Synthesis, characterization, thermal degradation, and comparative chain dynamics studies of weak-link polysulfide polymers

Synthesis, spectroscopic and thermal characterization of two new classes of polysulfide polymers: poly[1(phenoxymethyl) ethylene polysulfide] (PPMEP), and poly [1-(phenoxy) ethylene polysulfide] (PPEP) is presented. The direct pyrolysis mass spectrometry (DP-MS) technique, used to study the thermal degradation behavior of these polysulfide polymers, indicated that the polymers underwent degradation through the weak-links scission. The thermal stability of the polysulfide polymers decreased as the ``rank'' (number of sulfur atoms in the polysulfide linkage; n=1, 2, 4) increased. The main-chain flexibility of these polysulfide polymers in terms of their C-13 NMR spinlattice relaxation time (T-1) measurements on the backbone methine (-CH-) and methylene (-CH2-) carbons are reported here for the first time. A comparative study of the solution chain dynamics indicated that it increased as ``rank'' of the polysulfide linkages decreased as well as by introducing side chain spacers such as, ether (-O-) or methyleneoxy (-CH2O-) groups.

Optical, dielectric and morphological studies of sol-gel derived nanocrystalline TiO2 films

Nanocrystalline TiO2 films have been synthesized on glass and silicon substrates by sol-gel technique. The films have been characterized with optical reflectance/transmittance in the wavelength range 300-1000nm and the optical constants (n, k) were estimated by using envelope technique as well as spectroscopic ellipsometry. Morphological studies have been carried Out using atomic force microscope (AFM). Metal-Oxide-Silicon (MOS) capacitor was fabricated using conducting coating on TiO2 film deposited on silicon. The C-V measurements show that the film annealed at 300 degrees C has a dielectric constant of 19.80. The high percentage of transmittance, low surface roughness and high dielectric constant suggests that it can be used as an efficient anti-reflection coating on silicon and other optical coating applications and also as a MOS capacitor.

Solution NMR studies of acetohydroxy acid synthase I: Identification of the sites of inter-subunit interactions using multidimensional NMR methods

The novel multidomain organization in the multimeric Escherichia coli AHAS I (ilvBN) enzyme has been dissected to generate polypeptide fragments. These fragments when cloned, expressed and purified reassemble in the presence of cofactors to yield a catalytically competent enzyme. Structural characterization of AHAS has been impeded due to the fact that the holoenzyme is prone to dissociation leading to heterogeneity in samples. Our approach has enabled the structural characterization using high-resolution nuclear magnetic resonance methods. Near complete sequence specific NMR assignments for backbone H-N, N-15, C-13 alpha and C-13(beta) atoms of the FAD binding domain of ilvB have been obtained on samples isotopically enriched in H-2, C-13 and N-15. The secondary structure determined on the basis of observed C-13(alpha) secondary chemical shifts and sequential NOEs indicates that the secondary structure of the FAD binding domain of E. coli AHAS large Subunit (ilvB) is similar to the structure of this domain in the catalytic subunit of yeast AHAS. Protein-protein interactions involving the regulatory subunit (ilvN) and the domains of the catalytic subunit (ilvB) were studied using circular dichroic and isotope edited solution nuclear magnetic resonance spectroscopic methods. Observed changes in circular dichroic spectra indicate that the regulatory subunit (ilvN) interacts with ilvB alpha and ilvB beta domains of the catalytic subunit and not with the ilvB gamma domain. NMR chemical shift mapping methods show that ilvN binds close to the FAD binding site in ilvB beta and proximal to the intrasubunit ilvB alpha/ilvB beta domain interface. The implication of this interaction on the role of the regulatory subunit oil the activity of the holoenzyme is discussed. NMR studies of the regulatory domains show that these domains are structured in solution. Preliminary evidence for the interaction of ilvN with the metabolic end product of the pathway, viz., valine is also presented.

