Synthesis of Selenium and Tellurium Core-Modified Azuliporphyrinogens and Benziporphyrinogens and Corresponding Carbaporphyrinoids.

The synthesis of selenium and tellurium core-modified carbaporphyrinogens was carried out by the reaction of functional selenophene/tellurophene diols with azulene or a benzitripyrrane in the presence of acid. The products were obtained in moderate yields and were characterized by using 1H and 13C NMR, UV-vis, FT-IR, CV, and HRMS spectroscopic techniques. Further, oxidation of the obtained core-modified carbaporphyrinogens in the presence of DDQ in CHCl3 afforded the corresponding carbaporphyrins in good yields. Benziporphyrins showed no indication of a ring current or macrocyclic aromaticity as confirmed by using proton NMR spectroscopy, but the addition of TFA gave rise to the formation of weakly diatropic dications.

Synthesis of 21,23-selenium- and tellurium-substituted 5-porphomethenes, 5,10-porphodimethenes, 5,15-porphodimethenes, and porphotrimethenes and their interactions with mercury.

The 3+1 condensation of symmetrical 16-Selena/telluratripyrranes with symmetrical selenophene-2,5-diols/tellurophene-2,5-diols in the presence of BF3-etheratre or BF3-methanol followed by oxidation with DDQ gave 5,10-porphodimethenes, whereas the process with unsymmetrical selenophene-2,5-diols/tellurophene-2,5-diols gave 5-porphomethenes. In addition, the reaction of unsymmetrical 16-Selena/telluratripyrranes with symmetrical selenophene-2,5-diols/tellurophene-2,5-diols gave the corresponding porphotrimethenes, whereas the process with unsymmetrical selenophene-2,5-diols/tellurophene-2,5-diols gave the 5,15-porphodimethenes. The structures of different products were characterized by IR, (1)H and (13)C NMR, (1)H-(1)H COSY, CHN analysis, and mass spectrometry. The binding of mercury with the calix[4]phyrins mentioned above had been observed in the decreasing order of porphodimethenes > porphomethenes > porphotrimethenes by UV-vis and (1)H NMR spectroscopy.

Quality traits of Indian peanut cultivars and their utility as nutritional and functional food.

Peanut (Arachis hypogaea L.) is considered as a highly nutritious foodstuff. Of late, the importance of peanut as a functional food has been growing. Kernels of forty-one Indian peanut cultivars were analyzed for their oil, fatty acid profiles, sucrose, raffinose family oligosaccharides (RFOs); phenolics, and free amino acids contents along with antioxidant capacity. The range and the mean value (given in parenthesis) for each of the traits analysed were, oil: 44.1-53.8% (50.1%), O/L ratio: 0.9-2.8 (1.4), sucrose: 2.61-6.5% (4.63%), RFOs: 0.12-0.76% (0.47%), phenolics: 0.14-0.39% (0.23%), free amino acids: 0.052-0.19% (0.12%) and antioxidant capacity: 1.05-6.97 (3.40) µmol TEg(-1). The significant correlation between phenol content and antioxidant capacity suggests phenol content as an easy marker for rapid screening of genotypes for their antioxidant capacity. A few cultivars with desirable traits and their prospective utility were identified which would be useful for future breeding programme to develop nutritional superior peanuts.

Surfactant assisted self-assembly of zinc 5,10-bis (4-pyridyl)-15,20-bis (4-octadecyloxyphenyl) porphyrin into supramolecular nanoarchitectures.

The surfactant assisted self-assembly (SAS) method has been used in the formation of nanocubes, nanorods and microrods from zinc 5,10-bis (4-pyridyl)-15,20-bis (4-octadecyloxyphenyl) porphyrin. By the dropwise addition of chloroform solution of the zinc porphyrin into an aqueous solution of cetyltrimethylammonium bromide (CTAB), cuboidal nanostructures are formed at the initial stage. The nanocubes are transformed into nanorods and microrods by aging under ambient conditions. The longer nanorods with well defined edges have been formed with lower concentration of porphyrin solution whereas the shorter nanorods have been formed with higher concentration of zinc porphyrin. The synergistic effect of hydrophobic interactions by the long alkyl chains substituted on the peripheral phenyl rings of porphyrin and axial coordination of pyridyl nitrogen atoms with central zinc is mainly responsible for the formation of different nanostructures. The nanostructures were characterized by UV-visible spectra, fluorescence spectroscopy, scanning electron microscopy (SEM), transmission electron microscopy (TEM), atomic force microscopy (AFM), IR spectroscopy and X-ray diffraction (XRD) pattern.

