Non-aqueous titration of the acidic groups in coals: a warning!

Non-aqueous potentiometric titration using ethylenediamine as a solvent and sodium aminoethoxide as a titrant has been shown to be reliable for the estimation of total acidity only when the substrate is completely dissolved in the solvent.     

Sequencing of N‐vinyl‐2‐pyrrolidone/glycidyl methacrylate copolymers by one‐dimensional and two‐dimensional nuclear magnetic resonance spectroscopy

Copolymers of N‐vinyl‐2‐pyrrolidone (V) and glycidyl methacrylate (G) monomers of different compositions were prepared by free‐radical solution polymerization. The copolymer composition of these copolymers was determined with ¹H‐NMR spectra. The reactivity ratios calculated from the Kelen–Tudos and nonlinear least‐square error‐in‐variable methods were r_V = 0.03 ± 0.01 and r_G = 5.05 ± 0.84 and r_V = 0.02 and r_G = 4.72, respectively. The triad sequence distribution in terms of V and G centered triads was determined from ¹³C{¹H}‐NMR spectroscopy. The complete spectral assignment of ¹³C{¹H}‐ and ¹H‐NMR spectra was performed with the help of distortionless enhancement by polarization transfer and two‐dimensional ¹³C–¹H heteronuclear single quantum coherence. The ¹H–¹H couplings were explained with total correlation spectroscopy and nuclear Overhauser enhancement spectroscopy spectra. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 50–60, 2002; DOI 10.1002/app.10186     

Studies of mechanical and moisture regain properties of methyl methacrylate grafted silk fibers

The mechanical properties such as the tenacity, breaking extension, initial modulus, elastic and work recovery, and stress relaxation behavior of methyl methacrylate (MMA) grafted silk fibers prepared under different conditions were measured and explained in terms of the relative dominance of the stress concentration, reduction in the interchain cohesion, and fiber matrix stiffening at different grafting percentages. The moisture regain characteristics of fibers grafted in the presence of different solvents were also studied and compared. The grafting of MMA on silk was found to improve the recovery properties significantly without affecting the stress relaxation behavior. The moisture regain studies indicate that moisture regain is reduced with increasing length of the grafted poly(MMA) chains. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 969–974, 2002; DOI 10.1002/app.10202     

Natural rubber–ethylene‐propylene‐diene rubber covulcanization: Effect of reinforcing fillers

Filled covulcanizates of elastomer blend comprising natural rubber (NR) and ethylene‐propylene‐diene rubber (EPDM) of commercial importance were successfully prepared by using a multifunctional rubber additive; namely, bis(diisopropyl)thiophosphoryl disulfide (DIPDIS). A Two‐stage vulcanization technique further improved the physicochemical properties of the blend vulcanizates by restricting, through the formation of polar rubber bound intermediates, the migration of curative and filler from lower to highly unsaturated rubber. Scanning electron microscopy studies indicate homogeneity and coherency in the morphology of the two‐stage vulcanizates. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 1001–1010, 2002; DOI 10.1002/app.10361     

Modelling the Effective Thermal Conductivity in Polydispersed Bed Systems: A Unified Approach using the Linear Packing Theory and Unit Cell Model

A comprehensive, unified approach, using the Linear Packing Theory and Unit Cell Model, is proposed for calculating of the effective thermal conductivity of polydispersed packed beds. In this new approach, the effect of packing density is incorporated by the use of (i) an initial porosity to take into account the packing of mono‐sized particles, and (ii) the packing size ratio as a measure of the particle‐particle interaction. The proposed approach was validated with the experimental measurements of binary and ternary beds. This new approach demonstrates that the effective thermal conductivity of beds composed of polydispersed particles can be simulated for any composition without the need to measure the in situ porosity.     

Synthesis and structure-activity relationship of the isoindolinyl benzisoxazolpiperidines as potent,selective, and orally active human dopamine D4 receptor antagonists

A new class of potent dopamine D(4) antagonists was discovered with selectivity over dopamine D(2) and the alpha-1 adrenoceptor. The lead compound was discovered by screening our compound collection. The structure-activity relationships of substituted isoindoline rings and the chirality about the hydroxymethyl side chain were explored. The isoindoline analogues showed modest differences in potency and selectivity. The S enantiomer proved to be the more potent enantiomer at the D(4) receptor. Several analogues with greater than 100-fold selectivity for D(4) over D(2) and the alpha-1 adrenoreceptor were discovered. Several selective analogues were active in vivo upon oral or intraperitoneal administration. A chiral synthesis starting from either D- or L-O-benzylserine is also described.     

