Search results for: linear alcohols

Authors: Buti Suryabrahmam, V. A. Raghunathan

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We study the effect of short chain alcohols on mechanical properties of saturated lipid bilayers in the fluid phase. The Bending rigidity of 1,2-dimyristoyl-sn-glycero-3-phosphocholine (DMPC) membrane was measured at 28 °C by employing Vesicle Fluctuation Analysis technique. The concentration and chain length (n) of alcohol in the buffer solution were varied from 0 to 1.5 M and from 2 to 8 respectively. We observed a non-linear reduction in the bending rigidity from ~17×10⁻²⁰ J to ~10×10⁻²⁰ J, for all chain lengths of alcohols used in our experiment. We observed approximately three orders of the concentration difference between ethanol and octanol, to show the similar reduction in the bending values. We attribute this phenomenon to thinning of the bilayer due to the adsorption of alcohols at the bilayer-water interface.

Keywords: alcohols, bending rigidity, DMPC, lipid bilayers

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Authors: Durata Haciu, Berti Manisa, Ozgur Birer

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ZnO nanoparticles have been synthesized by ultrasonic irradiation from simple linear alcohols and water/ethanolic mixtures, at 50 oC. By changing the composition of the solvent, the shape could be altered. While no product was obtained from methanolic solutions, in ethanol, sheet like lamellar structures prevail.n-propanol and n-butanol resulted in needle like structures. The morphology of ZnO could be thus tailored in a simple way, by varying the solvent, under ultrasonic irradiation, in a relatively less time consuming method. Variation of the morphology and size of Zn also provides a means for modulating the band-gap. Although the chemical effects of ultrasound do not come from direct interaction with molecular species, the high energy derived from acoustic cavitation creates a unique interaction of energy and matter with great potential for synthesis.

Keywords: ultrasound, ZnO, linear alcohols, morphology

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Authors: Vinaya Kambappa

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Propylphosphonic anhydride (T3P®)-DMSO is used as an efficient and mild reagent for the one-pot synthesis of 3,4-dihydropyrimidin-2(1H)-ones/thiones from aromatic alcohols. Alcohols are oxidized in situ to aldehydes under mild conditions, which in turn undergo a three-component reaction with β-ketoester and urea/thiourea to afford 3,4-dihydropyrimidin-2(1H)-ones/thiones. The synthesis of 3,4-dihydropyrimidin-2(1H)-ones/thiones directly from alcohols has been reported for the first time best to our knowledge, under mild reaction conditions in good yield. The easy work-up procedure, low cost and less toxicity of the reagent are the main advantages of this protocol.

Keywords: β-ketoester, propylphosphonic anhydride, three-component reaction, pyrimidine

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Authors: Ali Gharib, Leila Vojdanifard, Nader Noroozi Pesyan, Mina Roshani

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We describe an efficient method for oxidation of alcohols to related aldehydes and ketones by hydrogen peroxide as oxidizing agent, under reflux conditions. Nano-graphene oxide (NGO) as a heterogeneous catalyst was used and had their activity compared with other various catalysts. This catalyst was found to be an excellent catalyst for oxidation of alcohols. The effects of various parameters, including catalyst type, nature of the substituent in the alcohols and temperature, on the yield of the carboxylic acids were studied. Nano-graphene oxide was synthesized by the oxidation of graphite powders. This nanocatalyst was found to be highly efficient in this reaction and products were obtained in good to excellent yields. The recovered nano-catalyst was successfully reused for several runs without significant loss in its catalytic activity.

