1.

論文

論文
早川, 和一 ; 山本, 敦 ; 宮崎, 元一
出版情報: 衛生化学 = Eisei kagaku.  40  pp.1-12,  1994-01-01.  日本薬学会 = The Pharmaceutical Society of Japan
URL: http://hdl.handle.net/2297/44934
概要: Ion chromatography (IC), which was introduced in 1975, has become widely used for the sensitive and simultaneous determination of ions. In the early stage, the IC system consisted of two ion-exchange columns (separator and suppressor, respectively) and a conductivity detector. Although this combination is still the most popular, new forms of separation and suppression have been developed. On the other hand, an indirect photometric detection using a UV detector has become popular in IC and other detectors commonly used in HPLC also have been used. Each of them has specific advantages for different types of analyses. Thus, IC is now defined as a form of liquid chromatography of ions. This article reviews new developments of the different forms of IC and their applications, especially to environmental samples, foods, biological materials and drugs, from reports published since 1990. 続きを見る
2.

論文

論文
早川, 和一 ; 宮崎, 元一
出版情報: 衛生化学 = Eisei kagaku.  34  pp.210-224,  1988-01-01.  日本薬学会 = The Pharmaceutical Society of Japan
URL: http://hdl.handle.net/2297/44916
概要: Ion chromatography (IC) with conductivity detection, which was introduced in 1975, has become widely used for the simultaneous determination of inorganic and organic ions. On the other hand, photometric ion chromatography (PIC) based on the difference of absorbances of sample and eluent (mobile phase) species has attracted much attention in the recent field of IC, since this technique has potential advantages over IC methods with conductivity detection. This technique which allows IC on a conventional single column HPLC system with an absorbance detector gives compatible sensitivity to conductivity detection. This paper deals mainly with indirect PIC methods performed by both ion exchange and reversedphase modes, where non-UV-absorbing ions are detected as positive and negative peaks by using UV-absorbing ions in the eluent (mobile phase). The features of PIC have been reasonably well known, but it is necessary to understand principles and conditions of PIC for the effective use of this technique. This paper reviews a number of significant reports which deal with the optimisations of separating column, eluent (mobile phase), detection wavelength, sensitivity and restrictions of PIC with its applications. It is also the purpose of this paper to discuss alternative methods and innovations of PIC. 続きを見る
3.

論文

論文
早川, 和一 ; 山本, 敦
出版情報: 分析化学 = Japan analyst.  44  pp.417-436,  1995-06-05.  The Japan Society for Analytical Chemistry = 日本分析化学会
URL: http://hdl.handle.net/2297/24839
概要: 金沢大学医薬保健研究域薬学系<br />これまで, 液体クロマトグラフィーにおける吸光度検出器は専ら光吸収を有する化合物を検出する装置であり, その原理と検出器は既に完成されたものとの印象が強かった.本総説は, 上述の概念を大き く変革しつつある吸光度検出法の新展開として, 光吸収のない対象物質を検出できる間接吸光度検出法と, 更にその考え方を光学活性物質の検出に向けた偏光吸光度検出法に焦点を合わせ, 著者らの研究成果も含めて紹介する. New photometric detection methods developed for use in liquid chromatography have been reviewed. Differential photometric detection using UV-visible absorbing modifiers enabled us to examine the retention and detection mechanism of not only analytes but also mobile phases. Indirect photometric detection ion chromatography based on this theory separately and sensitively determines ionic compounds using a conventional high-performance liquid chromatographic system with a UV-visible absorbance detector. This method is useful for many kinds of samples such as environmental water, foods and biological materials. Polarized photometric detection mathods with two polarizers on either side of a UV-visible absorbance detector flow cell have been developed. The monitor determines optically active compounds as the change in absorbance. This method was effectively applied for determining sugars and organic acids 続きを見る
4.

