Synthesis and antibacterial activity of some 5-hydroxy-5-trifluoromethyl-4,5-dihydropyrazol-1-thiocarboxamides, 3-trifluoromethylpyrazol-1-thiocarboxamides and 4-aryl-2-(5(3)-trifluoromethyl-1-pyrazolyl)thiazoles

5-Hydroxy-5-trifluoromethyl-4,5-dihydropyrazol-1-thiocarboxamides 3 and 3-trifluoromethylpyrazol-1-thiocarboxamides 4, regioselectively obtained by the condensation of trifluoromethyl-β-diketones with thiosemicarbazide under neutral and acidic conditions, on further reaction with phenacyl bromides 5 afforded 4-aryl-(5-trifluoromethyl-pyrazol-1-yl)thiazoles 6 and 4-aryl-(3-trifluoromethyl-pyrazol-1-yl)thiazoles 7, respectively. Five 4,5-dihydropyrazoles (3a–e) and two pyrazolylthiazoles (6a and 6c) were tested against one Gram-positive and one Gram-negative bacteria to assess their in vitro antibacterial activity. Compounds 3a, 3b and 3e showed moderate antibacterial activity against Gram-positive bacterium, Bacillus pumilus.     

Determination of organic acid impurities in lactic acid obtained by fermentation of sugarcane juice

Lactic acid produced by fermentation process mostly contains a number of aliphatic carboxylic acids as impurities. In this work, carboxylic acid impurities in lactic acid samples from a number of sources were determined at ppm levels. A simple HPLC method was developed that utilized a new generation polar embedded reverse phase, 20mM phosphate buffer at pH 2.20 (±0.05) and UV detection at 210 nm. The method enabled quantitative analysis of the above acids in lactic acid matrix. The experimental conditions for column temperature, mobile phase pH and flow rate were optimized. A detailed validation of the method was performed for linearity, precision, accuracy, selectivity, limit of detection (LOD), limit of quantitation (LOQ), ruggedness and repeatability and reproducibility (R&R).     

Do commercially available metal salts mediate calixarene formation via hydrogen-bonded dimers?

In this article we report the first example of a Lewis acid promoted, one-pot, Br?nsted acid free, high-yielding synthesis of the calixarene macrocycle from the "monomer" p-tert-butylphenol. We report that when a commercially available metal salt (Lewis acid) is incorporated within the calixarene-forming reaction, a certain amount of control over the size of the calixarenes produced can be gained. Although a detailed mechanistic rationale on how the macrocycle is assembled is unclear, what is evident from this work is that the metal cation, the counteranion, and the oxidation state of the salt employed are all important contributors to the outcome of the reaction process. Indeed, evidence to date suggests that a subtle "symbiotic" relationship exists between the metal cation, its oxidation state, and the anion that allows the efficient transformation of the "monomeric" p-tert-butylphenol into linear oligomers and, ultimately, into macrocyclic calixarenes. Athough the metal salt mediated process described herein is efficient and high-yielding, what is also fundamentally important is that a comprehensive mechanistic understanding of how the calixarenes are assembled be accrued. Searching for possible indicators or clues, we propose that oligomeric methylene-linked phenolic entities are initially formed and that these, we tentatively suggest, generate metal and/or anion hydrogen-bonded supramolecular intermediates. It is possible that the preorganization of the linear polyphenolic oligomers allows the formation of hydrogen-bonded structures which, critically, result in the formation of supramolecular assemblies that are subsequently "stitched" together, generating the p-tert-butylcalix[n]arenes (n = 4-9) in excellent yields. Substantiating the possibility that hydrogen-bonded entities are generated (and that these subsequently afford metal-templated assemblies), we make reference to a seldom cited 1962 Nature publication that reported the propensity of polyphenolic linear oligomers to form "well-defined intramolecularly hydrogen-bonded conformations".     

