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101.
The versatile reagent [η5-C5H5)Fe(CO)2(THF)]BF4 has been isolated from the reaction of (η5-C5H5)Fe(CO)2I and AgBF4 in THF and shown to react in CH2Cl2 with olefins to yield [(η5-C5H5)Fe(CO)2(η2-olefin)]BF4 complexes. For most olefins the yields are high. The yield in these reactions can be increased by treating the CH2Cl2 solution of [(η5-C5H5)Fe(Co)2(THF)]BF4 and olefin with gaseous BF3 in order to complex the THF as the BF3-THF adduct. Most striking is the increase in yield for the cyclohexene complex from 17% to 92%. 相似文献
102.
The reactions of 4-carboxy-1,2-cyclohexanedionedioxime and nickel(II) were studied in alkaline media. Spectrophotometric studies indicate the presence of a 1:1 complex ion, NiD-. Magnetic susceptibility measurements on a series of solutions of varying ratios of vic-dioxime and nickel(II) showed that the 1:1 complex ion was diamagnetic and that two paramagnetic complexes, probably NiD24- and NiD37-, are present in solution. The stability constants for the three complexes were calculated from spectrophotometric and magnetic susceptibility data. The log K values were found to be log K1 = 28.74 ± 0.60, log K2 = 0.76 ± 0.15, and log K3 = 3.67 ± 0.73, respectively. 相似文献
103.
Micha Kijak Anna Zieli ska Charles Chamchoumis Jerzy Herbich Randolph P. Thummel Jacek Waluk 《Chemical physics letters》2004,400(4-6):279-285
Depending on the polarity and protic abilities of the solvent, 2-(2′-pyridyl)pyrrole can exist in either syn or anti rotameric forms. In nonpolar solvents, intramolecular excited state single proton transfer is observed, manifested by the appearance of low-energy tautomeric emission. The solvent-assisted excited state double proton transfer reaction is also detected. DFT calculations confirm low barriers for both single and double proton transfer processes in the lowest excited singlet state and show different character of the tautomerization in both cases: in the intramolecular reaction, mutual approach of two nitrogen atoms plays an important role. 相似文献
104.
Siwy Z Trofin L Kohli P Baker LA Trautmann C Martin CR 《Journal of the American Chemical Society》2005,127(14):5000-5001
There is increasing interest in the concept of using nanopores as the sensing elements in biosensors. The nanopore most often used is the alpha-hemolysin protein channel, and the sensor consists of a single channel embedded within a lipid bilayer membrane. An ionic current is passed through the channel, and analyte species are detected as transient blocks in this current associated with translocation of the analyte through the channel-stochastic sensing. While this is an extremely promising sensing paradigm, it would be advantageous to eliminate the very fragile lipid bilayer membrane and perhaps to replace the biological nanopore with an abiotic equivalent. We describe here a new family of protein biosensors that are based on conically shaped gold nanotubes embedded within a mechanical and chemically robust polymeric membrane. While these sensors also function by passing an ion current through the nanotube, the sensing paradigm is different from the previous devices in that a transient change in the current is not observed. Instead, the protein analyte binds to a biochemical molecular-recognition agent at the mouth of the conical nanotube, resulting in complete blockage of the ion current. Three different molecular-recognition agents, and correspondingly three different protein analytes, were investigated: (i) biotin/streptavidin, (ii) protein-G/immunoglobulin, and (iii) an antibody to the protein ricin with ricin as the analyte. 相似文献
105.
The infrared spectrum for the vapour, liquid and solid states of epifluorohydrin has been studied, and evidence has been obtained for the presence of rotational isomers. The dominant conformer in all phases corresponds to a gauche structure, which was the only form identified in the vapour by microwave spectroscopy [1]. Similar evidence for conformational equilibria has been found for the chloro, bromo and iodo derivatives, and the enthalpy differences between the rotational isomers of these compounds were measured respectively as 4580 ± 970, 3950 ± 400, and 2350 ± 170 J mol?1 respectively. At low temperatures, epiiodohydrin was found to crystallize in one of two possible crystalline phases. These two phases correspond to the two rotational isomeric conformations of the molecule. 相似文献
106.
The C-C coupling reaction between ethyl acetoacetate and aryl halides in the presence of CuI is described. The effects of solvent, ligands such as vicinal diamines and amino acids, base and temperature are reported. The arylated acetoacetate ester is deacylated under the reaction conditions resulting in the generation of 2-arylacetic acid esters, constituting a mild alternative to direct arylation of carboxylate esters. 相似文献
107.
Charles H. Warren 《Chemical physics letters》1980,72(2):233-236
Upper state vibronic levels associated with totally symmetric fundamentals of the fluorosulfate radical were populated by means of dye laser excitation. The analysis of the resulting fluorescence confirmed the assignment of these levels. Theoretical intensities using the Green's function approach to vibronic coupling were calculated and compared to the experimental values. 相似文献
108.
Charles R. Ojala William H. Ojala Doyle Britton Christopher J. Cramer 《Acta Crystallographica. Section C, Structural Chemistry》2007,63(9):o518-o523
Three polymorphs of 4,4′‐diiodobenzalazine (systematic name: 4‐iodobenzaldehyde azine), C14H10I2N2, have crystallographically imposed inversion symmetry. 4‐Chloro‐4′‐iodobenzalazine [systematic name: 1‐(4‐chlorobenzylidene)‐2‐(4‐iodobenzylidene)diazane], C14H10ClIN2, has a partially disordered pseudocentrosymmetric packing and is not isostructural with any of the polymorphs of 4,4′‐diiodobenzalazine. All structures pack utilizing halogen–halogen interactions; some also have weak π (benzene ring) interactions. A comparison with previously published methylphenylketalazines (which differ by substitution of methyl for H at the azine C atoms) shows a fundamentally different geometry for these two classes, namely planar for the alazines and twisted for the ketalazines. Density functional theory calculations confirm that the difference is fundamental and not an artifact of packing forces. 相似文献
109.
110.
Charles E. Carraher D'Orsay Winthers Frank Millich 《Journal of polymer science. Part A, Polymer chemistry》1969,7(10):2763-2773
The stirred interfacial polycondensation of phenylphosphonic dichloride and 1,6-hexanediamine has been studied as a function of several reaction variables. The reaction is rapid, being completed in less than 1 min. When organic solvent is varied and reactant molar ratio is varied with an excess of the acid chloride, yield is constant. When reactant molar ratio is varied polymer yield increases with increase in amine concentration. When reactant concentration is increased yield increases. With the addition of a soluble salt in the aqueous phase yield is increased. The above indicates that the diffusion of the amine to the reaction zone is of primary importance in determining polymerization rate and that the diffusion of the acid chloride is relatively unimportant. Polymer yield was found to be dependent on the pH of the amine in the aqueous phase. The observed trend is related to the apparent solubility of the amine in the aqueous phase such that the greater the apparent solubility of the amine, the less the polymer yield. Polymer molecular weight is found to be independent of reaction variables tested. Polymer was also formed from the condensation of phenylphosphonic dichloride with p-phenylenediamine, H2N-D-NH2 (where D is a 36-carbon hydrocarbon chain), 1,3-di-4-piperidylpropane, and 4-aminomethylpiperidine; phenyl phosphorodichloridate with 1,6-hexanediamine; chloromethyl phosphonic dichloride with 1,6-hexanediamine. 相似文献