液相基质辅助激光解吸电离-傅里叶变换离子回旋共振质谱研究

选用液相基质制样,考察了激光强度、回旋池开门时间等因数对基质辅助激光解吸电离-傅里叶变换离子回旋共振质谱(MALDI—FT—ICR—MS)检测结果的影响,优化了实验条件。使用液相制样方法对5类实际样品进行了MALDI—FT-ICR—MS检测,结果表明：液相基质具有很好的通用性,质谱信号稳定、持久。利用FT-ICR—MS特有的超高分辨率与准确度,能够很准确地测定化合物组成。     

常压激光离子源辅助基质的研究进展及其在食品领域的应用

基于激光的电离质谱具有空间分辨率高、样品预处理简单、易于便携化和可实现成像分析等特点。基质辅助的激光离子源质谱可以避免高能量对分子结构的破坏,在生物大分子分析和检测方面获得了广泛应用。传统辅助基质在低分子量范围的干扰较强,极大地限制了常压基质辅助激光离子源的应用,为解决这一问题,一系列基于新型材料的辅助基质被设计和开发出来。这些新型材料可分为两大类:新型有机基质和无机材料。质量范围的扩展和目标化合物灵敏度的增强,显著扩展了常压基质辅助激光离子化技术在原位分析中的应用。该文针对新型辅助基质在常压激光离子源及其在食品安全领域的应用进行了综述,并展望了未来的研究趋势。     

聚酰胺基质亲水性亲和膜上染料配基辛巴蓝含量的测定

发展了以聚酰胺为基质的亲水性亲和膜上活性染料配基辛巴蓝含量的测定方法。将实验室制备的聚酰胺基质亲和膜在12．0mol／L盐酸中水解后,采用分光光度法对水解液直接进行检测,即可得到膜上染料配基含量。实验确定了适宜的分析条件,探讨了体系的吸收光谱和影响因素。对亲和膜体系分析得到了体系中辛巴蓝浓度和吸光度之间的线性关系,相关系数均在0．999以上,检出限为0．31～0．34mg／L;相对标准偏差为1．1％—3．4%。实验体系中的共存物质对于检测结果影响较小。用本方法对样品进行分析,回收率在99．8％—104．2%之间;与元素分析法等进行比较,表明本法能较准确地确定聚酰胺基质亲和膜上配基含量,且具有简便、适用和快速的特点。     

芳香环状聚膦酸酯齐聚物的基质辅助激光解吸电离飞行时间质谱分析

用基质辅助激光解吸电离飞行时间质谱方法对一系列芳香环状聚膦酸酯低聚物进行了结构分析。比较了不同基质及阳离子剂对芳香环状聚膦酸酯分析结果的影响。1,8,9-蒽三酚基质仅对含有羰基基团聚膦酸酯环状齐聚物分析有效,而视黄酸基质则对所有聚膦酸酯环状剂聚物有效,是这类新型芳香环状齐聚物的适宜基质。环状聚膦酸酯齐聚物的阳离子齐分析表明,氯化锂是这种环状齐聚物的适宜的阳离子添加剂。     

基质中加入少量盐类改善MALDI-TOF MS的谱图信噪比

自20世纪80年代发明基质辅助激光解吸电离(Matrix assisted laser desorption ionization,MALDI)质谱以来,该技术已在生物分子分析方面得到了广泛应用．作为一种离子化方法,MALDI具有灵敏度高,对样品要求低,能耐高浓度盐和缓冲剂等优点．测定过程中使用合适的基质不仅能提高测试灵敏度和分辨率,还能扩增测试样品的种类。     

几种常用激光解吸电离/质谱基质的基质簇峰行为研究

以常用于DNA分析的基质3-羟基吡啶甲酸(3-HPA),以及常用于高分子聚合物分析的基质2-(4-羟基苯基偶氮)苯甲酸(HABA)、反式-3-吲哚基丙烯酸(IAA)和1,8,9-三羟基蒽(Dithranol)为研究对象,考察了基质溶剂、浓度及激光强度对基质本身在激光解吸电离/质谱(LDI/MS)过程中产生基质簇峰的影响,对基质簇峰可能形成的过程进行了推测,并对各基质簇峰进行了归属,提出了基质簇离子峰m/z值遵循的计算公式。     

应用基质辅助激光解吸电离飞行时间质谱法测定牛甲状腺球蛋白的分子量

应用基质辅助激光解吸电离飞行时间质谱法测定了牛甲状腺球蛋白的纯度与相对分子量.选择芥子酸为适宜的基质,并对所得的结果进行了讨论.实验结果表明分析方法具有灵敏度高、重现性好、信息直观等特点,明显优于其他传统测定蛋白质的方法.     

