Catalysis of poly(urethane imidine) copolymer formation from amine‐blocked isocyanate and bisphthalide

The catalysis of imidine formation between an amine‐blocked polyurethane prepolymer and bisphthalide was studied with a series of metal alkoxides, phenoxides, and organotin compounds and tertiary amines. The carbon dioxide released during the reaction was followed for monitoring of the reaction. The metal alkoxides and phenoxides catalyzed the imidine formation reaction but did not catalyze the deblocking reaction, whereas the organotin compounds and tertiary amines showed no catalytic activity in the reaction between isocyanate and phthalide. With tin catalysts, the imidine formation reaction depended on the deblocking of the blocked prepolymer, but it was independent of deblocking with amine catalysts. The resultant poly(urethane imidine) copolymers were characterized with Fourier transform infrared, ¹H NMR, ¹³C NMR, gel permeation chromatography, and thermogravimetric analysis techniques. The thermal stability of polyurethane increased significantly with the incorporation of imidine groups. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 4236–4242, 2001     

Aqueous dispersions of polyurethane cationomers: a new approach for hydrophobic modification and crosslinking

Polyurethanes (PUs) containing tertiary nitrogen atoms were synthesised from poly (tetramethylene oxide) glycol, toluene diisocyanate and N-methyl diethanolamine. These polymers were converted into cationomers by quarternising with alkyl bromides of different chain lengths and then dispersed in water. Finally the cationic PU dispersions were further crosslinked with dibromo compounds of different spacer lengths. The effect of percent ionisation, percent crosslinking, chain length of the ioniser and crosslinker on particle size, viscosity and interfacial tension of the dispersions and on the thermal, mechanical and surface tension properties of the dispersion cast films were studied. The hydrophilicity of the polymer is more in the dispersed state than when cast as a film, which exhibited low critical surface tension values. With increase in chain length of the ioniser and the crosslinker, the hydrophobicity of the dispersion cast film increases without appreciable change in the hydrophilicity of the polymer in the dispersed phase, as can be seen from the interfacial tension and critical surface tension values.     

Density functional theoretical studies on photoswitching and charge migration dynamics of thio and selenoureidopeptides

Density functional theoretical calculations have been performed to investigate the changes in electronic structure at ground and excited states of ureidopeptides on substitution with higher chalcogens like sulphur and selenium for oxygen. This replacement results in a reduced preference towards the intramolecular hydrogen bonding interaction, thus linear conformers are found to be stable at both states. Nevertheless, conformational switching observed during this process is mainly due to n to π* transition that leads to the dihedral angle ω change from trans to cis with a rotational barrier of 10 to 17 kcal mol^‐1. The computed barrier is lesser than that reported for oxopeptides (20 kcal mol^‐1). And, the hole migration dynamics after immediate ionization illustrates that the hole originated at ureido end evolves in time (2?4 fs) while the hole generated at the carboxylate end will not evolve as reported for ureidopeptides. The usage of these candidates as photoswitches has also been explored.     

Analysis of arylamine isomers by micellar electrokinetic chromatography

Analysis of carcinogenic substances is a high-priority area. Carcinogenic arylamines draw the analyst's attention because dyes and pigments are in production and used in large volumes. Identification of carcinogenic isomers of arylamines employing micellar electrokinetic chromatography (MEKC), a mode of capillary electrophoresis was studied as it offers better scope for separation science. Mixed micellar modes of MEKC techniques were employed to achieve acceptable analyses. Success of this analytical method was proved by real-sample analysis, which confirmed that this is a promising technique for the arylamine species.     

Cosmology from MAXIMA-1, BOOMERANG, and COBE DMR cosmic microwave background observations

Recent results from BOOMERANG-98 and MAXIMA-1, taken together with COBE DMR, provide consistent and high signal-to-noise measurements of the cosmic microwave background power spectrum at spherical harmonic multipole bands over 2相似文献   

Simultaneous determination of arsenite and arsenate in arsenic trioxide injection by dual detection ion chromatography

This paper describes a rapid method to determine arsenite assay and arsenate impurity in Arsenic Trioxide Injection using a single conductivity detector. The arsenite assay was determined in a non-suppressed conductivity detection mode and arsenate impurity was quantified in a suppressed conductivity detection mode. Dual-conductivity detections were enabled by valve switching and time programming. The method was validated with respect to specificity, linearity, precision, accuracy, stability, and limit of quantification. The limit of detection and quantification for arsenite were 0.855 mg/L and 2.593 mg/L, and 0.044 mg/L and 0.133 mg/L for arsenate, respectively.     