Keywords: nano-graphene oxide, oxidation, aldehyde, ketone, catalyst

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Authors: Moataz Elsawy, Hala F. Naguib, Hilda A. Aziz, Eid A. Ismail, Labiba I. Hussein, Maher Z. Elsabee

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Jojoba oil-wax is extracted from the seeds of the jojoba (Simmondsia chinensis Link Schneider), a perennial shrub that grows in semi-desert areas in Egypt and in some parts of the world. The main uses of jojoba oil wax are in the cosmetics and pharmaceutical industry, but new uses could arise related to the search of new energetic crops. This paper summarizes a process to convert the jojoba oil wax to biodiesel by transesterification with ethanol and a series of aliphatic alcohols using a more economic and energy saving method in a domestic microwave. The effect of time and power of the microwave on the extent of the transesterification using ethanol and other aliphatic alcohols has been studied. The separation of the alkyl esters from the fatty alcohols rich fraction has been done in a single crystallization step at low temperature (−18°C) from low boiling point petroleum ether. Gas chromatography has been used to follow up the transesterification process. All products have been characterized by spectral analysis.

Keywords: jojoba oil, transesterification, microwave, gas chromatography jojoba esters, jojoba alcohol

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Authors: Bai-Jing Peng, Shyh-Chyun Yang

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Organic reactions in water have recently attracted much attention, not only because unique reactivity is often observed in water but also because water is a safe and economical substitute for conventional organic solvents. Thus, development of environmental safe, atom-economical reactions in water is one of the most important goals of synthetic chemistry. The recent paper has documented renewed interest in the use of allylic substrates in the synthesis of new C−C, C−N, and C−O bonds. We have reported our attempts and some successful applications of a process involving the C-O bond cleavage catalyzed by palladium or platinum complexes in water. Because of the importance of heterocycle indole derivatives, much effort has been directed toward the development of methods for functionalization of the indole nucleus at N1 site. In our research, the palladium-catalyzed 2,3-disubstitued indoles with allylic alcohols was investigated under different conditions. Herein, we will establish a simple, convenient, and efficient method, which affords high yields of allylated indoles.

Keywords: palladium-catalyzed, allylic alcohols, indoles, water, allylation

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Authors: Abdel Ghany F. Shoair, Mai M. A. H. Shanab

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The basic aqueous systems NiSO4.6H₂O / K₂S₂O₈ (PH= 14) or NiSO₄.6H₂O / KBrO₃ (PH = 11.5) were ‎investigated ‎for the ‎catalytic conversion benzyl alcohol and ‎some para-substituted benzyl ‎alcohols to their ‎corresponding ‎acids in 75-97 % yield at room ‎temperature. The active species ‎was isolated and characterized by scanning ‎electron ‎microscopy (SEM), ‎‎transmission electron microscopy (TEM), X-ray ‎powder diffraction, EDX and ‎‎FT-IR ‎techniques and identified as NiO₂ nanoparticles (NPNPs). The SEM and ‎TEM images of nickel peroxide samples show a fine spherical-like ‎aggregation of ‎NiO₂ molecules with a nearly homogeneous partial size and confirm the ‎aggregation's size ‎to ‎be in the range of 2-3 nm. The yields, turnover (TO) and turn ‎over frequencies (TOF) were calculated. ‎It was noticed ‎that the aromatic alcohols ‎containing para-substituted electron donation groups gave better ‎‎yields than ‎those having electron-withdrawing groups. The optimum conditions for this ‎‎catalytic reaction ‎were studied using benzyl alcohol as a model. The mechanism ‎of the ‎catalytic conversion reaction was ‎suggested, in which the produced ‎(NPNPs) convert alcohols ‎to acids in two steps through the formation of the ‎‎corresponding aldehyde. The produced ‎NiO, because of this conversion, is ‎converted again to (NPNPs) by ‎an excess of K₂S₂O₈ or KBrO₃. This ‎catalytic cycle continues ‎until all the substrate is oxidized.

