质谱法精密测定重水中的氢同位素丰度

介绍了用高分辨气体质谱计精密测定重水中氢同位素丰度的分析方法．实验自制了一套重水分解系统,以金属铀作还原剂,在一定的温度下还原重水为氘气．采用低温活性碳作为吸收剂,将样品分解、制备成气体试样,用高分辨气体质谱计测定重水中氢同位素丰度．该方法测定高浓度（〉99％）重水的氘丰度,测量结果的相对标准偏差不大于0．02％。     

Applications of inductively coupled plasma mass spectrometry and laser ablation inductively coupled plasma mass spectrometry in materials science

Inductively coupled plasma mass spectrometry (ICP-MS) and laser ablation ICP-MS (LA-ICP-MS) have been applied as the most important inorganic mass spectrometric techniques having multielemental capability for the characterization of solid samples in materials science. ICP-MS is used for the sensitive determination of trace and ultratrace elements in digested solutions of solid samples or of process chemicals (ultrapure water, acids and organic solutions) for the semiconductor industry with detection limits down to sub-picogram per liter levels. Whereas ICP-MS on solid samples (e.g. high-purity ceramics) sometimes requires time-consuming sample preparation for its application in materials science, and the risk of contamination is a serious drawback, a fast, direct determination of trace elements in solid materials without any sample preparation by LA-ICP-MS is possible. The detection limits for the direct analysis of solid samples by LA-ICP-MS have been determined for many elements down to the nanogram per gram range. A deterioration of detection limits was observed for elements where interferences with polyatomic ions occur. The inherent interference problem can often be solved by applying a double-focusing sector field mass spectrometer at higher mass resolution or by collision-induced reactions of polyatomic ions with a collision gas using an ICP-MS fitted with collision cell. The main problem of LA-ICP-MS is quantification if no suitable standard reference materials with a similar matrix composition are available. The calibration problem in LA-ICP-MS can be solved using on-line solution-based calibration, and different procedures, such as external calibration and standard addition, have been discussed with respect to their application in materials science. The application of isotope dilution in solution-based calibration for trace metal determination in small amounts of noble metals has been developed as a new calibration strategy. This review discusses new analytical developments and possible applications of ICP-MS and LA-ICP-MS for the quantitative determination of trace elements and in surface analysis for materials science.     

液相色谱同位素稀释串联质谱法测定人血清中17β-雌二醇含量

研究建立了以人血清中E2-16,16,17-d3为内标测定17β-雌二醇的液相色谱/串联质谱(ID-LC/MS/MS)方法。血清样品经固相萃取装置(SPE)提取雌二醇,乙酸乙酯萃取净化,吹干复溶后用10-乙基吖啶酮-2-磺酰氯(EASC)进行衍生。以Agilent Eclipse XDB-C18色谱分离柱,乙腈、水梯度洗脱,使用电喷雾三重四极杆串联质谱的多重反应监测模式测定,以校准曲线法进行定量。所建立的液相色谱同位素稀释串联质谱法(ID-LC/MS/MS)对于分析血清17β-雌二醇的批内、批间RSD分别为0.29%～0.73%和0.18%～0.28%,回收率为99.6%～100.2%,采用IFCC RELA比对(JCTLM比对)样品进行了方法比较,测定结果与其他实验室相比偏差在0.8%范围内。方法可作为人血清中17β-雌二醇含量测量参考方法。     

Improve accuracy and sensibility in glycan structure prediction by matching glycan isotope abundance

Mass Spectrometry (MS) is a powerful technique for the determination of glycan structures and is capable of providing qualitative and quantitative information. Recent development in computational method offers an opportunity to use glycan structure databases and de novo algorithms for extracting valuable information from MS or MS/MS data. However, detecting low-intensity peaks that are buried in noisy data sets is still a challenge and an algorithm for accurate prediction and annotation of glycan structures from MS data is highly desirable. The present study describes a novel algorithm for glycan structure prediction by matching glycan isotope abundance (mGIA), which takes isotope masses, abundances, and spacing into account. We constructed a comprehensive database containing 808 glycan compositions and their corresponding isotope abundance. Unlike most previously reported methods, not only did we take into count the m/z values of the peaks but also their corresponding logarithmic Euclidean distance of the calculated and detected isotope vectors. Evaluation against a linear classifier, obtained by training mGIA algorithm with datasets of three different human tissue samples from Consortium for Functional Glycomics (CFG) in association with Support Vector Machine (SVM), was proposed to improve the accuracy of automatic glycan structure annotation. In addition, an effective data preprocessing procedure, including baseline subtraction, smoothing, peak centroiding and composition matching for extracting correct isotope profiles from MS data was incorporated. The algorithm was validated by analyzing the mouse kidney MS data from CFG, resulting in the identification of 6 more glycan compositions than the previous annotation and significant improvement of detection of weaker peaks compared with the algorithm previously reported.     

