Structure, Disorder, and Molecular Dynamics in Zn(d,l-histidine)2:  EPR of Copper Ion Dopants, X-ray Diffraction, and Calorimetric Studies

Autores
Dalosto, Sergio Daniel; Calvo, Rafael; Pizarro, José; Arriortua, María
Año de publicación
2001
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
We report EPR, X-ray crystallographic, and calorimetric measurements in copper-doped and pure Zn(II) bis(d,l-histidino)pentahydrate (C12H26N6O9Zn), to be called Zn(d,l-histidine)2. EPR data in copper-doped single crystals were obtained at 9.8 GHz as a function of the orientation of the magnetic field B at 298 and 80 K, and as a function of temperature (T) for fixed orientations of B. Powder samples were studied at 9.8 and 35 GHz. Steep changes of the EPR spectra with temperature occur around Tc = 268 K. Above Tc we observe spectra arising from a single copper with rhombic g and copper hyperfine A tensors. The resonances display a strong dependence of the line width with the hyperfine component. Below Tc the spectra can be assigned to two different copper ions displaying axial symmetry and related by a C2 rotation. As T increases approaching Tc, they collapse into the high-temperature spectrum. A peak in the differential specific heat of pure Zn(d,l-histidine)2 between 235 and 270 K indicates a transition intrinsic to the host material. Full X-ray structural studies were performed at 293 and at 150 K, above and below Tc. At 293 K our results are similar to those reported before. The low-temperature data show disorder in the water molecules. We interpret the experimental results with a model where the copper atoms hop randomly between different states. This dynamics is related to the fluctuating disorder in the lattice and produces steep changes on the EPR spectra of copper ion dopants. The role of dynamic Jahn−Teller distortions is discussed. A bonding scheme for the copper ions in Zn(d,l-histidine)2 is proposed, and it is compared with that encountered in type 1 blue copper proteins.
Fil: Dalosto, Sergio Daniel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Desarrollo Tecnológico para la Industria Química. Universidad Nacional del Litoral. Instituto de Desarrollo Tecnológico para la Industria Química; Argentina
Fil: Calvo, Rafael. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Desarrollo Tecnológico para la Industria Química. Universidad Nacional del Litoral. Instituto de Desarrollo Tecnológico para la Industria Química; Argentina
Fil: Pizarro, José. Universidad del País Vasco; España
Fil: Arriortua, María. Universidad del País Vasco; España
Materia
Epr
Jahn-Teller
Metal 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:11336/27790
Acceder
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oai_identifier_str oai:ri.conicet.gov.ar:11336/27790
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Structure, Disorder, and Molecular Dynamics in Zn(d,l-histidine)2:  EPR of Copper Ion Dopants, X-ray Diffraction, and Calorimetric StudiesDalosto, Sergio DanielCalvo, RafaelPizarro, JoséArriortua, MaríaEprJahn-TellerMetal Amino Acidshttps://purl.org/becyt/ford/1.3https://purl.org/becyt/ford/1We report EPR, X-ray crystallographic, and calorimetric measurements in copper-doped and pure Zn(II) bis(d,l-histidino)pentahydrate (C12H26N6O9Zn), to be called Zn(d,l-histidine)2. EPR data in copper-doped single crystals were obtained at 9.8 GHz as a function of the orientation of the magnetic field B at 298 and 80 K, and as a function of temperature (T) for fixed orientations of B. Powder samples were studied at 9.8 and 35 GHz. Steep changes of the EPR spectra with temperature occur around Tc = 268 K. Above Tc we observe spectra arising from a single copper with rhombic g and copper hyperfine A tensors. The resonances display a strong dependence of the line width with the hyperfine component. Below Tc the spectra can be assigned to two different copper ions displaying axial symmetry and related by a C2 rotation. As T increases approaching Tc, they collapse into the high-temperature spectrum. A peak in the differential specific heat of pure Zn(d,l-histidine)2 between 235 and 270 K indicates a transition intrinsic to the host material. Full X-ray structural studies were performed at 293 and at 150 K, above and below Tc. At 293 K our results are similar to those reported before. The low-temperature data show disorder in the water molecules. We interpret the experimental results with a model where the copper atoms hop randomly between different states. This dynamics is related to the fluctuating disorder in the lattice and produces steep changes on the EPR spectra of copper ion dopants. The role of dynamic Jahn−Teller distortions is discussed. A bonding scheme for the copper ions in Zn(d,l-histidine)2 is proposed, and it is compared with that encountered in type 1 blue copper proteins.Fil: Dalosto, Sergio Daniel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Desarrollo Tecnológico para la Industria Química. Universidad Nacional del Litoral. Instituto de Desarrollo Tecnológico para la Industria Química; ArgentinaFil: Calvo, Rafael. