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Experimental support for the dominance of van der Waals dispersion forces in aromatic stacking interactions occurring in organic solution is surprisingly limited. The size‐dependence of aromatic stacking in an organic solvent was examined. The interaction energy was found to vary by about 7.5 kJ mol−1 on going from a phenyl–phenyl to an anthracene–pyrene stack. Strikingly, the experimental data were highly correlated with dispersion energies determined using symmetry‐adapted perturbation theory (SAPT), while the induction, exchange, electrostatic, and solvation energy components correlated poorly. Both the experimental data and the SAPT‐dispersion energies gave high‐quality correlations with the change in solvent accessible area upon complexation. Thus, the size‐dependence of aromatic stacking interactions is consistent with the dominance of van der Waals dispersion forces even in the presence of a competing polarizable solvent.  相似文献   
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Cheminformatics protocols have been developed and assessed that identify a small set of fragments which can represent the compounds in a chemical library for use in fragment-based ligand discovery. Six different methods have been implemented and tested on Input Libraries of compounds from three suppliers. The resulting Fragment Sets have been characterised on the basis of computed physico-chemical properties and their similarity to the Input Libraries. A method that iteratively identifies fragments with the maximum number of similar compounds in the Input Library (Nearest Neighbours) produces the most diverse library. This approach could increase the success of experimental ligand discovery projects, by providing fragments that can be progressed rapidly to larger compounds through access to available similar compounds (known as SAR by Catalog).  相似文献   
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Graft copolymers of acrylamide and yellow dextrin were prepared using cerium(IV) as initiator. The yellow dextrin had a very broad molecular weight distribution but was fractionated utilizing dialysis and ultrafiltration membranes. Initiator efficiencies were determined using size exclusion chromatography and were found to be between 2.4 and 34%. Initiator efficiency increased with acrylamide concentration at constant cerium (IV) and yellow dextrin concentrations, and decreased with increasing cerium(IV) concentration at constant acrylamide and yellow dextrin concentrations. Plots of acrylamide conversion and intrinsic viscosity vs initial acrylamide concentration at constant yellow dextrin and ceric ion concentrations showed a maximum at about 2.0 M.  相似文献   
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The novel monomer, π-(2, 4-hexadiene- l-yl acrylate) tricarbonyliron (HATI), has been prepared by two routes. It was homopolymerized and copolymerized with acrylonitrile, vinyl acetate, styrene, and methyl acrylate in benzene solutions. In all cases azobisisobutyronitrile was the initiator. The relative reactivity ratios, where HATI is defined as M1, were determined: r1 = 0.34, r2 = 0.74, M2 = acrylonitrile; r1 = 2.0, r2 = 0.05, M2 = 0.74, M2 = acrylonitrile; r1 = 2.0, r2 = 0.05, M2 = vinyl acetate; r1 = 0.26, r2 = 1.81, M2 = styrene; and r1 = 0.30, r2 = 0.74, M2 = methyl acrylate. The homo-and copolymers had high values of Tg. When polymerizations are carried out at high concentrations, a very high molecular weight tail is observed in HATI hompolymerizations and in HATI-methyl acrylate copolymerizations. The polymers were characterized by IR, gel permeation chromatography, viscosity, and differential scanning calorimetry studies. Finally, thermal decompositions carried out in air resulted in decomposition of the Fe(CO)3 group, producing Fe2O3 as a fine powder. Thermal decomposition under nitrogen (in solution and on solids ground into KBr pellets) resulted in slow destruction of the Fe(CO)3 groups but the resulting polymer mass was insoluble, and the question of what form the iron exists in (Fe metal, oxides, carbides, etc.) has not been answered.  相似文献   
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Mixtures of methane and olefins (ethylene, propylene, butenes, butadiene, and styrene) have been polymerized over HSO3 F-SbF3 to yield an oily oligomer with a molecular weight ranging from 100 to 700. The NMR spectra of each polymer showed a sharp peak at or near 1.25 &, suggesting the presence of block methylene in the polymer. The formation of block methylene is surprising considering the fact that the polymerization reaction is carbonium ion in nature. A primary cation has been invoked to explain the results. The formation of this primary cation must involve some extraordinary stabilization by some component in the acid.  相似文献   
217.
Absolute efficiency calibration of radiometric detectors is frequently difficult and requires careful detector modeling and accurate knowledge of the radioactive source used. In the past we have calibrated the β–γ coincidence detector of the Automated Radioxenon Sampler/Analyzer (ARSA) using a variety of sources and techniques which have proven to be less than desirable (Reeder et al., J Radioanal Nucl Chem, 235, 1989). A superior technique has been developed that uses the conversion-electron (CE) and X-ray coincidence of 131mXe to provide a more accurate absolute gamma efficiency of the detector. The 131mXe is injected directly into the beta cell of the coincident counting system and no knowledge of absolute source strength is required. In addition, 133Xe is used to provide a second independent means to obtain the absolute efficiency calibration. These two data points provide the necessary information for calculating the detector efficiency and can be used in conjunction with other noble gas isotopes to completely characterize and calibrate the ARSA nuclear detector. In this paper we discuss the techniques and results that we have obtained.  相似文献   
218.
A directional microphone system for field recording of sounds in the air often involves a parabolic reflector to focus the sound waves on the microphone (transducer) element. Some deficiencies of such a system are noted with respect to reproduction of spectra. The reflector system, involving as it does a structure comparable to a wavelength in linear dimension, is not susceptible to traditional high- or low-frequency approximate methods of computation. Modern numerical techniques now permit precise calculation of the directional responses of small reflectors of various shapes. One result is a proposal for a very economical and effective system involving a plane reflector. Other baffle shapes are also investigated, which may be of interest in special applications.  相似文献   
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