (25xCH2), 25.50 (CH2), 22.67 (CH2), 14.09 (Me-16, Me- 16").+ve ESI MS m /a (reJ. int.): 567 |M|+ CasHevOs (3.5), 328 [M-CO(CH2)i4CH3]+ (16.4).

Caricaoleolauryl phosphate (CP-8)Elution of column with CHCb-MeOH (19:1) (fraction No. 256-260) afforded light brown amorphous powder of CP-8, recrystaUised from methanol, 425 mg (0.021% yield).Rf 0.60 (Toluene:ethyl acetate: acetic acid; 5:3:2). m.p.: 226-228°C.UV Xmax (MeOH): 240 nm (log e 4.3).IR v„ax (KBr): 3434, 2434, 2950, 2845, 1734,1638,1528, 1420, 1120, 775 cm-i. iH NM R (CDCI3): 8 5.36 (2H, m, H-9', H-10'), 4.42 (IH, m, H-2), 3.92 (2H, m, H2-3), 3.59 (2H, brs, H2-I), 2.27 (2H, m, H2-2 '), 2.01 (2H, m, H 2-2"), 1.62 (4H, brs, H2-8', H2-II'), 1.25 (40 H, brs, 2OXCH2), 0.87 (3H, t,/=6 .0 Hz, Me-18'), 0.84 (3H, t,7=6.2 Hz, Me-12'0 +ve ESI M S /n A 618 [M]+(C33H63O8P).

p-sitostefol glycoside (CP-9)Elutiofl of die column with chloroform-medianol (19:1) (fraction No. 161-163) furnished colourless amorphous powder of GP-9, recrystallized from metfaianol, 260mg (0.013% yield). m.p,; 270-272“C.

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Rf: 0.53 (benzene: chlofofomi: methanol; 5:4:1).UVA<inax (MeOH): 264 nm (log s4.5).IRVn,aK(KBr):3450,2917, 2849, 2383,1636,1460,1074, 795 cm-’. iH NM R (DMSO-d'tf): 6 5.33 (IH, brs, H-6), 4.90 (IH, d, J = 9.61Hz, H-1), 4.44 (IH, d,J=6.0 Hz, H-5), 4.23 (IH m, H-4), 4.20 (IH, dd j= 7 .63 , 6.0 (Hz, H-2% 3.63 (IH, m, H-3'), 3.34 (IH, brm, a; -/,=16.50Hz, H-3a), 3.04 (2H, brs, Ha-e*), 0.95 (3H, brs, Me-19), 0.91 (3H, dJ=6.5Hz, Me-21), 0.89 (3H. d,/=7.0 Hz, Me - 29), 0.82 (3H, d,/=5.69 Hz, Me-26), 0.80 (3H, d,/=6.39 Hz, Me -27), 0. 65 (3H, bfs,M el8).«C NM R (D M SO -d^: 5 36.74 (C-1), 31.34 (C-2), 76.57 (C-3), 41.18 (C-4), 139.95 (C-5), 121.35 (C-6), 33.37 (C-7), 29.13 (C-8), 49.58 (C-9), 36.74 (C-10), 22.50 (C-11), 35.55 (C-12), 45.24 (C-13), 56.16 (C-14), 25.48 (C-15), 28.58 (C-16), 56.16 (C-17), 11.35 (C-18), 20.49 (C-19), 33.37 (C-20), 18.84 (C-21), 31.34 (C-22), 29.13 (C-23), 49.58 (C-24), 27.67 (C-25), 19.32 (C-26), 18.84 (027), 22.50 (C-28),11.35 (C-29), 100.68 (C-l^ 73.22 (C-2'), 76.57 (C-3’) 70.55 (C-4'), 78.18 (C-5') 62.06 (C-6').+ve ESI MS T u /z (reJ. int.): 576 (C35 HeoOe) (N.O.), 413 [H]+ (C29 H50O)(4.3), 398 (15.5), 396 (20.5), 381 (15.3), 272 (4.3), 255 (11.7), 240 (7.6), 213 (8.2), 186 (10.3), 159 (14.8), 145 (15.9), 138 (13.5), 133 (14.7), 131 (16.1), 121 (18.5), 105 (31.6), 91 (32.7), 81 (37.8) 77 (48.1), 69 (24.3), 57 63.8), 43 (100).Acid hydrolysis of CP-9: Compound CP-9 (15 m ^ was refluxed with 2N HCl in 80% MeCDH (1:1, 15 ml) for four hours. After cooling, the reaction mixture was pouted into crushed ice, and ± e hydrolysate was then extracted with EtOAc to give the aglycone, and m.p. 138-140" C, Co-TLC comparable. The neutralized and concentrated aqueous hydrolysate showed the presence of glucose on comparison with authentic sugar on siUca gel TLC, Rf 0.4 (EtO Ac: HOAc: H2 O: MeOH; 6:1:1:2).

Carica trimyristate (CP-10)Elution of column with CHCU-MeOH (93:7) (fraction No. 164-170) afforded brown amorphous powder of CP-10, recrystallised from methanol, 310 mg (0.0155% yield).Rf. 0.70 (CHCl3:EtOAc:MeOH; 8:1:1). m.p.: 180°C (D).UV >miax (MeOH): 261 nm (log e 4.5).IR Vmax(KBr): 2955,2842, 1730,1725,1655,1422,1401,1219,1020,772 cm- . iH NM R (DMSO-d'ff): 5 4.65 (IH, m, H-2), 4.37 (2H, m, H2-I), 4.25 (2H, m, H2-3), 2.56 (6H, brs, H2-2 ', H2-2", H2-2 '"), 1-25 (66H, brs, 33xCH2), 0.98 (3H, brs. Me), 0.87 (6H, brs, 2xCH3).+ve ESI MS w/sr. 722 [M]+ (C45H86O6).

Carica tristearate (CP-11)Elusion of column with CHCls-MeOH (17:3) (fraction No. 174-200) afforded brown amorphous powder o f CP-11, methanol, 250 tng (0.0125% yield). Rr.0.85(CHCl3:EtOAc:MeOH; 8:2:2). m.p.: 124-126®C.UV (MeOH): 259 nm (log s 4.7).