Keywords: Nickel, oxidation, catalysts, benzyl alcohol

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Authors: Anıl Dinçer, Dilek Duranoğlu

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Ketones, which are widely used as solvent and chemical intermediates in chemical process industry, are commercially produced by using catalytic dehydrogenation of secondary alcohols at higher temperature (300-500ºC), and pressure (1-5 bar). Although it is possible to obtain high conversion values (60-87%) via gas phase catalytic dehydrogenation, working high temperature and pressure can result in side reactions and shorten the catalyst life. In order to overcome these challenges, catalytic dehydrogenation in the presence of an appropriate liquid solvent has been started to use. Hence, secondary alcohols can be converted to respective ketones at relatively low temperature (150-200ºC) under atmospheric pressure. In this study, methyl ethyl ketone and acetone was produced via catalytic dehydrogenation of appropriate secondary alcohols (isopropyl alcohol and sec-butyl alcohol) in the presence of liquid solvent at 160-190ºC. Obtained methyl ethyl ketone and acetone were analyzed by using FTIR and GC spectrometer. Effects of temperature, amount of catalyst and solvent on conversion and reaction rate were investigated. Optimum process conditions, which gave high conversion and reaction rate, were determined. According to GC results, 70% of secondary butyl alcohol and 42% of isopropyl alcohol was converted to related ketone (methyl ethyl ketone and acetone, respectively) at optimum process conditions. After distillation, 99.13% methyl ethyl ketone and 99.20% acetone was obtained. Consequently, liquid phase dehydrogenation process, which can compete with commercial gas phase process, was developed.

Keywords: dehydrogenation, liquid phase, methyl ethyl ketone, secondary alcohol

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Authors: Dehong Li, Yuchen Chen, Alireza Kaboorani, Denis Rodrigue, Xiaodong (Alice) Wang

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Utilizing solar energy for thermal energy storage has emerged as an appealing option for lowering the amount of energy that is consumed by buildings. Due to their high heat storage density, and non-corrosive and non-polluting properties, alcohols can be a good alternative to petroleum-derived paraffin phase change materials (PCMs). In this paper, ternary eutectic PCMs with suitable phase change temperatures were designed and prepared using lauryl alcohol (LA), cetyl alcohol (CA), stearyl alcohol (SA), and xylitol (X). The differential scanning calorimetry (DSC) results revealed that the phase change temperatures of LA-CA-SA, LA-CA-X, and LA-SA-X were 20.52°C, 20.37°C, and 22.18°C, respectively. The latent heat of phase change of the ternary eutectic PCMs was all stronger than that of the paraffinic PCMs at roughly the same temperature. The highest latent heat was 195 J/g. It had good thermal energy storage capacity. The preparation mechanism was investigated using Fourier-transform Infrared Spectroscopy (FTIR), and it was found that the ternary eutectic PCMs were only physically mixed among the components. Ternary eutectic PCMs had a simple preparation process, suitable phase change temperature, and high energy storage density. They are suitable for low-temperature architectural packaging applications.

Keywords: thermal energy storage, buildings, phase change materials, alcohols

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Authors: Atena Naeimi, Asghar Amiri, Zahra Ghasemi

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A stable suspension of nanocomposite simple manganese(III) meso-tetraphenylporphyrin nanoaggregates and Ag was prepared by a host–guest procedure, in which ethanol and water are used as ‘green’ solvents. The oxidation of alcohols by tetrabutylammonium Peroxomonosulfate(TP) were efficiently enhanced with excellent selectivity under the influence of simple Mn(TPP)OAc (TPP = meso-tetraphenylporphyrin) nanoparticles. Enhanced stabilities and activities were achieved with nanostructured Mn catalysts compared to those of the individual counterparts in solution according to turnover numbers and UV/Vis studies. The title nanocatalyst facilitates a greener reaction because the reaction solvent is water and TP is safe to use. The efficiency of the oxidation system depends critically upon the steric hindrances and electronic structures of both nitrogen donor ligand sand porphyrin nanoparticles.

