Mass Measurements on Short-Lived Nuclides with ISOLTRAP

Penning trap mass spectrometry has reached a state that allows its application to very short-lived nuclides available from various sources of radioactive beams. Mass values with outstanding accuracy are achieved even far from stability. This paper illustrates the state of the art by summarizing the status of the ISOLTRAP experiment at ISOLDE/CERN. Furthermore, results of mass measurements on unstable rare earth isotopes will be given. This revised version was published online in July 2006 with corrections to the Cover Date.     

On the resonant neutrinoless double-electron-capture decay of Ce

The double-electron-capture Q value for the ¹³⁶Ce decay to ¹³⁶Ba has been determined at JYFLTRAP. The measured value 2378.53(27) keV excludes the energy degeneracy with the ⁰⁺$0^{+}$ excited state of the decay daughter ¹³⁶Ba at 2315.32(7) keV in a resonant 0νECEC$0\nu \mathrm{ECEC}$ decay by 11.67 keV. The new Q value differs from the old adopted value 2419(13) keV (Atomic Mass Evaluation 2003) by 40 keV and is 50 times more precise. Our calculations show that the precise Q   value renders the resonant 0νECEC$0\nu \mathrm{ECEC}$ decay of ¹³⁶Ce undetectable by the future underground detectors. We measured also the double-β decay Q value of ¹³⁶Xe to be 2457.86(48) keV which agrees well with the value 2457.83(37) keV measured at the Florida State University.     

Analysis of peptides and protein digests by reversed phase high performance liquid chromatography–electrospray ionisation mass spectrometry using neutral pH elution conditions

In this study, the advantages of carrying out the analysis of peptides and tryptic digests of proteins under gradient elution conditions at pH 6.5 by reversed-phase liquid chromatography (RP-HPLC) and in-line electrospray ionisation mass spectrometry (ESI-MS) are documented. For these RP separations, a double endcapped, bidentate anchored n-octadecyl wide pore silica adsorbent was employed in a capillary column format. Compared to the corresponding analysis of the same peptides and protein tryptic digests using low pH elution conditions for their RP-HPLC separation, this alternative approach provides improved selectivity and more efficient separation of these analytes, thus allowing a more sensitive identification of proteins at different abundance levels, i.e. more tryptic peptides from the same protein could be confidently identified, enabling higher sequence coverage of the protein to be obtained. This approach was further evaluated with very complex tryptic digests derived from a human plasma protein sample using an online two-dimensional (2D) strong cation-exchange (SCX)-RP-HPLC-ESI-MS/MS system. Again, at pH 6.5, with mobile phases of different compositions, improved chromatographic selectivities were obtained, concomitant with more sensitive on-line electrospray ionisation tandem mass spectrometric (ESI-MS/MS) analysis. As a consequence, more plasma proteins could be confidently identified, highlighting the potential of these RP-HPLC methods with elution at pH 6.5 to extend further the scope of proteomic investigations.     

A review of electron-capture and electron-transfer dissociation tandem mass spectrometry in polymer chemistry

Mass spectrometry (MS)-based studies of synthetic polymers often characterise detected polymer components using mass data alone. However when mass-based characterisations are ambiguous, tandem MS (MS/MS) offers a means by which additional analytical information may be collected. This review provides a synopsis of two particularly promising methods of dissociating polymer ions during MS/MS: electron-capture and electron-transfer dissociation (ECD and ETD, respectively). The article opens with a summary of the basic characteristics and operating principles of ECD and ETD, and relates these techniques to other methods of dissociating gas-phase ions, such as collision-induced dissociation (CID). Insights into ECD- and ETD-based MS/MS, gained from studies into proteins and peptides, are then discussed in relation to polymer chemistry. Finally, ECD- and ETD-based studies into various classes of polymer are summarised; for each polymer class, ECD- and ETD-derived data are compared to CID-derived data. These discussions identify ECD and ETD as powerful means by which unique and diagnostically useful polymer ion fragmentation data may be generated, and techniques worthy of increased utilisation by the polymer chemistry community.     

