PubMed Health⌕ Search

Biomedical subjects

Hiroaki Tao

Publications and source records attributed to Hiroaki Tao.

17 recordsLinked to original sources

A rapid fractionation method for heavy metals in soil by continuous-flow sequential extraction assisted by focused microwaves.

A microwave-assisted continuous-flow sequential extraction system was developed for rapid fractionation analysis of heavy metals in soil. Insertion of pressure-adjusted air between the extractants provided stable flows of the extractants without mutual mixing and back-pressure influence of a column packed with soil, thereby facilitating reliable continuous-flow extractions. In addition, use of pure water as a pumping solvent removed metal contamination because of direct contact between corrosive extractants and the pump containing metallic materials. Focused microwave irradiation to the soil accelerated the selective extractions of the acid-soluble and reducible fractions of heavy metals in soil in the first and second steps of the sequential extraction conditions, as defined by the Commission of the European Bureau of Reference (BCR). The microwave-assisted continuous-flow extraction provided high correlations in amounts of six heavy metals except Zn in the first step and Cu in the second step extracted from a reference sludge soil, BCR CRM 483, with a conventional batchwise extraction proposed by BCR; continuous-flow extraction assisted by conductive heating provided lower correlations for all the six metals. The proposed method drastically reduced the time required for the sequence extraction to ca. 65 min without losing accuracy and precision of the fractionation analysis of heavy metals in soil, whereas the BCR batchwise method requires ca. 33 h.

Chemical Fractionation↗

Quartz crystal microbalance immunosensors for environmental monitoring.

This paper presents discussion of quartz crystal microbalance (QCM) immunosensors for environmental monitoring. Factors limiting the practical application of antibodies to analytical problems are also presented. Among several candidates for the QCM immunosensor device, selected QCM devices and oscillating circuits were tested thoroughly and developed to obtain highly stable and sensitive frequency signals. The biointerface of QCM immunosensor was designed and controlled to immobilize antibody on the QCM surface, to reduce non-specific binding and to suppress denaturation of immobilizing antibody by self-assembled monolayer technique and artificial phospholipid (2-methacryloyloxyethyl phosphorylcholine (MPC)) polymer. MPC polymer as a antibody-stabilizing reagent was added to reduce non-specific binding of the antigen solution and stabilize the immunologic activity of the antibody-immobilized QCM. In addition, it provides examples for detection and quantitation of environmental samples using QCM immunosensors. The analytical results for fly ash extracted samples of dioxins using the QCM immunosensor indicated a good relationship with GC/MS methods. The integrating protocols of the competitive immunoassay and signal-enhancing step are for detecting low molecular analytes with extremely low detection limits using an QCM immunosensor. Furthermore, its detect limitation was extended from 0.1 to 0.01 ng/ml by the signal-enhancing step when the anti-bisphenol-A antibody conjugated MPC polymeric nanoparticles was used. The QCM immunosensor method has demonstrated its effectiveness as an alternative screening method for environmental monitoring because these results were compared with results obtained through environmental monitoring methods such as ELISA and GC/MS.

Biosensing Techniques↗

A high-efficiency photooxidation reactor for speciation of organic arsenicals by liquid chromatography-hydride generation-ICPMS.

A novel postcolumn photooxidation reactor with remarkably high efficiency was developed. It was installed into a system of liquid chromatography (LC) combined with inductively coupled plasma mass spectrometry (ICPMS) using a hydride generation (HG) technique to enable sensitive speciation of organic arsenicals. An LC eluent was passed into a reaction tube that runs through a low-pressure mercury lamp of a high-efficiency photooxidation (HEPO) reactor. It provided efficient irradiation with vacuum ultraviolet light at 185 nm, which induced oxidative decomposition of persistent organic arsenicals, for example, arsenobetaine, to the final product, arsenate, for an extremely short time, 3.5 s, without using any oxidizing agents. That arsenate was subsequently detectable by HG-ICPMS. In contrast, conventional photooxidation reactors require more than 100 s for completion, even when using a peroxodisulfate solution as an oxidizing agent. Because of the absence of broadening and dilution of the LC-separated peaks caused by mixing with the oxidant solution, the detection limits for 10 arsenic species including the persistent organic arsenicals by the proposed LC-HEPO-HG-ICPMS ranged from 2.3 to 18 ng of As/L, which were about one-tenth as low as those by LC-ICPMS. The proposed method revealed for the first time the occurrence of 20 arsenic species, including the unknown trace species, which were undetectable by LC-ICPMS and LC-HG-ICPMS, in human urine.

