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        Spectral and Mechanistic Investigation of Oxidative Decarboxylation of Phenylsulfinylacetic Acid by Cr(VI)

        Subramaniam, Perumal,Selvi, Natesan Thamil,Devi, Soundarapandian Sugirtha Korean Chemical Society 2014 대한화학회지 Vol.58 No.1

        The oxidative decarboxylation of phenylsulfinylacetic acid (PSAA) by Cr(VI) in 20% acetonitrile -80% water (v/v) medium follows overall second order kinetics, first order each with respect to [PSAA] and [Cr(VI)] at constant [$H^+$] and ionic strength. The reaction is acid catalysed, the order with respect to [$H^+$] is unity and the active oxidizing species is found to be $HCrO_3^+$. The reaction mechanism involves the rate determining nucleophilic attack of sulfur atom of PSAA on chromium of $HCrO_3^+$ forming a sulfonium ion intermediate. The intermediate then undergoes ${\alpha}$,${\beta}$-cleavage leading to the liberation of $CO_2$. The product of the reaction is found to be methyl phenyl sulfone. The operation of substituent effect shows that PSAA containing electron-releasing groups in the meta- and para-positions accelerate the reaction rate while electron withdrawing groups retard the rate. An excellent correlation is found to exist between log $k_2$ and Hammett ${\sigma}$ constants with a negative value of reaction constant. The ${\rho}$ value decreases with increase in temperature evidencing the high reactivity and low selectivity in the case of substituted PSAAs.

      • MC3T3-E1 osteoblast adhesion to laser induced hydroxyapatite coating on Ti alloy

        Huang, Lu,Goddard, Samuel C.,Soundarapandian, Santhanakrishnan,Cao, Yu,Dahotre, Narendra B.,He, Wei Techno-Press 2014 Biomaterials and biomedical engineering Vol.1 No.2

        An in vitro cell study evaluating cell adhesion to hydroxyapatite (HA) coated prosthetic Ti-6Al-4V alloy via laser treatment is presented in comparison with uncoated alloy. Based on our previous in vitro biocompatibility study, which demonstrated higher cell attachment and proliferation with MC3T3-E1 preosteoblast cells, the present investigation aims to reveal the effect of laser coating Ti alloy with HA on the adhesion strength of bone-forming cells against centrifugal forces. Remaining cells on different substrates after centrifugation were visualized using fluorescent staining. Semi-quantifications on the numbers of cells were conducted based on fluorescent images, which demonstrated higher numbers of cells retained on HA laser treated substrates post centrifugation. The results indicate potential increase in the normalized maximum force required to displace cells from HA coated surfaces versus uncoated control surface. The possible mechanisms that govern the enhancing effect were discussed, including surface roughness, chemistry, wettability, and protein adsorption. The improvement in cell adhesion through laser treatment with a biomimetic coating could be useful in reducing tissue damage at the prosthetic to bone junction and minimizing the loosening of prosthetics over time.

      • KCI등재

        Spectral and Mechanistic Investigation of Oxidative Decarboxylation of Phenylsulfinylacetic Acid by Cr(VI)

        Perumal Subramaniam,Natesan Thamil Selvi,Soundarapandian Sugirtha Devi 대한화학회 2014 대한화학회지 Vol.58 No.1

        The oxidative decarboxylation of phenylsulfinylacetic acid (PSAA) by Cr(VI) in 20% acetonitrile - 80% water (v/v) medium follows overall second order kinetics, first order each with respect to [PSAA] and [Cr(VI)] at constant [H+] and ionic strength. The reaction is acid catalysed, the order with respect to [H+] is unity and the active oxidizing species is found to be HCrO3 +. The reaction mechanism involves the rate determining nucleophilic attack of sulfur atom of PSAA on chromium of HCrO3 + forming a sulfonium ion intermediate. The intermediate then undergoes α,β-cleavage leading to the liberation of CO2. The product of the reaction is found to be methyl phenyl sulfone. The operation of substituent effect shows that PSAA containing electron-releasing groups in the meta- and para-positions accelerate the reaction rate while electron withdrawing groups retard the rate. An excellent correlation is found to exist between log k2 and Hammett σ constants with a negative value of reaction constant. The ρ value decreases with increase in temperature evidencing the high reactivity and low selectivity in the case of substituted PSAAs.

      • KCI등재

        Design and Optimization of Microstructure for Improved Corrosion Resistance in Laser Surface Alloyed Aluminum with Molybdenum

        Hitesh D. Vora,Narendra B. Dahotre,Ravi Shanker Rajamure,Santhanakrishnan Soundarapandian,S. G. Srinivasan 한국정밀공학회 2013 International Journal of Precision Engineering and Vol. No.

        The in-situ measurement of dilution during the laser surface alloying process is an enormously difficult task, due to the localized nature of laser energy and very short laser-material interaction time. Therefore, a computational approach (finite-element method and analysis of variance) was effectively employed to evaluate the dilution during the laser surface alloying process. Firstly, a finiteelement model based on COMSOL™ multiphysics was developed to predict the dilution of Mo with Al during non-equilibrium laser surface alloying process. Secondly, the optimization model based on Design-Expert® was developed to find the optimal laser surface alloying parameters (laser power, scanning speed, and fill spacing) to obtain a microstructure suitable for improved corrosion resistance that is primarily attributed to the formation of Al5Mo intermetallic phase (16.7 at% Mo). The present optimization model utilized the prior experimental and computational (finite-element) modeling data for the concentration of Mo (at%). The optimization analyses were carried out for the all the current datasets and the analysis revealed 44 optimal solutions that indicate the highest desirability. The confirmation runs were carried out to validate the optimization model. The experimental observation showed that the sample processed with optimal processing conditions demonstrates good corrosion resistance.

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