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1.
Europium (Eu+) ions were confined in a Paul trap and detected by non-destructive method. Storage time of Eu+ ions achieved in vacuum was improved by orders of magnitude employing buffer gas cooling. The experimentally detected signal
was fitted to the ion response signal and the total number of ions trapped was estimated. It is found that the peak signal
amplitude as well as the product of FWHM and the peak signal amplitude is proportional to the total number of trapped ions.
The trapped ion secular frequency was swept at different rates and its effect on the absorption line profile was studied both
experimentally and theoretically. 相似文献
2.
M. Mayr K. -H. Speidel M. Knopp W. Karle T. Faestermann F. Hagelberg H. -J. Simonis P. N. Tandon J. Gerber 《Zeitschrift für Physik A Hadrons and Nuclei》1987,327(2):157-161
[Theg-factor ratio of the first excited 3? and 5? states in40Ca was measured to beg 3/g 5=1.01(10) employing the implantation perturbed angular correlation technique. The static hyperfine fields (SF) in Fe and Gd hosts were used. In addition the lifetime of the 5? state was measured to be τ=426(7)ps. The values of the SF in Gd and Fe hosts were deduced and compared with systematics in this element region. 相似文献
3.
Summary Observation of fluorescence reactions on TLC plates is a valuable additional tool within the scope of screening procedures for many toxicologically relevant substances commonly encountered in clinical- and forensic-toxicological analysis. The reactions are based on native fluorescence without any treatment and on reactions obtained with an approved derivatization procedure. Due to the enormous sensitivity of the fluorescence detection, the method is also applicable to very low concentrations and small amounts of biological materials. The procedures described in this article have proven their high pragmatic usefulness in many practical cases.Dedicated to Professor Dr. Wilhelm Fresenius on the occasion of his 80th birthday 相似文献
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Würthwein EU Lang G Schappele LH Mayr H 《Journal of the American Chemical Society》2002,124(15):4084-4092
A literature survey on the kinetics of hydride abstractions from CH-groups by carbocations reveals a general phenomenon: Variation of the hydride acceptor affects the rates of hydride transfer to a considerably greater extent than an equal change of the thermodynamic driving force caused by variation of the hydride donor. The origin of this relationship was investigated by quantum chemical calculations on various levels of ab initio and DFT theory for the transfer of an allylic hydrogen from 1-mono- and 1,1-disubstituted propenes (XYC=CH-CH(3)) to the 3-position of 1-mono- and 1,1-disubstituted allyl cations (XYC=CH-CH(2)(+)). The discussion is based on the results of the MP2/6-31+G(d,p)//RHF/6-31+G(d,p) calculations. Electron-releasing substituents X and Y in the hydride donors increase the exothermicity of the reaction, while electron-releasing substituents in the hydride acceptors decrease exothermicity. In line with Hammond's postulate, increasing exothermicity shifts the transition states on the reaction coordinate toward reactants, as revealed by the geometry parameters and the charge distribution in the activated complexes. Independent of the location of the transition state on the reaction coordinate, a value of 0.72 is found for Hammond-Leffler's alpha = deltaDeltaG/deltaDelta(r)G degrees when the hydride acceptor is varied, while alpha = 0.28 when the hydride donor is varied. The value of alpha thus cannot be related with the position of the transition state. Investigation of the degenerate reactions XYC=CH-CH(3) + XYC=CH-CH(2)(+) indicates that the migrating hydrogen carries a partial positive charge in the transition state and that the intrinsic barriers increase with increasing electron-releasing abilities of X and Y. Substituent variation in the donor thus influences reaction enthalpy and intrinsic barriers in the opposite sense, while substituent variation in the acceptor affects both terms in the same sense, in accord with the experimental findings. Marcus theory is employed to treat these effects quantitatively. 相似文献
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A series of poly(norborn-2-ene) (poly-NBE), poly(7-oxanorborne-2-ene-5,6-dicarboxylic acid) (poly-ONDCA), as well as poly(norborn-2-ene-co-7-oxanorborne-2-ene-5,6-dicarboxylic acid) (poly-NBE-co-ONDCA) based silica supports were prepared via ring-opening metathesis polymerization (ROMP) using both coating and grafting techniques. Poly-NBE-grafted and poly-NBE-coated supports were used for the reversed-phase separation of phenols; poly-NBE, poly-ONDCA as well as poly-NBE-co-ONDCA-grafted supports were used for comparative studies on the separation of a series of anilines and lutidines. As expected, grafted supports possess superior separation capabilities compared to their coated analogues. Compared to pure poly-NBE- and poly-ONDCA-grafted stationary phases, supports consisting of poly-NBE-co-ONDCA block-copolymers possess both hydrophobic and ion-exchange sites and represent optimum stationary phases for the separation of isomeric basic analytes. 相似文献
10.
Allenyl cations, generated from allenyl or alkynyl halides and Ag+, attack styrene at the side chain or at the aromatic nucleus. The allenyl/alkynyl product ratio is dependent on the structure of the precursor halide except for highly substituted systems. 相似文献