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91.
In Situ Total X‐Ray Scattering Study of WO3 Nanoparticle Formation under Hydrothermal Conditions
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Dr. Dipankar Saha Dr. Kirsten M. Ø. Jensen Dr. Christoffer Tyrsted Espen D. Bøjesen Dr. Aref Hasen Mamakhel Dr. Ann‐Christin Dippel Dr. Mogens Christensen Prof. Dr. Bo B. Iversen 《Angewandte Chemie (International ed. in English)》2014,53(14):3667-3670
Pair distribution function analysis of in situ total scattering data recorded during formation of WO3 nanocrystals under hydrothermal conditions reveal that a complex precursor structure exists in solution. The WO6 polyhedra of the precursor cluster undergo reorientation before forming the nanocrystal. This reorientation is the critical element in the formation of different hexagonal polymporphs of WO3. 相似文献
92.
LetV
t be the virtual waiting time at timet in a queue having marked point process input generated by a finite Markov process {Jt}, such that in addition to Markovmodulated Poisson arrivals there may also be arrivals at jump times of {Jt}. In this setting, Poisson's equation isA
g=–f whereA is the infinitesimal generator of {(Vt, Jt)}. It is shown that the solutiong can be expressed asKf for some suitable kernelK, and the explicit form ofK is evaluated. The results are applied to compute limiting variance constants for (normalized) time averages of functionsf(V
t, Jt), in particularf(V
t,Jt)=Vt. 相似文献
93.
Spindle-inhibiting effects of chemical compounds may be studied indirectly by quantitation of chromosomal contraction. The effects of the trimethyltin (TMT), dimethyltin (DMT), tributyltin (TBT), dibutyltin (DBT), triphenyltin (TPhT) and diphenyltin (DPht) moieties as the chloride on chromosomal contraction was studied by measurement of the average length of chromosome No. 1 from asynchronous cultures of human peripheral lymphocytes. TMT, TBT, TPhT and DPhT appear to be very strong inducers of chromosomal supercontraction, indicating that these compounds conceivably are spindle inhibitors, whilst DMT and DBT seem to be ineffective. The different effects of aryl versus alkyl and trivalent versus divalent organic substituents of tin on chromosome length may relate to different modes of action. 相似文献
94.
Applications of on-line weak affinity interactions in free solution capillary electrophoresis 总被引:2,自引:0,他引:2
The impressive selectivity offered by capillary electrophoresis can in some cases be further increased when ligands or additives that engage in weak affinity interactions with one or more of the separated analytes are added to the electrophoresis buffer. This on-line affinity capillary electrophoresis approach is feasible when the migration of complexed molecules is different from the migration of free molecules and when separation conditions are nondenaturing. In this review, we focus on applying weak interactions as tools to enhance the separation of closely related molecules, e.g., drug enantiomers and on using capillary electrophoresis to characterize such interactions quantitatively. We describe the equations for binding isotherms, illustrate how selectivity can be manipulated by varying the additive concentrations, and show how the methods may be used to estimate binding constants. On-line affinity capillary electrophoresis methods are especially valuable for enantiomeric separations and for functional characterization of the contents of biological samples that are only available in minute quantities. 相似文献
95.
Acetylenic scaffolding with derivatives of tetraethynylethene (TEE, 3,4-diethynylhex-3-ene-1,5-diyne) and (E)-1,2-diethynylethene (DEE, (E)-hex-3-ene-1,5-diyne) provides carbon-rich compounds with interesting physicochemical properties. Thus, these modules are building blocks for monodisperse, linearly pi-conjugated oligomers [polytri(acetylene)s, PTAs] extending in length beyond 10nm, and for large, macrocyclic, all-carbon cores (dehydroannulenes and expanded radialenes) exhibiting strong chromophoric properties. The advanced materials' properties were strongly influenced by the presence of electron-donating substituents at the lateral positions, decreasing the decreasing the (HOMO-LUMO) gap in both PTAs and expanded radialenes. Arylated TEEs were found to undergo photochemically induced cis-trans isomerization, paving the way for applications as light-driven molecular switches in optoelectronic devices. Derivatives of 1,3-diethynylallene are new modules that offer the prospect of scaffolding in an orthogonal manner; that is, they represent precursors for helical oligomers. 相似文献
96.
