Recent advances and trends in capillary electrophoresis of inorganic ions

Capillary electrophoresis (CE) continues its invasion into the domain of inorganic analysis. This review summarizes the progress and significant developments of CE of inorganic ions over the first two years of the new century. As manifested by the substantial number of published articles, this field is still witnessing a growing activity of many separation scientists. To provide an in-depth treatment of fundamental and methodological aspects of inorganic ion analysis by CE, an extensive fraction of the relevant literature is covered whereas only most innovative application reports are briefly considered. Most of the recent advancements have focused on CE system modernization designed to improve a limited detection sensitivity, which still remains a major obstacle to overcome in order to ensure the method's wider practical acceptance. Attention is also given to how and in which directions the future research could be performed to implement CE in routine inorganic analysis.     

Analysis of inorganic and small organic ions by CE with amperometric detection

Capillary electrophoresis has become a widely useful analytical technology. Amperometric detection is extensively employed in capillary electrophoresis for its many inherent virtues, such as rapid response, remarkable sensitivity, and low cost of both detectors and instrumentations. Analysis of inorganic and small organic ions by capillary electrophoresis is an important research field. This review focuses on the recent developments of capillary electrophoresis coupled with amperometric detection for analysis of inorganic and small organic ions. Advancements in electrophoresis separation modes, amperometric detection modes, working electrodes, and applications of inorganic ions, amino acids, phenols, and amines are discussed.     

Recent advances in amino acid analysis by CE

This paper describes a number of articles that have been published on amino acid (AA) analysis using CE during the period from June 2005 to May 2007. This review article follows the format of the previous articles of Smith (Electrophoresis 1999, 20, 3078-3083), Prata et al.. (Electrophoresis 2001, 22, 4129-4138), and Poinsot et al.. (Electrophoresis 2003, 24, 4047-4062 and Electrophoresis 2006, 27, 176-194). Several new developments in AA analysis with CE are reported describing the use of laser-emitting diodes for LIF, MS, and chips. In addition, we describe articles concerning clinical studies and neuroclinical applications.     

Application of capillary electrophoresis to the analysis of inorganic ions in environmental samples

A comprehensive review is presented of the state-of-the-art of capillary electrophoresis for application to the analysis of inorganic species, mainly ions, in environmental samples. This brief review covers the developments principally in sensitivity and matrix interference for the determination of inorganic ions in the following samples: drinking, mineral, surface, and ground waters, rainwater, snow, seawater, brine and waste waters, aerosol, and others. References published mainly from 1995 to 1997 were summarized in this review.     

Recent advances in the analysis of antibiotics by CE and CEC

This article reviews the most recent developments concerning the determination of antibiotics by CE and CEC. The most employed CE separation modes were CZE and MEKC although microemulsion electrokinetic capillary chromatoghraphy was also employed. For the first time, CE was coupled to MS that was applied as a specific and confirmatory detection technique for the analysis of antibiotics. The analytical characteristics of the developed methodologies as well as the different applications reported in the literature on this subject from June 2005 until May 2007 are included in this article. To give the most relevant information on this topic, the experimental conditions employed to achieve the analysis of antibiotics by CE and CEC are provided together with the main applications performed in the pharmaceutical, agrochemical, biological, food, and environmental fields, emphacizing sample preparation requirements needed in each case.     

Recent progress in mass spectrometry for inorganic analysis

Mass spectrometry for inorganic analysis was originally developed with an r.f. spark ion source, a double focussing Mattauch-Herzog mass spectrograph and photographic plate detection. Current equipment is roughly equivalent to that which became available more than 25 years ago, but considerable technological and methodological progress has been achieved recently. Ion bombardment developed into an interesting alternative ionisation method for solid samples. Secondary ion mass spectrometry (SIMS) is widely used for surface inorganic and organic analysis, and localised microanalysis. Other alternative excitation modes have been proposed more recently : the inductively coupled plasma, the hollow cathode discharge and the pulsed laser. The inductively coupled plasma source appears to be promising for the sensitive mass spectrometric analysis of solutions. The laser source is emerging as a viable alternative for the spark source in existing spectrometers because of its more reproducible operating characteristics and the localised nature of the laser-solid interaction. The pulsed laser has led to the development and commercialisation of sensitive microanalysers with a lateral resolution of 1–3 μm. These instruments make use of time-of-flight mass analysers.Advances in the measurement techniques and in the instrumentation are described and a few representative examples of state of the art performance are discussed. Examples are selected from the experience in our own laboratory with SSMS, SIMS with the ion microscope and laser microprobe mass analysis with the transmission type LAMMA instrument. They will be selected from the field of environmental analytical chemistry and from that of the analytical chemistry of pure industrially important materials.     

Recent uses of liquid ion exchangers in inorganic analysis

A review of recent uses of liquid ion exchangers in inorganic analysis is presented.     

