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81.
Rados?aw Kamiński Timothy Graber Jason B. Benedict Robert Henning Yu‐Sheng Chen Stephan Scheins Marc Messerschmidt Philip Coppens 《Journal of synchrotron radiation》2010,17(4):479-485
The accuracy that can be achieved in single‐pulse pump‐probe Laue experiments is discussed. It is shown that with careful tuning of the experimental conditions a reproducibility of the intensity ratios of equivalent intensities obtained in different measurements of 3–4% can be achieved. The single‐pulse experiments maximize the time resolution that can be achieved and, unlike stroboscopic techniques in which the pump‐probe cycle is rapidly repeated, minimize the temperature increase due to the laser exposure of the sample. 相似文献
82.
Reynolds BJ Ruegg ML Mates TE Radke CJ Balsara NP 《Langmuir : the ACS journal of surfaces and colloids》2006,22(22):9192-9200
Dynamics of adsorption and desorption of a diblock copolymer to an interface between two homopolymers was measured using dynamic secondary-ion mass spectrometry (SIMS). Thin films were constructed consisting of a layer of saturated polybutadiene with 90% 1,2-addition (sPB90), followed by a layer of saturated polybutadiene with 63% 1,2-addition (sPB63), and finally by another layer of the sPB90 homopolymer. A sPB90-sPB63 diblock copolymer was initially included only in the top sPB90 layer of the film at a volume fraction of 0.05. The thin films were annealed at ambient temperature for times ranging between 0.2 and 108 h, and the concentration profiles of the diblock copolymer through the films were measured using SIMS. The dynamics of adsorption and desorption of the diblock copolymer at the two sPB90-sPB63 interfaces was gauged by comparing the different transient concentration profiles. The sorption process was modeled as diffusion in an external field, generated from self-consistent field theory (SCFT). All parameters for the model were determined independently. Although the model neglects the dynamics of conformational change, experimental results matched theory very well. 相似文献
83.
Kitagawa T Dey A Lugo-Mas P Benedict JB Kaminsky W Solomon E Kovacs JA 《Journal of the American Chemical Society》2006,128(45):14448-14449
Superoxide reductases (SORs) are cysteine-ligated, non-heme iron enzymes that reduce toxic superoxide radicals (O2-). The functional role of the trans cysteinate, as well as the mechanism by which SOR reduces O2-, is unknown. Herein is described a rare example of a functional metalloenzyme analogue, which catalytically reduces superoxide in a proton-dependent mechanism, via a trans thiolate-ligated iron-peroxo intermediate, the first example of its type. Acetic-acid-promoted H2O2 release, followed by Cp2Co reduction, regenerates the active Fe(II) catalyst. The thiolate ligand and its trans positioning relative to the substrate are shown to contribute significantly to the catalyst's function, by lowering the redox potential, changing the spin state, and dramatically lowering the nuFe-O stretching frequency well-below that of any other reported iron-peroxo, while leaving nuO-O high, so as to favor superoxide reduction and Fe-O, as opposed to O-O, bond cleavage. Thus we provide critical insight into the relationship between the SOR structure and its function, as well as important benchmark parameters for characterizing highly unstable thiolate-ligated iron-peroxo intermediates. 相似文献
84.
Bellinazzi M Barbon A Kahr B Benedict JB Brustolon M 《Physical chemistry chemical physics : PCCP》2006,8(3):379-385
Mixed crystals of potassium hydrogen phthalate containing 3,6-diaminoacridine were photoexcited with visible light and the resulting triplet excited states were analyzed by time resolved EPR spectroscopy. Spectra from discrete growth sectors were compared with powders and polycrystalline glasses prepared at various pHs. The data yield the predominant protonation state and orientation of the triplets in each of a pair of growth sectors bounding the positive and negative ends of the polar crystal. 相似文献
85.
86.
87.
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
88.
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
89.
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
90.
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