基质辅助激光解析电离-飞行时间质谱分析寡核苷酸G-四链体

我们发展了一种利用基质辅助激光解析电离飞行时间质谱技术(MALDI-TOF MS)分析对金属离子具有较高亲和力的寡核苷酸G-四链体的方法.考察了不同基质:3-羟基吡啶甲酸(3-HPA)与柠檬酸氢二铵(DHC)混合基质、3,4-二胺基苯基苯甲酮(DABP)及DABP/DHC混合基质,应用于G-四链体分析的效果.实验结果表...     

稀土配合物杂化发光材料的组装及光物理性质研究进展

稀土配合物兼具无机物稳定性好以及有机物荧光量子效率高的优点,而且具有可设计性,制备简便,容易修饰,荧光性质优异（发射谱带窄、色纯度高、荧光寿命长、量子产率高以及发射光谱范围覆盖可见和近红外光区等）．但配合物的光、热、化学稳定性和机械加工性能相对较差,因而限制了其在很多领域中的实际应用．近年来的研究表明,将稀土配合物引入到各种基质材料中可以改善其稳定性及机械加工性能,并对其光物理性质产生调制作用．根据基质材料的不同,杂化材料可分为无机基质、无机／有机复合基质及有机基质杂化材料．本文综述了这些不同基质稀土配合物杂化发光材料的研究进展,探讨了主客体间相互作用对杂化材料光物理性质及稳定性的影响,为实现稀土配合物杂化发光材料在光学器件领域（LED照明、光纤维、光学放大器及激光等）及生命分析领域的应用提供了重要的理论依据．     

应用激光解吸电离飞行时间质谱法研究芳香聚硫醚醚砜环状低聚物

应用激光解吸电离飞行时间质谱法对芳香环状聚硫醚醚砜低聚物结构进行了分析,比较了四种不同基质对环状物结构分析结果的影响,发现1,8,9-蒽三酚为此类芳香环状低聚物的有效基质。探讨了金属阳离子对此类芳香环状低聚物的影响,认为三氟乙酸银是此种芳香环状低聚物的有效阳离子剂。     

High resolution detection of high mass proteins up to 80,000 Da via multifunctional CdS quantum dots in laser desorption/ionization mass spectrometry

CdS quantum dots (∼5 nm) are used as multifunctional nanoprobes as an effective matrix for large proteins, peptides and as affinity probes for the enrichment of tryptic digest proteins (lysozyme, myoglobin and cytochrome c) in laser desorption/ionization time-of-flight mass spectrometry (LDI-TOF MS). The use of CdS quantum dots (CdS QDs) as the matrix allows acquisition of high resolution LDI mass spectra for large proteins (5000-80,000 Da). The enhancement of mass resolution is especially notable for large proteins such as BSA, HSA and transferrin (34-49 times) when compared with those obtained by using SA as the matrix. This technique demonstrates the potentiality of LDI-TOF-MS as an appropriate analytical tool for the analysis of high-molecular-weight biomolecules with high mass resolution. In addition, CdS QDs are also used as matrices for background-free detection of small biomolecules (peptides) and as affinity probes for the enrichment of tryptic digest proteins in LDI-TOF-MS.     

Meso-四(对烷氧苯基)卟啉金属银配合物的激光解吸电离飞行时间质谱表征

通过激光解吸电离飞行时间质谱对meso-四(对烷氧苯基)卟啉金属银配合物进行了表征.样品溶解在氯仿中,以正离子方式记录谱图,结果发现除了产生目标化合物分子离子峰外,没有任何碎片峰.激光解吸电离飞行时间质谱是表征这种meso-四(对烷氧苯基)卟啉金属银配合物有效的方法.     

稠环齐聚物结构的激光解吸电离飞行时间质谱表征

应用激光解吸电离飞行时间质谱对几种不同结构的吡嗪稠环齐聚物进行了表征.样品溶解在二甲基亚砜中,以正离子方式记录谱图,结果发现除了产生目标化合物的质子化的分子离子峰外,还产生了少量的碎片分子离子峰.结果表明激光解吸电离飞行时间质谱能有效地、快速准确地给出这类化合物的分子离子峰,为吡嗪类稠环齐聚物的研究提供了有效的表征方法.     

