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81.
82.
The 3D‐structure of extracellular matrix glycosaminoglycans is central to function, but is currently poorly understood. Resolving this will provide insight into their heterogeneous biological roles and help to realize their significant therapeutic potential. Glycosaminoglycan chemical isoforms are too numerous to study experimentally and simulation provides a tractable alternative. However, best practice for accurate calculation of glycosaminoglycan 3D‐structure within biologically relevant nanosecond timescales is uncertain. Here, we evaluate the ability of three potentials to reproduce experimentally observed glycosaminoglycan monosaccharide puckering, disaccharide 3D‐conformation, and characteristic solvent interactions. Temporal dynamics of unsulfated chondroitin, chondroitin‐4‐sulfate, and hyaluronan β(1→3) disaccharides were simulated within TIP3P explicit solvent unrestrained for 20 ns using the GLYCAM06 force‐field and two semi‐empirical quantum mechanics methods, PM3‐CARB1 and SCC‐DFTB‐D (both within a hybrid QM/MM formalism). Comparison of calculated and experimental properties (vicinal couplings, nuclear Overhauser enhancements, and glycosidic linkage geometries) showed that the carbohydrate‐specific parameterization of PM3‐CARB1 imparted quantifiable benefits on monosaccharide puckering and that the SCC‐DFTB‐D method (including an empirical correction for dispersion) best modeled the effects of hexosamine 4‐sulfation. However, paradoxically, the most approximate approach (GLYCAM06/TIP3P) was the best at predicting monosaccharide puckering, 3D‐conformation, and solvent interactions. Our data contribute to the debate and emerging consensus on the relative performance of these levels of theory for biological molecules. © 2010 Wiley Periodicals, Inc. J Comput Chem, 2010 相似文献
83.
Hsiao-Fang Lee Benedict A. Samuel M. A. Haque 《Journal of Thermal Analysis and Calorimetry》2010,99(2):495-500
We present a new analytical model for thermal conductivity measurement of one-dimensional nanostructures on substrates. The
model expands the capability of the conventional 3ω technique, to make it versatile with both in and out of plane thermal
conductivity measurement on specimens either freestanding or attached to substrates. We demonstrate the model on both conducting
(aluminum) and semi-conducting (focused ion beam deposited platinum) specimens. The agreement with the established values
in the literature suggests the superiority of this technique in terms of convenience and robustness of measurement. 相似文献
84.
Summary A detection scheme based upon peroxyoxalate chemiluminescence, which utilizes two post-column pumps and two stages of depressurization is investigated. The chemiluminescent detection limit for perylene is 23 times lower than determined by fluorescence, and is in the attomole range. This detection technique is investigated for packed column supercritical fluid chromatography (SFC). Due to the interface design used and the chemical band narrowing effects of chemiluminescence, an apparent increase in efficiency is observed. The interface design affords a wide range of pressures to be used for a separation. During pressure programming the column effluent changes flow rate. Because of a back-pressure regulator, the reaction and detection take place at nearly constant pressure. Therefore pressure gradient work is possible without concern for post-column reagent solubility (which is a concern for high-performance liquid chromatography). The effects of the expanded CO2 from the SFC on the chemiluminescence signal and background are studied. The post-column detection is optimized for pH, photomultiplier voltage, concentrations and flow rates of the peroxide and oxalate ester. 相似文献
85.
Joyce W. Burrill Benedict R. Bonazza David W. Garrett C.Peter Lillya 《Journal of organometallic chemistry》1976,104(3):C37-C40
ψ-Endo to ψ-exo leakage during solvolysis of a ψ-endo-dienol—Fe(CO)3 dinitrobenzoate ester does not proceed via a syn, syn-cis-dienyl—Fe(CO)3 cation. The most probable leakage mechanism involves non-stereospecific ionization of the dinitrobenzoate ester. syn,syn-cis-Dienyl—Fe(CO)3 cations are formed from ψ-exo-dienol—Fe(CO)3 complex during chromatography on grade I neutral alumina. 相似文献
86.
