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991.
992.
Crystals of oxo-bis[tribenzylgermanium(IV)], O[(PhCH2)3Ge]2, are rhombohedral, space group R, having a = 9.621(2) Å, α = 85.48(3)°. The structure was solved by Patterson methods using diffractometer data and refined by full-matrix least squares to R = 0.0876. The structure consists of molecules lying along the 3-fold axis of the unit cell, in which the GeOGe fragments are strictly linear and centrosymmetric. The GeO distance is 1.730(1) Å and the GeC distance is 1.980(5) Å. 相似文献
993.
A. Abel Lozano M. Dolores Santana Gabriel García J. Elaine Barclay Sin C. Davies David J. Evans 《无机化学与普通化学杂志》2005,631(11):2062-2066
A series of heteronuclear nickel‐iron complexes [Fe2(CO)6(μ‐SH)(μ3‐S){NiCl(PPh3)2}] ( 1 ), [Fe2(CO)6(μ‐SH)(μ3‐S){NiCl(dppe)}] ( 2 ), [Fe2(CO)6(μ3‐S)2{Ni(PPh3)2}] ( 3 ), [Fe2(CO)6(μ3‐S)2{Ni(dppe)}] ( 4 ) and [Fe2(CO)6(μ‐SPh)(μ3‐S){NiCl(dppe)}] ( 5 ) have been prepared. The structure of 4 has been determined by X‐ray crystallography. The central metal‐sulfur core of 4 has a trigonal bipyramidal shape with a NiFe2 base plane with two axial sulfur atoms. Each iron atom is 5‐coordinate forming a distorted square pyramid; the nickel is square planar coordinated by two sulfur atoms and two phosphorus atoms. 相似文献
994.
The optical spectrum of diatomic RuC has been recorded from 17 800 to 24 200 cm(-1). Three previously unidentified excited electronic states were analyzed and identified as having Omega' = 0, Omega' = 2, and Omega' = 3. The Omega' = 3 state was determined to be a 3Delta3 state that is suggested to arise from a mixture of the 10sigma(2)11sigma(2)5pi(3)2delta(3)12sigma(1)6pi(1) and 10sigma(2)11sigma(1)5pi(3)2delta(3)12sigma(2)6pi(1) electronic configurations. Three additional bands belonging to the previously observed [18.1] (1)Pi<--X (1)Sigma(+) system were analyzed to obtain B(e) (')=0.558 244(48) cm(-1), alpha(e) (')=0.004 655(27) cm(-1), omegae' = 887.201(37) cm(-1), and omega(e) 'xe' = 5.589(7) cm(-1) for the 102Ru 12C isotopomer (1sigma error limits). A Rydberg-Klein-Rees analysis was then performed using the determined spectroscopic constants of the [18.1] 1Pi state, and similar analyses were performed for the previously observed states. The resulting potential energy curves are provided for the 100Ru 12C, 101Ru 12C, 102Ru 12C, and 104Ru 12C isotopic species. 相似文献
995.
Two methacrylate‐modified clays have been prepared and used to produce nanocomposites of polystyrene and poly(methyl methacrylate) by in situ polymerization. These nanocomposites have been characterized by X‐ray diffraction (XRD), transmission electron microscopy (TEM), thermogravimetric analysis (TGA), cone calorimetry and the evaluation of mechanical properties. When the clay contains only a single methacrylate unit, the styrene system is exfoliated but methacrylate is intercalated. When two methacrylate units are present on the cation of the clay, both systems are exfoliated. TGA data show that the thermal stability of all the nanocomposites is improved, as expected. The relationships between the fire properties and nanostructure of the nanocomposites are complicated, as shown by cone calorimetry. The conclusions that one may reach using cone calorimetry do not completely agree with those from XRD and TEM. The evaluation of mechanical properties shows an increase in Young's modulus for all nanocomposites along with a decrease in elongation; tensile strength is decreased for methacrylate nanocomposites but increased for styrenics systems. Copyright © 2004 John Wiley & Sons, Ltd. 相似文献
996.
Susan Robertson David Ellis Georgina M. Rosair Alan J. Welch 《Journal of organometallic chemistry》2003,680(1-2):286-293
The reaction of the labelled carborane ligand [3-Et-7,8-Ph2-7,8-nido-C2B9H8]2− with a source of {Pt(PMe2Ph)2}2+ affords non-isomerised 1,2-Ph2-3,3-(PMe2Ph)2-6-Et-3,1,2-closo-PtC2B9H8 (1). The analogous reaction between [3-F-7,8-Ph2-7,8-nido-C2B9H8]2− and {Pt(PMe2Ph)2}2+ yields 1,8-Ph2-2,2-(PMe2Ph)2-4-F-2,1,8-closo-PtC2B9H8 (3). Compound 1 has a heavily slipped structure (Δ 0.72 Å), which to some degree obviates the need for C atom isomerisation. However, that it is a kinetic product of the reaction is evident from the fact that it reverts to isomerised 1,8-Ph2-2,2-(PMe2Ph)2-4-Et-2,1,8-closo-PtC2B9H8 (2) slowly at room temperature but more rapidly with gentle warming. The heteroatom and labelled-B atom positions in the isomerised compounds 2 and 3 may be explained most simply by the rotation of a CB2 face of an intermediate based on the structure of 1. Compounds 1–3 were characterised by a combination of spectroscopic and crystallographic techniques. 相似文献
997.
