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131.
The ratio of the Br + Br2 halogen atom exchange rate, k2, to the Br + HI reaction rate k1, has been determined experimentally by using an isotopically selective, laser-initiated chemical reaction. At 294 K, k2/k1 = 4, and thus, k2 = 4 × 10?11 cm3 molecule?1 s?1. 相似文献
132.
Judy N. Hart Laure Bourgeois Raoul Cervini Yi-Bing Cheng George P. Simon Leone Spiccia 《Journal of Sol-Gel Science and Technology》2007,42(2):107-117
TiO2 nanoparticles are widely used for many applications and an understanding of the crystallization behavior of TiO2 is essential, so that heat treatment conditions can be optimized for particular applications. The effect of sol–gel synthesis
conditions on the crystallization behavior of TiO2 has, therefore, been investigated. Complete crystallization to the anatase phase (determined by XRD and TEM analysis) was
achieved during drying of the synthesis product at 95 °C. The nanoparticles grew during heat treatment, reaching ∼10–15 nm
in diameter with a heat treatment at 450 °C. Explanations are offered for the observed differences in the crystallization
and particle growth behavior of TiO2 synthesized under various conditions. 相似文献
133.
The C2H2 + O(3P) and HCCO + O(3P) reactions are investigated using Fourier transform infrared (FTIR) emission spectroscopy. The O(3P) radicals are produced by 193 nm photolysis of an SO2 precursor or microwave discharge in O2. The HCCO radical is either formed in the first step of the C2H2 + O(3P) reaction or by 193 nm photodissociation of ethyl ethynyl ether. Vibrationally excited CO and CO2 products are observed. The microwave discharge experiment [C2H2 + O(3P)] shows a bimodal distribution of the CO(v) product, which is due to the sequential C2H2 + O(3P) and HCCO + O(3P) reactions. The vibrational distribution of CO(v) from the HCCO + O(3P) reaction also shows its own bimodal shape. The vibrational distribution of CO(v) from C2H2 + O(3P) can be characterized by a Boltzmann plot with a vibrational temperature of approximately 2400 +/- 100 K, in agreement with previous results. The CO distribution from the HCCO + O(3P) reaction, when studied under conditions to minimize other processes, shows very little contamination from other reactions, and the distribution can be characterized by a linear combination of Boltzmann plots with two vibrational temperatures: 2320 +/- 40 and 10 300 +/- 600 K. From the experimental results and previous theoretical work, the bimodal CO(v) distribution for the HCCO + O(3P) reaction suggests a sequential dissociation process of the HC(O)CO++ --> CO + HCO; HCO --> H + CO. 相似文献
134.
Esteves PM De M Carneiro JW Cardoso SP Barbosa AG Laali KK Rasul G Prakash GK Olah GA 《Journal of the American Chemical Society》2003,125(16):4836-4849
The mechanism of electrophilic aromatic nitration was revisited. Based on the available experimental data and new high-level quantum chemical calculations, a modification of the previous reaction mechanism is proposed involving three separate intermediates on the potential energy diagram of the reaction. The first, originally considered an unoriented pi-complex or electron donor acceptor complex (EDA), involves high electrostatic and charge-transfer interactions between the nitronium ion and the pi-aromatics. It explains the observed low substrate selectivity in nitration with nitronium salts while maintaining high positional selectivity, as well as observed oxygen transfer reactions in the gas phase. The subsequent second intermediate originally considered an oriented "pi-complex" is now best represented by an intimate radical cation-molecule pair, C(6)H(6)(+)(*)()/NO(2), that is, a SET complex, indicative of single-electron transfer from the aromatic pi-system to NO(2)(+). Subsequently, it collapses to afford the final sigma-complex intermediate, that is, an arenium ion. The proposed three discrete intermediates in electrophilic aromatic nitration unify previous mechanistic proposals and also contribute to a better understanding of this fundamentally important reaction. The previously obtained ICR data of oxygen transfer from NO(2)(+) to the aromatic ring are also accommodated by the proposed mechanism. The most stable intermediate of this reaction on its potential energy surface is a complex between phenol and NO(+). The phenol.NO(+) complex decomposes affording C(6)H(6)O(+)(*)/PhOH(+) and NO, in agreement with the ICR results. 相似文献
135.
Gianluca Melillo Lorella Izzo Roberto Centore Angela Tuzi Alexander Z. Voskoboynikov Leone Oliva 《Journal of molecular catalysis. A, Chemical》2005,230(1-2):29-33
The meso ansa zirconocene with dimethylsilyl bridge, activated by methylalumoxane, catalyses the ethylene polymerization, producing ethyl-branched polyethylene. With respect to the polymers obtained with the previously investigated meso zirconocenes, we have found higher branching amount and lower molecular weight. The rapid β-H transfer from the growing chain to the coordinated monomer could account for both these features of the polymer. The investigation on the structural parameters of the complex, through X-ray diffraction analysis, and on the electrophilicity of the cationic center, through NMR experiments, suggests, as a possible rationalization of this behavior, the obstruction in the inward site. 相似文献
136.
