Analysis of monodispersed polyaniline oligomers by matrix-assisted laser desorption ionization mass spectrometry

Monodispersed polyaniline oligomers was studied by matrix-assisted laser desorption ionization-time of flight mass spectrometry (MALDI-TOF-MS), It is found that MALDI-TOF-MS is not only a direct, accurate and rapid tool for the analysis of monodispersed polyaniline oligomers, but also a useful technique for the design of synthetic route.

Analysis of poly (arylene phosphonate) cyclic oligomer by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry

Matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MAIDI-TOF-MS) was used for analysis of poly(arylene phosphonate) cyclic oligomers. A comparison was made by using 1,8,9-dithranol, 2,5-dihydroxybenzoic acid and retinoic acid as the matrix. The result showed that the retinoic acid produced the strongest ion signals under the conditions used. Different salts of metals were used as the cationization agents to examine the effect on the cyclic oligomers. It was found that the salts could produce metal-cyclic oligomer cation spectra and lithium was the stronger one than those of silver so, the suitable matrix and cationization agent for the new cyclic oligmer were obtained. They were very effective for the analysis of poly(arylene phosphonate) cyclic oligomer.

Characterization of cyclic arylether ketone (sulfone) containing hexafluoroisopropylidene unit by matrix-assisted laser desorption ionization time-of-flight mass spectrometry

The cyclic aryletherketone( sulfone) oligomers containing hexafluoroisopropylidene unit were characterized by matrix-assisted laser desorption ionization time-of-night mass spectrometry(MALDI-TOF-MS) using Na+ and Ag+ as cationization agents. The affinities of cyclic oligomers to the cation were studied. The analysis result showed that 1,8,9-dithranol, in the presence of silver trifluoroacetate, was very effective for the characterization of cyclic arylether ketone ( sulfone) containing hexafluoroisopropylidene unit.

Application of matrix-assisted laser desorption/ionization-time of flight-mass spectrometry and sodium dodecyl sulfate-polyacrylamide gel electrophoresis in determining arginine esterase from snake venom

Using matrix-assisted laser desorption/ionization-time of flight-mass spectrometry (MALDI-TOF-MS). The homogeneities and molecular weights of three arginine esterases from snake venom, which possessing therapeutic use in myocardial infarction, were determined and compared, MALDI-TOF-MS is possessed of high accuracy, high sensitivity and rapidity. MALDI-TOF-MS and sodium dodecyl sulfate-polyacrylamide gel electrophoresis (SDS-PAGE) can provide complementary and confirmatory results information. MALDI-TOF-MS can be directly used as an important method for the purification of snake venom complexes successfully.

The application of matrix-assisted laser desorption jonization mass spectrometry in enzymes of Agkistrodon blomhoffii Ussurensis venom analysis

The matrix-assisted laser desorption ionization mass spectrometry (MALDI-TOF-MS) spectra of four enzymes (PLA, AEase, Fibrolase, L-a.a. oxidase) in Agkistrodon blomhoffii Ussurensis venom, were given and interpreted. The experiment data showed that MALDI-TOF-MS can be used directly in enzyme analysis with high sensitivity and rapidity. In addition, the results were better than those from sodium dodecyl sulfate-polyacrylamide.

Characterization of cyclic (aryletherketone)s by matrix-assisted laser desorption ionization time of flight mass spectrometry

Matrix-assisted laser desorption ionization-time of flight mass spectrometry (MALDI-TOF MS) was used to identify cyclic(aryl ether ketone) oligomers, using 2,5-dihydroxybenzoic acid as a matrix, and Na+ and K+ as cationization agents, The existence of different ring-sized cyclic oligomers up to 9 and their distribution were determined and compared with GPC results, The results indicated that MALDI-TOF MS was a powerful and rapid analytical tool for the cyclic oligomers.

Behavior of silver cluster on laser desorption/ionization time-of-flight mass spectrometry

A successful analysis of silver was reported utilizing laser desorption/ionization time-of-flight mass spectrometry (LDI/TOF-MS) in this paper, The silver cluster ions Ag-n(+) and AgnO+ (n=2 similar to 5) were formed during laser desorption/ionization. In the presence of I-, K+ and Na+, the peaks corresponding, to the cluster ions [AgnIn-1](+) (n=2 similar to 6) and the adduct ions [AgI](+), [AgI]Na+ and [AgI]K+ were observed in the positive ion spectrum; the peaks corresponding to [AgnIn+1](-) (n=1 similar to 3) were found in the negative ion spectrum, all of which accompanied by sliver isotope distribution, The formation of silver cluster ions was accomplished through two-stage reaction: the first step was the generation of clusters, which was followed by the processes of photoionization and ion/molecule reaction.

