Mechanism of oxidation of alanine by chloroaurate(III) complexes in acid medium: Kinetics of the rate processes

The kinetics of the oxidation of alanine by chloroaurate(III) complexes in acetate buffer medium has been investigated. The major oxidation product of alanine has been identified as acetaldehyde by ¹H NMR spectroscopy. Under the experimental conditions, AuCl and AuCl₃(OH)^? are the effective oxidizing species of gold(III). The reaction is first order with respect to Au(III) as well as alanine. The effects of H⁺ and Cl^? on the second‐order rate constant k₂′ have been analyzed, and accordingly the rate law has been deduced: k₂′ = (k₁[H⁺][Cl^?] + k₃K₄K₅)/(K₄K₅ + [H⁺][Cl^?]). Increasing dielectric constant of the medium has an accelerating effect on the reaction rate. Activation parameters associated with the overall reaction have been calculated. A mechanism involving the two effective oxidizing species of gold(III) and zwitterionic species of alanine, consistent with the rate law, has been proposed. © 2009 Wiley Periodicals, Inc. Int J Chem Kinet 41: 473–482, 2009     

Effect of phase transition and particle size on thermoluminescence characteristics of nanocrystalline K2Ca2(SO4)3:Cu+ phosphor

A new K₂Ca₂(SO₄)₃:Cu⁺ nanocrystalline TLD phosphor was prepared by chemical coprecipitation method using calcium chloride, potassium chloride and ammonium sulphate as reactants and copper chloride (Cu₂Cl₂, as impurity) in the presence of ethanol. The samples were characterized by X-ray diffraction (XRD), Transmission electron microscopy (TEM), Differential thermal and thermogravimetric analysis (DT-TGA) techniques. XRD and DTA data show that there is a phase transformation from orthorhombic to cubic occurring at around 550 K. The effects of impurity concentration, annealing temperature and γ rays dose on TL characteristics of the material have been studied. Different glow curves have been theoretically deconvoluted using computerized glow curve deconvolution (CGCD method) into simple glow peaks to determine their trapping parameters. The results show that different phases existing in the material on annealing might have reorganized the electron-traps (energy levels) and hole-traps (luminescence centers) and are responsible for changing glow curve structures. This is very important to know as any change in the glow curve structure would cause errors in estimation of doses of high-energy radiations and also may lose its reusability. The photoluminescence (PL) studies show that there are no redox reactions (Cu⁺

Cu²⁺) taking place and Cu remains in its Cu⁺ form after annealing and even after irradiation.     

Computing the Shortest Essential Cycle

An essential cycle on a surface is a simple cycle that cannot be continuously deformed to a point or a single boundary. We describe algorithms to compute the shortest essential cycle in an orientable combinatorial surface in O(n ²log n) time, or in O(nlog n) time when both the genus and number of boundaries are fixed. Our results correct an error in a paper of Erickson and Har-Peled (Discrete Comput. Geom. 31(1):37–59, 2004).     

A quadrature-based LES/transported probability density function approach for modeling supersonic combustion

The joint-scalar probability density function (PDF) approach provides a comprehensive framework for large eddy simulation (LES) based combustion modeling. However, currently available stochastic approaches for solving the high-dimensional PDF transport equation can be error prone and numerically unstable in highly compressible shock-containing flows. In this work, a novel Eulerian approach called the direct quadrature method of moments (DQMOM) is developed for evolving the PDF-based supersonic combustion model. The DQMOM technique uses a set of scalar transport equations with specific source terms to recover the PDF. The new technique is coupled to a compressible LES solver through the energy equation. The DQMOM approach is then used to simulate two practical flow configurations: a supersonic reacting jet and a cavity-stabilized supersonic combustor. Comparisons with experimental data demonstrate the predictive accuracy of the method.     

