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91.
M.Mark Midland Ronald L. Halterman Charles A. Brown Angela Yamaichi 《Tetrahedron letters》1981,22(42):4171-4172
The isomerization of optically-active secondary propargyl alcohols, RCHOHCC(CH2)nCH3, to terminal acetylenic alcohols, RCHOH(CH2)n+1 C=CH, by potassium 3-aminopropylamide (KAPA) proceeds without loss of configuration at the hydroxy center. 相似文献
92.
The total synthesis is described of (±) 6-(7-carboxy hept-1-yl) 3-hydroxy 2-methyl piperidine [(±) carpamic acid] in five steps from 1-ethoxycarbonyl 6-methyl hept-5-en-2-one. 相似文献
93.
Glassy carbon electrodes modified with (5-amino-1,10-phenanthroline)bis(bipyridine)ruthium(II) chloride hydrate, [(bpy)2Ru(5-phenNH2)]Cl2·H2O, are shown to oxidize hydrazine with excellent sensitivity. The presence of an amine group on the ruthenium complex facilitates electropolymerization onto the electrode surface. Using cyclic voltammetry, a large catalytic current is observed upon oxidation of hydrazine in phosphate buffer (pH 5.0), compared to the current obtained from the ruthenium-modified electrode with no hydrazine present. The sensitivity of cyclic voltammetry is sufficient for obtaining a linear calibration curve for hydrazine over the range of 10−5 to 10−2 M. Hydrodynamic amperometry was used to determine the working potential for flow injection analysis. The limit of detection for hydrazine was determined to be 8.5 μM using FIA. The thickness of these films was shown to increase linearly with the number of electropolymerization cycles, in the range of 1000-2500 nm for 5-20 cycles, respectively, using Rutherford backscattering spectrometry (RBS). RBS analysis also suggests that the film is multilayered with the outermost layers containing a high ruthenium concentration, followed by layers where the concentration of ruthenium decreases linearly and approaches zero at the electrode surface. 相似文献
94.
1,1-Dimethyl-3-phenylpyrazolium-5-oxide (1) was isolated as a minor product (3%) in the reaction of ethyl benzoylacetate with 1,1-dimethylhydrazine and also was obtained as the major product (58%) from the reaction of methyl p-toluenesulfonate with ethyl benzoylacetate dimethylhydrazone. The structural assignment was made on the basis of chemical reactions and spectral data and the formula is represented by a resonance structure for which there are two principal canonical forms. Reaction of 1 with methanol at room temperature afforded methyl benzoylacetate dimethylhydrazone. Ethyl benzoylacetate dimethylhydrazone was shown to exist as a tautomeric mixture containing 65% of the imine form at room temperature. 相似文献
95.
Winter B Weber R Hertel IV Faubel M Jungwirth P Brown EC Bradforth SE 《Journal of the American Chemical Society》2005,127(19):7203-7214
Photoelectron spectroscopy combined with the liquid microjet technique enables the direct probing of the electronic structure of aqueous solutions. We report measured and calculated lowest vertical electron binding energies of aqueous alkali cations and halide anions. In some cases, ejection from deeper electronic levels of the solute could be observed. Electron binding energies of a given aqueous ion are found to be independent of the counterion and the salt concentration. The experimental results are complemented by ab initio calculations, at the MP2 and CCSD(T) level, of the ionization energies of these prototype ions in the aqueous phase. The solvent effect was accounted for in the electronic structure calculations in two ways. An explicit inclusion of discrete water molecules using a set of snapshots from an equilibrium classical molecular dynamics simulations and a fractional charge representation of solvent molecules give good results for halide ions. The electron binding energies of alkali cations computed with this approach tend to be overestimated. On the other hand, the polarizable continuum model, which strictly provides adiabatic binding energies, performs well for the alkali cations but fails for the halides. Photon energies in the experiment were in the EUV region (typically 100 eV) for which the technique is probing the top layers of the liquid sample. Hence, the reported energies of aqueous ions are closely connected with both structures and chemical reactivity at the liquid interface, for example, in atmospheric aerosol particles, as well as fundamental bulk solvation properties. 相似文献
96.
