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31.
Robson F. Storey Kent R. Herring Douglas C. Hoffman 《Journal of polymer science. Part A, Polymer chemistry》1991,29(12):1759-1777
Difunctional hydroxy-terminated poly(ε-caprolactone-co-ε-valerolactone) (PCV) oligomers were synthesized by the diol-initiated bulk copolymerization of ε-caprolactone (C) and δ-valerolactone (V). The two homopolymers were semicrystalline, with almost identical melting temperatures; copolymerization significantly lowered the melting point (Tm) compared to either homopolymer. Copolymer melting points were found to decrease with decreasing molecular weight and to be dependent on composition, i.e., the incorporation of a comonomer into either homopolymer resulted in a decrease in Tm, with the maximum decrease occurring at a copolymer composition of about 60 mol % ε-caprolactone. The molar compositions of the copolyesters were determined from 13C-NMR spectra. The reactivity ratios of the two monomers (M1 = C, M2 = V) were determined to the r1 = 0.25 and r2 = 0.49. Number average molecular weight (M?n) of the PCV diols was inversely proportional to the initial diol concentration within the studied molecular weight range of 900 to 11,100 g/mol. Crosslinked polyurethane networks were prepared by reacting PCV diols with triphenylmethane triisocyanate. Network characterization included determination of sol content by solvent extraction, glass transition (Tg) and Tm by DSC, and tensile properties by stress-strain measurements. Completely amorphous networks resulted from PCV diols of M?n ≤ 2,400; semicrystalline networks resulted from PCV diols of M?n ≥ 3,600. 相似文献
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The membrane fluidity of erythrocytes from patients with Lecithin: cholesterol acyltransferase (LCAT) deficiency was studied by means of electron spin resonance. The temperature dependence of the separation of the outer extrema of the spectra of 2-(3-carboxy-propyl)-4,4-dimethyl, 2-tridecyl-3-oxazolidinyloxyl spin probe was monitored for normal, presumed carrier and clinically affected subjects. The temperature profile of controls was significantly different from that of the presumed carriers and the clinically affected individuals. The results show that the compositional abnormalities previously noted in erythrocyte membranes from patients with LCAT deficiency are associated with alterations in the physiocochemical state of the membrane. An investigation of the spectral lineshapes below 10 degrees C allowed a distinction to be made at the membrane level between clinically affected subjects and clinically normal heterozygous carriers. Alterations in the temperature dependence of elec-ron spin resonance parameters may provide a sensitive index of red cell membrane alterations in pathological states of generalized membrane involvement. 相似文献
34.
Ion transport properties of mechanically stable symmetric ABCBA pentablock copolymers with quaternary ammonium functionalized midblock
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Tsung‐Han Tsai Di Zeng Melissa A. Vandiver Ahmet Kusoglu Soenke Seifert Ryan C. Hayward Adam Z. Weber Andrew M. Herring E. Bryan Coughlin Matthew W. Liberatore 《Journal of Polymer Science.Polymer Physics》2017,55(7):612-622
Anion exchange membranes (AEMs) are a promising class of materials for applications that require selective ion transport, such as fuel cells, water purification, and electrolysis devices. Studies of structure–morphology–property relationships of ion‐exchange membranes revealed that block copolymers exhibit improved ion conductivity and mechanical properties due to their microphase‐separated morphologies with well‐defined ionic domains. While most studies focused on symmetric diblock or triblock copolymers, here, the first example of a midblock quaternized pentablock AEM is presented. A symmetric ABCBA pentablock copolymer was functionalized to obtain a midblock brominated polymer. Solution cast films were then quaternized to obtain AEMs with resulting ion exchange capacities (IEC) ranging from 0.4 to 0.9 mmol/g. Despite the relatively low IEC, the polymers were highly conductive (up to 60 mS/cm Br? at 90 °C and 95%RH) with low water absorption (<25 wt %) and maintained adequate mechanical properties in both dry and hydrated conditions. X‐ray scattering and transmission electron microscopy (TEM) revealed formation of cylindrical non‐ionic domains in a connected ionic phase. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55 , 612–622 相似文献
35.
