Developing of a fast cryodetector read-out for mass spectrometry

We report on the development of a SQUID read-out for a fast cryogenic detector with superconducting phase transition thermometer. To avoid the usual transformer matching and modulation–demodulation technique we are using a second SQUID to amplify the signal of a first stage input SQUID. A bandwidth of 2 MHz and a slew rate of 2×10⁵ Φ₀ s⁻¹ were achieved. The system is developed for the detection of large protein molecules in a time of flight mass spectrometer.     

激发-发射荧光矩阵光谱结合多维辩别分析用于葡萄干分类研究

葡萄干因其种类繁杂,产地来源多,制作工艺多样,导致品质各异。因此需要建立能够科学、准确的鉴别葡萄干种类、产地、品质的分析方法,以确保葡萄干产品质量、保护消费者利益、规范葡萄干商品市场。该实验基于葡萄干中富含多种荧光物质,以甲醇为萃取剂,应用微波提取法,结合三维荧光光谱技术,在激发波长300~700 nm,发射波长360~720 nm范围,获取三维荧光矩阵数据,应用多维主成分分析(M-PCA),多维偏最小二乘辨别分析(N-PLS-DA)和平行因子算法-偏最小二乘辨别分析(PARAFAC-PLS-DA)等多维模式识别方法,对三种主色为绿色、两种主色为红色的五个不同种类的葡萄干进了分类研究。M-PCA研究结果显示不同种类的葡萄干存在聚类趋势,而N-PLS-DA和PARAFAC-PLS-DA则给出了比较满意的分类结果。相对而言,由于PARAFAC-PLS-DA是基于PARAFAC分解得到浓度得分结果基础之上进行的分类,去除了不相干的冗余信息,因此取得了100%准确的分类结果。两种算法的品质因子比较结果也说明基于荧光光谱法和多维模式识别技术相结合的分析技术可以很好的用于葡萄干种类的识别研究,并有望用于葡萄干质量等级识别及产地追溯。     

High-volume cellular screening for anticancer agents with combinatorial chemical libraries: A new methodology

Summary A single-step cancer cell cytotoxic assay system for anticancer drug discovery has been developed which facilitates rapid screening of large combinatorial chemical libraries synthesized using the one-bead-one-compound (OBOC) methodology. Each OBOC library bead incorporates two orthogonally cleavable linkers that release the bead-bound compound at a different pH. The assay utilizes high concentrations of tumor cells mixed directly with OBOC beads and plated in soft agarose containing tissue culture medium. One of the orthogonal linkers is cleaved at neutral pH in tissue culture releasing an aliquot of compound to diffuse at a relatively high local concentration into the soft agarose immediately surrounding the bead. Active compounds are identified visually from a clear ring of tumor cell lysis which forms within 48 h around just the rare bead releasing a cytotoxic compound. The bead releasing a cytotoxin is then plucked from the agar and the remaining compound still linked to the bead can be released for structural analysis, followed by compound resynthesis and confirmatory testing. This assay system has been successfully applied to identification of lead cytotoxic compounds from model peptidic and non-peptidic combinatorial chemical libraries. Use of this methodology may facilitate anticancer drug discovery.     

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.     

Microfluidic chip-inductively coupled plasma mass spectrometry for trace elements and their species analysis in cells

Abstract

Accurate identification and quantification of trace elements and their species in cells is an important prerequisite for the exploration of their physiological function and related mechanisms of process involving trace elements/species in human body. Inductively coupled plasma mass spectrometry (ICP-MS) is a powerful analytical instrument for trace elements detection, while it still suffers from insufficient limits of detection, interference from complex cell matrix, and incompatible sample consumption in cells analysis. Microfluidic chips which possess advantages of low sample/reagent consumption, rapid analysis speed and high spatial resolution provide perfect miniaturized and integrated platforms for cell analysis. In this article, microfluidic chip-ICP-MS techniques for trace elements and their species analysis in cells were reviewed. Both chip-based pretreatment techniques (e.g., magnetic solid phase microextraction (MSPME), monolithic capillary microextraction (MCME), liquid phase microextraction (LPME)) including chip-based array microextraction techniques for trace elements and their species analysis and droplet chip for single cell analysis were introduced. The newly developed methods of microfluidic chips in combination with ICP-MS for trace elements and their species analysis in small numbers of cells and even single cell were critically discussed, including chip-based MSPME/MCME/LPME-(electrothermal vaporization-ICP-)MS, on-line chip-based array MSPME/MCME-ICP-MS, on-line chip-based array MSPME-high performance liquid chromatography-ICP-MS and online droplet chip-time-resolved ICP-MS. These methodologies were demonstrated with high sensitivity, high throughput, good matrix resistance and low sample/reagent consumption, contributing to the quantification of trace elements/species in cells and even single cells. Relevant 20 references are included herein, and the development trend of microfluidic chip-ICP-MS techniques for cells analysis is prospected.     

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.     