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IR v„,ax(KBi-): 2950, 2845, 1730, 1725,1635,1470, 1210, 1120, 1030, 725 cm-’. iH NMR (DMSO-dfi): 6 4.51 (IH, m, H-2), 4.49 (4H, m, H 2-I, H 2-3), 2.56 (6H, brs, m, 3 X CH2), 1.30 (90H, brs, 45xCH2), 0.91 (9H, bfs, 3xCHi).+ve ESI MS m /z: 890 [MJ * (CstHiioOc).

Caticadioleophenyl glyceride (CP-12)Elution of colximn witli CHCb-MeOH (4:1) (ftaction No, 201-205) affotded brown amorphous powder of CP-12, recrystallised from methanol, 320 mg (0.016% )^eld).Rf! 0.65 (CHCl3:EtOAc:MeOH; 6:2:2). m.p.: 186-88" CLTV (MeOH): 266 nm (log e 5.7).IR v,n^ (KBr): 3410, 3120, 2959, 2855,1730,1725,1135, 1025,773 cm-^‘H NM R (DMSO-rftf): 6 7.17 (IH, d,/=8.4 Hz, H-6'), 6.95 (IH, d,/=8.4 Hz, H- 7') 5.32 (2H, m, H-9", H-10"), 5.18 (2H, m, H-9'", H-10'"), 4.81 (IH, m, H-2), 4.65 (2H, brs, H2-I), 3.86 (2H, brs, H2-3), 2.50 (4H, brs, H2-2 ", H2-2"'), 2.27 (4H, brs, H2-S”, H2-II"), 1.98 (4H, brs, H2-8 '", H2-II'"), 1-53 (4H, brs, 2xCH2), 1.23 (36H, brs, I 8XCH2), 0.85 (3H, t,/=6.1 Hz, Me-18"), 0.83 (3H, t,J=6.1 Hz, Me- 18'”)-+ V C ESI MS t n / ^ . 744 (M]+ (C44H72O9).

Carica triglyceride A (CP-13)Elution of column with CHCh-MeOH (4:1) (fraction No. 206-208) afforded brown amorphous powder of CP-13, recrystaUised ftom methanol, 460 mg (0.023% yield).Rf. 0.75 (CHClj:MeOH;NHj; 2:1:0.5). m.p.: 180-182°C.UV Xmax (MeOH): 240 nm (log 8 3.7).IR (KBr): 2925,2845,1730,1725,1626,1450,1180,773 cm-i. m NM R (CDCI3): 8 4.58, (IH, m, H-2), 4.47 (2H, brs, H2-I), 4.29 (2H, brs, H 2- 3), 2.58 (2H, brs, H2-2 '"), 2.49 (4H, brs, Hz-2', H2-2"), 1.25 (74H, brs, 37xCH2), 0.87 (3H, t, 7=6.5 H2, Me), 0,84 (3H, t , /= 6,l Hz, Me), 0.82 (3H, t, 7=5.9 Hz, Me).-Hve ESI MS iw A 778 pvq+ (C49H94O6).

Carica triglyceride B (CP-14)Elution of column with CHQs-MeOH (3:1) (fraction No. 230) afforded brown sticky mass of CP-14, recrystallised from methanol, 250 mg (0.0125% yield).Rf: 0.70 (n Butanol: glacial acetic acid: water; 4:4:1). m.p.: 174-75“C.UV (MeOH): 241 nm (log s 3.7).IR Vmax (KBf): 2955,2845, 1730,1725,1534,1458,1260, lU O , 980, 776 cm \‘H NM R (CDCI3): 8 5.27 (2H, m, H-9', H-10'), 4.28 (IH, m, H-2), 3.69 (2H, m, H2-I), 3.59 (2H, m, H2-3), 2.28 (2H, m, H2-2 '), 1.94 (4H, m, H i-l", H2-2 '"), 1.57

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(4H, m, H2-8 ', H2- i r ) , 1.18 (66H, bts, 33 x CH2), 0.81 (6H, brs, 2xMe), 0.79 (3H, tj= 6 .1 Hz, Me).+ive ESI MS m /2r. 776 [M]+ (C49H92O6).

Distearin phosphate (CP-15)Elution of column with MeOH (fraction No. 248) afforded brown sticky mass of CP-15, recrystaUised from medianol, 440 mg (0.022% yield).Rf. 0.60 (Cyclohexane: diediyl edier;MeOH; 8:1:1). m.p.: 220*^0 p ec).UV X,max (MeOH): 259 nm (log s 5.2).IR Vmax (KBf); 3415,2950,2855,1730,1725,1528,1250,1035, 773 cm'^ iH NM R (DMSO-dtr): .5 4.88 (IH, m, H-2), 4.52 (2H, m, H 2-2 '), 4.28 (2H, m, H2-3), 4.37 (2H, m, H2-2 ”), 3.69 (2H, brs, CH2-I), 2.51 (4H, brs, 2xCH2), 1.23 (60Hz, bfs, 30 X CH2), 0.85 (3H, t,}=6.6 Hz, Me-18'), 0.83 (3H, t,/=6.6 Hz, Me- 18").+ve ESI MS m A : 704 [M]+ (C39H77O8P).

3.4 RESULTS AND DISCUSSIONCompound CP-1 named CaiicadUinoleflide, a mixed triglyceride was obtained as light brown waxy mass from petroleum ether-chloroform (1:3) eluents. It decolourized bromine water and produce foam on saponification. Its IR spectrum showed characteristic absorption bands for ester group (2851 and 1740 cm- ), unsatLiration (1462 cm- ) and long aliphatic chain (794, 774, 732 cm-'). The ESI MS of CP-1 showed molecular ion peak at m l \ 852 corresponding to molecular formula CssHoeOe. It indicated the presence of five double bonds in the molecule. The NMR spectrum of the compound exhibited three multiplets at 5 5.35 (2H), 5.33 (4H) and 4.28 (4H) for ten vinylic protons whereas methylene protons adjacent to vtnyUc linkages appeared as broad signals at 6 2.01 (4H), 1.98 (4H), 1.61 (4H) and 1.59 (4H) that were assigned to H 2-II" , H2-II" ', H2-8', H2-II ', H2-8", H2-8 '", H2-I4" and H2-14'", respectively. Four one-proton doublets at 5 4.32 (/=4.2 Hz), 4.28 (J= 4.2 Hz) 4.17 (/=5.7 Hz) and 4.13 (/=5.7 H2) were ascribed to oxygenated methylene protons Ha-la, H2-lb, H2-3a and H2- 3b, respectively whereas the oxygenated methine proton H-2 appeared as a multiple! at 8 3.66. Three two-proton broad signals at 5 2.34, 2.31 and 2.28 were due to H2-2 ', H2-2 " and H2-2 '" methylene protons adjacent to ester groups. The remaining methylene protons appeared as broad signals at 5 1.30 (17xCH2) and1.25 (IOXCH2). Three-proton triplets at 5 0.89 (J=5.7 Hz), 0.88 (J=6.6 Hz) and 0.85 (f=6.6 Hz) were assigned to terminal primary methyl protons ie, Me-16', Me-18" and Me-18'", respectively. On the basis of forgoing discussions the structure of CP-1 has been elucidated as Prop-l-(hexadeca-9'-en)-2,3-di- (octadeca-9",12"-dien)-trioate.

