Theoretical study of the substituent effects on the S-H bond dissociation energy and ionization energy of 3-pyridinethiol: Prediction of novel antioxidant

The S-H bond dissociation enthalpies [BDE(S-H)] of a set of 5-X- and 6-X-3-pyridinethiols (X = F, Cl, CH3, OCH3, NH2, N(CH3)2, CF3, CN, and NO2) have been computed using the density functional theory based (RO)B3LYP procedure with 6-311++G(2df,2p) basis set. The effects of substituents on the BDE(S-H), proton affinity of the pyridinethiol anion [PA(S-)] and ionization energy (IE) are analyzed and their correlations with Hammett's substituent constants are examined. Subsequently, a series of 6-substituted 3-pyridinethiols have been explored to find out their antioxidant potentials. Finally, a number of 3-pyridinethiol based compounds are theoretically proposed as novel antioxidants.     

Direct glycosylation: synthesis of alpha-indoline ribonucleosides

A selective synthesis of α-anomers of indoline nucleosides is described. Ribonucleosides of indoline, dimethylindoline and 5-bromoindoline are readily prepared in good yield by reacting indoline bases directly with the protected sugar, 2,3-O-(1-methylethylidene) 5-O-(triphenylmethyl)-D-ribofuranose in dry ethanol or methylene chloride in presence of molecular sieves at 40-60 °C.     

Gold nano-popcorn-based targeted diagnosis, nanotherapy treatment, and in situ monitoring of photothermal therapy response of prostate cancer cells using surface-enhanced Raman spectroscopy

Prostate cancer is the second leading cause of cancer-related death among the American male population, and the cost of treating prostate cancer patients is about $10 billion/year in the United States. Current treatments are mostly ineffective against advanced-stage prostate cancer and are often associated with severe side effects. Driven by these factors, we report a multifunctional, nanotechnology-driven, gold nano-popcorn-based surface-enhanced Raman scattering (SERS) assay for targeted sensing, nanotherapy treatment, and in situ monitoring of photothermal nanotherapy response during the therapy process. Our experimental data show that, in the presence of LNCaP human prostate cancer cells, multifunctional popcorn-shaped gold nanoparticles form several hot spots and provide a significant enhancement of the Raman signal intensity by several orders of magnitude (2.5 × 10(9)). As a result, it can recognize human prostate cancer cells at the 50-cells level. Our results indicate that the localized heating that occurs during near-infrared irradiation can cause irreparable cellular damage to the prostate cancer cells. Our in situ time-dependent results demonstrate for the first time that, by monitoring SERS intensity changes, one can monitor photothermal nanotherapy response during the therapy process. Possible mechanisms and operating principles of our SERS assay are discussed. Ultimately, this nanotechnology-driven assay could have enormous potential applications in rapid, on-site targeted sensing, nanotherapy treatment, and monitoring of the nanotherapy process, which are critical to providing effective treatment of cancer.     

Synthesis, spectral and biological studies of nitrogen–sulphur donor macrocyclic ligands and their transition metals complexes

Mn(II), Co(II), Ni(II) and Cu(II) complexes have been synthesized with 22 and 24 membered tetramide macrocyclic ligands viz; 1,9,12,20-tetraaza-2,8,13,19-tetraone-5,16-dithiacyclodocosane [L¹] and 1,9,13,21-tetraaza-2,8,14,20-tetraone-5,17-dithiacyclotetracosane [L²] and characterized by elemental analysis, molar conductance, magnetic susceptibility measurements, mass, IR, electronic EPR spectral studies and electrochemical properties. The molar conductance of all the complexes in DMSO solution is corresponding to 1:2 electrolyte. Thus these complexes may be formulated as [M(L′)]Cl₂ [where M = Mn(II), Co(II), Ni(II) and Cu(II) L′ = L¹ and L²]. On the basis of spectral studies a distorted octahedral geometry has been assigned for all the complexes. The ligands and their complexes were also screened in vitro against two pathogenic fungi (F. moniliformae and R. solani) to assess their growth inhibiting potential.     

