Updated on 2021/06/22

写真b

 
MIYABE Kanji
 
*Items subject to periodic update by Rikkyo University (The rest are reprinted from information registered on researchmap.)
Affiliation*
College of Science Department of Chemistry
Graduate School of Science Field of Study: Chemistry
Graduate School of Science Field of Study: Chemistry
Title*
Professor
Degree
博士(工学) ( 東京大学 )
Research Theme*
  • 分析化学、分離化学。高速液体クロマトグラフィー及びキャピラリー電気泳動法の新たな解析体系(モーメント理論、実験法や解析手順)を構築し、分離系の特性や機構を解明する。流通式実験法を化学反応(分子間相互作用)や物質移動(分子集合体界面における物質透過)現象の速度解析法へと展開すると共に、特徴的な構造特性を有する分離剤や新規分離システムの開発による分離系の高性能化や高機能化についても研究を行っている。

  • Research Interests
  • Separation Chemistry

  • Analytical Chemistry

  • Chromatography

  • Campus Career*
    • 4 2012 - Present 
      College of Science   Department of Chemistry   Professor
    • 4 2012 - Present 
      Graduate School of Science   Field of Study: Chemistry   Professor
    • 4 2012 - Present 
      Graduate School of Science   Field of Study: Chemistry   Professor
     

    Research Areas

    • Nanotechnology/Materials / Analytical chemistry

    Research History

    • 4 2012 - Present 
      RIKKYO UNIVERSITY   Graduate School of Science Field of Study: Chemistry   Professor

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    • 4 2012 - Present 
      RIKKYO UNIVERSITY   College of Science Department of Chemistry   Professor

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    • 4 2012 - Present 
      RIKKYO UNIVERSITY   Graduate School of Science Field of Study: Chemistry   Professor

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    • 4 2012 - Present 
      The University of Toyama   Professor Emeritus

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    • 4 2004 - 3 2012 
      University of Toyama   Graduate School of Science and Engineering

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    • 12 2002 - 3 2004 
      Nagoya Institute of Technology   Graduate School of Engineering

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    • 10 1995 - 11 2002 
      University of Toyama

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    • 4 1998 - 8 1999 
      テネシー大学   化学科   博士研究員

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    • 4 1982 - 9 1995 
      栗田工業株式会社   主任研究員

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    • 4 1990 - 3 1992 
      The University of Tokyo   Institute of Industrial Science

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    Education

    • - 3 1982 
      University of Toyama   Graduate School, Division of Natural Science

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      Country: Japan

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    • - 3 1982 
      University of Toyama   Graduate School, Division of Natural Science

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      Country: Japan

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    • - 3 1980 
      University of Toyama   Faculty of Liberal Arts and Science (Natural Sciences)

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      Country: Japan

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    Committee Memberships

    • 1 2012 - Present 
      クロマトグラフィー科学会   評議員

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      Committee type:Academic society

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    • 4 2011 - Present 
      日本吸着学会   学会誌編集委員

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      Committee type:Academic society

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    • 4 2003 - Present 
      日本吸着学会   評議員

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      Committee type:Academic society

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    • 4 2011 - 9 2012 
      日本分析化学会   日本分析化学会第61年会実行委員

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      Committee type:Academic society

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    • 4 2007 - 3 2012 
      化学工学会   関西支部北陸地区装置懇話会理事

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      Committee type:Academic society

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    • 1 2008 - 12 2011 
      クロマトグラフィー科学会   学会誌編集委員長

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    • 1 2004 - 12 2011 
      クロマトグラフィー科学会   理事

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      Committee type:Academic society

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    • 4 2010 - 3 2011 
      日本分析化学会   中部支部副支部長

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      Committee type:Academic society

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    • 4 2010 - 3 2011 
      化学工学会   代議員

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      Committee type:Academic society

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    • 4 2008 - 3 2010 
      日本分析化学会   中部支部常任幹事

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      Committee type:Academic society

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    • 4 2007 - 3 2009 
      化学工学会   関西支部幹事

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      Committee type:Academic society

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    • 12 2008 
      クロマトグラフィー科学会   HPLC2008 Kyoto実行委員

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    • 11 2008 
      日本分析化学会   中部支部第18回基礎及び最新の分析化学講習会実行委員長

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    • 4 2006 - 3 2008 
      化学工学会   人材育成センター資格制度試験委員会A委員

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      Committee type:Academic society

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    • 8 2007 
      日本分析化学会   中部支部夏期セミナー実行委員

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    • 5 2007 
      クロマトグラフィー科学会   第14回クロマトグラフィーシンポジウム実行委員長

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    • 1 2002 - 12 2003 
      クロマトグラフィー科学会   評議員

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      Committee type:Academic society

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    • 4 2002 - 9 2002 
      日本分析化学会   中部支部常任幹事

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      Committee type:Academic society

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    • 4 2001 - 3 2002 
      日本分析化学会   中部支部幹事

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      Committee type:Academic society

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    • 8 2000 
      日本分析化学会   中部支部若手交流会実行委員長

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      Committee type:Academic society

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    • 9 1996 
      日本分析化学会   中部支部夏期セミナー実行委員

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    Awards

    • 11 2009  
      クロマトグラフィー科学会  平成21年度クロマトグラフィー科学会学会賞 (モーメント理論に基づくクロマトグラフィー挙動解析法の開発) 
       
      宮部寛志

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      Award type:Award from Japanese society, conference, symposium, etc.  Country:Japan

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    • 5 2000  
      富山県未来財団  平成12年度とやま賞(学術研究部門) (液体クロマトグラフィー系における物質移動機構の解明に関する研究) 
       
      宮部寛志

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      Award type:Award from publisher, newspaper, foundation, etc.  Country:Japan

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    • 1 1997  
      日本分析化学会液体クロマトグラフィー研究懇談会  1997年液体クロマトグラフィー努力賞 (逆相液体クロマト分離系における物質移動現象の解析) 
       
      宮部寛志

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      Award type:Award from Japanese society, conference, symposium, etc.  Country:Japan

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    • 11 1995  
      日本吸着学会  平成7年度日本吸着学会奨励賞 (逆相液体クロマト分離に関する研究) 
       
      宮部寛志

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      Award type:Award from Japanese society, conference, symposium, etc.  Country:Japan

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    Papers

    • Kinetic Study of Chiral Intermolecular Interactions by Moment Analysis Based on Affinity Capillary Electrophoresis Peer-reviewed

      Suzuki, N, Kinoshita, M, Miyabe, K

      Anal. Chem.90   11048 - 11053   2018

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      Language:English   Publishing type:Research paper (scientific journal)  

      DOI: 10.1021/acs.analchem.8b02823

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    • Moment Analysis for Mass Transfer Kinetics at the Interface of Spherical Molecular Aggregates Peer-reviewed

      Miyabe, K

      J. Chromatogr. A1572   172 - 178   2018

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      Language:English   Publishing type:Research paper (scientific journal)  

      DOI: 10.1016/j.chroma.2018.08.036

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    • Moment Analysis for Reaction Kinetics of Intermolecular Interactions Peer-reviewed

      Miyabe, K

      Electrophoresis39   3032 - 3039   2018

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      Language:English   Publishing type:Research paper (scientific journal)  

      DOI: 10.1002/elps.201800218

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    • Moment analysis of mass transfer kinetics in micellar electrokinetic chromatography systems Peer-reviewed

      Kanji Miyabe, Nozomu Suzuki

      Analytical Sciences34 ( 2 ) 215 - 220   2018

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      Language:English   Publishing type:Research paper (scientific journal)   Publisher:Japan Society for Analytical Chemistry  

      Moment equations were developed for quantitatively studying the separation characteristics of micellar electrokinetic chromatography (MEKC). They explain how the first absolute and second central moments of elution peaks are correlated with some fundamental parameters of the partition equilibrium and mass transfer kinetics in MEKC systems. In order to discuss the influence of the mass transfer kinetics on peak broadening, the moment equations were used to analyze the separation behavior in MEKC systems. Separation conditions were chosen on the basis of practical MEKC experiments previously conducted. It was quantitatively clarified that both the solute permeation at the interfacial boundary of surfactant micelles and axial diffusion of solute molecules in a capillary had a predominant contribution to the spreading of the elution peaks in MEKC systems. This is a preliminary study for the analytical determination of rate constants concerning solute permeation at the interface of surfactant micelles from elution peak profiles measured by MEKC. In addition, it was also indicated that the experimental conditions of MEKC systems could be controlled so that the interfacial solute permeation would have a predominant role for the band broadening. For example, the contribution of the interfacial permeation was about 33 times larger than that of the axial diffusion of solute molecules under the MEKC conditions in a previous study. This means that the rate constants could appropriately be determined for the interfacial solute permeation.

      DOI: 10.2116/analsci.34.215

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    • Numerical Correction for Asymmetrical Peak Profiles for Moment Analysis of Chromatographic Behavior Peer-reviewed

      Miyabe, K

      J. Chromatogr. A1567   155 - 163   2018

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      Language:English   Publishing type:Research paper (scientific journal)  

      DOI: 10.1016/j.chroma.2018.06.067

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    • Evaluation of Migration Time and Variance for Accurate Kinetic Studies Based on Affinity Capillary Electrophoresis Peer-reviewed

      Nozomu Suzuki, Kanji Miyabe

      ANALYTICAL CHEMISTRY89 ( 19 ) 10487 - 10495   10 2017

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      Language:English   Publishing type:Research paper (scientific journal)   Publisher:AMER CHEMICAL SOC  

      Affinity capillary electrophoresis (ACE) has been widely applied to evaluate binding constants of various systems. Recently, moment equations were derived based on the moment analysis (MA) theory for describing the influence of reaction kinetics and longitudinal diffusion on the elution peak profiles measured by ACE (MA-ACE). The equations enable one to obtain not only the binding constants but also the reaction rate constants from the migration time and variance of elution peaks. However, it is necessary to consider other factors (e.g., sample injection, detector window, Joule heating, and ramp time of the voltage increase) to improve the accuracy of MA-ACE. The variance of these effects was quantified under typical experimental conditions. Such quantification clarified the process to obtain the rate constants. The best experimental conditions to achieve high accuracy were discussed.

      DOI: 10.1021/acs.analchem.7b02598

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    • Moment Analysis Theory for Size Exclusion Capillary Electrochromatography with Chemical Reaction of Intermolecular Interaction Peer-reviewed

      Kanji Miyabe, Nozomu Suzuki

      ANALYTICAL SCIENCES33 ( 10 ) 1147 - 1154   10 2017

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      Language:English   Publishing type:Research paper (scientific journal)   Publisher:JAPAN SOC ANALYTICAL CHEMISTRY  

      New moment equations were developed for size exclusion capillary electrochromatography (SECEC), in which intermolecular chemical reactions simultaneously took place. They explain how the first absolute and second central moments of elution peaks are correlated with some fundamental equilibrium and kinetic parameters of mass transfer and chemical reaction in SECEC column. In order to demonstrate the effectiveness of the moment equations, they were used to predict chromatographic behavior under hypothetical SECEC conditions. It was quantitatively studied how the association and dissociation rate constants of intermolecular interaction affected the position and spreading of elution peaks. It was indicated that both the intermolecular reaction kinetics and axial dispersion of solute molecules in a capillary column had a predominant contribution to the band broadening.

      DOI: 10.2116/analsci.33.1147

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    • Determination of Association and Dissociation Rate Constants in an Inclusion Complex System between Thymol and Sulfated-beta-cyclodextrin by Moment Analysis - Affinity Capillary Electrophoresis Peer-reviewed

      Kanji Miyabe, Nozomu Suzuki, Youki Shimazaki

      BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN89 ( 10 ) 1219 - 1224   10 2016

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      Language:English   Publishing type:Research paper (scientific journal)   Publisher:CHEMICAL SOC JAPAN  

      The combination of moment analysis (MA) theory with affinity capillary electrophoresis (ACE) leads to a new method (MA-ACE) for the kinetic study of intermolecular interaction. The reaction rate constants, i.e., association (k(a)) and dissociation (k(d)) rate constants, can be analytically determined by the MA theory from the first absolute and second central moments of the elution peaks measured by ACE. In order to verify the validity of the MA-ACE method, the values of ka and kd were analytically determined for the formation and dissociation of the inclusion complex between thymol and sulfated-beta-cyclodextrin. The resulting values of k(a) and k(d) were comparable with those in our previous study, which were determined by chromatographic capillary electrophoresis with the MA theory. It was demonstrated that the MA-ACE method was effective for the kinetic study of intermolecular interactions. The rate constants can be analytically determined with no immobilization and no chemical modification, i.e., fluorescence labelling, of solute and ligand molecules.

      DOI: 10.1246/bcsj.20160193

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    • Kinetic Study of Solute Permeation across Surfactant Micelle/Bulk Solvent Interface by Moment Analysis - Chromatographic Capillary Electrophoresis (MA-CCE) Peer-reviewed

      Kanji Miyabe, Nozomu Suzuki

      BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN89 ( 10 ) 1212 - 1218   10 2016

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      Language:English   Publishing type:Research paper (scientific journal)   Publisher:CHEMICAL SOC JAPAN  

      We applied moment analysis (MA) with chromatographic capillary electrophoresis (CCE) to the analytical determination of rate constants (kin and kat) of solute permeation at the interface between a bulk solvent and surfactant micelles. CE experiments were carried out in the MEKC system using thymol and sodium dodecylsulfate (SDS) as the solute and surfactant, respectively, under CCE conditions. In CCE mode, experimental conditions are controlled so that the migration of micelles, which dissolve single or plural solute molecules, is stopped in the axial direction of a capillary. Only solute molecules migrate in the capillary and are detected to record elution peak profiles. The mass-transfer kinetics of solute molecules in the capillary are determined from the elution peak profiles by the MA theory. The values of k(in) and k(out) were respectively determined as 1.5 x 10(-6) and 2.6 x 10(-9)m s(-1) for the permeation of thymol molecules at the interfacial boundary of SDS micelle. It was demonstrated that MA-CCE was effective for the kinetic study of solute permeation across the interface between a bulk solvent and spherical molecular aggregates, e.g., surfactant micelles.

      DOI: 10.1246/bcsj.20160185

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    • Moment Analysis Theory for Kinetic Study of Intermolecular Interaction by Affinity Capillary Electrophoresis Peer-reviewed

      Kanji Miyabe, Nozomu Suzuki

      BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN89 ( 7 ) 746 - 753   7 2016

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      Language:English   Publishing type:Research paper (scientific journal)   Publisher:CHEMICAL SOC JAPAN  

      The moment analysis (MA) theory was introduced into the analysis of elution peak profiles measured by affinity capillary electrophoresis (ACE). New moment equations were developed, which were essential for analytically determining the association (k(a)) and dissociation (k(d)) rate constants of intermolecular interactions from the ACE data. The combination of the MA theory and ACE procedure leads to a method for the kinetic study of intermolecular interactions (MA-ACE). Because ACE has quite frequently been used for determining binding (association equilibrium) constants of intermolecular interactions, it must be important that k(a) and k(d) can also be determined from ACE elution peaks. An attempt was made to analyze ACE elution peaks in a published paper by the MA method to determine the rate constants. The values of k(a) and k(d) were analytically determined for the intermolecular interaction between three boronic acids and fructose. They were comparable with those determined by the other method based on the macroscopic approach for studying kinetics at equilibrium. It was demonstrated that the MA method was effective for extracting information about affinity kinetics of intermolecular interactions from elution peaks measured by ACE. This means that the MA method makes it possible to use ACE data previously published as a source for kinetic study of intermolecular interactions.