Thermal decomposition processes of polyaniline and poly-o-toluidine investigated by direct pyrolysis mass spectrometry

The thermal decomposition of polyaniline(PAn) and poly-o-toluidine(POT) was studied by means of direct pyrolysis mass spectrometry(DM) and MS/MS, The results showed that both benzene-diamine and quinone-diimine units were produced, and the intensities of fragments corresponding to quinone-diimine units increased as the oxidation degrees increased, The mechanism of thermal decomposition of PAn and POT was given for the first time.

Determination of tetrodotoxin by liquid chromatography coupled with electrospray ion-trap mass spectrometry

Two methods for tetrodotoxin analysis using liquid chromatography coupled with electrospray iontrap mass spectrometry (LC-ESI-MS) have been established with C,, reversed phase column and hydrophilic interaction liquid chromatography (HILIC) column, respectively. Sensitivity and reproducibility of the methods were compared. The method using C-18 column in selected ion monitoring (SIM) mode had a detection limit (S/N = 3) of 120 pg, and a good linearity of the calibration curve was obtained for tetrodotoxin (r = 0. 9992). High reproducibility of the method was observed, with a relative standard deviation (RSD) below 10%. The method using HILIC column in SIM mode and selected reaction monitoring (SRM) mode had detection limits (S/N = 3) of 15 and 3.75 pg, respectively. Good linearity of the calibration curves was obtained for tetrodotoxin (r = 0. 9996 and 0. 9998 in SIM and SRM mode, respectively). T he reproducibility was high in SIM mode but relatively poor in SRM mode. Based on the results, the method using HILIC column in SIM mode was suggested for the analysis of tetrodotoxin with LC-MS system.

Development of a sensitive fluorescent derivatization reagent 1,2-benzo-3,4-dihydrocarbazole-9-ethyl chloroformate (BCEOC) and its application for determination of amino acids from seeds and bryophyte plants using high-performance liquid chromatography with fluorescence detection and identification with electrospray ionization mass spectrometry

A pre-column derivatization method for the sensitive determination of amino acids and peptides using the tagging reagent 1,2-benzo-3,4dihydrocarbazole-9-ethyl chloroformate (BCEOC) followed by high-performance liquid chromatography with fluorescence detection has been developed. Identification of derivatives was carried out by liquid chromatography/electrospray ionization mass spectrometry (LC/ESI-MS/MS). The chromophore of 2-(9-carbazole)-ethyl chloroformate (CEOC) reagent was replaced by 1,2-benzo-3,4-dihydrocarbazole functional group, which resulted in a sensitive fluorescence derivatizing reagent BCEOC. BCEOC can easily and quickly label peptides and amino acids. Derivatives are stable enough to be efficiently analyzed by high-performance liquid chromatography. The derivatives showed an intense protonated molecular ion corresponding m/z (M + H)(+) under electrospray ionization (ESI) positive-ion mode with an exception being Tyr detected at negative mode. The collision-induced dissociation of protonated molecular ion formed a product at m/z 246.2 corresponding to the cleavage of C-O bond of BCEOC molecule. Studies on derivatization demonstrate excellent derivative yields over the pH 9.0-10.0. Maximal yields close to 100% are observed with a 3-4-fold molar reagent excess. Derivatives exhibit strong fluorescence and extracted detzvatization solution with n-hexane/ethyl acetate (10:1, v/v) allows for the direct injection with no significant interference from the major fluorescent reagent degradation by-products, such as 1,2-benzo-3,4-dihydrocarbazole-9-ethanol (BDC-OH) (a major by-product), mono- 1,2-benzo-3,4-dihydrocarbazole-9-ethyl carbonate (BCEOC-OH) and bis-(1,2-benzo-3,4-dihydrocarbazole-9-ethyl) carbonate (BCEOC)(2). In addition, the detection responses for BCEOC derivatives are compared to those obtained with previously synthesized 2-(9-carbazole)-ethyl chloroformate (CEOC) in our laboratory. The ratios AC(BCEOC)/AC(CEOC) = 2.05-6.51 for fluorescence responses are observed (here, AC is relative fluorescence response). Separation of the derivatized peptides and amino acids had been optimized on Hypersil BDS C-18 column. Detection limits were calculated from 1.0 pmol injection at a signal-to-noise ratio of 3, and were 6.3 (Lys)-177.6 (His) fmol. The mean interday accuracy ranged from 92 to 106% for fluorescence detection with mean %CV < 7.5. The mean interday precision for all standards was < 10% of the expected concentration. Excellent linear responses were observed with coefficients of > 0.9999. Good compositional data could be obtained from the analysis of derivatized protein hydrolysates containing as little as 50.5 ng of sample. Therefore, the facile BCEOC derivatization coupled with mass spectrometry allowed the development of a highly sensitive and specific method for the quantitative analysis of trace levels of amino acids and peptides from biological and natural environmental samples. (c) 2005 Elsevier B.V. All rights reserved.