Subramaniam V Alves ID Salgado GF Lau PW Wysocki RJ Salamon Z Tollin G Hruby VJ Brown MF Saavedra SS 《Journal of the American Chemical Society》2005,127(15):5320-5321
Transmembrane proteins (TMPs), particularly ion channels and receptors, play key roles in transport and signal transduction. Many of these proteins are pharmacologically important and therefore targets for drug discovery. TMPs can be reconstituted in planar-supported lipid bilayers (PSLBs), which has led to development of TMP-based biosensors and biochips. However, PSLBs composed of natural lipids lack the high stability desired for many technological applications. One strategy is to use synthetic lipid monomers that can be polymerized to form robust bilayers. A key question is how lipid polymerization affects TMP structure and activity. In this study, we have examined the effects of UV polymerization of bis-Sorbylphosphatidylcholine (bis-SorbPC) on the photoactivation of reconstituted bovine rhodopsin (Rho), a model G-protein-coupled receptor. Plasmon-waveguide resonance spectroscopy (PWR) was used to compare the degree of Rho incorporation and activation in fluid and poly(lipid) PSLBs. The results show that reconstitution of Rho into a supported lipid bilayer composed only of bis-SorbPC, followed by photoinduced lipid cross-linking, does not measurably diminish protein function. 相似文献
97.
R. Anil Rugunanan Michael E. Brown 《Journal of Thermal Analysis and Calorimetry》1991,37(6):1193-1211
Thermogravimetry (TG) and differential scanning calorimetry (DSC) have been used to examine the thermal behaviour, in N2 and in air, of the Si/Sb2O3, Si/KNO3, Si/Fe2O3 and Si/SnO2 pyrotechnic systems, in relation to the behaviour of the individual constituents.TG curves for Si powder, heated alone in air, showed that limited oxidation of Si occurred above 700°. In N2, Sb2O3 sublimed completely between 500 and 900° and, in air, sublimation was accompanied by oxidation to Sb2O4. The Sb2O4 decomposed at higher temperatures. DSC curves for KNO3 heated in N2 showed the usual crystalline transition and melting endotherms followed by endothermic decomposition between 400 and 950°. DSC and TG curves of SnO2and Fe2O3 revealed no thermal events when samples were heated to 1000° in either N2 or air.For the Si/Sb2O3 system, the oxidation of Si by Sb2O3 between 590 and 700°, was complicated by sublimation of Sb2O3 in N2 and also by the oxidation of Sb2O3 in air. No thermal events were observed for the Si/SnO2and Si/Fe2O3 systems when heated under a variety of conditions in either N2 or in air, although these systems do sustain combustion on suitable ignition. In the Si/KNO3 system, oxidation of Si occurs in a KNO3 melt at temperatures above 560° in nitrogen and in air.