X-ray crystallographic and NMR studies of pantothenate synthetase provide insights into the mechanism of homotropic inhibition by pantoate

The structural basis for the homotropic inhibition of pantothenate synthetase by the substrate pantoate was investigated by X-ray crystallography and high-resolution NMR spectroscopic methods. The tertiary structure of the dimeric N-terminal domain of Escherichia coli pantothenate synthetase, determined by X-ray crystallography to a resolution of 1.7 Å, showed a second molecule of pantoate bound in the ATP-binding pocket. Pantoate binding to the ATP-binding site induced large changes in structure, mainly for backbone and side chain atoms of residues in the ATP binding HXGH(34–37) motif. Sequence-specific NMR resonance assignments and solution secondary structure of the dimeric N-terminal domain, obtained using samples enriched in 2H, 13C, and 15N, indicated that the secondary structural elements were conserved in solution. Nitrogen-15 edited two-dimensional solution NMR chemical shift mapping experiments revealed that pantoate, at 10 mm, bound at these two independent sites. The solution NMR studies unambiguously demonstrated that ATP stoichiometrically displaced pantoate from the ATP-binding site. All NMR and X-ray studies were conducted at substrate concentrations used for enzymatic characterization of pantothenate synthetase from different sources [Jonczyk R & Genschel U (2006) J Biol Chem 281, 37435–37446]. As pantoate binding to its canonical site is structurally conserved, these results demonstrate that the observed homotropic effects of pantoate on pantothenate biosynthesis are caused by competitive binding of this substrate to the ATP-binding site. The results presented here have implications for the design and development of potential antibacterial and herbicidal agents.

Dielectric anisotropy and relaxation studies of the homologous series of N-(4-n-alkyloxy-2-hydroxy-benzylidene)-4-carbethoxyaniline

Dielectric properties of the homologous series of newly synthesized nonchiral compounds N-(4-n-alkyloxy-2-hydroxy-benzylidene)-4-carbethoxyaniline, (n = 6, 8, 10, 12) having wide temperature range (∼60°C) smectic A (SmA) phase, have been studied by the impedance spectroscopy in the frequency range of 100 Hz to 1 MHz. Measurements have been carried out for two principal alignments (planar as well as homeotropic) of the SmA phase. Dielectric anisotropy (Δε' = ε'∥ - ε'⊥) for all the members of the series has been found to be negative for the whole temperature range of SmA phase. Magnitude of the dielectric anisotropy (|Δε'|) has been found to decrease with the number of alkyl chains. Relaxation frequencies corresponding to the rotation of the individual molecules about their short axes, lie below 1 MHz and obey the Arrhenius law by which activation energies have been determined. However, the relaxation frequencies corresponding to the rotation of the molecules about their short axes apparently lie above 10 MHz.

One-dimensional zig-zag type coordination polymers of Ni(II) and Cu(II) containing 1,3-benzenedicarboxylate and 1,3-diaminopropane: Structural, spectral and thermal studies

Two coordination polymers [Ni(ipt)(dap)(2)](n) (1) and [Cu(ipt)(dap)H2O](n) center dot nH(2)O (2) with an overall one-dimensional arrangement and having isophthalate (ipt) as bridging moieties and chelating 1,3-diaminopropane (dap) as structure modulating units have been prepared and characterized by crystallographic, spectroscopic and thermo-analytical studies. Both have an overall one-dimensional zig-zag nature but with a distorted octahedral NiN4O2 chromophore for 1 and a distorted square pyramidal CuN2O3 chromophore for 2. Even though the ipt units are acting as bridging units through mono-dentatively coordinating carboxylate functions in both polymers, compound 1 has the carboxylate oxygen linkages at the trans positions, while in 2 the oxygen linkages occur at the cis positions leading to a different type of zig-zag arrangement. Relevant spectral and bonding parameters also could be evaluated for the compounds using UV-Vis and EPR spectra. Thermal stability and possible structural modifications on thermal treatment of the compounds were also investigated and the relevant thermodynamic and kinetic parameters evaluated from the thermal data. (C) 2007 Elsevier B.V. All rights reserved.

