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Biomedical subjects

Shunitz Tanaka

Publications and source records attributed to Shunitz Tanaka.

At least 19 recordsLinked to original sources

Electrochemical detection and control of interactions between DNA and electroactive intercalator using a DNA-alginate complex film modified electrode.

The surface of a glassy carbon electrode was modified with a DNA-alginate complex film in which water-soluble DNA was encapsulated into a calcium-alginate gel. The resulting modified electrode (DAFE) was used to detect ethidium bromide (EtBr), after its accumulation on the electrode. The intercalative behavior of EtBr for dsDNA in the film was investigated by measuring the electrode response based on the intercalation of EtBr separated from nonspecific interactions (electrostatic interaction). The accumulation of EtBr in the dsDAF was enhanced by applying a negative potential below -200 mV at the dsDAFE. When a positive potential above +700 mV was applied to the dsDAFE for a constant time with stirring in a Tris buffer solution, the amount accumulated decreased. These results indicate that it is possible to electrochemically control the accumulation and release of EtBr when a dsDAFE is used. In addition, the accumulation and detection of EtBr in spiked river water samples and daunomycin, an antitumor agent, is described.

Alginates↗

Voltammetric behavior and determination of 17 beta-estradiol at multi-wall carbon nanotube-Nafion modified glassy carbon electrode.

For the purpose of low cost and sensitive electrochemical detection of 17 beta-estradiol (E2), a multi-wall carbon nanotube (MWNT)-Nafion modified electrode was fabricated. The MWNT modified electrode shows enhancement for the anodic peak current of E2 compared with the value obtained using a bare electrode. The anodic peak current measured by square wave voltammetry after 5 min open-circuit accumulation was proportional to the concentration of E2 over the range of 2.5 x 10(-7) to 10 10(-6) M, and a detection limit of 1 x 10(-8) M was obtained.

Biosensing Techniques↗

Electrochemical oxidation for low concentration of aniline in neutral pH medium: application to the removal of aniline based on the electrochemical polymerization on a carbon fiber.

Aniline, which causes serious environmental problems, was electrochemically treated and thereby removed from aqueous solution. This method demonstrated herein is based on the formation of polyaniline at an electrode surface by electrochemical oxidation. Initially, the electrode behavior of aniline at several conditions was investigated on a platinum, glassy carbon (GC), and carbon fiber (CF) electrode using voltammetric techniques. On the platinum electrode, aniline did not polymerize at low concentrations. However, electropolymerization of aniline was observed on both the GC and CF electrodes even at low concentrations in neutral pH solutions. The removal of aniline was carried out using a CF bundle with a large surface area. High removal efficiency for aniline was obtained by applying potentials greater than 0.8 V. Although generation of p-benzoquinone as a byproduct was observed during electrochemical treatment, its generation was suppressed by applying a potential lower than 0.9 V. The cyclic voltammograms and X-ray photoelectron spectra of the CF after the treatment for aniline solution showed that polymeric aniline existed on the CF surface. The maximum surface coverage of electropolymerized aniline was estimated to be about 1.49 x 10(-8) mol/cm2. Furthermore, the continuous treatment of aniline was demonstrated using a flow system.

Aniline Compounds↗

Removal of organic compounds by alginate gel beads with entrapped activated carbon.

The adsorption of alginate gel (AG) beads and AG with activated carbon entrapped (AG-AC) beads prepared using different types of metal ions were investigated by measuring the removal of several organic compounds with different charges and size. AG-AC beads prepared in a CaCl2 solution adsorbed strongly positively charged compounds as well as electrically neutral and low molecular weight compounds such as p-chlorophenol. However, a high molecular weight humic acid was not adsorbed by AG-AC. The AG-AC selectively adsorbed p-chlorophenol from a humic acid solution. The adsorption capacity obtained from the adsorption isotherm of AC entrapped in AG was compared with that of AC. The AG-AC beads prepared in a solution of FeCl3 were able to specifically adsorb negatively charged gallic acid. Thus, entrapping AC into AG resulted in the selective adsorption.

Adsorption↗

Quantitative analysis of 17beta-estradiol in river water by fluorometric enzyme immunoassay using biotinylated estradiol.

