Anionic copper complex fragmentations from enkephalins under low-energy collision-induced dissociation in an ion trap mass spectrometer

Peptide metallation with Cu2+ was explored in the negative ESI mode using an ion trap mass spectrometer. Under these conditions, the [(M-3H) + CuII]- species formed were investigated under low-energy collision-induced dissociation conditions. MS2 experiments indicate a very different behavior of CuII metallated complexes compared with [M-H]- species. CuII induces an easy loss of CO2 and specific side-chain cleavages (by radical losses) at the C-terminal residue, as observed previously by prompt 'in source' dissociation experiments. The loss of CO2 yields an unstable carbylide that leads to further dissociations involving the migration of a proton or a hydrogen radical (through the reduction of CuII). Multistage MS3 experiments were carried out to rationalize this behavior. Fragmentation pathways are proposed in order to explain the product ions observed. The side-chain radical loss at the C-terminus was demonstrated to be a consecutive process. Finally, evidence is provided that the specific side-chain cleavages can be used for the differentiation of Leu/Ile and Gln/Lys residues when they are located at the C-terminus. The existence of a zwitterionic form in the case of the anionic YGGFK-CuII complex is proposed.     

AMS测量中同量异位素的鉴别方法

在加速器质谱测量中,存在同位素和同量异位素的干扰.排除同位素的干扰是开展超微量核素分析的重要课题之一.主要介绍了加速器质谱测量中同量异位素的几种鉴别、排除方法,以及这些方法的原理、发展及应用. There are interference of isotopes and isobars in accelerator mass spectrometry (AMS) measurements. Eliminating the isobaric interference is the important aspect in AMS measurements. Several methods of isobaric identification in AMS measurements are discussed in this paper. Principles, developments and applications of these methods are also introduced.     

热晕瞬态效应的数值模拟

根据瞬态四维（４Ｄ）热晕程序，研究了激光大气传输中热晕瞬变效应及如何过渡到等压近似下的热晕状态，并与等压近似下４Ｄ热晕程序计算结果作了对比，在大约四倍流体力学时间，瞬态４Ｄ热晕程序计算结果逼近等压近似下的结果；另外，还作了相位补偿计算，对光强每平方厘米几千瓦的情况，在理想的自适应光学系统动力学条件下，瞬变阶段的热畸变能相当有效地实时补偿。     

AMS重核素测量的入射离子X射线探测法

介绍了在加速器质谱学中发展的入射离子 X射线的探测技术,以便应用于测定中重同位素的同量异位素鉴别 .描述了在中国原子能科学研究院加速器质谱计上建立的入射离子 X射线探测装置和实验结果 .通过测量入射离子 X射线,实现了64Cu测量中对同量异位素64Ni和64Zn的鉴别 ,以及79Se测量中对79Br的鉴别. In recent years, a new technique to detect the charteristic X ray from projectile ions in accelerator mass spectrometry (AMS) has been developed. After analysis in the routine AMS system, the ions are stopped in an appropriately chosen target in steat of an ion detector and induced X ray are detected for identification of ions by atomic number. For the application of AMS to higher mass isotopes with mass number>20 using small accelerator, the characteristic X rays technique is better...     

Chiral magnetic effect in isobar collisions from stochastic hydrodynamics

We studied the chiral magnetic effect in AuAu, RuRu, and ZrZr collisions at \begin{document}$\sqrt{s_{{NN}}}=200\;{\rm{GeV}}$\end{document}. The axial charge evolution was modeled with stochastic hydrodynamics, and geometrical quantities were calculated with the Monte Carlo Glauber model. By adjusting the relaxation time of the magnetic field, we found our results are in good agreement with background subtracted data for AuAu collisions at the same energy. We also made predictions for RuRu and ZrZr collisions. We found a weak centrality dependence on initial chiral imbalance, which implies that the centrality dependence of chiral magnetic effect signals results mainly from the effects of the magnetic field and volume factor. Furthermore, our results show an unexpected dependence on system size. While the AuAu system has larger chiral imbalance and magnetic field, it was observed to have a smaller signal for the chiral magnetic effect due to the larger volume suppression factor.     

Consequences of Holba-Šesták equation

It was proved on the basis of Holba-Šesták equation (1972) that the one is very interesting point of view to define the relative rate of reaction/process. Thereby, the assumption about interconnection between three-parametric equation and thermodynamic condition determined by equilibrium conversion degree in given temperature, is strengthened. Further considerations, still based on analysis of the inequality, made possible proposition of thesis about maximal rate of reaction/process in dynamic conditions in relation to modified van’t Hoff’s isobar (equation).     