      DOI: 10.1246/bcsj.20160068

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    • Moment Analysis of Affinity Kinetics in Inclusion Complex System between Thymol and Sulfated-beta-cyclodextrin by Chromatographic Capillary Electrophoresis (CCE) Peer-reviewed

      Kanji Miyabe, Youki Shimazaki

      BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN88 ( 11 ) 1603 - 1611   11 2015

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      Language:English   Publishing type:Research paper (scientific journal)   Publisher:CHEMICAL SOC JAPAN  

      We developed a capillary electrophoretic (CE) method for the kinetic study of intermolecular interactions. Neither immobilization nor chemical modification, e.g., fluorescence labelling, of solute and ligand molecules is required. A concept of chromatographic capillary electrophoresis (CCE) was introduced as an experimental CE procedure. In the CCE mode, the migration of solute ligand complex in a capillary is stopped. Only solute molecules migrate and are detected. New moment equations were developed, which were essential for determining association and dissociation rate constants from elution peak profiles measured under the CCE conditions. The combination of the CCE concept and the moment theory leads to the CE method, i.e., moment analysis by CCE (MACCE). However, because it was hard to really perform CE experiments under the CCE conditions, we also developed practical experimental and data analysis procedures for the MACCE measurement. The reaction rate constants were analytically determined by the MACCE method for the formation and dissociation of the inclusion complex between thymol and sulfated-beta-cyclodextrin. It is unnecessary to fit elution curves numerically calculated to those experimentally measured for determining the rate constants. It was demonstrated that the MACCE method was effective for the kinetic study of intermolecular interactions.

      DOI: 10.1246/bcsj.20150203

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    • Kinetic Study of Interaction between Solute Molecule and Surfactant Micelle Peer-reviewed

      Kanji Miyabe, Ryohei Takahashi, Youki Shimazaki

      ANALYTICAL SCIENCES31 ( 10 ) 1019 - 1025   10 2015

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      Language:English   Publishing type:Research paper (scientific journal)   Publisher:JAPAN SOC ANALYTICAL CHEMISTRY  

      We developed moment analysis of affinity kinetics by chromatographic capillary electrophoresis (MKCCE) method for the kinetic study of intermolecular interactions. Association and dissociation rate constants of the interaction in a micellar electrokinetic chromatography (MEKC) system between thymol and sodium dodecylsulfate micelle were determined by the MKCCE method. It is a method based on the moment theory for the kinetic study of intermolecular interactions under the conditions that neither immobilization nor chemical modification of molecules is required. In CCE mode, experimental conditions are controlled so that the migration of solute-micelle complex is stopped and only solute molecules migrate in a capillary. Mass transfer behavior of solute molecules in the CCE system is analogous to that in a chromatographic system. However, because it was difficult in practice to really perform CE experiments under the CCE conditions, CE data were measured with changing experimental conditions, i.e., applied pressure, under the conditions that the migration velocity of solute-micelle complex was around zero. The rate constants could be analytically determined from the CE data. In the MKCCE method, it is not necessary to fit elution curves numerically calculated to those experimentally measured for the determination of the rate constants. Regarding the interaction between thymol and SDS association equilibrium constant and association and dissociation rate constants were determined as 6.35 x 10(3) dm(3) mol(-1), 5.6 x 10(4) dm(3) mol(-1) s(-1), and 8.7 s(-1), respectively. It was demonstrated that the MKCCE method was effective for the kinetic study of intermolecular interactions.

      DOI: 10.2116/analsci.31.1019

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    • Kinetic Study of the Intermolecular Interaction between 2-Phenoxypropionic Acid and beta-Bromo-cyclodextrin Affixed on the Stationary Phase by Liquid Chromatography Peer-reviewed

      Kanji Miyabe, Satoshi Kamiya

      ANALYTICAL SCIENCES31 ( 8 ) 743 - 749   8 2015

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      Language:English   Publishing type:Research paper (scientific journal)   Publisher:JAPAN SOC ANALYTICAL CHEMISTRY  

      The intermolecular interaction between 2-phenoxypropionic acid and beta-bromo-cyclodextrin affixed on the stationary phase surface in a chiral HPLC system was studied by the moment analysis method. At first, pulse response and peak parking experiments were conducted to measure some parameters concerning the column geometry, adsorption equilibrium, and mass-transfer kinetics. Then, the first absolute moment (mu(1)) and second central moment (mu(2)') of the elution peaks were analyzed by the moment equations, which were developed by assuming that the reaction kinetics between the solute molecules and the functional ligands can be represented by the Langmuir-type rate equation. Finally, the flow-rate dependence of HETP calculated from mu(1) and mu(2)' was analyzed by using the values of the parameters to determine the association and dissociation rate constants of the intermolecular interaction. It was demonstrated that the combination of the chromatographic experiments and moment analysis is one of the effective strategies for the kinetic study of intermolecular interactions.

      DOI: 10.2116/analsci.31.743

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    • Moment equations for chromatography based on Langmuir type reaction kinetics Peer-reviewed

      Kanji Miyabe

      JOURNAL OF CHROMATOGRAPHY A1356   171 - 179   8 2014

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      Language:English   Publishing type:Research paper (scientific journal)   Publisher:ELSEVIER SCIENCE BV  

      Moment equations were derived for chromatography, in which the reaction kinetics between solute molecules and functional ligands on the stationary phase was represented by the Langmuir type rate equation. A set of basic equations of the general rate model of chromatography representing the mass balance, mass transfer rate, and reaction kinetics in the column were analytically solved in the Laplace domain. The moment equations for the first absolute moment and the second central moment in the real time domain were derived from the analytical solution in the Laplace domain. The moment equations were used for predicting the chromatographic behavior under hypothetical HPLC conditions. The influence of the parameters relating to the adsorption equilibrium and to the reaction kinetics on the chromatographic behavior was quantitatively evaluated. It is expected that the moment equations are effective for a detailed analysis of the influence of the mass transfer rates and of the Langmuir type reaction kinetics on the column efficiency. (C) 2014 Elsevier B.V. All rights reserved.

      DOI: 10.1016/j.chroma.2014.06.052

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    • Moment Analysis of Chromatographic Behavior of Separation Media for Fast HPLC Peer-reviewed

      Kanji Miyabe, Yuhi Murata

      ANALYTICAL SCIENCES30 ( 2 ) 277 - 283   2 2014

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      Language:English   Publishing type:Research paper (scientific journal)   Publisher:JAPAN SOC ANALYTICAL CHEMISTRY  

      The van Deemter equation and moment equations were used for analyzing the flow rate dependence of HETP experimentally measured in order to clarify chromatographic behavior from the kinetic points of view in columns packed with C-18-silica monolith and C-18-core-shell particles under RPLC conditions. They provided some information about molecular diffusion, eddy diffusion, and mass transfer kinetics in the columns. Additionally, the value of intra-stationary phase diffusivity was determined in the range of 10(-7) - 10(-6) cm(2) s(-1) by the moment analysis. Information about the contribution of the mass transfer resistance in the external liquid film around the stationary phase to HETP was also obtained. Its contribution increases with an increase in the flow velocity of the mobile phase. It was concluded that the moment equations can provide more detailed information about the kinetic behavior in the columns than the van Deemter equation.

      DOI: 10.2116/analsci.30.277

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    • Estimation of Molecular Diffusivity in Liquid Phase Systems on the Basis of the Absolute Rate Theory Peer-reviewed

      Kanji Miyabe, Ryo Isogai

      ANALYTICAL SCIENCES29 ( 4 ) 467 - 472   4 2013

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      Language:English   Publishing type:Research paper (scientific journal)   Publisher:JAPAN SOC ANALYTICAL CHEMISTRY  

      This study was concerned about an estimation of molecular diffusivity (D-m) in liquid phase systems. An equation based on the absolute rate theory of diffusion was derived by considering the aggregation of not only solvent molecules, but also solute molecules. It was also studied how the replacement of the molar volume of a solvent with its molecular weight influences the accuracy in estimating D-m. The values of D-m estimated by the equation were compared with those experimentally measured. The mean square deviation for the estimation of D-m was calculated as being about 14% for 217 D-m data measured in aqueous solutions of methanol and acetonitrile, which is comparable to that obtained by the Wilke-Chang equation. However, D-m of some solutes in carbon tetrachloride was more accurately estimated by this equation than by the Wilke-Chang equation. It is expected that the equation proposed in this study is effective for estimating D-m in liquid phase systems.

      DOI: 10.2116/analsci.29.467

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    • Measurement of Pore Diffusivity in Separation Media for High Performance Liquid Chromatography Peer-reviewed

      Kanji Miyabe, Yuko Matsumoto, Nobuho Ando, Yumi Teratani

      ANALYTICAL SCIENCES29 ( 3 ) 315 - 323   3 2013

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      Language:English   Publishing type:Research paper (scientific journal)   Publisher:JAPAN SOC ANALYTICAL CHEMISTRY  

      It was demonstrated that the peak parking-moment analysis (PP-MA) method could be used as an alternative for the measurement of pore diffusivity (D-p) in porous packing materials for HPLC. The value of D-p of uracil was measured by the PP-MA method under non-retained conditions in the RPLC systems using C-18-silica gel particles and C-18-silica monolith as the stationary phase and 70 vol% methanol as the mobile phase. The value of D-p was compared with that derived by the pulse response-moment analysis (PR-MA) method under the same conditions. The D-p values of uracil derived by the PP-MA and PR-MA methods were almost in agreement with each other. Because the PP-MA and PR-MA methods have complementary characteristics as experimental methods for studying mass transfer kinetics, it is expected that the combination of the two methods would lead to an effective strategy for the measurement of Dp in porous separation media for HPLC.

      DOI: 10.2116/analsci.29.315

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    • Moment Analysis of Chromatographic Behavior of Superficially Porous Particles Peer-reviewed

      Kanji Miyabe, Kazuhiro Noiri, Kouki Kobayashi

      ANALYTICAL SCIENCES27 ( 11 ) 1097 - 1105   11 2011

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      Language:English   Publishing type:Research paper (scientific journal)   Publisher:JAPAN SOC ANALYTICAL CHEMISTRY  

      Peak parking experiments were conducted to study the chromatographic behavior in a RPLC system consisting of a column packed with superficially porous C(18)-particles and a mixture of methanol and water (70/30, v/v). The values of the surface diffusion coefficient and the retention equilibrium constant of a column packed with superficially porous C(18)-particles were comparable to those of columns packed with a C(18)-silica monolith and full-porous C(18)-silica gel particles. The flow-rate dependence of HETP was hypothetically calculated by using moment equations to clarify the influence of the structural characteristics on the chromatographic behavior. The column efficiency of a column packed with the superficially porous particles is higher in the high flow-rate range than that with full-porous spherical particles. This is attributed to the smaller contribution of the intraparticulate mass transfer in the superficially porous particles to band broadening. The moment equations are effective for the quantitative analysis of chromatographic behavior of superficially porous particles.

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    • Estimation of Molecular Diffusivity in Aqueous Solution of Acetonitrile by the Wilke-Chang Equation Peer-reviewed

      Miyabe, K

      J. Sep. Sci.34   2674 - 2679   10 2011

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      Language:English   Publishing type:Research paper (scientific journal)  

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    • Moment Equations for Chromatography Using Superficially Porous Spherical Particles Peer-reviewed

      Kanji Miyabe

      ANALYTICAL SCIENCES27 ( 10 ) 1007 - 1017   10 2011

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      Language:English   Publishing type:Research paper (scientific journal)   Publisher:JAPAN SOC ANALYTICAL CHEMISTRY  

      New moment equations were developed for chromatography using superficially porous (shell-type) spherical particles, which have recently attracted much attention as one of separation media for fast separation with high efficiency. At first, the moment equations of the first absolute and second central moments in the real time domain were derived from the analytical solution in the Laplace domain of a set of basic equations of the general rate model of chromatography, which represent the mass balance, mass-transfer rate, and reaction kinetics in the column packed with shell-type particles. Then, the moment equations were used for analyzing the experimental data of chromatography of kallidin in a Halo column, which were published in a previous paper written by other researchers. It was tried to predict the chromatographic behavior of shell-type particles having different shell thicknesses. The new moment equations are useful for a detailed analysis of the chromatographic behavior of shell-type spherical particles. It is also concluded that they can be used for the preliminarily optimization of their structural characteristics.

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    • Estimation of molecular diffusivity in liquid phase systems by the Wilke-Chang equation Peer-reviewed

      Kanji Miyabe, Ryo Isogai

      JOURNAL OF CHROMATOGRAPHY A1218 ( 38 ) 6639 - 6645   9 2011

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      Language:English   Publishing type:Research paper (scientific journal)   Publisher:ELSEVIER SCIENCE BV  

      This study deals with the application of the Wilke-Chang equation to the estimation of molecular diffusivity (D(m)) in liquid phase systems including polar solutes and/or solvents. First, D(m) of benzene in six different organic solvents was experimentally measured by the peak parking method. The value of association coefficient (alpha) was calculated from the D(m) values by assuming that D(m) can be represented by the Wilke-Chang equation. Then, them alpha value was correlated with the solubility parameter (delta) and E(T) of the solvents. Two different curved correlations were observed between alpha and the two physico-chemical parameters. This means that alpha of given solutes and solvents can be obtained from the values of delta and/or E(T). Finally, D(m) was estimated by a modified Wilke-Chang equation, which is derived by considering the aggregation of not only solvent molecules but also solute molecules. Although alpha is necessary for the estimation, it was calculated from delta for various solutes and solvents. The D(m) values estimated were compared with those reported in literature. The mean square deviation between the D(m) values was calculated less than 19% for 71 D(m) data. It was demonstrated that the modified Wilke-Chang equation can be used for estimating D(m) in liquid phase systems containing polar solutes and solvents. (C) 2011 Elsevier B.V. All rights reserved.

      DOI: 10.1016/j.chroma.2011.07.018

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    • Extrathermodynamic Study of Retention Equilibrium in RP-LC Using a C-18-Silica Monolithic Stationary Phase Peer-reviewed

      Kanji Miyabe, Akane Matsushima

      CHROMATOGRAPHIA74 ( 3-4 ) 179 - 187   8 2011

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      Language:English   Publishing type:Research paper (scientific journal)   Publisher:SPRINGER HEIDELBERG  

      This study is concerned with the explanation of some thermodynamic properties of the retention equilibrium on a C-18-silica monolithic column. Pulse response experiments were carried out in a reversed-phase liquid chromatography system using a methanol/water mixture (70/30, v/v) and n-alkylbenzene homologs as the mobile phase and sample compounds, respectively, in the temperature range between 278 and 318 K. The retention equilibrium constant (K-a) was calculated from the first absolute moment of elution peaks. The dependence of K-a on the column temperature was analyzed using the modified van't Hoff plot proposed by Krug et al. to derive the changes of the Gibbs free energy, the enthalpy and the entropy concerning the retention behavior. First, the presence of a real enthalpy-entropy compensation (EEC) for the retention equilibrium was demonstrated. Then, a thermodynamic model based on the real EEC was developed to explain the temperature dependence of the linear free energy relationship (LFER) of the retention equilibrium. The model indicates how the slope and intercept of the LFER are correlated with the compensation temperatures and several molecular thermodynamic parameters. The model was effective for explaining the thermodynamic properties of the retention equilibrium of the C18-silica monolithic stationary phase.

      DOI: 10.1007/s10337-011-2062-y

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    • Monolithic silica rod columns for high-efficiency reversed-phase liquid chromatography Peer-reviewed

      Shota Miyazaki, Masakazu Takahashi, Masayoshi Ohira, Hiroyuki Terashima, Kei Morisato, Kazuki Nakanishi, Tohru Ikegami, Kanji Miyabe, Nobuo Tanaka

      JOURNAL OF CHROMATOGRAPHY A1218 ( 15 ) 1988 - 1994   4 2011

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      Chromatographic properties of a new type of monolithic silica rod columns were examined. Silica rod columns employed for the study were prepared from tetramethoxysilane, modified with octadecylsilyl moieties, and encased in a stainless-steel protective column with two polymer layers between the silica and the stainless-steel tubing. A 25 cm column provided up to 45,000 theoretical plates for aromatic hydrocarbons, or a minimum plate height of about 5.5 mu m, at optimum linear velocity of ca. 2.3 mm/s and back pressure of 7.5 MPa in an acetonitrile-water (80/20, v/v) mobile phase at 40 degrees C. The permeability of the column was similar to that of a column packed with 5 mu m particles, with K-F about 2.4 x 10(-14) m(2) (based on the superficial linear velocity of the mobile phase), while the plate height value equivalent to that of a column packed with 2.5 mu m particles. Generation of 80,000-120,000 theoretical plates was feasible with back pressure below 30 MPa by employing two or three 25 cm columns connected in series. The use of the long columns enabled facile generation of large numbers of theoretical plates in comparison with conventional monolithic silica columns or particulate columns. Kinetic plot analysis indicates that the monolithic columns operated at 30 MPa can provide faster separations than a column packed with totally porous 3-mu m particles operated at 40 MPa in a range where the number of theoretical plates (N) is greater than 50,000. (C) 2010 Elsevier B.V. All rights reserved.

