Synthetic and physicochemical studies of uranium complexes with semicarbazone and hydrazone

Uranyl complexes of two Schiff bases, semicarbazone and hydrazone containing OON donor atoms have been synthesized and characterized on the basis of NMR, IR and electronic spectral studies, conductance, magnetic susceptibility and thermogravimetric data. The 1H NMR spectrum of the semicarbazone complex shows low field signals due to OH, NH and ---CH=N groups at 10.23, 9.31 and 8.17 ppm, respectively. The aromatic protons appear in the range 7.74–7.40 ppm. On complexation with U(VI) the signals due to OH and NH disappear evidently due to their participation in coordination. The coordination number of the o-vanillin semicarbazone (oVSC) complex is 6 whereas, that of the o-vanillin isonicotinic acid hydrazone (oVINAH) complex is 8, in addition to the two oxygen atoms already bonded to U(VI) in each species. The thermograms show the presence of 3 and 2 water molecules in these complexes, respectively and the IR spectral data also support the above conclusion. Suitable structures have been assigned.

Temperature dependent free energy surface of polymer folding from equilibrium and quench studies

Langevin dynamics simulation studies have been employed to calculate the temperature dependent free energy surface and folding characteristics of a 500 monomer long linear alkane (polyethylene) chain with a realistic interaction potential. Both equilibrium and temperature quench simulation studies have been carried out. Using the shape anisotropy parameter (S) of the folded molecule as the order parameter, we find a weakly first order phase transition between the high-temperature molten globule and low-temperature rodlike crystalline states separated by a small barrier of the order of k(B)T. Near the melting temperature (580 K), we observe an intriguing intermittent fluctuation with pronounced ``1/f noise characteristics'' between these two states with large difference in shape and structure. We have also studied the possibilities of different pathways of folding to states much below the melting point. At 300 K starting from the all-trans linear configuration, the chain folds stepwise into a very regular fourfold crystallite with very high shape anisotropy. Whereas, when quenched from a high temperature (900 K) random coil regime, we identify a two step transition from the random coiled state to a molten globulelike state and, further, to a anisotropic rodlike state. The trajectory reveals an interesting coupling between the two order parameters, namely, radius of gyration (R-g) and the shape anisotropy parameter (S). The rodlike final state of the quench trajectory is characterized by lower shape anisotropy parameter and significantly larger number of gauche defects as compared to the final state obtained through equilibrium simulation starting from all-trans linear chain. The quench study shows indication of a nucleationlike pathway from the molten globule to the rodlike state involving an underlying rugged energy landscape. (C) 2010 American Institute of Physics. doi:10.1063/1.3509398]