Tsung-Han Tsai Ashley M. Maes Melissa A. Vandiver Craig Versek Sönke Seifert Mark Tuominen Matthew W. Liberatore Andrew M. Herring E. Bryan Coughlin 《Journal of polymer science. Part A, Polymer chemistry》2013,51(24):1751-1760
Block copolymers of polystyrene-b-poly(vinyl benzyl trimethylammonium tetrafluoroborate) (PS-b-[PVBTMA][BF4]) were synthesized by sequential monomer addition using atom transfer radical polymerization. Membranes of the block copolymers were prepared by drop casting from dimethylformamide. Initial evaluation of the microphase separation in these PS-b-[PVBTMA][BF4] materials via SAXS revealed the formation of spherical, cylindrical, and lamellar morphologies. Block copolymers of polystyrene-b-poly(vinyl benzyl trimethylammonium hydroxide) (PS-b-[PVBTMA][OH]) were prepared as polymeric alkaline anion exchange membranes materials by ion exchange from PS-b-[PVBTMA][BF4] with hydroxide in order to investigate the relationship between morphology and ionic conductivity. Studies of humidity [relative humidity (RH)]-dependent conductivity at 80 °C showed that the conductivity increases with increasing humidity. Moreover, the investigation of the temperature-dependent conductivity at RH = 50, 70, and 90% showed a significant effect of grain boundaries in the membranes against the formation of continuous conductive channels, which is an important requirement for achieving high ion conductivity. © 2012 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2013, 51, 1751–1760, 2013 相似文献
36.
Zhe-Yi Hu Robert B. Parker Vanessa L. Herring S. Casey Laizure 《Analytical and bioanalytical chemistry》2013,405(5):1695-1704
Dabigatran etexilate (DABE) is an oral prodrug that is rapidly converted by esterases to dabigatran (DAB), a direct inhibitor of thrombin. To elucidate the esterase-mediated metabolic pathway of DABE, a high-performance liquid chromatography/mass spectrometry based metabolite identification and semi-quantitative estimation approach was developed. To overcome the poor full-scan sensitivity of conventional triple quadrupole mass spectrometry, precursor–product ion pairs were predicted to search for the potential in vitro metabolites. The detected metabolites were confirmed by the product ion scan. A dilution method was introduced to evaluate the matrix effects on tentatively identified metabolites without chemical standards. Quantitative information on detected metabolites was obtained using “metabolite standards” generated from incubation samples that contain a high concentration of metabolite in combination with a correction factor for mass spectrometry response. Two in vitro metabolites of DABE (M1 and M2) were identified, and quantified by the semi-quantitative estimation approach. It is noteworthy that CES1 converts DABE to M1 while CES2 mediates the conversion of DABE to M2. M1 and M2 were further metabolized to DAB by CES2 and CES1, respectively. The approach presented here provides a solution to a bioanalytical need for fast identification and semi-quantitative estimation of CES metabolites in preclinical samples. Figure
The scheme of the semi-quantitative estimation approach 相似文献
37.
Thompson CM Kovnir K Eveland S Herring MJ Shatruk M 《Chemical communications (Cambridge, England)》2011,47(19):5563-5565
LaCo(2)As(2) can be synthesized as pure crystalline material by annealing a mixture of elements in Bi flux. The reaction, however, is accompanied by the incorporation of a small quantity of Bi into the structure and the formation of vacancies in the Co sublattice, which lead to substantial changes in structural and magnetic properties of the material. 相似文献
38.
N. R. Jagannathan F. G. Herring 《Journal of polymer science. Part A, Polymer chemistry》1987,25(3):897-905
One- and two-dimensional 400-MHz proton NMR experiments are reported for the epoxy resin monomer, triglycidylether of para-aminophenol (TGPAP). Assignment of the epoxy protons becomes difficult due to many overlapping signals from the glycidylamine and glycidylether regions. To solve this problem we employed the homonuclear proton shift-correlated (SUPERCOSY) and J-resolved two-dimensional techniques. The combination of these methods permits the complete elucidation of the complex spectrum. 相似文献
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C.P. Herring 《Physics letters. A》1974,47(2):103-104
The intermediate-mixed state laminar domain structure has been decorated on high purity dished niobium discs at 4.2°K. The Landau-Lifshitz-Sharvin theory is tested and used and the interphase surface energy is estimated at (3.7 ± 0.9) × 10-3 ergs cm-2. 相似文献