      DOI: 10.1016/j.chroma.2010.11.032

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    • Numerical Method for the Estimation of Column Radial Heterogeneity and of the Actual Column Efficiency from Tailing Peak Profiles Peer-reviewed

      Kanji Miyabe, Georges Guiochon

      ANALYTICAL CHEMISTRY83 ( 1 ) 182 - 192   1 2011

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      Language:English   Publishing type:Research paper (scientific journal)   Publisher:AMER CHEMICAL SOC  

      It is probably impossible to prepare high-performance liquid chromatography (HPLC) columns that have a completely homogeneous packing structure. Many reports in the literature show that the radial distributions of the mobile phase flow velocity and the local column efficiency are not flat, even in columns considered as good. A degree of radial heterogeneity seems to be a common property of all HPLC columns and an important source of peak tailing, which prevents the derivation of accurate information on chromatographic behavior from a straightforward analysis of elution peak profiles. This work reports on a numerical method developed to derive from recorded peak profiles the column efficiency at the column center, the degree of column radial heterogeneity, and the polynomial function that best represents the radial distributions of the flow velocity and the column efficiency. This numerical method was applied to two concrete examples of tailing peak profiles previously described. It was demonstrated that this numerical method is effective to estimate important parameters characterizing the radial heterogeneity of chromatographic columns.

      DOI: 10.1021/ac102195x

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    • External mass transfer in silica monolithic stationary phases Peer-reviewed

      Kanji Miyabe, Nobuho Ando, Takuya Nakamura, Georges Guiochon

      CHEMICAL ENGINEERING SCIENCE65 ( 22 ) 5950 - 5960   11 2010

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      Language:English   Publishing type:Research paper (scientific journal)   Publisher:PERGAMON-ELSEVIER SCIENCE LTD  

      A detailed analysis of a procedure of measurement of the external mass transfer coefficients (k(f)) in RPLC systems is provided. Application is described for a system consisting of a C-18-silica monolithic column and a methanol/water eluent (70/30, v/v). The k(f) values of butylbenzene at 298 K were derived from peak profiles recorded in pulse response experiments by subtracting the contributions of the kinetic processes, i.e., axial molecular diffusion, eddy diffusion, pore and surface diffusion, from the band variance. This approach provided the Sherwood number (Sh) for a range of Reynolds number (Re) between 0.002 and 0.005 and a Schmidt number (Sc) equal to 2.7 x 10(3). The experimental values of k(f) were compared with those estimated from literature correlations, giving a relative error of ca. 11% when Pfeffer equation was used for estimating k(f). The exponents obtained for Re and Sc in Sh were 0.43 and 0.39, values comparable with those found in literature correlations, i.e., 0.33. The k(f) values estimated using the reference correlations are of the same order of magnitude as the experimental k(f) values. The acquisition of more experimental data is needed for deriving an improved correlation affording more accurate estimates of k(f) in stationary phases of cylindrical shape, like silica monoliths. (C) 2010 Elsevier Ltd. All rights reserved.

      DOI: 10.1016/j.ces.2010.08.020

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    • Peak parking-moment analysis: A strategy for the measurement of molecular diffusivity in liquid phase Peer-reviewed

      Kanji Miyabe, Jun-ichi Nagai, Georges Guiochon

      CHEMICAL ENGINEERING SCIENCE65 ( 12 ) 3859 - 3864   6 2010

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      Language:English   Publishing type:Research paper (scientific journal)   Publisher:PERGAMON-ELSEVIER SCIENCE LTD  

      The peak-parking (PP) method permits the measurement of molecular diffusivities (D(m)) in solutions. D(m) is first measured for benzene in pure methanol and acetonitrile (ACN), using an empty open tube. This yields an effective axial diffusion coefficient (D(ax,m)) equal to D(m) because there is no tortuosity nor constriction in the flow channel. The same measurements made for the same combinations of solute and solvents, using a column packed with non-porous silica particles provides the obstructive factor (Y(m)), defined as the ratio D(ax,m)/D(m), which accounts for the influence of tortuosity and constriction of the interparticulate space in packed columns on axial molecular dispersion. The value obtained for Y(m), 0.74-0.75, is constant, irrespective of the solvent. Then, PP experiments were made with the same apparatus and column to measure D(m) for benzene, toluene, and ethylbenzene in aqueous solutions of methanol and ACN. The values of D(m) obtained by correcting the experimental D(ax,m) values with Y(m) were compared with values previously reported and those estimated by several literature correlations. They were in good agreement with each other. The average relative error is estimated at 4.5-10%, demonstrating that the PP method is practically effective for experimental measurements of D(m). (C) 2010 Elsevier Ltd. All rights reserved.

      DOI: 10.1016/j.ces.2010.03.027

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    • Kinetic study on external mass transfer in high performance liquid chromatography system Peer-reviewed

      Kanji Miyabe, Yuuki Kawaguchi, Georges Guiochon

      JOURNAL OF CHROMATOGRAPHY A1217 ( 18 ) 3053 - 3062   4 2010

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      Language:English   Publishing type:Research paper (scientific journal)   Publisher:ELSEVIER SCIENCE BV  

      External mass transfer coefficients (k(f)) were measured for a column packed with fully porous C(18)-silica spherical particles (50.6 mu m in diameter), elutecl with a methanol/water mixture (70/30,v/v). The pulse response and the peak-parking methods were used. Profiles of elution peaks of alkylbenzene homologues were recorded at flow rates between 0.2 and 2.0 mL min(-1). Peak-parking experiments were conducted under the same conditions, to measure intraparticle and pore diffusivity, and surface diffusion coefficients. Finally, the values of k(f) for these compounds at 298 K were derived from the first and second moments of the elution peaks by subtracting the contribution of intraparticle diffusion to band broadening. As a result, the Sherwood number (Sh was measured under such conditions that the Reynolds (Re) and the Schmidt numbers (Sc) varied from 0.004 to 0.05 and from 1.8 x 10(3) to 2.7 x 10(3), respectively. We found that Sh is proportional to Re(alpha) and Sc(beta) and that the correlation between these three nondimensional parameters is almost the same as those given by conventional literature equations. The values of alpha and beta were close to those in the literature correlations, between 0.26 and 0.41 and between 0.31 and 0.36, respectively. The use of the Wilson-Geankoplis equation to estimate k(f) values entails a relative error of ca. 15%. So, conventional literature correlations provide correct estimates of k(f) in HPLC systems, even for particle sizes of the order of a micrometer. (C) 2010 Elsevier B.V. All rights reserved.

      DOI: 10.1016/j.chroma.2010.02.075

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    • An estimation of the column efficiency made by analyzing tailing peak profiles Peer-reviewed

      Kanji Miyabe, Yuko Matsumoto, Yusuke Niwa, Nobuho Ando, Georges Guiochon

      JOURNAL OF CHROMATOGRAPHY A1216 ( 47 ) 8319 - 8330   11 2009

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      It has been shown previously that most columns are not radially homogeneous but exhibit radial distributions of the mobile phase flow velocity and the local efficiency. Both distributions are best approximated by fourth-order polynomial, with the velocity in the column center being maximum for most packed columns and minimum for monolithic columns. These distributions may be an important source of tailing of elution peaks. The numerical calculation of elution peaks shows how peak tailing is related to the characteristics of these two distributions. An approach is proposed that permits estimations of the true efficiency and of the degree of column radial heterogeneity by inversing this calculation and using the tailing profiles of the elution peaks that are experimentally measured. This method was applied in two concrete cases of tailing peak profiles that had been previously reported and were analyzed by applying this new inverse approach. The results obtained prove its validity and demonstrate that this numerical method is effective for deriving the true column efficiency from experimental tailing profiles. (C) 2009 Elsevier B.V. All rights reserved.

      DOI: 10.1016/j.chroma.2009.09.006

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    • Surface Diffusion in C-18-Silica Monolithic Stationary Phase Peer-reviewed

      Kanji Miyabe

      JOURNAL OF CHROMATOGRAPHIC SCIENCE47 ( 6 ) 452 - 458   7 2009

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      Language:English   Publishing type:Research paper (scientific journal)   Publisher:OXFORD UNIV PRESS INC  

      A peak parking-moment analysis method was used for the measurement of surface diffusion coefficient (D-s) in a reversed-phase liquid chromatography (RPLC) system consisting of a C-18-silica monolithic column and a mixture of methanol and water (70/30, v/v). The D-s values experimentally measured were analyzed by considering the correlation with corresponding values of molecular diffusivity (D-m) and the retention equilibrium constant (K-a). It seems that the correlation between D-s/D-m and K-a is represented by a single curve irrespective of the RPLC conditions of temperature and the type of sample compounds. The increase in K-a is accompanied with the decrease in D-s/D-m. Oppositely, the ratio of D-s/D-m increases and approaches around unity when K-a infinitely decreases. It seems that surface diffusion is originally similar to molecular diffusion and that it is restricted due to the sample retention. These characteristics of surface diffusion are the same between the C-18-silica monolithic stationary phase and the conventional C-18-silica gel particles. In addition, the values of K-a and D-s are also comparable between them. It is concluded that basic properties concerning the retention equilibrium and surface diffusion of the C-18-silica monolithic stationary phase are almost the same as those of the conventional C-18-silica gel particles in spite of the difference between their structural characteristics.

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    • Peak parking method for measurement of molecular diffusivity in liquid phase systems Peer-reviewed

      Kanji Miyabe, Nobuho Ando, Georges Guiochon

      JOURNAL OF CHROMATOGRAPHY A1216 ( 20 ) 4377 - 4382   5 2009

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      Language:English   Publishing type:Research paper (scientific journal)   Publisher:ELSEVIER SCIENCE BV  

      The combination of series of measurements of band broadening made with the peak parking (PP) method, using successively an open capillary tube and a HPLC column, gives a convenient procedure for the measurement of the molecular diffusivity (D(m)) of compounds in solutions, of their axial dispersion coefficient (D(ax,m)) in chromatographic columns, and of the tortuosity or obstructive factor of the column bed. The molecular cliffusivity measured for benzene in methanol was in excellent agreement with literature data. The ratio of the axial dispersion coefficient to this diffusivity gives the obstructive factor (gamma(m)) of the packed bed. which was 0.74 for the column used. The values of D(m) in other solutions were obtained from the D(ax,m) values measured by the PP method, by correcting the D(ax,m) values with the gamma(m) value. The D(m) values determined by this method were in good agreement with those previously reported or estimated using literature correlations. These results showed that the PP method is effective for the experimental measurement of D(m). (C) 2009 Elsevier B.V. All rights reserved.

      DOI: 10.1016/j.chroma.2009.02.058

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    • Extrathermodynamic Study on Retention Equilibrium in Reversed-Phase Liquid Chromatography Peer-reviewed

      Miyabe, K

      Anal. Sci.25   219 - 227   2 2009

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    • Extrathermodynamic Study on Retention Equilibrium in Reversed-Phase Liquid Chromatography Peer-reviewed

      Miyabe, K

      Anal. Sci.25   219 - 227   2 2009

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    • Peak Parking - Moment Analysis Method for the Measurement of Surface Diffusion Coefficient Peer-reviewed

      Miyabe, K, Matsumoto, Y, Ando, N

      Anal. Sci.25   211 - 218   2 2009

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    • External mass transfer in high performance liquid chromatography systems Peer-reviewed

      Kanji Miyabe, Motoki Ando, Nobuho Ando, Georges Guiochon

      JOURNAL OF CHROMATOGRAPHY A1210 ( 1 ) 60 - 67   11 2008

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      Language:English   Publishing type:Research paper (scientific journal)   Publisher:ELSEVIER SCIENCE BV  

      External mass transfer in a HPLC system operated in the reversed-phase mode was studied by pulse response experiments, using a column packed with non-porous C-18-silica gel spherical particles. 18 pm in diameter. The first and second moments of the elution peaks, measured under different flow velocities and temperatures, were analyzed by the moment method to determine the external mass transfer coefficient (k(f)). The dependence of the Sherwood number on the Reynolds and the Schmidt numbers is almost the same as that observed in previous investigations of conventional literature correlations. The exponent of the last two nondimensional parameters was derived as being in the range from 0.28 to 0.41. When the Kataoka equation is used, the mean square deviation was calculated to be 0.21 for the values of kf estimated in this study. It is concluded that conventional correlations can be used to estimate kf values, even when the particle diameter is of the order of a micrometer. (c) 2008 Elsevier B.V. All rights reserved.

      DOI: 10.1016/j.chroma.2008.09.035

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    • Influence of mobile phase composition on surface diffusion in reversed-phase liquid chromatography Peer-reviewed

      Kanji Miyabe

      JOURNAL OF CHROMATOGRAPHY A1194 ( 2 ) 184 - 191   6 2008

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      Influence of column temperature and mobile phase composition (phi) on surface diffusion was studied in reversed-phase liquid chromatography using a C(18)-silica gel column and methanol-water mixtures. The temperature dependence of surface diffusion coefficient (Ds) was explained by considering that of the molecular diffusivity, suggesting the presence of a kind of correlation between surface and molecular diffusions. The influence of phi on D(s) was accounted for by considering the restriction energy (E(r)) for surface diffusion. Physical meanings of the linear correlation between E(r) and the enthalpy change due to sample retention are discussed in connection with the mechanism of surface diffusion. (c) 2008 Elsevier B.V. All rights reserved.

      DOI: 10.1016/j.chroma.2008.04.054

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    • Evaluation of chromatographic performance of various packing materials having different structural characteristics as stationary phase for fast high performance liquid chromatography by new moment equations Peer-reviewed

      Kanji Miyabe

      JOURNAL OF CHROMATOGRAPHY A1183 ( 1-2 ) 49 - 64   3 2008

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      Chromatographic performance of various separation media having different structural characteristics as the stationary phase for fast HPLC was quantitatively evaluated by using the new moment equations recently developed with considering the shape and porous structure of the packing materials. Four types of separation media, i.e., full-porous, partially porous (pellicular or shell) type, and non-porous spherical particles and full-porous cylindrical fiber, were chosen as examples. The moment equations were used for predicting the chromatographic behaviors of benzene under hypothetical RPLC conditions. The overall performance of the four types of packing materials as the separation media for fast HPLC was compared with each other from the viewpoint of the peak capacity, which depends on both the retention equilibrium and the mass transfer kinetics. It seems that the full-porous cylindrical fiber and the pellicular type spherical particle are more preferable than the others, i.e., the full-porous and non-porous spherical particles. Now we can use the new moment equations for the quantitative prediction of the chromatographic behaviors of the various packing materials on the basis of a related experimental information and for the evaluation of their performance from various chromatographic points of view. The new moment equations are effective not only for the detailed analyses of chromatographic behaviors but also for the preliminarily evaluation of new types of separation media for fast HPLC. (C) 2008 Elsevier B.V. All rights reserved.

      DOI: 10.1016/j.chroma.2007.12.064

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    • New moment equations for chromatography using various stationary phases of different structural characteristics Peer-reviewed

      Kanji Miyabe

      ANALYTICAL CHEMISTRY79 ( 19 ) 7457 - 7472   10 2007

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      Language:English   Publishing type:Research paper (scientific journal)   Publisher:AMER CHEMICAL SOC  

      New moment equations were systematically developed for chromatography using various types of separation media having different structural characteristics, i.e., shape (spherical particle, cylindrical fiber, flat plate) and porous structure (full-porous, partially porous (pellicular), nonporous). First, a set of basic equations of the general rate model of chromatography representing the mass balance and the mass-transfer kinetics were analytically solved in the Laplace domain. Then, the moment equations in the real-time domain of the first absolute moment and the second central moment were derived from the analytical solution in the Laplace domain. The new moment equations were used for predicting the chromatographic behaviors of benzene in the hypothetical RPLC systems using the full-porous, partially porous (pellicular), and nonporous spherical particles as packing materials. The influence of the difference in their structure on the total performance of the three types of spherical particles as the separation media for the fast HPLC with a high efficiency was quantitatively evaluated from the viewpoints of the column efficiency, column back pressure, and sample retention strength. The framework of the new moment equations can provide not only the qualitative but also the quantitative information about the intrinsic characteristics of the chromatographic behaviors of various separation media having the different shapes and structures. This study is devoted to demonstrating the important advantage of the moment analysis strategy over the conventional plate theory and rate models of chromatography.

