Natural flavonoids interact with dinitrobenzene system in aprotic media: an electrochemical probing

Three structurally related natural flavonoids (FlOH), quercetin (Q), rutin (R) and morin (M), were investigated by cyclic voltammetry to probe their interactions with hazardous 1,4-dinitrobenzene (1,4-DNB) using a glassy carbon electrode. Scavenging of 1,4-DNB by FlOH was inferred from a positive shift in reduction potential, decrease in anodic peak current, and irreversible electrochemical behavior of 1,4-DNB on increasing the flavonoid concentration. The homogeneous bi-molecular rate constant (k2) was determined using the Nicholson-Shain equation and found to be higher for the dianion. Morin posed a comparatively higher k2 value for its interaction with the 1,4-DNB electrochemical system owing to its more acidic nature and least intramolecular hydrogen bonding. The cyclic voltammetric (CV) results were further supported by HyperchemPM3 quantum mechanical semi-empirical calculations, which point towards E(r)C(i) interactions between flavonoids and 1,4-DNB. The present investigation is biologically significant in terms of natural flavonoidal scavenging activity toward toxins such as dinitroaromatics.     

Variation in fat soluble vitamins (A,D, E,K) in in vitro and ex vitro germinated chickpea (Cicer arietinum L.) seedlings,as revealed by high performance liquid chromatography

In present communication, effect of in vitro and ex vitro culture conditions was investigated on the yield of fat soluble vitamins in chickpea (Cicer arietinum L.) seedlings analyzed by high performance liquid chromatography (HPLC). Amongst the tested culture conditions (in vitro and ex vitro); in vitro condition proved to be highly effective compared to ex vitro. We noticed a significant difference in vitamins D (ergocalciferol), E (α-tocopherol) and K (phylloquinone) yields in chickpea seedlings grown in two different conditions. Maximum yield with a linear increase in vitamins D and E was noticed upto 9 days old in vitro grown seedlings. Vitamin K yield was also high in in vitro grown seedlings with a linear increase upto 11 days. Although, vitamin A was not detected, the vitamin production in germinating seeds was, therefore, age and culture condition dependent. The study revealed that, in in vitro condition, the level of fat soluble vitamins enhanced in seedlings, which could be used for human consumption with value addition in the diet of vegetarians.     

Activation of phosphorus by group 14 elements in low oxidation states

The activation of phosphorus remains a popular and competitive area of research driven by the dual goals of finding ways to avoid the environmentally questionable P-Cl compounds applied in many industrial processes and the target of catalytic functionalization of P(4). In recent years the activation, degradation, fragmentation, and functionalization of white phosphorus by compounds with heavier main group elements have become a fertile area of research. The isolation of various carbenes and functionalized silylenes has prompted chemists to investigate their reactions with white phosphorus. The most intriguing fact in these reactions is the subtle change in the substituents may afford strikingly different compounds. For example, from the reaction of P(4) with PhC(NtBu)(2)SiCl a cyclic Si(2)P(2) derivative is obtained, whereas the analogous reaction with PhC(NtBu)(2)SiN(SiMe(3))(2) resulted in an acyclic Si(2)P(4) framework. Similar phenomena have also been observed in the carbene mediated P(4) activation. Apart from these, a new entry point into phosphorus chemistry is the gentle activation of P(4) by an alkyne analogue of tin. In this feature article we have covered the activation of phosphorus by compounds with low valent group 14 elements with special concern to the recent developments in this topic.     

Recent trends in chiral separations on immobilized polysaccharides CSPs

Polysaccharide CSPs are recognized widely in chiral chromatography but the introduction of immobilized phases (Chiralpak IA, Chiralpak IB and Chiralpak IC columns) is a remarkable achievement. The immobilized CSPs can be used with organic, normal and reversed phase modes; even with prohibited solvents too (tetrahydrofuran, chlorofom, dichloromethane, acetone, 1,4-dioxane, ethylacetate, and certain other ethers). Their susceptibilities to work with a wide range of solvents have increased the range of applications including chiral recognition mechanisms. Besides, these are also useful for monitoring the progress of stereo-specific reactions; normally need prohibited solvents. The present review describes the various aspects of commercial available immobilized chiral columns. Attempts have been made to discuss immobilized polysaccharides CSPs, immobilized vs coated CSPs, comparison of immobilized CSPs, method development, optimization, chiral recognition mechanism and applications. The chiral recognition capabilities of commercial columns were in the order of Chiralpak IA > Chiralpak IB > Chiralpak IC columns; but complimentary to each other. Of course, these CSPs are not fully developed and need more advancements and applications. Definitely, the future of immobilized CSPs is quite better. Hopefully, in the coming years they will be the choice of the chromatographers for chiral separations in liquid chromatography.     

