Synthesis and spectral studies of cadmium(II) complexes derived from di-2-pyridyl ketone and N-phenylsemicarbazide: First structural report of a cadmium(II) complex of semicarbazone

A new semicarbazone (HL) based on di-2-pyridyl ketone and its three cadmium(II) complexes [CdL(CH₃COO)]₂ · 2CH₃OH (1), Cd(HL)Br₂ (2) and [Cd₂L₂N₃]₂ · H₂O (3) were synthesized and characterized by different physicochemical techniques. The complex, [CdL(CH₃COO)]₂ · 2CH₃OH (1) is having a dimeric structure. In complexes 1 and 3, the ligand moieties are coordinated as monoanionic (L⁻) forms and in complex 2, the ligand is coordinated as neutral (HL) one. The coordination geometry around cadmium(II) in 1 is distorted octahedral, as obtained by X-ray diffraction studies.     

Sum Uncertainty Relations: Uncertainty Regions for Qubits and Qutrits

International Journal of Theoretical Physics - We investigate the notion of uncertainty region using the variance based sum uncertainty relation for qubits and qutrits. We compare uncertainty...     

Desolvation of BSA-ligand complexes measured using the quartz crystal microbalance and dual polarization interferometer

By taking advantage of their unique difference in hydration sensitivity, we have shown that dual polarization interferometer (DPI) and quartz-crystal microbalance with dissipation monitoring (QCM-D) measurements can be used together to explore the degree of desolvation involved in the binding of small drug molecules to an immobilized bovine serum albumin film in real time. Results with DPI and QCM-D show significantly different mass values for three ligands of varying hydrophobicities that may be attributed to changes in the degree of hydration of the ligand-protein complexes in accordance with the physicochemical properties of the ligands. Furthermore, our data suggest that masses measured by QCM-D can be overwhelmed by changes in water content of ligand-protein, binary complexes, which has important consequences for future studies using mechanical resonators to study protein-binding events.     

Substituent-dependent anomeric effects as a source of conformational preference in pyridinium methylides

A systematic density functional theory level investigation of differently substituted pyridinium methylides was carried out to determine the role of C(ylidic) lone-pair-associated hyperconjugative and negative hyperconjugative interactions in deciding conformational preferences. Deviation from the coplanar orientation of the carbanionic center with the pyridine ring and its substituent dependence has been found to correlate well with the relative opportunities for conjugative and negative hyperconjugative interactions of a ylidic moiety with different substituent groups present at the ylidic carbon. The contribution of individual n-->pi* conjugative, n-->sigma* negative hyperconjugative, and sigma-->pi* hyperconjugative interactions in a particular conformation of pyridinium dichlorophosphinomethylides was assessed from donor-acceptor stabilization energies, as obtained from natural bond orbital (NBO) analysis. The relative extent of conjugative and negative hyperconjugative interactions with the substituents present at the ylidic carbon plays an important role in permitting the delocalization of ylidic charge into the pyridine ring, thereby controlling the relative orientation of the latter with the carbanionic plane.     

Effect of Ga incorporation on valence band splitting of OVC CuIn3Se5 thin films

Polycrystalline thin films of CuIn_2.95Ga_0.05Se₅ produced by the incorporation of Ga into the ordered vacancy compound CuIn₃Se₅ by a two-stage vacuum evaporation process were structurally, compositionally and optically characterized using X-ray diffraction, energy dispersive analysis of X-rays and optical absorbance measurements. From the X-ray diffraction data of the films, the structural parameters like lattice constants, tetragonal deformation, bond lengths and anion displacement were evaluated and their effect on the optical behavior of films was discussed. The Hopfields quasi-cubic model adapted for chalcopyrites with tetragonal deformation was used to elucidate the crystal field and spin orbital splitting parameters in the uppermost valence band of the compound, using the three energy gaps 1.649, 1.718 and 1.92 eV corresponding to the threefold absorption in the fundamental absorption region of the optical spectra of these films. The percentage contributions of Se p and Cu d orbitals to p-d hybridization in this compound were calculated using linear hybridization of orbitals model and the effects of p-d hybridization on the band gaps were studied.     