A sensitive and simple immunoassay to determine 17beta-estradiol (E2) in fresh water was developed. The method is based on a solid-phase avidin-biotin binding assay and solid phase extraction. The binding event of E2 to the antibody is detected indirectly by the competitive reaction between E2 and biotinylated estradiol (BE) as a tracer for the limited binding sites of antibodies immobilized onto the wall of a microtiter plate. Namely, E2 concentrations are determined from the strong interaction between BE and avidin conjugated with horseradish peroxidase (avidin-HRP). In order to achieve a sensitive measurement for the binding of BE to the antibody immobilized on the microtiter plate substrate, QuantaBlu fluorogenic peroxidase substrate (QFPS) was employed. The detection limit and the linear range of E2 determination were 27 pM and 27 - 7480 pM, respectively. The relative standard deviations (RSD) for the E2 assay were between 0.3 and 12.0% (n = 3). The cross-reactivities of several other estrogens in this assay system were also investigated. No serious influences from any cross-reaction caused by other estrogens tested in this experiment were observed. The determination of E2 in water samples from eight rivers and a marsh in Hokkaido was performed by the immunoassay combined with solid phase extraction. It was found that the concentration of E2 was in the range between 0.06 and 67 pM.

Biotinylation↗

Caged multiwalled carbon nanotubes as the adsorbents for affinity-based elimination of ionic dyes.

Multiwalled carbon nanotubes (MWCNTs) were used as the active elements for the first time for affinity-based elimination of ionic dyes. MWCNTs were encapsulated in cross-linked alginate (ALG) microvesicles using Ba2+ as the bridging ion. The Ba2+-alginate matrix constitutes a cage which holds the physically trapped MWCNTs. The cage carries negative charges on its surface. The cage restricts the access of anions of large molecular weight, such as humic acids, because of electrostatic repulsion. The cage also restricts the access of colloids of large size, because of size exclusion. Ionic dyes partition into the cage and then are captured by MWCNTs probably on the basis of van der Waals interactions occurring between the hexagonally arrayed carbon atoms in the graphite sheet of MWCNTs and the aromatic backbones of the dyes. As a result of these interactions the target species, namely, the ionic dyes, are eliminated efficiently by the MWCNTs of Ba2+-ALG/MWCNT composite adsorbents. The adsorptive capacities for elimination of acridine orange, ethidium bromide, eosin bluish, and orange G (the model species used for this study) were found as high as 0.44, 0.43, 0.33, and 0.31 micromol, respectively, for 1.0 mg of the caged MWCNTs. Adsorptive experiments with carbon nanofibers and activated carbons as the adsorbents were also performed. The MWCNT-based adsorbents provided the best capability for the affinity-based elimination of these targeted species. Biocompatibility experiments performed in vitro and in vivo provided promising results, suggesting potential applications of the caged MWCNTs in in situ environmental remediation.

Adsorption↗

Determination of monovalent inorganic anions in high-ionic-strength samples by electrostatic ion chromatography with suppressed conductometric detection.

A new ion chromatographic (IC) system has been established by using micelles of 3-(N,N-dimethylmyristylammonio)propanesulfonate (Zwittergent 3-14) loaded onto a reversed-phase packed column as the separation column with an electronic rotary switching valve packed-bed suppressor for conductometric detection of inorganic anions. An aqueous H3BO3-Na2B4O7 solution has been demonstrated to be the most desirable eluent for this IC system. The relationship between retention time and the concentration of the borate eluent was determined for a series of model anionic analytes and this relationship was found to be opposite to that exhibited in a conventional anion-exchange IC system. The rapid elution and complete separation of monovalent inorganic anions were obtained by initially using a high-concentration borate solution as the eluent for a short-period, and then switching to a lower-concentration borate eluent to complete the separation. Detection limits for nitrite, bromide, nitrate, and chlorate were 0.85, 0.88, 0.95 and 4.8 microM, respectively, when a 7.0 mM Na2B4O7 eluent was used. Moreover, the ability to directly detect these monovalent anions in samples containing high concentrations of sulfate and/or chloride ions provided a major advantage of this approach.

Anions↗

Evaluation of solubilizing ability of humic aggregate basing on the phase-separation model.

Solubilizing abilities of aggregates of humic acid (HA) to chlorinated benzenes (CBs) were investigated by means of the apparent water solubility enhancement. Both the water solubilities of 1,4-dichlorobenzene (DCB) and 1,2,4,5-tetrachlorobenzene (TeCB) linearly increased with increasing concentration of HA above the critical micelle concentration (CMC). Such solubilization behavior of CBs for HA was compatible with those for sodium dodecyl sulfate (SDS). These results indicate that the solubilization of CBs in the aqueous solution of HA above the CMC can be interpreted on the basis of the phase-separation model. Thus, the partition coefficients (K(mic)) of CBs between water and HA aggregate phases were calculated by assuming this model. The fact that the K(mic) value increased with increasing K(ow) of CBs supported the partition into the HA aggregate phase by hydrophobic interaction. The estimated K(mic) values of DCB were not dependent on the solution pH. Both K(mic) values of DCB and TeCB for the HA aggregate were found to be 4-5-fold lower than those of SDS.

Chlorobenzenes↗

Electrochemical removal of bisphenol A based on the anodic polymerization using a column type carbon fiber electrode.

