Synthesis and evaluation of a chiral stationary phase based on quinine: Enantioresolution of dinitrophenyl derivatives of α-amino acids

Autores
Keunchkarian, Sonia; Padró, Juan Manuel; Gotta, Javier; Nardillo, Angel Miguel; Castells, Cecilia Beatriz Marta
Año de publicación
2011
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
The natural alkaloid quinine (QN) was immobilized on porous silica particles, and part of the material was subsequently endcapped with n-hexyl hydrocarbon chains. Two synthetic strategies for silanization of the support were first compared. These columns were thoroughly evaluated in order to study the influence of endcapping in the enantiorecognition features. Enantioseparations of twenty N-derivatized 2,4-dinitrophenyl α-amino acids (DNP-amino acids) were studied by changing mobile phase pH, buffer concentration, type of organic solvent in the mobile phase, and column temperature. Maximum retention factors were observed at pH ≈6, at this intermediate pH the tertiary amine of the quinine is protonated to a high degree and therefore available for strong electrostatic interactions with unprotonated anionic DNP-amino acids. The enantioselectivity factors, however, increased as the pH did in the range between 5 and 7. The increase in ionic strength had influence on retention, but not on enantioselectivity, allowing the use of this variable for optimization of retention factors. Finally, the thermodynamic transfer parameters of the enantiomers from the mobile to both CSPs (with and without endcapping, QN-CSP(EC) and QN-CSP, respectively) were estimated from van’t Hoff plots within the range of 10–40 °C. Thus, the differences in the transfer enthalpy, Δ(ΔH°), and transfer entropy, Δ(ΔS°), enabled an investigation of the origin of the differences in interaction energies.
Fil: Keunchkarian, Sonia. Provincia de Buenos Aires. Gobernación. Comisión de Investigaciones Científicas. Centro de Investigaciones en Tecnología de Pinturas. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Centro de Investigaciones en Tecnología de Pinturas; Argentina
Fil: Padró, Juan Manuel. Provincia de Buenos Aires. Gobernación. Comisión de Investigaciones Científicas. Centro de Investigaciones en Tecnología de Pinturas. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Centro de Investigaciones en Tecnología de Pinturas; Argentina
Fil: Gotta, Javier. Provincia de Buenos Aires. Gobernación. Comisión de Investigaciones Científicas. Centro de Investigaciones en Tecnología de Pinturas. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Centro de Investigaciones en Tecnología de Pinturas; Argentina
Fil: Nardillo, Angel Miguel. Provincia de Buenos Aires. Gobernación. Comisión de Investigaciones Científicas. Centro de Investigaciones en Tecnología de Pinturas. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Centro de Investigaciones en Tecnología de Pinturas; Argentina
Fil: Castells, Cecilia Beatriz Marta. Provincia de Buenos Aires. Gobernación. Comisión de Investigaciones Científicas. Centro de Investigaciones en Tecnología de Pinturas. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Centro de Investigaciones en Tecnología de Pinturas; Argentina
Materia
CINCHONA ALKALOIDS
CHIRAL STATIONARY PHASES
ENANTIOSELECTIVE ANION EXCHAGERS
N-PROTECTED A-AMINO ACIDS
Nivel de accesibilidad
acceso abierto
Condiciones de uso
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
Repositorio
CONICET Digital (CONICET)
Institución
Consejo Nacional de Investigaciones Científicas y Técnicas
OAI Identificador
oai:ri.conicet.gov.ar:11336/95423
Acceder
