The Application of Chemical Modification in Electrothermal Vaporization-inductively Coupled Plasma Atomic Emission Spectrometry

Electrothermal vaporization (ETV) as a means of sample introduction for inductively coupled plasma atomic emission spectrometry (ICP-AES) has been paid great attention by many researchers since its first report in 1974. It can offer many advantages over conventional pneumatic nebulization method of sample introduction. These include:high transport efficiency, small amount sample required, low absolute detection limit and the ability to analyse both liquid and solid samples. Recent developments of this technique have been reviewed by Carey and Caruso, Hu et al and Moens et al, the authors summarized most of its crucial aspects.     

一种新型超临界流体萃取-高效液相色谱在线联用系统的构建

天然产物研究一直是植物学、化学和药学的重要研究领域．通过从天然产物中寻找生物活性成分和先导物是创制新药的有效途径之一．有效成分的提取是天然产物研究中最基本和最关键的环节．超临界流体萃取（Supercritical fluid extraction,简称SFE）是近年来发展较快的一种新型样品提取技术．超临界CO2作为最常用的萃取剂已被用于天然药物中非极性和弱极性有效成分的提取,尤其是挥发性和热敏性的物质．此外,通过加入适当的添加剂还可有效地萃取极性化合物,和传统的化学方法相比,     

Methanol chemical ionization quadrupole ion trap mass spectrometry of O-ethyl S-[2-(diisopropylamino)ethyl] methylphosphonothiolate (VX) and its degradation products

Mass spectrometric analysis of O-ethyl S-[2-(diisopropylamino)ethyl] methylphosphonothiolate (VX) degradation products by electron ionization produces extensive fragmentation with little or no molecular ion information making product identification difficult. Milder chemical ionization (CI) is commonly used to provide molecular mass and structure confirmation. In this study, methanol was used as a CI reagent in combination with an ion trap detector for detection and identification of over 30 compounds present in a thermally degraded sample of VX. The use of methanol provides superior results for this class of compounds with less fragmentation than commonly observed with gas reagents and offers logistical advantages for on-site analysis by being easier to transport and safer to use than gas cylinders.     

Coupled pervaporation/mass spectrometry for investigating membrane mass transport phenomena

The integration of organophilic pervaporation into processes of varying feed concentration, such as bioconversions, chemical reactions, or analytical sample preparation, requires not only the understanding of mass transport phenomena across the membrane under steady-state conditions, but also the insight into the transient response of the pervaporation membrane to changes as they occur in practice. For this purpose, a laboratory-scale pervaporation unit was coupled to a mass spectrometer for on-line permeate analysis, maintaining the overall pervaporation operating conditions controllable independently, and without introducing any inert gases for sample transfer.The experimental set-up was employed for investigating the transport of aroma compounds across a POMS–PEI composite membrane, focusing in particular on the so-called “membrane conditioning”; the possible synergetic effect of ethanol on the flux of one model aroma compound, ethyl hexanoate; the application of the system proposed to the rapid screening of the effect of the hydrodynamic upstream conditions on the degree of concentration polarisation.The method proposed proved to be robust and flexible, not only allowing insights into transient mass transport phenomena otherwise not attainable, but also reducing experimental workload significantly when characterising the effect of varying operating conditions on the pervaporation performance.     

Analysis of Silver Nanoparticles Using Single-Particle Inductively Coupled Plasma – Mass Spectrometry (ICP-MS): Parameters Affecting the Quality of Results

Single–particle analysis using inductively coupled plasma mass spectrometry offers a new tool for the characterisation of inorganic nanoparticles. Its development is connected with new generations of ultrafast spectrometers. This work is concerned with thorough investigation of parameters affecting the quality of the analysis of Ag nanoparticles, i.e., nanoparticle stability, transport efficiency and sensitivity of determination. The short-term stability of Ag nanoparticles in demineralised water can be prolonged to at least 7?h by the addition of 0.05% gelatin. The sensitivity was affected by plasma power and the nebuliser Ar flow. The transport efficiency decreased with increasing sample uptake, so a compromise between the efficiency and the total number of particles entering the spectrometer should be selected. The estimate of transport efficiency is distorted when more concentrated dispersions of nanoparticles are analysed because of the overlapping of signals of multiple nanoparticles. This effect was observed for dispersions of concentration greater than 1?×?10⁶?mL^?1 where an apparent decrease in transport efficiency from an initial value 7–8% to 1% was observed. The following parameters were found by method validation: concentration limit of detection of 97?mL^?1, nanoparticle diameter limit of detection 15?nm, linearity from 20 to at least 100?nm and repeatability of 1.3%. After validation, the method was applied to determine Ag nanoparticles in river water from the Vltava in Prague. Nanoparticles with diameters of 32–114?nm were found, and their number concentration increased from 340?mL^?1 to 1670?mL^?1 as the stream of water passed through urban agglomeration.     

