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121.
Janos Fazakas 《Spectrochimica Acta Part B: Atomic Spectroscopy》1982,37(10):921-927
Atomization under pressure considerably influences the absolute and relative sensitivities of resonance and non-resonace lines. Whereas for resonance lines the peak height and area senstitivities decrease with increasing pressure, for non-resonance lines the sensitivity initially increases probably because the increase of the temperature of the atomic vapor compensates for the Lorentz broadening and the red shift. At higher pressures probably absorption line broadening and red shift effect become predominant so that the sensitivity of the non-resonance lines becomes poorer. In spite of this the relative sensitivity of the non-resonance lines as compared to the resonance lines under the same conditions. improves steadily with increasing pressure. It is possible that the absorption profiles of the resonance and the non-resonance lines are affected differently by pressure. The peak characterization times differ considerably for the resonance and non-resonance lines. Calibration curves become more linear with increasing pressure. The improvement is more pronounced for the resonance line. 相似文献
122.
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124.
Yushin Nakamura Roger Hollenstein Janos Zsindely Hans Schmid Willi E. Oberhnsli 《Helvetica chimica acta》1975,58(7):1949-1977
Intramolecular cyloadditions of binaphtyl compounds Three new bridged ketones, 7,8 and 9 , have been isolated in 44%, 3% and 19% yields respectively (Scheme 2) by heating 2,2′-bis-allyloxy-1,1′-binaphthyl ( 5 ) at 215° for 16 hours. These compounds could be epimerized about C(16) by bases, and in particular 9 yielded the new epimer 10 . The structures of the alcohols obtained by reduction of the keto group are also given (Scheme 2). The constitution of all compounds was derived from spectroscopic data, chiefly from their 1H-NMR, spectra (tab. 2, 3 and fig. 1). The assignments were based on the observed long-range coupling constant between H(endo)-C(16) and H(endo)-C(5) in 7 and 10 and on the analysis of chemical shifts and coupling constants in both the ketones and their derivatives. Moreover, the structures of the compounds investigated have been proved by x-ray analysis of ketone 8 (chap. 3, fig. 2). The thermal conversion of binaphthylether 5 to the bridged ketones proceeds via an intramolecular Diels-Alder reaction, followed by Claisen rearrangement (Scheme 8). On heating, the bis-beta-methylallyl ether 20 yielded the ketone 21 and a small amount of the ether 23 (Schemes 5 and 7). Ether 23 and binaphthyl monoallyl ether 26 were converted thermally to the bridged ketones 31 (Scheme 7) and 27 (Scheme 6) respectively. In addition, 26 underwent an intramolecular ene-reaction to give the spiroketone 28 (Schemes 6 and 9). The structures of these compounds were also established, mainly by analysis of their 1H-NMR. spectra. 相似文献
125.
126.
Janos P 《Journal of chromatography. A》2004,1037(1-2):15-28
Chemical interactions, such as acid-base, complex-forming, ion association and other equilibria, are widely exploited to improve the separation efficiency in liquid chromatography as well as in electrophoresis. On the other hand, these techniques can be advantageously used to study the chemical equilibria affecting the separations. If the equilibium is sufficiently fast in comparison with the separation process, then the retention characteristics in chromatography (retention factors) or the migration characteristics in electrophoresis (effective mobilities) may be expressed as functions of the composition of mobile phase or background electrolyte (BGE), respectively. Using a proper experimental arrangement, the dependencies of retention (migration) characteristics on the mobile phase (background electrolyte) composition can be measured and utilized to calculate the equilibrium constants for equlibria taking place in the mobile phase (background electrolyte). Although principles of these measurements have been known for a long time, only more recent studies utilizing HPLC and capillary electrophoretic techniques are reviewed in this paper. 相似文献
127.
Abstract— Some photochemical reactions of bacteriorhodopsin (BR) embedded in NaCl pellets (BR-NaCI) in the visible region are described here. BR in these preparations is a mixture of two classes of species: a drastically blue-shifted form and the unchanged purple pigment. Depending on the illumination history of the BR before being immobilized, both kinds of BR could be demonstrated in light-adapted (LA) and dark-adapted (DA) forms, but light adaptation was not possible once the pellets were made. Analogously to BR suspensions, the light-adapted blue-shifted BRexhibited an a/l-trans type photocycle, but the thermal steps were greatly slowed down (time constants 1 to 5 min). The parent species absorb at 506 nm. The DA blue-shifted BR exhibited absorption changes resolved into two photoreactions, one all-(rans- like (as in LA-BR) and another, 13-cw like, whose decay rate is also greatly slowed down (recovery time several hours). The parent species of the 13-cis like cycle absorb at 480 nm. That pigment fraction in the pellets whose absorption was not blue-shifted, also exhibited similar photoreactions to BR in suspension, but with an overall turnover rate only one order of magnitude slower. From a previous report (Lazarev and Terpugov, Biochim. Biophys. Acta 590 ,324–338,1980) and this one, it appears that the very slow photocycles in NaCl-BR of low moisture content originate from blue-shifted chromophores rather than from unchanged BR. 相似文献
128.
Plasma peptides are widely used in clinical diagnosis and therapy monitoring. Our aim was an efficient system development for the enrichment of small, low abundant peptides from plasma by robotized sample preparation. The automation of SPE yields additional time saving and improves system robustness and repeatability. Automation is based on combining a Waters SPE kit with Oasis HLB sorbent and a multichannel liquid handling workstation with cheap commercially available electronic devices such as a programmable logic controller (PLC) and an AVR controller. Reversed phase nano liquid chromatography coupled with a sensitive quadrupole time of flight mass spectrometer (QTOF MS) was used for the quantitative determination of somatostatin (SST). We quantified SST from mouse plasma, where lower limit of detection (LLOD) and lower limit of quantification (LLOQ) were 2.5 and 8.3 fmol/ml, respectively. We investigated linearity of response, accuracy, precision, recovery, reproducibility and stability of SST during both short-term sample processing and long-term storage. This method allows reliable quantification of plasma peptides. The developed automated sample preparation solid phase extraction method can be easily and conveniently adopted for different volumes and amounts of sample in routine analysis using controlled vacuum. The highest advantage is enhanced reproducibility, which makes it suitable for the investigations of large sample cohorts in clinical studies. 相似文献
129.
Pintér G Batta G Horvath P Löki I Kurtan T Antus S Kéki S Zsuga M Nagy G Aradi J Gunda T Herczegh P 《Langmuir : the ACS journal of surfaces and colloids》2007,23(10):5283-5285
The formation of supramolecular polymeric aggregates with a molecular mass of 100 kDa in a nonaqueous solution from a telechelic dimer of isopropylidene guanosine in the presence of K(+) ions is reported. The possible structure of macromonomers resulting from the development of G4 quartets was deduced from DOSY NMR, circular dichroism spectra, and dynamic light scattering measurements. 相似文献
130.
Huwiler C Kunzler TP Textor M Vörös J Spencer ND 《Langmuir : the ACS journal of surfaces and colloids》2007,23(11):5929-5935
We present a novel approach for the fabrication of tailored nanomorphology gradients on metal oxide surfaces. We first show the direct formation of a nanocolloidal density gradient by a dip-coating process. The obtained silica nanoparticle gradients are then subjected to a heat treatment. Control of this sintering step allows the precise tailoring of the particle morphology on the surface. Both these processes together provide a new tool to form precise, tunable, and material-independent nanomorphology gradients. 相似文献