Activity-guided isolation of antioxidants from the leaves of Terminalia arjuna.

An activity-guided isolation and purification process was used to identify the l,l-diphenyl-2-picrylhydrazyl (DPPH) free radical-scavenging components of the food plant (Terminalia arjuna) of Antheraea mylitta. Dry leaves of T. arjuna were extracted with different solvents and tested for their antioxidant activity against DPPH(•). The acetone-water (8:2) extract expressed strong DPPH radical-scavenging activity, and was subjected to column chromatography over silica gel. Gallic acid, apigenin, luteolin, quercetin, epicatechin, ellagic acid and 1-O-ß-galloyl glucose were isolated as active components and characterised by using different spectroscopic techniques.

Activity-guided isolation of antioxidants from the roots of Rheum emodi.

An activity-guided isolation and purification process was used to identify the DPPH free radical scavenging components of Rheum emodi. The activity-guided isolation revealed that eugenol, gallic acid, quercetin, rutin, epicatechin, desoxyrhapontigenin, rhapontigenin and mesopsin are the major phenolic compounds responsible for the antioxidant activity of the roots of R. emodi.

Electron transfer in natural and unnatural flavoporphyrins.

The development of chemical models for enzymes and their chemical and physical studies constitutes an important area of research from a scientific as well as an industrial point of view. Covalently linked flavin and porphyrin (flavoporphyrins) have attracted attention due to their applications as chemical models for flavoproteins and related enzymes. In this review, the literature has been surveyed to provide a comprehensive coverage of the synthetic methodology and characterization techniques of various types of synthetic flavoporphyrins.

Growth promotion and yield enhancement of peanut (Arachis hypogaea L.) by application of plant growth-promoting rhizobacteria.

Although plant growth-promoting rhizobacteria (PGPR) have been reported to influence plant growth, yield and nutrient uptake by an array of mechanisms, the specific traits by which PGPR promote plant growth, yield and nutrient uptake were limited to the expression of one or more of the traits expressed at a given environment of plant-microbe interaction. We selected nine different isolates of PGPR from a pool of 233 rhizobacterial isolates obtained from the peanut rhizosphere on the basis of ACC-deaminase activity. The nine isolates were selected, initially, on the basis of germinating seed bioassay in which the root length of the seedling was enhanced significantly over the untreated control. All the nine isolates were identified as Pseudomonas spp. Four of these isolates, viz. PGPR1, PGPR2, PGPR4 and PGPR7 (all fluorescent pseudomonads), were the best in producing siderophore and indole acetic acid (IAA). In addition to IAA and siderophore-producing attributes, Pseudomonas fluorescens PGPR1 also possessed the characters like tri-calcium phosphate solubilization, ammonification and inhibited Aspergillus niger and A. flavus in vitro. P. fluorescens PGPR2 differed from PGPR1 in the sense that it did not show ammonification. In addition to the traits exhibited by PGPR1, PGPR4 showed strong in vitro inhibition to Sclerotium rolfsii. The performances of these selected plant growth-promoting rhizobacterial isolates were repeatedly evaluated for 3 years in pot and field trials. Seed inoculation of these three isolates, viz. PGPR1, PGPR2 and PGPR4, resulted in a significantly higher pod yield than the control, in pots, during rainy and post-rainy seasons. The contents of nitrogen and phosphorus in soil, shoot and kernel were also enhanced significantly in treatments inoculated with these rhizobacterial isolates in pots during both the seasons. In the field trials, however, there was wide variation in the performance of the PGPR isolates in enhancing the growth and yield of peanut in different years. Plant growth-promoting fluorescent pseudomonad isolates, viz. PGPR1, PGPR2 and PGPR4, significantly enhanced pod yield (23-26%, 24-28% and 18-24%, respectively), haulm yield and nodule dry weight over the control in 3 years. Other attributes like root length, pod number, 100-kernel mass, shelling out-turn and nodule number were also enhanced. Seed bacterization with plant growth-promoting P. fluorescens isolates, viz. PGPR1, PGPR2 and PGPR4, suppressed the soil-borne fungal diseases like collar rot of peanut caused by A. niger and PGPR4 also suppressed stem rot caused by S. rolfsii. Studies on the growth patterns of PGPR isolates utilizing the seed leachate as the sole source of C and N indicated that PGPR4 isolate was the best in utilizing the seed leachate of peanut, cultivar JL24. Studies on the rhizosphere competence of the PGPR isolates, evaluated on the basis of spontaneous rifampicin resistance, indicated that PGPR7 was the best rhizoplane colonizer and PGPR1 was the best rhizosphere colonizer. Although the presence of growth-promoting traits in vitro does not guarantee that an isolate will be plant growth promoting in nature, results suggested that besides ACC-deaminase activity of the PGPR isolates, expression of one or more of the traits like suppression of phytopathogens, solubilization of tri-calcium phosphate, production of siderophore and/or nodulation promotion might have contributed to the enhancement of growth, yield and nutrient uptake of peanut.

