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161.
Martin Gilges Heribert Husmann Maria-Helen Kleemiß Stephan R. Motsch Gerhard Schomburg 《Journal of separation science》1992,15(7):452-457
Mixtures of several basic proteins have been used to test CZE capillaries with surfaces modified by new pretreatment procedures; the performance obtained has been compared with that achieved using capillaries treated by procedures described in the literature. It has been shown that addition of non-ionic polyvinylalcohols (PVA) to CZE buffer solutions deactivates even bare, i.e. untreated, fused silica surfaces and renders them suitable for separations of basic proteins. The performance obtained from such surfaces was comparable with that of capillaries modified by the more elaborate procedures of etching, silanol derivatization, and/or adsorptive coating (again with polymers). A home-made device is described which enables derivatization and coating reactions to be performed on fused silica capillaries under an inert atmosphere, i.e. one free from oxygen and water. 相似文献
162.
Charles H. Womack Robert T. Gampe B. Kaye Lemke Kailash N. Sawhney Thomas L. Lemke Gary E. Martin 《Journal of heterocyclic chemistry》1982,19(5):1105-1107
Treatment of 2-pivaloyl-1,3-indandione with hydroxylamine leads to the formation of a pair of isomeric indenoisoxazoles, the product formed dependent upon the cyclization conditions. Under acidic conditions, 8-t-butylindeno[1,2-c]isoxazol-7-one ( 5 ) is formed while under neutral or basic conditions, an oxime, 2 , is generated which may then be cyclized under acidic conditions to give 3-t-butylindeno[1,2-c]isoxazol-4-one ( 4 ). Although these isomeric indenoisoxazoles may be discriminated by chemical means, we were interested in developing an unequivocal method for distinguishing these and potentially other isomeric pairs by spectroscopic means. A 13C-nmr based method for the discrimination of these isomers which is based on the utilization of chemical shift arguments and spin-lattice relaxation data is thus presented. 相似文献
163.
Solutions of nitronium tetrafluoroborate in acetonitrile prepared by anodic oxidation of nitrogen dioxide, efficiently nitrate aromatics, enolsilyethers, alkenes and conjugated dienes to afford respectively nitroaromatics, α-nitroketones, vicinal nitroamides and mixtures of nitroacetamides by 1,2- and 1,4-addition. 相似文献
164.
Zusammenfassung Aus den Erfahrungen mit Neutronenaktivierungsanalysen von hochreinen Materialien der Elektronik werden die wichtigsten Fehlerquellen und die Möglichkeiten zu deren Vermeidung aufgezeigt. Von den spurenanalytischen Problemen muß vor allem der Probenhomogenität, den Oberflächenverunreinigungen und, bei chemischen Operationen vor der Bestrahlung, auch dem Blindwert erhöhte Aufmerksamkeit gewidmet werden. Hinzu kommen die für Aktivierungsanalysen spezifischen Gefahren der Probenveränderung durch Strahlungsaufheizung und Strahlungsrückstoß, der Ablauf unerwarteter Kernreaktionen bei extrem hohen Neutronenflüssen sowie die für chemische Trennungen störende Bildung heißer Atome. An Hand einiger Beispiele wird die Nützlichkeit der Ortung von Verunreinigungselementen durch autoradiographische Aufnahmen nachgewiesen.Vorgetragen anläßlich des 3. Seminars Aktivierungs-analyse im Kernforschungszentrum Karlsruhe, 30./31.Mai 1972. 相似文献
165.
The coefficients of R?6 and R?9 in the long-range expansion of the parallel and perpendicular components of the polarizability of a pair of hydrogen atoms at a separation R have been calculated. The results are A(6)6 = 2558.59. A(6)⊥ = 1268.25, A(8)6 = 90639.5 and A(8)⊥ = 22010.3 au. The values of A(6)6 and A(6)6 and A(6)| are somewhat larger than previous theoretical estimates and much larger than the classical values of 729 and 182.25 au. The terms in R?8 arise from distortion associated with the dispersion forces and from the field of the quadrupole moment induced by the field-gradient at each atom. 相似文献
166.