Matrix-assisted laser desorption/ionization time-of-flight mass spectrometry with a matrix of carbon nanotubes for the analysis of low-mass compounds in environmental samples

The use of matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF-MS) for environmental analysis has been mainly focused on qualitative analysis of high-mass molecules, such as toxins, humic acid, and microorganisms. Herein,we describe a novel MALDI-TOF-MS method with a matrix of oxidized carbon nanotubes for analysis of low-mass compounds in environmental samples. A number of chemicals in the environment were qualitatively analyzed by the present method, and it was found that most of them, especially the highly polar chemicals, were measurable with high sensitivity. With the intrinsic ability to measure high-mass chemicals, this method can compensate for the current shortage of methods for environmental analysis for the measurement of highly polar or high-mass chemicals. For sample analysis, arsenic speciation in Chinese traditional medicines was qualified and diphenylolpropane in water samples was quantified. With the relatively high tolerance of the method to interfering molecules, a simple pretreatment or even no pretreatment could be employed before MS detection. Furthermore, this method can be employed in a high-throughput format.

Integration of ion-exchange chromatography fractionation with reversed-phase liquid chromatography-atmospheric pressure chemical ionization mass spectrometer and matrix-assisted laser desorption/ionization time-of-flight mass spectrometry for isolation and identification of compounds in Psoralea corylifolia

An approach for the separation and identification of components in a traditional Chinese medicine Psoralea corylifolia was developed. Ion-exchange chromatography (IEC) was applied for the fractionation of P corylifolia extract, and then followed by concentration of all the fractions with rotary vacuum evaporator. Each of the enriched fractions was then further separated on an ODS column with detection of UV absorbance and atmospheric pressure chemical ionization mass spectrometer (APCI/MS), respectively, and also analyzed by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF/MS) with matrix of oxidized carbon nanotubes. Totally more than 188 components in P. corylifolia extract were detected with this integrated approach, and 12 of them were preliminary identified according to their UV spectra and mass spectra performed by APCI/MS and MALDI-TOF/MS. The obtained analytical results not only demonstrated the powerful resolution of integration IEC fractionation with reversed-phase liquid chromatography (RPLC)-APCI/MS and MALDI-TOF/MS for analysis of compounds in a complex sample, but also exhibited the superiority of APCI/MS and MALDI-TOF/MS for identification of low-mass compounds, such as for study of traditional Chinese medicines (TCMs) and metabolome. (c) 2005 Published by Elsevier B.V.

Separation and detection of compounds in Honeysuckle by integration of ion-exchange chromatography fractionation with reversed-phase liquid chromatography-atmospheric pressure chemical ionization mass spectrometer and matrix-assisted laser desorption/ionization time-of-flight mass spectrometry analysis

A hyphenated method for the isolation and identification of components in a traditional Chinese medicine of Honeysuckle was developed. Ion-exchange chromatography (IEC) was chosen for the fractionation of Honeysuckle extract, and then followed by concentration of all the fractions with rotary vacuum evaporator. Each of the enriched fractions was then further analyzed by reversed-phase liquid chromatography-atmospheric pressure chemical ionization mass spectrometer (RPLC-APCI/MS) and matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF/MS) with matrix of oxidized carbon nanotubes, respectively. It can be noted totally more than 117 components were detected by UV detector, APCI/MS and MALDI-TOF/MS in Honeysuckle extract except the, 145 components identified by MALDI-TOF/MS alone with this integrated approach, and 7 of them were preliminary identified according to their UV spectra and mass spectra performed by APCI/MS and MALDI-TOF/MS, respectively. The obtained analytical results not only indicated the approach of integration IEC fractionation with RPLC-APCI/MS and MALDI-TOF/MS is capable of analyzing complex samples, but also exhibited the potential power of the mass spectrometer in detection of low-mass compounds, such as traditional Chinese medicines (TCMs) and complex biological samples. (c) 2005 Elsevier B.V. All rights reserved.