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network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Synthesis and evaluation of a chiral stationary phase based on quinine: Enantioresolution of dinitrophenyl derivatives of α-amino acidsKeunchkarian, SoniaPadró, Juan ManuelGotta, JavierNardillo, Angel MiguelCastells, Cecilia Beatriz MartaCINCHONA ALKALOIDSCHIRAL STATIONARY PHASESENANTIOSELECTIVE ANION EXCHAGERSN-PROTECTED A-AMINO ACIDShttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1https://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1The natural alkaloid quinine (QN) was immobilized on porous silica particles, and part of the material was subsequently endcapped with n-hexyl hydrocarbon chains. Two synthetic strategies for silanization of the support were first compared. These columns were thoroughly evaluated in order to study the influence of endcapping in the enantiorecognition features. Enantioseparations of twenty N-derivatized 2,4-dinitrophenyl α-amino acids (DNP-amino acids) were studied by changing mobile phase pH, buffer concentration, type of organic solvent in the mobile phase, and column temperature. Maximum retention factors were observed at pH ≈6, at this intermediate pH the tertiary amine of the quinine is protonated to a high degree and therefore available for strong electrostatic interactions with unprotonated anionic DNP-amino acids. The enantioselectivity factors, however, increased as the pH did in the range between 5 and 7. The increase in ionic strength had influence on retention, but not on enantioselectivity, allowing the use of this variable for optimization of retention factors. Finally, the thermodynamic transfer parameters of the enantiomers from the mobile to both CSPs (with and without endcapping, QN-CSP(EC) and QN-CSP, respectively) were estimated from van’t Hoff plots within the range of 10–40 °C. Thus, the differences in the transfer enthalpy, Δ(ΔH°), and transfer entropy, Δ(ΔS°), enabled an investigation of the origin of the differences in interaction energies.Fil: Keunchkarian, Sonia. Provincia de Buenos Aires. Gobernación. Comisión de Investigaciones Científicas. Centro de Investigaciones en Tecnología de Pinturas. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Centro de Investigaciones en Tecnología de Pinturas; ArgentinaFil: Padró, Juan Manuel. Provincia de Buenos Aires. Gobernación. Comisión de Investigaciones Científicas. Centro de Investigaciones en Tecnología de Pinturas. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Centro de Investigaciones en Tecnología de Pinturas; ArgentinaFil: Gotta, Javier. Provincia de Buenos Aires. Gobernación. Comisión de Investigaciones Científicas. Centro de Investigaciones en Tecnología de Pinturas. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Centro de Investigaciones en Tecnología de Pinturas; ArgentinaFil: Nardillo, Angel Miguel. Provincia de Buenos Aires. Gobernación. Comisión de Investigaciones Científicas. Centro de Investigaciones en Tecnología de Pinturas. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Centro de Investigaciones en Tecnología de Pinturas; ArgentinaFil: Castells, Cecilia Beatriz Marta. Provincia de Buenos Aires. Gobernación. Comisión de Investigaciones Científicas. Centro de Investigaciones en Tecnología de Pinturas. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Centro de Investigaciones en Tecnología de Pinturas; ArgentinaElsevier Science2011-06info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/95423Keunchkarian, Sonia; Padró, Juan Manuel; Gotta, Javier; Nardillo, Angel Miguel; Castells, Cecilia Beatriz Marta; Synthesis and evaluation of a chiral stationary phase based on quinine: Enantioresolution of dinitrophenyl derivatives of α-amino acids; Elsevier Science; Journal of Chromatography - A; 1218; 23; 6-2011; 3660-36680021-9673CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/http://www.sciencedirect.com/science/article/pii/S0021967311004870info:eu-repo/semantics/altIdentifier/doi/10.1016/j.chroma.2011.04.019info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-29T09:37:53Zoai:ri.conicet.gov.ar:11336/95423instacron:CONICETInstitucionalhttp://ri.conicet.gov.ar/Organismo científico-tecnológicoNo correspondehttp://ri.conicet.gov.ar/oai/requestdasensio@conicet.gov.ar; lcarlino@conicet.gov.arArgentinaNo correspondeNo correspondeNo correspondeopendoar:34982025-09-29 09:37:54.15CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Synthesis and evaluation of a chiral stationary phase based on quinine: Enantioresolution of dinitrophenyl derivatives of α-amino acids