Compound CP-2 named Caiicadiatchidolide, a mixed triglyceride was obtained as Ught brown Waxy mass from chloroform eluertts. It decoloriaied bromine water and form soap on saponification. Its IR spectrum showed absorption biands for

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ester group (2815, 1735 cm-') and unsaturation (1599 cm-^) and long aliphatic chain (7996, 732 cm-'). The ESI MS of CP-2 indicated a molecular formula GiHiifiOfi. Its ‘H NMR spectrum exhibited a two-proton multiplet at 6 5.34 assigned to vinylic protons H-9' and H-10'. The mediylene protons adjacent to vinylic linkage H2-8' and H2-II ' appeared at 6 2.01 and 1.63, integrated for two protons each, respectively. Two multiplets at 6 4.28 and 4.17, integrating two protons each, were ascribed to oxygenated methylene protons H 2-I and H2-3, respectively. A one-proton multiplet at 8 3.(56 was ascribed to methiiie proton H-2. Two three-proton doublets at 8 2.37 ([=7.5 Hz) and 2.32 (J=^7.5 H2) were accounted to methylene protons adjacent to ester group. The remaining methylene protons appeared at 8 1.30 (22H) and 1.25 (68H). Three three-proton triplets at 5 0.88 (/=6.6 Hz), 0.85 (/=6.6 Hz), 0.81 (/=6.2 Hz) were assigned to Me-18', Me-20" and Me-20” ' terminal primary methyl protons, respectively. On the basis of foregoing discussion the structure of CP-2 has been elucidated as Prop“l“(octadeca-9'-en)-2,3-dieicoan-trioate.

Compound. CP-3 named Caricadistearide, a mixed glyceride was obtained as brown sticky mass from CHCls-MeOH (49:1) eluents. It responded positively for test of unsaturation with bromine water. Its IR spectrum exhibited absorption bands for ester group (2855, 1730 cm-'), unsaturation (1640 cm-') and long aliphatic chain (795 cm-'). Its UV absorption maxima at 249 nm is characteristic of conjugated double bonds. The ESI MS of CP-3 showed a molecular ion peak at m j^ 806 corresponding to molecular formula C57H 106O6. It showed two double bond equivalent that were adjusted in two conjugated double bonds. 'H NMR of CP-3 exhibited two up field one-proton multiplets at 5 6.89 and 6.85 due to vinylic protons H-10' and H-12', respectively whereas vinylic protons at H-9' and H-13' appeared as two-proton multiplet at 6 5.34. The oxygenated methylene protons at C-1 appeared as two one-proton doublets at 8 4.30 (/=6,6 Hz) and4.26 (J~6.6 Hz). Two multiplets at 8 3.94 (IPl) and 3.78 (2H) were assigned to other oxygenated methine protons at C-2 and methylene protons at C-3, respectively. The methylene protons adjacent to ester group at C-2' appeared as two one-protons doublets at 8 2.34 (/=9.0 Hz) and 2.31 (J=9.0 Hz) whereas those at C-2" and C-2'" appeared as two two-proton broad signals at 8 2.27 and 2.01, respectively. Methylene protons adjacent to the vinylic linkage at C-11', C-8' and C-14' resonated as three two-protons multiplet signals at 8 2.78, 1.83 and 1.64, respectively, The remaining methylene protons appeared as multiplets at1.59 (4H) and 1.25 (72 H). Three three-protons triplets at 8 0.97 (J-5A Hz), 0.96 (/=6.0 Hz) and 0.87 (J-6.1 Hz) were assigned to methyl proton at Me-18, Me-18' and Me- 18". On die basis of these foregoing discussions the structure of CP-3 has been characterized as Pfop-l-(octadeca-9, 12-dien)-2,3-di (octadeca)- rioate.

Compound CP-4 named Caricaphetiyl tdol, was obtained as cream , c61bured amorphous mass from CHClj-MeOH (49:1) eluents. It resporided positively to ferric chloride indicating phenolic nature of the rtiolecule. I ts , iR exhibited

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chatacteristic absorption bands for hydroxyl group (3415 cm-i) and aromatic nucleus (1513, 1210 and 950 cm'i). The ESI MS spectrum of CP-4 showed a molecular ion peak at 140 corresponding to molecular formula CyHaOs. The iH NMR of CP-4 exhibited a deshielded D2O exchangeable one-proton signal at 8 10.37 for the hydroxyl proton. Two one-proton oriAo-conpled doublets at 5 7.79 (1=8.4 Hz) and 6.82 (f=SA Hz) were assigned to H-3 and H-4 aromatic protons, respectively. A three-proton broad signal at 8 2.26 was ascribed to C-7 methyl protons attached to aromatic ring. Further evidence in support of the structure of CP-4 was provided by its NMR spectral data that showed the existence of seven carbon atoms in the molecule. The carbon signals at 8 167.24 (C-1) and 161.64 (C-2, C-6) were due to carbinol carbons. The remaining aromatic carbons resonated in the range 8 131.57-115.16. The C-7 methyl carbon appeared at 8 29.04. On the basis of for3egoing discussions the structure of CP-4 has been elucidated as 5-nnethyl-l, 2, 6-trihydroxybenzene.

