Ruthenium(III) catalysed oxidation of glycerol by acidified KBrO3: a kinetic study

Kinetic investigations on the Ru^III-catalysed oxidation of glycerol by an acidified solution of KBrO₃ in the presence of Hg(OAc)₂ as a scavenger have been carried out in the 30–50 °C range. First order kinetics in the lower KBrO₃ concentration range tended to zero order at higher concentrations. The reaction follows zero order kinetics in glycerol and [H⁺]; the order is one with respect to [Ru^III]. An increase in [Cl^–] showed a positive effect, while addition of NaClO₄ has a negligible effect on the reaction rate. Hg(OAc)₂ and D₂O have an insignificant effect on the reaction rate. A suitable mechanism in conformity with the kinetic observations has been proposed and thermodynamic parameters computed.     

Protective Effects of PollenAid Plus Soft Gel Capsules’ Hydroalcoholic Extract in Isolated Prostates and Ovaries Exposed to Lipopolysaccharide

Pollen extract represents an innovative approach for the management of the clinical symptoms related to prostatitis and pelvic inflammatory disease (PID). In this context, the aims of the present work were to analyze the phenolic composition of a hydroalcoholic extract of PollenAid Plus soft gel capsules, and to evaluate the extract’s cytotoxic effects, in human prostate cancer PC3 cells and human ovary cancer OVCAR-3 cells. Additionally, protective effects were investigated in isolated prostate and ovary specimens exposed to lipopolysaccharide (LPS). The phytochemical investigation identified catechin, chlorogenic acid, gentisic acid, and 3-hydroxytyrosol as the prominent phenolics. The extract did not exert a relevant cytotoxic effect on PC3 and OVCAR-3 cells. However, the extract showed a dose-dependent inhibition of pro-inflammatory IL-6 and TNF-α gene expression in prostate and ovary specimens, and the extract was effective in preventing the LPS-induced upregulation of CAT and SOD gene expression, which are deeply involved in tissue antioxidant defense systems. Finally, a docking approach suggested the capability of catechin and chlorogenic acid to interact with the TRPV1 receptor, playing a master role in prostate inflammation. Overall, the present findings demonstrated anti-inflammatory and antioxidant effects of this formulation; thus, suggesting its capability in the management of the clinical symptoms related to prostatitis and PID.     

Dinuclear Copper(II) Complexes Incorporating a New Septadentate Polyimidazole Ligand

The dinuclear copper(II) complexes [Cu(2)(tmihpn)(prz)](ClO(4))(2).2CH(3)CN (6) and [Cu(2)(tmihpn)(O(2)CCH(3))](ClO(4))(2).CH(3)CN (7) were prepared, where tmihpn is the deprotonated form of N,N,N',N'-tetrakis[(1-methylimidazol-2-yl)methyl]-1,3-diaminopropan-2-ol and prz is the pyrazolate anion. The crystal structures of 6 and 7 were determined and revealed that both complexes contain bridging alkoxide ligands as well as bridging pyrazolate and acetate ions, respectively. Crystal data: compound 6, triclinic, P&onemacr;, a = 18.089(2) ?, b = 22.948(3) ?, c = 9.597(2) ?, alpha = 93.37(2) degrees, beta = 94.49(2) degrees, gamma = 81.69(2) degrees, V = 3925.1 ?(3), Z = 4; compound 7, triclinic, P&onemacr;, a = 12.417(2) ?, b = 15.012(3) ?, c = 10.699(2) ?, alpha = 104.76(2) degrees, beta = 102.63(2) degrees, gamma = 99.44(2) degrees, V = 1830.1 ?(3), Z = 2. In compound 6, the coordination geometry around both copper centers resembles a distorted square pyramid, while the stereochemistry around the copper centers in 7 is best described as trigonal bipyramidal. Both complexes display well-resolved isotropically shifted (1)H NMR spectra. Selective substitution studies and integration data have been used to definitively assign several signals to specific ligand protons. Results from the solution (1)H NMR studies suggest that the basal and apical imidazole groups do not exchange rapidly on the NMR time scale and the solid state structures of the complexes are retained in solution. In addition, the magnetochemical characteristics of 6 and 7 were determined and provide evidence for "magnetic orbital switching". Antiferromagnetic coupling in 6 (J = -130 cm(-)(1)) is strong, while the copper centers in compound 7 are ferromagnetically coupled (J = +16.4 cm(-1)). Differences in the magnetic behavior of the two copper centers have been rationalized using the "ligand orbital complementary" concept. The ground state magnetic orbitals involved in spin coupling in 6 (d(x)()()2(-)(y)()()2) are different from those in 7 (d(z)()()2).     