Bio-waste derived,phosphorus decorated composite for highly efficient flame retardant for cotton fabric

In this, an efficient flame retardant composite has been prepared using biowaste derived phosphorous groups decorated graphene supported nanomaterial. The eggshell was utilized as a source of calcium carbonate, which was converted to monocalcium phosphate (CP) by phosphoric acid treatment. As-prepared monocalcium phosphate was functionalized with graphene to prepare graphene functionalized monocalcium phosphate (GCP). The GCP-coated fabric didn't ignite during the flame test and sustained more than 600 s on continuous exposure to flame without changing its initial length and shape. Whereas, graphene oxide (GO), and CP coated cotton fabric burnt out very easily within a short time. The efficient flame retardant property of as synthesized GCP coated cotton fabric was confirmed with a high limiting oxygen index (34.1) and char length of 2.5 cm was generated from the VFT test. The synthesized GCP coated cotton fabric also confirmed efficient flame retardant properties. This facile method enables an easy process for mass production of cost-effective, bio-waste derived nanomaterial for a significantly highly efficient candidate for different applications in sustainable chemistry, including flame-retardant applications.

Graphical abstract

     

Evidence of protonation during the oxidation of some aryl alcohols by permanganate in perchloric acid medium and mechanism of the oxidation processes

The oxidation of benzyl alcohol and methoxy-, chloro-, and nitro- substituted benzyl alcohols by permanganate has been studied in aqueous and acetic acid medium in presence of perchloric acid. The reaction is first-order in [MnO₄^?] and [XC₆H₄CH₂OH], but the order is complex with respect to [H⁺]. Different thermodynamic parameters have been evaluated. The reaction occurs through the protonation of alcohol in a fast preequilibrium followed by a slow rate-determining oxidation step. A two-electron transfer oxidation step has been suggested for benzyl alcohol and chloro- and nitro- substituted alcohols, while the oxidation of methoxy compounds involves a one-electron transfer via a free-radical mechanism. © 1995 John Wiley & Sons, Inc.     

Excited-state proton transfer from pyranine to acetate in methanol

Excited-state proton transfer (ESPT) of pyranine (8-hydroxypyrene-1,3,6-trisulphonate, HPTS) to acetate in methanol has been studied by steady-state and time-resolved fluorescence spectroscopy. The rate constant of direct proton transfer from pyranine to acetate (k ₁) is calculated to be ∼1 × 10⁹ M⁻¹ s⁻¹. This is slower by about two orders of magnitude than that in bulk water (8 × 10¹⁰ M⁻¹ s⁻¹) at 4 M acetate.     

Evidence of esterification during the oxidation of some aromatic aldehydes by permanganate

Summary The permanganate ion oxidation of PhCHO in HClO₄ medium is first order in [MnO _inf4 ^sup- ], but of complex order with respect to [aldehyde] as well as [H⁺]. The influence of substituents on the reaction rate and mechanism has also been studied in 40% (v/v) aqueous AcOH and convincing evidence favours an ester formation mechanism. Thermodynamic values associated with 11 intermediate ester formation and the activation parameters associated with the disproportionation steps involved have been evaluated.     

Influence of Crosslinking Agent on the Release of Drug from the Matrix Transdermal Patches of HPMC/Eudragit RL 100 Polymer Blends

The present work was designed to develop suitable transdermal matrix patches using the polymer blends of hydroxy propyl methyl cellulose (HPMC) and Eudragit RL100 (ERL) with triethyl citrate as a plasticizer in group A and in group B, other than HPMC and ERL, crosslinking agent, succinic acid was added. A 3² full factorial design was employed for both groups. The concentration of HPMC and ERL were used as independent variables, while percentage drug release was selected as dependent variable. Physical evaluation was performed such as moisture content, moisture uptake, tensile strength, flatness and folding endurance. In vitro diffusion studies were performed using cellulose acetate membrane (pore size 0.45 μ) in a Franz's diffusion cell. The concentration of diffused drug was measured using UV-visible spectrophotometer (V-530, Jasco) at λ _max 272 nm. The experimental results shows that the transdermal drug delivery system (TDDS) containing ERL in higher proportion gives sustained the release of drug and patches containing crosslinking agent shows more release than those do not contains succinic acid.