Compound CP-5 named Caricaoleiolide phosphate was obtained as brown semisolid from chloroform-methanol (97:3) eluents. It responded positively to test for unsaturation with bromine water and TNM. Its IR spectrum showed characteristic absorption bands for hydroxyl group (3424 cm- ), ester group (1725 cm- ), unsaturation (1640 cnr^) and long aliphatic chain (795 and 773 cm-i). The ESI MS of CP-5 exhibited molecular ion peak at 436 corresponding to molecular formula C21H41O7P. The NMR spectrum showed two one-proton multiplets at 8 5.27 and 5,00 assigned to vinylic protons H-9' and H-10', respectively. A t-wo-proton broad signal at 8 4.20 was ascribed to oxygenated methylene protons H2-3 . A two-proton broad signal at 8 4.00 and one-proton multiplet at 8 3.69 was accounted to oxygenated methylene protons H2-I and carbinol proton H-2, respectively. Two one-proton doublets at 8 2,28 (J=12.9 Hz) and 2.23 (f=12.9 Hz) were associated with methylene protons H2-2 ' adjacent to ester group. Two two-proton multiplets appeared at 8 2.13 and 1.94 were assigned to methylene protons H2-8 ' and H2-IO' adjacent to vinylic linkage. The rest of the protons appeared as multiplets at 8 1.57 (2H), 8 1.49 (2H), 8 1.40 (2H) and 8 1.18 (16H). The terminal primary methyl (Me-18') appeared as a triplet at 8 0.75 (/=6.1 Hz), The ^ C NMR spectrum of CP-5 exhibited signals for the vinylic carbons at 8 132.11 (C-9') and 129.23 (C-10'). The ester carbon C-1' and carbinol methine carbon C-2 resonated at 8 128.26 and 66.77, respectively. The oxygenated carbons C-1 and C-3 appeared at 8 61,55 and 60,01, respectivdy. The remaining carbons resonated between 843.48-22.11. An upfield signal at 8 13.63 was assigned to primary C-18' methyl carbon. On the basis of foregoing discussions the structure of CP-5 has been elucidated as Prop-2-hydroxy-l- (octadeca-9-n)-oyl-3-pphosphate.

Compound CP-6 named carpaine, was obtained as colourless mass from CHCI3- MeOH (24:1) eluents. Its IR spectrum showed characteristic absorption bands for ester group (1725 cm-^) and long aliphatic chain (773 cm‘ ). The ESI MS of CP-6 displayed molecular ion peak at 478 corresponding to molecular formula C28H 50N2O4. The NMR spectrum of CP-6 exhibited two one-proton multiplets at. 8 4.64 and 4.30 assigned to carbinol H-3 and H-3', a one-proton

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multiplet at 5 3.89 assigned to methine protons H -6 and H-6' and a four-proton broad singlet at 8 2.51 accounted to methylene protons Ha-8 and H2-8 ' adjacent to the ester group. The remaining methylene protons appeared as broad signals at 8 1.48(4H, brs, H.2-4, H2-4 '), 1.43 (4H, brs, Ha-S, Ha-S') andl.23 (24H, brs, 12 x CH2). A six-proton broad signal at 5 0.87 was attributed to primary methyl protons Me-7 and Me-7'. On the basis of these discussions die structure of CP-7 was elucidated as caipaine.

Compound CP-7 named Caiicadipalmitate, was obtained as buff-white amorphous powder from chloroform-methanol (24:1) eluents. Its IR spectrum showed characteristic absorption bands for hydroxyl group (3417 estergroup (1725 cm-i) and long aliphatic chain (771 cm*'). The ESI MS of CP-7 displayed molecular ion peak at 546 corresponding to molecular formula C35H67O5. An important fragment ion at m /^ 328 [M-CO(CH2)i4-CH3] arouse due to ester cleavage. The NMR spectrum of CP-7 exhibited a two one- proton multiplet at 5 4.87 and one-proton broad singlets at 8 4.57 and 4.36 assigned to oxygenated methylene protons Ha-la and Ha-lb where as two broad signals at 8 3.96 and 3.81 integrated for one-proton each were ascribed to carbinol protons at C-3. Two two-protons broad signals at 6 2.73 and 5 1.57 were assigned to H-2 ' and H-2" methylene protons adjacent to ester group. The remaining methylene protons appeared as a broad signal integrating for 52 protons at 8 1.25. A six-proton broad signal at 8 0.87 was attributed to primary methyl protons Me-16' and Me-16". The NMR of CP-7 showed two signals at 8 77.41 and 76.99 associated with ester carbon signals. The C-3 carbinol carbon appeared at 8 61.17, Two oxygenated carbons C-2 and C-1 resonated at 8 71.23 and 63.13. The signals at 8 31.90 (CHa), 29.67 (25 x CHa), 25.50 (CHa) and 22.67 (CHa) were due to methylene carbons. The terminal primary methyl carbons (Me-16', Me-16") appeared at S 14.09. On the basis of above discussion the structure of CP-7 was elucidated as Pfop-1, 2, 3 -trihydfoxy-l, 2- dihexadecanoate.

Compound CP-8 named Caricaoleolatiryl phosphate, a diglyceride phosphate, was obtained as light brown amorphous powder from CHCU-MeOH (19:1) eluents. Its IR spectrum showed characteristic absorption bands for ester group (1734 cm’i), unsaturation (1638, 1528 cm'^) and long aliphatic chain (775 cm- ). The ESI MS of CP-8 displayed molecular ion peak zt m l 618 corresponding to molecular CssHssOsP. The *H NMR of CP-8 exhibited a two-prdtoii multiplet at 8 5.36 assigned for vinylic protons H-9' and H-10'. One-proton multiplet at 8 4.42 was accounted to oxygenated methine protons (H-2). Two oxygenated Ha-S and H-1 protons appeared as two-proton multiplet and as two-proton broad signals at 8 3.92 and 3.59, respectivdy. The methylene protons adjacent to ester linkage H-2 ' and H-2" resonated as multiplet at 8 2.27 and 2 .01 . A broad signal for fbur-protons appearing at 8 1.62 was assigned to metlgdene prbtXMis H2-8' and H a-ir. The remaining methylene protons (20 x CHa) appeared at 8 1.25. Two three-proton triplets at 8 0.87 ([=6.0 Hz) and 0.84 (/=6.2 Hz) w