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    • Surface diffusion in reversed-phase liquid chromatography using silica gel stationary phases of different C-1 and C-18 ligand densities Peer-reviewed

      Kanji Miyabe

      JOURNAL OF CHROMATOGRAPHY A1167 ( 2 ) 161 - 170   10 2007

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      Surface diffusion phenomena were studied from kinetic and thermodynamic points of view. The existence of a linear free energy relationship between surface diffusion and the retention equilibrium suggests that the mechanism of surface diffusion is the same irrespective of the density of C-1 and C-18 ligands. Surface diffusion coefficient (D-s) of weakly retained compounds seems to be of the same order of magnitude with corresponding molecular diffusivity. There would be an intimate correlation between surface diffusion and molecular diffusion. The value of D, decreases with increasing retention strength. The magnitude of the restriction for surface diffusion is comparable to about one third the enthalpy change due to the sample retention. This means that it is necessary for sample molecules adsorbed to be partially desorbed from the stationary phase surface when they migrate by surface diffusion. The results of this study provide the fundamental information for developing an appropriate model of surface diffusion, which explains some intrinsic characteristics and mechanism of surface diffusion. (C) 2007 Elsevier B.V. All rights reserved.

      DOI: 10.1016/j.chroma.2007.08.045

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    • Peak parking-moment analysis. A strategy for the study of the mass-transfer kinetics in the stationary phase Peer-reviewed

      Kanji Miyabe, Yuko Matsumoto, Georges Guiochon

      ANALYTICAL CHEMISTRY79 ( 5 ) 1970 - 1982   3 2007

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      The combination of peak parking and moment analysis is proved to be a powerful strategy for studying the molecular diffusivity of solute molecules in stationary phases and for determining the corresponding kinetic parameters. The physical meaning of the traditional kinetic parameter, gamma D-s(s), the diffusion coefficient of solute molecules in stationary phases, is first clarified. A second kinetic parameter, D-Ls, is then derived from gamma D-s(s), and the correspondence between D-Ls and the surface diffusion coefficient, D-sur, is discussed. Then, the results of peak parking experiments carried out with RPLC systems using aqueous methanol solutions and C-18-silica columns are reported. The moments of pulse responses were measured and are analyzed. The values and some characteristics of D-Ls measured by the peak parking-moment analysis method are compared with those of D-sur determined using the pulse response-moment analysis method. The comparison of the numerical values of D-Ls and D-sur suggests that D-Ls is nearly equal to D-sur and that it exhibits the same dependence on the retention strength as does D-sur with regard to the mass-transfer kinetics and extrathermodynamics. This comparison allows us to conclude that D-Ls corresponds to D-sur. The advantages and disadvantages of the peak parking-moment analysis method were compared with those of the pulse response-moment analysis method. The combination of these two methods provides a comprehensive strategy for measuring the mass-transfer kinetics in the stationary phase.

      DOI: 10.1021/ac061321h

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    • Surface diffusion in reversed-phase liquid chromatography using silica gels bonded with C-1 and C-18 ligands of different densities Peer-reviewed

      Kanji Miyabe

      TALANTA71 ( 5 ) 1915 - 1925   3 2007

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      Surface diffusion in reversed-phase liquid chromatography (RPLC) using silica gels bonded with C-1 and C-18 alkyl ligands of different densities was studied from the viewpoints of two extrathermodynamic relationships, i.e., enthalpy-entropy compensation (EEC) and linear free energy relationship (LFER). First, according to the four methods proposed by Krug et al., the values of surface diffusion coefficient (D-s) were analyzed to confirm that an actual EEC resulting from substantial physico-chemical effects takes place for surface diffusion. Then, it was also demonstrated that a LFER is observed between surface diffusion and the retention equilibrium. The establishment of EEC and LFER suggests a mechanistic similarity of molecular migration by surface diffusion, irrespective of the alkyl chain length and the densities of C-1 and C-18 ligands. Finally, a thermodynamic model for the LFER based on the real EEC was used to estimate D-s values under various RPLC conditions. The D-s values can be estimated with a mean square deviation of about 25-30%. The agreement between the D-s values estimated and those experimentally measured suggests that the total mass flux by surface diffusion consists of the two contributions due to C-1 and C(1)8 ligands and that the contribution of each ligand is proportional to the ligand density. (c) 2006 Elsevier B.V. All rights reserved.

      DOI: 10.1016/j.talanta.2006.08.020

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    • A Kinetic Parameter Concerning Mass Transfer in Silica Monolithic and Particulate Stationary Phases Measured by the Peak-Parking and Slow-Elution Methods Peer-reviewed

      Miyabe, K, Kobayashi, H, Tokuda, D, Tanaka, N

      J. Sep. Sci.29   2452 - 2462   11 2006

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    • Faster axial band dispersion in a monolithic silica column than in a particle-packed column Peer-reviewed

      H Kobayashi, D Tokuda, J Ichimaru, T Ikegami, K Miyabe, N Tanaka

      JOURNAL OF CHROMATOGRAPHY A1109 ( 1 ) 2 - 9   3 2006

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      The contribution of molecular diffusion to peak broadening was studied in a reversed-phase HPLC system, consisting of a monolithic silica C Is column and methanol-water mobile phase. Study on the band broadening effect of holding a solute in a column or elution at very low linear velocity of mobile phase allowed facile determination of the contribution of the molecular diffusion term. Less obstruction against molecular diffusion, or the faster axial band dispersion in a monolithic silica column than in a particle-packed column, was found both in mobile phase and in stationary phase. (c) 2005 Elsevier B.V. All rights reserved.

      DOI: 10.1016/j.chroma.2005.11.053

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    • Extrathermodynamic interpretation of retention equilibria in reversed-phase liquid chromatography using octadecylsilyl-silica gels bonded to C-1 and C-18 ligands of different densities Peer-reviewed

      K Miyabe, G Guiochon

      JOURNAL OF CHROMATOGRAPHY A1099 ( 1-2 ) 136 - 148   12 2005

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      The retention behavior on silica gels bonded to C-18 and C-1 alkyl ligands of different densities was studied in reversed-phase liquid chromatography (RPLC) from the viewpoints of two extrathermodynamic relationships, enthalpy-entropy compensation (EEC) and linear free energy relationship (LFER). First, the four tests proposed by Krug et al. were applied to the values of the retention equilibrium constants (K) normalized by the alkyl ligand density. These tests showed that a real EEC of the retention equilibrium originates from substantial physico-chemical effects. Second, we derived a new model based on the EEC to explain the LFER between the retention equilibria under different RPLC conditions. The new model indicates how the slope and intercept of the LFER are correlated to the compensation temperatures derived from the EEC analyses and to several parameters characterizing the molecular contributions to the changes in enthalpy and entropy. Finally, we calculated K under various RPLC conditions from only one original experimental K datum by assuming that the contributions of the C-18 and C-1 ligands to K are additive and that their contributions are proportional to the density of each ligand. The estimated K values are in agreement with the corresponding experimental data, demonstrating that our model is useful to explain the variations of K due to changes in the RPLC conditions. (c) 2005 Elsevier B.V. All rights reserved.

      DOI: 10.1016/j.chroma.2005.09.001

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    • Effect of the silanization conditions on chromatographic behavior of an open-tubular capillary column coated with a modified silica-gel thin layer Peer-reviewed

      Y Nakano, S Kitagawa, K Miyabe, T Tsuda

      ANALYTICAL SCIENCES21 ( 10 ) 1167 - 1170   10 2005

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      The performance of an open-tubular capillary column coated with a modified silica-gel thin layer was investigated, particularly concerning the effect of the silanization process on it. Although the increase in the octadecyltriethoxysilane (ODTES) concentration in the silanization process could enhance the retention factor of naphthalene, its theoretical plate number was significantly reduced (ODTES, 5 to 50%; k, 0.2 to 4.3; N, 79600 to 2600 m(-1)). Namely, the increase in the retention factor was accompanied by a decrease in the theoretical plate number. A similar phenomenon was also observed when octadecyldimethylchlorosilane (ODCS) was used as the silanization regent. However, increases in both the retention factor and the theoretical plate number could be achieved (sample, naphthalene; k, 0.05 to 0.09; N, 149000 to 220000 m-1) by a NaOH treatment to the fabricated thin porous silica-get layer before silanization with ODCS. The electrochromatographic separation of proteins and peptides by using the NaOH-treated column could obtain more peaks than electrophoretic separation.

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    • Extrathermodynamic Study of Surface Diffusion in Reversed-Phase Liquid Chromatography with Silica Gels Bonded with Alkyl Ligands of Different Chain Lengths Peer-reviewed

      Miyabe, K, Guiochon, G

      J. Phys. Chem. B109   12038 - 12048   6 2005

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    • Preparation of a new type of fiber adsorbent attached with silica microparticles Peer-reviewed

      T Tsuda, M Hisanaga, T Inagaki, S Kitagawa, K Miyabe

      ANALYTICAL SCIENCES20 ( 7 ) 1061 - 1064   7 2004

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      A new type of fiber adsorbent attached with silica microparticles was prepared. The silica microparticles were formed by the polymerization of silica oligomers on glass fibers, which were woven into a glass filter. The surface of the silica microparticles was chemically modified by bonding C(18)-ligands. SEM images indicated that the diameter of the uniform and spherical silica microparticles fixed on glass fibers was on the order of micrometers. It was confirmed that the glass filter adsorbent was effective for the adsorptive removal of toluene of low concentrations.

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    • Comparison of the characteristics of adsorption equilibrium and surface diffusion in liquid-solid and gas-solid adsorption on C-18-silica gels Peer-reviewed

      K Miyabe, G Guiochon

      JOURNAL OF PHYSICAL CHEMISTRY B108 ( 9 ) 2987 - 2997   3 2004

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      Four parameters characterizing the adsorption equilibrium, surface diffusion, and related thermodynamic properties were derived from pulse-response experiments in various reversed-phase liquid chromatography (RPLC) systems using C-18-silica gels and aqueous solutions of three different organic modifiers, methanol, acetonitrile, and tetrahydrofuran. The results were compared with corresponding data similarly measured by gas-solid chromatography on the same type of surface-modified silica gel, with helium. Information on the solvent effect on the adsorption characteristics was provided by the comparison of these experimental results. While the adsorption equilibrium constant and the heat of adsorption at infinite dilution were much larger in the gas-solid than in the RPLC system, the surface diffusion coefficient (D-s) and the activation energy of surface diffusion (E-s) were of the same order of magnitude in both systems. Regarding surface diffusion, the logarithm of the frequency factor was linearly correlated with E-s by the same straight line, suggesting the fundamental similarity of the surface diffusion mechanism in the gas-solid and liquid-solid systems. Calculations made on the basis of a surface-restricted diffusion model provide an explanation for the comparable values of D-s and E-s in the two systems. In conclusion, the liquid phase in RPLC influences the thermodynamic parameters of surface diffusion as well as those of adsorption equilibrium, but similar values of D-s and E-s are observed in both the two adsorption systems. A quantitative explanation of the similarities and differences of the characteristics and the mechanism of surface diffusion in gas-solid and liquid-solid adsorption systems is proposed.

      DOI: 10.1021/jp0309421

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    • Moment analysis of mass-transfer kinetics in C-18-silica monolithic columns Peer-reviewed

      K Miyabe, A Cavazzini, F Gritti, M Kele, G Guiochon

      ANALYTICAL CHEMISTRY75 ( 24 ) 6975 - 6986   12 2003

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      The moment analysis of elution peak profiles based on new moment equations provides information on the mass-transfer characteristics of C-18-silica monolithic columns. The flow rate dependence of the HETP data was analyzed using the generalized van Deemter equation, after correction of these data by subtraction of the external mass-transfer contribution to band broadening. Kinetic parameters and diffusion coefficients related to the mass-transfer processes in monolithic columns were derived by taking advantage of the different flow velocity dependence of their contributions to band broadening. At high flow rates, axial dispersion and diffusive migration across the monolithic C-18-silica skeleton contribute much to band broadening, suggesting that it remains important to reduce the influence of eddy diffusion and the mass-transfer resistance in the stationary phase to achieve fast separations and a high efficiency. Surface diffusion plays a predominant role for molecular migration in the monolithic stationary phase. Although the value of the surface diffusion coefficient (D-s) depends on an estimate of the external mass-transfer coefficient, D-s values of the order of 10(-7) cm(2) s(-1) were calculated for the first time for the C-18-silica monolithic skeleton. The value of D-s decreases with increasing retention of sample compounds. Analysis of a kind of time constant calculated from Ds suggests that the "chromatographic corresponding particle size" is similar to4 mum for the C-18-silica monolithic stationary phase used in this study. The accuracy of the D-s values determined was discussed.

      DOI: 10.1021/ac0302206

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    • Kinetic Study on Hydrodechlorination of Trichloroethene in Water Peer-reviewed

      Miyabe, K, Taniguchi, N, Imura, A, Tezuka, Y

      Water Environment Research75   472 - 477   9 2003

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    • Moment analysis of retention equilibrium, mass transfer kinetics, and thermodynamic properties in reversed-phase liquid chromatography using phenyl bonded silica gel Peer-reviewed

      K Miyabe, Y Sakai, M Sarashina, C Yokokawa

      ANALYST128 ( 12 ) 1425 - 1433   2003

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      Information about retention equilibrium, mass transfer kinetics, and related thermodynamic properties of chromatography using phenyldimethylsilyl (Ph)-silica gel was derived by moment analysis of pulse response peak profiles. The results for the Ph-silica gel were compared with those for octadecyldimethylsilyl (C-18)-silica gel. Some parameters characterizing the chromatographic behavior of the two stationary phases were correlated with the hydrophobic surface area of sample molecules. Surface diffusion had a predominant role for intraparticle diffusion. An enthalpy-entropy compensation was established for both the retention equilibrium and surface diffusion. A linear correlation was observed between the logarithm of surface diffusion coefficient (D-s) and that of retention equilibrium constant (K-a), suggesting the establishment of a linear free energy relationship. The ratio of D-s to molecular diffusivity (D-m) decreased with increasing K-a and was correlated by a single curved line. The value of D-s was of the same order of magnitude with D-m when K-a became negligible. These results suggest the presence of a sort of correlation between surface diffusion and molecular diffusion and the restriction of the molecular mobility by surface diffusion due to the retention strength.

      DOI: 10.1039/b308293h

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    • Thermodynamic interpretation of retention equilibrium in reversed-phase liquid chromatography based on enthalpy-entropy compensation Peer-reviewed

      K Miyabe, G Guiochon

      ANALYTICAL CHEMISTRY74 ( 23 ) 5982 - 5992   12 2002

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      The fundamentals of the retention equilibrium in reversed-phase liquid chromatography (RPLC) are studied on the basis of enthalpy-entropy compensation (EEC). First, retention data were acquired and the influence of the nature of the compounds, organic solvent modifier, and temperature on these data was assessed. Then, the data were analyzed according to the four different methods proposed by Krug et al., and an EEC was formally established. Linear correlations were observed between the logarithm of the adsorption equilibrium constants under the different RPLC conditions, suggesting linear free energy relationships (LFERs). Finally, the variations of the retentions with the experimental conditions are shown to be quantitatively explained by a new model based on EEC. Ibis model affords a comprehensive interpretation of the variations of retention originating from changes of either one parameter alone or several simultaneously. The slope and intercept of the LFER that relates two equilibrium systems are accounted for by the new model. The parameters of this model are the changes of enthalpy and entropy associated with the retention, the compensation temperatures, and the experimental conditions.