title Synthesis and evaluation of a chiral stationary phase based on quinine: Enantioresolution of dinitrophenyl derivatives of α-amino acids
spellingShingle Synthesis and evaluation of a chiral stationary phase based on quinine: Enantioresolution of dinitrophenyl derivatives of α-amino acids
Keunchkarian, Sonia
CINCHONA ALKALOIDS
CHIRAL STATIONARY PHASES
ENANTIOSELECTIVE ANION EXCHAGERS
N-PROTECTED A-AMINO ACIDS
title_short Synthesis and evaluation of a chiral stationary phase based on quinine: Enantioresolution of dinitrophenyl derivatives of α-amino acids
title_full Synthesis and evaluation of a chiral stationary phase based on quinine: Enantioresolution of dinitrophenyl derivatives of α-amino acids
title_fullStr Synthesis and evaluation of a chiral stationary phase based on quinine: Enantioresolution of dinitrophenyl derivatives of α-amino acids
title_full_unstemmed Synthesis and evaluation of a chiral stationary phase based on quinine: Enantioresolution of dinitrophenyl derivatives of α-amino acids
title_sort Synthesis and evaluation of a chiral stationary phase based on quinine: Enantioresolution of dinitrophenyl derivatives of α-amino acids
dc.creator.none.fl_str_mv Keunchkarian, Sonia
Padró, Juan Manuel
Gotta, Javier
Nardillo, Angel Miguel
Castells, Cecilia Beatriz Marta
author Keunchkarian, Sonia
author_facet Keunchkarian, Sonia
Padró, Juan Manuel
Gotta, Javier
Nardillo, Angel Miguel
Castells, Cecilia Beatriz Marta
author_role author
author2 Padró, Juan Manuel
Gotta, Javier
Nardillo, Angel Miguel
Castells, Cecilia Beatriz Marta
author2_role author
author
author
author
dc.subject.none.fl_str_mv CINCHONA ALKALOIDS
CHIRAL STATIONARY PHASES
ENANTIOSELECTIVE ANION EXCHAGERS
N-PROTECTED A-AMINO ACIDS
topic CINCHONA ALKALOIDS
CHIRAL STATIONARY PHASES
ENANTIOSELECTIVE ANION EXCHAGERS
N-PROTECTED A-AMINO ACIDS
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv The natural alkaloid quinine (QN) was immobilized on porous silica particles, and part of the material was subsequently endcapped with n-hexyl hydrocarbon chains. Two synthetic strategies for silanization of the support were first compared. These columns were thoroughly evaluated in order to study the influence of endcapping in the enantiorecognition features. Enantioseparations of twenty N-derivatized 2,4-dinitrophenyl α-amino acids (DNP-amino acids) were studied by changing mobile phase pH, buffer concentration, type of organic solvent in the mobile phase, and column temperature. Maximum retention factors were observed at pH ≈6, at this intermediate pH the tertiary amine of the quinine is protonated to a high degree and therefore available for strong electrostatic interactions with unprotonated anionic DNP-amino acids. The enantioselectivity factors, however, increased as the pH did in the range between 5 and 7. The increase in ionic strength had influence on retention, but not on enantioselectivity, allowing the use of this variable for optimization of retention factors. Finally, the thermodynamic transfer parameters of the enantiomers from the mobile to both CSPs (with and without endcapping, QN-CSP(EC) and QN-CSP, respectively) were estimated from van’t Hoff plots within the range of 10–40 °C. Thus, the differences in the transfer enthalpy, Δ(ΔH°), and transfer entropy, Δ(ΔS°), enabled an investigation of the origin of the differences in interaction energies.