Basic and translational studies on species B adenoviruses

Human adenoviruses (Ads) have been classified into six species (A to F) currently containing 55 serotypes. For almost 2 decades vectors derived from group C serotype Ad5 have been extensively used for gene transfer studies. These Ad5 based vectors are able to efficiently infect many mammalian cell types (including both mitotic and post-mitotic cells) through interaction with a primary attachment receptor, the coxsackie and adenovirus receptor (CAR). Despite the many advantages of Ad5 based vectors a number of limitations have affected their therapeutic application to many diseases. Although they can transduce many tissue types, Ad5 based vectors are unable to efficiently transduce several potential disease target cell types, including hematopoietic stem cells and malignant tumor cells. Therefore, newer vectors have been developed based on Ad serotypes other than Ad5. This thesis focuses on species B Ads. Species B Ads are comprised of three groups based on their receptor usage. Group 1 of species B Ads (Ad16, 21, 35, 50) nearly exclusively utilize CD46 as a receptor; Group 2 (Ad3, Ad7, 14) share a common, unidentified receptor/s, which is not CD46 and which was tentatively named receptor X; Group 3 (Ad11) preferentially interacts with CD46, but also utilizes receptor X if CD46 is blocked. Species B group Ads are important human pathogens. Species B group 2 serotypes are isolated from patients with respiratory tract infections, whereas the Group 1 viruses are described as causing kidney and urinary tract infections. B-group Ad infections often occur in immunocompromised patients, including AIDS patients, recipients of bone marrow transplants, or chemotherapy patients. Recent studies performed in U.S. military training facilities indicate an emergence of diverse species B serotypes at the majority of sites. This included the group 1 serotype 21 and the group 2 serotypes 3, 7, and 14. CD46-targeting vectors derived from Ad35 and Ad11 are important tools for in vitro gene transfer into human stem cells, including hematopoietic stem cells and induced pluripotent stem cells. Ad35 and Ad11 have been used as tools for cancer therapy, because CD46 appears to be uniformely overexpressed on many cancers. Furthermore, receptor X-targeting vectors, i.e vectors derived from Ad3 or vectors containing Ad3 fibers have shown superior in the transduction of tumor cells both in vitro and in vivo and are currently being used clinically in cancer patients. While extensive basic virology studies have been done on Ad5, the information of species B group 1 interaction with CD46 is limited. Furthermore, the receptor for a major subgroup of species B Ads (receptor X) is unknown. The goal of this thesis was it therefore to better understand virological and translational aspects of species B Ads. The specific findings described in this thesis include i) the identification of CD46 binding sites within the Ad35 fiber knob, ii) the study of the in vitro and in vivo properties of Ad vectors with increased affinity to CD46. iii) the study of the receptor usage of a newly emergent Ad14a, iv) the identification of desmoglein 2 as the receptor for Ad3, Ad7, Ad11, and Ad14, v) the delineation of structural details of Ad3 virus interaction with DSG2, and vi) the analysis of functional consequences of Ad3-DSG2 interaction. As a result of these basic virology studies two Ad-derived recombinant proteins have been generated that can be used to enhance cancer therapy by monoclonal antibodies.

Chemical toughening of epoxies. II. Mechanical, thermal, and microscopic studies of epoxies toughened with hydroxyl-terminated poly(butadiene-co-acrylonitrile)

Diglycidyl ether–bisphenol-A-based epoxies toughened with various levels (0–12%) of chemically reacted liquid rubber, hydroxyl-terminated poly(butadiene-co-acrylonitrile) (HTBN) were studied for some of the mechanical and thermal properties. Although the ultimate tensile strength showed a continuous decrease with increasing rubber content, the toughness as measured by the area under the stress-vs.-strain curve and flexural strength reach a maximum around an optimum rubber concentration of 3% before decreasing. Tensile modulus was found to increase for concentrations below 6%. The glass transition temperature Tg as measured by DTA showed no variation for the toughened formulations. The TGA showed no variations in the pattern of decomposition. The weight losses for the toughened epoxies at elevated temperatures compare well with that of the neat epoxy. Scanning electron microscopy revealed the presence of a dual phase morphology with the spherical rubber particles precipitating out in the cured resin with diameter varying between 0.33 and 6.3 μm. In contrast, a physically blended rubber–epoxy showed much less effect towards toughening with the precipitated rubber particles of much bigger diameter (0.6–21.3 μm).

CD and NMR studies on the aggregation of amphotericin-B in solution

We report in this paper the aggregation properties of amphotericin-B (amp-B) in solution using CD and 1H-NMR techniques. Our results indicate that the preferred structure of amp-B in dimethylsulfoxide is a monomer at low concentrations (10−4M and below) and a stable dimer at higher concentrations (range 5 · 103 M to 10−2M). In a DMSO/ethanol mixture (1:1 (v/v)), the antibiotic is monomeric, irrespective of the concentration within the range studied. We propose a head-to-tail model based on NMR data. An understanding of the head-to-tail dimer, is, we believe important, particularly in view of the recent report wherein it is proposed that the drug inserts into bilayers as head-to-tail oligomers.