Evaluation and application of micro-sampling system for inductively coupled plasma mass spectrometry

Two Meinhard microconcentric nebulizers, model AR30-07-FM02 and AR 30-07-FM005, were employed as a self-installed micro-sampling system for inductively coupled plasma-mass spectrometry (ICP-MS). The FM02 nebulizer at 22 muL/min of solution uptake rate gave the relative standard deviations of 7.6%, 3.0%, 2.7%, 1.8% for determinations (n = 10) of 20 mug/L Be, Co, In and Bi, respectively, and the detection limits (3s) of 0.14, 0.10, 0.02 and 0.01 mug/L for Be, Co In and Bi, respectively. The mass intensity of In-115 obtained by this micro-sampling system was 60% of that by conventional pneumatic nebulizer system at 1.3 mL/min. The analytical results for La, Ce, Pr and Nd in 20 muL Wistar rat amniotic fluid obtained by the present micro-sampling system were precisely in good agreement with those obtained using conventional pneumatic nebulization system.

ICP-OES的悬浮进样方式及ICP-MS的碰撞/反应池技术的研究与应用

本论文分为两部分：1. 综述部分（第一章和第二章），评述了悬浮进样方式在电感耦合等离子体发射光谱法（ICP-OES）中的研究与应用；电感耦合等离子体质谱（ICP-MS）中碰撞/反应池技术研究的新进展。2. 实验部分（第三章至第九章），内容包括针对不同性质的样品悬浮液选择适当的稳定剂和悬浮雾化ICP-OES的校准方法研究；以混合碰撞/反应气体解决难度较大的高纯氧化钕中稀土杂质测定的干扰问题；以及浊点萃取-石墨炉原子吸收法测定环境样品中痕量镉、氢化物发生-原子荧光光谱法测定铅基合金中砷和植物样品中锗等实用性强的分析方法研究。 ICP的传统进样方式是将样品转化成水溶液形式，以溶液方式进样。然而大多数样品是以固态形式存在，许多样品相当难溶或难熔。采用直接固体进样方法对这些样品进行分析，是分析工作者追求的目标之一。悬浮液进样是一种固体直接进样方法，除了具有其它固体进样技术的优点外，其最大优点是可以像溶液雾化一样用标准水溶液校准。本研究针对实际分析工作中遇到的具体样品，对悬浮进样ICP-OES技术进行了比较深入的研究，成功解决了样品处理繁琐和样品难以处理等困难。对特殊地质样品和激光晶体材料（Nd:YAG）的悬浮进样分析进行了探索。主要工作为：①建立分析地质样品中主量和微量元素的方法，标准水溶液可以成功地用于校准。优点是可以同时对地质样品中的Si和其它元素进行分析，避免了传统分析时需分别处理样品的麻烦。②探索了分析铌钽矿中铌和钽的应用。由于铌和钽具有强抗化学腐蚀性，所以溶液进样分析时样品处理过程复杂。结果表明，以标准水溶液校准时，只要样品研磨时间延长至5 h，即可获得悬浮进样的满意的回收率。③研究了分析掺钕钇铝石榴石(Nd:YAG)中钕掺杂量的可行性。研究表明，加入适量聚丙烯酸作分散剂并调节pH为6，可以得到稳定悬浮液；以通用标准加入法（GSAM）校准可以得到满意的结果。 我国的稀土资源占世界的80％以上，高纯稀土氧化物是高科技领域中的重要材料。碰撞/反应池技术是目前四极杆ICP-MS消除干扰的先进技术，可以选择性地减少某些基体干扰，使背景和检测限得到显著的改进。本实验选择氧化钕（有7个同位素）作为研究对象，采用碰撞/反应池技术重点解决四极杆ICP-MS方法对高纯Nd2O3中稀土杂质进行测定时，基体Nd对Tb、Dy和Ho严重的氧化物或氢氧化物干扰难题。研究结果如下：①在四极杆高分辨率模式下，可以消除Nd对Pr的相邻峰的拖尾干扰；②采用碰撞/反应池技术，设计了10% O2-10% Ar-80% He混合气体作为碰撞/反应气，将Tb、Dy和Ho分别转化为相应的氧化物离子进行测定，成功地消除了基体Nd对Ho的干扰；Nd对Tb和Dy造成干扰的表观浓度显著降低。本方法可直接测定纯度为6N的高纯Nd2O3中的Ho；对纯度为6N的高纯Nd2O3中的Tb和Dy进行扣除，可以分析纯度达5N的高纯Nd2O3中的Tb和Dy。与文献报道的其它消除基体Nd干扰的方法相比较，此方法能够对纯度更高的Nd2O3进行直接分析，且操作简便。此方法也可进一步拓宽，有望解决其它轻稀土氧化物对中重稀土检测的质谱干扰问题。 论文的7～9章的工作包括：浊点萃取-GFAAS测定环境样品中痕量镉、HG-AFS分析铅基合金中砷和植物样品中锗的研究。针对实际分析工作中的具体困难，以上工作分别解决了分析元素含量低、测定干扰严重及样品处理的问题，建立了实用性强、准确度高的分析方法，具有实际应用价值。