Liao Y Eichinger BE Firestone KA Haller M Luo J Kaminsky W Benedict JB Reid PJ Jen AK Dalton LR Robinson BH 《Journal of the American Chemical Society》2005,127(8):2758-2766
A series of novel nonlinear optical (NLO) chromophores 1-4 incorporating the ferrocenyl (Fc) group as an electron donor and 2-dicyanomethylene-3-cyano-4-methyl-2,5-dihydrofuran (TCF) derivatives as electron acceptors are presented. The use of a constant Fc donor and varied acceptors and bridges makes it possible to systematically determine the contribution of the conjugated bridge and the acceptor strength to chromophore nonlinear optical activity. The X-ray crystal structures of all four chromophores allow for the systematic investigation of the structure-property relationship for this class of molecules. For example, the crystal structures reveal that both cyclopentadienyl groups in the ferrocenyl donor contribute to the electron donating ability. The first-order hyperpolarizabilities beta of these chromophores, measured by hyper-Rayleigh scattering (HRS) relative to p-nitroaniline are reported. These beta values are compared to those calculated by density functional theory (DFT). The excellent agreement between the theoretical and experimental beta values demonstrates that a linear relation exists between the hyperpolarizability and the bond length alternation. An electrooptic coefficient, r(33), of approximately 25 pm/V at 1300 nm, for compound 4, incorporated into a polymer matrix, is competitive with organic chromophores. Moreover, this r(33) is more than 30 times larger than the previously reported value for an organometallic chromophore in a poled polymer matrix. This work not only underscores the potential for Fc donor moieties, which have been underutilized, but also demonstrates that experimental characterization and theoretical simulations are now congruent, viable methods for assessing potential performance of NLO materials. 相似文献
87.
Qi Xue Bryan Kit Yue Ng Ho Wing Man Tai-Sing Wu Yun-Liang Soo Molly Mengjung Li Shogo Kawaguchi Kwok Yin Wong Shik Chi Edman Tsang Bolong Huang Tsz Woon Benedict Lo 《Chemical science》2021,13(1):50
Precisely tuning the nuclearity of supported metal nanoclusters is pivotal for designing more superior catalytic systems, but it remains practically challenging. By utilising the chemical and molecular specificity of UiO-66-NH2 (a Zr-based metal–organic framework), we report the controlled synthesis of supported bi- and trinuclear Cu-oxo nanoclusters on the Zr6O4 nodal centres of UiO-66-NH2. We revealed the interplay between the surface structures of the active sites, adsorption configurations, catalytic reactivities and associated reaction energetics of structurally related Cu-based ‘single atoms’ and bi- and trinuclear species over our model photocatalytic formic acid reforming reaction. This work will offer practical insight that fills the critical knowledge gap in the design and engineering of new-generation atomic and nanocluster catalysts. The precise control of the structure and surface sensitivities is important as it can effectively lead to more reactive and selective catalytic systems. The supported bi- and trinuclear Cu-oxo nanoclusters exhibit notably different catalytic properties compared with the mononuclear ‘Cu1’ analogue, which provides critical insight for the engineering of more superior catalytic systems.The controlled synthesis of novel bi- and trinuclear Cu-oxo nanoclusters supported on UiO-66-NH2 that show notably different catalytic properties in the photocatalytic formic acid decomposition reaction is reported. 相似文献
88.
Journal of Chemical Crystallography - The synthesis and structure of a novel ortho-fluoroazobenzene, methyl 4-bromo-3-((2,6-difluorophenyl)diazenyl) benzoate is described. The title molecule... 相似文献
89.
Benedict H. Gross 《Israel Journal of Mathematics》1999,113(1):61-93
In this paper, we develop an algebraic theory of modular forms, for connected, reductive groupsG overQ with the property that every arithmetic subgroup Γ ofG(Q) is finite. This theory includes our previous work [15] on semi-simple groupsG withG(R) compact, as well as the theory of algebraic Hecke characters for Serre tori [20]. The theory of algebraic modular forms
leads to a workable theory of modular forms (modp), which we hope can be used to parameterize odd modular Galois representations.
The theory developed here was inspired by a letter of Serre to Tate in 1987, which has appeared recently [21]. I want to thank
Serre for sending me a copy of this letter, and for many helpful discussions on the topic. 相似文献
90.
Shanshan Qin Lancang Shui Benedict Osuagwu Nikita Denisov Dr. Alexander B. Tesler Prof. Patrik Schmuki 《ChemistryOpen》2022,11(3):e202200010
Titanium dioxide (TiO2) and, in particular, its anatase polymorph, is widely studied for photocatalytic H2 production. In the present work, we examine the importance of reactive facets of anatase crystallites on the photocatalytic H2 evolution from aqueous methanol solutions. For this, we synthesized anatase TiO2 nanocrystals with a large amount of either {001} facets, that is, nanosheets, or {101} facets, that is, octahedral nanocubes, and examined their photocatalytic H2 evolution and then repeated this procedure with samples where Pt co-catalyst is present on all facets. Octahedral nanocubes with abundant {101} facets produce >4 times more H2 than nanosheets enriched in {001} facets if the reaction is carried out under co-catalyst-free conditions. For samples that carry Pt co-catalyst on both {001} and {101} facets, faceting loses entirely its significance. This demonstrates that the beneficial role of faceting, namely the introduction of {101} facets that act as electron transfer mediator is relevant only for co-catalyst-free TiO2 surfaces. 相似文献