Supercapacitor studies of electrochemically deposited PEDOT on stainless steel substrate

There has been increasing interest on various properties and applications of electronically conducting polymers. Polyethylenedioxythiophene (PEDOT) is an interesting polymer of this type as it exhibits very high ionic conductivity. In the present study, PEDOT has been electrochemically deposited on stainless steel (SS) substrate for supercapacitor studies. PEDOT/SS electrodes prepared in 0.1M H2SO4 in presence of a surfactant, sodium dodecylsulphate (SDS), have been found to yield higher specific capacitance (SC) than the electrodes prepared from neutral aqueous electrolyte. The effects of concentration of H(2)SO4(,) concentration of SDS, potential of deposition, and nature of supporting electrolytes used for capacitor studies on SC of the PEDOT/SS electrodes have been studied. SC values as high as 250 F/g in 1M oxalic acid have been obtained during the initial stages of cycling. However, there is a rapid decrease in SC on repeated charge-discharge cycling. Spectroscopic data reflect structural changes in PEDOT on extended cycling. (C) 2007 Wiley Periodicals, Inc.

Topography of the combining region of a Thomsen-Friedenreich-antigen-specific lectin jacalin (Artocarpus integrifolia agglutinin). A thermodynamic and circular-dichroism spectroscopic study

Thermodynamic analysis of carbohydrate binding by Artocarpus integrifolia (jackfruit) agglutinin (jacalin) shows that, among monosaccharides, Me alpha GalNAc (methyl-alpha-N-acetylgalactosamine) is the strongest binding ligand. Despite its strong affinity for Me alpha GalNAc and Me alpha Gal, the lectin binds very poorly when Gal and GalNAc are in alpha-linkage with other sugars such as in A- and B-blood-group trisaccharides, Gal alpha 1-3Gal and Gal alpha 1-4Gal. These binding properties are explained by considering the thermodynamic parameters in conjunction with the minimum energy conformations of these sugars. It binds to Gal beta 1-3GalNAc alpha Me with 2800-fold stronger affinity over Gal beta 1-3GalNAc beta Me. It does not bind to asialo-GM1 (monosialoganglioside) oligosaccharide. Moreover, it binds to Gal beta 1-3GalNAc alpha Ser, the authentic T (Thomsen-Friedenreich)-antigen, with about 2.5-fold greater affinity as compared with Gal beta 1-3GalNAc. Asialoglycophorin A was found to be about 169,333 times stronger an inhibitor than Gal beta 1-3GalNAc. The present study thus reveals the exquisite specificity of A. integrifolia lectin for the T-antigen. Appreciable binding of disaccharides Glc beta 1-3GalNAc and GlcNAc beta 1-3Gal and the very poor binding of beta-linked disaccharides, which instead of Gal and GalNAc contain other sugars at the reducing end, underscore the important contribution made by Gal and GalNAc at the reducing end for recognition by the lectin. The ligand-structure-dependent alterations of the c.d. spectrum in the tertiary structural region of the protein allows the placement of various sugar units in the combining region of the lectin. These studies suggest that the primary subsite (subsite A) can accommodate only Gal or GalNAc or alpha-linked Gal or GalNAc, whereas the secondary subsite (subsite B) can associate either with GalNAc beta Me or Gal beta Me. Considering these factors a likely arrangement for various disaccharides in the binding site of the lectin is proposed. Its exquisite specificity for the authentic T-antigen, Gal beta 1-3GalNAc alpha Ser, together with its virtual non-binding to A- and B-blood-group antigens, Gal beta 1-3GalNAc beta Me and asialo-GM1 should make A. integrifolia lectin a valuable probe for monitoring the expression of T-antigen on cell surfaces.

