Thermodynamic properties of the alkali metals at high temperatures and high pressures using mean-field potential model

We have carried out theoretical calculations for the thermodynamic properties of alkali metals at high temperatures and pressures. In the present study, we have used recently proposed mean-field potential (MFP) model of Wang and Li for evaluating the vibrational contribution to the total free energy. The recently proposed local pseudopotential of Filohais et al. is used to construct mean-field potential in terms of the total energy-volume relation. We have calculated static and shock compressions, bulk moduli (B_T and B_S), thermal expansion, specific heats (C_P and C_V), anharmonic contribution to the specific heat , enthalpy (E_H) and temperature along shock Hugoniot. We find that our computed results (except for C_P and C_V) are in good agreement with experiments as well as comparable with those generated by using first principles methods and other theoretical models. The present study indicates that in comparison with other theoretical models the present model is computationally simple, physically transparent and reliable to study the thermodynamic properties in the high pressures and high temperatures environment.     

Tandem C-C coupling--intramolecular acetylenic Schmidt reaction under Pd/C-Cu catalysis

A new one-pot reaction for the regioselective construction of a six-membered fused N-heterocyclic ring leading to isoquinolones under Pd/C-Cu catalysis is described.     

Groovy drops: effect of groove curvature on spontaneous capillary flow

Spontaneous capillary flow (SCF) of a drop in a groove with an ideally sharp corner is possible when the Concus-Fin (CF) condition is fulfilled. However, since ideally sharp corners do not exist in reality, it is important to understand the effect of finite corner curvature on SCF. This effect is analytically studied for long drops in a V-shaped groove with a curved corner, leading to a generalization of the CF condition for such drops. The generalized condition implies that SCF depends on the geometry of the corner as well as on the dimensionless length of the drop, in addition to its dependence on the opening angle and contact angle that is covered by the CF condition. Specific calculations are presented for rounded corners. In addition, this effect is numerically calculated for short drops in V-shaped grooves with rounded corners, using the Surface Evolver software. The results of both types of calculations show that even a relatively small corner radius strongly affects the possibility of SCF: when the corner is not ideally sharp, SCF requires conditions that are more difficult to achieve than predicted by the CF condition; also, the spreading of the drop stops at a finite length and does not proceed indefinitely.     

Determination of vitamin B12 in fortified bovine milk-based infant formula powder, fortified soya-based infant formula powder, vitamin premix, and dietary supplements by surface plasmon resonance: collaborative study

A collaborative study was conducted on an inhibition-based protein-binding assay using the Biacore Q biosensor instrument and the Biacore Qflex Kit Vitamin B12 PI. The samples studied included infant formula, cereals, premixes, vitamin tablets, dietary supplements, and baby food. The collaborative study, which involved 11 laboratories, demonstrated that the assay showed an RSDr of 1.59-27.8 and HorRat values for reproducibility of 0.34-1.89 in samples with levels ranging from ppm to ppb. The assay studied is a label-free protein binding-based assay that uses the principle of surface plasmon resonance (SPR) to measure the interaction between vitamin B12 and a specific binding protein. A Biacore Q biosensor uses this principle to detect binding directly at the surface of a sensor chip with a hydrophilic gold-dextran surface. The instrument passes a mixture of prepared sample extract and binding protein solution across a covalently immobilized vitamin B12 chip surface, and the response is given as free-binding protein as the mixture binds to the immobilized surface. This technique uses the specificity and robustness of the protein-ligand interaction to allow minimal sample preparation and a wide range of matrixes to be analyzed rapidly. The reagents and accessories needed to perform this assay are provided as the ready-to-use format "Qflex Kit Vitamin B12 PI." The method is intended for routine use in the quantitative determination of vitamin B12 (as cyanocobalamin) in a wide range of food products, dietary vitamin supplements, and multivitamin premixes.     

Copper-catalyzed 1,2-addition of nucleophilic silicon to aldehydes: mechanistic insight and catalytic systems

Activation of the Si-B inter-element bond with copper(I) alkoxides produces copper-based silicon nucleophiles that react readily with aldehydes to yield α-silyl alcohols (that is, α-hydroxysilanes) after hydrolysis. Two independent protocols were developed, one employing a well-defined NHC-CuOtBu complex and one using the simple CuCN-NaOMe combination without added ligand. The mechanism of the aldehyde addition was investigated in detail by stoichiometric and catalytic experiments as well as NMR spectroscopic measurements. The primary reaction product of the addition of the Si-B reagent and the aldehyde (a boric acid ester of the α-silyl alcohol) and also the "dead-end" intermediate, formed in the competing [1,2]-Brook rearrangement, were characterized crystallographically. Based on these data, a reasonable catalytic cycle is proposed. The NHC-CuOtBu catalytic setup performs nicely at elevated temperature. A more reactive catalytic system is generated from CuCN-NaOMe, showing fast turnover at a significantly lower temperature. Both aromatic and aliphatic aldehydes are transformed into the corresponding α-silyl alcohols in good to very good yields under these mild reaction conditions.     