Rhenium,part XIV. Studies on the action of hydrogen halides on [ReO2en2]+

Summary The products from the reaction oftrans-dioxobis(ethylenediamine)rhenium(V) halides with hydrogen halides have been investigated. Dilute (2M) and concentrated hydrochloric acid react with (ReO₂en₂)Cl in the cold to give ReO(OH)enCl₂ and IRe(OH)₂enCl₂]Cl respectively, while with hot 6M HCl [ReOCl₅]^2– is formed. Dilute solutions of HX protonate [ReO₂en₂]X (X = Br and I) giving [ReO(OH)en₂]X₂ which are converted slowly into ReO(OH)enBr₂ and [ReO(OH)en2](I₃)₂. Hot and concentrated solutions of HX reduce Re^v in (ReO₂en2 )X (X = Br and I) giving enH₂(ReBr₆) and ReI₄en. The thermal decomposition of (ReO₂en₂)X (X = Cl, Br and I) has been studied by thermogravimetry and a polymeric compound, Re₂O₇en₂, has been isolated by heating (ReO₂en₂)X at 200°. The compounds have been characterised by molecular conductivities, magnetic susceptibility and i.r. spectra.     

Biligand metal chelates of 1,10-phenanthroline and several salicyclic acid derivatives in solution

Summary Mixed ligand complexes of copper(II), zinc(II), nickel(II) and cobalt(II) ions involving 1,10-phenanthroline (phen) as primary and 3,5-dinitrosalicylic acid (dnsa), 5-nitrosalicylic acid (nsa), 5-chlorosalicylic acid (csa) and 3,5-dibromosalicylic acid (dbsa) as secondary ligands in solution have been investigated potentiometrically [25°, µ = 0.1 M [NaClO₄], medium 50% v: v aqueous ethanol]. The stability order of mixed ligand complexes with respect to the metal ions obeys the natural order: cobalt(II) < nickel(II) < copper(II) > zinc(II). The stabilities of the heterometal chelates have been compared with the corresponding homometal chelates of the secondary ligands and have been interpreted in terms of metal-ligand effects and coulombic interactions between various ligand anion species present.     

Photometric determination of trivalent gallium,indium and thallium with Xylenol orange

Summary Xylenol orange reacts very sensitively with gallium(III), indium (III) and thallium(III) to form reddish violet colored chelates having _max 560 nm in case of Ga and In and _max 590 nm in case of Ti at P_H 4.0. The molar ratio for all the chelates is 1 1 (metal reagent). Optimum conditions including the range for adherence to Beer's law, effect of P_H on the color intensity, effect of excess reagent, and sensitivity are reported for the photometric determination of these metal ions using Xylenol orange.

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Zusammenfassung Xylenolorange reagiert sehr empfindlich mit Gallium(III), Indium(III) und Thallium(III) unter Bildung rötlich-violetter Chelate mit einem Absorptionsmaximum bei 560 nm im Falle von Ga und In bzw. 590 nm für Tl bei p_H 4,0. Das Molverhältnis ist in jedem Fall 11. Die besten Arbeitsbedingungen, der Gültigkeitsbereich des Beerschen Gesetzes, der Einfluß des P_H auf die Farbintensität und des Reagensüberschusses sowie die Empfindlichkeit werden für die photometrische Bestimmung der genannten Ionen angegeben.

     

Effects of hydrogen-bond environment on single particle and pair dynamics in liquid water

We have performed molecular dynamics simulations of liquid water at 298 and 258 K to investigate the effects of hydrogen-bond environment on various single-particle and pair dynamical properties of water molecules at ambient and supercooled conditions. The water molecules are modelled by the extended simple point charge (SPC/E) model. We first calculate the distribution of hydrogen-bond environment in liquid water at both temperatures and then investigate how the self-diffusion and orientational relaxation of a single water molecule and also the relative diffusion and relaxation of the hydrogen-bond of a water pair depend on the nature of the hydrogen-bond environment of the tagged molecules. We find that the various dynamical quantities depend significantly on the hydrogen-bond environment, especially at the supercooled temperature. The present study provides a molecular-level insight into the dynamics of liquid water under ambient and supercooled conditions.     

Facile Synthesis of Imidazole Fused Fluoroquinolones

Studies on synthetic design of 7,8‐imidazole fused fluoroquinolones from 8‐amino‐6‐fluoro‐4‐hydroxy‐N‐methyl‐7‐(methyl amino)quinoline‐3‐carboxamide and ketones/carboxylic acids and their antibacterial activity.