Fil: Keunchkarian, Sonia. Provincia de Buenos Aires. Gobernación. Comisión de Investigaciones Científicas. Centro de Investigaciones en Tecnología de Pinturas. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Centro de Investigaciones en Tecnología de Pinturas; Argentina
Fil: Padró, Juan Manuel. Provincia de Buenos Aires. Gobernación. Comisión de Investigaciones Científicas. Centro de Investigaciones en Tecnología de Pinturas. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Centro de Investigaciones en Tecnología de Pinturas; Argentina
Fil: Gotta, Javier. Provincia de Buenos Aires. Gobernación. Comisión de Investigaciones Científicas. Centro de Investigaciones en Tecnología de Pinturas. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Centro de Investigaciones en Tecnología de Pinturas; Argentina
Fil: Nardillo, Angel Miguel. Provincia de Buenos Aires. Gobernación. Comisión de Investigaciones Científicas. Centro de Investigaciones en Tecnología de Pinturas. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Centro de Investigaciones en Tecnología de Pinturas; Argentina
Fil: Castells, Cecilia Beatriz Marta. Provincia de Buenos Aires. Gobernación. Comisión de Investigaciones Científicas. Centro de Investigaciones en Tecnología de Pinturas. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Centro de Investigaciones en Tecnología de Pinturas; Argentina
description The natural alkaloid quinine (QN) was immobilized on porous silica particles, and part of the material was subsequently endcapped with n-hexyl hydrocarbon chains. Two synthetic strategies for silanization of the support were first compared. These columns were thoroughly evaluated in order to study the influence of endcapping in the enantiorecognition features. Enantioseparations of twenty N-derivatized 2,4-dinitrophenyl α-amino acids (DNP-amino acids) were studied by changing mobile phase pH, buffer concentration, type of organic solvent in the mobile phase, and column temperature. Maximum retention factors were observed at pH ≈6, at this intermediate pH the tertiary amine of the quinine is protonated to a high degree and therefore available for strong electrostatic interactions with unprotonated anionic DNP-amino acids. The enantioselectivity factors, however, increased as the pH did in the range between 5 and 7. The increase in ionic strength had influence on retention, but not on enantioselectivity, allowing the use of this variable for optimization of retention factors. Finally, the thermodynamic transfer parameters of the enantiomers from the mobile to both CSPs (with and without endcapping, QN-CSP(EC) and QN-CSP, respectively) were estimated from van’t Hoff plots within the range of 10–40 °C. Thus, the differences in the transfer enthalpy, Δ(ΔH°), and transfer entropy, Δ(ΔS°), enabled an investigation of the origin of the differences in interaction energies.
publishDate 2011
dc.date.none.fl_str_mv 2011-06
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/publishedVersion
http://purl.org/coar/resource_type/c_6501
info:ar-repo/semantics/articulo
format article
status_str publishedVersion
dc.identifier.none.fl_str_mv http://hdl.handle.net/11336/95423
Keunchkarian, Sonia; Padró, Juan Manuel; Gotta, Javier; Nardillo, Angel Miguel; Castells, Cecilia Beatriz Marta; Synthesis and evaluation of a chiral stationary phase based on quinine: Enantioresolution of dinitrophenyl derivatives of α-amino acids; Elsevier Science; Journal of Chromatography - A; 1218; 23; 6-2011; 3660-3668
0021-9673
CONICET Digital
CONICET
url http://hdl.handle.net/11336/95423
identifier_str_mv Keunchkarian, Sonia; Padró, Juan Manuel; Gotta, Javier; Nardillo, Angel Miguel; Castells, Cecilia Beatriz Marta; Synthesis and evaluation of a chiral stationary phase based on quinine: Enantioresolution of dinitrophenyl derivatives of α-amino acids; Elsevier Science; Journal of Chromatography - A; 1218; 23; 6-2011; 3660-3668
0021-9673
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/url/http://www.sciencedirect.com/science/article/pii/S0021967311004870
info:eu-repo/semantics/altIdentifier/doi/10.1016/j.chroma.2011.04.019
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
eu_rights_str_mv openAccess
rights_invalid_str_mv https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
dc.format.none.fl_str_mv application/pdf
application/pdf
application/pdf
application/pdf
dc.publisher.none.fl_str_mv Elsevier Science
publisher.none.fl_str_mv Elsevier Science
dc.source.none.fl_str_mv reponame:CONICET Digital (CONICET)
instname:Consejo Nacional de Investigaciones Científicas y Técnicas
reponame_str CONICET Digital (CONICET)
collection CONICET Digital (CONICET)
instname_str Consejo Nacional de Investigaciones Científicas y Técnicas
repository.name.fl_str_mv CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicas
repository.mail.fl_str_mv dasensio@conicet.gov.ar; lcarlino@conicet.gov.ar
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score 13.070432

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