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81.
金属有机框架CPL-1填充柱气相色谱分析氢同位素 总被引:1,自引:0,他引:1
金属有机框架(MOFs)材料CPL-1的比表面积大、孔径均一,在低温条件下对氢同位素具有良好的量子筛分效应,是气相色谱固定相潜在的应用材料。采用CPL-1填充制备了长0.5 m、内径1 mm的微孔填充柱,借助单晶Al_2O_3颗粒间隙构建了色谱载气流通路径,在低温条件下探索研究了CPL-1填充柱的氢同位素分析性能。结果表明,在77 K时CPL-1对H_2和D_2的吸附量接近4 mmol/g,优于MnCl2/γ-Al_2O_3和γ-Al_2O_3,CPL-1填充柱在取样量0.25~2 mL范围内对低浓度氢同位素样品的检测具有良好的线性关系,检测的相对误差小于4%。CPL-1填充柱具有线性范围宽、重复性好、准确度高等优点,在氢同位素色谱分析中具有潜在的应用价值。 相似文献
82.
Bernard Lavielle Bertrand Thomas Eric Gilabert Gregory Canchel Denis Horlait Sylvain Topin Fabien Pointurier Christophe Moulin 《Journal of mass spectrometry : JMS》2016,51(10):908-913
A double focusing sector field mass filter used in Nier–Johnson geometry has been built in order to perform Kr isotope enrichment for 81Kr and 85Kr isotopes. The principle consists in implanting Kr+ ions accelerated at 7 keV in Al foils after separation using the magnetic sector. A specific ion source has been designed capable of generating high Kr+ ion beams (>0.5 μA) to transfer into the collecting Al foils in 3 to 5 h significant fractions of large Kr samples (1015 to 1016 atoms) initially introduced in the instrument. Implanted Kr isotopes can be further selectively released from the Al foil by surface ablation using an infrared laser beam. Implantation yields and enrichment factors are measured using a conventional mass spectrometer. Copyright © 2016 John Wiley & Sons, Ltd. 相似文献
83.
A method is presented for the simultaneous determination of Cr(III) and Cr(VI) in yeast using species-specific double-spike
isotope dilution (SSDSID) with anion-exchange liquid chromatography (LC) separation and sector field inductively coupled plasma
mass spectrometric (SF-ICP-MS) detection. Total Cr is quantitated using ID SF-ICP-MS. Samples were digested on a hot plate
at 95±2 °C for 6 h in an alkaline solution of 0.5 M NaOH and 0.28 M Na2CO3 for the determination of Cr(III) and Cr(VI), whereas microwave-assisted decomposition with HNO3 and H2O2 was used for the determination of total Cr. Concentrations of 2,014±16, 1,952±103 and 76±48 mg kg−1 (one standard deviation, n=4, 3, 3), respectively were obtained for total Cr, Cr(III) and Cr(VI) in the yeast sample. Significant oxidation of Cr(III)
to Cr(VI) (24.2±7.6% Cr(III) oxidized, n=3) and reduction of Cr(VI) to Cr(III) (37.6±6.5% Cr(VI) reduced, n=3 ) occurred during alkaline extraction and subsequent chromatographic separation at pH 7. Despite this significant bidirectional
redox transformation, quantitative recoveries for both Cr(III) and Cr(VI) were achieved using the SSDSID method. In addition,
mass balance between total Cr and the sum of Cr(III) and Cr(VI) concentrations was achieved. Method detection limits of 0.3,
2 and 30 mg kg−1 were obtained for total Cr, Cr(VI) and Cr(III), respectively, based on a 0.2-g sub-sample. 相似文献
84.
Fragmentation pathways of a series of pentacoordinated bisaminoacylspirophosphoranes were elucidated by electrospray ionization multistage mass spectrometry (ESI-MS(n)) in negative mode. The deprotonated ions of pentacoordinated bisaminoacylspirophosphoranes tend to eliminate a corresponding amino acid to form base peak. The hydrogen/deuterium exchange experiment, the high-resolution mass spectrometry, (13)C stable isotope labeling experiment and theoretical calculations were used to rationalize the proposed fragmentation pathways and to verify the differences between the fragmentation pathways. The results indicate that the negative molecular ions of pentacoordinated bisaminoacylspirophosphoranes dissociate through its open-chain tricoordinated tautomers. The relative Gibbs free energies (ΔG) of the product ions and proposed fragmentation pathways were estimated using the B3LYP/6-31 + + G(d, p) model. The results have some potential applications in the identification structures of similar spirophosphorane compounds by ESI-MS(n). 相似文献
85.
