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排序方式: 共有236条查询结果,搜索用时 15 毫秒
91.
Vipond J Woods M Zhao P Tircsó G Ren J Bott SG Ogrin D Kiefer GE Kovacs Z Sherry AD 《Inorganic chemistry》2007,46(7):2584-2595
Interest in macrocyclic lanthanide complexes such as DOTA is driven largely through interest in their use as contrast agents for MRI. The lanthanide tetraamide derivatives of DOTA have shown considerable promise as PARACEST agents, taking advantage of the slow water exchange kinetics of this class of complex. We postulated that water exchange in these tetraamide complexes could be slowed even further by introducing a group to sterically encumber the space above the water coordination site, thereby hindering the departure and approach of water molecules to the complex. The ligand 8O2-bridged DOTAM was synthesized in a 34% yield from cyclen. It was found that the lanthanide complexes of this ligand did not possess a water molecule in the inner coordination sphere of the bound lanthanide. The crystal structure of the ytterbium complex revealed that distortions to the coordination sphere were induced by the steric constraints imposed on the complex by the bridging unit. The extent of the distortion was found to increase with increasing ionic radius of the lanthanide ion, eventually resulting in a complete loss of symmetry in the complex. Because this ligand system is bicyclic, the conformation of each ring in the system is constrained by that of the other; in consequence, inclusion of the bridging unit in the complexes means only a twisted square, antiprismatic coordination geometry is observed for lanthanide complexes of 8O2-bridged DOTAM. 相似文献
92.
Ultra-performance liquid chromatography (UPLC)/MS/MS was applied to measure vitamin D in various foods and nutritional supplements. The run-time of the chromatographic separation was cut from 20 min in HPLC/MS/MS to 10 min in UPLC/MS/MS, while equal or better separation efficiency was achieved to deal with complex food matrixes. Under the optimized conditions, all the previtamins of vitamin D3, D2, and isotope-labeled vitamin D3 were baseline-separated from their corresponding vitamins. It was also demonstrated that many sterol isomers in complex food matrixes that interfere in the analysis could be well-separated from the analytes. Accuracy of this method was evaluated by analysis of NIST SRM 1849 infant formula reference material. With eight replicates, the average vitamin D3 concentration was 0.251 +/- 0.012 mg/kg, an excellent agreement with the certified value of 0.251 +/- 0.027 mg/kg. In addition, spike recovery from a commercial infant formula matrix was in the range of 100 to 108% for both vitamins D3 and D2 at three spike concentration levels. The spike recovery for an even more complex matrix, pet food, was 101-105%. LOQ values were 0.026 and 0.033 IU/g, or 0.086 and 0.11 IU/mL in solution, for vitamins D3 and D2, respectively. The dynamic range had three orders of magnitude, which made the method flexible and useful to deal with the wide concentration range of vitamin D in various samples. The method was robust based on the results of changing the parameters of LC separation and MS measurement. This accurate and reliable vitamin D method increased instrument efficiency and analysis productivity significantly. 相似文献
93.
Tun ZM Heston AJ Panzner MJ Medvetz DA Wright BD Savant D Dudipala VR Banerjee D Rinaldi PL Youngs WJ Tessier CA 《Inorganic chemistry》2011,50(18):8937-8945
Phosphazene polymers are classically synthesized by the high-temperature, ring-opening polymerization (ROP) of [PCl(2)N](3) to give [PCl(2)N](n), followed by functionalization of [PCl(2)N](n) with different side groups. We investigated the interactions of [PCl(2)N](3) with Lewis acids because Lewis acids have been used to induce the high-temperature ROP of [PCl(2)N](3). The reactions of [PCl(2)N](3) with MX(3) (M = group 13, X = halides), under strict anaerobic conditions gave adducts [PCl(2)N](3)·MX(3). Adducts were characterized by X-ray crystallography and multinuclear and variable-temperature NMR studies, and mechanistic understanding of their fluxional behavior in solution was achieved. The properties of the [PCl(2)N](3)·MX(3) adducts at or near room temperature strongly suggests that such adducts are not involved directly as intermediates in the high-temperature ROP of [PCl(2)N](3). 相似文献
94.