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associated \villi terminal primaty protons Me-18' and Me-12". Based on the foregoing discussions the structure of CP-8 has been elucidated as Pfop- l(hexadecane-9'-enyl)-2-docosatiyl-3-phosphate.Compound CP-9 named p-sitosterol glycoside, gave a positive Liebermann- Burcahrd test and a negative Ehrlich reaction. Its IR spectrum exliibited strong bands at 3450 and 1080 cm- characteristic of a glycoside. The ESI MS of CP-9 gave a fragment ion at m /z 413 [M-glucose]+, 398 [413-Me]H-, 396 (576 - C6Hi20fi]+, 381 [396- Me]+, 273 [413-CioH2i, side chain]+, 255 [273-H20]+, 240 [255-Me]+ and 213 [255-ring D fission]-*' which were characteristic for P- sitosterol 3-P-D-glycoside. The NMR spectrum of CP-9 exhibited a one- proton doublet at S 5.31 0=5.21 Hz) assigned to C-6 proton. A one-proton broad multiplet at 8 4.3 with wi/2 18.5 Hz showed the presence of 3a-methine proton (axial) interacting witli C-2 equatorial, C-2 axial, C-4 axial and C-4 equatorii protons. Four doublets at S 0.94 (J=6.5 Hz), 0.89 (J=7.7 Hz), 0.81 0=5.69 Hz) and 6.79 0=6.39 Hz); integrating three protons each, were ascribed corresponding to C-21, C-26, C-27 secondary methyl and C-29 primary methyl protons. The C-18 and C-19 tertiary methyl protons appeared as broad signals at 8 0.64 and 0.97, respectively. The '^C NMR spectrum of CP-9 displayed 35 carbon signals for steroidal glycoside including two vinylic carbons at 5 140.47 (C-5) and 121.19 (C-6) and one carbinol carbon at 5 76.99 as well as six glucose carbons at 5 100.84 (C-1'). 73.47 /(C-2'), 76.75 (C-3') 70.10 (C-4'), 78.19 (C-5') and 61.10 (C-6'). Acid hydrolysis of KA-4 yielded D-glucose and an aglycone, which was identified as p-sitosterol by spectral data and by direct comparison with the authentic samples (Co-TLC, m.p.). On die basis of these findings the structure of CP-9 was established as stigmast-5-en-3-0-p-D-glucopyranoside.

Compound CP-10 named Carica trimyristate, was obtained as brown amorphous powder from CHCls-MeOH (93:7) eluents. Its IR spectrum showed characteristic bands for ester group (1730, 1725 cm- ) and long aliphatic chain (772 cm- ). Its ESI MS showed a molecular ion peak at at 722 corresponding to molecular formula C45H86O 6. The 'H NMR spectrum of CP-10 displayed two multiplet signals at 5 4.37 and 4.25, integrating for two protons each, assigned to oxygenated H2-I and H2-3 methylene. A one-proton multiplet at 5 4.65 was ascribed to carbinol H-2 proton. A six-proton broad singlet at 5 2.56 was assigned to methylene protons adjacent to ester group vi^ H2-2 ', H2-2" and H- 2'". The remaining protons appeared as a broad signal at 5 1.25 integrating fot 66 protons. Two broad signals at 5 0.98 and 0.87, integrating for tiiree-and six- protons, respectively were accounted to three primary methyl protons. On the basis of foregoing discussions the structure of CP-10 has been elucidated as glycetyl-1,2 ,3-tritetfadecanoate.

Compound CP-11 named as Carica tristearate, was obtained as brown amorphous powder from chloroformrmethanol (17:3) eluents. Its IR spectrum showed characteristic absorption bands for ester gtoup (1730, 1725 cm'*) and long aUphatic chain (725 cm- ). The +ve ESI MS of CP-11 exhibited a molecular ion peak at 890 cotresponding to a molecular formula C57H 110O6. The *H NMR

Chapter 3 papaya

89

spectrum of CP-11 displayed two multiplets at 5 4.51 (IH) and 4.49 (4H) assigned for cafbinol H-2 and oxygenated methylene H-1 and H-3 pfotons, respectively. A six-proton broad singlet at 52.56 was assigned to methylene protons adjacent to ester groups v/z, H-2', H-2" and H-2'". The remaining methylene protons appeared as a broad signal, integrating for 90 protons at 5 1.30. A broad signal at 5 0.91 integrating for nine protons was associated with three primary methyl groups. On the basis of foregoing discussions the structure of CP-11 was elucidated as glyceryl- 1,2,3-trioctadecanoate.

Compound CP-12 named as Caricadioleophenyl glyceride, a triglyceride was obtained as brown amorphous powder from chloroform-methanol (4:1) eluents. It responded positively to FeClj test for phenolic moiety and with bromine water and tetranitroniethane test for unsaturation. Its IR spectrum showed characteristic absorption bands for hydroxyl group (3410 cm-^), ester group (2855, 1730 cm-’), unsaturation (1640, 1542 cm- ) and a benzene ring (1025, 773 cm- ). The ESI MS of CP-12 displayed a molecular ion peak at 744 corresponding to molecular formula C44H72O9. NMR of CP-12 exhibited two up field one-proton doublets at 5 7.17 (/=8.4 Hz) and 6.95 (/~8.4 HZ) assignable to owi&o-coupled aromatic protons H-6 ' and H-7', respectively. Two two-proton multiplets at 6 5.32 (H-9" and H-10") and 5.18 (H-9'" and H-IG"") arouse due to respective vinyl protons whereas the methylene protons adjacent to die vinylic linlcage at Hj-S" and H2- I I” and H2-8 '" and H 2-II '" appeared as a pair broad signals at 5 2.27 and 1.98, four-proton each, respectively. Two two-proton broad signals at 8 4.65 and 3.86 were ascribed to oxygenated methylene protons at C-1 and C-3 where as the oxygenated methine proton at C-2 appeared as broad signal at 8 4.81, respectively. The remaining methylene protons appeared as broad singlets at 6 1.53 (2 x CHa) and 1,23 (18 x CHa). Two primary methyl protons triplets, three-proton each appeared at 6 0.85 (/=6.1 Hz) and 0.83 (/=6.1 Hz) was due to Me-18" and Me-18'", respectively. On the basis o f foregoing discussions the structure of CP-12 has been elucidated as Prop-l(3'-4^S'-trihydfoxy ben2oyl)-2 ,3-dioleide.

