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Sabbe MK Saeys M Reyniers MF Marin GB Van Speybroeck V Waroquier M 《The journal of physical chemistry. A》2005,109(33):7466-7480
A complete and consistent set of 95 Benson group additive values (GAV) for the standard enthalpy of formation of hydrocarbons and hydrocarbon radicals at 298 K and 1 bar is derived from an extensive and accurate database of 233 ab initio standard enthalpies of formation, calculated at the CBS-QB3 level of theory. The accuracy of the database was further improved by adding newly determined bond additive corrections (BAC) to the CBS-QB3 enthalpies. The mean absolute deviation (MAD) for a training set of 51 hydrocarbons is better than 2 kJ mol(-1). GAVs for 16 hydrocarbon groups, i.e., C(C(d))(3)(C), C-(C(d))(4), C-(C(t))(C(d))(C)(2), C-(C(t))(C(d))(2)(C), C-(C(t))(C(d))(3), C-(C(t))(2)(C)(2), C-(C(t))(2)(C(d))(C), C-(C(t))(2)(C(d))(2), C-(C(t))(3)(C), C-(C(t))(3)(C(d)), C-(C(t))(4), C-(C(b))(C(d))(C)(H), C-(C(b))(C(t))(H)(2), C-(C(b))(C(t))(C)(H), C-(C(b))(C(t))(C)(2), C(d)-(C(b))(C(t)), for 25 hydrocarbon radical groups, and several ring strain corrections (RSC) are determined for the first time. The new parameters significantly extend the applicability of Benson's group additivity method. The extensive database allowed an evaluation of previously proposed methods to account for non-next-nearest neighbor interactions (NNI). Here, a novel consistent scheme is proposed to account for NNIs in radicals. In addition, hydrogen bond increments (HBI) are determined for the calculation of radical standard enthalpies of formation. In particular for resonance stabilized radicals, the HBI method provides an improvement over Benson's group additivity method. 相似文献
3.
Mexiletine— and lysine hydrochloride—o-phthalaldehyde and mexiletine hydrochloride—, cysteine—, cysteamine—, homocysteine— and lysine hydrochloride—fluorescamine derivatives were subjected to Triton and β-cyclodextrin enhancement treatments. Of several classical fluorescence-enhancing reagents tested (Triton, β-cyclodextrin, sodium dodecyl sulphate, Brij), Triton provided the best results, followed by β-cyclodextrin. Increases in fluorescence emission by a factor of up to about 10 (mexiletine—fluorescamine—Triton X-100) were observed, with a generally negligible influence of the enhancing reagents on the excitation and emission maxima. Fluorescence enhancement by the addition of a suitable reagent solution to the final analyte solution may, in specific instances, enhance the detectability of native or chemically induced fluorophores. 相似文献
4.
Gierczak T Jiménez E Riffault V Burkholder JB Ravishankara AR 《The journal of physical chemistry. A》2005,109(4):586-596
Rate coefficients for the gas-phase thermal decomposition of HO(2)NO(2) (peroxynitric acid, PNA) are reported at temperatures between 331 and 350 K at total pressures of 25 and 50 Torr of N(2). Rate coefficients were determined by measuring the steady-state OH concentration in a mixture of known concentrations of HO(2)NO(2) and NO. The measured thermal decomposition rate coefficients k(-)(1)(T,P) are used in combination with previously published rate coefficient data for the HO(2)NO(2) formation reaction to yield a standard enthalpy for reaction 1 of Delta(r)H degrees (298K) = -24.0 +/- 0.5 kcal mol(-1) (uncertainties are 2sigma values and include estimated systematic errors). A HO(2)NO(2) standard heat of formation, Delta(f)H degrees (298K)(HO(2)NO(2)), of -12.6 +/- 1.0 kcal mol(-1) was calculated from this value. Some of the previously reported data on the thermal decomposition of HO(2)NO(2) have been reanalyzed and shown to be in good agreement with our reported value. 相似文献
5.