A review on reactive adsorption for potential environmental applications

The aim of this paper is to present a critical review on reactive adsorption processes. The impact of surface modification on adsorption behavior of various adsorbents in context of reactive adsorption has been reviewed. Various characterization and detection methods involved to access and verify the surface morphology of adsorbent, presence of surface functionalities on adsorbent, and concentration of adsorbate have been concisely presented. The paper also delves into the inadequately researched grey areas of reactive adsorption which require further attention such as modeling and adsorbent regeneration so as to make the process more economic. The applicability of reactive adsorption to ensure a cleaner environment has also been briefly discussed. This article also underlines the areas, in which reactive adsorption can be implemented on a pilot scale.     

A scheme to observe universal breathing mode and Berezinskii–Kosterlitz–Thouless phase transition in a two-dimensional photon gas

A system of two-dimensional photon gas has recently been realized experimentally. We show that this setup can be used to observe a universal breathing mode of photon gas and a modification in the experimental setup would open up a possibility of observing the Berezinskii–Kosterlitz–Thouless (BKT) phase transition in such a system. Furthermore, the universal jump in the superfluid density of light in the output channel can be used as an unambiguous signature for the experimental verification of the BKT transition.     

Integrated pharmacophore and docking‐based designing of dual inhibitors of aldose reductase (ALR2) and protein tyrosine phosphatase 1B (PTP1B) as novel therapeutics for insulin‐resistant diabetes and its complications

The dual inhibitors against aldose reductase (ALR2) and protein tyrosine phosphatase 1B (PTP1B) may present an anti‐diabetic potency in insulin resistance without risks of serious diabetic complications. Therefore, in the present study, we constructed two separate pharmacophore mapping‐based 3D quantitative structure–activity relationship models for ALR2 (AADRR.1109₃ with standard deviation 0.663, 0.719, F 22.3, root‐mean‐square error 0.705, 0.647, Pearson‐r 0.802) and PTP1B (AARR.15₅ with standard deviation 0.146, 0.945, F 82.70, root‐mean‐square error 0.351, 0.621, Pearson‐r 0.831) employing the dataset of 54 flavonoids as ALR2 inhibitors and 46 naphthoquinones as PTP1B inhibitors to identify structural features necessary for the inhibition of both enzymes. These models were subsequently used as 3D query search for hierarchical virtual screening‐based designing using the PHASE database of 1.5 million compounds. Designed dual inhibitors were further subjected to GLIDE XP docking analysis using high‐resolution 3D structures of ALR2 (1US0, at resolution of 0.66 Å) and PTP1B (2F71 at resolution of 1.55 Å) available in the Protein Data Bank to authenticate identified structural features with important binding interactions necessary for dual inhibition. Copyright © 2014 John Wiley & Sons, Ltd.     

Gas chromatographic separation of methoxylated polychlorinated biphenyl atropisomers

Several polychlorinated biphenyls (PCBs) and their hydroxylated metabolites display axial chirality. Here we describe an enantioselective, gas chromatographic separation of methylated derivatives of hydroxylated (OH-)PCB atropisomers (MeO-PCB) using a chemically bonded beta-cyclodextrin column (Chirasil-Dex). The atropisomers of several MeO-PCBs could be separated on this column with resolutions ranging from 0.42 to 0.87 under isothermal or temperature-programmed conditions. In addition, the enantiomeric fraction of OH-PCB 136 metabolites was determined in male and female rats treated with racemic PCB 136. The methylated derivatives of two OH-PCB 136 metabolites showed an enantiomeric enrichment in liver tissue, whereas PCB 136 itself was near racemic.     

Cyclodextrin based novel drug delivery systems

The versatile pharmaceutical material cyclodextrin’s (CDs) are classified into hydrophilic, hydrophobic, and ionic derivatives. By the early 1950s the basic physicochemical characteristics of cyclodextrins had been discovered, since than their use is a practical and economical way to improve the physicochemical and pharmaceutical properties such as solubility, stability, and bioavailability of administered drug molecules. These CDs can serve as multi-functional drug carriers, through the formation of inclusion complex or the form of CD/drug conjugate and, thereby potentially serving as novel drug carriers. This contribution outlines applications and comparative benefits of use of cyclodextrins (CDs) and their derivatives in the design of novel delivery systems like liposomes, microspheres, microcapsules, nanoparticles, cyclodextrin grafted cellulosic fabric, hydrogels, nanosponges, beads, nanogels/nanoassemblies and cyclodextrin-containing polymers. The article also focuses on the ability of CDs to enhance the drug absorption across biological barriers, the ability to control the rate and time profiles of drug release, drug safety, drug stability, and the ability to deliver a drug to targeted site. The article highlight’s on needs, limitations and advantages of CD based delivery systems. CDs, because of their continuing ability to find several novel applications in drug delivery, are expected to solve many problems associated with the delivery of different novel drugs through different delivery routes.