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41.
August W. Bosse Scott W. Sides Kirill Katsov Carlos J. García-Cervera Glenn H. Fredrickson 《Journal of polymer science. Part A, Polymer chemistry》2006,44(18):2495-2511
In recent years, there has been increased interest in using microphase-separated block copolymer thin films as submicrometer/suboptical masks in next generation semiconductor and magnetic media fabrication. With the goals of removing metastable defects in block copolymer thin film simulations and potentially examining equilibrium defect populations, we report on two new numerical techniques that can be used in field-theoretic computer simulations: (1) a spectral amplitude filter (SF) that encourages the simulation to relax into high symmetry states (representing zero defect states), and (2) different variants of force-biased, partial saddle point Monte Carlo algorithms that allow for barrier crossing toward lower energy defect-free states. Beyond their use for removing defects, the force-biased Monte Carlo algorithms will be seen to provide a promising tool for studying equilibrium defect populations. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 2495–2511, 2006 相似文献
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Given compact Lie groups H⊂G, we study the space of G-invariant metrics on G/H with nonnegative sectional curvature. For an intermediate subgroup K between H and G, we derive conditions under which enlarging the Lie algebra of K maintains nonnegative curvature on G/H. Such an enlarging is possible if (K,H) is a symmetric pair, which yields many new examples of nonnegatively curved homogeneous metrics. We provide other examples
of spaces G/H with unexpectedly large families of nonnegatively curved homogeneous metrics. 相似文献
44.
Ryu DY Lee DJ Kim JK Lavery KA Russell TP Han YS Seong BS Lee CH Thiyagarajan P 《Physical review letters》2003,90(23):235501
The effect of hydrostatic pressure (P) on closed-loop phase behavior of deuterated polystyrene-block-poly(n-pentyl methacrylate) copolymers [dPS-PnPMA] was investigated by using small-angle neutron scattering and birefringence. For P<20.7 bar, dPS-PnPMA exhibited a lower disorder-to-order transition temperature (T(LDOT)) at 175 degrees C, and then an upper order-to-disorder transition temperature (T(UODT)) at 255 degrees C. With increasing pressure both T(LDOT) and T(UODT) were markedly changed, where dT(LDOT)/dP was 725 degrees C/kbar and dT(UODT)/dP was -725 degrees C/kbar. These are consistent with predictions by the Clausius-Clapeyron equation using measured values of the volume and enthalpy changes of both transitions. The large pressure coefficients imply that the closed-loop phase behavior observed for PS-PnPMA is an entropic-driven phase transition. 相似文献
45.
A series of well-characterized outer-sphere electron-transfer agents were used to study the reduction of trichloroethylene (TCE). Through comparison of the final product ratios of cis-dichloroethylene (cDCE) to trans-dichloroethylene (tDCE) of the outer-sphere reductants to that observed for vitamin B12, it was found that an outer-sphere electron-transfer mechanism is not the likely major pathway in the reduction of TCE by B12. The results provide kinetic support for a two-step reduction mechanism by outer-sphere reductants that involves both vinyl radicals and vinyl anions. The results suggest that the [cDCE]:[tDCE] ratio can be used as a diagnostic for the mechanism of TCE reduction. 相似文献
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Peter R. Tentscher Prof. Soren N. Eustis Prof. Kristopher McNeill Prof. J. Samuel Arey 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(34):11216-11223
Sulfonamide antibiotics are an important class of organic micropollutants in the aquatic environment. For several, sulfur dioxide extrusion products have been previously reported upon photochemical or dark oxidation. Using quantum chemical modeling calculations and transient absorption spectroscopy, it is shown that single‐electron oxidation from sulfadiazine produces the corresponding aniline radical cation. Density functional theory calculations indicate that this intermediate can exist in four protonation states. One species exhibits a low barrier for an intramolecular nucleophilic attack at the para position of the oxidized aniline ring, in which a pyrimidine nitrogen acts as a nucleophile. This attack can lead to a rearranged structure, which exhibits the same connectivity as the SO2‐extruded oxidation product that was previously observed in the aquatic environment and characterized by NMR spectroscopy. We report a detailed reaction mechanism for this intramolecular aromatic nucleophilic substitution, and we discuss the possibility of this reaction pathway for other sulfonamide drugs. 相似文献
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Huichang Bi Kristopher W. Krausz Soumen K. Manna Fei Li Caroline H. Johnson Frank J. Gonzalez 《Analytical and bioanalytical chemistry》2013,405(15):5279-5289
In this study, a liquid chromatography mass spectrometry (LC/MS)-based metabolomics protocol was optimized for quenching, harvesting, and extraction of metabolites from the human pancreatic cancer cell line Panc-1. Trypsin/ethylenediaminetetraacetic acid (EDTA) treatment and cell scraping in water were compared for sample harvesting. Four different extraction methods were compared to investigate the efficiency of intracellular metabolite extraction, including pure acetonitrile, methanol, methanol/chloroform/H2O, and methanol/chloroform/acetonitrile. The separation efficiencies of hydrophilic interaction chromatography (HILIC) and reversed-phase liquid chromatography (RPLC) with UPLC-QTOF-MS were also evaluated. Global metabolomics profiles were compared; the number of total detected features and the recovery and relative extraction efficiencies of target metabolites were assessed. Trypsin/EDTA treatment caused substantial metabolite leakage proving it inadequate for metabolomics studies. Direct scraping after flash quenching with liquid nitrogen was chosen to harvest Panc-1 cells which allowed for samples to be stored before extraction. Methanol/chloroform/H2O was chosen as the optimal extraction solvent to recover the highest number of intracellular features with the best reproducibility. HILIC had better resolution for intracellular metabolites of Panc-1 cells. This optimized method therefore provides high sensitivity and reproducibility for a variety of cellular metabolites and can be applicable to further LC/MS-based global metabolomics study on Panc-1 cell lines and possibly other cancer cell lines with similar chemical and physical properties. Figure
Optimized harvesting, extraction and analytical protocols for cell metabolomics analysis. 相似文献