Arsenicals↗

Characterization of ribosomal proteins as biomarkers for matrix-assisted laser desorption/ionization mass spectral identification of Lactobacillus plantarum.

For rapid identification of bacteria by matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS), a bioinformatics approach using ribosomal subunit proteins as biomarkers has been proposed. This method compares the observed masses for biomarkers with calculated masses as predicted from the amino acid sequences registered on protein databases. To evaluate this approach, the expressed ribosomal proteins of a genome-sequenced bacterium, Lactobacillus plantarum NCIMB 8826, were characterized as a model sample. The protein expression of 42 ribosomal subunit proteins, together with 10 ribosome-associated proteins in the isolated ribosome fraction, was confirmed through two-dimensional gel electrophoresis combined with peptide mass fingerprinting. The observed masses of the proteins in the isolated ribosome fraction were then determined by MALDI-MS. We preliminarily selected 44 biomarkers whose observed masses were matched with the calculated masses predicted from the amino acid sequence registered in the protein databases by considering N-terminal methionine loss only. Of these, the finally selected reliable biomarkers were 34 proteins including 31 ribosomal subunit proteins and 3 ribosome-associated proteins that could be observed in the MALDI mass spectra of the cell lysate sample. These biomarkers were usable in MALDI-MS characterization of two industrial L. plantarum cultures.

Bacterial Proteins↗

On-line preconcentration system using mini-column packed with a chelating resin for the characterization of seasonal variations of trace elements in seawater by ICP-MS and ICP-AES.

An on-line column preconcentration technique coupled with inductively coupled plasma-mass spectrometry (ICP-MS) and -atomic emission spectrometry (ICP-AES) was developed using a mini-column (ca. 3 mm i.d., 40 mm length), that was packed with chelating resin (0.2 g) of iminodiacetic acid groups, Muromac A-1. After the preconcentration step, the column was washed with ammonium acetate buffer (pH 5.5) and water to remove major elements, such as Ca and Mg, and then eluted with 4 ml of 2 mol l(-1) nitric acid. Eleven trace elements (Al, V, Fe, Co, Ni, Cu, Zn, Cd, Pb, Th and U) in seawater were determined by ICP-MS/AES. Recoveries for most of the elements tested were over 90%, although those for Al, V and Th were around 70%. The accuracy of the proposed method was evaluated by analyzing a standard reference material of seawater (NASS-4, NRC Canada). The values of Fe, Co, Ni, Cu, Zn, Cd and Pb obtained with the present method showed good agreement with the certified values as judged from the standard deviation. The method was successfully applied to characterize seasonal variations of trace elements in deep seawater (DSW) and surface seawater (SSW). In addition, no serious decrease in analytical performance of the present column system was observed during the experimental period of about 1 year.

Adsorption↗

Gene sensors based on peptide nucleic acid (PNA) probes: relationship between sensor sensitivity and probe/target duplex stability.

Gene sensors based on peptide nucleic acid (PNA) probes were prepared and the relationship between sensor sensitivity and the duplex stability of the probe PNAs and target complementary DNAs was studied using five synthesized PNAs (10-, 15-, 17-, 20-, and 22-mers). It was found that the association constants for the probe PNA/target DNA pairs depend not only on the length but also on the base pair sequence, and that the trend in the sensor responses was the same as that in the association constants for the corresponding pairs. In addition, by using two kinds of probe PNAs with different lengths, it was demonstrated that fabrication of sensors based on probe PNAs with comparable association constants yielded similar response curves and sensor sensitivities.

Animals↗

Laser desorption/ionization on porous silicon mass spectrometry for accurately determining the molecular weight distribution of polymers evaluated using a certified polystyrene standard.