Keywords: oxidation, nanoaggregates, porphyrinoids, silver

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Authors: Saeed Chehri, Sirvan Moradi, Amin Rostami

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Cooperative catalyst systems have been developed as highly promising sustainable alternatives to traditional catalysts. In these catalysts, two or more catalytic centers cooperate to reduce the energy of chemical transformations. In nature, such systems are abundantly seen in metalloenzymes that use metal and an organic cofactor. We have designed a reusable cooperative catalyst oxidation system consisting of palladium nanoparticles and polyoxometalate. This biomimetic cooperative catalytic system was synthesized by the stepwise immobilization of palladium nanoparticlesandpolyoxometalateinto the same cavity of siliceous mesocellularfoams (Pd-POM@MCF)and wascharacterizedby SEM, EDX, FT-IR, TGAand ICP techniques. POM-Pd@MCF/HQexhibits high activity toward aerobic oxidation of alcohols to the corresponding carbonyl compoundsin water solvent at room temperature. The major novelties and advantages of this oxidation method are as follows: (i) this is the first report of the co-immobilization of polyoxometalateand palladium for use as a robust and highlyefficient heterogeneouscooperative oxidative nanocatalyst system for aerobic oxidation of alcohols, (ii) oxidation of alcoholswere performed using an ideal oxidant with good to high yields in a green solvent at ambient temperature and (iii) the immobilization of the oxygen-activating catalyst(polyoxometalate) and oxidizing catalyst (Pd) onto MCF provide practical cooperative catalyst the system that can be reused several times without a significant loss of activity (vi) the methodsconform to several of the guiding principles of green chemistry.

Keywords: palladium nanoparticles, polyoxometalate, reusable cooperative catalytic system, biomimetic oxidation reaction

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Authors: Skezeer John B. Paz, Ederlina G. Nocon

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Finding an optimal binary linear code is a central problem in coding theory. A binary linear code C = [n, k, d] is called optimal if there is no linear code with higher minimum distance d given the length n and the dimension k. There are bounds giving limits for the minimum distance d of a linear code of fixed length n and dimension k. The lower bound which can be taken by construction process tells that there is a known linear code having this minimum distance. The upper bound is given by theoretic results such as Griesmer bound. One way to find an optimal binary linear code is to make the lower bound of d equal to its higher bound. That is, to construct a binary linear code which achieves the highest possible value of its minimum distance d, given n and k. Some optimal binary linear codes were presented by Andries Brouwer in his published table on bounds of the minimum distance d of binary linear codes for 1 ≤ n ≤ 256 and k ≤ n. This was further improved by Markus Grassl by giving a detailed construction process for each code exhibiting the lower bound. In this paper, we construct new optimal binary linear codes by using some construction processes on existing binary linear codes. Particularly, we developed an algorithm applied to the codes already constructed to extend the list of optimal binary linear codes up to 257 ≤ n ≤ 300 for k ≤ 7.

Keywords: bounds of linear codes, Griesmer bound, construction of linear codes, optimal binary linear codes

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Authors: Leonard D. Agana, Wendell Ace Dela Cruz, Arjan C. Lingaya, Bonifacio T. Doma Jr.

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The purpose of this paper is to study the predict the fuel performance parameters, which include drivability index (DI), vapor lock index (VLI), and vapor lock potential using distillation curve and Reid vapor pressure (RVP) of dual alcohol-gasoline fuel blends. Distillation curve and Reid vapor pressure were predicted using artificial neural networks (ANN) with macroscopic properties such as boiling points, RVP, and molecular weights as the input layers. The ANN consists of 5 hidden layers and was trained using Bayesian regularization. The training mean square error (MSE) and R-value for the ANN of RVP are 91.4113 and 0.9151, respectively, while the training MSE and R-value for the distillation curve are 33.4867 and 0.9927. Fuel performance analysis of the dual alcohol–gasoline blends indicated that highly volatile gasoline blended with dual alcohols results in non-compliant fuel blends with D4814 standard. Mixtures of low-volatile gasoline and 10% methanol or 10% ethanol can still be blended with up to 10% C3 and C4 alcohols. Intermediate volatile gasoline containing 10% methanol or 10% ethanol can still be blended with C3 and C4 alcohols that have low RVPs, such as 1-propanol, 1-butanol, 2-butanol, and i-butanol. Biography: Graduate School of Chemical, Biological, and Materials Engineering and Sciences, Mapua University, Muralla St., Intramuros, Manila, 1002, Philippines

Keywords: dual alcohol-gasoline blends, distillation curve, machine learning, reid vapor pressure

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Authors: Manal Azzidani

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This research consideres the extension of special functions called Positive Linear Operators. the bounded linear operator which defined from normed space to Banach space will extend to the closure of the its domain, And extend identified linear functional on a vector subspace by Hana-Banach theorem which could be generalized to the positive linear operators.

