Proline and benzylpenicillin derivatives grafted into mesoporous MCM-41: Novel organic-inorganic hybrid catalysts for direct aldol reaction

New organic-inorganic hybrid catalysts were synthesized by covalent grafting of proline and benzylpenicillin derivatives into mesoporous MCM-41. These catalysts were extensively characterized using FT-IR,¹³C CP MAS solid stateNMR, XRD and TEM techniques. These were used as catalysts for direct, asymmetric aldol reaction between acetone and activated aromatic aldehydes. In the reaction of 4-nitro and 4-fluoro benzaldehyde, the aldol products were obtained in 36% and 59%ee respectively. The catalysts were reusable with neither significant drop in enantioselectivity nor loss of mesostructure. An attempt was made to substantiate the proposed ’enamine’ mechanism for direct aldol reaction by trapping the intermediate between proline-MCM-41 and acetone. Dedicated to Professor C N R Rao on his 70th birthday     

17O NMR spectra of equatorial and axial hydroxycyclohexanes and 5-hydroxy-1,3-dioxanes and their methyl ethers

¹⁷O chemical shifts of axial hydroxyl groups in cyclohexanols are upfield of those of corresponding equatorial groups, but in 5-hydroxy-1,3-dioxanes the opposite is observed: the axial OH resonates downfield of the equatorial OH. The situation is the same in the corresponding methyl ethers and is, thus, not a result of intramolecular hydrogen bonding in the axial 5-hydroxy-1,3-dioxane, but appears to parallel the effect on ¹³C and ¹⁹F shifts observed in corresponding equatorial and axial 5-methyl- and 5-fluoro-1,3-dioxanes, which has been attributed to an upfield shifting effect of the antiperiplanar γ-located heteroatoms. Surprisingly, the reciprocal effect is not seen in the ring ¹⁷O shifts of the 5-hydroxy-1,3-dioxanes. A δ compression shift is seen in the ¹⁷O spectrum of trans-3,3,5-trimethylcyclohexanol (syn-axial OH and CH₃), analogous to the effect earlier reported in ¹³C spectra. Conversion of four of the alcohols to methyl ethers produces a large upfield effect on the ¹⁷O shift, larger in the cyclohexanols than in the 1,3-dioxane-5-ols. Similar upfield shifts have been recorded in the literature; their extent depends on whether the alcohols are primary, secondary or tertiary.     

Some NP-complete problems in linear programming

Degeneracy checking in linear programming is NP-complete. So is the problem of checking whether there exists a basic feasible solution with a specified objective value.     

Polarography of europium in aqueous and aqueous methanolic solutions

The standard rate constants for the reduction of europium in perchlorate and chloride media and the formal rate constants in sulphate, acetate and lactate solutions are reported. The rate increases in the order of increasing polarisability of the anion or the increasing stability of the complex,viz., perchlorate < sulphate > lactate ≈ acetate. The effect of methanol on the polarography of europium has been studied. In perchlorate and chloride media, the half-wave potential shifts to negative values and then to positive values as the methanol content is increased. In acetate solutions, the shift is continuously to negative potentials. This is attributed to the effect of complex formation in acetate media and ion-pairing in perchlorate and chloride media. The effect of viscosity on the diffusion current was found to obey the Stokes-Einstein equation.     

σ-Ferrier rearrangement of carbohydrate derived vinylcyclopropanes: a facile approach to oxepane analogs

This article presents our work on the σ-Ferrier ring-expansion of carbohydrate derived vinylcyclopropanes (VCPs) under electrophilic conditions mediated by chloramine-T and a phase-transfer catalyst. The present work serves as the first example on the studies of the reactivity of carbohydrate VCPs towards the synthesis of densely functionalized oxepane analogues. The work elaborates on a reasonable mechanism for the product formation and our observations on the diastereoselectivity based on control experiments and gas-phase calculations.     

Application of various spectroscopic techniques to characterize the archaeological pottery excavated from Manaveli,Puducherry, India

This paper is focused on a spectroscopic study of some ancient pottery shreds from an archaeological site Manaveli village, Puducherry, India. Analytical characterization using Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD) and differential scanning colorimetric coupled with thermo gravimetric analysis were carried out on red and black ware and red ware recently excavated from the above site. The experimental results of FT-IR and XRD are similar and allowed us to identify the mineralogical composition of pottery samples. In addition, TGA was applied in order to study the dehydration of hydroscopic water and decomposition of carboxyl group in the powdered pottery samples during heating. Moreover, this paper proves that all the above spectroscopic techniques are very useful analytical tool for the examination of ancient pottery, which is also suitable for the identification of its firing temperature and firing atmosphere.     