Desorption/ionization on porous silicon-mass spectrometry (DIOS-MS) is a novel soft ionization MS technique that does not require any matrix reagent, ideally resulting in fewer obstructive peaks in the lower mass region. In this study, the etching conditions of porous silicon spots as an ionization platform of DIOS-MS were investigated for determining the molecular weight distribution (MWD) of polymers. To evaluate the accuracy of DIOS mass spectra observed using porous silicon spots prepared under various etching conditions, a certified polystyrene (PS) standard sample with an average molecular weight of ca. 2400 was used as a model sample. By optimizing the etching conditions, the MWD of the PS sample could be accurately observed by DIOS-MS using both p-type and n-type porous silicon spots. Especially, in the case of a suitable n-type spot, an accurate peak distribution with very fewer obstructive background peaks could be observed using the minimum laser power, comparable to the conventional matrix-assisted laser desorption/ionization-mass spectrometry (MALDI-MS).

Journal Article↗

Rapid separation of microorganisms by quartz microchip capillary electrophoresis.

We developed and optimized a system coupling microchip capillary electrophoresis (MCE) and laser-induced fluorescence (LIF) detection for the analysis of microorganisms. The MCE-LIF system successfully separated pure cultures of lactic acid bacteria and Saccharomyces cerevisiae within 200 s. The results indicate that the MCE system can be conveniently used for the rapid and highly sensitive detection of microorganisms. Thus, MCE can provide a cheap and simple method for the on-line detection of microbial contamination.

Bacteria↗

High-performance liquid chromatography-ultrasonic nebulizer high-power nitrogen microwave-induced plasma mass spectrometry, real-time on-line coupling for selenium speciation analysis.

The coupling of a high-power nitrogen (N2) microwave-induced plasma (MIP) mass spectrometry--(MS) (1.3 kW) with high-performance liquid chromatography, connected with concentric nebulizer (CN), ultrasonic nebulizer (USN) and a hydride generation (HG) systems, for the optimization and determination of selenium compounds, has been carried out. The MIP-MS system fulfils the ideal requirement being an on-line real-time chromatographic detector for Se speciation analysis. Interchanging of MIP-MS system fabricated nebulizer (concentric) with an ultrasonic nebulizer increases about 3.4-12 (peak height) and 6.5-10 (peak area) times ion signals for the selenium compounds. The detection limits for selenate, selenite, trimethylselenonium ion (TmSe), selenomethionine (Semet) and selenoethionine (Seet) (in Milli-Q-water) obtained with the optimized HPLC-USN-N2MIP-MS system are 0.11, 0.14, 0.09, 0.14 and 0.10 microg L(-1), respectively, about 12-48 times lower than the HPLC-CN-MIP-MS and 1.5-4.4 (peak height) times lower compared to the HPLC-CN-inductively coupled plasma (ICP)-MS coupling. Considering peak area, the repeatability (R.S.D. for three successive analyses) and intermediate precision (R.S.D. for three successive analyses performed on three different days), achieved for five Se compounds are 0.8-5.6, and 1.1-5.9%, comparable with the HPLC-CN-ICP-MS, HPLC-HG-MIP-MS and HPLC-CN-MIP-MS systems. The combined HPLC-USN-N2MIP-MS has been adequately applied for the determination of Se compounds in certified National Institute for Environmental studies human urine CRM No. 18. The results reasonably agree with the HPLC-CN-ICP-MS values. This encouraging combination may be an alternative ion source of mass spectrometry for coming generation in regard to the selenium speciation analysis.

Chromatography, High Pressure Liquid↗

Data processing method for the determination of accurate molecular weight distribution of polymers by SEC/MALDI-MS.

A novel data processing method for a hyphenated technique, size exclusion chromatography/matrix-assisted laser desorption/ionization-mass spectrometry (SEC/MALDI-MS), has been proposed to determine accurate molecular weight distributions on the basis of the individual oligomer species of a polymer. This method is based on the concept that the individual peak intensities of MALDI mass spectrum observed for every SEC fraction with narrow molecular weight distribution could be adjusted to the quantified values to reveal the accurate molecular weight distribution using the signal intensity of the corresponding fraction on the SEC chromatogram observed with a refractive index detector. At first, the theory of the proposed date processing is described in detail. Then, experimental verification of the method is described. This was performed through the characterization of mixtures of three kinds of monodispersed polystyrene reference materials (weight average molecular weight = ca. 6000, 10000, and 18000) as model samples. An accurate trimodal molecular weight distribution for the individual oligomer species of the sample was obtained without any influence of the chromatographic band broadening observed in the original SEC chromatogram. Moreover, the method for depicting the elution profiles of individual oligomer species during SEC separation was also obtained as a "mass chromatogram" using the data processing procedure.