Keywords: extension, positive operator, Riesz space, sublinear function

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Authors: Myung Hwan Na, Ho- Chun Song, EunHee Hong

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We widely use normal linear mixed-effects model to analysis data in repeated measurement. In case of detecting heteroscedasticity and the non-normality of the population distribution at the same time, normal linear mixed-effects model can give improper result of analysis. To achieve more robust estimation, we use heavy tailed linear mixed-effects model which gives more exact and reliable analysis conclusion than standard normal linear mixed-effects model.

Keywords: reliability, tires, field data, linear mixed-effects model

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Authors: Fatma Susilawati Mohamad, Azizah Abdul Manaf, Fadhillah Ahmad, Zarina Mohamad, Wan Suryani Wan Awang

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A simple and robust multi-class linear classifier is proposed and implemented. For a pair of classes of the linear boundary, a collection of segments of hyper planes created as perpendicular bisectors of line segments linking centroids of the classes or part of classes. Nearest Neighbor and Linear Discriminant Analysis are compared in the experiments to see the performances of each classifier in discriminating ripeness of oil palm. This paper proposes a multi-class linear classifier using Linear Discriminant Analysis (LDA) for image identification. Result proves that LDA is well capable in separating multi-class features for ripeness identification.

Keywords: multi-class, linear classifier, nearest neighbor, linear discriminant analysis

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Authors: S. H. Nasseri, A. Ebrahimnejad

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Fuzzy set theory has been applied to many fields, such as operations research, control theory, and management sciences. In this paper, we consider two classes of fuzzy linear programming (FLP) problems: Fuzzy number linear programming and linear programming with trapezoidal fuzzy variables problems. We state our recently established results and develop fuzzy primal simplex algorithms for solving these problems. Finally, we give illustrative examples.

Keywords: fuzzy linear programming, fuzzy numbers, duality, sensitivity analysis

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Authors: Gurpreet Kaur, Manoj Kumar, Vandana Bhalla

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Strong acceptor-weak acceptor system FN-TPy has been designed and synthesized which undergoes solvent dependent self-assembly in mixed aqueous media to generate through space intermolecular charge transfer assemblies. The as prepared entropically favoured assemblies of FN-TPy exhibit excellent photostability and photosensitizing properties in the assembled state to activate aerial oxygen for efficient generation of reactive oxygen species (ROS) through Type-I and Type-II pathways. The FN-TPy assemblies exhibit excellent potential for regulated oxidation of alcohols and aldehydes under mild reaction conditions (visible light irradiation, aqueous media, room temperature) using aerial oxygen as the ‘oxidant’. The present study demonstrates the potential of FN-TPy assemblies to catalyze controlled oxidation of benzyl alcohol to benzaldehyde and to corresponding benzoic acid.

Keywords: oxidations, photosensitizer, reactive oxygen species, supramolecular assemblies, through space charge transfer.

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Authors: R. B. Ogunrinde, C. C. Jibunoh

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In this paper, a spectral decomposition method is developed for the direct integration of stiff and nonstiff homogeneous linear (ODE) systems with linear, constant, or zero right hand sides (RHSs). The method does not require iteration but obtains solutions at any random points of t, by direct evaluation, in the interval of integration. All the numerical solutions obtained for the class of systems coincide with the exact theoretical solutions. In particular, solutions of homogeneous linear systems, i.e. with zero RHS, conform to the exact analytical solutions of the systems in terms of t.