論文

論文
平山, 直樹
出版情報: 分析化学 = Japan analyst.  43  pp.255-256,  1994-03-05.  The Japan Society for Analytical Chemistry = 日本分析化学会
URL: http://hdl.handle.net/2297/25009
概要: 金沢大学理工研究域<br />Relationships between ion-chromatographic retention behaviors of several anions and their dissociat ion constants were studied from two standpoints. In Part 1,the influence of the dissociation equilibria on the measured capacity factor of a sample was interpreted. In this study, the ratio of the capacity factor of the sample to that of a standard anion was used for the analysis of the retention behavior. The dissociation constants and the ratio of the capacity factors of various species of the sample to that of the standard were calculated and the retention behavior was estimated. In Part 2,the differences in the retention times of substituted benzoate anions having similar structure were analyzed by dividing the substituent effect into an LFER-applicable effect term, a steric effect term and a positional effect correction term. The first was introduced by putting the theory of linear free energy relationships into the relationship between the anion-exchange equilibria and the dissociation equilibria. The second depends on kind and number of the introduced substituents, and the last on the position of them. Furthermore, the estimation of the retention times of these anions and the determination of the dissociation constants of substituted naphthoic acids were done. 続きを見る
5.

論文

論文
平山, 直樹
出版情報: 分析化学 = Japan analyst.  48  pp.33-43,  1999-01-05.  The Japan Society for Analytical Chemistry = 日本分析化学会
URL: http://hdl.handle.net/2297/25008
概要: 金沢大学理工研究域<br />2-ピリジルメチル基や1-ピラゾリルメチル基, 2-ヒドロキシフェニルメチル基などの"芳香環ペンダントアーム(pendantarm)"を複数有する多座配位子の, 陽イオン分離や陰 イオン分離への分析化学的利用可能性について, 各種の基礎的な検討を行った. これらの配位子は疎水性や電子的効果, 構造的剛直性, 立体的選択性などに関し, 芳香環ペンダントアームに基因する特異性を有するため, 各種金属イオンの抽出分離において, 従来の抽出試薬とは異なる選択性を示した. 例えば, N,N-ビス(2-ヒドロキシフェニルメチル)-N,N'-ビス(2-ピリジルメチル)エチレンジアミン(H_2bbpen)による二価遷移金属イオンのキレート抽出選択性はIrving-Williams則に従わず, 配位子の空孔サイズに基づくイオンサイズ認識が行われていることが示唆された. 又, N,N'-ビス(5-ニトロサリチリデン)エチレンジアミン(H_2Nsalen)による三価ランタノイドイオンの抽出では, 配位子の構造的剛直性に基づく高い相互分離能が実現された. 更に, 各種金属イオンと強く錯形成したビス(2-ピリジルメチル)アミノ基(bpa-基)をイオンクロマトグラフィーの固定相陰イオン交換基として用いると, イオン交換と配位子交換の2種類の相互作用の併存により, 陰イオンのクロマトグラフ分離において, 溶出順序の反転など従来とは異なる分離機能が実現された. The analytical use of polydentate ligands having plural "aromatic-ring pendant arms," such as 2-pyridylmethyl, 1-pyrazolylmethyl and 2-hydroxyphenylmethyl groups, for not only the separation of cations, but also that of anions, was investigated fundamentally. These ligands generally have a specific nature at many points, such as hydrophobicity, electric effects, structural rigidity and sterical selectivity, originating from the aromatic-ring pendant arms; also, upon the mutual separation of many kinds of metal cations by solvent extraction they can act as extraction reagents having specific reaction selectivity. As one example, the extraction selectivity of divalent transition metal cations using N,N'-bis(2-hydroxyphenylmethyl)-N,N'-bis(2-pyridylmethyl)-1,2-ethanediamine (H_2bbpen) did not agree with the Irving-Williams series of stability; it was suggested that ion-size recognition based on the cavity size of the ligand acted in this extraction system. Upon the extraction of trivalent lanthanoids, as another example, N,N'-bis(5-nitrosalicylidene)-1,2-ethanediamine (H_2Nsalen) showed high performance for their mutual separation, originating from the structural ligidity of the ligand. Furthermore, an immobilized charged complex between bis(2-pyridylmethyl)amino group (bpa-group) and a metal cation was useful as an anion-exchange group in ion chromatography, having specific anion selectivity originating from its additional ligand-exchange ability. 続きを見る