Capillary electrophoresis mass spectrometry with sheathless electrospray ionization for high sensitivity analysis of underivatized amino acids

A high durability sheathless electrospray ionization interface of CE-MS is applied for the sensitive analysis of underivatized amino acids. The sheathless interface was realized using an ionophore membrane-packed electro-conduction channel. The interface functioned well with a volatile alkaline background electrolyte (BGE) and uncoated fused-silica capillaries for CE-MS analysis of underivatized amino acids. High electroosmotic flow with alkaline BGE facilitated high separation efficiency (>100,000 theoretical plates) and short analysis time (<15 min). Both the short-term stability and long-term durability are particularly suited for routine applications. Using electrokinetic injection and the multiple reaction monitoring (MRM) mode with a triple-quadrupole analyzer, high sensitivity was achieved, which yielded detection limits of 0.05-0.81 μM. For the quantitation of underivatized amino acids, quantification precisions (RSDs) for intra- and inter-day analyses were less than 3%. Recoveries from serum were 96.3-101.8% for isotope dilution mass spectrometry (IDMS). When compared with HPLC-IDMS for human serum samples, highly agreeable (96.9-102.0%) results were obtained with the proposed CE-IDMS method.     

Accuracy in the Isotope Dilution Mass Spectrometry of Uranium in Rubidium Uranium Sulphate Rb2U(SO4)3

Abstract

Problems encountered in the determination of uranium in rubidium uranium sulphate (Rb₂U(SO₄)₃) employing isotope dilution thermal ionisation mass spectrometry (ID-TIMS) are discussed. The positive bias of 0.2 to 0.3% in the determination of uranium in Rb₂U(SO₄)₃ by ID-TIMS with respect to the stoichiometric composition has been resolved by modifying the chemical exchange procedures. The concentration of uranium in Rb₂U(SO₄)₃ could be determined with an accuracy better than 0.1% employing the HClO₄ treatment for proper isotopic exchange between the spike and sample isotopes.     

The role of the active site glutamate in the rearrangement of glutamate to 3-methylaspartate catalyzed by adenosylcobalamin-dependent glutamate mutase

BACKGROUND: Adenosylcobalamin (coenzyme B(12))-dependent enzymes catalyze a variety of chemically difficult reactions that proceed through the generation of free radical intermediates. A long-standing question is how proteins stabilize what are normally regarded as highly reactive organic radicals and direct them towards productive reactions. In glutamate mutase the carboxylate of Glu171 hydrogen bonds with the amino group of the substrate. We have investigated the role of this residue in the enzyme mechanism. RESULTS: Several sterically and functionally conservative mutations were introduced at position 171. In the most impaired mutant, Glu171Gln, k(cat) is reduced 50-fold, although the K(m) for glutamate is little affected. In the wild-type enzyme activity was pH-dependent and the acidic limb of the activity curve titrated with an apparent pK(a) of 6.6 on V(max), whereas for the sluggish Glu171Gln mutant activity is independent of pH. The steady state deuterium kinetic isotope effect is reduced in the mutant enzyme, but the steady state concentration of free radical species on the enzyme (as measured by the steady state concentration of cob(II)alamin) is unaffected by the mutation. CONCLUSIONS: The properties of the mutant proteins are consistent with the hypothesis that Glu171 acts as a general base that serves to deprotonate the amino group of the substrate during catalysis. Deprotonation is expected to facilitate the formation of the glycyl radical intermediate formed during the inter-conversion of substrate and product radicals, but to have little effect on the stability of product or substrate radicals themselves.     

改善ITER 弹丸注入芯部加料的研究

研究了五种不同组合的固态氢同位素靶丸H₂、HD、D₂、DT 和T₂ 在聚变等离子体中的消融率。结果表明, 燃料靶丸的同位素效应, 可导致更深的靶丸消融物质沉积。在同样的本底等离子体条件和弹丸初始参数下, 注入氚丸比氢丸的穿透深度增加约40%。适度减轻一些ITER 的加料困难。进一步的研究表明从中平面高场侧注入靶丸对芯部加料有显著改善。考虑托卡马克非均匀磁场的影响, 被电离的消融云内的垂直漂移电流产生极化, 引起带电消融物沿大半径方向朝外漂移。数值模拟计算表明, 只要用初始速度为每秒几百米的低速弹丸, 便能使靶丸的消融物质沉积到ITER 等离子体中心。     

Hyperfine structure and isotope shifts in the 5d6s2 a2D3/2--5d6s(a3D)6p z4F5/2 ° transition of Hf II

The hyperfine structure and isotope shifts of the transition between the 5d6s² a²D_3/2 ground state and the 5d6s(a³D)6p z⁴F_5/2 ^° excited state of singly ionized hafnium at \lambda=340 nm have been investigated by laser spectroscopy using a radio-frequency quadrupole ion trap. The magnetic dipole coupling constant A and electric quadrupole coupling constant B of the two atomic levels for both stable isotopes ¹⁷⁷Hf and ¹⁷⁹Hf are determined. The changes of mean square nuclear charge radii \delta[ r²] of the stable Hf isotopes and the radioactive isotope ¹⁷²Hf (T_1/2=1.87a) have been extracted from the data. This revised version was published online in August 2006 with corrections to the Cover Date.