同步辐射真空紫外光电离质谱研究乙烯扩散火焰

本文利用探针取样法结合同步辐射真空紫外光电离和分子束质谱技术研究了常压下的乙烯扩散火焰.通过测量光电离质谱和光电离效率谱分辨了该火焰中大部分的燃烧中间体及产物;通过改变探针取样位置以及半定量计算得到了其中部分燃烧中间体及产物的摩尔分数曲线.实验结果为探索多环芳烃和烟尘在扩散火焰中形成的最初阶段的反应机理提供了依据.     

用组态相互作用理论研究He原子的非谐振光致电离

本文用组态相互作用理论研究Ｈｅ原子的非谐振光致电离。本文详细分析双重激发自电离态，考察第一电离阈值附近的非谐振谱，计算非谐振区的ｅ－Ｈｅ＋，１，３Ｐ散射位相移动及来自ｌｓｎｓ１，３Ｓ的光致电离截面，本文计算结果与实验观测值及现有的理论结果相比较，相当符合。     

酪氨酸光电离过程的激光闪光光谱研究:pH效应

运用２４８ｎｍ激光闪光光解瞬态吸收光谱研究了不同ｐＨ值水溶液中酪氨酸光解过程,结果表明,溶液ｐＨ值影响酪氨酸的光电离过程;ｐＨ值增大,通过单光子途径的分子增多,而通过双光子途径的分子减少,反之则反。进一步阐明,酪氨酸光电离的ｐＨ效应源于其酚羟基的电离。     

Derivatization of Drugs and Bioorganics for Improved Detection by Gas Chromatography and Photoionization Detection (GC-PID)

Abstract

Pentafluorophenyldimethylsilylchloride (flophemesyl chloride, FICI) has recently been used for derivatizations of alcohols, leading to significant improvements in detectability by gas chromatography (GC)-photoionization detection (PID) and electron capture detection (ECD). This off-line reaction has now been applied to a number of related alcohol derivatives, naturally occurring bioorganics such as cholesterol, androsterone, and similar sterols and steroids. Standard GC-ECD-PID analytical parameters have been determined, such as detection limits, calibration plots, ECD and PID relative response factors (RRF), ECD/PID relative response factor ratios, etc. for underivatized and derivatized substrates. Packed and capillary column GC conditions have been used with a 10.2 eV PID lamp. Application of the optimized derivatization-GC-ECD-PID method is reported for bioorganics in biological media. The overall results demonstrate the immediate applicability of such an approach for a number of alcohol derivatives, especially those having biological properties.     

New perspective on the determination of flame retardants in sewage sludge by using ultrahigh pressure liquid chromatography–tandem mass spectrometry with different ion sources

Analysis of 11 polybrominated diphenyl ethers (PBDEs), tetrabromobisphenol A bis 2,3-dibromopropylether (TBBPA-bis), tetrachlorobisphenol A (TCBPA), tetrabromobisphenol A (TBBPA) and hexabromocyclododecanes (HBCDs) was optimized by ultrahigh pressure liquid chromatography/tandem mass spectrometry (UPLC–MS/MS) operating in negative ion (NI) mode. Electrospray ionization (ESI), atmospheric pressure photoionization (APPI) and atmospheric pressure chemical ionization (APCI) sources were tested and for PBDEs APCI gave higher sensitivity than APPI while for TBBPA-bis APCI and APPI showed similar performance. ESI was the best option for TCBPA, TBBPA and HBCDs. Detection limits were between 20 and 59 fg for the compounds analyzed by ESI, 0.10 and 0.72 pg for PBDEs and 6 pg for TBBPA-bis. The matrix effect of sewage sludge extract was also tested showing negligible ion suppression for APCI and an increase of the background level of all investigated pollutants leading to a worsening of the limits of quantification by a factor between 1.2 and 3.3. The UPLC-APCI/MS/MS method for PBDEs, after pressurized liquid extraction (PLE), was validated by comparison with the concentration values from the NIST 1944 standard reference material. The advantages of the methods include low detection limits, PBDE congeners specificity using selected multiple reaction monitoring (MRM) transitions, and the absence of thermal degradation of higher PBDE congeners, especially BDE-209. The methods were applied for the determination of the above reported flame retardants in sewage sludge in order to get more information about the degradation on PBDEs (in particular BDE-209) during municipal wastewater treatments.     

Analytical capabilities of high performance liquid chromatography – Atmospheric pressure photoionization – Orbitrap mass spectrometry (HPLC-APPI-Orbitrap-MS) for the trace determination of novel and emerging flame retardants in fish

A new analytical method was established and validated for the analysis of 27 brominated flame retardants (BFRs), including so called “emerging” and “novel” BFRs (EBFRs and NBFRs) in fish samples. High performance liquid chromatography (HPLC) coupled to Orbitrap mass spectrometry (Orbitrap-MS) employing atmospheric pressure photoionization (APPI) interface operated in negative mode was used for the identification/quantitation of contaminants. HPLC-Orbitrap-MS analysis provided a fast separation of selected analytes within 14 min, thus demonstrating a high throughput processing of samples. The developed methodology was tested by intralaboratory validation in terms of recovery, repeatability, linear calibration ranges, instrumental and method limits of quantitation (i-LOQ and m-LOQ), and where possible, trueness was verified by analysis of certified reference materials (CRMs). Recoveries of analytes were between 80 and 119%, while the repeatability in terms of relative standard deviations (RSDs) was in the range from 1.2 to 15.5%. The measured values for both analyzed CRMs agreed with the provided consensus values, revealing the recovery of reference concentrations in 72–119% range. The elaborated method met the sensitivity criterion according to Commission Recommendation 2014/118/EU on monitoring of BFRs in food products for majority of the compounds. The concentrations of polybrominated diphenyl ethers (PBDEs) in real samples determined by HPLC-APPI-Orbitrap-MS method and validated gas chromatography–high-resolution mass spectrometry (GC–HRMS) method were found to be in a good agreement.     

The evolution of electronic structure in lanthanide metal clusters: Threshold photoionization spectra of and

The photoionization spectra of Pr₂-Pr₂₁ and Ce₂-Ce₁₇ have been measured near threshold. The ionization potentials (IPs) of and vary discontinuously with size, but trend downward toward the work function of the bulk metals. In general, the IPs of cerium clusters display more variation than those of praseodymium clusters. The sudden discontinuities observed in the IPs of both and is akin to that displayed by clusters of transition metal atoms, suggesting that as in transition metal clusters, the rapid evolution in geometric structure with size is the source of these discontinuities. Received: 2 January 1998 / Accepted: 10 March 1998