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711.
Marianne Nofz Jens-Rainer Lochmann Hans-Georg Bartel Werner Haberditzl 《Monatshefte für Chemie / Chemical Monthly》1982,113(5):547-552
The procedure described in1,2 was used to calculate the magnetic susceptibility contributions of C-H bonds to the diamagnetism of various hydrocarbons. It was found a correlation between these C-H-bond contributions and the bond lengths. The transferability of the evaluated C-H-bond susceptibilities from one molecule to another is discussed. 相似文献
712.
713.
TiOBr was prepared by reaction of Ti with TiO2 and Br2. The compound forms fiat reddish-brown needles and shows a temperature independent weak paramagnetism. It crystallises in the orthorhombic system (Pmmn; a = 3.787, b = 3.487, c = 8.529 Å) with the FeOCl type of structure. The interatomic distances are Ti?O = 1.952; 2.245 Å (2X) and Ti?Br = 2.544 Å (2X). 相似文献
714.
715.
The 13C NMR α-substituent effects within the series methane to neopentane and ethene to isobutene have been calculated using Hartree—Fock perturbation theory with MINDO/3. The sign and order of magnitude of the calculated α-effects are in agreement with new experimental values, including effects of multiple substitution. 相似文献
716.
Stavitski E Kox MH Weckhuysen BM 《Chemistry (Weinheim an der Bergstrasse, Germany)》2007,13(25):7057-7065
A combination of in-situ optical and fluorescence microspectroscopy has been employed to investigate the oligomerization of styrene derivatives occurring in the micropores of coffin-shaped H-ZSM-5 zeolite crystals in a space- and time-resolved manner. The carbocationic intermediates in this reaction act as reporter molecules for catalytic activity, since they exhibit strong optical absorption and fluorescence. In this way, reactant selectivity and restricted transition-state selectivity for 14 substituted styrene molecules can be visualized and quantified. Based on a thorough analysis of the time- and space-resolved UV/Vis spectra, it has been revealed that two main parameters affect the reaction rates, namely, the carbocation stabilization effect and the diffusion hindrance. The stabilization effect was tested by comparison of the reaction rates for 4-methoxystyrene versus 4-methylstyrene and in the series 4-bromo-, 4-chloro and 4-fluorostyrene; in both cases less electronegative substituents were found to accelerate the reaction. As to the steric effect, bulkier chemical groups bring down the reaction rate, as evident from the observation that 4-methoxystyrene is more reactive than 4-ethoxystyrene due to differences in their diffusivity, while heavily substituted styrenes, such as 3,4-dichlorostyrene and 2,3,4,5,6-pentafluorostyrene, cannot enter the zeolite pore system and therefore do not display any reactivity. Furthermore, beta-methoxystyrene and trans-beta-methylstyrene show limited reactivity as well as restricted reaction-product formation due to steric constraints imposed by the H-ZSM-5 channel system. Finally, polarized-light optical microspectroscopy and fluorescence microscopy demonstrate that dimeric styrene compounds are predominantly formed and aligned within the straight channels at the edges of the crystals, whereas a large fraction of trimeric carbocations along with dimeric compounds are present in the straight channels of the main body of the H-ZSM-5 crystals. Our results reinforce the observation of a non-uniform catalytic behavior within zeolite crystals, with specific parts of the zeolite grains being less accessible and reactive towards reactant molecules. The prospects and potential of this combined in-situ approach for studying large zeolite crystals in the act will be discussed. 相似文献
717.
Prasuhn DE Yeh RM Obenaus A Manchester M Finn MG 《Chemical communications (Cambridge, England)》2007,(12):1269-1271
Icosahedral virus particles decorated with a Gd(DOTA) analogue by Cu-mediated azide-alkyne cycloaddition (CuAAC) and/or with Gd(3+) ions by coordination to the viral nucleoprotein show increased T(1) relaxivity relative to free Gd(DOTA) complexes in solution. 相似文献
718.
The conformation and titration curves of weak polyampholytes are examined using Monte Carlo simulations with screened Coulomb potentials in the Grand Canonical ensemble. Two different types of monomers are considered. Depending on the solution pH, monomers A are weak acidic sites that can either be negatively charged or uncharged (as carboxylic groups), whereas monomers B are weak basic sites that can either be positively charged or uncharged (as amino groups). The influence of the chain stiffness, primary structure, and ionic concentration on the acid/base properties of the polyampholyte chains are systematically investigated. By adjusting the pH values, titration curves and then the fractions of positively and negatively ionized charged monomers are calculated. Stiffness influence is estimated by comparing two models of chain: a fully flexible and a rod-like polyampholyte. Different primary structures such as statistical (diblock, octablock, and alternating) and random polyampholytes are also considered. We demonstrate that the primary structure plays important roles in the acid/base properties as well as the charge distribution along the polymer backbone of a statistical rod-like polyampholyte. When flexible polyampholytes are considered, polyampholyte conformations promote the attractive electrostatic interactions between positively and negatively charged monomers, hence leading to more or less compact conformations and acid/base properties relatively different in comparison to the rod-like polyampholytes. Various conformations such as extended, globular, and pearl-necklace conformations are found in good agreement with the literature by adjusting the interaction parameter between monomers and monomer stoichiometry. 相似文献
719.
Brask J Damstrup ML Nielsen PM Holm HC Maes J De Greyt W 《Applied biochemistry and biotechnology》2011,163(7):918-927
An integrated biodiesel process that combines enzymatic esterification and alkaline transesterification is suggested. With
focus on the enzymatic step, the paper provides proof of concept and suggestions for further process development. Hence, palm
fatty acid distillate (PFAD) has been enzymatically converted to fatty acid methyl esters in a two-step process using the
immobilized lipase Novozym 435 in packed-bed columns. With only a small excess of methanol, the first reaction stage could
reduce the free fatty acid (FFA) content from 85% to 5%. After removal of water by simple phase separation, it was possible
to lower the FFA content to 2.5% in a second reaction stage. Both reaction stages are relatively fast with suggested reaction
times of 15 min in column 1 (productivity 10 kg/kg/h) and 30 min in column 2 (productivity 5 kg/kg/h), resulting in 15% FFA
after column 1 and 5% FFA after column 2. A lifetime study indicated that approximately 3,500 kg PFAD/kg Novozym 435 can be
treated in the first reaction stage before the enzyme has become fully inactivated. With further optimization, the enzymatic
process could be a real alternative to today’s sulfuric acid catalyzed process. 相似文献
720.
Gollmer A Arnbjerg J Blaikie FH Pedersen BW Breitenbach T Daasbjerg K Glasius M Ogilby PR 《Photochemistry and photobiology》2011,87(3):671-679
The development of efficient and selective luminescent probes for reactive oxygen species, particularly for singlet molecular oxygen, is currently of great importance. In this study, the photochemical behavior of Singlet Oxygen Sensor Green® (SOSG), a commercially available fluorescent probe for singlet oxygen, was examined. Despite published claims to the contrary, the data presented herein indicate that SOSG can, in fact, be incorporated into a living mammalian cell. However, for a number of reasons, caution must be exercised when using SOSG. First, it is shown that the immediate product of the reaction between SOSG and singlet oxygen is, itself, an efficient singlet oxygen photosensitizer. Second, SOSG appears to efficiently bind to proteins which, in turn, can influence uptake by a cell as well as behavior in the cell. As such, incorrect use of SOSG can yield misleading data on yields of photosensitized singlet oxygen production, and can also lead to photooxygenation‐dependent adverse effects in the system being investigated. 相似文献