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131.
Quasiclassical, direct dynamics trajectories have been used to study the reaction of formaldehyde cation with molecular hydrogen, simulating the conditions in an experimental study of H2CO+ vibrational effects on this reaction. Effects of five different H2CO+ modes were probed, and we also examined different approaches to treating zero-point energy in quasiclassical trajectories. The calculated absolute cross-sections are in excellent agreement with experiments, and the results provide insight into the reaction mechanism, product scattering behavior, and energy disposal, and how they vary with impact parameter and reactant state. The reaction is sharply orientation-dependent, even at high collision energies, and both trajectories and experiment find that H2CO+ vibration inhibits reaction. On the other hand, the trajectories do not reproduce the anomalously strong effect of nu2(+) (the CO stretch). The origin of the discrepancy and approaches for minimizing such problems in quasiclassical trajectories are discussed. 相似文献
132.
Charles U. Pittman Thane D. Rounsefell 《Journal of polymer science. Part A, Polymer chemistry》1973,11(3):621-628
Three programs have been written for calculations involving use of the penultimate copolymerization model. The first computes the penultimate reactivity ratios from composition-conversion data, without constraints, at any conversion. A nonlinear leastsquares technique using Marquardt's algorithm is employed. The second program computes the four optimum starting monomer feed ratios, M10/M20 which should be used by the experimenter from the penultimate reactivity ratios. These optimum feed ratios are obtained by choosing the conditions necessary to minimize the determinant of the variance-covariance matrix. The input for the first program includes estimates of known values of the penultimate reactivity ratios. By using these two programs sequentially the experimenter has an optimized experimental approach toward evaluating penultimate reactivity ratios at any conversion. Finally, a program has been provided to calculate composition–conversion data, given penultimate reactivity ratios. 相似文献
133.
Katleen Boussu Jérémie De Baerdemaeker Charles Dauwe Marc Weber Kelvin G Lynn Diederik Depla Steliana Aldea Ivo F J Vankelecom Carlo Vandecasteele Bart Van der Bruggen 《Chemphyschem》2007,8(3):370-379
This study presents a methodology for an in-depth characterization of six representative commercial nanofiltration membranes. Laboratory-made polyethersulfone membranes are included for reference. Besides the physical characterization [molecular weight cut-off (MWCO), surface charge, roughness and hydrophobicity], the membranes are also studied for their chemical composition [attenuated total reflectance Fourier spectroscopy (ATR-FTIR) and X-ray photoelectron spectroscopy (XPS)] and porosity [positron annihilation spectroscopy (PAS)]. The chemical characterization indicates that all membranes are composed of at least two different layers. The presence of an additional third layer is proved and studied for membranes with a polyamide top layer. PAS experiments, in combination with FIB (focused ion beam) images, show that these membranes also have a thinner and a less porous skin layer (upper part of the top layer). In the skin layer, two different pore sizes are observed for all commercial membranes: a pore size of 1.25-1.55 angstroms as well as a pore size of 3.20-3.95 angstroms (both depending on the membrane type). Thus, the pore size distribution in nanofiltration membranes is bimodal, in contrast to the generally accepted log-normal distribution. Although the pore sizes are rather similar for all commercial membranes, their pore volume fraction and hence their porosity differ significantly. 相似文献
134.
Sharon E. Davis A. Cameron Church Rebecca C. Tummons Charles F. Beam 《Journal of heterocyclic chemistry》1997,34(4):1159-1162
C(α)-Carboxylic acid esters were treated with excess lithium diisopropylamide, condensed with methyl salicylates or methyl thiosalicylate, followed by acid cyclization to either 4-hydroxy-3-substituted, 2H-1-benzopyran-2-ones (coumarins), or 2H-1-benzothiopyran-2-ones (thiocoumarins). 相似文献
135.
An azacrown system has been developed for selective membrane binding of phosphatidylinositol-4,5-bis(phosphate) recognition. Neutral and cationic forms of the metacyclophane macrocycles have been synthesized by divergent routes in acceptable yields. Such diversity will be useful in identifying anion receptors that operate best at membrane interfaces. 相似文献
136.
Arseniyadis S Subhash PV Valleix A Wagner A Mioskowski C 《Chemical communications (Cambridge, England)》2005,(26):3310-3312
The high-yielding synthesis and application of the first polymer supported reagent for the kinetic resolution (KR) of amines through enantioselective acetylation is described; this new supported chiral reagent allows the KR of primary amines with excellent selectivities at room temperature; moreover, this supported approach is highly efficient as the Merrifield-supported chiral scaffold can be quantitatively recovered and recycled. 相似文献
137.
