用激光解吸附电离飞行时间质谱法检测悬浮土壤颗粒物

在自行研制的气溶胶飞行时间激光质谱仪(ATOFLMS)上实时探测单个悬浮土壤颗粒的粒径和化学成分。利用双束连续激光对单个粒子的空气动力学粒径进行测量,并用266 nm的Nd∶YAG激光器对气溶胶单粒子进行解吸附电离作用,产物离子通过飞行时间质谱仪的无场漂移区后完成单粒子化学成分的检测。本实验中使用了4个不同地区的土壤样本,在实验室内对分析的样本进行预处理和再悬浮,通过导管引入ATOFLMS进行测量,得到大量单粒子的粒径和质谱数据。发现在众多的单粒子的阳离子质谱中,金属成分以地壳元素(Fe, K, Al, Ca)为主,在其他阳离子质谱中包含了Mg和Na等。对悬浮土壤粒子的粒径进行实时检测的结果表明这些粒子多以粗粒子为主, 粒径主要集中在1～2 μm。实验结果表明该仪器在大气气溶胶环境监测及相关研究领域具有重要的实用价值。     

激光解吸电离技术在线测量苯水相二次有机气溶胶

利用气溶胶激光飞行时间质谱仪激光解吸电离技术开展了苯水相二次有机气溶胶在线测量研究。实验结果表明,苯水相光氧化反应形成的二次有机气溶胶粒子粒径小于1.0μm,激光解吸电离质谱中存在醛类m/z 29(CHO~+)、57(CHOCO~+),羧酸m/z 44(COO~+),苯环m/z 77(C_6H~+_5)、65(C_5H~+_5)和酚类化合物m/z 93(C_6H_5O~+)特征裂解碎片峰。醛类、羧酸和酚类化合物是苯水相SOA粒子的化学组分,各类型组分含量大小关系为:醛类化合羧酸酚类化合物。气溶胶激光飞行时间质谱仪激光解吸电离技术能够用于水相SOA粒子化学组分的在线测量,可用于水相SOA形成机理和过程的研究。     

基于模糊聚类算法的大气粒子激光电离质谱数据分析

实验室自行研制了一台大气气溶胶飞行时间激光质谱仪(ATOFLMS),它可以在线地对气溶胶单粒子进行物理和化学特性分析,利用双束连续激光对单个粒子的空气动力学粒径进行测量,并通过飞行时间完成单粒子化学成分的检测。该仪器在运行过程中将产生海量的实验数据,对这些数据的快速、自动处理并提取有价值的信息是整机系统的关键之一。文章介绍模糊聚类算法FCM(fuzzy c-means)在大气气溶胶单粒子聚类分析中的成功运用。利用该算法对连续24 h采集的室内空气气溶胶单粒子质谱数据进行了聚类分析,在得到的5个聚类结果中包含了无机的海盐粒子、矿物质粒子以及其他的三种二次气溶胶成分粒子类型。在对室内空气气溶胶粒子的粒径进行实时检测的结果表明室内可吸入颗粒物以细粒子为主,其中大于1 μm的粒子所占比重较小。小于1 μm的粒子均占95％以上, 在0.4～0.8 μm之间的粒子占据主要部分。     

可调谐二极管激光吸收光谱二次谐波信号的模拟与分析

可调谐二极管激光吸收光谱技术(TDLAS)作为近年来发展起来的一种气体检测技术,具有高分辨率、高灵敏度和快速测量等特点。波长调制光谱信号的二次谐波分量常作为检测信号,用于气体浓度信息的反演。利用MATLAB中的可视化建模仿真平台Simulink,模拟了基于TDLAS的波长调制光谱信号,利用锁相放大原理提取二次谐波分量。采用数字锁相,正交双通道结构实现锁相算法。通过比较不同调制系数下二次谐波信号的变化情况,分析了二次谐波信号与调制系数的关系,以便确定最佳参数,用于二次谐波的提取。     

Silicon nitride nanoparticles for surface-assisted laser desorption/ionization of small molecules

Conventional matrix-assisted laser desorption/ionization mass spectrometry is limited to analyses of higher molecular weight compounds due to high background noise generated by the matrix in the lower mass region. Surface-assisted laser desorption/ionization (SALDI) mass spectrometry is an alternative solution to this problem. Nanoparticles, structured silicon surfaces and carbon allotropes are commonly used as SALDI surfaces. Here, for the first time, we demonstrate the application of silicon nitride nanoparticles as a suitable medium for laser desorption/ionization of small drug molecules.     

Efficient fabrication of substrates for surface-assisted laser desorption/ionization mass spectrometry using laser ablation in liquids

Substrates for the surface-assisted laser desorption ionization (SALDI) technique were prepared using electrophoresis of gold nanoparticles produced by laser ablation in liquids. Throughout the preparation, no supplemental reagent was added for the stabilization and deposition of nanoparticles. Nanoparticles were deposited more uniformly using the electrophoresis technique than using dropping of the solution. Results demonstrated that the higher uniformity of the deposition of nanoparticles improved the reproducibility of SALDI measurements. Furthermore, the thickness of the deposited nanoparticles influences the SALDI efficiency.     

