In vitro antioxidant activities of the methanol extract and its different solvent fractions obtained from the fruit pericarp of Terminalia bellerica

Terminalia bellerica has been used as a traditional medicine in a variety of ailments including anaemia, asthma, cancer, inflammation, rheumatism and hypertension. In this study, the free radical scavenging and antioxidant activities of methanol extract (ME) and its different solvent fractions (namely hexane (HE), ethyl acetate (EA), butanol (BL) and water (WA)) of the T. bellerica fruit pericarp were evaluated and compared with standard antioxidant compounds like gallic acid (GA), catechin and ascorbic acid. Among the different fractions tested, the EA fraction exhibited higher antioxidant and radical scavenging activity against 1,1-diphenyl-2-picrylhydrazyl (DPPH), superoxide and hydroxyl radicals than the other fractions, which may be attributed to its higher phenolic and flavonoid content, since a linear relation was observed between the phenolic content and the antioxidant parameters. The HPTLC analysis of the EA fraction revealed that it mainly contains GA and ferulic acid (FA) as major phenolics, and the higher antioxidant activities of EA fraction may be due to the presence of these compounds.     

Synthesis of 5‐aryl and 5‐amidocamptothecins

A variety of 5‐aryl‐(20S)‐camptothecin derivatives were synthesized by the reaction of 5‐hydroxy‐(20S)‐camptothecin with aromatic hydrocarbons under Friedel‐Craft reaction conditions in moderate to good yield as diastereomeric pairs. The methodology was then extended for the synthesis of 5‐amido‐(20S)‐camptothecin derivatives by reacting 5‐hydroxy‐(20S)‐camptothecin with alkyl and aryl nitriles under Ritter type reaction conditions. The reaction is presumed to proceed through an iminium ion intermediate under Friedel Craft and Ritter type reaction condition, which is further trapped by nucleophile present in the reaction medium. J. Heterocyclic Chem., 00 , 00 (2011).     

A simple chemosensor for Hg2+ and Cu2+ that works as a molecular keypad lock

A new chemosensor which can detect Hg(2+) in water and Hg(2+)/Cu(2+) in acetonitrile and its application as a molecular keypad lock using Cu(2+) and F(-) as ionic inputs are demonstrated.     

Nickel(II) complexes of tripodal 4N ligands as catalysts for alkane oxidation using m-CPBA as oxidant: ligand stereoelectronic effects on catalysis

Several mononuclear Ni(II) complexes of the type [Ni(L)(CH(3)CN)(2)](BPh(4))(2) 1-7, where L is a tetradentate tripodal 4N ligand such as N,N-dimethyl-N',N'-bis(pyrid-2-ylmethyl)ethane-1,2-diamine (L1), N,N-diethyl-N',N'-bis(pyrid-2-ylmethyl)ethane-1,2-diamine (L2), N,N-dimethyl-N'-(1-methyl-1H-imidazol-2-ylmethyl)-N'-(pyrid-2-ylmethyl)ethane-1,2-diamine (L3), N,N-dimethyl-N',N'-bis(1-methyl-1H-imidazol-2-ylmethyl)ethane-1,2-diamine (L4), N,N-dimethyl-N',N'-bis(quinolin-2-ylmethyl)ethane-1,2-diamine (L5), tris(benzimidazol-2-ylmethyl)amine (L6) and tris(pyrid-2-ylmethyl)amine (L7), have been isolated and characterized using CHN analysis, UV-Visible spectroscopy and mass spectrometry. The single-crystal X-ray structures of the complexes [Ni(L1)(CH(3)CN)(H(2)O)](ClO(4))(2) 1a, [Ni(L2)(CH(3)CN)(2)](BPh(4))(2) 2, [Ni(L3)(CH(3)CN)(2)](BPh(4))(2) 3 and [Ni(L4)(CH(3)CN)(2)](BPh(4))(2) 4 have been determined. All these complexes possess a distorted octahedral coordination geometry in which Ni(II) is coordinated to four nitrogen atoms of the tetradentate ligands and two CH(3)CN (2, 3, 4) or one H(2)O and one CH(3)CN (1a) are located in cis positions. The Ni-N(py) bond distances (2.054(2)-2.078(3) ?) in 1a, 2 and 3 are shorter than the Ni-N(amine) bonds (2.127(2)-2.196(3) ?) because of sp(2) and sp(3) hybridizations of the pyridyl and tertiary amine nitrogens respectively. In 3 the Ni-N(im) bond (2.040(5) ?) is shorter than the Ni-N(py) bond (2.074(4) ?) due to the stronger coordination of imidazole compared with the pyridine donor. In dichloromethane/acetonitrile solvent mixture, all the Ni(ii) complexes possess an octahedral coordination geometry, as revealed by the characteristic ligand field bands in the visible region. They efficiently catalyze the hydroxylation of alkanes when m-CPBA is used as oxidant with turnover number (TON) in the range of 340-620 and good alcohol selectivity for cyclohexane (A/K, 5-9). By replacing one of the pyridyl donors in TPA by a weakly coordinating -NMe(2) or -NEt(2) donor nitrogen atom the catalytic activity decreases slightly with no change in the selectivity. In contrast, upon replacing the pyridyl nitrogen donor by the strongly σ-bonding imidazolyl or sterically demanding quinolyl/benzimidazolyl nitrogen donor, both the catalytic activity and selectivity decrease, possibly due to destabilization of the intermediate [(4N)(CH(3)CN)Ni-O˙](+) radical species. Adamantane is selectively (3°/2°, 12-17) oxidized to 1-adamantanol, 2-adamantanol and 2-adamantanone while cumene is selectively oxidized to 2-phenyl-2-propanol. In contrast to cyclohexane oxidation, the incorporation of sterically hindering quinolyl/benzimidazolyl donors around Ni(ii) leads to a high 3°/2° bond selectivity for adamantane oxidation. A linear correlation between the metal-ligand covalency parameter (β) and the turnover number has been observed.     

