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921.
Murat Durandurdu 《哲学杂志》2018,98(8):633-645
We generate an amorphous MgCu model using the rapid solidification of the melt through a first-principles molecular dynamics approach within a generalised gradient approximation and reveal, for the first time, its structural features and mechanical properties in details. The liquid and glassy MgCu are found to acquire slightly distinct local structures. Yet in both forms of MgCu, most Cu atoms have a tendency to form the ideal and defective icosahedrons while Mg atoms are arranged in complex configurations. The mean coordination number of Cu and Mg at 300 K is 11.31 and 13.73, respectively. The short-range order of MgCu glass is projected to be different than the known crystalline MgCu and Mg2Cu phases. The mechanical properties of MgCu glass and the CsCl-type MgCu crystal are computed and compared. On the basis of the enthalpy analyses, a possible pressure-induced crystallisation of the MgCu glass into a CsCl-type structure is proposed to occur at around 11 GPa. 相似文献
922.
Hollow materials with different configurations are of interest due to their unique structural features, which induce interesting properties e.g. catalysis. Here, the synthesis of asymmetrical hollow ball‐in‐tube (HBT) structured CeO2 is reported, which is achieved using a dual template engaged solid–liquid interfacial reaction. In this reaction, the SiO2 sphere (hard template)‐embedded Ce(OH)CO3 nanorod (sacrificial template) composite is first treated with NaOH solution, followed by an acid wash to obtain asymmetrical hollow structured CeO2. Such HBT structured CeO2 is demonstrated to be a good support for Au nanoparticles toward CO oxidation as compared to simple hollow CeO2 nanotubes, leading to significantly increase catalytic activity. 相似文献
923.
New insights into water‐soluble and water‐coordinated copper 15‐metallacrown‐5 gadolinium complexes designed for high‐field magnetic resonance imaging applications
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Marina A. Katkova Galina S. Zabrodina Evgeny V. Baranov Maria S. Muravyeva Evgeny A. Kluev Andrey S. Shavyrin Grigory Yu Zhigulin Sergey Yu Ketkov 《应用有机金属化学》2018,32(7)
The development of contrast agents specifically designed for high‐field magnetic resonance imaging (MRI) is required because the relaxation efficiency of classic Gd(III) contrast agents significantly decreases with increasing magnetic field strengths. With an idea of exploring the unique structure of lanthanide (Ln) 15‐MC‐5 metallacrowns, we developed a series of water‐soluble Gd(III) aqua‐complexes, bearing aminohydroxamate (glycine, α‐alanine, α‐phenylalanine and α‐tyrosine) ligands, with increasing number of water molecules directly coordinated to the Gd(III) ion: Gd(H2O)4[15‐MCCu(II)Glyha‐5](Cl)3 ( 1 (Gd)), Gd(H2O)4[15‐MCCu(II)Alaha‐5](Cl)3 ( 2 (Gd)), Gd(H2O)3[15‐MCCu(II)Phalaha‐5](Cl)3 ( 3 (Gd)) and Gd(H2O)3[15‐MCCu(II)Tyrha‐5](Cl)3 ( 4 (Gd)). In these systems, the Ln(III) central ion is coordinated by five oxygen donor atoms of the ligands and three or four inner‐sphere water molecules. The X‐ray crystal structure of metallacrown Ln(H2O)3,4[15‐MCCu(II)Rha‐5]3+ agrees with density functional theory predictions. The calculations demonstrate that the exchange of coordinated water molecules can proceed easily, resulting in increased relaxivity parameters. The longitudinal relaxivities (r1) of 1 (Gd)– 4 (Gd) in water at ultrahigh magnetic field of 9.4 T were determined to be 11.5, 14.8, 13.9 and 12.2 mM?1 s?1, respectively. The ability to increase the number of Ln(III) inner‐sphere water molecules up to four, the planar metallacrown structure and the rich hydration shell due to strong hydrogen bonds between the [15‐MC‐5] moiety and bulk water molecules provide new opportunities for potential MRI applications. 相似文献
924.
925.
Manoj K. Kolel‐Veetil Kenan P. Fears Syed B. Qadri Christopher A. Klug Teddy M. Keller 《Journal of polymer science. Part A, Polymer chemistry》2012,50(15):3158-3170
A semicrystalline inorganic–organic hybrid crosslinked network containing polyhedral oligomeric silsesquioxane (POSS) cores was constructed by the unusual hydrosilylation of the terminal vinyl groups of an internal acetylene‐containing silane linker by a POSS monomer. Products from the thermal treatments of this network in either argon or air at 250, 550, and 1000 °C, respectively, were characterized by Fourier transform infrared, Solid‐state 13C and 29Si magic angle spinning NMR, X‐ray diffraction and XPS analyses. The highly symmetrically functionalized POSS silica clusters, in the fluorite silica phase, in the network were found to remain unchanged on thermal treatment possibly due to the shielding of the silica core by the functionalities and a cancellation of thermal stresses on the silica core. Stabilization of the metastable α‐cristobalite phase, which is typically formed on cooling by a β‐ to α‐transition of the β‐cristobalite phase formed above 1400 °C, was observed in the amorphous regions in the network sample treated only to 1000 °C in air. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012 相似文献
926.