Topological metastability and oxide ionic conduction in La(2)-(x)Eu(x)Mo(2)O(9)

The effect of partial substitution, up to x = 0.4, of La by trivalent Eu on the phase stability, thermal expansion, and transport properties of La2Mo2O9 are investigated using temperature-controlled X-ray powder diffraction, differential thermal analysis, and complex impedance spectroscopy. At low europium content (x < or = 0.1), the alpha-beta phase transition is observed at a temperature dependent on the sample shaping (powder, pellet, etc.). At high europium content (x > or = 0.25), the samples remain cubic (beta phase), regardless of the shaping. In the intermediate range of europium content (x = 0.15, 0.2), the phase stability is highly sensitive to the thermal history and the sample shaping, with a double-reversed beta-alpha-beta transition suppressed by the shaping/sintering process. The influence of the amount of europium on the transport mechanisms and parameters is studied in both low- (Arrhenius) and high-temperature (Vogel-Tammann-Fulcher = VTF) regimes. If the effect of substitution is rather mild and monotonous within each transport regime and crystallographic phase, an abrupt change in the Arrhenius parameters between the alpha- and beta-type phases is observed.     

电热蒸发-电感耦合等离子体质谱(ETV-ICP-MS)技术中气溶胶传输效率研究进展

蒸发效率和传输效率是影响电热蒸发-电感耦合等离子体质谱(ETV-ICP-MS)技术分析性能的关键因素。综述有关气溶胶传输效率的研究进展,在归纳常用的传输系统评价方法的基础上,重点对影响气溶胶传输效率的电热蒸发装置的改进、蒸发过程的探讨、基体改进剂的选择等研究现状进行评述。有关ETV蒸发过程中基体干扰的作用机制仍有待进一步系统研究,这对于校正策略的优化、新型校正技术的创新与集成具有重要的理论指导意义,可推动ETV-ICP-MS在地质、环境、生物等学科的更广泛应用。     

The isotope exchange depth profiling (IEDP) technique using SIMS and LEIS

The determination of the mass transport kinetics of oxide materials for use in electrochemical systems such as fuel cells, sensors and oxygen separators is a significant challenge. Several techniques have been proposed to derive these data experimentally with only the oxygen isotope exchange depth profile technique coupled with secondary ion mass spectrometry (SIMS) providing a direct measure of these kinetic parameters. Whilst this allows kinetic information to be obtained, there is a lack of knowledge of the surface chemistry of these complex processes. The advent of low-energy ion scattering (LEIS) now offers the opportunity of correlating exchange kinetics with chemical processes at materials atomic surfaces, giving unprecedented levels of information on electrochemical systems with isotopic discrimination. Here, the challenges of these techniques, including sample preparation, are discussed and the advantages of the combined approach of SIMS and LEIS illustrated with reference to key literature data.     

电感耦合等离子体质谱法(ICP-MS)测定钼矿石中的铼

以硝酸+氢氟酸+高氯酸消解钼矿石中的铼,不经分离富集,用电感耦合等离子体质谱法直接测定钼矿石样品中的铼。方法检出限可达0.012μg/g,通过对国家岩石一级标准样品的测试,测定结果一致;对GBW07285标准样品11次测定的相对标准偏差(RSD)为1.1%。     

Dried Blood Spot Proteomics: Surface Extraction of Endogenous Proteins Coupled with Automated Sample Preparation and Mass Spectrometry Analysis

Dried blood spots offer many advantages as a sample format including ease and safety of transport and handling. To date, the majority of mass spectrometry analyses of dried blood spots have focused on small molecules or hemoglobin. However, dried blood spots are a potentially rich source of protein biomarkers, an area that has been overlooked. To address this issue, we have applied an untargeted bottom-up proteomics approach to the analysis of dried blood spots. We present an automated and integrated method for extraction of endogenous proteins from the surface of dried blood spots and sample preparation via trypsin digestion by use of the Advion Biosciences Triversa Nanomate robotic platform. Liquid chromatography tandem mass spectrometry of the resulting digests enabled identification of 120 proteins from a single dried blood spot. The proteins identified cross a concentration range of four orders of magnitude. The method is evaluated and the results discussed in terms of the proteins identified and their potential use as biomarkers in screening programs.