Electrochemical removal based on the polymerization of organic pollutants on an anode surface was performed on bisphenol A (BPA) and its derivatives, bisphenol S (BPS) and diphenolic acid (DPA). It was confirmed by voltammetric techniques that the electrochemical oxidation of these compounds leads to the formation of a polymeric film on a carbon electrode surface. The electrochemical removals of BPA, BPS and DPA based on the anodic polymerization were attempted in the batch type cell. A carbon fiber (CF) was used as an anode with a very large surface area. The high removal efficiency for BPA, BPS, and DPA was obtained by applying a potential at 0.75-, 1.0-, and 0.8-V, respectively. The removal efficiency for BPA does not decrease in the presence of 10ppm humic acid. The electropolymerized BPA film formed on the CF surface was characterized by FT-IR and UV/vis. The continuous treatment of BPA was achieved by using the flow system with a column type of CF electrode. The applicability of this method for removal of BPA from aqueous solution was tested at several different conditions, i.e., flow rate of solution and concentration of electrolyte and BPA. This system can be applied for removal of a low concentration BPA even from low electrolyte concentrations of aqueous solution.

Benzhydryl Compounds↗

Removal of Cr(VI) from contaminated soil by electrokinetic remediation.

A new process for the removal of hexavalent chromium [Cr(VI)] contaminated soil is described. The process provides for an efficient removal of anionic chemicals from contaminated soils. Chromate anions were removed from the soil to the anodic reservoir by the moving force of electromigration. In this process, the chromate anions that accumulate in the anodic reservoir are simultaneously eliminated by using a column packed adsorbent. The adsorbent (immobilized tannin) used was chemically incorporated into cellulose. Cr(VI) was found to be adsorbed to this adsorbent efficiently. In the electrokinetic process, the pH of the aqueous solution in the anodic reservoir was decreased by the electrolysis of water. In the present study, the pH of the solution in the anodic reservoir is maintained at pH 6 by the addition of an aqueous alkaline solution during the electrokinetic process. The advantage of pH control is that it promotes the release of Cr(VI) from the soil by electromigration, thus permitting the maximum adsorption of Cr(VI) on the immobilized tannin. Simultaneous collection of Cr(VI) from the anodic reservoir leads to the protection from secondary contamination with Cr(VI).

Adsorption↗

Electrokinetic remediation of clayey soils containing copper(II)-oxinate using humic acid as a surfactant.

The utility of humic acid (HA) as a surfactant for use in the electrokinetic remediation (ER) of the clayey soils containing copper(II)-oxinate (Cu(OX)(2)) was examined. A small simulator of ER was devised, which consisted of three types of artificial soils on the basis of the commercial kaolin: kaolin, kaolin + HA and kaolin + Cu(OX)(2). The layers of kaolin containing HA and Cu(OX)(2) were sandwiched between two kaolin layers. In all experiments, a constant dc voltage gradient of 2.2V/cm was applied through the soil for 30h, and the pH of the solution in the anodic chamber was maintained at 7.0. Generally, HA has a negative charge at a neutral pH. However, the HA was mainly transferred to the cathodic chamber. This shows that the driving force of the HA in the system used herein is predominantly due to electroosmotic flow. Moreover, the amount of Cu(OX)(2) removed from the clayey soils in the presence of HA was three times larger than those in the absence of HA. This can be attributed to the fact that the water solubility of Cu(OX)(2) is enhanced by the presence of HA. Thus, we conclude that HA has a potential for use as an amendment for the ER of hydrophobic chemicals, such as Cu(OX)(2).

Aluminum Silicates↗

A new and selective capillary column coated with cationic diazacrown ether for separation of organic and inorganic anions by capillary electrophoresis.

A new coated capillary has been introduced for capillary electrophoretic separation of anions by using a positively charged diazacrown ether with a 12-membered ring. A positive charge spread over the inner capillary surface led to a substantial anodic electroosmotic flow (EOF) over the range of migrating buffer of pH 2-11. Under the optimum conditions of 25 mM phosphate buffer at pH 7, the diazacrown-coated capillary showed a successful simultaneous separation of 7 inorganic anions and 13 aromatic anions (including positional isomers) in less than 15 min. The migration times of the sample anions and EOF marker for consecutive runs on a single column were highly reproducible, giving a relative standard deviation of 1%. Theoretical treatment of the migration behavior clearly demonstrated that ion association between the diazacrown and analyte anions is strongly dependent on the nature of the functional groups of anions (e.g., sulfonate groups > carboxyl groups) and the number of negative charges (e.g., trivalent anions > divalent anions > monovalent anions) on the analyte.

Anions↗

Electrochemical immunoassay at a 17beta-estradiol self-assembled monolayer electrode using a redox marker.

