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81.
In this paper we present a series of work covering a range of aspects relating molecular simulation to experiment. The importance
of surface mediation type effects to the adsorption of simple and complex gases is demonstrated. Coupled with the adsorption
of simple gases is their projection area when used for surface area determination. The pressure dependence of a projection
area is demonstrated for argon at 77 and 87.3 K. A simple model is used to account for the degree of graphitisation of a surface
is demonstrated and used to account for the isosteric heat behaviour of non-graphitised carbon blacks. Turning from surfaces
to porous solids, an alternative treatment of experiment data (either sub or super critical) is presented that avoids the
ambiguity of excess amounts adsorbed. Using this method one is able to obtain pore size distributions and amounts adsorbed
without relying on such things as helium expansion volumes. Since this type of method is usually applied to composite solids
we also demonstrate the correct method for calculating the heat of adsorption using independent sets of simulations. The final
topic covered in this paper is an example of the information that can be gained from the heat capacity of an adsorbed phase. 相似文献
82.
Self-assembly of a new precursor [Cu(L)](ClO4)2 (1) (L = macrocyclic ligand) with octacyanometalates [M(CN)8]3- (M = Mo, W) produced two-dimensional cyano-bridged Cu(II)-M(V) bimetallic assemblies [Cu(L)]3n[M(CN)8]2n.6nH2O [M = Mo (2), W (3)] with novel honeycomblike structures, characterized by spectroscopic data, single-crystal X-ray diffraction studies, and magnetic measurements. The crystallographic determination reveals that compounds 2 and 3 are isostructural and crystallize in the triclinic system (P). The Cu atom in a distorted octahedral environment experiences a tetragonal elongation of apical nitrogen atoms exhibiting average Cu-Nax lengths of 2.566 Angstroms for 2 and 2.593 Angstroms for 3, which accounts for the Jahn-Teller effect of a Cu(II) ion. The Cu-NC angles are magnetically important, ranging from 135.7 to 159.2 degrees. Three types of L in the crystal lattice are observed, which are dependent on the relative positions of the pendant hydroxyl groups with respect to the CuN4 basal plane. The positions are correlated with hydrogen bonding of OH groups to neighboring atoms. The magnetic data indicate that ferromagnetic and antiferromagnetic interactions between Cu(II) and M(V) through the CN linkage coexist. 相似文献
83.
An analytical method has been developed for determination of dextromethorphan (DMP) and dextrorphan (DRP) in human hair by gas chromatography–mass spectrometry (GC–MS). Hair samples (30 mg) were washed with distilled water and acetone and cut into small fragments (<1 mm) before extraction with methanol. The extracts were evaporated to dryness and then derivatized by use of BSTFA containing 1% TMCS, for preparation of the trimethylsilyl (TMS) derivative of DRP. The extract (1 μL) was then injected into the GC–MS. Recoveries of DMP and DRP at 7.0 and 22.5 ng mg?1 were in the range 90.6–97.2% with intra-assay and inter-assay precision of less than 5.7% and 4.7%, respectively. LOD and LOQ were, respectively, 0.67 and 2.13 ng mg?1 for DMP and 0.14 and 0.47 ng mg?1 for DRP. The responses were linear with correlation coefficients (r > 0.9995) for the drugs studied. The applicability of the method was proven by analysis of authentic hair samples. 相似文献
84.