Compound CP-13 named Carica triglyceride A, was obtained as light brown amorphous powder from chloroform-metlaanol (4:1) eluents. Its IR spectrum showed characteristic absorption bands for ester group (1730, 1725 cm-‘) and long aliphatic chain (773 cm-^). The ESI MS exhibited a molecular ion peak at

778, corresponding to molecular formula C49H94O6. The ^H NMR of CP-13 displayed a one-proton multiplet at 5 4.58 (IH) was assigned to H-2 carbinol protons whereas two broad signals at 5 4.47 (2H) and 4.29 (2H) were assigned to oxygenated methylene protons H-1 and H-3, respectively. Two broad signals at 5 2.58 (2H) and S 2.49 (4H) were attributed to metiiylene protons adjacent to ester groups H2-2 '" , Ha-2' and H 2-2". The remaining protons appeared as a broad signal, integrating for 74 protons, at 8 1.25. Three triplets at 6 0.87 (/=6.5 Hz), 0.84 (/=6.1 Hz) and 0.82 (/=5.9 Hz) integrated for three protons each were assigned to three terminal piimary methyl protons. On the basis of foregoing

Chapter 3_________________________________________________C papaya

90

discussions the structure of CP-13 has been elucidated as Pfop-3-tetradeca-l, 2- dihexadecanoate.

Compound CP-14 named Carica triglyceride B, a mixed glyceride was obtained as brown sticky mass from chloroform-medianol (3:1) eluents. Its IR spectrum showed characteristic absorption bands for ester group (1730, 1725 cm->), unsaturatton (1534 cm'^) and long aliphatic chain (776 cm-i). Its ESI MS displayed a molecular ion peak at mJ^116 corresponding to molecular formula C49H92O6. It showed one double bond equivalent, which was adjusted in a double bond. The IH NMR spectmm of CP-14 exhibited a two-proton multipiet at 6 5.27 for vinylic protons H-9' and H-10'. Two multiplets at 5 3.69 (2H) and 3.59 (2H) were assigned to oxygenated methylene protons H2-I and Ha-S. The oxygenated methine protons H-2 appeared as a multipiet at 5 4.28. Two multiplets at 5 2.28 (2H) and 1.94 (4H) were ascribed to methylene protons adjacent to ester group. A four-proton mxiltiplet at 5 1.57 appeared due to methylene protons (H-8' and H-11') adjacent to vinylic linkage. A broad signal, integrating for 66 protons, appearing at 5 1.18 was due to the remaining methylene protons. A six-proton broad signal at 5 0.81 and a three-proton triplet and 5 0.79 (J=6.\ Hz) were due to three terminal primary methyls, respectively. On the basis of above discussions the structure of CP-14 has been elucidated as Prop-l-(octadec-9-eti)-2,3- ditetradecanoate.

Compound CP-15 named Distearin phosphate, a glyceride phosphate was obtained as brown amorphous mass from methanol eluents. Its IR spectrum displayed characteristic absorption bands for hydroxyl group (3415 cm- ), ester group (1730, 1725 cm- ) and long aliphatic chain (773 cm- ). The ESI MS ^splayed a molecular ion peak at ml corresponding to molecular formula C39H77O8P. NMR spectrum of CP-15 exhibited a one-proton multipiet at 5 4.88 for oxygenated methine proton at H-2 whereas a multipiet and a broad signal, of two-protons each, appearing at 5 4.28 and 3.69 were assigned to oxygenated metiiylene protons at H2-I and Ha-S, respectively. Methylene protons adjacent to ester groups appeared as two two-protons multiplets at 5 4.52 (Hz-2') and 4,37 (H2-2"). The remaining protons resonated at 6 2.51 (2 x CH2) and 1.23 (30 x CH2). Two triplets of three-protons each appearing at 5 0.85 (/=6.6 Hz) and 5 0.83 (J=6.6 Hz) were assigned for primary terminal methyl protons at H-18' and H-18". On the basis of foregoing discussions the structure of CP-15 has been elucidated as Distearin phosphate.

Chapter 3_______________________ ________________________ C papaya

91

Chapter 3 C. papaya

Table-3.1. Compounds Isolated itoxa C. papaya

Codej No.1

CommonNam e

m.p.(°C)

Mol.Formula

lUPAC Name

CP-1 1 Caricadilinile 1 nide

CssHpsOfi Prop-1 - (hexadeca- 9'- en)-2,3-di-(octadeca- 9",12”-dien)-trioate.

CP-2 Caricadiarchi ; dolide

......i

CfiiHiifiOfi Pfop-l-(octadeca--9'-en)-2,3-ieicoan-trioate

CP-3 Caidcadisteadde

CsvHiofiOfl Prop-1 - (octadeca-9,12-dien)-2,3-di(octadeca)-rioate

CP-4 Carica phenyl ■ ttiol

218-30 C7H8O3 5-methyl-1, 2, 6- trihydroxybenzene

CP-5 Caiicaoleiolid i e phosphate

231-34 C21H41O7P Piop-2-hydtoxy-l-(octadeca-9-n)-oyl-3-phosphate

l'CP-6' Catpine 118-20 ^28 -50^204 CarpineCP-7 Cai'icadipalmi

tate170-72 CisHevOs Prop-1,2,3-

trihydroxy-1, 2- dihexadecanoate

CP-8 Caticaoleolau ! ryl phosphate !

226-28 ;I

C33H63O 8P

!i

Prop-1 (hexadecane-9'-enyl)-2-docosanyl-3-phosphate

CP-9 P-sitostetolglycoside

270-72 ; C35 HfioOe Stigmast-5-en-3-0-p-D-g;lucopy£anoside

CP-10 Carica 180 C45H86O6 Prop-1, 2, 3-trimyristate Pec.) tritettadecanoate

I CP-il1( .

Caricatiistearate

124-26 C57H110O6 Prop-1,2,3- trioctadecanoate

CP42{

Caticadioleop !henylglyceride

156-58 ;

i

C44H72O9 Prop-1 (3'-4',5'- ttihydtoxy benzoyl)- 2,3-dioIeide

CP-13 Carica | 180-82 ; C49H94O 6 Pfop-3-tetradecaa-l,triglyceride A i 2-^exadecanoate

CP-14 : Caricatriglyceride A 1

i

174-75 j C49H92O6

1Prop-l-(octadec-9- en)-2,3-V ditettadecanoate

CP-15 Distearinphosphate

220(pec.) :