Computational studies on structural and excited-state properties of modified chlorophyll f with various axial ligands

Time-dependent density functional theory (TDDFT) calculations have been used to understand the excited-state properties of modified chlorophyll f (Chlide f), Chlide a, Chlide b, and axial ligated (with imidazole, H(2)O, CH(3)OH, CH(3)COOH, C(6)H(5)OH) Chlide f molecules. The computed differences among the Q(x), Q(y), B(x), and B(y) band absorbance wavelengths of Chlide a, b, and f molecules are found to be comparable with the experimentally observed shifts for these bands in chlorophyll a (chl a), chl b, and chl f molecules. Our computations provide evidence that the red shift in the Q(y) band of chl f is due to the extended delocalization of macrocycle chlorin ring because of the presence of the -CHO group. The local contribution from the -CHO substituent to the macrocycle chlorin ring stabilizes the corresponding molecular orbitals (lowest unoccupied molecular orbital (LUMO) of the Chlide f and LUMO-1 of the Chlide b). All the absorption bands of Chlide f shift to higher wavelengths on the addition of axial ligands. Computed redox potentials show that, among the axial ligated Chlide f molecules, Chlide f-imidazole acts as a good electron donor and Chlide f-CH(3)COOH acts as a good electron acceptor.     

Synthesis and Characterization of Thermotropic Liquid Crystalline Polyesters

Abstract

Synthesis and characterization of polyesters of 4,4′-dihydroxy biphenyl with succinic, adipic, suberic and sebacic acids were carried out. Initially the diacids were converted to the corresponding acid chlorides in dimethyl formamide (DMF). 4,4′-dihydroxy biphenyl was prepared from 4-hydroxy biphenyl by bromination and subsequent hydrolysis. The low molecular weight polyesters were prepared by the condensation of diacid chlorides with 4,4′-dihydroxy biphenyl in DMF at appropriate temperature. All the polymers were characterized by ¹H NMR, FT-IR, DSC and hot stage polarizing microscope. Thermotropic liquid crystalline behaviour was established by high temperature X-ray (HTXRD) at various temperature intervals. It was found that among the four compounds prepared, three of them showed nematic phase liquid crystallinity with the exception of the ester of succinic acid.     

Thermophysical and Spectroscopic Studies of Pure 1-Butyl-3-methylimidazolium Tetrafluoroborate and Its Aqueous Mixtures

Intermolecular interactions in the aqueous mixtures of the room temperature ionic liquid, 1-butyl-3-methylimidazolium tetrafluoroborate ([BMIM][BF₄]), have been studied. The thermophysical properties: density ρ, speed of sound u, specific conductivity κ and refractive index n _D have been measured over the whole composition range at different temperatures (293.15–323.15 K) and are discussed. The results from thermophysical measurements are explained with the help of spectroscopy. In order to interpret the nature of molecular interactions occurring between [BMIM][BF₄] and water molecules, as well as to identify the moieties in which interactions are taking place, ¹H, ¹³C NMR and FT-IR spectra of the solutions have been studied. Excess molar volume V ^E, excess molar isentropic compressibility $ K_{S}^{\text{E}} $ , partial molar excess volume $ V_{i}^{\text{E}} $ , partial molar excess isentropic compressibility $ K_{S,i}^{\text{E}} $ , deviation in specific conductivity ?κ, and deviation in refractive index ?R have also been determined and analyzed to have a better understanding of the interactions taking place between the different components. Additionally, the excess ultrasonic speed u ^E and excess isentropic compressibility $ k_{S}^{\text{E}} $ , in terms of volume fractions, have been calculated and analyzed. It has been observed that temperature has a significant effect on the thermophysical properties of the studied system. Spectroscopic measurements confirm the disruption of ion-pair interactions of [BMIM][BF₄] and hydrogen-bonded network of water in the aqueous mixture of [BMIM][BF₄].     

Novel AB crosslinked polymer networks from telechelic 4‐vinylbenzyl carbamate terminated polyurethanes and different vinyl monomers

Novel AB crosslinked polymer (ABCP) networks were synthesized from telechelic 4‐vinylbenzyl carbamate terminated polyurethanes and monomers such as styrene, 4‐vinylpyridine, methyl methacrylate and butyl acrylate. Telechelic 4‐vinylbenzyl carbamate terminated polyurethanes were synthesized from polypropylene glycol‐based NCO‐terminated polyurethane and vinylbenzyl alcohol. Effect of changing the molecular weight of polypropylene glycol on the static and dynamic mechanical properties of ABCP networks from polyurethane‐polymethyl methacrylate was studied in detail. Dynamic mechanical thermal analysis results show that polymethyl methacrylate and polystyrene‐based ABCPs have good damping over a broad temperature range. ABCP networks prepared from 4‐vinylbenzyl carbamate terminated polyurethane and different monomers such as methyl methacrylate, butyl acrylate and styrene exhibit single tan δ_max value which implies excellent interlocking between the two polymers present in the ABCP networks. Static mechanical studies showed that methyl methacrylate and styrene‐based ABCP networks exhibit better tensile properties compared to other ABCP networks from butyl acrylate and 4‐vinyl pyridine monomers. Thermogravimetric analysis results revealed that the ABCP networks showed an improved thermal stability. Copyright © 2009 John Wiley & Sons, Ltd.