Temperature modulated differential scanning calorimetry (TMDSC) in the region of phase transitions. Part 2: some specific results from polymers

By means of four different examples (pressure crystallised, gel crystallised, nascent and highly stretched polyethylenes (PEs)) it is shown that temperature modulated DSC offers advantages against common DSC. It is possible to see dynamic processes inside the sample during melting. This way we found (i) that during melting of high pressure crystallised PE the so-called ₂-process (known from DMA) takes place, (ii) the lamellae doubling in gel crystallised UHMWPE can be seen in TMDSC signals, though no balance heat flow rate is visible in the common DSC, (iii) the same is true for the recrystallisation in nascent and highly stretched PE many degrees before the melting peak appears. To separate these results from the measured curves the knowledge of the heat transport into and within the sample is needed. A simple low pass filter model has proved its worth for this purpose.     

Fast CEC-MS using poly(dimethylsiloxane) microinjector, short packed column, and low-sheath-flow interface

A fast CEC-MS approach based on a microinjector and a short CEC column was developed. Poly(dimethylsiloxane) was used as the substrate for microinjector fabrication. A short capillary column (～5 cm) packed with 5 μm octadecyl silica particles was inserted into the microinjector. The microinjector CEC device was interfaced to ESI-MS using a low-flow sheath liquid interface. The device delivers the advantages of sample introduction, pre-concentration, elution, and fast analysis as in chip-CEC yet avoids the difficulty of packing stationary material into the chip. The online pre-concentration and CEC-MS analysis capabilities of this device were demonstrated by analysis of a six-triazine mixture. A signal enhancement of 20-99-fold was achieved with a sample loading time of 180 s.     

电感耦合等离子体质谱中的基质效应

电感耦合等离子体质谱(Inductively coupled plasma mass spectrometry,ICP-MS)是痕量元素分析中最常用的检测技术,尽管ICP-MS在元素分析中表现出诸多优势,但其在检测复杂基质样品时,仍会遇到许多问题。复杂基质所引起的基质效应通常会导致分析物信号的抑制或者增强。基质效应影响程度取决于基质成分的绝对浓度,还与基质的种类、分析物的物理和化学性质以及仪器条件有关。该文介绍了ICP-MS中几种常见的基质效应及其影响因素,包括元素基质、含碳基质、酸基质和仪器条件等,探究了基质效应产生的可能原因,对国内外去除基质效应的方法,如样品前处理方法、样品引入系统、优化仪器参数和校准法等进行了系统的归纳和总结,并对基质效应的研究进行了展望。     

超临界流体萃取与其它分析技术的联用

用超临界流体萑取进行分析样品处理，有快速，高效，低消耗，污染少等优点。本文对ＳＦＥ的原理，特点，与其它技术的联用及其在分析化学诸领域的应用作了综述，其中重点介绍了ＳＦＥ与色谱技术的在线联用，内容包括接口等。     

Enhanced electronic correlation and thermoelectric response by Cu-doping in Ca(3)Co(4)O(9) single crystals

The structure, anisotropic magnetic, electrical and thermal transport properties for single crystals of Ca(3)Co(4-x)Cu(x)O(9) (x = 0, 0.2, 0.4, 0.6 and 0.8) have been investigated systematically. The Cu-doping with x = 0.2 at Co-site is sufficient to drive the low-temperature spin-glass state in the Ca(3)Co(4)O(9) system. The value of resistivity along ab-plane decreases monotonously with increasing x in the whole temperature range studied, and around room temperature, the in-plane resistivity of Ca(3)Co(3.2)Cu(0.8)O(9) is about 71% smaller than that of the undoped sample. The temperature region where the Fermi-liquid transport mechanism dominates becomes remarkably narrowed due to the Cu-doping while the electronic correlation in the system is enhanced. With further addition of Cu in the Ca(3)Co(4)O(9) system, the in-plane thermopower (S(ab)) increases slowly and the room-temperature S(ab) for Ca(3)Co(3.2)Cu(0.8)O(9) is about 17% larger than that of the undoped sample. As a result, the power factor along the ab-plane is enhanced by about 3.8 times compared to the undoped sample. The results are suggested to originate from the variations of carrier concentration and electronic correlation in this system via the different Cu-doping states: Cu(3+)/Cu(2+) (Cu(3+) major) into the CoO(2) layer for x ≤ 0.4, while Cu(2+)/Cu(3+) (Cu(2+) major) into the Ca(2)CoO(3) layers for x > 0.4.     