Constructing identities for finite quasigroups

An algorithm for producing identities which hold in any given finite quasigroup is described. Identities produced by the algorithm are used to prove several results concerning varieties of quasigroups. In particular varieties of quasigroups associated with various combinatorial designs are examined.     

Total synthesis of 8,12-iso-iPF3alpha-VI, an EPA-derived isoprostane: stereoselective introduction of the fifth asymmetric center

[reaction: see text] A new and stereoselective approach for the synthesis of all-syn isoprostanes is reported. This method, which is based on acid-catalyzed Diels-Alder reaction, allows the introduction of the side chain with a predetermined stereochemistry of the hydroxy group. The first total synthesis of an eicosapentaenoic acid (EPA)-derived iP, 8,12-iso-iPF3alpha-VI 10, was performed using this approach.     

Classical Behavior After a Phase Transition: I. Classical Order Parameters

We analyze the onset of classical field configurations after a phase transition. Firstly, we motivate the problem by means of a toy model in quantum mechanics. Subsequently, we consider a scalar field theory in which the system-field interacts with its environment, represented both by further scalar fields and by its own short-wavelength modes. We show that for very rapid quenches, the order parameter can be treated classically by the time taken for it to achieve its ground state values (spinodal time).     

Aquachloroiridium (III)-catalyzed oxidation of some unsaturated acids in acetone by acidic quinolinium fluorochromate

Kinetic investigation in Ir(III)-catalyzed oxidation of fumaric acid (FA) and crotonic acid (CA) in an acidified solution of quinolinium fluorochromate (QFC) has been studied in the temperature range of 30–45 °C. First-order kinetics was observed in the case of catalyst Ir(III) as well as oxidant QFC. The order of reaction with respect to substrate (unsaturated acids) was found to be zero. Increase in [Cl^?] showed fractional negative order. The influence of [H⁺] and ionic strength on the rate was found to be insignificant. The main product of oxidation of fumaric acid (FA) and crotonic acid (CA) were identified as pyruvic acid and acetone, respectively. The reaction has been studied in ten different solvents. The first-order rate constant had no effect with decrease in the dielectric constant of the medium. The values of rate constants observed at four different temperatures (30, 35, 40 and 45 °C) were utilized to calculate the activation parameters. A suitable mechanism in conformity with the kinetic observations has been proposed and the rate law has been derived on the basis of obtained data. A transient complex formed between Ir^III and oxidant in a slow and rate-determining step, further reacts with substrate to give the products in a series of fast steps.     

129Xe contact shift in oxygen gas

We have determined the temperature dependence of σ₁ of ¹²⁹Xe in oxygen gas. These results were obtained by measurement of the resonance frequency of ¹²⁹Xe in gas samples of known densities in Xe and O₂. The shift of the resonance frequency due to Xe-Xe interactions has been measured in pure Xe gas samples with improved precision. This allows the determination of σ₁(Xe-O₂) by subtracting out the known effect of Xe-Xe interactions in mixed Xe-O₂ samples. σ₁(Xe-O₂) values are reported here for the temperature range 220 to 440 K. The values of σ₁(Xe-O₂) are adequately described by the polynomial function in p.p.m. amagat^-1 σ₁(Xe-O₂) = - 1·061 + 3·64 × 10^-3τ - 2·19 × 10^-5τ² + 9·58 × 10^-8τ³ - 2·08 × 10^-10τ⁴, where τ = (T - 300 K). It is found that the temperature dependence of σ₁(Xe-O₂) can be interpreted in terms of a contact interaction between Xe and the paramagnetic O₂ molecule.     

Relationship among glottal area, static supraglottic compression, and laryngeal function studies in unilateral vocal fold paresis and paralysis

In this study, we evaluated the relationship between laryngeal function measures and glottal gap ratio and normalized measures of supraglottic behaviors in patients with unilateral vocal fold paresis (UVFP). Thirty-one patients were found to have unilateral vocal fold paresis by videoendoscopy and laryngeal electromyography, and 13 controls participated in this study. Patients with UVFP demonstrated significantly larger glottal gap ratios (p = 0.016) than control subjects. The nonparalyzed or contralateral vocal fold was associated with significantly more static false vocal fold compression (p = 0.03) compared with the paralyzed vocal fold or with the controls. Patients with unilateral vocal fold paresis were divided into subgroups: those with normal or abnormal maximum phonation time, flow, or pressure measures. Smaller glottal gap ratios were identified in patients with normal maximum phonation times and flow measures. Greater false vocal fold activity was identified in unilateral vocal fold paresis patients with normal laryngeal function measures than in unilateral vocal fold paresis patients with abnormal measures. These findings suggest that some patients with documented unilateral paresis and glottal incompetence can compensate for vocal fold weakness such that their acoustic and aerodynamic measures are normal.