Gold nanoparticles as assisted matrices for the detection of biomolecules in a high-salt solution through laser desorption/ionization mass spectrometry

Citrate-capped gold nanoparticles (AuNPs) serve as matrices for the determination of biomolecules in a high-salt solution through matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF-MS). In the case of using 2,5-dihydroxybenzoic acid (2,5-DHB) as a matrix, the signal intensities of neutral steroids were severely suppressed in a high-salt solution. A high concentration of NaCl caused the formation of the sodium adduct ions during the desorption/ionization process, resulting in a decrease of the signal intensities of the protonated ions. In comparison, by applying AuNP-assisted LDI-TOF-MS, the signal intensities of neutral steroids remained almost constant when the concentration of NaCl was increased to 500 mM. Because the use of citrate-capped AuNPs as matrices primarily offers alkali metal ion adducts, AuNP matrices have a higher tolerance to high NaCl concentrations relative to that of 2,5-DHB matrices. The relevant phenomena are also discovered in the case of analysis of neutral carbohydrate, monosialoganglioside, indolamine, and angiotensin I. The quantification of small molecules in a high-salt solution has been accomplished by AuNP-assisted LDI-TOF-MS coupled to a unique sample preparation, in which samples are deposited onto the sample plate before AuNPs. The present method has been further applied to the determination of urea, creatinine, uric acid, and glucose in a urine sample.     

Au@SiO2 core-shell nanoparticles for laser desorption/ionization time of flight mass spectrometry

In matrix-assisted laser desorption/ionization time of flight mass spectrometry (MALDI-TOF-MS), the analysis capability, especially for small molecules, is often compromised by the addition of organic matrices due to the existence of background signals. Herein we report a new detection method on the utility of core-shell nanoparticles (CSNPs) as energy transfer structure in LDI-TOF-MS. The LDI-TOF-MS based on gold-silica core-shell nanoparticles with ultrathin silica shell of 2-4 nm (Au@utSiO(2) CSNPs) was effectively applied to the analysis of many compounds, especially for small functional molecules and polymers, which was more promising than MALDI-TOF-MS.     

Analysis of quinapril by two solvent-saving methods: application of capillary column high-performance liquid chromatography with ultraviolet absorbance detection and LDI-TOF-MS

A capillary column high-performance liquid chromatography (CapLC) method and a laser desorption ionization-time of flight (LDI-TOF)-MS method are described for the determination of quinapril, an angiotensin-converting enzyme inhibitor. Effective separation was achieved by using a C18 capillary column at a flow rate of 10 microL/min. For CapLC, quinapril and 7-hydroxycoumarin (internal standard) were detected at 210 and 320 nm, respectively. Phenformin replaced 7-hydroxycoumarin as the internal standard for the LDI-TOF-MS method successfully developed to detect quinapril. The calibration curves showed good linearity in the range of 1-100 micro/mL in these two methods. For high throughput purposes, the LDI-TOF-MS method was simpler and faster than the CapLC method. Both green methods were suitably validated and successfully applied to determine quinapril in commercial tablets.     

Characterization of synthesized titanium oxide nanoclusters by MALDI-TOF mass spectrometry

Titania represents an important material that has wide applications. The bactericidal efficiency of TiO(2) has been shown to be dependent on the size of the nanoparticles, so it is important to be able to reliably estimate their dimensions. In this study, a stable TiO(2) cluster suspension is produced by the thermal solvent process, and ultrasmall clusters (<1 nm) with different sizes are obtained by size-selection treatment. MALDI-TOF-MS and LDI-TOF-MS are shown to be useful for characterization of these ultrasmall nanoparticles. Peak maxima are found to correlate with nanoparticle size, and the possibility of using these mass spectrometry-based approaches to estimate nanoparticle size is affirmed. The size distributions of TiO(2) nanoparticles obtained from MALDI- and LDI-TOF-MS are in good agreement with parallel TEM observations. Finally, PSD analysis of inorganic nanomaterials is performed and valuable information about the structure of analytes has been obtained.     