      DOI: 10.1021/ac0202233

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    • Extrathermodynamic relationships in reversed-phase liquid chromatography Peer-reviewed

      K Miyabe, G Guiochon

      ANALYTICAL CHEMISTRY74 ( 22 ) 5754 - 5765   11 2002

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      Enthalpy- entropy compensation (EEC) and linear free energy relationships (LFER) are extrathermodynamic correlations frequently used to discuss the mechanistic similarities of chemical equilibria and reaction kinetics. Although empirical, they are widely applied, proving the substantial effectiveness of fundamental studies based on them. Many attempts have been made to interpret theoretically the necessary conditions (or preconditions) of EEC and LFER. LFER is known to rest on the existence of EEC. However, the intimate correlations between EEC on one hand and LFER and the temperature dependence of LFER on the other hand were insufficiently discussed from the viewpoint of molecular structure contributions. We present a simple LFER model relating the slope and intercept of LFER to the compensation temperatures, themselves derived from EEC analyses, and to several parameters characterizing the molecular contributions to the changes in enthalpy and entropy associated with the passage from one phase of the chromatographic system to the other. A theoretical explanation is supplied for the intimate correlation between the two types of extrathermodynamic relationships, EEC and LFER. We demonstrate also that the characteristics of EEC and LFER depend on the structural parameters. This new model allows a proper interpretation of the temperature dependence of LFER. It should permit further progress of fundamental studies of chemical reaction mechanisms based on extrathermodynamic relationships.

      DOI: 10.1021/ac020245p

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    • The Moment Equations of Chromatography for Monolithic Stationary Phases Peer-reviewed

      Miyabe, K, Guiochon, G

      J. Phys. Chem. B106   8898 - 8909   8 2002

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    • New model of surface diffusion in reversed-phase liquid chromatography Peer-reviewed

      K Miyabe, G Guiochon

      JOURNAL OF CHROMATOGRAPHY A961 ( 1 ) 23 - 33   6 2002

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      A new model of surface diffusion in reversed-phase liquid chromatography (RPLC) was derived by assuming a correlation between surface and molecular diffusion. Analysis of surface diffusion data under different conditions of sample compounds, mobile and stationary phases, and temperature in RPLC systems validates this assumption and shows that surface diffusion should be regarded as a molecular diffusion restricted by the adsorptive interactions between the adsorbate molecule and the stationary phase surface. A surface-restricted molecular diffusion model was proposed as a first approximation for the mechanism of surface diffusion. The model is formulated according to the absolute rate theory. The activation energy of surface diffusion (E-s) was quantitatively interpreted assuming that E-s consists of the contributions of two processes, a hole-making and a jumping one. The former contribution is nearly equal to the activation energy of molecular diffusion and is correlated with the evaporative energy of the mobile phase solvent. The latter contribution is a fraction of the isosteric heat of adsorption. An appropriate explanation based on this new model of surface diffusion is provided for two contradictory results related to the relationship between retention equilibrium and surface diffusion in RPLC and to the surface diffusion coefficient for weakly retained sample compounds. (C) 2002 Elsevier Science BV All rights reserved.

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    • Characteristics and mechanism of surface diffusion in reversed-phase liquid chromatography using various alkyl ligand bonded silica gels Peer-reviewed

      K Miyabe

      ANALYTICAL CHEMISTRY74 ( 9 ) 2126 - 2132   5 2002

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      Kinetic and thermodynamic parameters concerning surface diffusion were derived in reversed-phase liquid chromatography (RPLC) systems using a series of silica gel packing materials bonded with C-1, C-4, C-8, and C-18 alkyl ligands. In this paper, a more detailed study on some characteristics and the mechanism of surface diffusion in the RPLC systems using the different alkyl ligand bonded silica gels was made from a thermodynamic point of view by analyzing the surface diffusion data with consideration of the correlation between the parameters concerning surface diffusion and those relating to the retention equilibrium. The mechanism of surface diffusion seems to be the same irrespective of the length of the alkyl ligands because of the presence of the extrathermodynamic relationships, i.e., the enthalpy-entropy compensation and the linear free energy relationship. It was indicated that the surface diffusion coefficient (D-s) of weakly retained compounds was of the same order of magnitude with corresponding molecular diffusivity and that D-s decreased with increasing retention. The activation energy of surface diffusion (E-s) was formulated as a linear function of the isosteric heat of adsorption (Q(st)). A modified Arrhenius equation, which is derived by taking into account the linear correlation between the two thermodynamic parameters E-s and Q(st), appropriately explains the intrinsic characteristics and mechanism of surface diffusion.

      DOI: 10.1021/ac011184i

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    • Analysis of Surface Diffusion in Reversed-Phase Liquid Chromatography Peer-reviewed

      Miyabe, K

      Proceedings of the Seventh International Conference on Fundamentals of Adsorption   93 - 100   1 2002

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    • Retention equilibrium and mass transfer characteristics in reversed-phase liquid chromatography using methanol-water mixtures Peer-reviewed

      K Miyabe, A Okada

      ANALYST127 ( 11 ) 1420 - 1426   2002

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      Pulse response experiments (i.e., elution chromatography) were made in reversed-phase liquid chromatography (RPLC) using a C-18 silica gel column and methanol-water mixtures of different compositions (phi). The moment analysis of the elution peak profiles measured in the RPLC system provided some items of information about four parameters characterizing the retention equilibrium and the mass transfer kinetics in the column, i.e., adsorption equilibrium constant, isosteric heat of adsorption, surface diffusion coefficient and activation energy of surface diffusion. Characteristics of the chromatographic behavior were studied by analyzing the dependence of the four parameters on phi and the correlation between them. It was found that surface diffusion was one of the important processes of molecular migration having a significant contribution to the mass transfer kinetics in the column. Both the adsorption equilibrium constant and the surface diffusion coefficient varied depending on phi. The direction of their changes was approximately opposite, suggesting that the mass transfer in the manner of surface diffusion was restricted owing to the retention of the sample molecules on the stationary phase.

      DOI: 10.1039/b203667n

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    • Chromatographic Behavior of Alkyl Ligands Bonded Silica Gels Peer-reviewed

      Miyabe, K, Guiochon, G

      Anal. Sci.17 Supplement   i209 - i212   12 2001

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    • Correlation between Surface Diffusion and Molecular Diffusion in Reversed-Phase Liquid Chromatography Peer-reviewed

      Miyabe, K, Guiochon, G

      J. Phys. Chem. B105   9202 - 9209   9 2001

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    • Analysis of the surface diffusion of alkylbenzenes and p-alkylphenols in reversed phase liquid chromatography using the surface-restricted molecular diffusion model Peer-reviewed

      K Miyabe, G Guiochon

      ANALYTICAL CHEMISTRY73 ( 13 ) 3096 - 3106   7 2001

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      Surface diffusion of alkylbenzene and p-alkylphenol derivatives was measured in reversed-phase liquid chromatography on a C-18-silica column with a methanol/water mixture (70/30, v/v) as the mobile phase. They were analyzed on the basis of the restricted molecular diffusion model for surface diffusion, The temperature dependence of the surface diffusion coefficient (D-s) arises probably from that of molecular diffusivity, suggesting a correlation between surface and molecular diffusion. Other correlations were also observed: (1) an enthalpy-entropy compensation of the retention equilibrium constant, (2) a linear free energy relationship between the retention and surface diffusion, and (3) a linear correlation between the restriction energy of surface diffusion and the isosteric heat of adsorption, The physical meaning of parameters involved in the surface-restricted molecular diffusion model is discussed on the basis of these results. A practical and convenient procedure for the estimation of D-s is also suggested. This study demonstrates how surface diffusion phenomena can be accounted for on the basis of the correlation between surface and molecular diffusion.

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    • Retention and mass transfer characteristics in reversed-phase liquid chromatography using a tetrahydrofuran-water solution as the mobile phase Peer-reviewed

      K Miyabe, S Sotoura, G Guiochon

      JOURNAL OF CHROMATOGRAPHY A919 ( 2 ) 231 - 244   6 2001

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      The characteristics of the retention and the mass transfer kinetics in reversed-phase liquid chromatography (RPLC) were measured on a system consisting of a C-18-silica gel and a tetrahydrofuran-water (50:50, v/v) solution. These parameters were derived from the first and the second moments of the elution peaks, respectively. Further information on the thermodynamic properties of this system was derived from the temperature dependence of these moments. Some correlations previously established were confirmed for this system, namely, an enthalpy-entropy. compensation for both retention and surface diffusion and a linear free-energy relationship. These results are compared with those observed in other similar systems using methanol-water (70:30, v/v) and acetonitrile-water (70:30, v/v) solutions. The contribution of surface diffusion to intraparticle diffusion in C-18-silica gel particles was shown to be important. The analysis of the thermodynamic properties of surface diffusion suggests that, in these three RPLC systems, its activation energy is lower than the isosteric heat of adsorption. The nature and the extent of the influence of the mobile phase composition on the parameters describing the retention and the mass transfer kinetics are different but the chromatographic mechanisms involved in RPLC systems appear similar, irrespective of the nature of the organic modifier in the mobile phase. (C) 2001 Elsevier Science B.V. All rights reserved.

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    • 射出成形した生分解性プラスチックの土壌・水中および活性汚泥中での分解性 Peer-reviewed

      水野 渡, 前田芳子, 小島佳奈子, 高道智美, 宮部寛志, 竹内茂彌

      高分子論文集58   59 - 65   2 2001

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    • Influence of the modification conditions of alkyl bonded ligands on the characteristics of reversed-phase liquid chromatography Peer-reviewed

      K Miyabe, G Guiochon

      JOURNAL OF CHROMATOGRAPHY A903 ( 1-2 ) 1 - 12   12 2000

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      The parameters characterizing retention and the mass transfer mechanisms in reversed-phase liquid chromatography were derived from data acquired for a series of compounds on a silica gel bonded to alkyl ligands of various lengths and Ligand densities. The adsorption equilibrium constant, the absolute value of the isosteric heat of adsorption, and the activation energy of surface diffusion increase while the surface diffusion coefficient decreases with increasing length of the alkyl chain and density of the C-18 ligand. These results are consistent with increasing restriction of the mobility of an increasingly adsorbable molecule. There is a critical level of carbon content above which the four parameters just listed no longer change with increasing alkyl ligand density. This level is likely to depend on the sizes of the alkyl ligand and the sample molecule. Even at high densities of C-18 chains, there may be a limitation in the contact area of the sample molecule and the alkyl ligand, The retention behavior on the stationary phases studied is explained by assuming that the sample molecules penetrate into the layer of alkyl ligands. Enthalpy-entropy compensation was demonstrated for surface diffusion. Its mechanism is probably similar on the different stationary phases studied, irrespective of the length and density of the bonded ligand. (C) 2000 Elsevier Science B.V. All rights reserved.

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    • A kinetic study of mass transfer in reversed-phase liquid chromatography on a C18-silica gel Peer-reviewed

      K Miyabe, G Guiochon

      ANALYTICAL CHEMISTRY72 ( 21 ) 5162 - 5171   11 2000

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      The characteristic features of mass-transfer kinetics in a reversed-phase (RP) column packed with a C18-silica were studied. The relevant information on phase equilibrium thermodynamics and mass-transfer kinetics was obtained by frontal analysis and the pulse method, respectively. The equilibrium isotherm was accounted for by the simple Langmuir model. The ratio of the axial dispersion coefficient to the mobile-phase now velocity increased almost linearly with increasing solute concentration. Similarly, the mass-transfer rate coefficient (k(m)) showed a linear dependence on the solute concentration. The positive concentration dependence of k(m) resulted from that of the surface diffusion coefficient, which was interpreted with the chemical potential driving force model. The contribution of axial dispersion to band broadening was predominant in the RP column packed with the medium-size packing material used (particle diameter, 12 mum) whereas that of the kinetics of adsorption/desorption was negligibly small, The results of this study demonstrate how an analysis of the dependence of the mass-transfer kinetics on the flow velocity and the solute concentration allows a better understanding of this kinetics.

      DOI: 10.1021/ac0002801

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    • Influence of the column radial heterogeneity on the determination of single-component isotherms by the elution by characteristic point method Peer-reviewed

      K Miyabe, G Guiochon

      JOURNAL OF CHROMATOGRAPHY A891 ( 2 ) 217 - 233   9 2000

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      The influence of the column radial heterogeneity on the determination of equilibrium isotherm data by the elution by characteristic point (ECP) method is studied using nondimensional numerical calculations and taking into account typical radial distributions of the mobile phase flow velocity and the column efficiency across a column. Overloaded elution peaks were calculated with the equilibrium-dispersive model as a function of four dimensionless parameters, the number of theoretical plates at the center of the column, the Langmuir equilibrium constant, the retention and the loading factors. The influence of the mass transfer resistances and the radial heterogeneity of the column on the ECP data was analyzed by comparing the true isotherm and the one estimated from the diffuse profile of overloaded peaks. The results provide information on the accuracy of the ECP method. The error made increases with increasing degree of radial heterogeneity. This error can be corrected by using the results of the nondimensional numerical calculations, allowing a further extension of the applicability of the ECP method. (C) 2000 Elsevier Science B.V. All rights reserved.

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    • Interpretation by the Solvophobic Theory on the Linear Additive Representation of the Logarithm of Ion-Pair Extraction Constant with Individual Contributions of Cation, Anion, and Organic Solvent Peer-reviewed

      Miyabe, K, Taguchi, S, Kasahara, I, Goto, K

      J. Phys. Chem. B104   8481 - 8490   9 2000

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    • A Study of Mass Transfer Kinetics in an Enantiomeric Separation System Using a Polymeric Imprinted Stationary Phase Peer-reviewed

      Miyabe, K, Guiochon, G

      Biotechnol. Prog.16   617 - 629   8 2000

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    • Determination of the lumped mass transfer rate coefficient by frontal analysis Peer-reviewed

      K Miyabe, G Guiochon

      JOURNAL OF CHROMATOGRAPHY A890 ( 2 ) 211 - 223   8 2000

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      The validity of measurements of the lumped mass transfer rate coefficient (k(m,L)) is studied on the basis of experimental data acquired under Langmuir isotherm conditions, in reversed-phase liquid chromatography. Two different methods were used, the perturbation method and frontal analysis. Accurate values of k(m,L) can be properly obtained by the perturbation method because, with this method, the chromatographic processes take place under locally linear isotherm conditions. Values of k(m,L) can also be derived from the breakthrough curves obtained in frontal analysis. Because the contribution of axial dispersion to band broadening was larger than that of the mass transfer resistances, the apparent axial dispersion coefficient (D-a) was first derived from the breakthrough curve by applying the equilibrium-dispersive model. Then, the value of k(m,L) was calculated from D-a. The values of k(m,L) determined by the two methods were in close agreement in the range of nondimensional Langmuir equilibrium constants (r = 1/[1+KLC0]) between 0.32 and 0.85, irrespective of the mobile phase flow velocity. Thus, frontal analysis can be used for kinetic studies of the mass transfer in chromatographic columns. (C) 2000 Elsevier Science B.V. All rights reserved.

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    • Kinetic study of the concentration dependence of the mass transfer rate coefficient in enantiomeric separation on a polymeric imprinted stationary phase Peer-reviewed

      K Miyabe, G Guiochon

      ANALYTICAL SCIENCES16 ( 7 ) 719 - 730   7 2000

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      Kinetic data previously acquired on the enantiomeric separation of L- and D-phenylalanine anilide (PA) on a polymeric stationary phase imprinted with L-PA were reinterpreted. The parameters characterizing the mass transport processes active in the column, i.e., axial dispersion, fluid-to-particle mass transfer, intraparticle diffusion, and adsorption/desorption were calculated. Intraparticle diffusion was shown to have a dominant contribution to band broadening. The surface diffusion coefficient (D-s) showed a positive concentration dependence which could explain the dependence of the lumped mass transfer rate coefficient on the enantiomer concentration. It is likely that the positive concentration dependence of D-s could be explained by the heterogeneity of the surface of the stationary phase and that the distribution of adsorption energy on the surface of the imprinted polymer has an exponential decay profile.

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    • Restricted diffusion model for surface diffusion in reversed-phase liquid chromatography Peer-reviewed

      K Miyabe, G Guiochon

      ANALYTICAL CHEMISTRY72 ( 7 ) 1475 - 1489   4 2000

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      The analysis of experimental results in reversed-phase liquid chromatography (RPLC) allows further discussion of the restricted diffusion model of surface diffusion formulated on the basis of the absolute rate theory. Chromatographic data were acquired on different RPLC systems with two series of homologous compounds, several stationary phases having different alkyl ligand densities and ligands of various lengths, and methanol/ water mobile phases of different compositions, The enthalpy-entropy compensation observed and the linear free energy relationships found for surface diffusion suggest that the surface diffusion mechanism remains probably the same in all RPLC conditions studied, Whereas the isosteric heat of adsorption approaches zero with decreasing retention, the activation energy of surface diffusion tends toward a finite limit and the surface diffusion coefficient tends toward a value near the corresponding molecular diffusivity. These results support the validity of the restricted diffusion model. The influence of different factors on the validity of this model (i.e., the activation energy and the frequency factor of surface diffusion, and the surface tortuosity) was also considered.