Ultra trace determination of fluorobenzoic acids in reservoir and ground water using isotope dilution gas chromatography mass spectrometry

The accurate ultra-trace analysis of six fluorobenzoic acids (FBAs) via isotope dilution gas chromatography mass spectrometry through their deuterated analogues is described. North Sea reservoir and ground water samples were spiked with six deuterated FBAs (dFBAs), enriched using solid-phase extraction (SPE) and analysed using GC/MS after derivatisation with BF ₃· MeOH. All FBAs were enriched and determined simultaneously. SPE allowed a 250-fold enrichment of the acids if 100 mL of sample volume was used. The method enables the determination of FBAs down to the range of 8–37 ng L ^?1 with recoveries between 66 % and 85 %. It uses low amounts of chemicals and is adaptable to larger and smaller sample volumes.     

Tentative characterization of phenolic compounds in three species of the genus Embelia by liquid chromatography coupled with mass spectrometry analysis

Abstract

This article illustrates the chemical characterization of phenolic compounds, of the selected species of the genus Embelia viz., Embelia ribes, Embelia tsjeriam-cottam, and Embelia basaal using liquid chromatography coupled with mass spectrometry analysis with electrospray ionization (ESI) in negative mode. The analysis of samples allowed first-time identification of different phenolic compounds, which consists of various types of flavonoids, flavonoid glycosides, organic acids, and their derivatives, benzenoids, coumarins, and stilbens in this genus. Seventy-three different phenolic compounds were identified based on the fragment ions, and over thirty unknown compounds with unique fragmentation patterns were further noted. The results of the study offer that the selected species of the genus Embelia, which is being used in centuries-old traditional medical systems, is a promising source of medicinally valuable compounds like luteolin, sinesetin, rutin, naringenin, astragalin, narcissin, vanillic acid, resveratrol, and so on.     

Systematic evaluation of acetone and acetonitrile for use in hydrophilic interaction liquid chromatography coupled with electrospray ionization mass spectrometry of basic small molecules

Sub-2-μm particle size hydrophilic interaction liquid chromatography [HILIC] combined with mass spectrometry has been increasing in popularity as a complementary technique to reversed-phase LC for the analysis of polar analytes. The organic-rich mobile phase associated with HILIC techniques provides increases in compound ionization, due to increased desolvation efficiency during electrospray ionisation mass spectrometric (ESI-MS) analysis. Although recent publications illustrated selectivity and response comparisons between reversed-phase LC/MS and HILIC LC/MS, there are limited discussions evaluating the optimisation of the mass spectrometry parameters regarding analytes and alternative mobile phases. The use of acetone as an alternative organic modifier in HILIC has been investigated with respect to signal-to-noise in ESI-MS for a variety of polar analytes. Analyte reponses were measured based on a variety of cone and capillary voltages at low and high pH in both acetone and acetonitrile. In order to visualise compound behaviour in the ESI source, surface plots were constructed to assist in interpreting the observed results. The use of acetone in ESI is complicated at low m/z due to the formation of condensation products. Favourable responses were observed for certain analytes and we envisage offering an insight into the use of acetone as an alternative to acetonitrile under certain analytical conditions for particular compound classifications for small molecule analysis. We also highlight the importance of optimising source voltages in order to obtain the maximum signal stability and sensitivity, which are invariably, highly solvent composition dependent parameters.     

凝胶电泳与激光剥蚀-电感耦合等离子体质谱联用测定蛋白质中微量元素的应用进展

介绍了凝胶电泳(GE)和激光剥蚀-电感耦合等离子体质谱(LA-ICP-MS)联用测定蛋白质中微量元素的方法,对蛋白质分离、凝胶处理,包括染色及干燥,和检测过程中的定量校正等技术问题做了详述,并综述了LA-ICP-MS在硒蛋白、磷酸化蛋白及金属蛋白分析中的应用,指出了这种方法在蛋白质中微量元素检测中存在的问题和发展方向。     

Measuring technique for thermal ionisation mass spectrometry of human tracer kinetic study with stable cerium isotopes

Thermal ionisation mass spectrometry (TIMS) method has been developed for the simultaneous detection of different cerium isotopes in biological samples (i.e., blood and urine) at very low concentrations. The work has been done in the frame of a biokinetic study, where different stable cerium isotopes have been administered orally and intravenously as tracers to the human body.

In order to develop an appropriate detection method for the tracers in the biological samples, an optimum sample preparation technique has been set and adapted to the specific requirements of the analysis technique used, i.e., TIMS. For sample evaporation and ionisation, the double tantalum filament technique showed the best results. The ions produced were simultaneously collected on a secondary electron multiplier so that the isotopic ratios of the cerium isotopes in the biological samples could be measured.

The technique has been optimised for the determination of cerium down to 1 ng loaded on the evaporation filament corresponding to cerium concentrations of down to 1 ng ml^?1 in the blood or urine samples. It has been shown that the technique is reliable in application and enables studies on cerium metabolism and biokinetics in humans without employing radioactive tracers.