Solution cation-binding properties of segmented polyethylene oxide-A C-13 NMR spectroscopic study

Two segmented polyethylene oxides, SPEO-3 and SPEO-4, were prepared using a novel transetherification methodology. Their structures were confirmed by H-1 and C-13 NMR spectroscopy. The complexation of these SPEO's with alkali-metal ions in solution was investigated by C-13 NMR spectroscopy. The mole-fraction method was used to determine the complexation ratio of SPEO with LIClO4 at 25 degrees C, which showed that these formed 1:1 (polymer repeat unit/salt) complexes. The association constant, K, for the complex formation was calculated from the variation of the chemical shift values with salt concentration, using a standard nonlinear least-square fitting procedure. The maximum change in chemical shift (Delta delta) and the K values suggest that both SPEO-3 and SPEO-4 formed stronger complexes with lithium salts than with sodium salts. Unexpectedly, the K values were found to be different, when the variation of delta of different carbons was used in the fitting procedure. This suggests that several possible complexed species may be in equilibrium with the uncomplexed one. Structurally similar model compounds were also prepared and their complexation studies indicated that all of them also formed 1:1 complexes with Li salts. Interestingly, it was observed that the polymers gave higher K values suggesting the formation of more stable complexes in polymers when compared to the model analogues. (C) 2000 John Wiley & Sons, Inc.

Phase diagram and dielectric studies of binary organic materials

The phase equilibrium studies of organic system, involving resorcinol (R) and p-dimethylaminobenzaldehyde (DMAB), reveal the formation of a 1:1 molecular complex with two eutectics. The heat of mixing, entropy of fusion, roughness parameter, interfacial energy, and the excess thermodynamic functions were calculated based on enthalpy of fusion data determined via differential scanning calorimetric (DSC) method. X-ray powder diffraction studies confirm that the eutectics are not simple mechanical mixture of the components under investigation. The spectroscopic investigations (IR and NMR) suggest the occurrence of hydrogen bonding between the components forming the molecular complex. The dielectric measurements, carried out on hot-pressed addition compound (molecular complex), show higher dielectric constant at 320 K than that of individual components. The microstructural investigations of eutectic and addition compound indicate dendritic and faceted morphological features. (C) 2000 Elsevier Science B.V. All rights reserved.

Spectroscopic, microscopic and first rheological investigations in charge-transfer interaction induced organogels

This article describes two-component charge-transfer interaction mediated organogels (CT-gels) derived from anthracene carboxamides obtained from 2-amino 2-hydroxymethyl-1,3-propanediol (TRIS), and 2,3-dialkoxyanthracenes as donors, with 2,4,7-trinitrofluorenone (TNF) as the common acceptor. We demonstrate the versatility of TNF as an electron acceptor in the formation of these gels. The effect of subtle changes in the donor structure on the gelation ability has been investigated by varying the alkyl chain length in the dialkoxyanthracene donors, and by varying the position of the TRIS substituent in the anthracene carboxamide donors. Distinct differences have been observed in the nature of the CT-gels based on these two kinds of anthracene donors. It has been reported in the literature that 2,3-dialkoxyanthracenes form gels on their own in various aliphatic hydrocarbons and alcohols for linear alkyl chains bearing at least 6mcarbon atoms (C-6). In the present study, it is shown that themCT-complex of these molecules with TNF is able to gel many alcoholic and a few hydrocarbon solvents. Also, in the presence of TNF, the 2,3-dialkoxyanthracenes (C-4-C-5) which were non-gelators on their own at ambient temperatures, form CT-gels in a number of alcohols. The other series of gelators discussed, the anthracene carboxamides, require the mandatory presence of TNF to form gels. This donor-acceptor complex forms gels in various aliphatic alcohols. Interestingly, the formation of these CT-gels requires rapid cooling in most of the cases. Thermal stability studies with both types of CT-gels indicate an optimum stoichiometry of 1 : 1 between the donor and the acceptor. Dynamic rheological experiments reveal these gels as viscoelastic soft materials, with the mechanical strength of these gels depending on the amount of TNF present. This provides a means to tune the strength of the gel by varying the doping concentration of the acceptor.