The use of Raman microscopy and laser desorption ionization mass spectrometry in the examination of synthetic organic pigments in modern works of art

Synthetic organic pigments are widely used in modern and contemporary works of art. They have been examined by a variety of techniques including spectroscopic methods such as Fourier transform infrared spectroscopy, Raman, and X‐ray powder diffraction as well as chromatographic or mass spectrometric techniques such as pyrolysis‐gas chromatography/mass spectrometry and laser desorption ionization mass spectrometry (LDI–MS). Often, a combination of techniques has been used to examine these pigments. This paper describes use of Raman spectroscopy to create a database of colorants including two pigments not previously reported, PO1 and PO2. Then, using Raman spectroscopy in combination with LDI–MS, samples from modern works of art by artists including Mark Rothko, Barnett Newman, and José de Rivera were examined in order to identify the pigments present. One finding was that Rothko used a variety of red pigments over the course of his career including PR11 which has not been previously reported in artwork, and PO2 found with its positional isomer PR1. Knowledge of the colorants serves to inform conservators about display and treatment decisions. Published 2014. This article is a U.S. Government work and is in the public domain in the USA.     

Identification and quantification of amyloid beta-related peptides in human plasma using matrix-assisted laser desorption/ionization time-of-flight mass spectrometry

Proteolytic processing of the amyloid precursor protein (APP) by β-secretase and γ-secretase leads to the generation and deposition of amyloid β (Aβ) in Alzheimer’s disease (AD). N-terminally or C-terminally truncated Aβ variants have been found in human cerebrospinal fluid and cultured cell media using immunoprecipitation and mass spectrometry. Unfortunately, the profile of plasma Aβ variants has not been revealed due to the difficulty of isolating Aβ from plasma. We present here for the first time studies of Aβ and related peptides in human plasma. Twenty-two Aβ-related peptides including novel peptides truncated before the β-secretase site were detected in human plasma and 20 of the peptides were identified by tandem mass spectrometry. Using an internal standard, we developed a quantitative assay for the Aβ-related peptides and demonstrated plasma dilution linearity and the precision required for their quantitation. The present method should enhance the understanding of APP processing and clearance in AD progression.     

Silver nanoparticles as matrix for laser desorption/ionization mass spectrometry of peptides

Silver nanoparticle synthesized from chemical reduction has been successfully utilized as a matrix in matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF-MS) of peptides. Acting as a substrate to adsorb analytes, as well as a transmission medium for UV laser, silver nanoparticle was found to assist in the desorption/ionization of peptides with little or no induced fragmentation. The size of the nanoparticle was typically in the range of 160 ± 20 nm. One of the key advantages of silver nanoparticle for peptides analysis is its simple step for on-probe sample preparation. In addition, it also minimizes the interferences of sodium dodecyl sulfate (SDS) surfactant background signal, resulting in cleaner mass spectra and more sensitive signal, when compared to α–cyano-4-hydroxycinnamic acid (CCA) matrix.     

Application of nanodiamonds in human body fluid analysis by matrix-assisted laser desorption/ionization mass spectrometry

Direct mass spectrometric analysis of complex biological samples is very important and challenging. In this paper, nanodiamonds have been successfully used in matrix-assisted laser desorption/ionization mass spectrometric analysis of human serum and urine. As a practical tool and platform, it can be widely used in the field of humoral proteomics, and it plays a very promising role in clinical diagnosis, including identification of novel disease-associated biomarkers.     

Cobalt coated substrate for matrix-free analysis of small molecules by laser desorption/ionization mass spectrometry

Small molecule analysis is one of the most challenging issues in matrix-assisted laser desorption/ionization (MALDI) mass spectrometry. We have developed a cobalt coated substrate as a target for matrix-free analysis of small molecules in laser desorption/ionization mass spectrometry. Cobalt coating of 60-70 nm thickness has been characterized by scanning electron microscopy, energy dispersive X-ray analysis, X-ray diffraction, and laser induced breakdown spectroscopy. This target facilitates hundreds of samples to be spotted and analyzed without mixing any matrices, in a very short time. This can save a lot of time and money and can be a very practical approach for the analysis of small molecules by laser desorption/ionization mass spectrometry.     

飞秒激光激发空气电离的阈值研究

报道在脉宽50fs—22ps,波长800nm脉冲激光作用下的空气电离阈值的研究结果.利用探测等离子体发光信号的方法,实验测量了激发空气电离所需的阈值激光强度.结果表明,当激光脉冲宽度从50fs增加到22ps时,阈值光强I_th从8.7×10¹⁴W/cm²下降到2.7×10¹³W/cm²;I_th经历了由迅速降低逐渐发展为缓慢降低的过程.在50fs—1p 关键词： 飞秒激光 阈值 多光子电离 碰撞电离     

Multiphoton and tunneling ionization of atoms in an intense laser field

We study the ionization probabilities of atoms by a short laser pulse with three different theoretical methods,i.e.,the numerical solution of the time-dependent Schro¨dinger equation(TDSE),the Perelomov-Popov-Terent’ev(PPT) theory,and the Ammosov-Delone-Krainov(ADK) theory.Our results show that laser intensity dependent ionization probabilities of several atoms(i.e.,H,He,and Ne) obtained from the PPT theory accord quite well with the TDSE results both in the multiphoton and tunneling ionization regimes,while the ADK results fit well to the TDSE data only in the tunneling ionization regime.Our calculations also show that laser intensity dependent ionization probabilities of a H atom at three different laser wavelengths of 600 nm,800 nm,and 1200 nm obtained from the PPT theory are also in good agreement with those from the TDSE,while the ADK theory fails to give the wavelength dependence of ionization probability.Only when the laser wavelength is long enough,will the results of ADK be close to those of TDSE.     

用伪谱方法计算强激光场中一维原子的阈上电离谱

引入非线性空间变换,用伪谱方法求解了一维原子在强激光场中的薛定谔方程,再利用B样条函数和傅立叶级数的线性组合构造原子未微扰的本征函数,计算了一维原子在强激光场中的阈上电离谱,其结果与分裂算符法得到的结果符合得很好.