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61.
A paradigm shift in rate determining step from single electron transfer between phenylsulfinylacetic acids and iron(III) polypyridyl complexes to nucleophilic attack of water to the produced sulfoxide radical cation: a non‐linear Hammett
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Perumal Subramaniam Jebamoney Janet Sylvia Jaba Rose Rajasingh Jeevi Esther Rathinakumari 《Journal of Physical Organic Chemistry》2016,29(10):496-504
Mechanism of oxidative decarboxylation of phenylsulfinylacetic acids (PSAAs) by iron(III) polypyridyl complexes in aqueous acetonitrile medium has been investigated spectrophotometrically. An initial intermediate formation between PSAA and [Fe(NN)3]3+ is confirmed from the observed Michaelis–Menten kinetics and fractional order dependence on PSAA. Significant rate retardation with concentration of [Fe(NN)3]3+ is rationalized on the basis of coordination of a water molecule at the carbon atom adjacent to the ring nitrogen of the metal polypyridyl complexes by nucleophilic attack at higher concentrations. Electron‐withdrawing and electron‐releasing substituents in PSAA facilitate the reaction and Hammett correlation gives an upward ‘V’ shaped curve. The apparent upward curvature is rationalized based on the change in the rate determining step from electron transfer to nucleophilic attack, by changing the substituents from electron‐releasing to electron‐withdrawing groups. Electron‐releasing substituents in PSAA accelerate the electron transfer from PSAA to the complex and also stabilize the intermediate through resonance interaction leading to negative reaction constants (ρ). Conversely, electron‐withdrawing groups, while retarding the electron transfer exert an accelerating effect on the nucleophilic attack of H2O which leading to low magnitude of ρ+ compared to high ρ? values of electron‐releasing groups. Marcus theory is applied, and a fair agreement is seen with the experimental values. Copyright © 2016 John Wiley & Sons, Ltd. 相似文献
62.
Tvaskis V Christy ME Arrington J Asaturyan R Baker OK Blok HP Bosted P Boswell M Bruell A Cochran A Cole L Crowder J Dunne J Ent R Fenker HC Filippone BW Garrow K Gasparian A Gomez J Jackson HE Keppel CE Kinney E Lapikás L Liang Y Lorenzon W Lung A Mack DJ Martin JW McIlhany K Meekins D Milner RG Mitchell JH Mkrtchyan H Moreland B Nazaryan V Niculescu I Opper A Piercey RB Potterveld DH Rose B Sato Y Seo W Smith G Spurlock K van der Steenhoven G Stepanyan S Tadevosian V Uzzle A Vulcan WF Wood SA 《Physical review letters》2007,98(14):142301
We report on a study of the longitudinal to transverse cross section ratio, R=sigmaL/sigmaT, at low values of x and Q2, as determined from inclusive inelastic electron-hydrogen and electron-deuterium scattering data from Jefferson Laboratory Hall C spanning the four-momentum transfer range 0.06相似文献
63.
Rattanakorn Chiangnoon Weerasak Samee Pimpon Uttayarat Wullapa Jittachai Warintorn Ruksiriwanich Sarana Rose Sommano Sirivan Athikomkulchai Chuda Chittasupho 《Molecules (Basel, Switzerland)》2022,27(3)
Proliferation and migration of keratinocytes and fibroblasts play an important role in cutaneous wound healing, while oral mucosal squamous cell proliferation and migration are crucial for oral wound healing. In this study, the phytochemical profile of Pluchea indica branch ethanolic extract was characterized. The bioactive compound of Pluchea indica branch ethanolic extract was identified and analyzed by the validated HPLC method. The nanoparticles of P. indica branch extract were formulated by solvent displacement method to increase the solubility and the colloidal stability of the extract. The stability of the nanoparticles was investigated by using the dynamic light scattering technique. Effects of P. indica crude extract and nanoparticles on cell viability, proliferation and migration of primary epidermal keratinocytes, human dermal fibroblasts, and oral mucosal keratinocyte cells were investigated by MTT assay and scratch assay, respectively. The results showed that P. indica branch extract contained a high content of total phenolic and total flavonoids. The HPLC analysis revealed that the main compound in the extract was 4,5-O-dicaffeoylquinic acid. The cell viability of the extract and nanoparticles decreased when cells were exposed to a high concentration of extract and nanoparticles. These results demonstrate that P. indica branch extract and extract nanoparticles at specific concentrations possess in vitro wound healing activity and they may be possibly used to treat different types of wounds including dermal and oral mucosal wounds. 相似文献
64.
65.
We present a method for simultaneous determination of the aminopolycarboxylic acids DTPA, EDTA and NTA in dishwashing detergents, paper mill waters, and natural waters by capillary electrophoresis (CE). The complexing agents were examined as their copper(II) complexes and separated by conventional CE with reversed polarity of the applied voltage. The optimum separation conditions were established by varying the pH and phosphate and tetradecyltrimethylammonium bromide (TTAB) concentrations in the run buffer. The separations were carried out in a fused-silica capillary (61 cm×75 m i.d.) filled with phosphate buffer (80 mmol L–1, TTAB concentration 0.5 mmol L–1, pH 7.1, voltage –20 kV) using direct UV detection at 191 and 254 nm. With this CE method all the peaks in the electropherograms were properly separated, the calibration plots gave good correlation coefficients and all three complexing agents could be detected in less than 4 min. Linear calibration plots were obtained for CuDTPA, CuEDTA and CuNTA; limits of detection were 0.03 mmol L–1 for all complexing agents and recoveries for all tested samples were within the range 104±7%. Results obtained from dishwashing detergent samples were found to be reliable and comparable with those from HPLC (R2=0.989) and UV–Vis (R2=0.985) methods. 相似文献
66.
67.
Zolleis KR Ford CJ Kardynal B Ritchie DA Linfield EH Rose PD Jones GA 《Physical review letters》2002,89(14):146803
The tunneling current between an electron gas with a periodic potential in two dimensions and a plain two-dimensional electron system (2DES) has been studied. The strength of the periodic potential, the subband energy of the plain 2DES, and an applied in-plane magnetic field were varied, mapping the Fourier transform of the periodic wave function. Periodic peaks were observed and explained by translations in the reciprocal lattice. When the potential was strongly modulated to form an array of antidots, commensurability peaks were seen in lateral transport, but, as expected, not in tunneling. 相似文献
68.
Stephen E. Rose Stephen J. Wilson Fernando O. Zelaya Stuart Crozier David M. Doddrell 《Magnetic resonance imaging》1994,12(8):1183-1190
A method that incorporates cardiorespiratory-gated 2DFT spin-echo imaging with blood flow enhancement suppression is described which enables high resolution microimaging of the rodent heart. This methodology was applied to obtain in vivo cardiac mouse and rat images with in-plane resolutions of 100–200 μm using high field vertical bore magnet systems. Suppression of intraventricular blood flow enhancement was achieved using a combined spin-echo/gradient-refocussed sequence to dephase magnetization from flowing spins prior to imaging. 相似文献
69.
70.
John S. Rose 《Israel Journal of Mathematics》1973,15(4):375-383
LetG andK be finite groups whose orders have a common prime divisor. Then there is a groupK
* closely related toK for which there is a non-split extension ofK
* byG.
I wish to express thanks to the Mathematics Institute of the Hebrew University of Jerusalem for its hospitality from September
to December 1972, and to Dr. Avinoam Mann for his helpful comments. 相似文献