Nucleophile‐Dependent Regio‐ and Stereoselective Ring Opening of 1‐Azoniabicyclo[3.1.0]hexane Tosylate 下载免费PDF全文
Mi‐Kyung Ji Dietmar Hertsen Doo‐Ha Yoon Heesung Eum Hannelore Goossens Prof. Dr. Michel Waroquier Prof. Dr. Veronique Van Speybroeck Prof. Dr. Matthias D'hooghe Prof. Dr. Norbert De Kimpe Prof. Dr. Hyun‐Joon Ha 《化学:亚洲杂志》2014,9(4):1060-1067
1‐[(1R)‐(1‐Phenylethyl)]‐1‐azoniabicyclo[3.1.0]hexane tosylate was generated as a stable bicyclic aziridinium salt from the corresponding 2‐(3‐hydroxypropyl)aziridine upon reaction with p‐toluenesulfonyl anhydride. This bicyclic aziridinium ion was then treated with various nucleophiles including halides, azide, acetate, and cyanide in CH3CN to afford either piperidines or pyrrolidines through regio‐ and stereoselective ring opening, mediated by the characteristics of the applied nucleophile. On the basis of DFT calculations, ring‐opening reactions under thermodynamic control yield piperidines, whereas reactions under kinetic control can yield both piperidines and pyrrolidines depending on the activation energies for both pathways. 相似文献
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A Flexible Photoactive Titanium Metal–Organic Framework Based on a [TiIV3(μ3‐O)(O)2(COO)6] Cluster 下载免费PDF全文
Bart Bueken Dr. Frederik Vermoortele Dr. Danny E. P. Vanpoucke Dr. Helge Reinsch Dr. Chih‐Chin Tsou Dr. Pieterjan Valvekens Dr. Trees De Baerdemaeker Prof. Dr. Rob Ameloot Prof. Dr. Christine E. A. Kirschhock Prof. Dr. Veronique Van Speybroeck Prof. Dr. James M. Mayer Prof. Dr. Dirk De Vos 《Angewandte Chemie (International ed. in English)》2015,54(47):13912-13917
The synthesis of titanium–carboxylate metal–organic frameworks (MOFs) is hampered by the high reactivity of the commonly employed alkoxide precursors. Herein, we present an innovative approach to titanium‐based MOFs by the use of titanocene dichloride to synthesize COK‐69, the first breathing Ti MOF, which is built up from trans‐1,4‐cyclohexanedicarboxylate linkers and an unprecedented [TiIV3(μ3‐O)(O)2(COO)6] cluster. The photoactive properties of COK‐69 were investigated in depth by proton‐coupled electron‐transfer experiments, which revealed that up to one TiIV center per cluster can be photoreduced to TiIII while preserving the structural integrity of the framework. The electronic structure of COK‐69 was determined by molecular modeling, and a band gap of 3.77 eV was found. 相似文献
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9.
Mifsud N Mellon V Perera KP Smith DW Echegoyen L 《The Journal of organic chemistry》2004,69(18):6124-6127
Electron paramagnetic resonance (EPR) spectroscopy was successfully used for the first time to follow the Bergman cyclization of bis-ortho-diynyl arene (BODA) compounds. Five BODA monomers with different spacer (X) and terminal groups (R) were compared. In situ polymerization via EPR spectroscopy yielded first-order rate expressions. Monomers with spacer -O- or -C(CF(3))(2) and terminal group R = Ph exhibited similar kinetic behavior upon thermal polymerization, whereas monomers with pyridine and thiophene terminal groups gave significantly higher rates of polymerization over phenyl-terminated derivatives. A model compound, 1,2-bis(phenylethynyl)benzene, was used to probe the polymerization mechanism, and radical intermediates were found to be stable indefinitely at room temperature. 相似文献
10.
Prof. Dr. Karen Hemelsoet Qingyun Qian Thierry De Meyer Kristof De Wispelaere Dr. Bart De Sterck Prof. Dr. Bert M. Weckhuysen Prof. Dr. Michel Waroquier Prof. Dr. Veronique Van Speybroeck 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(49):16595-16606
The optical absorption properties of (poly)aromatic hydrocarbons occluded in a nanoporous environment were investigated by theoretical and experimental methods. The carbonaceous species are an essential part of a working catalyst for the methanol‐to‐olefins (MTO) process. In situ UV/Vis microscopy measurements on methanol conversion over the acidic solid catalysts H‐SAPO‐34 and H‐SSZ‐13 revealed the growth of various broad absorption bands around 400, 480, and 580 nm. The cationic nature of the involved species was determined by interaction of ammonia with the methanol‐treated samples. To determine which organic species contribute to the various bands, a systematic series of aromatics was analyzed by means of time‐dependent density functional theory (TDDFT) calculations. Static gas‐phase simulations revealed the influence of structurally different hydrocarbons on the absorption spectra, whereas the influence of the zeolitic framework was examined by using supramolecular models within a quantum mechanics/molecular mechanics framework. To fully understand the origin of the main absorption peaks, a molecular dynamics (MD) study on the organic species trapped in the inorganic host was essential. During such simulation the flexibility is fully taken into account and the effect on the UV/Vis spectra is determined by performing TDDFT calculations on various snapshots of the MD run. This procedure allows an energy absorption scale to be provided and the various absorption bands determined from in situ UV/Vis spectra to be assigned to structurally different species. 相似文献