Relativity and the Jahn–Teller,Berry pseudorotations of TBP clusters: group theory,spin–orbit and combinatorial nuclear spin statistics of TBP Desargues–Levi isomerization graph

Jahn–Teller and Berry pseudorotations in transition metal and main group clusters such as Hf₅, Ta₅, W₅ and Bi₅ are interesting because of the competition between relativistic effects and pseudorotations. Topological representations of various isomerization pathways arising from the Berry pseudorotation of pentamers constitute the edges of the Desargues–Levi graph. We have computed the combinatorics for multinomial colorings of the vertices, edges and 10-faces of the Desargues–Levi isomerization graph for all irreducible representations and the nuclear spin statistics of spin-7/2 ¹⁸¹Ta₅ as well as the TBP composite cluster particles. Topological insights into Jahn–Teller and Berry pseudorotations and relativistic effects are provided.     

Pyrenyl Carbon Nanotubes for Covalent Bilirubin Oxidase Biocathode Design: Should the Nanotubes be Carboxylated?

Understanding the characteristics of nanomaterials in the context of electrode designs for bio‐electrocatalysis is an emerging research direction. Applications for fuel cells, batteries, and biosensors are directly benefited. The objective of this study is to understand the influence of unfunctionalized multiwalled carbon nanotubes (MWNT) in comparison to carboxylated nanotubes (MWNT?COOH) for pi‐pi stacking with 1‐pyrenebutyric acid (Py) and covalent immobilization of bilirubin oxidase (BOD) enzyme toward the resulting oxygen reduction currents. We designed pyrolytic graphite‐edge electrodes modified with MWNT/Py, MWNT?COOH/Py, or only MWNT?COOH for carbodiimide activation and BOD immobilization. The relative increase in surface ?COOH groups as we move from MWNT to MWNT/Py to MWNT?COOH/Py modification is voltammetrically estimated. Although the MWNT?COOH/Py displayed the highest relative amount of surface ?COOH groups, the oxygen reduction current was the largest for the BOD‐immobilized MWNT/Py electrode than others. Results indicate that unfunctionalized MWNT is the optimal choice for pi‐pi stacking with pyrene linkers and covalent BOD immobilization as biocathode for energy devices. Favorable hydrophobic MWNT surface to interact more closely with the electron‐receiving T1 Cu site of BOD, as opposed to the relatively polar and more defective MWNT?COOH material due to functionalization, is suggested to be one of the underlying factors for the observed electrocatalytic trend.     

Stirring-ageing technique to develop zirconium-pillared bentonite clay along with its surface profiling using various spectroscopic techniques

Research on Chemical Intermediates - The pillared clays are getting wide attention due to the easiness in tailoring their surface for customized applications. In our laboratory, we have adopted a...     

Micellar induced regioselectivity in the two-step consecutive reaction of SO3(2-) with Br-(CH2CH2)n-Br (n=2-5)

High field (800 MHz) (1)H NMR was used to monitor the two-step consecutive reaction of excess SO(3)(2-) with symmetrical bifunctional alpha,omega-dibromoalkanes with butane (DBB), hexane (DBH), octane (DBO), and decane (DBD) chains in CTAB micelles at 25 degrees C. The first-order rate constant for the first substitution step for DBB and DBH is about 5 times faster than for the second, but the kinetics for DBO and DBD were not cleanly first-order. After 40 min, the solution contained about 80% of the intermediate bromoalkanesulfonate from DBB and DBH and the remainder is alkanedisulfonate and unreacted starting material. The same reactions were carried out in homogeneous MeOH/D(2)O solutions at 50 degrees C. The rate constants for all four alpha,omega-dibromoalkanes were first-order throughout the time course of the reaction and the same within +/-10%. However, because micellar solutions are organized on the nanoscale and bring together lipophilic and hydrophilic reactants into a small reaction volume at the micellar interface, they speed this substitution reaction considerably compared to reaction in MeOH/D(2)O. The CTAB micelles also induce a significant regioselectivity in product formation by speeding the first step of the consecutive reaction more than the second. The results are consistent with the bromoalkanesulfonate intermediates having a radial orientation within the micelles with the -CH(2)SO(3)(-) group in the interfacial region and the -CH(2)Br group directed into the micellar core such that the concentration of -CH(2)Br groups in the reactive zone, i.e., the micellar interface, is significantly reduced. These results provide the first example of self-assembled surfactant system altering the relative rates of the reaction steps of a consecutive reaction and, in doing so, enhancing monosubstitution of a symmetrically disubstituted species.     

