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31.
Bhatia SK Tran K Nguyen TX Nicholson D 《Langmuir : the ACS journal of surfaces and colloids》2004,20(22):9612-9620
We present new simulation results for the packing of single-center and three-center models of carbon dioxide at high pressure in carbon slit pores. The former shows a series of packing transitions that are well described by our density functional theory model developed earlier. In contrast, these transitions are absent for the three-center model. Analysis of the simulation results shows that alternations of flat-lying molecules and rotated molecules can occur as the pore width is increased. The presence or absence of quadrupoles has negligible effect on these high-density structures. 相似文献
32.
Single crystal structure determinations prove the two pyridine substituents in di(2-pyridyl)ketone (H4C4NC)2C=O to be twisted out of the carbonyl skeleton plane by torsion angles (OCCN) of 41° and –163°, in contrast to their planar arrangement in azo-di(2-pyridine) H4C4NC)-N=N-(CNC4H4). In order to rationalize the surprising difference between the two isoelectronic molecules, approximate PM3 enthalpy of formation hypersurfaces have been calculated for each of the two ring torsions, which are assumed to be the dominant ones among the 3N – 6 = 60 degrees of freedom. For both the ketone and the azo derivative, global minima are calculated, the torsion angles of which deviate from the crystal structure results, and, therefore, support the assumption that both the experimentally determined twisting of di(2-pyridyl)ketone as well as the flattening of azo-di(2-pyridine) might be affected by the crystal packing. 相似文献
33.
Synthesis and spectral characterization of some complexes of platinum(II) containing η-methyleugenol
Several complexes of the formula trans-[Pt(Meug)(Am)Cl2], Meug: methyleugenol (4-allyl-1,2-dimethoxybenzene), a η2-coordinated olefin, and Am: ammine, methylamine, diethylamine, o-toluidine, m-toluidine, p-toluidine, o-anisidine, m-anisidine and p-anisidine have been prepared. UV, IR, Raman, 1H NMR, 13C NMR and 2D NMR spectra of the complexes were recorded and analyzed. 相似文献
34.
[reaction: see text] Three novel domino reaction processes have been discovered and developed that employ the regioselective and stereoselective [Rh(CO)(2)Cl](2)-catalyzed alkylations of allylic trifluoroacetates with alpha-substituted sodiomalonates followed by an intramolecular Pauson-Khand annulation, a [5 + 2] cycloaddition, or a cycloisomerization. A unique aspect of the methodology is that a single catalyst is used to effect sequential transformations simply by increasing the temperature for the second reaction. 相似文献
35.
Proton affinities of a series of triphenyl Group Va compounds have been determined by bracketing using reactant ion monitoring: (C6H5)3N = 904 ± 8 kJ mol?1, (C6H5)3P = 968 ± 5 kJ mol?1, (C6H5)3As = 904 ± 8 kJ mol?1 and (C6H5)3Sb = 846 ± 8 kJ mol?1. The large difference in substituent effect of phenyl for hydrogen between As or P and N may result from overlap of the 2p orbitals of N with the sp2 orbitals on the ring carbons and lack of overlap for P or As. Proton affinities of phenylalkylphosphine oxides are essentially the same, 904 ± 8 kJ mol?1, independent of alkyl group. 相似文献
36.
Nguyen Van Do Tran Duc Thiep Truong Thi An Tran Minh Duc Han Ngoc Cuong 《Journal of Radioanalytical and Nuclear Chemistry》1986,107(1):29-37
Photon activation analysis has been success-fully applied to the fast and non-destructive analysis of tin in cassiterite ores
based on the 159.7 keV gamma line of123mSn produced in the124Sn/γ, n/123mSn reaction. In order to improve the accuracy of analytical results, corrections for self-absorption and pile-up effects were
performed. Under typical conditions /15 μA electron beam current, 15 MeV bremsstrahlung energy, 5 min irradiation time and
10 min measurement/ the sensitivity of the analysis is 10 ppm. The proposed method can be used for routine analysis of tin
in geological samples. 相似文献
37.
N,N-Diethyldithiocarbamate functionnalized 1,4-polyisoprenes were prepared from 1,4-polyisoprenes (natural or synthetic). The syntheses were performed by nucleophilic addition of N,N-diethyldithiocarbamate salts upon oxirane rings of epoxidized units according to a SN2 mechanism with ring opening. Studies on model molecules of epoxidized 1,4-polyisoprene units (1,2-epoxy-1-methylcyclohexane and 4,5-epoxy-4-methyloctane) were previously achieved to develop the procedure. The best yields were obtained at low temperature in polar medium, and more especially in water with sodium N,N-diethyldithiocarbamate (DEDT-Na) as reagent. A diastereospecific addition was noted when reaction was performed in water with DEDT-Na. Afterwards, the developed procedure was successfully generalized to epoxidized synthetic polyisoprenes and epoxidized natural rubber (in THF, then in latex medium). Excellent results were obtained in latex medium with epoxidized natural rubber (ENR) latices. As with the models, a diastereospecific addition of sodium N,N-diethyldithiocarbamate trihydrate onto epoxidized 1,4-polyisoprene units of ENR was observed at the condition to bring the latex medium to pH 8 before introduction of DEDT-Na. Influence of temperature, drc, and DEDT-Na concentration were successively examined to determine the best conditions of the addition on ENR latices. 相似文献
38.
E. M. Essassi R. Zniber A. Bernardini PH. Viallefont 《Journal of heterocyclic chemistry》1983,20(4):1015-1018
The inluence of the starting o-diamine on the reaction products is shown in the condensation of heteroaromatic o-diamines with acetylacetone; 2,3- and 3,4-diaminopyridines gave only a crotonic intermediate providing imidazopyridines. On the other hand, 1,5-diaminoimidazoles gave tow types of compounds, imidazotriazepines and imidazopyridines. Triazolopyridazines were formed from 3,4-diaminotriazoles. 相似文献
39.
Summary An ,-appended eighteen carbon chains hypercin derivative (2) was synthesized starting from emodin. The overall yield of the seven step synthesis was 12%. The1H and13C NMR, absorption, and emission spectroscopic properties were measured;2 can be dissolved even in apolar solvents and polyethylene.
Synthese und Eigenschaften eines mit C18-Ketten ,-substituierten Hypericinderivats
Zusammenfassung Ein in den Positionen , mit zwei C18-Ketten substituiertes Derivat des Hypericins (2) wurde ausgehend von Emodin synthetisiert. Die Gesamtausbeute der siebenstufigen Synthese betrug 12%. Die1H- und13C-NMR, absorptions- und emissionsspektroskopischen Eigenschaften wurden gemessen;2 kann sogar in apolaren Lösungsmitteln und Polyethylen gelöst werden.相似文献
40.
I. M. Skvortsov I. V. Antipova Yu. A. Pentin Tran Suan Khoan' S. V. Vasil'kovskii 《Chemistry of Heterocyclic Compounds》1975,11(8):949-955
1-(2-Furyl)-3-amino-4,4-dimethylpentane was used to obtain 3-tert-butyl-1,2-dihydropyrrolizine, the catalytic hydrogenation of which over Rh/Al2O3 at room temperature gives a mixture of cis- and trans-3,8-H-3-ter-butylpyrrolizidines with predominance of the cis isomer, whereas hydrogenation at 90–100 °C gives a mixture containing the trans isomer as the principal component. The three-dimensional structures of the isomers follow from data on the catalytic hydrogenation and isomerization and the IR, Raman, and PME spectra. A considerable percentage of the trans-fused form is characteristic for cis-3,8-H-3-tert-butylpyrrolizidine. 相似文献