A simple electrochemical immunoassay was demonstrated using a 17beta-estradiol modified electrode. 17beta-estradiol was immobilized on the gold electrode surface with a self-assembly technique. The specific binding between estradiol antibody and 17beta-estradiol on the electrode surface was evaluated by monitoring the change in the electrode response with three hydrophilic redox markers. The decrease in the electrode response for the redox marker was observed, when the antibody was bound to the estradiol self-assembled monolayer (SAM) electrode surface. The change in the electrode response of the redox marker is attributed to the steric hindrance between the antibody on the electrode surface and the redox marker. The relative standard deviation at 30 microg ml(-1) estradiol antibody was 4.1% (n = 3). The competitive reaction between the antigen in the solution and 17beta-estradiol immobilized on the electrode surface for the limited binding sites on the antibody produced an increase in the electrode response with hydroquinone as the marker. The binding affinity of three antigens including 17beta-estradiol to the estradiol antibody was evaluated. Furthermore, the result obtained from this method was compared with the previously reported enzyme binding assay using the biotinylated estradiol and the biotin-immobilized microtiter plate.

Antibodies↗

Use of phosphobetaine-type zwitterionic surfactant for the determination of alkali and alkaline earth metal ions and ammonium ion in human saliva by capillary electrophoresis.

With conventional capillary electrophoresis (CE), it was difficult to directly analyze samples containing proteins as a result of the irreversible adsorption of proteins onto the inner surface of the capillary column. This difficulty, however, was completely overcome by adding N-dodecylphosphocholine (DPC, a phosphobetaine-type zwitterionic surfactant) to the background electrolyte (BGE). DPC made two essential contributions to the determination of common inorganic cations in the protein-containing samples: protein adsorption onto the capillary walls was completely avoided, and the resolution of the analyte cations was essentially improved. The optimal BGE for analysis of biological samples was found to be 5 mM DPC, 5 mM copper(II) acetate/10 mM ethylenediamine (pH 8). The detection limits (signal-to-noise ratio =3 and UV at 215 nm) of sodium, potassium, calcium, magnesium, and ammonium ions were 25, 31, 24, 45, and 60 micro M, respectively. These five species of the common inorganic cations in human saliva samples were detected successfully within 2 min by the proposed system with direct sample injection.

Alkalies↗

Electrochemical evaluation of the interaction between endocrine disrupter chemicals and estrogen receptor using 17,beta-estradiol labeled with daunomycin.

A new electrochemical screening method for endocrine disrupting chemicals (EDCs) was developed. To evaluate the binding capacity of EDCs to the estrogen receptor (ER), 17beta-estradiol labeled with daunomycin as an electroactive compound was prepared. The electrochemical sensitivity of the prepared labeled estradiol (LE) was high, as compared with daunomycin. The interaction between LE and ER was observed by the decrease in the electrode response of LE, indicating the specific binding of LE with ER. The competitive reaction between LE and 17beta-estradiol for the limiting binding site on ER produced increases in the peak current of LE. The relative standard deviation at 1 x 10(-8) M 17beta-estradiol was about 10.0% (n = 7). The binding affinity between EDC and ER was also evaluated by comparison with 17beta-estradiol-ER interaction. Bisphenol A, p-nonylphenol and p,p'-DDT was used as a test compound. All test compounds demonstrated some ability to bind with ER. This electrochemical binding assay illustrates a new method for evaluating the binding capacity of EDCs to ER without the need for a separation procedure for the bound and free LE.

Animals↗

Electrochemical removal of p-nonylphenol from dilute solutions using a carbon fiber anode.

p-Nonylphenol, which is widely used as raw material in industrial activities has been regarded as an environmental endocrine disrupter. In an effort to develop a new treatment method for p-nonylphenol, we initially investigated the electrochemical behavior of p-nonylphenol by voltammetric techniques. The electrochemical oxidation of p-nonylphenol led to the formation of electropolymerized film on the glassy carbon electrode surface. The fouling on the electrode surface by the electropolymerized film was evaluated by monitoring the electrode response of ferrocyanide ions as the redox marker. The electrochemical removal of p-nonylphenol based on the formation of the electropolymerized film on an anode surface was performed using a carbon fiber (CF) with a very large surface area. The high removal efficiency for p-nonylphenol was obtained by applying a potential at 0.7 V. The maximum surface coverage of electropolymerized p-nonylphenol on the CF was about 5 x 10(-9) mol/cm2. The presence of humic acid hardly inhibited the removal of p-nonylphenol. Furthermore, the application to the removal of phenol, o-chlorophenol, p-chlorophenol, 2,4-dichlorophenol, and 2,4,5-trichlorophenol was attempted by using this method.

Carbon↗