The mass spectral fragmentation of carbazole was reinvestigated using metastable ion studies, exact mass measurements and 1,8-dideuteriocarbazole. 1,8-Dideuteriocarbazole was prepared by successive metalations and deuterations of carbazole. The 1H- and 13C-nmr spectra of 1,8-dideuteriocarbazole confirmed earlier assignments for carbazole. 相似文献
167.
The folding landscapes of polypeptides and proteins exhibit a hierarchy of local minima. The causes range from proline isomerization all the way down to microstructure in the free energy caused by residual frustration inherent in even the best 20 amino acid design. The corresponding time scales range from hours to submicroseconds. The smallest microstructures are difficult to detect. We have measured the folding/unfolding kinetics of the engineered trpzip2 peptide at different tryptophan fluorescence wavelengths, each yielding a different rate. Wavelength-dependent folding kinetics on 0.1-2 mus time scales show that different microstructures with a range of solvent exposure and local dynamics are populated. We estimate a lower limit for the roughness of the free energy surface based on the range of rates observed. 相似文献
168.
DNA-nanotube artificial ion channels 总被引:4,自引:0,他引:4
Harrell CC Kohli P Siwy Z Martin CR 《Journal of the American Chemical Society》2004,126(48):15646-15647
There is considerable interest in developing chemical devices that mimic the function of biological ion channels. We recently described such a device, which consisted of a single conically shaped gold nanotube embedded within a polymeric membrane. This device mimicked one of the key functions of voltage-gated ion channels: the ability to strongly rectify the ionic current flowing through it. The data obtained were interpreted using a simple electrostatic model. While the details are still being debated, it is clear that ion-current-rectification in biological ion channels is more complicated and involves physical movement of an ionically charged portion of the channel in response to a change in the transmembrane potential. We report here artificial ion channels that rectify the ion current flowing through them via this "electromechanical" mechanism. These artificial channels are also based on conical gold nanotubes, but with the critical electromechanical response provided by single-stranded DNA molecules attached to the nanotube walls. 相似文献
169.
Rudin M Mueggler T Allegrini PR Baumann D Rausch M 《Analytical and bioanalytical chemistry》2003,377(6):973-981
Modern drug development requires technologies that allow rapid translation from the preclinical to the clinical stage. It is obvious that non-invasive imaging modalities such as magnetic resonance imaging (MRI) will play a central role in this regard. This article reviews the use of structural and functional MRI readouts for characterization of central nervous system (CNS) disorders and evaluation of the efficacy of potential CNS drugs. Examples comprise dementia of Alzheimer's type, cerebral ischemia, and neuroinflammation covering both clinical and preclinical aspects. In these examples MRI has been used to obtain relevant structural information on brain atrophy, on the location and extent of ischemic brain areas, and on the number and distribution of demyelinated plaques. These structural data are complemented by readouts assessing the functional consequences associated with the pathomorphological changes. In the last decade, MRI has evolved into a standard tool for the development of CNS drugs. With regard to target-specific/molecular imaging applications MRI is limited by its inherently low sensitivity; complementary imaging modalities utilizing optical and radionuclear reporter systems will thus be required. 相似文献
170.
The effect of the parent basis set on the basis set superposition error caused by bond functions is investigated systematically. An important difference between BSSE at the SCF and correlated levels is pointed out. Three new basis sets are defined, denoted 6-311 + G(d,p)B, 6-311 + G(2d,p)B, and 6-311 + G(2df,p)B. BSSE for the first-row hydrides seems to increase uniformly with increasing atomic number of the central atom. Expansion of the valence part of the basis set from 6-31G to 6-311G, as well as adding f functions, has a significant effect on the BSSE. Additional BSSEs incurred by bond functions are less than or equal to 1 kcal/mol for the 6-311 + G(2df,p)B basis set. For the dissociation energies of the first-row hydride species, agreement with experiment within only a few kcal/mol can be obtained even without resorting to isogyric reaction cycles. For high-quality calculations, adding bond functions seems to have definite advantages over expanding the polarization space beyond the [2d1f] level. 相似文献