Strong metal-support interaction in Ni/TiO2 catalysts: in situ EXAFS and related studies

In situ EXAFS and X-ray diffraction investigations of Ni/TiO2 catalysts show that NiTiO3 is formed as an intermediate during calcination of catalyst precursors prepared by the wet-impregnation method; the intermediate is not formed when ion-exchange method is used for the preparation. On hydrogen reduction, NiTiO3 gives rise to Ni particles dispersed in the TiO2(rutile) matrix. The occurrence of the anatase-rutile transformation of the TiO2 support, the formation and subsequent decomposition/reduction of NiTiO3 as well as the unique interface properties of the Ni particles are all factors of importance in giving rise to metal-support interaction. Active TiO2(anatase) prepared from gel route gives an additional species involving Ni3+.

Structural, mechanical and biocompatibility studies of hydroxyapatite-derived composites toughened by zirconia addition

Hydroxyapatite(OHAp)-based ceramic composites with added ZrO2 have been prepared both by sintering at 1400 °C and by hot isostatic pressing (HIP) at 1450 °C and 140 MPa pressure (argon atmosphere). The development of the crystalline phases and the microstructure of the composites have been examined using X-ray diffraction, electron microscopy, infrared and magic-angle spinning nuclear magnetic resonance (MASNMR) spectroscopic techniques. The fracture toughness and biocompatibility of the composites have also been studied. The effect of the addition of CeO2- and Y2O3-stabilized ZrO2 and of simple monoclinic ZrO2 to the initial physical mixture, on the structure and properties of the resulting composites has been investigated. In most of the sintered or HIP samples, the OHAp decomposes into tricalcium phosphate (β-TCP). CaO, which forms as a product of decomposition, dissolves completely in ZrO2 and stabilizes the latter in its cubic/tetragonal phase. Presence of the β-TCP phase in the product seems to be the result of a structural synergistic effect of hexagonal OHAp. Two structurally distinct orthophosphate groups have been identified in the composites by MASNMR of 31P and attributed to decomposition products of OHAp at higher temperatures. The composites possess high KIC values (2–3 times higher than that of pure OHAp). Decomposition of hydroxyapatite gives rise to differences in microstructure between HIP and simply sintered composites although fracture toughness values are similar in magnitude indicating the presence of several toughening mechanisms. The in vitro SP2-O cell test suggests that these composites possess good biocompatibility. The combination of good biocompatibility, desirable microstructure and easy availability of initial reactants indicates that the simply sintered composite of OHAp and monoclinic ZrO2(ZAP-30) appears to be the most suitable for prosthetic applications.

CoMn2O4 spinel from a MOF: synthesis, structure and magnetic studies

A hydrothermal reaction of Mn(OAc)(2)center dot 4H(2)O, Co(OAc)(2)center dot 4H(2)O and 1,2,4 benzenetricarboxylic acid at 220 degrees C for 24 h gives rise to a mixed metal MOF compound, CoMn2(C6H3(COO)(3))(2)], I. The structure is formed by the connectivity between octahedral CoO6 and trigonal prism MnO6 units connected through their vertices forming a Kagome layer, which are pillared by the trimellitate. Magnetic susceptibility studies on the MOF compound indicate a canted anti-ferromagnetic behavior, due to the large antisymmetric DM interaction between the M2+ ions (M = Mn, Co). Thermal decomposition studies indicate that the MOF compound forms a tetragonal mixed-metal spinel phase, CoMn2O4, with particle sizes in the nano regime at 400 degrees C. The particle size of the CoMn2O4 can be controlled by varying the decomposition temperature of the parent MOF compound. Magnetic studies of the CoMn2O4 compound suggests that the coercivity and the ferrimagnetic ordering temperatures are dependent on the particle size.