Simultaneous determination of estrogenic and androgenic hormones in water by isotope dilution gas chromatography-tandem mass spectrometry

A rapid gas chromatography-tandem mass spectrometry (GC-MS/MS) analytical method was developed for the simultaneous analysis of 7 estrogenic hormones (17α-estradiol, 17β-estradiol, estrone, mestranol, 17α-ethynylestradiol, levonorgestrel, estriol) and 5 androgenic hormones (testosterone, androsterone, etiocholanolone, dihydrotestosterone, androstenedione) in aqueous matrices. This method is unique in its inclusion of all 12 of these estrogens and androgens and is of particular value due to its very short chromatographic run time of 15 min. The use of isotope dilution for all analytes ensures the accurate quantification, accounting for analytical variabilities that may be introduced during sample processing and instrumental analysis. Direct isotopically labelled analogues were used for 8 of the 12 hormones and satisfactory isotope standards were identified for the remaining 4 hormones. Method detection levels (MDLs) were determined to describe analyte concentrations sufficient to provide a signal with 99% certainty of detection. The established MDLs for most analytes were 1-5 ngL(-1) in a variety of aqueous matrices. However, slightly higher MDLs were observed for etiocholanolone, androstenedione, testosterone, levonorgestrel and dihydrotestosterone in some aqueous matrices. Sample matrices were observed to have only a minor impact on MDLs and the method validation confirmed satisfactory method stability over intra-day and inter-day analyses of surface water and tertiary treated effluent samples.     

潘宁源放电的全三维电磁粒子模拟/蒙特卡罗碰撞数值算法研究

深入研究潘宁放电的物理机制, 研制了全三维高品质算法粒子模拟软件(PIC), 设计并添加了相应物理情景的蒙特卡罗碰撞模块(MCC), 并对电子、氢分子离子(H₂⁺)、氢正离子(H⁺)、氢三正离子(H₃⁺)同时进行了跟踪, 成功研制了全三维电磁PIC/MCC数值算法. 结合国内研究较热的潘宁放电模型, 对该算法进行模拟验证. 模拟结果显示: 采用有效的滤波算法能抑制电磁数值噪声, 电子能量呈麦克斯韦分布, 由于电子的径向漂移和加速导致离子源顶端H₂⁺产量较大. 关键词： 潘宁离子源 高品质算法 粒子模拟/蒙特卡罗     

Substituent effect on ionisation potential in a series of related molecules: A theoretical study in a molecular orbital framework

The effect of replacing the hydrogen atoms in thioformaldehyde by halogen atoms (F, Cl) on the ionisation potential of the non-bonding electron is analysed by using the Hellman-Feynman theorem, regarding the nuclear charge of the substituent as a parameter in the many-electron Hamiltonian. The trends predicted by our theory nicely agree with the relevant ionisation potentials computed either by applying Koopmans’ theorem or by the ΔE _SCF method. For the carbonyls, avaible experimental data indicate the reliability of our prediction.     

Fake double layers in double plasma devices

The double layer like potential jumps have been observed in a double plasma device. They do not correspond to a switching of plasma potential from one metastable state to another but are caused by the ionisation of a very minute amount of the gas that inevitably leaks into the system during the probe movement.     

The Characteristics of Direct Hydroxylation of Benzene to Phenol with Molecular Oxygen Enhanced by Pulse DC Corona at Atmospheric Pressure

The direct hydroxylation of benzene using molecular oxygen by atmospheric pulse DC corona discharge was investigated. The conversion of benzene increased with the increase of oxygen content and input voltage but the selectivity of phenol decreased due to the formation of polymerized products. The reactivity was also influenced by the kind and content of background inert gas. By using argon as background gas, we could get 2.2% of phenol yield at 60°C and 1 atm with energy consumption of 50 W. The strategy of reductive oxidation, which added hydrogen to the reactant, was not favorable to the phenol formation in this reaction system. The polymerized product showed the oligomeric character and the analysis of its chemical structure with FT–IR was presented.