N.M.R. study of internal motion in hexahydrated acid fluorides of cobalt and nickel

A linear relationship between the viscosity B-coefficient of the Jones-Dole equation for aqueous solutions of certain alkali metal salts and the enthalpy of hydration of the gaseous monatomic constituent ions has been established. The assumption that a similar rectilinear law applies to ammonium halides appears justified and the enthalpies of solution of NH₄ ⁺(g)+X^-(g) have been estimated and used to obtain magnitudes for the lattice energies of NH₄X(c) [X=F, Cl, Br, I]. In conjunction with experimental thermochemical data, the latter yield consistent results for the proton affinity of ammonia ΔH ₁ ^?=860·5±2·0 kJ mol^-1 (298·15 K). The lattice energies of the salts are, (in kJ mol^-1) 834 (NH₄F), 708 (NH₄Cl), 682 (NH₄Br) and 637(NH₄I).     

Immobilized hyperbranched glycoacrylate films as bioactive supports

[Image: see text] We report on the low-pressure plasma immobilization, characterization and application of thin films of hyperbranched glycoacrylates, poly(3-O-acryloyl-alpha,beta-D-glucopyranoside) (AGlc), on PTFE-like fluorocarbon surfaces. This method is an efficient and versatile way to immobilize sugar-carrying branched acrylates as thin films of approximately 5 nm thickness on polymeric substrates while the functional groups and properties of the immobilized molecules are largely retained. The extent of poly(AGlc) degradation during plasma immobilization was investigated using FTIR-ATR spectroscopy and XPS. The thickness and topography of the immobilized films were characterized using spectroscopic ellipsometry and SFM, respectively. Studies of protein adsorption, as well as cell adhesion and proliferation on the poly(AGlc) surfaces, showed that these materials are suitable for the control of biointerfacial phenomena. Fluorescence images of fibronectin adsorbed on to the branched glycoacrylate with a mask.     

Manganese(III) Acetate Mediated Oxidation of Flavanones: A Facile Synthesis of Flavones

Oxidation of flavanones (1a–o) with manganese(III) acetate by heating in acetic acid in presence of perchloric acid afforded exclusively flavones (2a–o) by dehydrogenation in almost quantitative yields.     

Thallium(III) Nitrate Mediated Ring Contraction of 2‐Aryl‐1,2,3,4‐tetrahydro‐4‐quinolones: Stereoselective Synthesis of trans Methyl 2‐Aryl‐2,3‐dihydroindol‐3‐carboxylates

The ring contraction of N‐acetyl‐2‐aryl‐1,2,3,4‐tetrahydro‐4‐quinolones 1a–d with thallium(III) nitrate in trimethyl orthoformate afforded stereoselectively trans methyl N‐acetyl‐2‐aryl‐2,3‐dihydroindol‐3‐carboxylates 5a–d by oxidative rearrangement of aryl ring A.     

Syntheses and biological evaluation of new triazole-spirochromone conjugates as inhibitors of Mycobacterium tuberculosis

A series of novel 1,2,3-triazole fused spirochromone conjugates have been synthesized bearing both spirochromone moiety as well as a 1,2,3-triazole moiety. Some of the compounds have exhibited potential activity against Mycobacterium tuberculosis (virulent strain H37Rv). In particular 5e proved to be the most potent derivative exhibiting MIC = 0.78 μg/mL.     

Competition between alpha-cleavage and energy transfer in alpha-azidoacetophenones

Molecular modeling demonstrates that the first excited state of the triplet ketone (T1K) in azide 1b has a (pi,pi*) configuration with an energy that is 66 kcal/mol above its ground state and its second excited state (T2K) is 10 kcal/mol higher in energy and has a (n,pi*) configuration. In comparison, T1K and T2K of azide 1a are almost degenerate at 74 and 77 kcal/mol above the ground state with a (n,pi*) and (pi,pi*) configuration, respectively. Laser flash photolysis (308 nm) of azide 1b in methanol yields a transient absorption (lambdamax=450 nm) due to formation of T1K, which decays with a rate of 2.1 x 105 s-1 to form triplet alkylnitrene 2b (lambdamax=320 nm). The lifetime of nitrene 2b was measured to be 16 ms. In contrast, laser flash photolysis (308 nm) of azide 1a produced transient absorption spectra due to formation of nitrene 2a (lambdamax=320 nm) and benzoyl radical 3a (lambdamax=370 nm). The decay of 3a is 2 x 105 s-1 in methanol, whereas nitrene 2a decays with a rate of approximately 91 s-1. Thus, T1K (pi,pi*) in azide 1b leads to energy transfer to form nitrene 2b; however, alpha-cleavage is not observed since the energy of T2K (n,pi*) is 10 kcal/mol higher in energy than T1K, and therefore, T2K is not populated. In azide 1a both alpha-cleavage and energy transfer are observed from T1K (n,pi*) and T2K (pi,pi*), respectively, since these triplet states are almost degenerate. Photolysis of azide 1a yields mainly product 4, which must arise from recombination of benzoyl radicals 3a with nitrenes 2a. However, products studies for azide 1b also yield 4b as the major product, even though laser flash photolysis of azide 1b does not indicate formation of benzoyl radical 3b. Thus, we hypothesize that benzoyl radicals 3 can also be formed from nitrenes 2. More specifically, nitrene 2 does undergo alpha-photocleavage to form benzoyl radicals and iminyl radicals. The secondary photolysis of nitrenes 2 is further supported with molecular modeling and product studies.     

Green biosynthesis of silver nanoparticles and nanomolar detection of p-nitrophenol

Green biosynthesis of nanoparticles and their applications in sensor field is of great interest to the researchers. We report herein a simple green approach for the synthesis of silver nanoparticles (Ag-NPs) using Acacia nilotica Willd twig bark and its application for the detection of 4-nitro phenol (4-NP). The synthesized Ag-NPs were characterized by Transmission electron microscopy, X-ray diffraction and elemental analysis. The size of synthesized Ag-NPs was in the range of 10–50 nm. The Ag-NPs modified electrode shows a high sensitivity and selectivity towards the sensing of 4-NP. The fabricated modified electrode shows a low detection limit of 15 nM on the wider linear response range from 100 nM to 350 μM with the sensitivity of 2.58?±?0.05 μAμM^?1 cm^?2. In addition, the fabricated sensor shows good repeatability and reproducibility.

A convenient synthesis of enantiomerically pure (R)-mexiletine using hydrolytic kinetic resolution method

Enantiopure (R)-mexiletine was prepared in a simple and practical way using hydrolytic kinetic resolution method of terminal epoxide by Jacobsen’s catalyst. High enantiomeric purity (98% ee) was achieved and the method is well amenable to industrial scale-up.     

An alternate synthesis of enantiomerically pure levetiracetam (Keppra®)

A simple and efficient synthesis of levetiracetam has been achieved with high enantiopurity (>99%) starting from commercially available benzyl glycidyl ether. The method is amenable for industrial scale-up.