Direct-EI in LC-MS: towards a universal detector for small-molecule applications

This review article will give an up-to-date and exhaustive overview on the efficient use of electron ionization (EI) to couple liquid chromatography and mass spectrometry (LC-MS) with an innovative interface called Direct-EI. EI is based on the gas-phase ionization of the analytes, and it is suitable for many applications in a wide range of LC-amenable compounds. In addition, thanks to its operating principles, it prevents unwelcome matrix effects (ME). In fact, although atmospheric pressure ionization (API) methodologies have boosted the use of LC-MS, the related analytical methods are sometime affected by inaccurate quantitative results, due to unavoidable and unpredictable ME. In addition, API's soft ionization spectra always demand for costly and complex tandem mass spectrometry (MS/MS) instruments, which are essential to acquire an "information-rich" spectrum and to obtain accurate quantitative information. In EI a one-stage analyzer is sufficient for a qualitative investigation and MS/MS detection is only used to improve sensitivity and to cut chemical noise. The technology illustrated here provides a robust and straightforward access to classical, well-characterized EI data for a variety of LC applications, and readily interpretable spectra for a wide range of areas of research. The Direct-EI interface can represent the basis for a forthcoming universal LC-MS detector for small molecules.     

Threshold photoionization in time-of-flight mass spectrometry

Multi-photon excitation in a time-of-flight mass spectrometer (TOF-MS) is shown to lead to threshold ions with defined internal energy. A powerful technique for the production of threshold ions is based on the excitation of high long-lived Rydberg states embedded in the ionization continuum. The Rydberg molecules are separated with suitable separation techniques from ions produced by a direct multi-photon ionization process. Finally, the ionization of the Rydberg molecules in a delayed pulsed electric field leads to threshold ions. This work reviews several separation techniques, and reports on applications of threshold ionization for investigation of the structure, energetics, and dynamics of neutral molecules, molecular cations, and cluster cations.     

基于热电离质谱铀系定年与氧同位素对比的古气候研究

为了研究过去全球变化在我国高海拔低纬度地区的变化规律，在高精度、高分辨率热电离质谱铀（TIMS-U）系定年和氧同位素基本原理的基础上，以贵州都匀七星洞一石笋为例，建立了43．63～12．43ka B．P．期间古气候变化的时间序列．石笋δ^18O记录与生长率对比研究表明：此阶段都匀地区经历了暖湿-冷干-暖湿的3个阶段气候演变趋势，反映了受西南季风与东亚季风双重影响的相互作用过程．得出了中国西南地区石笋碳酸盐δ^18O值与其降水及全球变化的对应关系，即：全球变暖→西南地区年降水δ^18O值偏轻→石笋δ^18O值偏负；全球变冷→西南地区年降水δ^18O值偏重→石笋δ^18O值偏正．这既与全球古气候变化波动基本一致，同时也具有地区性的气候特点。     

Ab initio Calculations of Electron-Impact Excitation Cross Sections for N_2 Molecule

One of the great difficulties in understanding nitrogen plasma elementary processes is the lack of an available database of the cross-sections of electron-impact excitations and radiations. Ab initio calculations of vibrational excitation cross sections for electron collisions with nitrogen molecules in low-lying states using similarity function approach, such as a-a＇, a-w, B-B＇ and B-W transition systems, are reported here for the first time. In the meantime, the average excitation energies of neighboring levels of these systems have been calculated. In order to obtain the cross sections, accurate spectroscopic constants and transition dipole moments have been investigated. Potential energy curves and other electronic transition dipole moments for the low-lying states of N2 have been re-evaluated using complete active space self-consistent field （CASSCF） approach with aug-cc-pVqZ basis set. The calculated cross-sections could provide a database for studying the elementary processes and the properties in N2 plasma.     