Facile green strategy for micro/nano structured conducting polyaniline‐clay nanocomposite via template polymerization using amphiphilic dopant, 3‐pentadecyl phenol 4‐sulphonic acid

Novel self‐assembled nano/microstructured conducting PANICN was prepared by in situ intercalative emulsion polymerization of aniline in aqueous dispersion of clay using bifunctional amphiphilic dopant, 3‐pentadecyl phenol‐4‐sulphonic acid (PDPSA) derivable from renewable resource. X‐ray diffraction and scanning electron microscopy (SEM) studies revealed the formation of monolayer of protonated PANI intercalated nanoclays with template polymerized self‐assembled micro/nanostructured protonated PANI. Nano/micro structured PANIs were formed by the supra molecular self‐assembling of the inter‐chain hydrogen bonding, inter‐plane phenyl stacking and electrostatic layer by layer self‐assembling (ELBS) between polarized alkyl chains present dopant anions and were manifested using fourier transform infra red spectroscopy and differential scanning calorimetry. On the basis of the results, structure‐directing effect of ‘anilinium salt micelle’ was schematically illustrated in this article. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 2664–2673, 2007     

Properties of polystyrene and polymethyl methacrylate copolymers of polyhedral oligomeric silsesquioxanes: A molecular dynamics study

Molecular dynamics simulations were carried out on copolymers of both styrene and methyl methacrylate with polyhedral oligomeric silsesquioxane (POSS) derivatives to identify the origin of the property changes imparted upon the chemical incorporation of POSS. Simulations were carried out on these hybrid copolymers and the parent homopolymers to elucidate the effect of the T₈, T₁₀, and T₁₂ POSS cages. These POSS comonomers were derivatized with a single polymerizable function and 7, 9, and 11 nonpolymerizable hydrocarbon moieties, respectively. Glass transition temperatures (T_g) were computed from specific volume versus temperature plots. The packing of POSS units around the polymer backbone was analyzed via their radial distribution functions. The effect of POSS on polymer motion was analyzed through the mean square displacement function. The improvements in the elastic moduli upon incorporation of POSS were computed by employing the static deformation method. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 234–248, 2006     

A Mathematical Study on Effect of 2-Hydroxyl Ethyl Acrylate on Controlled Drug Diffusion from Smart Hydrogels Based on Poly(acrylamide-co-hydroxy ethyl acrylate-co-acrylic acid)

A series of poly (AM-co-HEA-co-AA) hydrogels have been synthesized and characterized by varying 2-hydroxy ethyl acrylate (HEA) content in the range of 0–16.22% in feed. The swelling ratio of resulting hydrogels was drastically decreased 10 times, i.e., from 101.12 to 9.23 in an almost linear fashion; but the dimensional stability of these hydrogels was increased significantly from 5 to 46 days with increasing HEA content. The hydrogels exhibited Smart nature in varying pH (2–10), temperature (15–65°C), ionic strength of NaCl solution (0.1M-1.5M), and different cation chloride salt solution having same ionic strength (0.1M). The swelling mechanism was shifted from non-Fickian to Fickian (at pH 2–7), super case to non-Fickian (at pH 10) with increasing HEA content. The controlled release of model drug (salicylic acid) from these hydrogels was investigated using early-time, late-time and Etters diffusion models and compared with the experimental data. It was observed that early model doesn't fit, but Etter and late-time model fitted excluding the initial phase. However, it was also observed that with increasing HEA content, the applicability of Etter's model improved, and for 16.22% HEA containing hydrogel Etters model was fitted in the full range, indicating that by varying hydrogel composition, the diffusion characteristics can be altered.     

On the structure of the Phytophthora α1 mating hormone: synthesis and comparison of four candidate stereoisomers

Two two-compound mixtures of candidate structures for the Phytophthora α1 mating hormone have been synthesized. The mixtures were designed to have differing configurations at C3, but proved to be identical. This suggests that epimerization occurred at C3, and comparison with the data for the natural samples suggest that this is also a mixture of isomers.