Reduced-order models for control of fluids using the eigensystem realization algorithm

As sensors and flow control actuators become smaller, cheaper, and more pervasive, the use of feedback control to manipulate the details of fluid flows becomes increasingly attractive. One of the challenges is to develop mathematical models that describe the fluid physics relevant to the task at hand, while neglecting irrelevant details of the flow in order to remain computationally tractable. A number of techniques are presently used to develop such reduced-order models, such as proper orthogonal decomposition (POD), and approximate snapshot-based balanced truncation, also known as balanced POD. Each method has its strengths and weaknesses: for instance, POD models can behave unpredictably and perform poorly, but they can be computed directly from experimental data; approximate balanced truncation often produces vastly superior models to POD, but requires data from adjoint simulations, and thus cannot be applied to experimental data. In this article, we show that using the Eigensystem Realization Algorithm (ERA) (Juang and Pappa, J Guid Control Dyn 8(5):620?C627, 1985) one can theoretically obtain exactly the same reduced-order models as by balanced POD. Moreover, the models can be obtained directly from experimental data, without the use of adjoint information. The algorithm can also substantially improve computational efficiency when forming reduced-order models from simulation data. If adjoint information is available, then balanced POD has some advantages over ERA: for instance, it produces modes that are useful for multiple purposes, and the method has been generalized to unstable systems. We also present a modified ERA procedure that produces modes without adjoint information, but for this procedure, the resulting models are not balanced, and do not perform as well in examples. We present a detailed comparison of the methods, and illustrate them on an example of the flow past an inclined flat plate at a low Reynolds number.     

A mathematical fractional model with nonsingular kernel for thrombin receptor activation in calcium signalling

In calcium signalling, activation of receptor is a very significant aspect. To understand the mechanism of calcium signalling, receptors are the important components. The mobilization of intracellular calcium from intracellular stores depends upon binding of agonist to cell surface receptor. Thrombin is chosen as model ligand. In order to understand thrombin receptor activation, we analyze fractional model incorporating derivative of arbitrary order and nonsingular kernel which can precisely describe the effect of memory and can explain the model in better and more efficient manner as compared with fractional operators with singular kernels. The problem has been solved by perturbation iterative method. Using fixed‐point theorem, it is proved that solution of the system will exist and also it will be unique.     

Pressure dependence electrical resistivity in DVT grown molybdenum dichalcogenides

Abstract

Single crystals of MoS _x Se_2?x (x=0, 1, 2) have been grown by direct vapour transport method. Pressure-dependent d.c. electrical resistivity measurements have been carried out on the grown crystals to check the possibility of phase transition up to 8 GPa. However, no such transition is observed in the present case but a decrease in resistivity is found with increase in pressure. The observed results have been analysed and discussed on the basis of band structure.     

Gold‐Nanoparticle‐Decorated Boron Nitride Nanosheets: Structure and Optical Properties

Synergetic cooperation of individual components of the nanocomposites (NCs) is responsible for their novel properties that lead to various technological applications. A simple chemical process depicting the deposition of functionalized gold nanoparticles on the surface of boron nitride nanosheets (BNNSs) in solution is reported. The structure, chemical composition, and optical properties of nanosheets are systematically studied. The deposition of Au nanoparticles on BNNS (BNNS_Au) results in plasmonic band modulation, thus altering the optoelectronic properties of BNNSs. The intense surface plasmon absorption band of BNNS_Au is narrowed and red‐shifted relative to the absorption band of as synthesized monometallic BNNSs. The observations reflect the strong interfacial interaction between BNNS and Au nanoparticles. This approach constitutes a basis for a simple process leading to the preparation of functionalized BNNSs and their utilization as nanoscale templates for assembly and integration with other nanoscale materials for futuristic optoelectronic devices.     

The partition problem

In this paper we describe several forms of thek-partition problem and give integer programming formulations of each case. The dimension of the associated polytopes and some basic facets are identified. We also give several valid and facet defining inequalities for each of the polytopes.Partial Support from NSF Grants DMS 8606188 and ECS 8800281 is gratefully acknowledged.     

Investigation of the Behaviour of Powders under and after Consolidation

A biaxial tester was utilized in order to characterize mechanical powder behaviour. Tests were aimed at characterizing the virgin consolidation behaviour of CRM 116 limestone powder, standardized by the Community Bureau of Reference (BCR). The tests indicated that the virgin consolidation behaviour of the powder can be represented by means of topographic maps and surface plots in the principal stress space irrespective of the consolidation stress paths. Resulting strains and bulk densities can also be represented in the same manner. Reloading tests were also carried out on samples consolidated by following different stress paths (consolidation procedures). By applying stresses to the previously consolidated samples and determination of points of initial plastic deformations, the yield surface for each specific type of consolidation was drawn. These tests revealed anisotropic behaviour of the powder, depending on the type of consolidation.