Morio Nakayama

Anion-exchange resin modified with bismuthiol-II, as a new functional resin for the selective collection of selenium(IV)

A functional resin for the collection of selenium(IV) has been prepared simply by the conversion of a common ion-exchange resin with bismuthiol-II which has three functional properties, namely the capabilities of selective reaction with selenium(IV), ion-exchange reaction with ion-exchange resin and strong physical sorption to the ion-exchange resin matrix. The binding ratio of selenium(IV) to bismuthiol-II on the resin was confirmed to be 1:4. The reaction was represented as follows: 4RSH + H(2)SeO(3)--> R-S-Se-S-R + R-S-S-R + 3H(2)O. Highly selective sorption of selenium(IV) was achieved, based on the formation of stable selenotrisulphide on the resin. Selenium(IV) sorbed on bismuthiol-II resin was eluted effectively with 8-13M nitric acid or some thiols, such as cysteine and penicillamine. In the cases of thiols, the elution of selenium was found to be also based on the formation of selenotrisulphide, and the bismuthiol-II resin was regenerated. Satisfactory results were obtained when this resin was applied to the determination of selenium(IV) in river, estuarine or sea water samples.

Effects of organic modifiers on the chiral recognition by different types of silica-immobilized bovine serum albumin

We prepared three columns containing bovine serum albumin immobilized on silica by different means and the effects of organic modifiers in the eluent on chiral separation were studied using N-substituted amino acids. Adsorption on silica, covalent immobilization to diol-silica with carbonyldiimidazole (CSP-II) and covalent immobilization to amino-silica with glutaraldehyde were studied. CSP-II had the highest stereoselectivity and was the most affected by organic modifiers in the eluent. The hydrophobicity of amino acid moiety affected the chiral recognition of N-benzoylamino acids and the aromaticity of the N-substituted group was important.

Determination of selenium(IV) and other forms of selenium dissolved in sea water by anion-exchange resin loaded with sulfonic acid derivative of bismuthiol-II and hydride generation atomic-absorption spectrometry

SummaryA sulfonic acid derivative of bismuthiol-II (bisIIS) was synthesized from 4-hydrazinobenzene sulfonic acid and carbon disulfide. Selenium(IV) was adsorbed selectively and quantitatively on the anion-exchange resin loaded with bis-IIS. Selenium adsorbed on the resin was eluted by the use of penicillamine and determined by hydride generation atomic absorption spectrometry (hydride generation/AAS). Selenium(VI) and other forms of selenium, which were not adsorbed onto the resin, were collected on the resin after digestion with nitric acid followed by reduction with hydrochloric acid. Separative preconcentration of selenium(IV), selenium(VI) and other forms of selenium in 0.5 mol/l sodium chloride could be carried out successfully by the proposed procedures. However, in the case of estuarial sea water containing a large quantity of organic substances, selenium(IV) could not be separated, because organic substances interfered with the reduction of selenium(VI) to selenium(IV) by the use of hydrochloric acid. Selenium(IV) and total amount of selenium(VI) and other forms of selenium dissolved in polluted sea water samples were determined by the proposed procedures.

Development of functional resins by modification of ion-exchange resins and their application to analytical chemistry

Some novel functional resins were developed for highly selective separation and/or determination of mercury, selenium, fluoride and hydrogen peroxide, by simple modification of common ion—exchange resin with appropriate reagents. These reagents should have three functional properties, namely selective reaction with the determinant of interest, an ion—exchange reaction with the resin and physical adsorption on the ion—exchange resin matrix. These functional resins were applied to the analysis of some environmental water samples and satisfactory results were obtained.

Hydroxamamide as a chelating moiety for the preparation of 99mTc-radiopharmaceuticals III. Characterization of various 99mTc-hydroxamamides

Abstract Five hydroxamamide (Ham) derivatives with various nonpolar substituents and different lipophilicities have been selected as ligands for preparation of 99m Tc-complexes. Analysis via high performance liquid chromatography (HPLC) resolved the 99m Tc-complexes of each ligand into two radioactive components, which are considered as isomers. The stability of both components was studied at pH 5 and 7, showing good stability at pH 7, but some transition between the components at pH 5. Use of a mixture of two ligands for complexation showed not only the complexes of the separate ligands, but also complexes containing both ligands. These results indicate that hydroxamamides very likely form complexes composed of Ham and 99m Tc in a 2:1 molar ratio. This may also explain the stability of the 99m Tc-Ham complexes in spite of the bidentate character of a Ham ligand.