In this paper, the extension of an upwind least‐square based meshless solver to high Reynolds number flow is explored, and the properties of the meshless solver are analyzed both theoretically and numerically. Existing works have verified the meshless solver mostly with inviscid flows and low Reynolds number flows, and in this work, we are interested in the behavior of the meshless solver for high Reynolds number flow, especially in the near‐wall region. With both theoretical and numerical analysis, the effects of two parameters on the meshless solver are identified. The first one is the misalignment effect caused by the significantly skewed supporting points, and it is found that the meshless solver still yields accurate prediction. It is a very interesting property and is opposite to the median‐dual control volume based vertex‐centered finite volume method, which is known to give degraded result with stretched triangular/tetrahedral cells in the near‐wall region. The second parameter is the curvature, and according to theoretical analysis, it is found in the region with both large aspect ratio and curvature, and the streamwise residual is less affected; however, the wall‐normal counterpart suffers from accuracy degradation. In this paper, an improved method that uses a meshless solver for the streamwise residual and finite difference for wall‐normal residual is developed. This method is proved to be less sensitive to the curvature and provides improved accuracy. This work presents an understanding of the meshless solver for high Reynolds number flow computation, and the analysis in this paper is verified with a series of numerical experiments. Copyright © 2012 John Wiley & Sons, Ltd. 相似文献
927.
Abstract Variation of bulk modulus of Si, Ge and GaAs with pressure is studied using four semiempirical equations of state, two of which being proposed very recently. Hence an expression for bulk modulus for arbitrary pressure for the semiconductors similar to Cohen's formula for zero pressure is arrived at. The applicability of these equations of state for the high pressure phases of Si and Ge is tested using the recent experimental and theoretical pressure-volume data of these phases. 相似文献
928.
An HPLC‐ECD method for monoamines and metabolites quantification in cuttlefish (cephalopod) brain tissue
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Flavie Bidel Sophie Corvaisier Christelle Jozet‐Alves Ivannah Pottier François Dauphin Nadège Naud Cécile Bellanger 《Biomedical chromatography : BMC》2016,30(8):1175-1183
The cuttlefish belongs to the mollusk class Cephalopoda, considered as the most advanced marine invertebrates and thus widely used as models to study the biology of complex behaviors and cognition, as well as their related neurochemical mechanisms. Surprisingly, methods to quantify the biogenic monoamines and their metabolites in cuttlefish brain remain sparse and measure a limited number of analytes. This work aims to validate an HPLC‐ECD method for the simultaneous quantification of dopamine, serotonin, norepinephrine and their main metabolites in cuttlefish brain. In comparison and in order to develop a method suitable to answer both ecological and biomedical questions, the validation was also carried out on a phylogenetically remote species: mouse (mammals). The method was shown to be accurate, precise, selective, repeatable and sensitive over a wide range of concentrations for 5‐hydroxyindole‐3‐acetic acid, serotonin, dopamine, 3,4‐dihydroxyphenylacetic acid and norepinephrine in the both extracts of cuttlefish and mouse brain, though with low precision and recovery for 4‐hydroxy‐3‐methoxyphenylethylene glycol. Homovanillic acid, accurately studied in rodents, was not detectable in the brain of cuttlefish. Overall, we described here the first fully validated HPLC method for the routine measurement of both monoamines and metabolites in cuttlefish brain. Copyright © 2016 John Wiley & Sons, Ltd. 相似文献
929.
Kazuo Koyama Takashi Hirao Akira Toriba Kazuichi Hayakawa 《Biomedical chromatography : BMC》2013,27(5):583-588
The quality of starch‐containing foods may be significantly impaired by contamination with very small amounts of α‐amylase, which can enzymatically hydrolyze the starch and cause viscosity loss. Thus, for quality control, it is necessary to have an analytical method that can measure low amylase activity. We developed a sensitive analytical method for measuring the activity of α‐amylase (from Bacillus subtilis) in starch‐containing foods. The method consists of six steps: (1) crude extraction of α‐amylase by centrifugation and filtration; (2) α‐amylase purification by desalting and anion‐exchange chromatography; (3) reaction of the purified amylase with boron‐dipyrromethene (BODIPY)‐labeled substrate, which releases a fluorescent fragment upon digestion of the substrate, thus avoiding interference from starch derivatives in the sample; (4) stopping the reaction with acetonitrile; (5) reversed‐phase solid‐phase extraction of the fluorescent substrate to remove contaminating dye and impurities; and (6) separation and measurement of BODIPY fluorescence by HPLC. The proposed method could quantify α‐amylase activities as low as 10 mU/mL, which is enough to reduce the viscosity of starch‐containing foods. Copyright © 2012 John Wiley & Sons, Ltd. 相似文献
930.
Synthesis of Depo‐Medrol–chitosan hydrogel as new drug slow‐release appliance and investigation of release kinetics by high‐performance liquid chromatography
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Reza Alizadeh Sara Majd Jabbari Amir H. Zarnani Hamidreza Barghi 《Biomedical chromatography : BMC》2016,30(9):1346-1353
The present study deals with preparation and optimization of a novel chitosan hydrogel‐based matrix by suspension cross‐linking method for controlled release of Depo‐Medrol. The controlled release of Depo‐Medrol for effective Rheumatoid arthritis disease has become an imperative field in the drug delivery system. In this context, it was intended to optimize loading circumstances by experimental design and also study the release kinetics of Depo‐Medrol entrapped in the chitosan matrix in order to obtain maximal efficiency for drug loading. The optimum concentrations of chitosan (2.5 g), glutaraldehyde (3.05 μL) and Depo‐Medrol (0.1 mg) were set up to achieve the highest value of drug loaded and the most sustained release from the chitosan matrix. In vitro monitoring of drug release kinetic using high‐performance liquid chromatography showed that 73% of the Depo‐Medrol was released within 120 min, whereas remained drug was released during the next 67 h. High correlation between first‐order and Higuchi's kinetic models indicates a controlled diffusion of Depo‐Medrol through the surrounding media. Moreover, recovery capacity >82% and entrapment efficiency of 58–88% were achieved under optimal conditions. Therefore, the new synthesized Depo Medrol–chitosan is an applicable appliance for arthritis therapy by slow release mechanism. Copyright © 2016 John Wiley & Sons, Ltd. 相似文献