Cargnoni F Nishibori E Rabiller P Bertini L Snyder GJ Christensen M Gatti C Iversen BB 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,10(16):3861-3870
The experimental electron density of the high-performance thermoelectric material Zn4Sb3 has been determined by maximum entropy (MEM) analysis of short-wavelength synchrotron powder diffraction data. These data are found to be more accurate than conventional single-crystal data due to the reduction of common systematic errors, such as absorption, extinction and anomalous scattering. Analysis of the MEM electron density directly reveals interstitial Zn atoms and a partially occupied main Zn site. Two types of Sb atoms are observed: a free spherical ion (Sb3-) and Sb2(4-) dimers. Analysis of the MEM electron density also reveals possible Sb disorder along the c axis. The disorder, defects and vacancies are all features that contribute to the drastic reduction of the thermal conductivity of the material. Topological analysis of the thermally smeared MEM density has been carried out. Starting with the X-ray structure ab initio computational methods have been used to deconvolute structural information from the space-time data averaging inherent to the XRD experiment. The analysis reveals how interstitial Zn atoms and vacancies affect the electronic structure and transport properties of beta-Zn4Sb3. The structure consists of an ideal A12Sb10 framework in which point defects are distributed. We propose that the material is a 0.184:0.420:0.396 mixture of A12Sb10, A11BCSb10 and A10BCDSb10 cells, in which A, B, C and D are the four Zn sites in the X-ray structure. Given the similar density of states (DOS) of the A12Sb10, A11BCSb10 and A10BCDSb10 cells, one may electronically model the defective stoichiometry of the real system either by n-doping the 12-Zn atom cell or by p-doping the two 13-Zn atom cells. This leads to similar calculated Seebeck coefficients for the A12Sb10, A11BCSb10 and A10BCDSb10 cells (115.0, 123.0 and 110.3 microV K(-1) at T=670 K). The model system is therefore a p-doped semiconductor as found experimentally. The effect is dramatic if these cells are doped differently with respect to the experimental electron count. Thus, 0.33 extra electrons supplied to either kind of cell would increase the Seebeck coefficient to about 260 microV K(-1). Additional electrons would also lower sigma, so the resulting effect on the thermoelectric figure of merit of Zn4Sb3 challenges further experimental work. 相似文献
97.
Nielsen MB Utesch NF Moonen NN Boudon C Gisselbrecht JP Concilio S Piotto SP Seiler P Günter P Gross M Diederich F 《Chemistry (Weinheim an der Bergstrasse, Germany)》2002,8(16):3601-3613
A selection of mono- and diacetylenic dithiafulvalenes was synthesized and employed for the construction of extended tetrathiafulvalenes (TTFs) with hexa-2,4-diyne-1,6-diylidene or deca-2,4,6,8-tetrayne-1,10-diylidene spacers between the two 1,3-dithiole rings. By stepwise acetylenic scaffolding using (E)-1,2-diethynylethene (DEE) building blocks, an extended TTF containing a total of 18 C(sp) and C(sp(2)) atoms in the spacer was prepared. The versatility of the acetylenic dithiafulvene modules was also established by the efficient synthesis of a thiophene-spaced TTF, employing a palladium-catalyzed cross-coupling reaction. The developed synthetic protocols allow functionalization of the extended TTFs in three general ways: with 1) peripheral substituents on the fulvalene cores, 2) alkynyl moieties laterally appended to the spacer, and 3) cobalt clusters involving acetylenic moieties. Strong chromophoric properties of the extended TTFs were revealed by linear and nonlinear optical spectroscopies. Extensive electrochemical studies and calculations on these compounds are also reported, as well as X-ray crystallographic analyses. 相似文献
98.
High-performance liquid chromatography on silica using eluents containing cetyltrimethylammonium (CTMA) bromide was investigated, and adsorption isotherms were determined for two silica packings of different pore diameter and surface area. It was found that about one CTMA ion was adsorbed per square nanometer of the silica surface at pH 7.5 and at a concentration of 6 mM CTMA bromide in 50% of methanol.Fourteen different silica packings were compared using a test mixture, and thirteen were found to exhibit the same selectivity towards the test mixture, which included acids, bases and non-ionic compounds, thus providing a chromatographic system that is largely independent of the origin of the column material.The retention mechanisms for the five test compounds are discussed. 相似文献
99.
Kit Granby Jens Hinge Andersen Hanne Bjerre Christensen 《Analytica chimica acta》2004,520(1-2):165-176
A method for analysing carbamates and other relatively polar pesticides by LC–MS–MS with electrospray ionisation has been developed. The method is based on extraction by ultrasonication using a methanolic ammonium acetate–acetic acid buffer. After centrifugation the samples are filtered in Miniprep filter HPLC vials and detected by LC–MS–MS. To compensate for variations in the MS response [13C6]-carbaryl was used as internal standard and matrix-matched pesticide solutions were used as external standards for the quantification. The method has been validated for the matrices apple, avocado, carrot, lettuce, orange, potato and wheat at the spiking levels—0.02; 0.04 and 0.20 mg kg−1. Recoveries were generally in the range 70–120%. Results from participation in three intercomparisons proved the accuracy of the method. As the analytical procedure does not include any concentration or cleanup steps, it is easy and fast to perform, making it applicable for routine analysis in large pesticide monitoring programmes. 相似文献
100.
We prove an addition formula for Jacobi functions
analogous to the known addition formula for Jacobi polynomials. We exploit the positivity of the coefficients in the addition
formula by giving the following application. We prove that the product of two Jacobi functions of the same argument has a
nonnegative Fourier-Jacobi transform. This implies that the convolution structure associated to the inverse Fourier-Jacobi
transform is positive.
The first author was partially supported by the Danish Natural Science Research Council. 相似文献