(1-x)La_(0.67)Ca_(0.33)MnO_3/xCuO复合体系与La_(0.67)Ca_(0.33)Mn_(1-x)Cu_xO_3电输运行为比较

用不同实验方法制备了名义组分为(1-x)La_(0.67)Ca_(0.33)MnO_3/xCuO(LCMO/CuO)和La_(0.67)Ca_(0.33)Mn_(1-x)Cu_xO_3(LCMCO)两组样品,在宽的温度范围内研究了样品的电输运行为随Cu含量x的变化关系,发现这两组样品表现出不同的行为.对于LCMCO,随x的增加,金属-绝缘体转变温度T_p迅速降低,当x=5.5%,样品表现出绝缘体导电行为;而LCMO/CuO复合样品,当x≤6%时,随x增加,Tp逐渐下降,x≥6%时,T_p不再继续降低,所有样品几乎表现出相同的电输运行为.另外,这两组样品均表现出较好的低场磁电阻效应(LFMR),在0.3 T下样品的最大磁电阻分别达到了～76%和88%.基于样品结构以及制备过程的分析,我们认为LFMR效应的增强主要是因为颗粒边界上形成的Cu相关自旋无序层引起的.     

Sensitive detector of exothermic processes (Sedex)

Sedex is a new apparatus to detect the initial temperature of exothermic processes in substances and reaction mixtures under industrial operating conditions. It is based on a slow heating of samples in a special oven, the detection of any difference between the oven and sample temperatures and the evaluation of this difference. The features and advantages of this method are indicated. The properties of this instrument make it especially useful for industrial applications or anywhere where large numbers of samples must be checked for exothermic processes. Additionally, Sedex provides information about the endothermic changes which may occur in the sample.     

Electrogenerated chemiluminescence triggered by electroseparation of Ru(bpy)3(2+) across a supported liquid membrane

We demonstrate here for the first time the detection of electrogenerated chemiluminescence (ECL) upon selective, electrochemically triggered tris(2,2'-bipyridyl)ruthenium(II) (Ru(bpy)(3)(2+)) transport across a supported liquid membrane doped with a lipophilic cation-exchanger. This approach allows one to separate the location of ECL generation from the sample compartment, thereby avoiding the contamination of the sample with compounds necessary for ECL.     

一体化碰撞反应 (iCRC)-电感耦合等离子体质谱法测定地质样品中痕量稀土元素

钡以及轻稀土元素氧化物对中、重稀土元素的干扰一直是质谱测试中存在的问题。建立了石墨粉垫底碳酸钠-硼酸混合熔剂熔融前处理样品,以_¹⁰³Rh为内标校正,一体化碰撞反应-电感耦合等离子体质谱仪法测定地质样品中稀土元素含量的方法。探讨了碳酸钠-硼酸混合熔剂熔融前处理样品注意事项、碰撞模式下碰撞气流量和离子透镜的参数的优化、干扰校正试验等问题,采用国家标准物质GBW07403、GBW07405、GBW07427、GBW07429验证,实验结果表明,各元素线性关系良好,相关系数均大于0.999,方法检出限在0.01～0.03mg/kg之间,相对误差为0.13%～7.1%,相对标准偏差为0.79%～6.59%,测试结果与标准值相吻合。对实际样品分析,得到平滑的球粒陨石归一化的稀土元素配分曲线,证明测定结果是合理可信的。该方法熔剂用量少,过程空白低,对器皿的侵蚀小,直接加热浸取,简化了操作过程,适用于大批量地质样品中稀土元素的测定。     

Applications of capillary electrophoresis in the fields of environmental,pharmaceutical, clinical,and food analysis (2019–2021)

So far, the potential of capillary electrophoresis in the application fields has been increasingly excavated due to the advantages of simple operation, short analysis time, high-resolution, less sample consumption, and low cost. This review examines the implementations and advancements of capillary electrophoresis in different application fields (environmental, pharmaceutical, clinical, and food analysis) covering the literature from 2019 to 2021. In addition, ultrasmall sample injection volume (nanoliter range) and short optical path lead to relatively low concentration sensitivity of the most frequently used ultraviolet-absorption spectrophotometric detection, so the pretreatment technology being developed has been gradually utilized to overcome this problem. Despite the review being focused on the development of capillary electrophoresis in the fields of environmental, pharmaceutical, clinical, and food analysis, the new sample pretreatment techniques of microextraction and enrichment fit excellently to capillary electrophoresis in recent three years are also described briefly.