Tomislav P. ivkovi 《Journal of mathematical chemistry》2009,45(4):1060-1101
Mathematical formalism of the Low Rank Perturbation method (LRP) is applied to the vibrational isotope effect in the harmonic
approximation with a standard assumption that force field does not change under isotopic substitutions. A pair of two n-atom isotopic molecules A and B which are identical except for isotopic substitutions at ρ atomic sites is considered. In the LRP approach vibrational frequencies ω
k
and normal modes of the isotopomer B are expressed in terms of the vibrational frequencies ν
i
and normal modes of the parent molecule A. In those relations complete specification of the normal modes is not required. Only amplitudes at sites τ affected by the isotopic substitutions and in the coordinate direction s (s = x, y, z) are needed. Out-of-plane vibrations of the (H,D)-benzene isotopomers are considered. Standard error of the LRP frequencies
with respect to the DFT frequencies is on average . This error is due to the uncertainty of the input data (± 0.5 cm−1) and in the absence of those uncertainties and in the harmonic approximation it should disappear. In comparing with experiment,
one finds that LRP frequencies reproduces experimental frequencies of (H,D)-benzene isotopomers better () than scaled DFT frequencies () which are designed to minimize (by frequency scaling technique) this error. In addition, LRP is conceptually and numerically
simple and it also provides a new insight in the vibrational isotope effect in the harmonic approximation. 相似文献
86.
Rate Coefficients and Kinetic Isotope Effects of Cl+XCl→XCl+Cl (X=H,D, Mu) Reactions from Ring Polymer Molecular Dynamics 下载免费PDF全文
The ring-polymer molecular dynamics (RPMD) was used to calculate the thermal rate coefficients and kinetic isotope effects of the heavy-light-heavy abstract reaction Cl+XCl\begin{document}$ \rightarrow $\end{document} XCl+Cl (X = H, D, Mu). For the Cl+HCl reaction, the excellent agreement between the RPMD and experimental values provides a strong proof for the accuracy of the RPMD theory. And the RPMD results are also consistent with results from other theoretical methods including improved-canonical-variational-theory and quantum dynamics. The most novel finding is that there is a double peak in Cl+MuCl reaction near the transition state, leaving a free energy well. It comes from the mode softening of the reaction system at the peak of the potential energy surface. Such an explicit free energy well suggests strongly there is an observable resonance. And for the Cl+DCl reaction, the RPMD rate coefficient again gives very accurate results compared with experimental values. The only exception is at the temperature of 312.5 K, results from RPMD and all other theoretical methods are close to each other but slightly lower than the experimental value, which indicates experimental or potential energy surface deficiency. 相似文献
87.
半导体同位素电池由于其寿命长、集成性优良、环境适应性强等特点成为解决MEMS能源问题的理想手段。利用4H-SiC材料的宽禁带特性,制造了4H-SiC肖特基同位素电池。对电池的耗尽层厚度以及掺杂浓度进行了优化设计,对肖特基金属进行了选择。使用4mCi/cm2的63Ni作为同位素电池的放射源对制造的同位素电池进行了测试。测试结果表明,该同位素电池可以获得31.3nW/cm2的功率密度、0.5V的开路电压、3.13×10-8A/cm2的短路电流密度和1.3%的转换效率。将电池的输出特性和硅基的平板型、3D结构电池输出特性进行了比较,证明4H-SiC肖特基同位素电池能够获得较高的功率密度。电池的性能可通过提升势垒高度、提高工艺质量、更换同位素等方式得到提高。 相似文献
88.
The most neutron-deficient isotopes 215;216U were produced in the complete-fusion reaction 180W(40Ar, 4-5n)215,216U. Evaporation residues recoiled from the target were separated in-flight from the primary beam by the gas-filled recoil separator SHANS and subsequently identified on the basis of correlated -decay chains. Two -decaying states were identified in 216U, one for the ground state and the other for the isomeric state with 8+(h9=2f7=2) configuration. The -decay properties for 215;216U and the systematics of 8+ isomeric state in N =124,126 isotones were investigated. 相似文献
89.
90.
O. Merwitz H. M. Nitzsche E. Hochhäuser 《Isotopes in environmental and health studies》2013,49(4):319-322
Abstract The dose-dependent isotope fractionation during decarboxylation (13C/12C) amplifies the radiation effect in the relatively low dose range. The fractionation of the nitrogen isotopes during deamination (15N/14N) at the dose of 17 Gy was found to be smaller than that of decarboxylation. 相似文献