Characterization of the water-insoluble fraction from fast pyrolysis liquids (pyrolytic lignin): Part III. Molar mass characteristics by SEC,MALDI-TOF-MS,LDI-TOF-MS,and Py-FIMS

Matrix assisted laser desorption ionisation-time of flight-mass spectrometry (MALDI-TOF-MS), laser desorption ionisation-time of flight-mass spectrometry (LDI-TOF-MS) and temperature resolved analytical pyrolysis field ionisation mass spectrometry (Py-FIMS) have been applied for the first time on two pyrolytic lignins (PL's), precipitated from different aged bio oil, and four PL-fractions for molar mass characterization. The results were compared with data from size exclusion chromatography (SEC). SEC was the only method that allowed a mathematical calculation of molar mass characteristics such as average molecular weight (Mw), dispersity (D), and the molar mass at the peak maximum of the elugram (Mp). The SEC Mp values of PL-fractions differ from visually interpolated MALDI-TOF-MS measurements by 20%. MALDI-TOF-MS spectra showed detailed structures of the molar mass distribution (MMD) of PL and PL-fractions. Especially, the spectrum of one PL showed various local maxima with intervals of 170–200 Da. The size of these intervals could represent the average absolute molar mass of PL-monomers. MALDI-TOF-MS was limited by the influence of superposing matrix signals in the spectrum at low molar masses. LDI-TOF-MS showed clearer spectra than MALDI-TOF-MS in mass ranges below 400 Da. No signals were obtained for fractions with higher masses or whole PL. Intervals between main signals were mostly 14–16 Da. In spectra of different PL-fractions, corresponding main signals can vary between 2 and 4 Da. These mass differences indicate variations in the aliphatic region of the PL molecules. Py-FIMS spectra contained masses of thermally ejected, but unfragmented monomers and dimers. It was the only method, which allowed partial identification of monomeric and dimeric structures of all samples. The detected monomers correspond to known lignin derived compounds in bio oil, the detected dimers have some similarities to phenylcoumaran structures. PL from aged bio oil showed an increased content of higher oligomers and a higher average molecular weight.     

Application of platinum nanoparticles as affinity probe and matrix for direct analysis of small biomolecules and microwave digested proteins using matrix-assisted laser desorption/ionization mass spectrometry

We report the use of platinum nanoparticles (PtNPs) for analysis of amino acids, peptides, proteins and microwave digested proteins (lysozyme and bovine serum albumin) without any tedious washing and separation procedures prior to matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF-MS). In the present study, PtNPs play three functions, such as matrix, affinity probe and acceleration of protein digestion by absorbing the microwave irradiation. Good signal intensity of the target molecules from the sample was obtained when laser energy, NPs concentration and incubation time were set to 35 μJ, 25 nM and 30 min, respectively. In addition, higher numbers of peptide sequence were obtained for microwave digested lysozyme protein using PtNPs as compared to previously reported methods for analysis of digested protein in MALDI-MS. Thus, the present method is a simple, rapid and one step preparation method for the analysis of amino acids, peptides, proteins and digested proteins in MALDI-TOF-MS without the need for any tedious purifications and washing procedures.     

Separation and measurement of flame-formed high molecular weight polycyclic aromatic hydrocarbons by size-exclusion chromatography and laser desorption/ionization time-of-flight mass spectrometry

The partial contribution of polycyclic aromatic hydrocarbons (PAH), capable of being detected by gas chromatography (GC-PAH), both to the total mass of the extractable organic fraction of flame-formed carbon particulates and to its UV-visible absorption and fluorescence spectra, has been determined by previous work. This contribution indicates the presence of PAH of molecular weight (MW) greater than 400 Da not accessible to conventional analysis. The detection of species in this higher MW range is important for both their potential toxicology and their possible role in soot formation. In the present work extracts of soots have been analyzed by linear mode laser desorption/ionization time-of-flight mass spectrometry (LDI-TOF-MS) to extend the MW range that can be analyzed beyond the GC-PAH. The results have been compared with both analysis by reflector mode LDI-TOF-MS and the MW evaluation obtained by SEC analysis, as the shortcomings and advantages of both techniques appear to be complementary. Matching the results from the two techniques could give interesting insights in the molecular mass range between GC-PAH and the first soot particles (of mass > 2000 Da). Mass spectra in this molecular mass range have been obtained with a main ion sequence spacing of 24 Th and a minor ion sequence also with a spacing of 24 Th but off-set by 12 Th with respect to the main sequence. The two ion progressions have been interpreted by attributing the predominant peaks mainly to PAH with even-carbon numbers and the smaller ones to cyclopenta-fused ring PAH. These distributions indicate the occurrence of two competitive mechanisms in the growth of PAH and soot nucleation, i.e. the addition of acetylene (HACA mechanism) and the incorporation of pentagons by large polycyclic aromatic molecules into their aromatic bonding network.