9,10-Anthraquinones and other biologically active compounds from the genus Rubia.

The secondary metabolites isolated from Rubia species, their biological activities, and colouration properties have been reviewed. Over 150 chemical constituents belonging to different classes of bioactive compounds such as anthraquinones and their glycosides, naphthoquinones and glycosides, terpenes, bicyclic hexapeptides, iridoids, and carbohydrates are listed together with their source(s) and corresponding references.

Oxidation of thiols with molecular oxygen catalyzed by cobalt(II) phthalocyanines in ionic liquid.

An efficient procedure for catalyst solubility, recycling and easy product isolation in oxidation of thiols to disulfides with molecular oxygen catalyzed by cobalt(II) phthalocyanines dissolved in ionic liquid at room temperature is reported.

Effect of side chain length on the aggregation of amphiphilic 5,10,15-tris (1-methylpyridinium-4-yl)-20-[4-(alkoxy) phenyl] 21H, 23H porphyrin tritosylates.

Self-aggregation of cationic amphiphilic 5, 10, 15-tris-(1-methylpyridinium-4-yl)-20-[4-(alkoxy)phenyl]-21H, 23H porphyrin tritosylates (2a-e) with different alkoxy chain length in aqueous and binary solvent systems has been studied by UV-visible, fluorescence and (I)H NMR spectroscopy. Binary solvent, concentration, ionic strength, presence of surfactants, and temperature govern the aggregations of 2a-e. Porphyrins having side chain length more than ten carbon atoms (2c-e) form higher aggregates, such as vesicles by sonication of dimers formed initially, whereas porphyrins with lesser side chain length (2a & b) form lower aggregates only. Further, the size and the formation of vesicles have been confirmed by transmission electron microscopy (TEM) and dye entrapment experiments for 2e.

Epoxidation of alkenes with hydrogen peroxide catalyzed by iron(III) porphyrins in ionic liquids.

An efficient procedure is described for catalyst recycling and easy product isolation in alkene epoxidation with hydrogen peroxide catalyzed by water-soluble iron(III) porphyrins in environmentally benign and ambient temperature ionic liquids.

Regioselective biomimetic oxidation of etodolac with iodosylbenzene catalyzed by halogenated and perhalogenated metalloporphyrins in dichloromethane.

The biomimetic oxidation of etodolac, an anti-inflammatory drug (1) with iodosylbenzene catalyzed by 5,10,15,20-tetraarylporphyrinatoiron(III) chlorides TAPFe(III)Cl (7a-e) in dichloromethane gives 4-hydroxyetodolac (6) and 4-oxoetodolac (5) regioselectively in moderate yields.

Formation of 6-formyl-7-hydroxy-8-methoxycoumarin and 5,8-dioxopsoralen by reaction of 8-methoxypsoralen with H2O2 and potassium superoxide (KO2) catalyzed by halogenated or perhalogenated 5,10,15,20-tetraarylporphyrinatoiron(III) chlorides.