Electrical switching and thermal studies on bulk Ge-Te-Bi glasses

Bulk, melt quenched Ge18Te82-xBix glasses (1 <= x <= 4) have been found to exhibit memory type electrical switching behavior, which is in agreement with the lower thermal diffusivity values of Ge-Te-Bi samples. A linear variation in switching voltages (V-th) has been found in these samples with increase in thickness which is consistent with the memory type electrical switching. Also, the switching voltages have been found to decrease with an increase in temperature which happens due to the decrease in the activation energy for crystallization at higher temperatures. Further. V-th of Ge18Te82-xBix glasses have been found to decrease with the increase in Bi content, indicating that in the Ge-Te-Bi system, the resistivity of the additive has a stronger role to play in the composition dependence of V-th, in comparison with the network connectivity and rigidity factors. In addition, the composition dependence of crystallization activation energy has been found to show a decrease with an increase in Bi content, which is consistent with the observed decrease in the switching voltages. X-ray diffraction studies on thermally crystallized samples reveal the presence of hexagonal Te, GeTe, Bi2Te3 phases, suggesting that bismuth is not taking part in network formation to a greater extent, as reflected in the variation of switching voltages with the addition of Bi. SEM studies on switched and un-switched regions of Ge-Te-Bi samples indicate that there are morphological changes in the switched region, which can be attributed to the formation of the crystalline channel between two electrodes during switching. (C) 2010 Elsevier B.V. All rights reserved.

Recognition of Polycyclic Aromatic Hydrocarbons and Their Derivatives by the 1,3-Dinaphthalimide Conjugate of Calix4]arene: Emission, Absorption, Crystal Structures, and Computational Studies

Polycyclic aromatic hydrocarbons (PAHs) are environmental pollutants as well as well-known carcinogens. Therefore, it is important to develop an effective receptor for the detection and quantification of such molecules in solution. In view of this, a 1,3-dinaphthalimide derivative of calix4]arene (L) has been synthesized and characterized, and the structure has been established by single crystal XRD. In the crystal lattice, intermolecular arm-to-arm pi center dot center dot center dot pi overlap dominates and thus L becomes a promising receptor for providing interactions with the aromatic species in solution, which can be monitored by following the changes that occur in its fluorescence and absorption spectra. On the basis of the solution studies carried out with about 17 derivatives of the aromatic guest molecular systems, it may be concluded that the changes that occur in the fluorescence intensity seem to be proportional to the number of aromatic rings present and thus proportional to the extent of pi center dot center dot center dot pi interaction present between the naphthalimide moieties and the aromatic portion of the guest molecule. Though the nonaromatic portion of the guest species affects the fluorescence quenching, the trend is still based on the number of rings present in these. Four guest aldehydes are bound to L with K-ass of 2000-6000 M-1 and their minimum detection limit is in the range of 8-35 mu M. The crystal structure of a naphthaldehyde complex, L.2b, exhibits intermolecular arm-to-arm as well as arm-to-naphthaldehyde pi center dot center dot center dot pi interactions. Molecular dynamics studies of L carried out in the presence of aromatic aldehydes under vacuum as well as in acetonitrile resulted in exhibiting interactions observed in the solid state and hence the changes observed in the fluorescence and absorption spectra are attributable for such interactions. Complex formation has also been delineated through ESI MS studies. Thus L is a promising receptor that can recognize PAHs by providing spectral changes proportional to the aromatic conjugation of the guest and the extent of aromatic pi center dot center dot center dot pi interactions present between L and the guest.

High Yield Room Temperature Synthesis And Spectral Studies Of Tri(Amino)Silanes: (R2n)3SIH

Tri(amino)silanes were prepared by the condensation of trichlorosilane with secondary amines in 1:6 molar ratio. Reactions of trichlorosilane with pyrrolidine, piperidine, hexamethyleneimine, morpholine, N-methylpiperazine and diethylamine afford the tri(amino)silanes in nearly quantitative yields. Their physical and spectroscopic properties are discussed. All these compounds are highly sensitive to moisture and hydrolyse to silica and the respective amine with the evolution of hydrogen. The compounds have been characterised by IR, 1H NMR, [1H]29Si NMR spectroscopic methods and CHN elemental analysis.