The Role of a1(1260) in π-p→a1-(1260)p and π-p→π-ρ0p Reactions Near Threshold

We report on a theoretical study of the π^-p→a₁^-(1260) p and π^-p→π^-ρ⁰p reactions near threshold within an effective Lagrangian approach. The production process is described by t-channel ρ⁰ meson exchange. For the π^-p→π^-ρ⁰p reaction, the final π^-ρ⁰ results from the decay of the a₁(1260) resonance, which is assumed as a dynamically generated state from the K^*K and ρπ coupled channel interactions. We calculate the total cross section of the π^-p→a₁^-(1260)p reaction. It is shown that, with the coupling constant of the a₁(1260) to ρπ channel obtained from the chiral unitary theory and a cut off parameter Λρ~1.5 GeV in the form factors, the experimental measurement can be reproduced. Furthermore, the total and differential cross sections of π^-p→a₁^-(1260)p→π^-ρ⁰p reaction are evaluated, and it is expected that our model calculations can be tested by future experiments. These reactions are important for the study of the a₁(1260) resonance and would provide further constraints on the properties of the a₁(1260) state.     

~(36)Cl的加速器质谱测量及其应用

长寿命核素36Cl的半衰期为3.01×105a,广泛分布于自然界中。加速器质谱是目前测量36Cl的最灵敏的方法。介绍了36Cl的样品制备及加速器质谱测量方法,重点描述了基于小型化加速器质谱发展起来的测量36Cl的探测方法及其特点,综述了各实验室利用36Cl在相关领域开展的工作及所取得的成果。     

X-Ray studies of phase diagrams of the system Mn-Cr-O in air

X-Ray analysis was made of solid solutions and heterogeneous compositions of the general formula Mn_3?xCr_xO_m (0?x ? 3, Δx = 0.05). Subsolidus portions of the high temperature phase equilibria diagram and the diagram of water-quenched phases of the system Mn-Cr-O in air were established in the temperature range 700–1400°C. Comparative analysis of these diagrams has revealed the mechanism of the processes occurring upon rapid cooling of the system (in water and in air in a ceramic crucible) from high temperatures to room temperature. Rapid cooling is shown to preserve the phase composition and crystal structure of nonspinel phases, but for equilibrium solid solutions with spinel or hausmannite structure, this is not always the case. Depending on the quench temperature and the solution composition the following phenomena are observed: (1) tetragonal distortion of a high temperature phase with spinel structure; (2) merging of a tetragonally distorted spinel and spinel and formation of a homogeneous phase with hausmannite structure; (3) decomposition of the homogeneous phase with spinel structure into two spinel-type phases with spinel and hausmannite structures. Possible causes of these phenomena are discussed.     

Discrimination of isomers and isobars by varying the reduced-field across drift tube in proton-transfer-reaction mass spectrometry (PTR-MS)

Proton-transfer-reaction mass spectrometry (PTR-MS) is a powerful technique for the real time trace gas analysis of volatile organic compounds (VOCs). However, quadrupole mass spectrometer (MS) used in PTR-MS has a relatively low mass resolution and is therefore not suitable for differentiating isobars. Furthermore, because of the lack of chemical separation before analysis, isomers can not be identified, either. In the present study, by varying the reduced-field E/N in the reaction chamber with a range of 50–180 Td in PTR-MS, we studied the product ion distribution (PID) of three sets of isobars/isomers, i.e. n-propanol/iso-propanol/acetic acid, propanal/acetone and four structural isomers of butyl alcohol. The profiles of the reduced-field dependence (PFD) of the PID under the chosen E/N-values show obvious differences which can be used to discriminate between these isobars/isomers thus enabling the titled method. Noticeably, we have observed that even the isomers, in the case of four structural isomers of butyl alcohol, which show little difference with each other at high reduced-field, can be discriminated easily at low reduced-field. Finally, two examples for the application of this method are discussed: (1) cyclohexanone was identified to be a major compound in the headspace of medical infusion sets; and (2) the differentiation and quantification of propanal and acetone in three synthetic mixtures with different ratios. This study presents a potential method to distinguish and quantify isobars/isomers conveniently in practical applications of PTR-MS analysis without additional instrumental configurations.