Correlation between chemical composition and antibacterial activity of essential oils from fifteen Eucalyptus species growing in the Korbous and Jbel Abderrahman arboreta (North East Tunisia)

The essential oils of fifteen Eucalyptus species harvested from the Jbel Abderrahman and Korbous arboreta (North East Tunisia) were screened for their antibacterial activities by the agar disc diffusion method. Eighteen major components as identified by GC/FID and GC/MS were selected for a study of the chemical and biological activity variability. The main one was 1,8-cineole, followed by spathulenol, trans-pinocarveol, α-pinene, p-cymene, globulol, cryptone, β-phellandrene, viridiflorol, borneol, limonene and isospathulenol. The chemical principal component analysis identified five species groups and subgroups, where each group constituted a chemotype, however that of the values of zone diameter of the inhibition (zdi) identified six groups of Eucalyptus oils, characterized by their antibacterial inhibition ability. The strongest activity was shown by E. platypus oil against Enterococcus faecalis and by E. lamannii oil against Staphylococcus aureus, Pseudomonas aeruginosa and Escherichia coli. A correlation between the levels of some major components and the antibacterial activities was observed.     

Indium bromide catalysed, ultrasound-assisted, regio-selective synthesis of ethyl-5-(trifluoromethyl)-1-(3-substituted-isoquinolin-1-yl)-1H-pyrazole-4-carboxylates

A series of pyrazole-4-carboxylates have been synthesised using indium bromide catalyst and the cyclisation of respective 3-substituted-isoquinolinylhydrazines 1 into their corresponding ethyl-2-(ethoxymethylene)-4,4,4-trifluoro-3-oxobutanoates 3 in ethanol solvent under ultrasonic irradiation at 90?°C for 30 min. The regio-selective cyclisation products were efficiently provided by indium bromide catalyst and are confirmed by nuclear Overhauser effect spectroscopy?Cnuclear magnetic resonance (NOESY?CNMR) studies.     

An efficient 2-(1H-benzotriazole-1-yl)-1,1,3,3-tetramethyluronium tetrafluoroborate (TBTU)-mediated synthesis of 5-(trifluoromethyl)-N-alkyl-1-(3-phenylisoquinoline-1-yl)-1H-pyrazole-4-carboxamides

A series of 5-(trifluoromethyl)-N-alkyl-1-(3-phenylisoquinoline-1-yl)-1H-pyrazole-4-carboxamides 4 has been effectively achieved in high yield and purity from the reaction of pyrazole carboxylic acid 2 with amines 3 in the presence of TBTU as a catalyst and diisopropyl ethylamine as a base in acetonitrile at room temperature.     

Synthesis and spectral characterization of chloro-organotin(IV) complexes of S-donor ligand: Crystal structure of chloro-t-dibutyltin[4-methyl-1-piperidine]thiocarboxylate

New chloromono- and diorganotin(IV) complexes of 4-methyl-1-piperidine dithiocarboxylic acid have been synthesized in anhydrous chloroform. The complexes were characterized by microanalysis, IR, ¹H and ¹³C NMR, mass spectrometry and XRD. The FTIR spectra clearly demonstrate that organotin(IV) moieties react with [S,S] atoms of the ligand. Compound (1) and (3) exhibits the 5-coordinated while the compound (2) exhibit 6-coordinated geometry in solid state. Compound (3) shows distorted trigonal bipyramidal geometry which is confirmed by X-ray single-crystal diffraction.     

Immobilized dimeric chiral Mn(III) salen complex on short channel ordered mesoporous silica as an effective catalyst for the epoxidation of non-functionalized alkenes

Chiral dimeric Mn(III) salen complex with 1R, 2R-(?)-diaminocyclohexane collar was immobilized on short channel large pore sized silica through a long linker of {(CH₂)₃–NH–melamine–piperazine} to investigate its performance in enantioselective epoxidation of chromenes, indene, styrene and cis β-methyl styrene in the presence of pyridine N-oxide (PyNO) as an axial base using aqueous NaOCl as an oxidant at 0 °C. The immobilized catalyst system showed high turnover frequency (TOF) and enantioselectivity for the smaller and bulkier alkenes like styrene, indene, 2,2-dimethylchromene and 6-cyano-2,2-dimethylchromene (ee up to 98%). These results are the best reported for heterogeneous catalyst under biphasic reaction conditions and were comparable to the dimeric Mn(III) salen system under homogeneous condition. The performance of the immobilized catalyst was retained for six reuse experiments. This protocol was extended to the synthesis of an antihypertensive drug (S)-Levchromakalim (ee 98%) at 1 g level.