Growth,spectral, optical,and dielectric studies on novel semiorganic NLO single crystal: d-phenylglycine hydrochloride

Good quality novel semiorganic nonlinear optical single crystal of d-phenylglycine hydrochloride has been grown from the aqueous solution by low temperature solution growth method. X-ray diffraction reveals that the crystal crystallises into orthorhombic system with noncentrosymmetric space group P2₁2₁2₁. Experimental parameters are evaluated based on single-crystal XRD and the calculated values of the polarisability were compared with the values of polarisability using Clausius–Mossotti equation. The functional groups present in the grown crystal were confirmed by Fourier transform infrared spectral analysis. The ¹H and ¹³C FT–NMR has been recorded to elucidate the molecular structure. Ultraviolet–visible-near infra-red absorption studies on this crystal reveal that the minimum absorption region is around 228 nm. The optical band gap of the crystal was found to be 2.9 eV. The scanning electron microscope study has been carried out to determine the surface morphology of the grown crystal. Photoluminescence studies show that the material emits violet fluorescence. Thermal studies bring forth that the crystal is thermally stable up to 255 °C. Dielectric studies reveal that both the dielectric constant and dielectric loss decrease with the increase in frequency as like the typical semiorganic nonlinear optical crystals such as bisthiourea zinc chloride, bisthiourea cadmium chloride and l-arginine dihydrogen phosphate. Electrical conductivity measurements were carried out and the Arrhenius plot is used to determine the value of activation energy. The Kurtz powder analysis on the crystal confirms the existence of second harmonic generation properties. The SHG efficiency was found to be 1.15 times that of KDP crystal.     

A study of shallow water waves with Gardner’s equation

In this paper the dynamics of solitary waves governed by Gardner’s equation for shallow water waves is studied. The mapping method is employed to carry out the integration of the equation. Subsequently, the perturbed Gardner equation is studied, and the fixed point of the soliton width is obtained. This fixed point is then classified. The integration of the perturbed Gardner equation is also carried out with the aid of He’s semi-inverse variational principle. Finally, Gardner’s equation with full nonlinearity is solved with the aid of the solitary wave ansatz method.     

Polarized naphthalimide CH donors enhance Cl- binding within an aryl-triazole receptor

The dipolar character of 1,8-naphthalimide together with polarization of the C(4)-H and C(5)-H donors has been utilized in receptor 1 to effectively bind chloride alongside triazole and phenylene units. The Cl(-) binding strength of 1 shows that the naphthalimide provides greater anion stabilization than an unactivated phenylene, and DFT calculations show that its collinear donor array can be a "urea-like" analog for CH···anion interactions.     

PAA-derived gold nanorods for cellular targeting and photothermal therapy

A single-step LbL procedure to functionalize CTAB-capped GNRs via electrostatic self-assembly is reported. This approach allows for consistent biomolecule/GNR coupling using standard carboxyl-amine conjugation chemistry. The focus is on cancer-targeting biomolecule/GNR conjugates and selective photothermal destruction of cancer cells by GNR-mediated hyperthermia and NIR light. GNRs were conjugated to a single-chain antibody selective for colorectal carcinoma cells and used as probes to demonstrate photothermal therapy. Selective targeting and GNR uptake in antigen-expressing SW 1222 cells were observed using fluorescence microscopy. Selective photothermal therapy is demonstrated using SW 1222 cells, where >62% cell death was observed after cells are treated with targeted A33scFv-GNRs.     

Quantum chemical studies on the conformational behaviour of substituted banana‐shaped mesogens with a central 1,3‐phenylene unit

Ab initio and DFT calculations on the HF/STO‐3G and B3LYP/6‐31G(d) level were performed on the conformational behaviour of isolated banana‐shaped molecules of 1,3‐phenylene bis[4‐(4‐n‐hexyloxyphenyliminomethyl)benzoate] systems (P‐6‐O‐PIMB). The influence of small substituents in both the central phenyl ring and the external phenyl rings on the shape, polarity and flexibility of these molecules was investigated by one‐ and two‐fold relaxed potential energy scans in a systematic way. The effect of substituents on the global polarity of banana‐shaped mesogens was analysed by the magnitude and direction of the dipole moment and its components in relation to the long axis of the molecules. Moreover, a simple model for the calculation of the bending angle was tested for banana‐shaped molecules with a central 1,3‐phenylene unit. The findings for the isolated banana‐shaped molecules are correlated with solid state X‐ray and liquid crystalline state NMR results. Banana‐shaped molecules with both hexyloxy (P‐6‐O‐PIMB) and hexyl (P‐6‐PIMB) terminal chains are included to study the effect of substituents in the external phenyl rings on the flexibility of these chains. An attempt will be made to correlate the results with experimental findings on banana‐shaped mesogens.