Neutron activation analysis of the inorganic ions in Langmuir-Blodgett multilayers

An application of neutron activation analysis for the determination of inorganic ions in Langmuir—Blodgett multilayers is described. A special technique for the removal of multilayers from the solids substrate has been used. Multilayers of arachidic acid and octadecylamine are analyzed with respect to Cd²⁺ and HPO ₄ ²⁻ . Ca²⁺, Ba²⁺, Cu²⁺, HAsO ₄ ²⁻ , Cro ₄ ²⁻ and other ions can also be determined by means of this method. The results obtained are compared with those of other authors.     

Recent developments in the separation of inorganic and small organic ions by capillary electrophoresis

Which method should I use for ion analysis, ion chromatography (IC) or capillary electrophoresis (CE)? In terms of actual theoretical plates CE has a clear-cut advantage. The separation ability of IC is adequate for many sample types, and many separation scientists feel that IC offers greater reliability and confidence than CE. However, IC is a more mature technique and there has been more time to solve problems such as peak tailing and to improve reproducibility. The two techniques should be viewed as complementary. A number of recent developments in ion analysis by CE are discussed. These include some simple ways to control electroosmotic flow and improve reproducibility, separation of isotopes, improved methods of indirect photometric detection, a new contactless conductivity detector, separation of ions at low pH, and in solutions of high salt content. Progress in a new technique called IC-CE will be described in which a soluble ion-exchange polymer is added to the capillary electrolyte to separate anions based on differences in both electrophoretic mobility and ion-exchange interactions.     

Recent directions of electrospray mass spectrometry for elemental speciation analysis

A brief survey is given of the last 2 years’ literature on electrospray mass spectrometry (ESI-MS) for speciation analysis. As observed for many years, the main recent applications in this field concern arsenic and selenium species, especially in studies encompassing combined use of molecular and element mass spectrometry. A further application field is the stoichiometric characterization of metal complexes by ESI-MS, which in some studies was assisted by nuclear magnetic resonance spectroscopy. A few examples are presented to illustrate arsenic species involved in metabolic pathways, sulfur species in oils and bitumen, and aluminum complexes. On the basis of this review, we also give an outlook of expected future developments and trends in this research field.     

CE determination of small ions: methods and techniques

This paper provides an overview on the current status of capillary electrophoresis (CE) in the analysis of inorganic and charged small organic species. The various CE strategies used to improve the separation of ionic analytes are summarized. Technical developments in the design of improved detection systems are described. A brief account of their advantages and limitations is given. The potential use of these devices for miniaturized CE systems is also described. Finally, special attention is focused on the on-capillary preconcentration techniques developed in attempts to overcome the poor detectability of CE. Recent review articles are frequently cited to provide readers with a source of information about pioneering work, theoretical treatments, and specific applications.     

Recent advances in capillary electrophoretic analysis of individual cells

Because variability exists within populations of cells, single-cell analysis has become increasingly important for probing complex cellular environments. Capillary electrophoresis (CE) is an excellent technique for identifying and quantifying the contents of single cells owing to its small volume requirements and fast, efficient separations with highly sensitive detection. Recent progress in both whole-cell and subcellular sampling has allowed researchers to study cellular function in the areas of neuroscience, oncology, enzymology, immunology, and gene expression.      

Study of the determination of inorganic arsenic species by CE with capacitively coupled contactless conductivity detection

The determination of arsenic(III) and arsenic(V), as inorganic arsenite and arsenate, was investigated by CE with capacitively coupled contactless conductivity detection (CE-C(4)D). It was found necessary to determine the two inorganic arsenic species separately employing two different electrolyte systems. Electrolyte solutions consisting of 50 mM CAPS/2 mM L-arginine (Arg) (pH 9.0) and of 45 mM acetic acid (pH 3.2) were used for arsenic(III) and arsenic(V) determinations, respectively. Detection limits of 0.29 and 0.15 microM were achieved for As(III) and As(V), respectively by using large-volume injection to maximize the sensitivity. The analysis of contaminated well water samples from Vietnam is demonstrated.     