Molecular Understanding of Collagen Stabilization: Interaction of Valeraldehyde with Collagen

The present study explains the molecular level interaction of valeraldehyde with collagen. Valeraldehyde is a monoaldehyde, which involves crosslinking with protein through covalent linkages. The role of valeraldehyde as a crosslinking agent for collagen stabilization was studied. Molecular modeling approaches was used to understand the interaction of collagen like peptide with valeraldehyde, which mimic the aldehyde tanning processes involved in protein stabilization. Crosslinking efficiency of valeraldehyde was found to increase with an increase in concentration due to the higher availability of aldehydic groups involved in crosslinking with collagen. Valeraldehyde interacted collagen membrane showed an increase in thermal stability by 25°C at pH 8. In the presence of valeraldehyde, collagen fibrils nucleation center was shifted from a lower to a higher range. Shift in the nucleation center was observed in the reduction of gelling time. Water accessibility in valeraldehyde interacted collagen membrane was reduced due to a higher crosslinking rate in the collagen. Modified collagen membrane by valeraldehyde at incubation of about 96 h showed higher resistance to collagenolytic activity of 81%. The amino groups reacting appear to be involved in crosslinking with valeraldehyde. Several interaction sites were identified and the docking energy obtained was ?5.539 kcal/mol. The participation of the aldehyde group with amino groups in collagen was observed, which plays a dominant role in the stabilization of peptide by valeraldehyde. It was found that complexes exhibit covalent bonding, hydrogen bonding and electrostatic interaction in the process of stabilization.     

Interaction of Coumarin 7 and Coumarin 314 with C-hexylpyrogallol[4]arene

We report in this paper the different modes of interaction of coumarin 7 and coumarin 314 with the cavity-containing molecule C-hexylpyrogallol[4]arene. The stoichiometry and the binding constant of coumarin 7 for its binding with C-hexylpyrogallol[4]arene are reported. The analysis is done with UV–Vis absorption, steady-state and time-resolved fluorescence, and 2D ROESY spectroscopy. The fluorescence quenching of the two coumarins is analyzed and the Stern–Volmer constants are reported. The mode of binding of coumarin 7 with the host molecule is optimized with 2D ROESY. Coumarin 314 does not form an inclusion complex and this result is supported by the spectral data. The ground and the excited state pK _a values for the coumarins, in the presence of C-hexylpyrogallol[4]arene, are reported.     

An activated carbon supercapacitor analysis by using a gel electrolyte of sodium salt-polyethylene oxide in an organic mixture solvent

A gel electrolyte of sodium bis(trifluoromethanesulfonyl)imide (NaTFSI)-polyethylene oxide (PEO) in an organic solvent mixture has been prepared and examined for supercapacitor applications by using activated carbon electrodes. The solvent was a mixture of propylene carbonate, dimethyl carbonate, and ethylene carbonate at equal molar ratio, and also, a propylene carbonate-based gel was used for a comparison. The polymer-salt interaction was viewed by infrared spectral study. The cells have been characterized in a two-electrode type using linear sweep voltammetry, cyclic voltammetry, galvanostatic cycling, and impedance techniques at 22 °C. The voltammograms evidence symmetry and reversibility of the cells. The ternary gel has shown better electrochemical performances. Moreover, the cell operative potential window was found to be stable at 2.5 V with high specific capacitance and also a good efficiency at low charge rate. The typical obtained specific capacitance, real power, and energy density values are 24 F g^?1, 0.52 kW kg^?1, and 18.7 Wh kg^?1, respectively, which may be viewable for a compact capacitor.     

An efficient algorithm for bounded spectral matching with affine constraint

Graph matching problem appears frequently in the applications of computer vision and machine learning. In this work, based on the spectral matching with affine constraint (SMAC) formulation, we present a new formulation, named bounded SMAC (BSMAC), for the graph matching problem by adding an upper‐bound constraint on the solution norm. We demonstrate the existence of a unique solution with BSMAC, whereas SMAC needs not to have any meaningful solution in general. We develop an effective numerical method to solve the BSMAC formulation as an optimization problem. Numerical experiments are presented to verify feasibility and to show the performance of the proposed numerical method.