Journal Article↗

Contamination and biomethylation of organotin compounds in pearl/fish culture areas in Japan.

Uwakai of Japan is famous for pearl and yellowtail fish culture. Recently, pearl culture farming in that region has suffered from a low production of pearls. An illegal use of organotin antifouling paints on fishing nets was reported. In the line of pollution studies, thus, the present investigation was carried out to examine the contamination status and fate of organotin compounds. Totally, 23 water, 10 sediment and 8 pearl oyster tissue samples were analyzed for tributyltin (TBT), triphenyltin (TPT), and their breakdown products (di- and mono compounds) by gas chromatography combined with inductively coupled plasma mass spectrometry (GC/ICP-MS). The results show that the TBT concentrations in water, sediment and biota were in the range from 0.11 to 10.6 ng Sn l(-1), 0.35 to 2500 ng Sn g(-1), and 50.4 to 181 ng Sn g(-1), respectively. The values for sediment and biota are expressed on the dry-weight basis. Triphenyltin in water, sediment and biota were in the range from 0.009 to 0.108 ng l(-1), non-detect to 12.7 ng g(-1), and non-detect to 6.83 ng g(-1), respectively. Although the TBT concentration in seawater is below the tentative assessment level of 10 ng l(-1) set by the Japanese Environment Agency in 1992, it may cause endocrine disruption/other effects in aquatic organisms. Octyltin compounds (mono-, di- and trioctyltin) were also quantified in seawater and sediment. The detection of dibutyldimethyltin (DBDMT) and tributylmonomethyltin (TBMMT) in sediment (methylated butyltins comprised 2.8-31% of total butyltins), and TBMMT in seawater suggested that biomethylation of anthropogenic tributyltins is a significant transformation pathway in the coastal environment.

Animals↗

Determination of selenium compounds in urine by high-performance liquid chromatography--inductively coupled plasma mass spectrometry.

Selenium species, selenite, selenate, selenomethionine (Semet), seneloethionine (Seet) and trimethylselenonium ion (TmSe) were separated in aqueous solution using a gel-permeation (polyvinyl alcohol-based resin) GS-220 column by eluting with 25 mM tetramethylammonium hydroxide and 25 mM malonic acid at pH 7.9. The GS-220 column coupled with inductively coupled plasma mass spectrometry was used for the separation, identification, and quantification of selenium compounds present in certified reference material (CRM) No. 18 human urine from the National Institute for Environmental Studies in Japan (NIES). Spiking of the authentic standard to the urine and use of a silica-based LC-SCX cation-exchange column validated the peak of selenium compounds. High concentrations of chloride and bromide in the urine eluted from the GS-220 column formed molecular ions 40Ar37Cl+ and 81Br1H+ in the plasma, and these molecular ions created additional peaks in the chromatograms when 77Se and 82Se isotopes were monitored respectively. Thus, both the isotopes were selected concurrently for signal monitoring to eliminate the interfering signals. On the LC-SCX column, chloride and bromide were eluted with selenate and complicated its determination, but the peak of TmSe was baseline separated from rest of the Se compounds. Two unknown Se compounds were detected in both the columns. An additional Se compound having the same retention time as that of Semet was detected on the LC-SCX column. Peaks of selenite, selenate, TmSe and unknown selenium compounds in the urine were baseline separated on the GS-220 column, and were free from interferences. Therefore, the GS-220 column was used for the determination of selenium compounds in NIES CRM No. 18. Unknown Se compounds were the predominant selenium species followed by selenite, TmSe and selenate. The estimated value of TmSe as Se, by the standard additions method using the GS-220 column, was 3.42 +/- 0.17 microg l(-1) and was in good agreement with the LC-SCX value [3.38 +/- 0.21 (n=5) microg l(-1)].

Cations↗