The oxidation of 8-methoxypsoralen (2) with hydrogen peroxide and potassium superoxide catalyzed by 5,10,15,20-(2,4,6-trimethylphenyl)porphyrinatoiron(III) chlorides [Me12TPPFe(III)Cl] (1a) and 5,10,15,20-(2,6-dichlorophenyl)porphyrinatoiron(III) chlorides [Cl8TPPFe(III)Cl] (1b) in dichloromethane gives 6-formyl-7-hydroxy-8-methoxycoumarin (3) in moderate yields, whereas the oxidation of (2) with H2O2 catalyzed by 5,10,15,20-(2,6-dichlorophenyl)-beta-octahaloporphyrinatoiron(III) chlorides [Cl8betaX8TPPFe(III)Cl] (X=Cl, Br) (1c, 1d) gives specifically 5,8-dioxopsoralen (4) in moderate yields.

Vesicle formation by amphiphilic 10-alkyl-3-methyl isoalloxazine in aqueous medium.

The synthetic 10-alkyl isoalloxazines have been found to form vesicles in aqueous and binary solvent systems and confirmed by UV-visible, fluorescence,transmission electron microscopy and quasi elastic light scattering experiments. The mean external diameters of vesicles have been calculated for isoalloxazine with different carbon atom chain at position 10 by transmission electron microscopy and quasi elastic laser light scattering. The gel to liquid phase transition of liposomes measured by differential scanning calorimetry shows reproducible endothermic peak which lies well in the range of typical aqueous vesicles.

Biomimetic oxidation of ibuprofen with hydrogen peroxide catalysed by horseradish peroxidase (HRP) and 5,10,15,20-tetrakis-(2',6'-dichloro-3'-sulphonatophenyl)porphyrinatoiro n(III) and manganese(III) hydrates in AOT reverse micelles.

The oxidation of ibuprofen with H2O2 catalysed by Horseradish peroxidase (HRP), Cl8TPPS4Fe(III)(OH2)2 and Cl8TPPS4Mn(III)(OH2)2 in AOT reverse micelles gives 2-(4'-isobutyl-phenyl)ethanol (5) and p-isobutyl acetophenone (6) in moderate yields. The reaction of ibuprofen (2) with H2O2 catalysed by HRP form carbon radicals by the oxidative decarboxylation, which on reaction with molecular oxygen to form hydroperoxy intermediate, responsible for the formation of the products 5 and 6. The yields of different oxidation products depend on the pH, the water to surfactant ratio (Wo), concentration of Cl8TPPS4Fe(III)(OH2)2 and Cl8TPPS4Mn(III)(OH2)2 and amount of molecular oxygen present in AOT reverse micelles. The formation of 2-(4'-isobutyl phenyl)ethanol (5) may be explained by the hydrogen abstraction from ibuprofen by high valent oxo-manganese(IV) radical cation, followed by decarboxylation and subsequent recombination of either free hydroxy radical or hydroxy iron(III)/manganese(III) porphyrins. The over-oxidation of 5 with high valent oxo-manganese, Mn(IV)radical cation intermediate form 6 in AOT reverse micelles by abstraction and recombination mechanism.

Incorporation of synthetic tetramethylene diamine 8,8'-bis(riboflavin tetraacetate) in DMPC vesicles.

The tetramethylene diamine 8,8'-bis(riboflavin tetraacetate) is synthesized by condensation of 8 alpha-bromo riboflavin tetraacetate and 1,4 diaminobutane. The incorporation of bis(riboflavin tetraacetate) in bilayer of DMPC vesicles has been studied by gel permeation chromatography, UV-visible and fluorescence spectroscopy.

Isolation and characterization of electrophiles from 2-haloethylnitrosoureas forming cytotoxic DNA cross-links and cyclic nucleotide adducts and the analysis of base site-selectivity by ab initio calculations.