Keywords: spectral decomposition, linear RHS, homogeneous linear systems, eigenvalues of the Jacobian

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Authors: B. Güney, Ç. Teke

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In recent years, rapid and correct decision making is crucial for both people and enterprises. However, uncertainty makes decision-making difficult. Fuzzy logic is used for coping with this situation. Thus, fuzzy linear programming models are developed in order to handle uncertainty in objective function and the constraints. In this study, a problem of a factory in food industry is investigated, required data is obtained and the problem is figured out as a fuzzy linear programming model. The model is solved using Zimmerman approach which is one of the approaches for fuzzy linear programming. As a result, the solution gives the amount of production for each product type in order to gain maximum profit.

Keywords: food industry, fuzzy linear programming, fuzzy logic, linear programming

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Authors: Hazem Al-Mofleh, John Daniels, Joseph McKean

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Within geostatistics research, effective estimation of the variogram points has been examined, particularly in developing robust alternatives. The parametric fit of these variogram points which eventually defines the kriging weights, however, has not received the same attention from a robust perspective. This paper proposes the use of the non-linear Wilcoxon norm over weighted non-linear least squares as a robust variogram fitting alternative. First, we introduce the concept of variogram estimation and fitting. Then, as an alternative to non-linear weighted least squares, we discuss the non-linear Wilcoxon estimator. Next, the robustness properties of the non-linear Wilcoxon are demonstrated using a contaminated spatial data set. Finally, under simulated conditions, increasing levels of contaminated spatial processes have their variograms points estimated and fit. In the fitting of these variogram points, both non-linear Weighted Least Squares and non-linear Wilcoxon fits are examined for efficiency. At all levels of contamination (including 0%), using a robust estimation and robust fitting procedure, the non-weighted Wilcoxon outperforms weighted Least Squares.

Keywords: non-linear wilcoxon, robust estimation, variogram estimation, wilcoxon norm

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Authors: Mehdi Jafari Matehkolaee

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In this paper, we have obtained the adjoint of an arbitrary operator (linear and nonlinear) in Hilbert space by introducing an n-dimensional Riemannian manifold. This general formalism covers every linear operator (non – differential) in Hilbert space. In fact, our approach shows that instead of using the adjoint definition of an operator directly, it can be obtained directly by relying on a suitable generalized space according to the action of the operator in question. For the case of nonlinear operators, we have to change the definition of the linear operator adjoint. But here, we have obtained an adjoint of these operators with respect to the definition of the derivative of the operator. As a matter of fact, we have shown one of the straight applications of the ''Frechet derivative'' in the algebra of the operators.

Keywords: adjoint operator, non-linear operator, differentiable operator, manifold

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Authors: Mishu Gupta, Rama Gupta

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It has been elucidated here that non- autonomous discrete non-linear Schrödinger equation is associated with saturable non-linearity through photo-refractive media. We have investigated the localized solution of non-autonomous saturable discrete non-linear Schrödinger equations. The similarity transformation has been involved in converting non-autonomous saturable discrete non-linear Schrödinger equation to constant-coefficient saturable discrete non-linear Schrödinger equation (SDNLSE), whose exact solution is already known. By back substitution, the solution of the non-autonomous version has been obtained. We have analysed our solution for the hyperbolic and periodic form of gain/loss term, and interesting results have been obtained. The most important characteristic role is that it helps us to analyse the propagation of electromagnetic waves in glass fibres and other optical wave mediums. Also, the usage of SDNLSE has been seen in tight binding for Bose-Einstein condensates in optical mediums. Even the solutions are interrelated, and its properties are prominently used in various physical aspects like optical waveguides, Bose-Einstein (B-E) condensates in optical mediums, Non-linear optics in photonic crystals, and non-linear kerr–type non-linearity effect and photo refracting medium.

