Solubility studies in aqueous media: I. Solubility product of silver permanganate and standard electrode potentials of silver—silver permanganate electrode in aqueous media

The solubility and solubility product of silver permanganate in water have been determined at the temperatures ranging from 15 to 35°C over 5°C intervals in the presence of an added electrolyte, sodium perchlorate. The solubility of silver permanganate ranges from 0.966 x 10^?5 mol 1^?1 at 15°C to 1.420x10^?5 moll^?1 at 35°C and the corresponding solubility product 0.933 x 10^?10 mol² 1^?2 at 15°C to 2.017 x 10^?10 mol² 1^?2 at 35°C. The standard potentials of the Ag(s)/AgMnO₄(s)/ MnO^?₄ electrode have been calculated at these temperatures. The mean activity coefficients of silver permanganate at various rounded molarities of sodium perchlorate solutions, and the standard thermodynamic quantities for the process AgMnO₄(s)→Ag⁺ (aq)+MnO^?₄(aq) have been calculated at these temperatures.     

Organophosphinic,phosphonic acids and their binary mixtures as extractants for molybdenum(VI) and uranium(VI) from aqueous HCl media

Extraction studies of uranium(VI) and molybdenum(VI) with organophosphoric, phosphinic acid and its thiosubstituted derivatives have been carried out from 0.1–1.0M HCl solutions. The extracted species are proposed to be UO₂R₂ and MoO₂ CIR on the basis of slope analysis for uranium(VI) and molybdenum(VI), respectively. The extraction efficiencies of PC-88A, Cyanex 272, Cyanex 301 and Cyanex 302 in the extraction of molybdenum(VI) and uranium(VI) are compared. Synergistic effects have been studied with binary mixtures of extractants. Separation of molybdenum(VI) from uranium(VI) is feasible by Cyanex 301 from 1M HCl, the separation factor log being 2.3.     

Kinetics of retarded polymerization: Investigation of the retardation of V5+–thiourea initiated polymerization of methyl acrylate by phenol

The kinetics and mechanism of the retarding action of phenol on the V⁵⁺–thiourea initiated polymerization of methyl acrylate (MA) have been studied within the temperature range of 30–50°C. The effects of retarder (phenol), metal ion (V⁵⁺), monomer (MA), sulfuric acid, some organic solvents and inorganic salts on the percentage and rate of polymerization have been studied. The remarkable observation of the present study is the positive intercept obtained from the plot of [M]/R_p vs. 1/[M]. This type of observation is significantly different from previous studies on retarded polymerization. The values of composite rate constants k₀k_t/k_ik_pkK have been calculated from plots of [M]/R_p vs. 1/[M]. On the basis of experimental findings a reaction mechanism has been suggested, and a suitable rate expression has been proposed and explained.     

Asymmetric synthesis of the protoberberine alkaloid (S)-(-)-xylopinine using enantiopure sulfinimines

A concise enantioselective synthesis of (S)-(-)-xylopinine (1) is described involving the addition of the laterally lithiated derivative of o-tolunitrile of 16 to enantiopure sulfinimine (+)-14. Treatment of the resulting cyano sulfinamide adduct (-)-17b with DIBAL-H accomplishes five operations in a single pot and furnishes the cyclic imine (+)-18 in good yield. Reduction and cyclization affords (S)-(-)-1. Alternatively basic hydrolysis of 17b,c gives isoquinolone 21 that is cyclized and reduced to give (S)-(-)-1.     

Application of microchip assay system for the measurement of C-reactive protein in human saliva

In the last decade, saliva has been advocated as a non-invasive alternative to blood as a diagnostic fluid. However, use of saliva has been hindered by the inadequate sensitivity of current methods to detect the lower salivary concentrations of many constituents compared to serum. Furthermore, developments in the areas related to lab-on-a-chip systems for saliva-based point of care diagnostics are complicated by the high viscosity and heterogeneous properties associated with this diagnostic fluid. The biomarker C-reactive protein (CRP) is an acute phase reactant and a well-accepted indicator of inflammation. Numerous clinical studies have established elevated serum CRP as a strong, independent risk factor for the development of cardiovascular disease (CVD). CVD has also been associated with oral infections (i.e. periodontal diseases) and there is evidence that systemic CRP may be a link between the two. Clinical measurements of CRP in serum are currently performed with "high sensitivity" CRP (hsCRP) enzyme-linked immunosorbent assay (ELISA) tests that lack the sensitivity for the detection of this important biomarker in saliva. Because measurement of salivary CRP may represent a novel approach for diagnosing and monitoring chronic inflammatory disease, including CVD and periodontal diseases, the objective of this study was to apply an ultra-sensitive microchip assay system for the measurement of CRP in human saliva. Here, we describe this novel lab-on-a-chip system in its first application for the measurement of CRP in saliva and demonstrate its advantages over the traditional ELISA method. The increased sensitivity of the microchip system (10 pg ml(-1) of CRP with 1000-fold dilution of saliva sample) is attributed to its inherent increased signal to noise ratio, resulting from the higher bead surface area available for antigen/antibody interactions and the high stringency washes associated with this approach. Finally, the microchip assay system was utilized in this study to provide direct experimental evidence that chronic periodontal disease may be associated with higher levels of salivary CRP.     

Kinetics of acid and base catalysed hydrolysis ofcis-α- andcis-β2-[Co(trien)(aniline)Cl]2+ cations

Summary The rate of hydrolysis of the title cations obey the rate law:-d ln[Complex]/dt=k_obs=k₀+k₁[OH^–] in the range: 1pH3. The rate and activation parameters for acid and base hydrolysis (k₀ and k₁ paths respectively) are reported in the 40–60 °C range.     

Covalent fixed multicyclic polystyrene conformers

Covalent fixed multicyclic polystyrene conformers were synthesized from inconvertible polystyrene conformers based on p‐tert‐butylthiacalix[4]arene by azidation and subsequent click coupling. Selective 1D NOESY analyses confirmed that the spatial structures of star polystyrene precursors and multicyclic polystyrenes were preserved during the azidation and click coupling processes. The conformation of star polymers affected degree of decrease in the hydrodynamic volume after cyclization but had little effect on glass transition behavior. The rigid core of star polymer increased the T_g but in the case of multicyclic polymer, this influence of core structure was reduced. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 4020–4026