Edge detection from a finite number of Fourier coefficients is challenging as it requires extracting local information from global data. The problem is exacerbated when the input data is noisy since accurate high frequency information is critical for detecting edges. The noise furthermore increases oscillations in the Fourier reconstruction of piecewise smooth functions, especially near the discontinuities. The edge detection method in Gelb and Tadmor (Appl Comput Harmon Anal 7:101–135, 1999, SIAM J Numer Anal 38(4):1389–1408, 2000) introduced the idea of “concentration kernels” as a way of converging to the singular support of a piecewise smooth function. The kernels used there, however, and subsequent modifications to reduce the impact of noise, were generally oscillatory, and as a result oscillations were always prevalent in the neighborhoods of the jump discontinuities. This paper revisits concentration kernels, but insists on uniform convergence to the “sharp peaks” of the function, that is, the edge detection method converges to zero away from the jumps without introducing new oscillations near them. We show that this is achievable via an admissible class of spectral mollifiers. Our method furthermore suppresses the oscillations caused by added noise. 相似文献
95.
96.
The single-mode phase-sensitive parametric amplifier has been proposed as an approximation to an ideal quantum phase amplifier. We demonstrate numerically that a real, multimode parametric amplifier operated in the spatial domain, and realized by the use of three-wave mixing in nonlinear media, behaves similar to a single-mode quantum phase amplifier, but exhibits smaller phase gain. Constraints for operation in this regime are found to be consistent with small departures of phase from the ideal deamplification condition. 相似文献
97.
Doug Pickrell 《Letters in Mathematical Physics》2009,87(3):283-291
In two dimensional constructive quantum field theory for scalar fields, it is necessary to regularize both the action and
the total (Gaussian) volume. In this paper we consider the compatibility of these regularizations.
相似文献
98.
The notion of black hole singularity and the proof of the singularity theorem were considered great successes in classical general relativity whereas they meanwhile brought with deep puzzles. Conceptual challenges were set up by the intractability of the singularity. The existence of black hole horizons which cover up the black hole interior including the singularity from outside observers, builds an information curtain, further hindering physicists from understanding the nature of the singularity and the interior structure of black holes. The regular black hole is a concept produced out of multiple attempts of establishing a tractable and understandable interior structure for black holes as well as avoiding the singularity behind the black hole horizon. The practicality of the new constructions of black holes would be considered more reliable if there can be found some connection between the interior of regular black holes and some far-reaching signals released from the black hole. After studying the Hawking radiation by fermion tunnelling from one type of regular black hole, structure dependent results were obtained. The result being structure dependent hints the prospects of employing the Hawking radiation as a method to probe into the structure of black holes. 相似文献
99.
利用基于多组态Dirac-Fock方法的程序包GRASP92和RATIP以及在此基础上最新发展的RERR06程序,计算了锂原子1s2nl(n=2,3; l=s, p) 的内壳层和外壳层的光电离截面. 计算中详细考虑了光电离过程中的弛豫效应. 结果表明:在锂原子内壳层电子的光电离过程中弛豫效应较强,而在外壳层电子的光电离过程中弛豫效应较弱. 另外,相应于不同态的内壳层光电离过程,其弛豫效应的影响也不同,对激发态的影响比对基态的影响大,对高激发态
关键词:
多组态Dirac-Fock方法
光电离截面
弛豫效应 相似文献
100.
EFFICIENCY OF REPAIR OF PYRIMIDINE DIMERS AND PSORALEN MONOADDUCTS IN NORMAL AND XERODERMA PIGMENTOSUM HUMAN CELLS 总被引:1,自引:0,他引:1
James E. Cleaver Wayne C. Charles Seouk Hwan Kong 《Photochemistry and photobiology》1984,40(5):621-629
Abstract —Repair of DNA damage produced by ultraviolet light or 5-methylisopsoralen in normal and xeroderma pigmentosum human cells involves many similar steps. Aphidicolin and cytosine arabinoside block repair of both kinds of damage with similar efficiency, indicating that DNA polymerase a has a major role in repair for these lesions. In xeroderma pigmentosum cells of various complementation groups, the relative efficiency of excision repair for both ultraviolet- and 5-methylisopsoralen-induced damage was group A < C < D, indicating a close resemblance between both kinds of lesions in relation to the repair deficiencies in these groups. At high doses, the maximum rate of repair of damage by ultraviolet light was about twice that for methylisopsoralen damage, possibly because ultraviolet-induced damage forms a substrate that is more readily recognized and excised than that of the psoralen adducts. Differences in the structural distortions to DNA caused by these kinds of damage could be detected using single strand specific nucleases which excised dimers but not 5-MIP adducts from double strand DNA. 相似文献