E- and Z-2-haloethyldiazotates--electrophilic species hitherto suggested as intermediates in the reactions of 2-haloethylnitrosoureas (HENUs) under physiological conditions--were synthesized and characterized by 1H-, 15N- and 13C-NMR (nuclear magnetic resonance). They were stabilized and solubilized in organic solvents as their 18-crown-6 ether complexes. Characterization of the Z-2-fluoroethyldiazotate by 19F- and 13C-NMR, and comparison with the Z-2-chloroethyl compound, confirmed facile cyclization to the 1,2,3-oxadiazoline and subsequent decomposition to nitrogen and ethylene oxide. The E-2-haloethyldiazotates form DNA interstrand cross-links at a rate, and to an extent, and with a DNA base dependence, which parallels the behaviour of the parent HENUs, while the Z isomers alkylate DNA but show minimal cross-linking. Both E-and Z-(2'-chloroethyl)thioethyldiazotates, neither of which can undergo cyclization, cross-link DNA efficiently. Self-consistent-field (SCF) ab initio calculations provided optimized geometries, atomic charges and LUMO (Lowest Unoccupied Molecular Orbital) atom contributions for the E- and Z-2-haloethyldiazohydroxides. The HSAB (Hard and Soft Acids and Bases) theory, in conjunction with HOMO (Highest Occupied Molecular Orbital) values on key DNA base sites, accounted for the observed site-selectivity in the formation of identified cross-links produced by 1,3-bis-(2-chloroethyl)-1-nitrosourea. Independent chemical studies on cytosine derivatives corroborated the predicted site selectivity of attack by electrophiles and the formation of ethanocytidine cyclic adducts.

Characterization of alkyldinitrogen species implicated in the carcinogenic, mutagenic and anticancer activities of N-nitroso compounds.

The syntheses of certain specifically 15N-labelled E and Z alkyldiazotates and alkylnitrosoamines, together with related dinitrogen species, including diazoalkanes, are reported. A study of their conformational and configurational equilibria by 15N and 13C nuclear magnetic resonance spectrometry has revealed: (1) corresponding pairs of E and Z alkyldiazotates do not interconvert at ambient temperatures in aprotic solvents; (2) a preferential Z conformer of the alkylnitrosamines; (3) a fast interchange of metal counterion between oxygen and nitrogen in the Z-diazotates, but a slow interchange of metal ion between oxygen and nitrogen in the corresponding E diazotates; (4) interconversion of Z aryldiazotates, via detectable Z and E diazohydroxides, to the E diazotates; and (5) rapid stereoelectronically-assisted decomposition of Z-alkyldiazotates to diazoalkanes, in contrast with the behaviour of the more stable E diazotates. Self-Consistent Field calculations ab initio show that Z methyl diazohydroxide is the higher energy and more reactive form, while the carbon is relatively soft. In contrast, the E isomer is the more stable (by congruent to 18.0 kcal/mol) and the carbon harder. These data are in accord with the view that the Z form (from N-nitrosodimethylamine) attacks G-O6 (softer center) preferentially by SN1, while the E form prefers to react at the harder G-N7 and by an SN2 mechanism. These data provide a rationale for the known propylation of G-N7 without rearrangement, for propylation of G-O6 with rearrangement and possibly for the origin of the characteristic G-O6 alkylation carcinogenic lesion.

Mechanism of action of (2-haloethyl)nitrosoureas on DNA. Isolation and reactions of postulated 2-(alkylimino)-3-nitrosooxazolidine intermediates in the decomposition of 1,3-bis(2-chloroethyl)-, 1-(2-chloroethyl)-3-cyclohexyl-, and 1-(2-chloroethyl)-3-(4'-trans-methylcyclohexyl)-1-nitrosourea.

Three examples of the postulated but hitherto unisolated 2-(alkylimino)-3-nitrosooxazolidines (2) have been prepared containing cyclohexyl, trans-4-methylcyclohexyl, and 2-chloroethyl groups at the 2 position, respectively. These compounds correspond to intermediates previously postulated to be formed in the aqueous decomposition of the antitumor agents 1-(2-chloroethyl)-3-cyclohexyl- (CCNU), 1-(2-chloroethyl)-3-(4'-trans-methylcyclohexyl)- (MeCCNU), and 1,3-bis(2-chloroethyl)-1-nitrosourea (BCNU), respectively, Compounds 2 decompose under physiological conditions to give a range of products similar to those formed from the corresponding (2-chloroethyl)nitrosoureas, including the hitherto unrecognized 2-hydroxyethl N-alkylcarbamates (9). Compounds 2a and 2b are converted with hydrochloric acid into CCNU and MeCCNU, respectively, suggesting that 2a and 2b may be reaction intermediates of decomposition. The corresponding 3-alkyl-1-nitroso-1-(2-hydroxyethyl)ureas (4) were characterized and, since they also decompose to give the same products as 2, may arise from the ring opening of 2. The intermediacy of compounds 4 can explain the formation of hydroxyethylated nucleosides isolated by other workers from the reaction of (2-chloroethyl)nitrosoureas on polynucleotides.