Dedicated to Professor Dr. H. J. Seifert on the occasion of his 60th birthday 相似文献
Zusammenfassung Mittels TG und DSC wurde das thermische Verhalten der pyrotechnischen Systeme Si/Sb2O3, Si/KNO3, Si/Fe2O3 und Si/SnO2in N2 und in Luft im Vergleich zum Verhalten der einzelnen Komponenten untersucht.TG-Aufnahmen über das Erhitzen von Si-Pulver in Luft zeigten eine begrenzte Oxidation von Silizium oberhalb 700°C. Sb2O3 sublimiert in Stickstoff vollständig zwischen 500 und 900°C, in Luft wird die Sublimation durch Oxidation zu Sb2O4 begleitet. Sb2O4 zersetzt sich bei höheren Temperaturen. DSC-Aufnahmen für KNO3 in N2 zeigen die gewohnten Umwandlungs- und Schmelzendothermen, gefolgt von einer endothermen Zersetzung zwischen 400 und 950°C. Die DSC- und TG-Kurven für SnO2und Fe2O3 zeigen bei Erhitzen bis 1000°C weder in N2 noch in Luft den Verlauf thermische Prozesse an.Bei dem System Si/Sb2O3 spielt sich neben der Oxidation von Si durch Sb2O3 zwischen 590 und 700°C auch eine Sublimation von Sb2O3 in N2 sowie eine Oxidation von Sb2O3 in Luft ab. Für die Systeme Si/SnO2und Si/Fe2O3 konnten durch Erhitzen unter einer Reihe von Bedingungen weder in Luft noch in N2 Thermoprozesse nachgewiesen werden, obwohl diese Systeme nach geeigneter Zündung den Brennvorgang aufrechterhalten. Im System Si/KNO3 erfolgt sowohl in N2 als auch in Luft oberhalb 560°C die Oxidation von Si in der KNO3-Schmelze.
Dedicated to Professor Dr. H. J. Seifert on the occasion of his 60th birthday 相似文献
98.
Reactions of CrO2F2 with MF or MF2 gave the corresponding M2CrO2F4 and MCrO2F4 fluorochromates. With the Lewis Acids (SO3, TaF5, SbF5) and (CF3CO)2O known and new chromyl compounds [CrO2(CF3COO)2, CrO2(SO3F)2, CrO2FTaF6, CrO2FSbF6, CrO2FSb2F11] were produced. Chromyl fluoride and inorganic salts (CF3COONa and NaNO3) produced the following complexes - Na2CrO2F2(CF3COO)2 and Na2CrO2F2(NO3)2. Unusual solid products were obtained with CrO2F2 and NO, NO2, SO2.A new method of preparing CrO2F2 is also presented. 相似文献
99.
The Maillard reaction comprises a complex network of reactions which has proven to be of great importance in both food science and medicine. The majority of methods developed for studying the Maillard reaction in food have focused on model systems containing amino acids and monosaccharides. In this study, a number of electrophoretic techniques, including two-dimensional gel electrophoresis and capillary electrophoresis, are presented. These have been developed specifically for the analysis of the Maillard reaction of food proteins, and are giving important insights into this complex process. 相似文献
100.
Anju Midha Rajender D. Verma K. Brown R. V. Parish 《Monatshefte für Chemie / Chemical Monthly》1983,114(6-7):661-667
Mixed dialkytin(IV) trifluoroacetates,Me EtSn(O2CCF3)2,Et Pr
n
Sn(O2CCF3)2 andPr
n
Bu
n
Sn(O2CCF3)2 have been prepared by metathetical reactions of the corresponding dialkyltin(IV) chlorides with silver trifluoroacetate in CH2Cl2. They are monomeric in benzene and nonconducting inMeNO2 andMeCN. Bidentate trifluoroacetate groups are indicated by their IR spectra.Mössbauer spectra confirmtrans-arrangement of theR-Sn-R moiety.1H,19F NMR and mass spectra are also discussed.
Gemischte Dialkylzinn(IV)-trifluoracetate
Zusammenfassung Die gemischten Dialkylzinn(IV)-trifluoroacetateMe EtSn(O2CCF3)2,Et Pr n Sn(O2CCF3)2 undPr n Bu n Sn(O2CCF3)2 wurden über Metathese-Reaktionen der entsprechenden Dialkylzinn(IV)-chloride mit Silbertrifluoracetat in CH2Cl2 dargestellt. Sie sind monomer in Benzol und nichtleitend inMeNO2 undMeCN. Die IR-Spektren zeigen zweizähnige Trifluoracetat-Gruppen an. DieMössbauer-Spektren bestätigen dietrans-Anordnung derR-Sn-R-Einheit. Die1H-,19F-NMR und die Massenspektren werden ebenfalls diskutiert.相似文献