C39H77O8P Distearin phosphate

^92

Chapter 3 C papaya

----- (OH,), — 6 h= S h(o ^)3<^

31_ofo----(CH,), — — ' &(o^),d%

o

.ar-<)a>—w ).-fh=S iS i<3;-B i(ati,d iS nA ' ^ ‘■ f l ' ' " *

7€P -1

im — 0 6 0 -----(0 ^)5—C&=5 !(CS )7

a p i—-dx)— (ai,)ir-csi

CP-2

II"'o

CP-6

- to — (CH )J3- C i 3

-i:o— (CH,)i7 --c l,

JI---- o C o----- (CHj),j

CH,— 0 & — (CH,)„ S i,

CP-3

OH

CI^— OH

CP-7

I niq— o-----to --“ (CHj)r~CH—

CH-_ -0 —^ o — (CHj)3,r-CH;IICH — O— ^ O H

OHCP-8

1 jMj— o<!:o(CB )7CH=asaa----- (Cfi )?— <^3

JCH---- OH oII3 CH — O-----!>— -OH

OH

CP-5

93

Chapter 3 C. papaya

CO(CHj),jCH3

2 ~ o — -CO (cHj),2CHj

3 CHj— O------C0(CH ),2CH^

CP-10

II ---- COCO(CHj),sCH3

i CH----O----C0 C0 (CI] )„CH3

3 ----COCO(CHj)jjCHj

CP-11

OH

T:i — O-

, r n p - 0 — CO (CH ,)nr-CH 3

1 CH---- o -----C0 (CH2) ^ C H 3

3 0 ) -“ 0 ----“CO(CH2)^ C H ,

CP-13

3 ^ 0 —00— (OH cifesssaS —(cjy?—c»

3*-o—oo—(a^),r-a%

a ^ o —00— (cs ),7 -ci%

CP-14

]H ~“ 0'" ■" CO (Ct^)j jCilj

— CO— (CH,),^CH,

HO OH

CP-15

1 ci^o----<!:d(cs^),cfi«ciP--(CHj),CH“ ■

CP-12

94

Chapter 3 C papaya

95

Chapter 3 C. papaya

339.07

384.70

Uu42|06

_4QQ______ 500-

520.71 554.27

I 1,11 I68&.S7

,Bnn- _2DQ_________SOIL.Mass Spectrum of CP-1

IR Spectrum of CP-1

m

Chapter 3 C. papaya

\I8 ®

i r j .y

I ' r n V

} W V 1 1 A K As a | |5 ! K ti! R S ( Efl Jfi 5V

iri cvi r.t Q~1

Ui

I..■..■.. ...r..■.......i........ V- r—«..'..>..r—'..''.'..1 ....■..........."t......... ....................................]...........'........... ''...........* Ji‘HNMRofCP-2

Mass Spectrum of CP-2

97

Chapter 3 C papaya

ill

..j.5. t. . . M*''. I -r »-..........\\.cn-......... :.(Ti.................:. ::: /

. i • { h - :........■ . ; K) ■ ■

.■

::p;...B..........

..................9 Q .......................................

■ i - : " ■

■ ■ ,® .......... :............

iS ;:.

IR Spectrum of CP-2

,.-i fT» »vi nj t n <>l <rO i>j i?u vs» cvi '■\i -•« —• —• —• —• «i» «■■

I...

v \

■■■'.J"*HNMRofCP-3

98

Chapter 3 C papaya

128,99

300:*?

«6,86:

588:52

528.33

41725

6S5:S4

754,43


:r : y

f 1 V ' 'i l i i ; - - ; . , : . : : ! ; - : : -

^ . . . . . . . .as.. .. . . . ... . 1 .. . . . . . .

.

,v

j8M) ttUU

IR Spectrum of CP-3

"luuii

99

Chapter 3 C. papaya

ioo;

Chapter 3 C. papaya

IcW

0,0- 106,88

0 .6 -

0.4-

120.99

0.2-156.92

231.88

0.0-J-WO.J-------------200-----' ■ '"-‘'- 300-------------- 400---------

Mass Spectrum of CP-4liSoI -700.-

rm-■■ ................... 3

%Mi: ...: ... : • ' ,r ■, . . ,-w- . \ ... ■. ;... : ...1,■k .... >■’ ■; .. '.d .: ,.; .. . '. . l i,'l Sfei

Vi ’If:;

;. .K:...:...a . 1 i ':::i: ;..;:.. ■..: : 5-* i ; .

ty:'. : -.t

......jii

m .wiv.'.en-.

’ V : . ;i

.■;ri. I . i : .

. 1 :: !

I..

IR Spectrum of CP-4

•:A'

Ih

m m i

101

Chapter 3 C papaya

^ S ' « T T i 'F i ' i i i i! i B I i i 11 i m i I f i® i i 1 1 B i Ii l l I I ! W N S \

B ||p |« iiW W "isf U)^(... .. Ill..... ...... "HI.... ’ m mA ......... ;■■■ ■■"..r

‘HNMRofCP-5

' - x;:‘ CNMRofCP-5

102

Chapter 3 C. papaya

103

Chapter 3 C. papaya

104:

Chapter 3 C papaya

:105

148.91

227.93

413.26

300.96

261.89 334.96498.12 555.44 628.36

iiiii L4 jitil....vliilj) til il[, (.4.1 >11115D0

6B4.57

700


fv . . i W-. .................................. -W" ......... y.

im

IR Spectrum of CP-6

105

Chapter 3 C papaya

102.21 156,93

231,89419,16

353,07

6&1,S8

+MS.a,3fn


.61i

r'nJ

II 1

I ’ 1iiiiiii; } :

• - X - - . 1

■v •:r ';■ I - , :

•v::

■:k:

• . . . ->< ... ■,;..: ' ;;

;v:;: ,tp:

mmm:

IR Spectrum of CP-7

-D6i5 ■"2 .'5D0

107

Chapter 3 C papaya

188.89

129.03

10? 72

0 •I..I"

15S.94

231,98

413,23

281.92 351.09y l . U l idLjLl

699.45

461.35

eoo

683,37 721.60764:26

i700 mi


108

Chapter 3 C. papaya

w -i.1 :LilJ-

::s | ■ IA» •i>

ft.U’. . \.. ................. .; 4>'. ■:: ;: ■; : •; -.r .c -iSiiil a . . ..at . * » i A W*

4»; ;u»;;.,, ■. ....................... . - . ] .W:T i ......1 ?? m-|. - i

. 1^ i

•■‘.'A................W u i S.W...... isr.;;:: -V M W'.............. {ft .'j...............i’j ■

; ->■>;■i /■( ; ■ .u i.,..'

■:p:

■ ■:;p . ’ . ’ .

