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991.
Travasso RD Buxton GA Kuksenok O Good K Balazs AC 《The Journal of chemical physics》2005,122(19):194906
Through a combination of simulation techniques, we determine both the structural evolution and mechanical properties of blends formed from immiscible ternary mixtures. In this approach, we first use the lattice Boltzmann method to simulate the phase separation dynamics of A/B/C fluid mixtures for varying compositions within the spinodal region. We also investigate the effect of an imposed shear on the phase ordering of the mixture. We assume that the fluid is quenched sufficiently rapidly that the phase-separated structure is preserved in the resultant solid. Then, the output from our morphological studies serves as the input to the lattice spring model, which is used to simulate the elastic response of solids to an applied deformation. These simulations reveal how the local stress and strain fields and the global Young's modulus depend on the composition of the blend and the stiffness of the components. By comparing the results for the sheared and unsheared cases, we can isolate optimal processing conditions for enhancing the mechanical performance of the blends. Overall, the findings provide fundamental insight into the relationship between structure, processing, and properties for heterogeneous materials and can yield guidelines for formulating blends with the desired macroscopic mechanical behavior. 相似文献
992.
Analytic gradient expressions for the spin-conserving and spin-flipping equation-of-motion coupled-cluster models with single and double substitutions are derived using a Lagrangian approach for the restricted and unrestricted Hartree-Fock references, both for the case of all orbitals being active in correlated calculations and for the frozen core and/or virtual orbitals. Details of the implementation within the Q-CHEM electronic structure package are discussed. The capabilities of the new code are demonstrated by application to cyclobutadiene. 相似文献
993.
Total antioxidant potential (TAP) is usually measured using photometric or fluorometric assays. Preliminary results of a reversed-phase high-performance liquid chromatography--electrochemical detection assay are given. The method is based on the generation of hydroxyl radicals in a Fenton reaction and analysis of the product of their interaction with p-hydroxybenzoic acid (3,4-dihydroxybenzoic acid). The method is applied to estimate the TAP of dopamine. As a result, depending on the concentration, dopamine is pro- or antioxidant. The results are compared with TAP measurements using a standard photometric method. 相似文献
994.
Mucsi Z Szabó A Hermecz I Kucsman A Csizmadia IG 《Journal of the American Chemical Society》2005,127(20):7615-7631
The activation parameters of the pericyclic Meisenheimer rearrangement and a competitive rearrangement of N-propargylmorpholine N-oxide were determined by experimental and computational methods. A number of aprotic and protic solvents of different polarities and hydrogen bond-forming abilities and the roles of electron-pair acceptor additives were investigated. The reaction kinetics were followed by means of NMR. In protic solvents, isotope-labeling experiments revealed a novel inverse secondary kinetic isotope effect (k(H)/k(D) about 0.8) for the rate-determining cyclization step, probably occurring because of a C(sp) --> C(sp(2)) change in hybridization at the reaction center. In molecular computations at the B3LYP/6-31++G(d,p) level of theory, implicit, explicit, and joint explicit-implicit solvent models were used. The explicit-implicit model and molecular dynamic simulations gave the most accurate results. The components of the rate-controlling solvent effect are discussed, and general equations are proposed for accurate prediction of the solvent-dependent activation parameters. 相似文献
995.
Isoelectric focusing (IEF) was used to distinguish 4 freshwater fish species that are sold in the European Union under the generic label of "perch": Perca fluviatilis (European perch), Lates niloticus (Nile perch), Stizostedion lucioperca (European pikeperch), and Morone chrysops x saxatilis (Sunshine bass). These species have different commercial values but are easily interchangeable because they are sold already filleted, in view of the numerous bones of the whole fish. IEF of the water-soluble proteins extracted from fish muscle resulted in species-specific patterns. None of the bands was common to all 4 species. Intraspecies polymorphism was low and did not concern the bands identified as characteristic of the species. 相似文献
996.
Crecelius AC Cornett DS Caprioli RM Williams B Dawant BM Bodenheimer B 《Journal of the American Society for Mass Spectrometry》2005,16(7):1093-1099
We have developed a method to visualize matrix-assisted laser desorption ionization imaging mass spectrometry (MALDI IMS) data aligned with optically determinable tissue structures in three dimensions. Details of the methodology are exemplified using the 3-D reconstruction of myelin basic protein (MBP) in the corpus callosum of a mouse brain. In this procedure, optical images obtained from serial coronal sections are first aligned to each other to reconstruct a surface of the corpus callosum from segmented contours of the aligned images. The MALDI IMS data are then coregistered to the optical images and superimposed into the surface to create the final 3-D visualization. Correlating proteomic data with anatomical structures provides a more comprehensive understanding of healthy and pathological brain functions, and holds promise to be utilized in more complex anatomical arrangements. 相似文献
997.
Alberghina G Cozzolino R Fisichella S Garozzo D Savarino A 《Rapid communications in mass spectrometry : RCM》2005,19(14):2069-2074
The verification of the cDNA-deduced sequence of the high molecular weight glutenin subunit 1Bx7 in Chinese Spring cultivar was achieved by direct matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOFMS) analysis of the tryptic fragments. The published sequence of the 1Bx7 subunit contains 5 Lys and 15 Arg residues but, due to the presence of three Arg-Pro bonds, which are generally resistant to cleavage by trypsin, or cleaved to a very limited extent by trypsin, 19 peptides can be predicted. The identification of the tryptic fragments was achieved by direct MALDI-MS analysis by using three different matrices (DHB, SA and HCCA) in combination with the most compatible sample preparation procedures in order to obtain the maximum sequence coverage. MALDI analysis of the 1Bx7 tryptic digest resulted in the identification of the expected peptides and additional fragments arising from non-specific cleavages; the fragments that were not detected are peptides with low mass (from 147.2 to 317.4), so we obtained a sequence coverage of 98.8%. The results reported here also indicated that the sequence of the 1Bx7 subunit from cv. Chinese Spring is different from the cDNA-deduced sequence reported in the literature; in particular, a possible insertion of the hexapeptide QPGQGQ within the sequence Gln630-Tyr725 was suggested. Finally, it is possible to rule out glycosylation of the 1Bx7 subunit, or any other post-translational modification, to within the detection limits of the method. 相似文献
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