Keywords: B-E-Bose-Einstein, DNLSE-Discrete non linear schrodinger equation, NLSE-non linear schrodinger equation, SDNLSE - saturable discrete non linear Schrodinger equation

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Authors: Rabia Khan, Nargis Munir, Suriya Gharib, Syeda Roshana Ali

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In this paper linear equations are discussed in detail along with elimination method. Gaussian elimination and Gauss Jordan schemes are carried out to solve the linear system of equation. This paper comprises of matrix introduction, and the direct methods for linear equations. The goal of this research was to analyze different elimination techniques of linear equations and measure the performance of Gaussian elimination and Gauss Jordan method, in order to find their relative importance and advantage in the field of symbolic and numeric computation. The purpose of this research is to revise an introductory concept of linear equations, matrix theory and forms of Gaussian elimination through which the performance of Gauss Jordan and Gaussian elimination can be measured.

Keywords: direct, indirect, backward stage, forward stage

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Authors: Qasim M. Kriri

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Few Saudi Arabia production companies face financial profit issues until this moment. This work presents a linear integer programming model that solves a production problem of a Saudi Food Company in Saudi Arabia. An optimal solution to the above-mentioned problem is a Linear Programming solution. In this regard, the main purpose of this project is to maximize profit. Linear Programming Technique has been used to derive the maximum profit from production of natural juice at Saudi Food Co. The operations of production of the company were formulated and optimal results are found out by using Lindo Software that employed Sensitivity Analysis and Parametric linear programming in order develop Linear Programming. In addition, the parameter values are increased, then the values of the objective function will be increased.

Keywords: parameter linear programming, objective function, sensitivity analysis, optimize profit

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Authors: M. Merabet-Khelassi, Z. Houiene, L. Aribi-Zouioueche, O. Riant

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Lipases (EC.3.1.1.3) are efficient biotools widely used for their remarkable chemo-, regio- and enantio-selectivity, especially, in kinetic resolution of racemates. They offer access to a large panel of enantiopure building blocks, such as secondary benzylic alcohols, commonly used as synthetic intermediates in pharmaceutical and agrochemical industries. Due to the stability of lipases in both water and organic solvents poor in water, they are able to catalyze both transesterifications of arylalkylcarbinols and hydrolysis of their corresponding acetates. The use of enzymatic hydrolysis in aqueous media still limited. In this presentation, we expose a practical methodology for the preparation of optically enriched acetates using a Candida antarctica lipase B-catalyzed hydrolysis in non-aqueous media in the presence of alkaline carbonate salts. The influence of several parameters which can intervene on the enzymatic efficiency such as the impact of the introduction of the carbonates salts, its amount and the nature of the alkaline earth metal are discussed. The obtained results show that the use of sodium carbonate with CAL-B enhances drastically both reactivity and selectivity of this immobilized lipase. In all cases, the resulting alcohols and remaining acetates are obtained in high ee values (up to > 99 %), and the selectivities reach (E > 500).

Keywords: alkaline-hydrolysis, enzymatic kinetic resolution, lipases, arylalkylcarbinol, non-aqueous media

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Authors: Suparman

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Piecewise linear regression models are very flexible models for modeling the data. If the piecewise linear regression models are matched against the data, then the parameters are generally not known. This paper studies the problem of parameter estimation of piecewise linear regression models. The method used to estimate the parameters of picewise linear regression models is Bayesian method. But the Bayes estimator can not be found analytically. To overcome these problems, the reversible jump MCMC algorithm is proposed. Reversible jump MCMC algorithm generates the Markov chain converges to the limit distribution of the posterior distribution of the parameters of picewise linear regression models. The resulting Markov chain is used to calculate the Bayes estimator for the parameters of picewise linear regression models.

Keywords: regression, piecewise, Bayesian, reversible Jump MCMC

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Authors: Sie Long Kek, Wah June Leong, Kok Lay Teo

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Linear quadratic Gaussian model is a standard mathematical model for the stochastic optimal control problem. The combination of the linear quadratic estimation and the linear quadratic regulator allows the state estimation and the optimal control policy to be designed separately. This is known as the separation principle. In this paper, an efficient computational method is proposed to solve the linear quadratic Gaussian problem. In our approach, the Hamiltonian function is defined, and the necessary conditions are derived. In addition to this, the output error is defined and the least-square optimization problem is introduced. By determining the first-order necessary condition, the gradient of the sum squares of output error is established. On this point of view, the stochastic approximation approach is employed such that the optimal control policy is updated. Within a given tolerance, the iteration procedure would be stopped and the optimal solution of the linear-quadratic Gaussian problem is obtained. For illustration, an example of the linear-quadratic Gaussian problem is studied. The result shows the efficiency of the approach proposed. In conclusion, the applicability of the approach proposed for solving the linear quadratic Gaussian problem is highly demonstrated.