Biosorbent for tungsten species removal from water: effects of co-occurring inorganic species

The effect of co-occurring inorganic species on the removal of tungsten from water was investigated using biosorbent (i.e., chitosan coated montmorillonite clay). Simulated natural water and well water from Fallon, NV were used for this study. The concentrations of tungsten (21-541 mg/L) and inorganic species ([H(2)CO(3)]=0-4.2 mg/L, [H(4)SiO(4)]=0-90 mg/L, and [SO(2-)(4)]=0-400 mg/L) in simulated feed water were varied. The concentration of tungsten in the well water was 26 microg/L. The pH level of simulated feed water and well water was adjusted to 4 since this pH was found to be the most effective pH for the tungsten removal using chitosan coated clay. Tungsten removal without the existence of co-occurring inorganic species decreases from 99.8 to 87.1% with an increase in initial tungsten concentration from 21 to 541 mg/L. It reduces further as the co-occurring inorganic species concentration increases. The percentage of the tungsten removal ranges between 68.2-93.8%, 66.7-94.2%, and 53.6-93.7% for simulated natural water containing varied amount of H(2)CO(3), H(4)SiO(4), and SO(2-)(4), respectively. The adsorption kinetic data could be best described by the pseudo second order expression. The adsorption equilibrium data was modeled with the Langmuir, Temkin, and Freundlich equations and was found to be represented well by the Langmuir equation. The essential characteristics of the Langmuir isotherm indicate that the adsorption of tungsten on chitosan coated clay is favorable regardless of the presence of interfering species. Compared to natural clay, chitosan coated clay has about 116 times larger adsorption capacity per gram of chitosan, which makes it a superior adsorbent. However, the maximum tungsten adsorption capacity decreases in the presence of co-occurring species since the co-occurring species suppress the adsorption. For the well water treated with biosorbent, the tungsten concentration in the product water was found to be lower than the detection limit (1 microg/L) of the inductively coupled plasma mass spectrometer (ICP-MS). The repeatable results obtained from the treatment of both simulated and well water suggest that using chitosan coated clay can be an efficient adsorbent for tungsten removal from contaminated sites.     

Cluster analysis of elemental constituents of individual atmospheric aerosol particles from the volcanic plume of Lonquimay eruption in 1989

Aerosol samples collected around the Chilean site Lonquimay during major volcanic activities in January 1989 have been subjected to microPIXE measurements of 1 mm lateral resolution in the Debrecen Institute. Elemental concentrations relative to calcium have been determined for Al, Si, P, S, K, Sc, Ti, V, Cr, Mn, Fe, Ni, Cu, Zn, and Ba in 187 individual aerosol particles with the particle sizes between 15 mm and 1 mm. On the basis of a cluster analysis performed on the data set we defined eight clusters. Scatter plots for selected pairs of elements as Si/Al, K/Si, S/Cl, and Al/S elemental ratios that are considered as signatures characterizing types and mechanisms in volcanic eruption - have been compared with published data available in the literature for various volcanic sites.     

Charting the trends in nuclear techniques for analysis of inorganic environmental pollutants

Publications in analytical abstracts in the period 1975-1984 and papers presented at the Modern Trends in Activation Analysis international conferences series in the period 1961-1986 have been used as an empirical basis for assessing general trends in research and publication activity. Some ebbs and flows in the specialty of instrumental techniques for analysis of environmental trace pollutants are revealed by a statistical analysis of the publications.     

Isomer population analysis of gaseous ions from infrared multiple photon dissociation kinetics

Infrared multiple photon dissociation (IRMPD) kinetics measured with tunable laser radiation from a free electron laser (FEL) are used to probe the relative populations of and interconversions between energetically competitive isomers of gas-phase ions at 298 K. On-resonance IRMPD kinetics of monoisomeric benzoate anion and anilinium (protonated aniline) are measured to determine the extent of overlap of the laser beam with the precursor ion population (～93%). IRMPD kinetics indicating different photodissociation behavior for different isomers obtained at isomer-specific resonances are used to determine relative populations of salt bridge and charge-solvated isomers for ArgGly·Na(+), Ser·Cs(+), and Arg·Na(+). These values and Gibbs free energy differences obtained from them for thermal precursor populations are compared to values reported using other, less direct population probes. Rapid interconversion of two charge-solvated isomers occurs for ArgGly·Li(+), precluding population analysis for this ion. ArgGly·Na(+), ArgGly·Li(+), and Arg·Na(+) exhibit IRMPD induction periods lasting many seconds for some isomers at the laser photon energies and power used, indicating that IRMPD relative spectral intensities are time-dependent for these ions and that the relative band intensities in IRMPD spectra measured with short irradiation times may not provide meaningful information about relative isomer populations. These results constitute the first direct probe of ion isomer populations using IRMPD kinetics obtained with a FEL and illustrate a number of caveats in interpreting IRMPD spectra measured with just a single irradiation time. These results also indicate that more complete overlap of the laser beam with the ions will be highly advantageous in future instrument designs for IRMPD kinetics and spectroscopy experiments.     

Recent advances in CE and CEC of pollutants

Recent advances in CE and CEC separation, detection and sample preparation/preconcentration methodologies, for the determination of a variety of compounds having current or potential environmental relevance, have been overviewed. The reviewed literature has illustrated the wide range of CE applications available, indicating a continuing interest in CE and CEC in the environmental field. New developments in chip-based CE systems are also discussed.