Syntheses and structural studies of new bicyclic 1,3-diphenyl-1,3,2.lambda.3,4.lambda.3-diazadiphosphetidines

Reactions of cis-[(C6H5N)PC1]z(1 ) with the difunctional reagents HO(CH2)20H,H (CH3)N(CHz)zN(CH3)HH, (CH3)N(CH& OH, and HO(CHz)30Hi n the presence of triethylamine yield the new bicyclic 1,3,2X3,4h3-diazadiphosphetidines[( C6H5- N)PIZ[-O(CHZ)Zo-l (2), [(C6H5N)PlZ[-(CH3)N(CHZ)ZN(CH3)-l (319 [(C6H~N)PlZ~-(CH3)N(cHZ)20 (4), and [(C6H5 N)P],[-Q(CH2),0-] (5), respectively. The products have been characterized by elemental analyses and IR and NMR spectroscopic data. The structures of 4 and 5 have been determined by single-crystal X-ray analysis. Crystal data for 4: monoclinic, P2,/c, a = 9.823 (2) A, b = 8.608 (1) A, c = 18.423 (3) A, i3 = 90.55 (1)O, Z = 4. Crystal data for 5 monoclinic, P2,/c, a = 9.727 (2) A, b = 8.064 (2) A, c = 19.702 (4) A, @ =I 91.31 (l)', 2 = 4. The structures have been solved by direct methods and refined to R = 0.028 for 4 and R = 0.050 for 5. Compound 4 is the first example of an aminoalkoxy-l,3,2X3,4X3-diazadiphosphetidine. The PzNz ring is slightly puckered in both 4 and 5 and the puckering occurs in a manner opposite to that observed for cis-[(RN)PX],structures.

An infrared spectroscopic study of C7 intramolecular hydrogen bonds in peptides

The ir-spectra in the N-H stretching region of Piv-Pro-NHMe and Boc-Pro-NHMe have been studied in carbon tetrachloride and chloroform solutions over a wide range of concentrations. Based on the concentration dependence of the N-H stretching bands, it has been shown that the characteristic N-H stretching band due to the C7 intramolecular hydrogen bond is around 3335 cm-'. Intermolecular hydrogen bonding also occurs to a small extent in these peptides, giving rise to a slight concentration dependence of the N-H stretching bands. The band around 3335 cm-* need not necessarily be due to C7 hydrogen bonds alone as proposed by Tsuboi et al. or to intermolecular hydrogen bonding alone as proposed by Maxfield et al.; this conclusion is supported by studies on Boc-Leu-NHMe, which undergoes only intermolecular hydrogen bonding We have shown that 2-Aib-Aib-OMe and Z-Aib- Ala-OMe form C7 intramolecular hydrogen bonds in addition to C5 intramolecular hydrogen bonds. The present studies also show that all the peptides studied exist in more than one conformation in solution.

Supramolecular Chirality in Organogels: A Detailed Spectroscopic, Morphological, and Rheological Investigation of Gels (and Xerogels) Derived from Alkyl Pyrenyl Urethanes

This Article addresses the formation of chiral supramolecular structures in the organogels derived from chiral organogelator 1R (or 2R), and its mixtures with its enantiomer (1S) and achiral analogue 3 by extensive circular dichroism (CD) spectroscopic measurements. Morphological analysis by atomic force microscopy (AFM) and scanning electron microscopy (SEM) were complemented by the measurements of their bulk properties by thermal stability and rheological studies. Specific molecular recognition events (1/3 vs 2/3) and solvent effects (isooctane vs dodecane) were found to be critical in the formation of chiral aggregates. Theoretical studies were also carried out to understand the interactions responsible for the formation of the superstructures.

A bibliographical review of the high pressure studies of ferroelectric phase transitions

A brief review of the various high pressure studies on the phase transitions in ferroelectric crystals carried out over the past two decades is presented. The theoretical framework in which high pressure studies have to be viewed is given. The pressure data of ferroelectric crystals are organized in the form of tables. High pressure spectroscopic and structural studies are included. The review contains a bibliography of over two hundred references.