R. Benedikt F. Ulzer Focke Finkener Th. Morawski Alfred H. Allen O. Schweissinger R. Marzahn Dieterich Hazura F. W. A. Woll Bruno Röse Ch. Dubois L. Padé R. Bensemann Audoynaud Levallois T. Leone A. Longi F. Benecke Joseph Herz P. Soltsien C. Schädler C. L. Reimer W. Will H. Hager 《Analytical and bioanalytical chemistry》1888,27(1):524-539
137.
Madonna AJ Van Cuyk S Voorhees KJ 《Rapid communications in mass spectrometry : RCM》2003,17(3):257-263
The application of whole cell analysis by matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS) has emerged as a valuable tool for rapidly identifying/detecting bacteria. This technique requires minimal sample preparation and is simple to perform, but is generally limited to purified samples of bacteria at concentrations greater than 1.0 x 10(6) cells/mL. In this paper, we describe a bacterial detection method that integrates immunomagnetic separation with bacteriophage amplification prior to MALDI-MS analysis. The developed method consists of three main stages: (1) isolation of a target bacterium by immunomagnetic separation; (2) infection of the immuno-captured bacterium with a lytic bacteriophage; and (3) assay of infected medium for bacteriophage progeny using MALDI-MS to produce a molecular weight signal for the virus capsid protein. With this technique, the presence of Escherichia coli in broth was determined in less then 2 h total analysis time at a concentration of approximately 5.0 x 10(4) cells/mL. 相似文献
138.
Sheila Ruiz‐Botella Dr. Pietro Vidossich Dr. Gregori Ujaque Dr. Cristian Vicent Prof. Eduardo Peris 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(29):10558-10565
Tetraannulation of a resorcinarene‐octaamino cavitand with ferrocenecarboxaldehyde allows the preparation of a tetrabenzimidazole‐resorcinarene cavitand with four ferrocenyl moieties directly linked to the C2 atom of the imidazole units. Oxidation of the four ferrocenyl moieties produces important structural modifications of the molecule, as indicated by DFT calculations performed for the neutral and tetraoxidized forms of the cavitand. By means of 1H NMR spectroscopic analysis, the encapsulating properties of the new tetraferrocenyl‐resorcinarene cavitand toward a series of ammonium salts were evaluated, and a clear cutoff point in binding affinity with respect to size was observed. Cyclic voltammetric studies allowed us to estimate the relative association constants for the neutral and oxidized forms of the cavitand, thus indicating that the guest was bound to the neutral (reduced) state of the cavitand and was released from the oxidized form. These redox‐addressable conformational and binding properties of the resorcinarene‐tetraferrocenyl cavitand constitute all the necessary features of a redox‐switchable molecular gripper. By means of mass‐spectrometric analysis, we could unambiguously confirm the molar stoichiometry of the host–guest complex (1:1) and assess the strong guest encapsulation, as indicated by triggering the covalent coupling between host and guest in the gas phase. 相似文献
139.
S. Kontogiorgis R. De Leone R. R. Meyer 《Journal of Optimization Theory and Applications》1996,90(1):1-29
We develop and compare three decomposition algorithms derived from the method of alternating directions. They may be viewed as block Gauss-Seidel variants of augmented Lagrangian approaches that take advantage of block angular structure. From a parallel computation viewpoint, they are ideally suited to a data parallel environment. Numerical results for large-scale multicommodity flow problems are presented to demonstrate the effectiveness of these decomposition algorithmims on the Thinking Machines CM-5 parallel supercomputer relative to the widely-used serial optimization package MINOS 5.4.This material is based on research supported by the Air Force Office of Scientific Research, Grants AFORS-89-0410 and F49620-1-0036, and by NSF Grants CCR-89-07671, CDA-90-24618, and CCR-93-06807. The work of the second author was supported partially by Grant 95.00732.CT01 from the Italian National Research Council (CNR). 相似文献
140.
Wilson BJ Forrest K van Teijlingen ER McKee L Haites N Matthews E Simpson SA 《Community genetics》2004,7(1):15-24
Although family communication is important in clinical genetics only a small number of studies have specifically explored the passing on of genetic knowledge to family members. In addition, many of these present exploratory or tentative findings based upon small sample sizes, or data collected only a short time after testing. Nevertheless, if health professionals are to develop effective strategies to help patients' deal with communication issues, we need to know more about what actually happens in families. The aim of this commentary is to identify factors which appear to influence whether patients share information about genetic risk with relatives who are unaware of that risk, with whom they share it and how they go about it. The paper draws upon evidence and thinking from the disciplines of psychology (including family therapy), sociology, medicine and genetic counselling. It is presented under the following headings: disease factors, individual factors, family factors and sociocultural factors. It concludes by highlighting a number of key issues which are relevant for health professionals. 相似文献