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    • Study on the accuracy of the elution by characteristic point method for the determination of single component isotherms Peer-reviewed

      K Miyabe, S Khattabi, DE Cherrak, G Guiochon

      JOURNAL OF CHROMATOGRAPHY A872 ( 1-2 ) 1 - 21   3 2000

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      The accuracy of the method of elution by characteristic point (ECP) used to determine single component isotherms was studied numerically. Overloaded elution peaks were calculated using the equilibrium-dispersive model of nonlinear chromatography while varying the four parameters, i.e., the number of theoretical plates, the dimensionless Langmuir equilibrium constant, the retention and the loading factor, involved in the fundamental equations of the problem. Single component isotherms were estimated by analyzing the diffuse profile of the elution peaks by the ECP method. Similar results were obtained with the transport-dispersive model. The comparison of these calculated isotherms with the initial Langmuir isotherms provided detailed information on the influence of the mass transfer resistances on the accuracy of the isotherms afforded by the ECP method. The systematic error made on the isotherms depends on the experimental conditions, described by the four parameters. It is expected that this error could be eliminated by correcting the influence of nonequilibrium in the column on the basis of results of the nondimensional calculations. The concentration range of the objective isotherm which can be determined by the ECP method can also be predicted by numerical calculations. The usefulness of the correction strategy and the prediction of the concentration range were experimentally demonstrated. (C) 2000 Elsevier Science B.V. All rights reserved.

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    • Kinetic study of the mass transfer of bovine serum albumin in anion-exchange chromatography Peer-reviewed

      K Miyabe, G Guiochon

      JOURNAL OF CHROMATOGRAPHY A866 ( 2 ) 147 - 171   1 2000

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      A kinetic study was made on the mass transfer phenomena of bovine serum albumin (BSA) in two different anion-exchange columns (Resource-Q and TSK-GEL-DEAE-5PW). The analysis of the concentration dependence of the lumped mass transfer rate coefficient (k(m,L)) provided the information about the kinetics of the several mass transfer processes in the columns and the anion exchangers, i.e., the axial dispersion, the fluid-to-particle mass transfer, the intraparticle diffusion,and the adsorption/desorption. In the Resource-Q column, the intraparticle diffusion had a dominant contribution to the band broadening compared with those of the other processes. The surface diffusion coefficient (D-s) Of BSA showed a positive concentration dependence, by which the linear dependence of k(m,L) on the BSA concentration seemed to be interpreted On the other hand, in the TSK-GEL-DEAE-5PW column, the contribution of the adsorption/desorption was also important and almost same as that due to the intraparticle diffusion. There are some differences between the intrinsic properties of the mass transfer kinetics inside the two anion exchangers. It was likely that the positive concentration dependence of D-s was explained by the heterogeneous surface model. (C) 2000 Elsevier Science B.V. All rights reserved.

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    • Thermodynamic Characteristics of Surface Diffusion in Reversed-Phase Liquid Chromatography Peer-reviewed

      Miyabe, K, Guiochon, G

      J. Phys. Chem. B103   11086 - 11097   12 1999

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    • Influence of column radial heterogeneity on peak fronting in linear chromatography Peer-reviewed

      K Miyabe, G Guiochon

      JOURNAL OF CHROMATOGRAPHY A857 ( 1-2 ) 69 - 87   10 1999

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      Using numerical calculations of elution peak profiles, an explanation of the fronting behavior of elution peaks in linear chromatography was found in certain radial distributions of the mobile phase flow velocity and local bed efficiency. Fronting peaks are observed only if the flow velocity is higher in the wall region than in the center part of the column and the local efficiency is lower near the wall than in the center. By contrast, tailing or symmetrical peaks are observed if only the how velocity or the local efficiency are radially heterogeneous. The degree of peak fronting increases with increasing amplitude of the radial distributions. The influence of the radial heterogeneity of the flow velocity on the degree of peak fronting is more severe for high than for low efficiency columns. An equation is suggested to correlate peak fronting behavior for columns of different efficiencies and a procedure proposed for the estimation of the radial distributions of the flow velocity and the local efficiency by analyzing some characteristics of asymmetric peaks. (C) 1999 Elsevier Science B.V. All rights reserved.

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    • Kinetic Study of the Concentration Dependence of the Mass Transfer Rate Coefficient in Anion-Exchange Chromatography of Bovine Serum Albumin Peer-reviewed

      Miyabe, K, Guiochon, G

      Biotechnol. Prog.15   740 - 752   8 1999

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    • Kinetic Study of the Mass Transfer of S-Tröger's Base in the System Cellulose Triacetate and Ethanol Peer-reviewed

      Miyabe, K, Guiochon, G

      J. Chromatogr. A849   445 - 465   7 1999

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    • Analysis of surface diffusion phenomena in reversed-phase liquid chromatography Peer-reviewed

      K Miyabe, G Guiochon

      ANALYTICAL CHEMISTRY71 ( 4 ) 889 - 896   2 1999

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      Surface diffusion data obtained for a reversed-phase liquid chromatographic system (octadecylsilyl silica gel and a 70/30 (v/v) methanol/water solution) were analyzed in relation to their molecular diffusivity (D-m). The adsortate-adsorbent interactions between the studied compounds and the stationary phase were taken into account. The surface diffusion coefficient (D-s) depends on the mobile-phase composition, especially on the nature and concentration of the organic modifiers. Differences between the values of D-s measured under various conditions stem probably from differences in D-m. It also seems that D-s tends toward D-m with decreasing retention factor. The surface diffusion mechanism was assumed to be a restricted molecular diffusion in a potential held of adsorption. A restriction energy for this diffusion (E-r) was introduced to correlate D-s with D-m. The ratio of E-r to the isosteric heat of adsorption (-Q(st))was found to be nearly constant, irrespective of the retention factor, with an average value of 0.32 for our phase system. An estimation procedure for D-s using the enthalpy-entropy compensation effect for the adsorption equilibrium is proposed. From the adsorption equilibrium constant at 298 K only, D-s could be estimated at different temperatures with an error less than similar to 50%.

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    • Adsorption characteristics in reversed-phase liquid chromatography using ethanol water mixed solvent Peer-reviewed

      K Miyabe, S Takeuchi, Y Tezuka

      ADSORPTION-JOURNAL OF THE INTERNATIONAL ADSORPTION SOCIETY5 ( 1 ) 15 - 24   1 1999

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      Adsorption characteristics were studied in a reversed-phase liquid chromatography consisting of an octadecylsilyl (ODS)-silica gel and ethanol/water mixture (70/30, v/v), and were compared with corresponding results obtained by using methanol/water and acetonitrile/water mixtures (70/30, v/v) as mobile phase. Similar tendencies were observed for some adsorption characteristics in the three chromatographic systems. However, the magnitude of the characteristics was not entirely identical in the three systems. Surface diffusion was dominant for intraparticle diffusion in the ODS-silica gel particles irrespective of the type of the organic modifiers in mobile phases. A few correlations were confirmed with regard to surface diffusion, i.e., an enthalpy-entropy compensation and a linear free-energy relation. The analogous correlations on surface diffusion phenomena suggest the similarity in the mechanism of surface diffusion in the three chromatographic systems.

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    • Estimation of the column radial heterogeneity from an analysis of the characteristics of tailing peaks in linear chromatography Peer-reviewed

      K Miyabe, G Guiochon

      JOURNAL OF CHROMATOGRAPHY A830 ( 1 ) 29 - 39   1 1999

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      An estimation procedure of the radial heterogeneity of the distributions of the mobile phase flow velocity and of the local column efficiency was derived from a comparison of experimental data and of the characteristics of these tailing peaks calculated numerically. The analysis of these characteristics indicated that the radial heterogeneity of the packing density of a column is a cause of peak tailing. This analysis showed also that it is possible to correlate the radial fluctuations of the flow velocity and the apparent efficiency of different columns. The comparison of experimental data and calculated results suggested also a correlation between the radial distributions of the Bow velocity and of the column efficiency. Previous experimental data concerning the radial heterogeneity of column packings validated the correlation. Information on the degree of heterogeneity of the radial distributions of the flow velocity and the column efficiency were obtained by analyzing the peak width and the asymmetry factor of elution peaks. It was also found that the exponentially modified Gaussian distribution cannot provide a comprehensive representation of all types of tailing profiles in chromatography. (C) 1999 Elsevier Science B.V. All rights reserved.

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    • Peak tailing and column radial heterogeneity in linear chromatography Peer-reviewed

      K Miyabe, G Guiochon

      JOURNAL OF CHROMATOGRAPHY A830 ( 2 ) 263 - 274   1 1999

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      The correlation between the radial heterogeneity of a column and the tailing of the elution profiles of chromatographic peaks was studied using a numerical method. A parabolic distribution of the linear flow velocity of the mobile phase and of the column efficiency in the radial direction were assumed. Moment analysis showed that peak tailing takes place under such experimental conditions and that it increases with increasing range of radial variations of the flow velocity and the column efficiency. It was also found that the higher the column efficiency, the larger the effect of a given degree of radial heterogeneity on the extent of peak tailing. Peak tailing behavior of columns having different efficiencies could be correlated with each other by an equation. Some characteristic features of tailing peaks were analyzed in connection with the column radial heterogeneity. (C) 1999 Elsevier Science B.V. All rights reserved.

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    • Estimation of surface diffusion coefficient in liquid phase adsorption Peer-reviewed

      K Miyabe, S Takeuchi

      CANADIAN JOURNAL OF CHEMICAL ENGINEERING76 ( 5 ) 887 - 892   10 1998

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      An estimation procedure of surface diffusion coefficient, D-s, in liquid phase adsorption was proposed. The procedure is based on a restricted diffusion model, in which D-s is correlated with molecular diffusivity by considering a restriction energy due to an adsorptive interaction between adsorbates and adsorbents. In some adsorption systems, D-s of different adsorbates could be calculated with an error less than about 50% from only one datum of each adsorption equilibrium constant. Irrespective of temperature, the procedure can be applied for the estimation of D-s even in a wide range of D-s of about 4 orders of magnitude.

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    • Estimation of the Surface-Diffusion Coefficient in Gas-Phase Adsorption Using Octadecylsilyl-Silica Gel Peer-reviewed

      Miyabe, K, Takeuchi, S, Tezuka, Y

      Bull. Chem. Soc. Jpn.71   1755 - 1761   8 1998

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    • Estimation of Surface Diffusion Coefficient in Reversed-Phase Liquid Chromatography Using Methanol/Water Mobile Phases Peer-reviewed

      Miyabe, K, Takeuchi, S, Tezuka, Y

      J. Chem. Eng. Jpn.31   347 - 354   6 1998

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    • Effect of the type of organic modifiers on mass transfer in reversed-phase liquid chromatography Peer-reviewed

      K Miyabe, S Takeuchi

      ANALYTICAL SCIENCES14 ( 2 ) 361 - 368   4 1998

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      The mass-transfer characteristics were studied in a reversed-phase liquid chromatography consisting of an octadecylsilyl-silica gel and acetonitrile/water mixture (70/30, vol), and were compared with those obtained by using methanol/water (70/30, vol). In the two chromatographic systems, similar tendencies were observed for various adsorption characteristics. However, their absolute values were not entirely identical. Irrespective of the type of organic modifiers, surface diffusion was dominant for intraparticle diffusion. Similar correlations were also demonstrated with regard to the surface diffusion, i.e., the enthalpy-entropy compensation and the linear free-energy relation, suggesing a similarity in the surface migration mechanism in the two chromatographic systems. A few estimation procedures of the surface diffusion coefficient were proposed.

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    • Retention behavior of p-alkylphenols in reversed-phase liquid chromatography using ethanol/water mixtures Peer-reviewed

      K Miyabe, N Nomura, F Morishita, S Kurata, H Asamura, Y Imada

      ANALYTICAL SCIENCES14 ( 2 ) 355 - 359   4 1998

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      The retention behavior of p-alkylphenols was studied in reversed-phase liquid chromatography using octadecylsilyl-silica gel and ethanol/water mobile phases. The results were compared with those in methanol/water systems. Linear correlations were observed between the logarithmic retention factor (ln k) and the carbon number of side chains in the solutes, irrespective of the type and volumetric fraction (phi) of the organic modifiers in the mobile phases. The straight lines measured at different phi converged at almost one point. By analyzing the slope of the linear correlations, a functional contribution of a methylene group to k and a reduction of the hydrophobic surface area of the solutes and octadecylsilyl ligands due to the retention were estimated. It was also attempted to analyze the characteristics of the retention in reversed-phase liquid chromatography on the basis of solvophobic theory.

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    • Surface diffusion of alkylbenzenes on octadecylsilyl-silica gel Peer-reviewed

      K Miyabe, S Takeuchi

      INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH37 ( 3 ) 1154 - 1158   3 1998

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      Surface diffusion phenomena of alkylbenzenes in reversed-phase liquid chromatography (RP-LC) using an octadecylsilyl-silica gel and methanol/water (70/30, v/v) were analyzed on the basis of a restricted molecular diffusion model, in which surface diffusion coefficient, D-s, was correlated with molecular diffusivity, D-m, by introducing a restriction energy, E-r. The average ratio of E-r to isosteric heat of adsorption Q(st), gamma, in RP-LC was about 0.3. It was also indicated that gamma at different temperatures could be represented as a linear function of the reciprocal of -Q(st) when a linear free-energy relation held and an enthalpy-entropy compensation for adsorption equilibrium was established. An estimation procedure of D-s was proposed on the basis of the results. It was demonstrated that D-s at a given temperature could be calculated with an error of less than about 10% from only one datum of the adsorption equilibrium constant.

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    • 銀触媒上での一酸化二窒素と水素の反応 - 有害物質の触媒反応に関する研究(2) - Peer-reviewed

      手塚昌郷, 宮部寛志

      富山大学教育学部紀要 B(理科系)52   19 - 23   2 1998

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    • Adsorption Characteristics in Reversed-Phase Liquid Chromatography Using Methanol/Water and Acetonitrile/Water Mobile Phases Peer-reviewed

      Miyabe, K, Takeuchi, S

      J. Chem. Eng. Jpn.30   1047 - 1053   12 1997

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    • Model for surface diffusion in liquid-phase adsorption Peer-reviewed

      K Miyabe, S Takeuchi

      AICHE JOURNAL43 ( 11 ) 2997 - 3006   11 1997

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      Based on the absolute-rate theory a consistent interpretation was provided for the dependence of surface-diffusion coefficient, D-s, on temperature and the amount adsorbed in various liquid-phase adsorption systems, such as the Langmuir-, Freundlich- and Jossens-type adsorption. It was demonstrated that a restricted molecular diffusion model for surface diffusion was useful for the analysis of the characteristic features of D-s. A formulation of D-s was derived based on the model and was applied to the analysis of surface-diffusion phenomena in various adsorption systems. The temperature dependence could be interpreted by assuming surface diffusion as an activated process. By taking into account the change in both the logarithmic slope of an adsorption isotherm and an adsorption potential, the concentration dependence of D-s could be interpreted irrespective of the type of the adsorption isotherms.

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    • Analysis of peak spreading phenomena in liquid chromatography Peer-reviewed

      K Miyabe, S Takeuchi

      ANALYTICAL SCIENCES13 ( 5 ) 713 - 720   10 1997

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      A nondimensional plate height equation was proposed for the kinetic analysis of peak spreading in liquid chromatography. The equation was derived on the basis of the theory of moment analysis. The equation represents the correlation between two dimensionless parameters, the reduced plate height, h, and reduced velocity, v, with several other parameters including a surface diffusion coefficient. Characteristic features of the equation proposed were compared with those of several ordinary equations. The influence of each of the several parameters in the equation on the correlation between h and v was individually evaluated by numerical calculations. The influence of surface diffusion on h was significant at sufficiently large values of v. The contributions of a few mass-transfer processes in a column, i.e., axial dispersion, fluid-to-particle mass-transfer, and intraparticle diffusion, to h were separately evaluated. It was demonstrated that peak spreading phenomena in liquid chromatography could be numerically analyzed under various conditions according to the nondimensional equation.