Caruntu D Remond Y Chou NH Jun MJ Caruntu G He J Goloverda G O'Connor C Kolesnichenko V 《Inorganic chemistry》2002,41(23):6137-6146
Study of the reactivity of 3d transition metal cations in diethylene glycol solutions revealed several key features that made it possible to develop a new method for synthesis of the nanocrystalline transition metal ferrites. The 3-7 nm particles of [MFe2O4]n[O2CR]m, where M = Mn, Fe, Co, Ni, and Zn, ligated on their surface with long-chain carboxylate anions, have been obtained in an isolated yield of 75-90%. The key features are the following. Complexation of the first-row transition metal cations with diethylene glycol at a presence of alkaline hydroxide is sufficient to enable control over the rate of their hydrolysis. The reaction of hydrolysis leads to the formation of metal oxide nanocrystals in colloidal solution. The nanoparticles growth is terminated by an added long-chain carboxylic acid, which binds to their surface and acts as a capping ligand. The isolated nanocrystalline powders are stable against agglomeration and highly soluble in nonpolar organic solvents. 相似文献
138.
I. Alex Vitkin Joshua Woolsey Brian C. Wilson R. Rox Anderson 《Photochemistry and photobiology》1994,59(4):455-462
Abstract The optical properties and the thermal diffusivity of natural cuttlefish ( Sepia officinalis ) melanin have been measured. The optical absorption and scattering properties of melanin particles were determined at 580 nm and 633 nm, using photometric and photothermal techniques. For the photometric studies, the absorption and the transport scattering coefficients were determined from the measurements of diffuse reflectance and transmittance. The scattering anisotropy was obtained from an additional measurement of the total attenuation coefficient and independently obtained by goniometry. For photothermal studies, pulsed photothermal radiometry was used to deduce the absorption and transport scattering coefficients via a model based on optical diffusion theory. Pulsed photothermal radiometry was also used to provide the thermal diffusivity of solid melanin pressed pellets. 相似文献
139.
John T. Shaw Christine E. Brotherton Robert W. Moon Mark D. Winland Mark D. Anderson Keith S. Kyler 《Journal of heterocyclic chemistry》1980,17(1):11-16
A much improved synthesis of the heretofore difficultly obtainable 2,6-diaminopyrazine (4) was afforded by the low-pressure catalytic hydrogenation (palladium on carbon) of 2,6-diazido-pyrazine (2) ; reaction of 2,6-dichloropyrazine (1) and sodium azide gave 2 in 84% yield. The outcome of the reduction was found to be solvent dependent: 1,2-dimethoxyethane containing aqueous ammonia gave 4 in 83% yield; 1,2-dimethoxyethane alone gave 5-aminotetrazolo[1,5-a]-pyrazine (3) in 26% yield. Additional alternative syntheses of 3 and 4 are described. A number of acyl and azo derivatives of 4 were prepared. Reactions of 2 with dimethyl acetylenedicarboxylate and ethyl acetate (base catalyzed) leading to vic-triazole derivatives are also described. 相似文献
140.
The potential generated by a plastic-membrane calcium ion-selective electrode (i.s.e.) is shown to be indirectly measurable by a non-zero current method based on bipolar pulse conductance. Linear current—voltage curves are obtained using 0–5-V pulses; the current axis intercept is related to the i.s.e. potential. A simple electrical contact (e.g., platinum or stainless steel) can be used instead of a poised reference electrode as the counter electrode in this two-electrode system. Long-term exposure of the i.s.e. to calcium solutions causes an upward drift in the measured current. This drift is minimized by avoiding long exposure times to solution, rinsing the electrode between measurements, and constructing current—voltage curves for determination of the current axis intercepts. Voltage pulses lasting 100 μs are optimum for this method. Shorter pulses are subject to error from capacitive charging currents, and longer pulses yield poorer precision, and degrade the electrode through faradaic reactions. The measured signal is dependent upon Ca2+ concentration (rather than activity), making ionic strength adjustment unnecessary. The concentration dependence is induced by application of voltage pulses greater than ~ 15 mV in amplitude. Selectivities of the potentiometric and conductometric methods are shown to be comparable for a variety of interfering monovalent and divalent cations. The conductometric method yields a fast i.s.e. response because of induced migration of Ca2+ into the membrane. Response time decreases as the pulse height increases. Pulses greater than 2 V in magnitude yield response times limited by the solution mixing time rather than by the electrode. 相似文献