An efficient copper-aluminum hydrotalcite catalyst for asymmetric hydrosilylation of ketones at room temperature

A catalyst system consisting of a copper-aluminum hydrotalcite-chiral diphosphine ligand effects asymmetric hydrosilylation of several ketones, using polymethylhydrosiloxane (PMHS) as the stoichiometric reducing agent at room temperature, with moderate-to-excellent enantioselectivities. The catalyst is recovered by simple centrifugation, and the efficiency of the catalyst remains almost unaltered even after several cycles.     

Synthesis, spectral characterization and crystal structure of copper(II) complexes of 2-benzoylpyridine-N(4)-phenylsemicarbazone

An interesting series of nine new copper(II) complexes [Cu₂L₂(OAc)₂]·H₂O (1), [CuLNCS]·½H₂O (2), [CuLNO₃]·½H₂O (3), [Cu(HL)Cl₂]·H₂O (4), [Cu₂(HL)₂(SO₄)₂]·4H₂O (5), [CuLClO₄]·½H₂O (6), [CuLBr]·2H₂O (7), [CuL₂]·H₂O (8) and [CuLN₃]·CH₃OH (9) of 2-benzoylpyridine-N(4)-phenyl semicarbazone (HL) have been synthesized and physico-chemically characterized. The tridentate character of the semicarbazone is inferred from IR spectra. Based on the EPR studies, spin Hamiltonian and bonding parameters have been calculated. The g values, calculated for all the complexes in frozen DMF, indicate the presence of the unpaired electron in the d_x²-y² orbital. The structure of the compound, [Cu₂L₂(OAc)₂] (1a) has been resolved using single crystal X-ray diffraction studies. The crystal structure revealed monoclinic space group P2₁/n. The coordination geometry about the copper(II) in 1a is distorted square pyramidal with one pyridine nitrogen atom, the imino nitrogen, enolate oxygen and acetate oxygen in the basal plane, an acetate oxygen form adjacent moiety occupies the apical position, serving as a bridge to form a centrosymmetric dimeric structure.     

CuFe2O4 nanoparticles: a magnetically recoverable and reusable catalyst for the synthesis of 5-substituted 1H-tetrazoles

An efficient and economical protocol for the synthesis of 5-substituted 1H-tetrazoles from various nitriles and sodium azide is described using magnetically recoverable and reusable CuFe₂O₄ nanoparticles. A wide variety of aryl nitriles underwent [2+3] cycloaddition under mild reaction conditions to afford tetrazoles in good to excellent yields. The catalyst was magnetically separated and reused five times without significant loss of catalytic activity.     

Free volume related fluorescent behavior in electron beam irradiated chalcone doped PVA

Effect of electron irradiation on the free volume related microstructural and optical properties of chalcone doped Poly(vinyl alcohol) composite films have been studied using FTIR, UV-Visible, XRD and Positron Annihilation techniques. The FTIR spectral study shows that the irradiation induces the crosslinking within the composite. Using UV-Visible absorption spectra the optical energy band gap and activation energies were estimated and the variation of these parameters suggests the existence of defects and molecular ordering within the irradiated composite. XRD diffractograms reveal that the crosslinking enhances the crystallinity of the sample. In this cross-linked polymer composite the fluorescence enhancement has been observed in the fluorescence spectral study. The Positron annihilation result suggests that the irradiation affects the free volume properties and crosslinking hinders the chalcone chromophore molecular rotation. Under this restricted condition the chromophore molecules likely to emit enhanced fluorescence and its mobility is directly related to the free volume around it.     

Activity-based chemical proteomics accelerates inhibitor development for deubiquitylating enzymes

Converting lead compounds into drug candidates is a crucial step in drug development, requiring early assessment of potency, selectivity, and off-target effects. We have utilized activity-based chemical proteomics to determine the potency and selectivity of deubiquitylating enzyme (DUB) inhibitors in cell culture models. Importantly, we characterized the small molecule PR-619 as a broad-range DUB inhibitor, and P22077 as a USP7 inhibitor with potential for further development as a chemotherapeutic agent in cancer therapy. A striking accumulation of polyubiquitylated proteins was observed after both selective and general inhibition of cellular DUB activity without direct impairment of proteasomal proteolysis. The repertoire of ubiquitylated substrates was analyzed by tandem mass spectrometry, identifying distinct subsets for general or specific inhibition of DUBs. This enabled identification of previously unknown functional links between USP7 and enzymes involved in DNA repair.     

A Recyclable and Highly Effective ZnO-beta Zeolite as a Catalyst for One-pot Three-Component Synthesis of Tetrahydrobenzo[b]pyrans

4H‐Benzo[b]pyrans was synthesized under reflux condition in ethanol via condensation of benzaldehyde, malononitrile and dimedone with ZnO‐beta zeolite as an inexpensive and effective catalyst. The key features of the reported protocols are good to excellent yields, short reaction time and recovery and reusability of catalytic material.