不同60Coγ剂量率下10位双极D/A转换器的总剂量效应

为探索电离辐射对数模混合电路的影响,对国产10位双极D/A转换器在60Coγ射线不同剂量率辐照下的电离辐射效应及退火特性进行研究。结果表明：D/A转换器对辐照剂量率十分敏感,在大剂量率辐照时,电路功能正常,各功能参数变化较小;在低剂量率辐照下,各参数变化显著,电路功能出现异常,表现出明显的低剂量率损伤增强效应。最后,结合空间电荷模型对其电离辐射损伤机理进行了初步探讨。     

新型平板电离室的研制与初步测试北大核心CSCD

研制一款同时测量质子束流与剂量的平板电离室。利用基于有限元分析的Ansys模拟软件和Geant4蒙特卡罗软件对电离室电场分布、等效水厚度、不同能量质子束穿过电离室后的横向散射等参数进行模拟,进而优化电离室结构。并利用YXLON 450 kV X射线管、6 MeV脉冲加速器与北京大学串列加速器对电离室进行初步测试,电离室运行稳定,射线位置二维分布信息采集准确,性能良好。     

RWM-B放射性水连续监测系统

核设施液态流出物的监测是鉴别核设施生产运行是否处于正常状况不可缺少的有力措施，也是评价核设施辐射安全的重要手段。本工作涉及RWM-B放射性水连续监测仪的研制。该监测系统采用高气压氙气电离室作为探测器，以8051单片计算机作为控制主机，电路上采用弱电流测量方法。如果5min 报告1次数据结果，取95%置信度，在普通天然本底条件下，探测下限则可达到2644Bq/m³。     

接地网的雷电冲击特性

为准确计算接地网的冲击特性,在场路结合的接地网暂态计算模型基础上,利用快速傅立叶变换提出了土壤电离计算模型。考虑了导体周围土壤火花放电对雷电暂态效应以及导体间阻性耦合和感性耦合的影响,利用快速傅立叶变换及其反变换,分析了不同地网结构,不同雷电流注入点等因素的接地网冲击特性。     

Thiogenistein—Antioxidant Chemistry,Antitumor Activity,and Structure Elucidation of New Oxidation Products

Isoflavonoids such as genistein (GE) are well known antioxidants. The predictive biological activity of structurally new compounds such as thiogenistein (TGE)–a new analogue of GE–becomes an interesting way to design new drug candidates with promising properties. Two oxidation strategies were used to characterize TGE oxidation products: the first in solution and the second on the 2D surface of the Au electrode as a self-assembling TGE monolayer. The structure elucidation of products generated by different oxidation strategies was performed. The electrospray ionization mass spectrometry (ESI-MS) was used for identifying the product of electrochemical and hydrogen peroxide oxidation in the solution. Fourier transform infrared spectroscopy (FT-IR) with the ATR mode was used to identify a product after hydrogen peroxide treatment of TGE on the 2D surface. The density functional theory was used to support the experimental results for the estimation of antioxidant activity of TGE as well as for the molecular modeling of oxidation products. The biological studies were performed simultaneously to assess the suitability of TGE for antioxidant and antitumor properties. It was found that TGE was characterized by a high cytotoxic activity toward human breast cancer cells. The research was also carried out on mice macrophages, disclosing that TGE neutralized the production of the LPS-induced reactive oxygen species (ROS) and exhibits ABTS (2,2′-azino-bis-3-(ethylbenzothiazoline-6-sulphonic acid) radical scavenging ability. In the presented study, we identified the main oxidation products of TGE generated under different environmental conditions. The electroactive centers of TGE were identified and its oxidation mechanisms were proposed. TGE redox properties can be related to its various pharmacological activities. Our new thiolated analogue of genistein neutralizes the LPS-induced ROS production better than GE. Additionally, TGE shows a high cytotoxic activity against human breast cancer cells. The viability of MCF-7 (estrogen-positive cells) drops two times after a 72-h incubation with 12.5 μM TGE (viability 53.86%) compared to genistein (viability 94.46%).     

高漏偏压下AlGaN/GaN HEMT噪声性能的研究

The advent of fully integrated GaN PA-LNA circuits makes it meaningful to investigate the noise performance under high drain bias. However, noise performance of AlGaN/GaN HEMTs under high bias has not received worldwide attention in theoretical studies due to its complicated mechanisms. The noise value is moderately higher and its rate of increase is fast with increasing high voltage. In this paper, several possible mechanisms are proposed to be responsible for it. Impact ionization under high electric field incurs great fluctuation of carrier density, which increases the drain diffusion noise. Besides, higher gate leakage current related shot noise and a more severe self-heating effect are also contributors to the noise increase at high bias. Analysis from macroscopic and microscopic perspectives can help us to design new device structures to improve noise performance of AlGaN/GaN HEMTs under high bias.