A universal temperature controlled membrane interface (TCMI) has been constructed for hollow-fibre membranes. The membrane temperature is controllable in the range -70 to 250 degrees C using an electric heater and a flow of cooled nitrogen or helium gas. Volatile and semi-volatile organic compounds may be detected either by continuous diffusion across the membrane or by in-membrane pre-concentration followed by thermal desorption into the detector. The TCMI interface is demonstrated in combination with mass spectrometry and GC-MS, for the determination of VOCs and SVOCs in aqueous and air samples and for the on-line monitoring of a bioreactor. 相似文献
998.
Sprous DG Lowis DR Leonard JM Heritage T Burkett SN Baker DS Clark RD 《Journal of combinatorial chemistry》2004,6(4):530-539
Products from combinatorial libraries generally share a common core structure that can be exploited to improve the efficiency of virtual high-throughput screening (vHTS). In general, it is more efficient to find a method that scales with the total number of reagents (Sigma growth) rather with the number of products (Pi growth). The OptiDock methodology described herein entails selecting a diverse but representative subset of compounds that span the structural space encompassed by the full library. These compounds are docked individually using the FlexX program (Rarey, M.; Kramer, B.; Lengauer, T.; Klebe, G. J. Mol. Biol. 1995, 251, 470-489) to define distinct docking modes in terms of reference placements for combinatorial core atoms. Thereafter, substituents in R-cores (consisting of the core structure substituted at a single variation site) are docked, keeping the core atoms fixed at the coordinates dictated by each reference placement. Interaction energies are calculated for each docked R-core with respect to the target protein, and energies for whole compounds are calculated by finding the reference core placement for which the sum of corresponding R-core energies is most negative. The use of diverse whole compounds to define binding modes is a key advantage of the protocol over other combinatorial docking programs. As a result, OptiDock returns better-scoring conformers than does serially applied FlexX. OptiDock is also better able to find a viable docked pose for each library member than are other combinatorial approaches. 相似文献
999.
An efficient approach is described for using accurate ab initio calculations to determine the rates of elementary condensation and evaporation processes that lead to nucleation of aqueous aerosols. The feasibility of the method is demonstrated in an application to evaporation rates of water dimer at 230 K. The method, known as ABC-FEP (ab initio/classical free energy perturbation), begins with a calculation of the potential of mean force for the dissociation (evaporation) of small water clusters using a molecular dynamics (MD) simulation with a model potential. The free energy perturbation is used to calculate how changing from the model potential to a potential calculated from ab initio methods would alter the potential of mean force. The difference in free energy is the Boltzmann-weighted average of the difference between the ab initio and classical potential energies, with the average taken over a sample of configurations from the MD simulation. In principle, the method does not require a highly accurate model potential, though more accurate potentials require fewer configurations to achieve a small sampling error in the free energy perturbation step. To test the feasibility of obtaining accurate potentials of mean force from ab initio calculations at a modest number of configurations, the free energy perturbation method has been used to correct the errors when some standard models for bulk water (SPC, TIP4P, and TIP4PFQ) are applied to water dimer. To allow a thorough exploration of sampling issues, a highly accurate fit to results of accurate ab initio calculations, known as SAPT-5s, as been used a proxy for the ab initio calculations. It is shown that accurate values for a point on the potential of mean force can be obtained from any of the water models using ab initio calculations at only 50 configurations. Thus, this method allows accurate simulations of small clusters without the need to develop water models specifically for clusters. 相似文献
1000.
Joseph M. Levy Athos C. Rosselli David S. Boyer Kathryn Cross 《Journal of separation science》1990,13(6):418-421
The usefulness and ease of utilizing supercritical fluid extraction (SFE) directly coupled to capillary gas chromatography (GC) as quantitative or qualitative analytical problem-solving tools will be demonstrated. As an alternative to conventional liquid solvent extractions, SFE presents itself as a means to achieve high extraction efficiencies of different compounds in complex solid matrices in very rapid tims frames. Moreover, SFE has an additional advantage of being able to achieve distinct extraction selectivities as a function of the solubilizing power of the supercritical fluid extracting phase. For on-line SFE/GC, the extraction effluent is directly transferred to the analytical chromatograph. On-line SFE/GC involves the decompression of pressurized extraction effluent directly into a heated, unmodified capillary split injection port of the GC. In this respect, SFE introduction into GC can be used as an alternative means of GC injection, comparable to such modes of injection as pyrolysis and thermal desorption. This paper will show applications of SFE/GC where mass spectrometric detection together with flame ionization detection was used for component identification from environmental, tobacco, and petroleum matrices. 相似文献