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    • Surface diffusion phenomena in reversed-phase liquid chromatography with methanol/water and acetonitrile/water mixtures Peer-reviewed

      K Miyabe, S Takeuchi

      INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH36 ( 10 ) 4335 - 4341   10 1997

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      Characteristics of surface diffusion phenomena were studied under low-loading or analytical conditions of reversed-phase Liquid chromatography. As mobile phases, methanol/water and acetonitrile/water mixtures were used. In both systems, several similar relationships were confirmed for the enthalpy-entropy compensation effect, the linear free-energy relation, and some correlations between the surface diffusion coefficient, D-s, and mobile-phase composition, phi, and between the ratio of D-s to molecular diffusivity and phi. Similarity of the correlations indicated that the surface diffusion mechanism was essentially identical irrespective of the type of the organic modifiers. A strong influence of phi on D-s was confirmed. A nomograph concerning corresponding mobile-phase compositions for D-s as well as for adsorption equilibrium constant was proposed for the both mobile-phase systems. On the basis of the several correlations, D-s under various conditions in low-concentration systems can be estimated.

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    • Analysis of Surface Diffusion Phenomena in Liquid Phase Adsorption Peer-reviewed

      Miyabe, K, Takeuchi, S

      J. Phys. Chem. B101   7773 - 7779   9 1997

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    • アセトニトリル-水混合溶媒を用いる逆相分配液体クロマトグラフ分離系の物質移動特性 Peer-reviewed

      宮部寛志, 蓮蔵優治, 竹内茂彌

      分析化学46   579 - 586   7 1997

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    • Effect of acetonitrile/water mobile-phase composition on adsorption characteristics of reversed-phase liquid chromatography Peer-reviewed

      K Miyabe, S Takeuchi

      ANALYTICAL CHEMISTRY69 ( 13 ) 2567 - 2574   7 1997

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      The influence of volumetric composition of acetonitrile in a mobile phase on adsorption characteristics of reversed-phase liquid chromatography using octadecylsilyl (ODS)-modified silica gel was studied by the pulse response method and the moment analysis. The results were compared with those obtained for the reversed-phase system consisting of ODS-silica gel and methanol/water mixtures, In both systems, surface diffusion was dominant for intraparticle diffusion in ODS-silica gel particles, The contributions of three mass transfer steps in a column to peak broadening were of about the same order of magnitude. The activation energy of surface diffusion, E-s, was found to be larger than the isosteric heat of adsorption, Q(st). Because similar tendencies were observed for these adsorption characteristics, adsorption mechanisms may be analogous in both chromatographic systems. However, absolute values of the adsorption equilibrium constant, K, the decreasing ratio of hydrophobic surface area, Delta A/A, Q(st), and E-s for acetonitrile/water systems were smaller than the corresponding values for methanol/water systems, Oppositely, greater values of D-s were obtained for acetonitrile/water systems, It was concluded that the interaction between ODS ligands and adsorbate molecules was weaker compared with that in methanol/water mobile-phase systems when acetonitrile was used as an organic modifier in a mobile phase of reversed-phase liquid chromatography.

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    • Numerical Analysis of Height Equivalent to a Theoretical Plate in Reversed-Phase Liquid Chromatography Peer-reviewed

      Miyabe, K, Takeuchi, S

      CHROMATOGRAPHY18   161 - 168   7 1997

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    • CHROMATOGRAPHIC STUDY ON LIQUID-PHASE ADSORPTION ON OCTADECYLSILYL-SILICA GEL Peer-reviewed

      K MIYABE, M SUZUKI

      AICHE JOURNAL41 ( 3 ) 548 - 558   3 1995

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      Adsorption characteristics of reversed-phase liquid chromatography and influence of solvent composition on the characteristics are studied by the chromatographic method and the moment analysis. Adsorption equilibrium constant increases by adding hydrophobic increments into adsorbate molecules. Contributions of fluid-to-particle mass transfer and intraparticle diffusion to mass-transfer resistance in the octadecylsilyl-silica gel (ODS) column are almost equally great. Surface diffusion is dominant for the intraparticle diffusion in ODS. The logarithm of the surface diffusion coefficient linearly increases with an increase in methanol fraction in the range from 40 to 100 vol. %. In liquid-phase adsorption, activation energy of surface diffusion is greater than the isosteric heat of adsorption and both increase when methanol fraction decreases in the range from 40 to 100 vol. %. An empirical correlation based on experimental data proposed estimates surface diffusion coefficients from physical properties of adsorbates.

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    • SOLVENT EFFECT ON ADSORPTION PHENOMENA IN REVERSED-PHASE LIQUID-CHROMATOGRAPHY Peer-reviewed

      K MIYABE, M SUZUKI

      AICHE JOURNAL41 ( 3 ) 536 - 547   3 1995

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      The effect of solvent and mobile-phase composition on adsorption characteristics in liquid-phase absorption is studied. Comparing experimental adsorption data for several organics in both gas- and liquid-phase systems confirms that adsorption equilibrium constant K and isosteric heat of adsorption Q(st) are smaller than those in corresponding gaseous systems. The logarithm of K almost linearly increases as methanol composition decreases. Solvophobic theory applied quantitatively analyzes these solvent effects. Estimation methods for three parameters influence calculation results: solvent effects on K can be quantitatively analyzed; the adsorbability of adsorbates can be estimated from the value of Delta G(solv) for each homologue in a reversed-phase liquid chromatographic system; and the solvent effect on Q(st) cannot be satisfactorily interpreted. It is, however, confirmed that Q(st) is influenced by a solvent and an apparent small value is observed in liquid-phase adsorption.

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    • Adsorption Characteristics of Reversed-Phase Liquid Chromatography with Various Alkyl Bonded Phases Peer-reviewed

      Miyabe, K, Suzuki, M

      J. Chem. Eng. Jpn.27   785 - 789   12 1994

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    • MASS-TRANSFER PHENOMENA ON THE SURFACE OF ADSORBENTS IN REVERSED-PHASE CHROMATOGRAPHY Peer-reviewed

      K MIYABE, M SUZUKI

      INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH33 ( 7 ) 1792 - 1802   7 1994

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      Characteristics of mass-transfer phenomena on the surface of adsorbents in reversed-phase chromatography were studied by the chromatographic method and moment analysis. Enthalpy-entropy compensation occurs for surface diffusion in various systems of reversed-phase chromatography. The mechanism of surface diffusion seems to be essentially identical regardless of adsorption conditions. The linear free-energy relation holds in reversed-phase liquid chromatographic systems. Analyzing the slope of the linear relations, it is concluded that the activation energy of surface diffusion is essentially smaller than the isosteric heat of adsorption in liquid-phase adsorption as well as in gaseous systems though the heat of adsorption is experimentally determined to be smaller than the activation energy. Surface diffusion coefficients were correlated to physical properties of adsorbates. Concentration dependence of surface diffusion coefficient was explained by the chemical potential driving force model. An estimation method of the surface diffusion coefficient at each given temperature and amount adsorbed in reversed-phase liquid chromatography was proposed.

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    • Estimation of Adsorption Parameters of a Binary System by Applying the Lewis Rule Peer-reviewed

      Miyabe, K, Suzuki, M

      J. Chem. Eng. Jpn.27   257 - 259   4 1994

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    • ADSORPTION CHARACTERISTICS OF OCTADECYLSILYL-SILICA GEL IN GASEOUS SYSTEMS Peer-reviewed

      K MIYABE, M SUZUKI

      AICHE JOURNAL39 ( 11 ) 1791 - 1798   11 1993

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      Adsorption rates and thermodynamic parameters were determined for the gas-phase adsorption of n-alkanes and benzene derivatives on octadecylsilyl-silica gel (ODS) by chromatographic measurement and moment analysis. Thermodynamic characteristics of adsorption phenomena on ODS were similar to those on the surface. The contribution of intraparticle diffusion to mass-transport resistance was dominant in the ODS column, and the role of surface diffusion was significant for the intraparticle diffusion. The values of the surface diffusion coefficient were of the order of 10(-5) cm2/s and could be estimated by assuming that the surface migration on ODS is a tracer diffusion of an adsorbate molecule in n-octadecane.

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    • 逆相液体クロマト分離の化学工学的研究

      宮部寛志

          18 3 1993

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    • Chromatographic Study of Liquid Phase Adsorption of p-tert-Octylphenol on Octadecylsilyl-Silica Gel Peer-reviewed

      Miyabe, K, Suzuki, M

      Proceedings of the Fourth International Conference on Fundamentals of Adsorption   437 - 444   1 1993

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    • CHROMATOGRAPHY OF LIQUID-PHASE ADSORPTION ON OCTADECYLSILYL-SILICA GEL Peer-reviewed

      K MIYABE, M SUZUKI

      AICHE JOURNAL38 ( 6 ) 901 - 910   6 1992

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      Intraparticle diffusion and adsorption equilibrium on octadecylsilyl-silica gel (ODS) were studied. As an adsorbate, p-tert-octylphenol (PTOP) was employed. The intraparticle diffusion coefficient was measured by the chromatographic technique and the moment analysis at zero and several surface coverages. Adsorption isotherms can be correlated by the Langmuir equation. The isosteric heat of adsorption and the activation energy of surface diffusion were constant regardless of the amount adsorbed. These results suggest that ODS has an energetically homogeneous surface. The effect of solvent on isosteric heat of adsorption in the liquid system was discussed qualitatively by the solvophobic theory. Surface diffusion coefficient of PTOP on ODS was of the order of 10(-7) to 10(-6) cm2/S. Surface diffusion was dominant for the intraparticle diffusion in ODS, and its coefficient increased with an increase in the amount adsorbed. Positive concentration dependence of the surface diffusion coefficient was interpreted in terms of diffusion by potential chemical driving force.

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    • Estimation of an Adsorption Isotherm by Analyzing a Desorption Curve Peer-reviewed

      Miyabe, K, Suzuki, M

      J. Chem. Eng. Jpn.24   772 - 777   12 1991

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    • DETERMINATION AND CHARACTERIZATION OF REVERSED-PHASE BONDED LIGANDS BY CHEMICAL CLEAVAGE WITH AQUEOUS HYDROFLUORIC-ACID Peer-reviewed

      K MIYABE, N ORITA

      TALANTA36 ( 9 ) 897 - 902   9 1989

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    • マルチカラムシステムによる逆相液体クロマトグラフィーの工業化 Peer-reviewed

      宮部寛志, 川添鉄也, 山口正人, 北澤厚治

      化学工学論文集15   475 - 480   5 1989

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    • 個々のイオン及び溶媒へのイオン対抽出定数の分割 -フェロン-陽イオン界面活性剤系- Peer-reviewed

      後藤克己, 田口茂, 宮部寛志, 春山健一

      分析化学32   678 - 682   11 1983

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    • EFFECT OF CATIONIC SURFACTANT ON THE FORMATION OF FERRON COMPLEXES Peer-reviewed

      K GOTO, S TAGUCHI, K MIYABE, K HARUYAMA

      TALANTA29 ( 7 ) 569 - 575   1982

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    • Moment theory for kinetic study of chromatography Invited Peer-reviewed

      Kanji Miyabe

      TRAC-TRENDS IN ANALYTICAL CHEMISTRY81   79 - 86   7 2016

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      Language:English   Publishing type:Book review, literature introduction, etc.   Publisher:ELSEVIER SCI LTD  

      It is required to study the mass transfer and reaction kinetics for well understanding some important characteristics and mechanisms of chromatography. A great number of studies have been pursued so far on the retention equilibrium in chromatography. On the contrary, some intrinsic difficulties prevent the progress of the kinetic study. Moment theory is one of effective strategies for analyzing chromatographic behavior from the kinetic point of view. In this review, at first, a framework of the moment analysis theory is explained. Then, the recent progress of some related research subjects is introduced. (C) 2016 Elsevier B.V. All rights reserved.

      DOI: 10.1016/j.trac.2016.01.003

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    • Development of New Strategy for Analysis of Chromatographic Behavior on the Basis of Moment Theory

      Miyabe, K

      CHROMATOGRAPHY31   1 - 15   3 2010

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      Language:English   Publishing type:Article, review, commentary, editorial, etc. (scientific journal)   Publisher:クロマトグラフィー科学会  

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    • Surface diffusion in reversed-phase liquid chromatography

      Kanji Miyabe, Georges Guiochon

      JOURNAL OF CHROMATOGRAPHY A1217 ( 11 ) 1713 - 1734   3 2010

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      More than 40 years ago, Giddings pointed out in "Dynamics of Chrornatography" that surface diffusion should become an important research topic in the kinetics of chromatographic phenomena However, few studies on Surface diffusion in adsorbents used in chromatography were published since then. Most scientists use ordinary rate equations to Study mass transfer kinetics in chromatography. They take no account of surface diffusion and overlook the significant contributions of this mass transfer process to chromatographic behavior and to column efficiency at high mobile phase flow rate. Only recently did the significance Of Surface diffusion in separation processes begin to be recognized in connection with the development of new techniques of fist flow, high efficiency chromatography In this review, we revisit the reports on experimental data oil surface diffusion and introduce a surface-restricted molecular diffusion model. derived as a first approximation for the mechanism of surface diffusion, Oil the basis of the absolute rate theory. We also explain how this model accounts for many intrinsic characteristics of surface diffusion that cannot properly be explained by the conventional models Of Surface diffusion (C) 2009 Elsevier B.V. All rights reserved.

      DOI: 10.1016/j.chroma.2009.12.054

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    • クロマトグラフィー技術開発の二面性

      宮部寛志

      LC talk72   2   4 2009

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      Language:Japanese   Publishing type:Article, review, commentary, editorial, etc. (trade magazine, newspaper, online media)   Publisher:株式会社 島津製作所  

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    • Moment Analysis of Chromatographic Behavior in Reversed Phase Liquid Chromatography

      Miyabe, K

      J. Sep. Sci.32   757 - 770   3 2009

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      Language:English   Publishing type:Article, review, commentary, editorial, etc. (scientific journal)   Publisher:Wiley  

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    • 外表面多孔性球状粒子分離剤を用いる高性能高速液体クロマトグラフィー

      宮部寛志

      ぶんせき ( 1 ) 30 - 31   1 2009

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      Language:Japanese   Publishing type:Article, review, commentary, editorial, etc. (other)   Publisher:日本分析化学会  

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    • Characterization of Monolithic Columns for HPLC

      Miyabe, K, Guiochon, G

      J. Sep. Sci.27   853 - 873   7 2004

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      Language:English   Publishing type:Article, review, commentary, editorial, etc. (scientific journal)   Publisher:Wiley  

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    • Measurement of the Parameters of the Mass Transfer Kinetics in High Performance Liquid Chromatography

      Miyabe, K, Guiochon, G

      J. Sep. Sci.26   155 - 173   3 2003

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      Language:English   Publishing type:Article, review, commentary, editorial, etc. (scientific journal)   Publisher:Wiley  

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    • Fundamental interpretation of the peak profiles in linear reversed-phase liquid chromatography

      K Miyabe, G Guiochon

      ADVANCES IN CHROMATOGRAPHY, VOL 4040   1 - 113   2000

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      Language:English   Publishing type:Book review, literature introduction, etc.   Publisher:MARCEL DEKKER  

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    • 逆相液体クロマトグラフィーにおける物質移動現象の解析

      宮部寛志

      分析化学47   769 - 782   11 1998

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      Language:Japanese   Publishing type:Article, review, commentary, editorial, etc. (scientific journal)   Publisher:日本分析化学会  

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    • 吸着等温線の簡易測定

      宮部寛志

      Adsorpt. News11   5 - 9   5 1997

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      Language:Japanese   Publishing type:Article, review, commentary, editorial, etc. (other)   Publisher:日本吸着学会  

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    • 逆相液体クロマト分離系の吸着平衡と吸着速度

      宮部寛志

      Adsorpt. News8   16 - 20   1 1994

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      Language:Japanese   Publishing type:Article, review, commentary, editorial, etc. (other)   Publisher:日本吸着学会  

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    • 逆相液体クロマトグラフィーの分離機構に関する研究の現状と課題

      宮部寛志, 鈴木基之

      生産研究45   343 - 349   5 1993

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      Language:Japanese   Publishing type:Article, review, commentary, editorial, etc. (bulletin of university, research institution)   Publisher:東京大学生産技術研究所  