Kato H Brink M Möllerstedt H Piqueras MC Crespo R Ottosson H 《The Journal of organic chemistry》2005,70(23):9495-9504
[Figure: see text]. A quantum chemical study has been performed to assess changes in aromaticity along the T1 state Z/E-isomerization pathways of annulenyl-substituted olefins. It is argued that the point on the T1 energy surface with highest substituent aromaticity corresponds to the minimum. According to Baird (J. Am. Chem. Soc. 1972, 94, 4941), aromaticity and antiaromaticity are interchanged when going from S0 to T1. Thus, olefins with S0 aromatic substituents (set A olefins) will be partially antiaromatic in T1 and vice versa for olefins with S0 antiaromatic substituents (set B olefins). Twist of the C=C bond to a structure with a perpendicular orientation of the 2p(C) orbitals (3p*) in T1 should lead to regaining substituent aromaticity in set A and loss of aromaticity in set B olefins. This hypothesis is verified through quantum chemical calculations of T1 energies, geometries (bond lengths and harmonic oscillator measure of aromaticity), spin densities, and nucleus independent chemical shifts whose differences along the T1 PES display zigzag dependencies on the number of -electrons in the annulenyl substituent of the olefin. Aromaticity changes are reflected in the profiles of the T1 potential energy surfaces (T1 PESs) for Z/E-isomerizations because olefins in set A have minima at 3p* whereas those in set B have maxima at such structures. The proper combination (fusion) of the substituents of set A and B olefins could allow for design of novel optical switch compounds that isomerize adiabatically with high isomerization quantum yields. 相似文献
85.
Viorica Lopez-Avila Richard Young Werner F. Beckert 《Journal of separation science》1997,20(9):487-492
This paper describes the extraction of 49 organophosphorus pesti-cides (OPPs) from water samples using solid-phase microextraction (SPME). Three fibers, including a 15-μm XAD-coated fiber, a 85-μm polyacrylate-coated fiber, and a 30-μm polydimethylsilox-ane-coated fiber (PDMS), were evaluated here. The effects of stirring and the addition of NaCl to the sample were examined for the polyacrylate-coated fiber. The precision of the technique was examined for all three fibers and the extraction kinetics were investigated using the XAD- and polyacrylate-coated fibers. With some exceptions, the XAD- and polyacrylate-coated fibers performed better than the PDMS-coated fiber. The superiority of the XAD-nd polyacrylate-coated fiber. The superiority of the XAD- and polyacrylate-coated fibers over the PDMS-coated fibers can be attribuibuted to the aromatic functionalities of the XAD and the polar functionalities in the polyacrylate. The relatively high percent RSDs indicate that the SPME technique needs to be further refined before it can be used for anything other than screening. A more effective form of agitation than mechanical stirring may be neccessary to reduce variability and achieve a faster equilibrium between the sample and the SPME fiber. 相似文献
86.
The second-order rate constants for the nucleophilic replacement of fluorine by isopropoxide in 5,6,7,8-tetrafluoro- and 6,7,-difluoro-1,2,3,4-tetrahydro-9-alkenyl-1,4-methanonaphthalenes and related 9-alkyl systems have been measured. A factor of 6 - 7 separates the most reactive compounds [the 9- (4′-trifluoromethylbenzylidene) derivatives] from the least reactive compounds [the syn-9-isopropyl derivatives] in both the tetrafluoro- and difluoro-series. It is concluded for these small reactivity differences. 相似文献
87.
Ovshinsky SR Young RT Allred DD DeMaggio G Van der Leeden GA 《Physical review letters》1987,58(24):2579-2581
88.
89.
Let T be a c.n.u. contraction on a Hilbert spaceH and let u-(u1,...,un) be an n-tuple of H(T). We calculate various joint spectra of u(T) and apply the results to study the spectral and index theories of elementary operators associated with n-tuples of the above type.Both authors have been partially supported by NSF grants. 相似文献
90.
Summary Real hypersurfaces of an almost Hermitian manifold naturally admit an almost contact metric structure and the (f, g, u, v, w, , , )-structure is defined on submanifolds of codimension 3 of an almost Hermitian manifold. We study the so-called semi-invariant submanifolds of a complex space form with almost contact metric compound structure which is a general notion of (f, g, u, v, w, , , )-structure.Dedicated to professor Eulyong Pak on his 60th birthdayThis research was partially supported by Korean Science and Engineering Foundation Grant. 相似文献