Optical absorption and photoluminescence studies of Nd3 doped alkali boro germanate glasses

Optical absorption and photoluminescence studies have been carried out at room temperature in 25 R2O-25 GeO2-49.5 B2O3-0.5 Nd2O3 glass systems, (Composition in mol%, R= Li, Na, K and Rb). Judd Ofelt Intensity parameters and other parameters like Racah (E-1, E-2 and E-3), Slater-Condon-Shortley (F-2, F-4 and F-6) Spin-Orbit Coupling (xi(4f)) and Configuration Interaction (alpha,beta and gamma) for Nd3+ ion in the glass system are calculated. The variation of the 02 parameters are interpreted in terms of the covalency of the RE ion in the glass matrix. Further the hypersensitive transition I-4(9/2) -> (4)G(5/2), (2)G(7/2) is analyzed with respect to the intensity ratio I-L/I-S and is found to be dependent on the type of alkali in the glass matrix. The Photoluminescence studies do not show any appreciable shift in the peak emission wavelength of the F-4(3/2) to I-4(11/2) transition with the change in alkali type. (C) 2010 Elsevier B.V. All rights reserved.

Preparation, Structural, and Electrical Studies of Polyaniline/ZnFe2O4 Nanocomposites

Polyaniline/ZnFe2O4 nanocomposites were synthesized by a simple and inexpensive one-step in situ polymerization method in the presence of ZnFe2O4 nanoparticles. The structural, morphological, and electrical properties of the samples were characterized by wide angle X-ray diffraction (WAXD), Fourier transform infrared (FTIR) spectroscopy, scanning electron microscopy (SEM), and thermogravimetric analysis (TGA). WAXD and SEM revealed the formation of polyaniline/ZnFe2O4 nanocomposites. Infrared spectroscopy indicated that there was some interaction between the ZnFe2O4 nanoparticles and polyaniline. The dc electrical conductivity measurements were carried in the temperature range of 80 to 300 K. With increase in the doping concentration of ZnFe2O4, the conductivity of the nanocomposites found to be decreasing from 5.15 to 0.92 Scm(-1) and the temperature dependent resistivity follows ln rho(T) similar to T-1/2 behavior. The nanocomposites (80 wt % of ZnFe2O4) show a more negative magnetoresistance compared with that of pure polyaniline (PANI). These results suggest that the interaction between the polymer matrix PANI and zinc nanoparticles take place in these nanocomposites. (C) 2011 Wiley Periodicals, Inc. J Appl Polym Sci 120: 2856-2862, 2011

Organometallic chemistry of diphosphazanes. Part IX: Syntheses and spectroscopic studies of molybdenum and tungsten tetracarbonyl complexes of unsymmetrical diphosphazanes

The unsymmetrical diphosphazanes X2PN(Pr(i))PYY'(1a-1h) {X = Ph, YY' = O2 C6H4 (1a) or YY' = O2C12H8 (1b); X = Ph, Y = Ph, Y' = OC6H4Me-4 (1c), OC6H4Br-4 (1d), OC6H3Me2-3,5 (1e), OC5H4N-2 (1f), N2C3HMe2-3,5 (1g) or Cl (1h)} react with [M(CO)4(NHC5H10)2] (M = Mo, W) to yield the cis-chelate complexes [M(CO)4{X2PN(Pr(i)) PYY'}] {M = Mo (2a-2h); M = W (3-f,3-g)}. These complexes have been characterized by H-1, P-31 and C-13 NMR and IR spectroscopic studies.

Pressure-induced band gap reduction, orientational ordering and reversible amorphization in single crystals of C70: Photoluminescence and Raman studies

Photoluminescence and Raman scattering experiments have been carried out on single crystals of C70 up to 31 GPa to investigate the effect of pressure on the optical band gap, vibrational modes and stability of the molecule. The photoluminescence band shifts to lower energies and the pressure dependence of the band maxima yields the hydrostatic deformation potential to be 2.15 eV. The slope changes in the pressure dependence of peak positions and linewidths of the Raman modes associated with the intramolecular vibrations at 1 GPa mark the known face-centred cubic-->rhombohedral orientational ordering transition. The reversible amorphization in C70 at P > 20 GPa has been compared with the irreversible amorphization in C60 at P > 22 GPa in terms of carbon-carbon distance between the neighbouring molecules at the threshold transition pressures, in conjunction with the interplay between the intermolecular and intramolecular interactions.