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    • 逆相液体クロマト分離の最適条件探索に関する研究の現状と課題

      宮部寛志, 鈴木基之

      生産研究45   275 - 282   4 1993

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      Language:Japanese   Publishing type:Article, review, commentary, editorial, etc. (bulletin of university, research institution)   Publisher:東京大学生産技術研究所  

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    Books and Other Publications

    • 分析化学用語辞典

      日本分析化学会編( Role: Joint author)

      オーム社  11 2011 

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      Language:Japanese Book type:Dictionary, encyclopedia

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    • 機器分析化学

      津田孝雄, 廣川健他( Role: Joint author)

      朝倉書店  12 2004 

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      Language:Japanese Book type:Scholarly book

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    Professional Memberships

    Works

    • 有機塩素化合物の還元無害化処理法実証調査 (平成6年度環境庁委託業務結果報告書) Other

      4 1994
      -
      3 1995

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      Work type:Other  

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    Research Projects

    • キャピラリー電気泳動を利用する分子間相互作用の速度解析法の開発

      立教大学  立教大学学術推進特別重点資金(立教SFR) 

      宮部寛志

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      4 2015 - 3 2016

      Authorship:Principal investigator  Grant type:Competitive

      外圧印加により会合体をCE分離系内で停止させるChromatographic CE(CCE)法を考案した。CCE概念の導入とモーメント理論の適用により、分子の固定化や化学修飾(蛍光標識化)を必要としない分子間相互作用の会合・解離速度定数の測定法を開発した。本法が分子集合体(界面活性剤ミセル)の界面における物質透過の速度解析にも適用できることを実証した。

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    • クロマトグラフィーによる分子間相互作用の速度解析

      日本学術振興会  科学研究費助成事業 

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      4 2012 - 3 2014

      Grant type:Competitive

      流通式実験法(パルス応答法とピークパーキング法)及びモーメント解析理論を組み合わせ、分子間相互作用の平衡論的情報(親和定数や解離定数)だけではなく、速度論的情報(結合速度定数や解離速度定数)も求めることができる解析法を開発する。
      光学異性体分離系を具体的実験系として取り上げ、本法を適用して速度解析を行う。クロマトグラフィーが物質分離や分子間相互作用の平衡論的解析だけではなく、その速度論的研究へも適用できることを実証する。

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    • モーメント理論に基づくクロマトグラフィー挙動解析基盤技術の確立

      日本学術振興会  科学研究費助成事業 

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      4 2009 - 3 2012

      Grant type:Competitive

      コアシェル粒子分離剤に対応する新規モーメント式を開発し、モーメント解析理論体系の基本的な枠組みを構築した。また、ピークパーキング法に基づく液相系分子拡散係数、液境膜物質移動係数、細孔拡散係数や表面拡散係数等の速度パラメータ測定法を開発した。相互補完的なパルス応答法とピークパーキング法を組み合わせ、様々な実験系に対応できる速度解析実験法を開発した。一方各速度パラメータの推算については、溶媒物性(会合係数)や分離剤の構造特性(円柱状材料の有効長)を考慮してWilke-Chang式やWilson-Geankoplis式を補正する速度物性推算法を開発した。さらに解析手順としては、充填層構造のカラム半径方向不均一性の影響による非対称性ピークの発現機構を解明し、非対称ピーク形状の正確な数値解析法等を開発した。

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    • タンパク質等の拡散係数を簡便かつ正確に測定する技術開発

      その他省庁等  JSTシーズ発掘試験研究 

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      4 2007 - 3 2008

      Grant type:Competitive

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    • 熱力学的特性の解析による逆相液体クロマトグラフィー系の分離挙動解析理論の開発

      日本学術振興会  科学研究費助成事業 

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      4 2005 - 3 2008

      Grant type:Competitive

      逆相液体クロマトグラフィー系の吸着平衡定数と表面拡散係数の温度依存性を解析し、熱力学データを集積した。アルキルリガンドを表面修飾したソフト界面を用いる異相分離系における吸着特性や物質移動挙動を熱力学及びExtrathermodynamicsの観点から研究した。Krugらの解析法を利用して、吸着平衡と表面拡散のエンタルピー-エントロピー補償作用の成立を証明した。その結果に基づき、吸着平衡と表面拡散各々の過程及び、両者間における直線自由エネルギー関係の特徴(温度依存性等)を定量的に解釈するための新たな熱力学的モデルを開発した。また、カラム内や多孔質粒子内における拡散現象の新規解析法としてピークパーキング法を開発した。さらに、様々な構造的特徴(形状や多孔性)を有する各種分離剤に対する新規モーメント解析式を開発し、モーメント解析理論の体系化を図った。

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    • 将来の精密分離のための完全二次元HPLCの開発

      日本学術振興会  科学研究費助成事業 

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      4 2002 - 3 2005

      Grant type:Competitive

      モノリス型シリカC18カラムを二次元目カラムとして用いる単純・完全二次元高速液体クロマトグラフィー(2D-HPLC)システムを開発した。分離性能を高めて2D-HPLCの応用を図ると共に、二次元HPLCの分離挙動や基本性能に関する基礎的研究を行った。

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    • 逆相液体クロマトグラフィー系における物質移動現象の速度論的解析

      日本学術振興会  科学研究費助成事業 

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      4 2000 - 3 2004

      Grant type:Competitive

      逆相液体クロマトグラフィー(RPLC)系の物質移動現象を解析した。固定相として鎖長や修飾率を変えたアルキル基飾シリカゲル、フェニル基修飾シリカゲル、及び多孔性有機ポリマー粒子等)、移動相として主にメタノール/水混合溶液、試料物質としてベンゼン誘導体やフェノール誘導体等を使用するRPLC系においてパルス応答実験を行った。溶出ピーク形状をモーメント解析し、保持平衡及び物質移動速度に関する情報を得た。特に、表面拡散に関する系統的な研究結果に基づき表面拡散現象に対して表面-制限分子拡散モデルを提案し、絶対反応速度論を適用してその定式化を行った。本モデルにより表面拡散の特徴や物質移動機構を統一的に解析すると共に、表面拡散係数の推算法を提案した。またカラム温度条件を変化させてパルス応答実験を行い、保持平衡及び表面拡散の熱力学的特性を解析した。

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    • 逆相液体クロマトグラフィー系の分離挙動に関する研究

      共同研究 

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      4 2000 - 3 2001

      Grant type:Competitive

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    • 動物細胞を用いた農薬類の毒性評価法の開発

      日本学術振興会  科学研究費助成事業 

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      4 1994 - 3 1997

      Grant type:Competitive

      農薬類を水源汚染のモデル物質と見なし、次のような動物細胞の応答に基づく毒性評価手法を開発した。
      (1)動物細胞の機能変化を指標とする毒性評価法
      (2)動物細胞の形態変化を指標とする毒性評価法
      (3)迅速・簡便な毒性評価法
      (4)水処理評価指標としての細胞毒性の検討
      本研究で開発した毒性評価手法を、従来の水質評価法及び既存の変異原性試験と比較した。その結果、将来の飲料水の水質評価指標のひとつに細胞毒性を導入すべきではないかという結論に達した。

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    Industrial property rights

    • A Method of Treatment of a Fluid Containing Volatile Organic Halogenated Compounds

      Miyabe, K, Orita, N, Iwasaki, M, Tsurumaru, Y, Nakahara, T

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      Announcement no:EP0563669(A1)  Date announced:6 10 1993

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    • A Method of Treatment of a Fluid Containing Volatile Organic Halogenated Compounds

      Miyabe, K, Orita, N, Iwasaki, M, Tsurumaru, Y, Nakahara, T

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      Announcement no:AU-A-35247/93  Date announced:30 9 1993

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    • A Method of Treatment of a Fluid Containing Volatile Organic Halogenated Compounds

      Miyabe, K, Orita, N, Iwasaki, M, Tsurumaru, Y, Nakahara, T

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      Announcement no:EP0563669(A1)  Date announced:6 10 1993

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    • A Method of Treatment of a Fluid Containing Volatile Organic Halogenated Compounds

      Miyabe, K, Orita, N, Iwasaki, M, Tsurumaru, Y, Nakahara, T

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      Announcement no:EP0563669(A1)  Date announced:6 10 1993

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    • Method of Treatment of a Fluid Containing Volatile Organic Halogenated Compounds

      Miyabe, K, Orita, N, Iwasaki, M, Tsurumaru, Y, Nakahara, T

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      Announcement no:US5490941  Date announced:13 2 1996

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    • Method of Treatment of a Fluid Containing Volatile Organic Halogenated Compounds

      Miyabe, K, Orita, N, Iwasaki, M, Tsurumaru, Y, Nakahara, T

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      Announcement no:US5531901  Date announced:2 7 1996

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    • Method of decomposing volatile organic halogenated compounds in water

      Miyabe, K, Orita, N, Iwasaki, M, Tsurumaru, Y, Nakahara, T

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      Announcement no:EP0745561(A1)  Date announced:4 12 1996

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    • Verfahren zum Zersetzen von organischen halogenierten fluchtigen Verbindungen in Wasser

      Miyabe, K, Orita, N, Iwasaki, M, Tsurumaru, Y, Nakahara, T

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      Announcement no:DE69328732(T2)  Date announced:5 10 2000

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    • Verfahren zur Behandlung einer Flussigkeit, die fluchtige, halogenierte organische Verbindungen enthalt

      Miyabe, K, Orita, N, Iwasaki, M, Tsurumaru, Y, Nakahara, T

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      Announcement no:DE69323226(T2)  Date announced:17 6 1999

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    • イオンクロマトグラフィー方法

      中村幸二, 宮部寛志, 坂本秀一, 古谷英司, 中津川信一

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      Announcement no:1989-320460  Date announced:26 12 1989

      Patent/Registration no:1994271  Date issued:22 11 1995

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    • フロンの分解方法

      中原敏次, 宮部寛志

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      Announcement no:1994-091136  Date announced:5 4 1994

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    • 低沸点有機物の処理装置

      織田信博, 宮部寛志

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      Announcement no:1993-269346  Date announced:19 10 1993

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    • 吸着剤の吸着能の測定方法

      宮部寛志, 鈴木基之

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      Announcement no:1993-034325  Date announced:9 2 1993

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    • 塩化水素含有ガスの中和処理装置

      山田登, 宮部寛志

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      Announcement no:1995-299327  Date announced:14 11 1995

      Patent/Registration no:3480039  Date issued:10 10 2003

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    • 嫌気性処理装置からの排出ガスの処理方法

      依田元之, 宮部寛志

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      Announcement no:1995-328387  Date announced:19 12 1995

      Patent/Registration no:3482688  Date issued:17 10 2003

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    • 揮発性有機ハロゲン化合物の処理方法

      山田登, 宮部寛志, 鶴丸陽佳

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      Announcement no:1995-204625  Date announced:8 8 1995

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    • 揮発性有機ハロゲン化合物の処理方法

      織田信博, 宮部寛志

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      Announcement no:1993-329330  Date announced:14 12 1993

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    • 揮発性有機ハロゲン化合物の処理方法

      宮部寛志, 岩崎誠, 中原敏次, 鶴丸陽佳

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      Announcement no:1994-086990  Date announced:29 3 1994

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    • 揮発性有機ハロゲン化合物の処理方法

      中原敏次, 鶴丸陽佳, 宮部寛志, 岩崎誠

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      Announcement no:1994-106172  Date announced:19 4 1994

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    • 揮発性有機ハロゲン化合物の処理方法

      宮部寛志, 岩崎誠, 中原敏次, 鶴丸陽佳

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      Announcement no:1994-106171  Date announced:19 4 1994

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    • 揮発性有機ハロゲン化合物の処理方法

      宮部寛志, 鶴丸陽佳, 岩崎誠

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      Announcement no:1994-226048  Date announced:16 8 1994

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    • 揮発性有機ハロゲン化合物の処理方法

      宮部寛志, 岩崎誠, 中原敏次, 鶴丸陽佳

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      Announcement no:1994-226046  Date announced:16 8 1994

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    • 揮発性有機ハロゲン化合物の処理方法

      宮部寛志, 鶴丸陽佳, 鍵和田正子, 岩崎誠

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      Announcement no:1994-285334  Date announced:11 10 1994

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    • 揮発性有機ハロゲン化合物の処理方法

      宮部寛志

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      Announcement no:1994-269784  Date announced:27 9 1994

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    • 揮発性有機ハロゲン化合物の処理方法

      山田登, 鶴丸陽佳, 宮部寛志

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      Announcement no:1995-080247  Date announced:28 3 1995

      Patent/Registration no:3326910  Date issued:12 7 2002

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    • 揮発性有機ハロゲン化合物の処理方法

      宮部寛志, 岩崎誠, 鶴丸陽佳

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      Announcement no:1994-343983  Date announced:20 12 1994

      Patent/Registration no:3360353  Date issued:18 10 2002

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    • 揮発性有機ハロゲン化合物の気相分解方法

      宮部寛志, 山田登, 鶴丸陽佳

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      Announcement no:1995-303818  Date announced:21 11 1995

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    • 揮発性有機ハロゲン化合物の還元処理用触媒

      宮部寛志, 中原敏次, 鶴丸陽佳, 岩崎誠

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      Announcement no:1994-134315  Date announced:17 5 1994

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    • 揮発性有機ハロゲン化合物含有ガスの処理方法

      宮部寛志, 山田登, 鶴丸陽佳

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      Announcement no:1995-124443  Date announced:16 5 1995

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    • 揮発性有機ハロゲン化合物含有ガスの処理方法

      宮部寛志, 中原敏次, 岩崎誠

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      Announcement no:1994-142454  Date announced:24 5 1994

      Patent/Registration no:3293207  Date issued:5 4 2002

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    • 揮発性有機ハロゲン化合物含有ガスの気相分解処理方法

      織田信博, 宮部寛志

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      Announcement no:1994-031135  Date announced:8 2 1994

      Patent/Registration no:3293181  Date issued:5 4 2002

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    • 揮発性有機ハロゲン化合物含有ガスの気相還元分解処理方法

      宮部寛志, 織田信博

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      Announcement no:1993-301025  Date announced:16 11 1993

      Patent/Registration no:3324139  Date issued:5 7 2002

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    • 揮発性有機ハロゲン化合物含有水の処理方法

      宮部寛志, 鶴丸陽佳, 岩崎誠

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      Announcement no:1994-182361  Date announced:5 7 1994

      Patent/Registration no:3239502  Date issued:12 10 2001

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    • 揮発性有機ハロゲン化合物含有水の処理方法

      宮部寛志, 織田信博

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      Announcement no:1993-269476  Date announced:19 10 1993

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    • 揮発性有機ハロゲン化合物含有流体の処理方法

      宮部寛志, 岩崎誠, 中原敏次, 鶴丸陽佳

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      Announcement no:1994-055182  Date announced:1 3 1994

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    • 揮発性有機塩素化合物の分解方法

      山田登, 宮部寛志, 鶴丸陽佳

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      Announcement no:1995-308543  Date announced:28 11 1995

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    • 被還元性物質の還元分解装置

      山田登, 宮部寛志, 鶴丸陽佳

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      Announcement no:1995-251029  Date announced:3 10 1995

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    Social Contribution

    • Editor (Chromatography Research International)(Hindawi)

      6 2010 - Present

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    • Editorial Advisory Board (Journal of Separation Science)(Wiley-VCH)

      1 2002 - Present

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    • 富山大学地域連携推進機構産学連携部門「スーパーエンジニア養成コース」講師

      4 2011 - 3 2012

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    • 文部科学省委託事業「社会人の学び直しニーズ対応教育推進プログラム」

      9 2008 - 3 2011

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      “働きながら学ぶ先導的技術者育成事業”(プロフェッショナルエンジニアコース、先端環境・バイオ工学特論Ⅱ)講師

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    • Nature Reader Advisory Panel

      10 2008 - 8 2010

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    • 社団法人富山県計量協会環境計量証明部会クロスチェック研究会講師

      11 2004

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    • 愛知県化学物質適正管理指針検討委員会委員

      4 2003 - 3 2004

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    • 金沢大学薬学部(社会人博士課程)博士論文審査副査

      8 2003

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    • 第3回高校生国際環境サミット富山大会分科会講師

      8 2001

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      11 1999

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