Keywords: iteration procedure, least squares solution, linear quadratic Gaussian, output error, stochastic approximation

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Authors: Seema Kothari, Dinesh Panday

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An observed correlation of the reaction rates with the changes in the nature of substituent present on one of the reactants often reveals the nature of transition state. Selective oxidation of organic compounds under non-aqueous media is an important transformation in synthetic organic chemistry. Inorganic chromates and dichromates being drastic oxidant and are generally insoluble in most organic solvents, a number of different chromium (VI) derivatives have been synthesized. Benzimidazolium dichromate (BIDC) is one of the recently reported Cr(VI) reagents which is neither hygroscopic nor light sensitive being, therefore, much stable. Not many reports on the kinetics of the oxidations by BIDC are seemed to be available in the literature. In the present investigation, the kinetics and mechanism of benzyl alcohol (BA) and a number of para- and meta-substituted benzyl alcohols by benzimidazolium dichromate (BIDC), in dimethyl sulphoxide, is reported. The reactions were followed spectrophotometrically at 364 nm by monitoring the decrease in [BIDC] for up to 85-90% reaction, the temperature being constant. The observed oxidation product is the corresponding benzaldehyde. The reactions were of first order with respect to each the alcohol and BIDC. The reactions are catalyzed by proton, and the dependence is of the form: kobs = a + b[H+]. The reactions thus follow both, an acid-dependent and acid-independent paths. The oxidation of [1,1 2H2]benzyl alcohol exhibited the presence of a substantial kinetic isotope effect ( kH/kD = 6.20 at 298 K ). This indicated the cleavage of a α-C-H bond in the rate-determining step. An analysis of the temperature dependence of the deuterium isotope effect showed that the loss of hydrogen proceeds through a concerted cyclic process. The rate of oxidation of BA was determined in 19 organic solvents. An analysis of the solvent effect by Swain’s equation indicated that though both the anion and cation-solvating powers of the solvent contribute to the observed solvent effect, the role of cation-solvation is major. The rates of the para and meta compounds, at 298 K, failed to exhibit a significant correlation in terms of Hammett or Brown's substituent constants. The rates were then subjected to analyses in terms of dual substituent parameter (DSP) equations. The rates of oxidation of the para-substituted benzyl alcohols show an excellent correlation with Taft's σI and σRBA values. However, the rates for the meta-substituted benzyl alcohols show an excellent correlation with σI and σR0. The polar reaction constants are negative indicating an electron-deficient transition state. Hence the overall mechanism is proposed to involve the formation of a chromate ester in a fast pre-equilibrium and then a decomposition of the ester in a subsequent slow step via a cyclic concerted symmetrical transition state, involving hydride-ion transfer, leading to the product. The first order dependence on alcohol may be accounted in terms of the small value of the formation constant of the ester intermediate. An another reaction mechanism accounting the acid-catalysis involve the formation of a protonated BIDC prior to formation of an ester intermediate which subsequently decomposes in a slow step leading to the product.

Keywords: benzimidazolium dichromate, benzyl alcohols, correlation analysis, kinetics, oxidation

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Authors: M. Berrehail, F. Benamira

Abstract:

We study the quantum motion of a particle in the presence of a time- dependent linear potential using an operator invariant that is quadratic in p and linear in q within the framework of the Lewis-Riesenfeld invariant, The special invariant operator proposed in this work is demonstrated to be an Hermitian operator which has an Airy wave packet as its Eigenfunction

Keywords: airy wave packet, ivariant, time-dependent linear potential, unitary transformation

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