Separation and determination of selenium(IV) in environmental water samples by an anion-exchange resin modified with bismuthiol-II and diaminonaphthalene fluorophotometry

ZusammenfassungDas Selen wurde mit Hilfe eines mit Bismuthiol II modifizierten Anionenaustauschers angereichert und fluorometrisch bestimmt. Die Adsorption, die auf der Bildung eines stabilen Selentrisulfids beruht, ist sehr selektiv. Das Verfahren wurde mit gutem Erfolg zur Selenbestimmung in Fluß- und Abwasser eingesetzt.SummarySelenium(IV) in environmental water samples was determined fluorometrically following its collection by the use of a new functional resin. The resin was easily prepared from an anion-exchange resin by modification with bismuthiol II. A highly selective adsorption of selenium(IV) was achieved by the formation of stable selenotrisulfide from bismuthiol II and selenium(IV) on the resin. The method was successfully employed for the determination of Se in river water and waste water.

The development of 99mTc-analog of Cu-DTS as an agent for imaging hypoxia

Works on dithiosemicarbazone (DTS) derivatives radiolabeled with divalent Cu (Cu-62, Cu-64) indicate its potentiality as an ischemic tissue detecting agent. Development of analogous derivatives labeled with the more accessible technetium-99m (Tc) is most desirable. Various synthesized DTS derivatives are radiolabeled with a novel approach, using a macromolecular Sn(II)-complex under an anaerobic condition at pH 3.4-4.5 and stabilization by ascorbate solution at pH 6.7-7.0. Characterization of Tc-DTS derivatives done by various analytical methods (TLC, HPLC, EP, PC) and by in vivo studies in normal mice and in rats myocardial LAD (left anterior descent coronary artery) occlusion model. Among tested DTS, only Tc-ATSE, Tc-ATSM and Tc-ATSM(2) showed distinctive characteristics, with the latter presenting high myocardium uptake in regions of ischemia in LAD rat myocardium model. Potentiality of the Cu-DTS mimetic agent, Tc-ATSM(2) as an ischemia-damaged myocardium agent is discussed.

Sequential collection of selenium(IV) and selenium(VI) by the use of an anion-exchange resin loaded with bismuthiol-II sulphonic acid

A new ligand-loaded anion-exchange resin has been developed which allows determination of Se(VI) and Se(IV) in mixtures of the two. The ligand is a sulphonic acid derivative of bismuthiol-II.

The integrity of the disulfide bond in a cyclic somatostatin analog during 99mTc complexation reactions

Recent development of a variety of thiol-free chelating agents has facilitated the design of 99mTc-labeled somatostatin analogs suitable for receptor imaging of somatostatin-positive tumors. However, it remains ambiguous whether the disulfide bonds in cyclic peptides are stable during 99mTc complexation reactions, and contradictory results have been reported regarding the integrity of disulfide bonds in cyclic somatostatin analogs. To estimate the stability of the disulfide bond in a synthetic somatostatin analog at low peptide concentrations, [125I]I-RC-160, in which radioiodine was incorporated into the 3-Tyr residue, was synthesized and the integrity of the disulfide bond of the peptide was investigated in the presence of reducing agents such as ascorbic acid, dithionite, and stannous ions. The disulfide bond in [125I]I-RC-160 remained stable in the presence of ascorbic acid in boiling water. The disulfide bond was also stable when treated with stannous ions at concentrations sufficient to reduce 99mTc for complexation with a thiol-free chelating agent, bis(hydroxamamide) analog when the 99mTc complexation reaction was performed at room temperature. However, the disulfide bond of [125I]I-RC-160 was slightly cleaved in the presence of a small amount of stannous ions when the reaction was performed in boiling water. Treatment of [125I]I-RC-160 with dithionite in boiling water markedly reduced the disulfide bond of the parental peptide. These findings indicated that synthetic somatostatin analogs may be labeled with 99mTc with stannous ions as the reducing agent without impairing their structure after conjugation of thiol-free chelating agents that provide 99mTc chelates under mild reaction conditions.

Hydroxamamide as a chelating moiety for the preparation of 99Tcm radiopharmaceuticals. I

Hydroxamamides contain a nitrogen and an oxygen as donor atoms, and can be synthesized by the simple reaction of nitriles with hydroxylamine. Benzohydroxamamide (BHam) was investigated as a new ligand for 99Tcm. The yield of the 99Tcm-BHam complex was determined by thin-layer chromatography using cellulose strips. A high yield of the complex was obtained at room temperature over a wide pH range, even at BHam concentrations as low as 5 × 10-7 M. Cellulose acetate electrophoresis indicated that the complex was uncharged. When the 99Tcm-BHam complex was injected into mice, it was cleared gradually from the blood by means of the hepatobiliary system with low urinary excretion. Uptake by the stomach and the spleen was low. These results demonstrate the high affinity of BHam for 99Tcm and the high stability of the 99Tcm-BHam complex. The hydroxamamide group may be a promising chelating moiety for designing new 99Tcm radiopharmaceuticals.