W

IR Spectrum of CP-8

THNMRofCP-9

109

Chapter 3 C. papaya

110

Chapter 3 C. papaya

V.. ..... SI i I I I

1 /

-.- 1

I I T l T f f \I

A---,,. --"A ,/■"> / /A >?§ ]S| ] ^ <Sk sfT3 if s

r ”" ’ ' S' ' ■ '..J.. ' ..'.. I .... .... P. 1 i‘HNMR of CP-10

111

Chapter 3 C papaya

IR Spectrum of CP-10

! !, i l l ! l i l i l i i i1 \ \ i / w w w n

~TH NMR of CP-11

t l2

Chapter 3 C. papaya

IS.

112,85

2ao.9$338,97

254.9S

100 200

386;79

574:80774.72 827.00


rt:

H iIR Spectrum of CP-11

113

Chapter 3 C papaya

vj- y' TTT T V n ‘ T7‘.S. ! ;vi i

y" i s r '" ' 'isd

' x A

A' ...........y.............T'H NMR of CP-12

iiM 102.19 231.87

«7.9a 185:86

701.39

52T.18

31&91,

100 200 : SdO 400

683.38743,27


114

Chapter 3 C papaya

“TT,1

M.m d .

mm-W B i

\rnmi I

.(. . . ii' .

\

: / ■. ■. a. . ,. ■ i . . . .

: l r r: l : r: i . r .

•: . .11 .U . .i.V!;::

►IS?

• •?•..............

.. . . . : ■ 'm :ha

■ ■ ■ - .................... : \ w . . . ."4i:

•/:.

.■ i::n' ' • 1

]■!.'i.: / •: 1....

■Ir i - :: !!:: l ! £ - ■.fi.®:': : 1:1i : . : -

. r . . 7 - 1. .;•

. . 1:•i':i ■ .. 1.'

. ii;

■mm--rrr- 'm m

(’Mil?“r»w*nw«

IR Spectrum of CP-12

115

Chapter 3 C. papaya

116

Chapter 3 C. papaya

117

Chapter 3 C. papaya

lib

Chapter 3 C. papaya

119

3.S REFERENCES

1. Adebiyi A, Ganesan A P and Ptasad R N V (2003) “Tocolytic and toxicactivity of papaya seed extract on isolated rat uterus”. In Ufe Sciences, 74(5), 581-592.

2. Almora K, Pino A J, Hernandez M, Duatte C, Gonzalez J and Roncal E(2004), “Evaluation of volatiles from ripening papaya {Carica papaja L., var. Maradol roja)”. In Food Chemistiy, 86(1), 127-130.

3. Anonymous (1992). In “The Wealth of India: Material ’, NISCOM,CSIR, New Delhi, 3,276-293.

4. Anonymous(2000). In “The Wealth of India: Raiv Material ’, NISCOM,CSIR, New Delhi, 2000,1,216-217.

5. Breithaupt E D, Weller P, Wolters M and Hahn A (2003), "Plasmaresponse to a single dose of dietary P-cryptoxanthin esters from papaya {Caricapapaja L.) or non-esterified P-cryptoxanthin in adult human subjects: A comparative study”. In British Journal of Nutrition, 90(4), 795-801.

6. Dubois T, Jaquet A, Schnek A G, Looze Y (1988), “The thiol proteinasesfrom the latex of Carica papaya L, I. Fractionation, purification and preliminaiy characterization”. In Biol Chem Hoppe Seyler, 369 (8), 733-740.

7. Echeverri F, Torres F, Quinones W, Cardona G, Archbold R, Roldan J,Brito I Luis, J G and Lahlou E H (1997), ‘Danielone, a phytoalexia from papaya fruit”. In Phjtochemstiy, 44(2), 255-256.

8. Gmeltn R and Kjaer A (1970), “Glucosinolates in the Caricaceae”. In'Photochemistry, 9, 591-593.

9. Kermanshai R, McCarry B E, Rosenfeld J, Summers P S, Weretilnyk E Aand Sorger G J (2001), “Benzyl isothiocyanate is the chief or sole anthelmintic in papaya seed extracts”. In T hytochemistry, 57, 427- 435.

10. Kirtikar K R and Basu B D (2000). In “Kirtikar and Basu’s IllustratedIndian Medicinal Plants”. Eds. Mahaskar K S, Blatter E and Caius J F, Sri Sat^ru Publications, Delhi, India, Vol. 5, pp 1526-1530.

11. Lohiya N K, Manivannan B, Mishra P K, Pathalt N, Sriram S, Bhande S Sand Panneerdoss S (2002), “Chloroform extract of Carica papcâ seeds induces long-term reversible azoospermia in langur monkey”. In 4(1), 17-26.

12. Lohiya N K, Pathak N, Mishra P K and Manivannan B (2000),“Contraceptive evaluation and toxicological study of aqueous extract of the seeds of Carica papcâ in male rabbits”. In }. Ethmpharmacol, IQ (1), 11-27.

13. Luz O, Masilungan A V, Cardeno V, Luna L, DeVera F, Elesio DC andEdna V (1972), “Possible antttumor constituent of Carica papqyd’. In Am n JPharm, 2 {2), 2(t-29.

14. Oderinde O, Noronha C, Oremosu A, Kusemiju T and Okanlawon O A(2002), “Abortifacient properties of aqueous extract of Carica papâ (Linn) seeds on female Sprague-Dawley rats”. In Niger Posi ad Med J, 9(2), 95-98.

Chapter 3 ___________________________________________ C. papaya

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15. Pathak N, Mishra P K, Manivannan B and Lohiya N K (2000), “Sterilitydue to inhibition of sperm motility by oral administration of benzene chromatographic fraction of the chloroform extract of the seeds of Caricapapaya in rats”. In Vlytomedicine, 7(4), 325-333.

16. Pino J A, Almora K and Marbot R (2003), ‘'Volatile components ofpapaya (Carica papaya L., Maradol variety) fruit”. In Flavour and Fragrance Journal, 18(6), 492-496.

17. Schwab W and Schreier P (1998), “Aiyl-P-D-glucosides from CaricaVapqya fruit”. In 'Phytochemistry, 27(6), 1813-1816.

18. Tona L, Kambu K, Ngimbi N, Cimanga K and Vlietinck A J (1998),"Antiamoebic and phytochemical screening of some Congolese medicinal plants”. In Ethnopharmacol, 1(1), 57-65.

19. Winterhalter P, Katzenberger D and Schreier P (1986), “6,7-epoxy-linalool and related oxygenated terpenoids from Carica papaya

in Phytochemistry, 25(6), 1347-1350.

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3.1 plant description - information and library...

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