Micellar association in simultaneous presence of organic salts/additives

Viscosity measurements under Newtonian flow conditions had been performed on cetyltrimethylammonium bromide (CTAB) aqueous solutions in the combined presence of sodium salts of aromatic acids (sodium salicylate, NaSal; sodium benzoate, NaBen; sodium anthranilate, NaAn) and organic additives (1-hexanol, C₆OH; n-hexylamine, C₆NH₂) at 30°C. On addition of C₆OH or C₆NH₂, the viscosity of 25 mM CTAB solution remained nearly constant without salt as well as with a lower salt concentration. This is due to low CTAB concentration which is not sufficient to produce structural changes in this concentration range of salts. However, as the salt concentration was increased further, the effect of C₆OH/C₆NH₂ addition was different with different salts: The viscosity first increased; then a decrease was observed with the former while with C₆NH₂ a decrease followed by constancy appeared in plots of relative viscosities (η _r ) vs. organic additive concentrations. At further higher salt concentration, the magnitude of η _r was much higher. The viscosity increase is explained in terms of micellar growth and the decrease in terms of swollen micelle formation (due to interior solubilization of organic additive) or micellar disintegration (due to formation of water + additive pseudophase).     

Half-of-the-sites reactivity of F235C {lambda}-repressor: implications for the structure of the whole repressor

A site-directed mutation, F235C, was created at the penultimateresidue of the -repressor. Measurement of dimer–monomerdissociation constant suggested that dimer–monomer dissociationof the mutant repressor is similar to that of the wild-type.Affinity towards a single operator O_R1 is also similar to thatof the wild-type repressor. The mutant repressor gene in a multi-copyplasmid confers immunity towards infection by a cI^- lambda phage,suggesting preservation of functional integrity. Far-UV circulardichroism spectra show no major change in the secondary structure.Fluorescence quenching experiments, however, suggest increasedexposure of some tryptophan residues. The urea denaturationprofile indicates decreased stability of a part of the C-terminaldomain. Under non-denaturing conditions, cysteine-235 showshalf-of-the-sites reactivity, i.e. on average only one out oftwo cysteine-235 residues in the dimer shows reactivity towardssulfhydryl reagents. Fluorescence energy transfer between randomlylabeled donor and acceptor fluorescent probes indicates thatonly one sulfhydryl per dimer is reactive, suggesting true half-of-the-sitesreactivity. The structural role of the C-terminal tail in thewhole repressor dimer is discussed.     

Microwave-Assisted Synthesis of Fine Particle Oxides Employing Wet Redox Mixtures

Interaction of electromagnetic radiation with a physical mixture of metal nitrates and amides/hydrazides is observed to initiate high-temperature reactions, useful for realizing several high-temperature ceramic materials. A judicious choice of such redox mixtures undergoes exothermic reactions when they couple with microwave radiation. The coupling of electromagnetic radiation with metal salts and amides/hydrazides depends on the dielectric properties of the individual components in the reaction mixture. The approach has been used to prepare γ-Fe₂O₃, Fe₃O₄, MgCr₂O₄, α-CaCr₂O₄, and La_0.7Ba_0.3MnO₃.     

Formation of Zinc–Antimony-Based Spinel Phases

Formation of spinel phases in ZnO–Sb₂O₃and ZnO–Sb₂O₃–Bi₂O₃systems is studied by the use of X-ray diffraction. The formation of nonstoichiometric Zn_2.33Sb_0.67O₄phase is observed in both the systems at ∼900°C. However, in these systems, at higher temperatures ( T ≥ 1100°C), formation of the inverse spinel phase Zn₇Sb₂O₁₂is observed. The study has been extended to understand the effect of CrO₃doping on the stability of the different spinel phases in the previously mentioned systems. Interestingly, in both the systems, samples doped with CrO₃, displayed the presence of Zn_2.33Sb_0.67O₄phase <1200°C, indicating the stabilization of the spinel phase by CrO₃.