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991.
Lingping Wang Aiguo Kong Bo Chen Hanming Ding Yongkui Shan Mingyuan He 《Journal of molecular catalysis. A, Chemical》2005,230(1-2):143-150
Transition metal copper substituted mesoporous silica (Cu-SBA-15) was synthesized using triblock copolymers surfactant as template agent under acidic condition. The result Cu-SBA-15 was characterized with XRD, ICP-AES, FT-IR and N2 adsorption–desorption measurements, which prove that Cu(II) was mainly incorporated into the framework of Cu-SBA-15. Its catalytic activity was studied for phenol hydroxylation using H2O2 (30%). The substituting element (Cu2+) is incorporated into the framework position forming a new type of active site which raises the phenol conversion to 62.4% and the diphenol (the mixture of catechol (CAT) and hydroquinone (HQ)) selectivity to 97%. The Cu-SBA-15 has very high selectivity for catechol (about 71% selectivity), which is completely different from that of the microporous titanium silicalite zeolites (47.1% phenol conversion and about 50% selectivity to CAT under same reaction conditions). The results obtained indicate that the selective oxidation of phenol with H2O2 by a radical substitution mechanism. 相似文献
992.
Martin Gruebele 《Theoretical chemistry accounts》2003,109(2):53-63
Vibrational energy flow in organic molecules occurs by a multiple-time-scale mechanism that can be modeled by a single exponential
only in its initial stages. The mechanism is a consequence of the hierarchical structure of the vibrational Hamiltonian, which
leads to diffusion of vibrational wavepackets on a manifold with far fewer than the 3N−6 dimensions of the full vibrational state space. The dynamics are controlled by a local density of states, which does not
keep increasing with molecular size. In addition, the number of vibrational coordinates severely perturbed during chemical
reaction is small, leading to preservation of the hierarchical structure at chemically interesting energies. This regularity
opens up the possibility of controlling chemical reactions by controlling the vibrational energy flow. Computationally, laser
control of intramolecular vibrational energy redistribution can be modeled by quantum-classical, or by purely quantum-mechanical
models of the molecule and control field.
Received: 26 July 2002 / Accepted: 30 September 2002 / Published online: 2 December 2002
Electronic Supplementary Material to this paper can be obtained by using the Springer Link server located at http://dx.doi.org/10.1007/s00214-002-0394-2.
Acknowledgements. This work was supported by NSF grant CHE 9986670.
Correspondence to: M. Gruebele e-mail: gruebele@scs.uiuc.edu 相似文献
993.
M. M. Kabachnik Z. S. Novikova I. A. Chadnaya A. A. Borisenko I. P. Beletskaya 《Russian Chemical Bulletin》1998,47(2):332-339
A series of phosphorus(iii)-substituted azomethines and enamines were synthesized by the reaction of lithium salts of aldimines and ketimines with derivatives
of phosphorus(iii) acids. Some properties of the compounds synthesized were studied.
Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 339–346, February, 1998. 相似文献
994.
Geometries and stabilization energies of various simple H-bonded complexes (water dimer, hydrogen fluoride dimer, formamide
dimer, formic acid dimer) have been determined by a gradient optimization that eliminates the basis set superposition error
(BSSE) by the counterpoise (CP) method in each gradient cycle as well as by the standard gradient optimization. Both optimization
methods lead to different potential energy surfaces (PES). The difference depends on the theoretical level used and is larger
if correlation energy is considered. Intermolecular distances from the CP-corrected PES are consistently longer, and this
difference might be significant (∼0.1 ?); also angular characteristics determined from both surfaces differ significantly.
Different geometries were obtained even when passing to larger basis sets (aug-cc-pVDZ). The standard optimization procedure
can result in a completely wrong structure. For example, the “quasi-linear” structure of the (HF)2 (global minimum) does not exist at the standard MP2/ 6-31G** PES (where only cyclic structure was detected) and is found
only at the CP-corrected PES. Stabilization energies obtained from the CP-corrected PES are always larger than these from
the standard PES where the BSSE is added only a posteriori for the final optimized structure; both energies converge only
when passing to a larger basis set (aug-cc-pVDZ).
Received: 11 March 1998 / Accepted: 19 June 1998 / Published online: 4 September 1998
RID="
ID=" <E6>Acknowledgements.</E6> The project was supported by the Grant Agency of the Czech Republic (Grant No. 203/98/1166).
RID="
ID=" <E5>Correspondence to</E5>: P. Hobza 相似文献
995.
Novel furo, thieno and pyrrolo[2,3‐b]pyrazole cyanine dyes were synthesized. The structure‐photosensitization properties correlation of the dyes were examined in 95% ethanol solution by absorption spectroscopy. The chemical structure of the starting biheterocyclic compounds and their derived cyanine dyes were confirmed by elemental analysis, IR and 1H NMR spectroscopy. 相似文献
996.
997.
Solvent shift in water of π → π* transitions of the carbonyl group is evaluated making use of a recently proposed computdtional procedure for the continuum solvent model. Comparisons with the discrete model and with composite discrete-continuum procedures are performed. 相似文献
998.
Solid Phase Extraction and Flame Atomic Absorption Spectrometric Determination of Trace Amounts of Zinc and Cobalt Ions in Water Samples 总被引:1,自引:0,他引:1
A simple and rapid method for the preconcentration of Co2+ and Zn2+ as their 2-guanidino-benzimidazole chelates is proposed using an octadecyl silica cartridge. The retained analytes were recovered with a mixture of 5mL of 0.01M HNO3 and 5mL of methanol. The metal ions in the effluent were determined by flame atomic absorption spectrometry. The effect of different parameters, such as sample matrix, amount of ligand, type of eluent for elution of ions from cartridge, flow rates of sample solution and eluent, breakthrough volume, and limit of detection, were evaluated. The effects of various cationic and anionic interferences on the percent recovery of Co2+ and Zn2+ were also studied. Quantitative extraction efficiencies were obtained by elution of the cartridge with a minimal amount of solvent. Hence, with a typical preconcentration factor of 50, the limits of detections of the proposed method are 0.26 and 1.62ngmL–1 for Zn2+ and Co2+, respectively. The method was applied to the determination of zinc and cobalt ions in different water samples. 相似文献
999.
V. I. Terenin E. A. Sumtsova M. A. Kovalkina S. Z. Vatsadze E. V. Kabanova A. P. Pleshkova N. V. Zyk 《Chemistry of Heterocyclic Compounds》2003,39(11):1487-1491
A series of previously unreported aldehydes has been prepared by the formylation reaction of dipyrrolo[1,2-a;2':,1'-c]pyrazines and their 5,6-dihydro analogs by DMF and phosphorus oxychloride. 相似文献
1000.
An electrochemical method has been developed for determining the relative amounts of V(II) and V(III) in polyolefin catalysts prepared using aluminum alkyls and vanadium trichloride. The catalyst, usually obtained as a slurry in n-heptane, is titrated potentiometrically with ceric sulfate using a platinum indicator electrode. Under proper experimental conditions, 2 breaks are obtained, corresponding to the reactions V(II) →V(III) + e and V(III) →V(IV) + e. Interferences from other components of the catalyst are negligible. The method is useful for the analysis of both laboratory catalysts and grab samples taken from pilot plant reactors. 相似文献