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Desarrollo Tecnológico para la Industria Química. Universidad Nacional del Litoral. Instituto de Desarrollo Tecnológico para la Industria Química; ArgentinaFil: Pizarro, José. Universidad del País Vasco; EspañaFil: Arriortua, María. Universidad del País Vasco; EspañaAmerican Chemical Society2001-01info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/27790Dalosto, Sergio Daniel; Calvo, Rafael; Pizarro, José; Arriortua, María; Structure, Disorder, and Molecular Dynamics in Zn(d,l-histidine)2:  EPR of Copper Ion Dopants, X-ray Diffraction, and Calorimetric Studies; American Chemical Society; Journal of Physical Chemistry A; 105; 1-2001; 1074-10851089-5639CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/doi/10.1021/jp003167ninfo:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-29T09:35:30Zoai:ri.conicet.gov.ar:11336/27790instacron: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 09:35:31.157CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Structure, Disorder, and Molecular Dynamics in Zn(d,l-histidine)2:  EPR of Copper Ion Dopants, X-ray Diffraction, and Calorimetric Studies
title Structure, Disorder, and Molecular Dynamics in Zn(d,l-histidine)2:  EPR of Copper Ion Dopants, X-ray Diffraction, and Calorimetric Studies
spellingShingle Structure, Disorder, and Molecular Dynamics in Zn(d,l-histidine)2:  EPR of Copper Ion Dopants, X-ray Diffraction, and Calorimetric Studies
Dalosto, Sergio Daniel
Epr
Jahn-Teller
Metal Amino Acids
title_short Structure, Disorder, and Molecular Dynamics in Zn(d,l-histidine)2:  EPR of Copper Ion Dopants, X-ray Diffraction, and Calorimetric Studies
title_full Structure, Disorder, and Molecular Dynamics in Zn(d,l-histidine)2:  EPR of Copper Ion Dopants, X-ray Diffraction, and Calorimetric Studies
title_fullStr Structure, Disorder, and Molecular Dynamics in Zn(d,l-histidine)2:  EPR of Copper Ion Dopants, X-ray Diffraction, and Calorimetric Studies
title_full_unstemmed Structure, Disorder, and Molecular Dynamics in Zn(d,l-histidine)2:  EPR of Copper Ion Dopants, X-ray Diffraction, and Calorimetric Studies
title_sort Structure, Disorder, and Molecular Dynamics in Zn(d,l-histidine)2:  EPR of Copper Ion Dopants, X-ray Diffraction, and Calorimetric Studies
dc.creator.none.fl_str_mv Dalosto, Sergio Daniel
Calvo, Rafael
Pizarro, José
Arriortua, María
author Dalosto, Sergio Daniel
author_facet Dalosto, Sergio Daniel
Calvo, Rafael
Pizarro, José
Arriortua, María
author_role author
author2 Calvo, Rafael
Pizarro, José
Arriortua, María
author2_role author
author
author
dc.subject.none.fl_str_mv Epr
Jahn-Teller
Metal Amino Acids
topic Epr
Jahn-Teller
Metal Amino Acids
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.3
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv We report EPR, X-ray crystallographic, and calorimetric measurements in copper-doped and pure Zn(II) bis(d,l-histidino)pentahydrate (C12H26N6O9Zn), to be called Zn(d,l-histidine)2. EPR data in copper-doped single crystals were obtained at 9.8 GHz as a function of the orientation of the magnetic field B at 298 and 80 K, and as a function of temperature (T) for fixed orientations of B. Powder samples were studied at 9.8 and 35 GHz. Steep changes of the EPR spectra with temperature occur around Tc = 268 K. Above Tc we observe spectra arising from a single copper with rhombic g and copper hyperfine A tensors. The resonances display a strong dependence of the line width with the hyperfine component. Below Tc the spectra can be assigned to two different copper ions displaying axial symmetry and related by a C2 rotation. As T increases approaching Tc, they collapse into the high-temperature spectrum. A peak in the differential specific heat of pure Zn(d,l-histidine)2 between 235 and 270 K indicates a transition intrinsic to the host material. Full X-ray structural studies were performed at 293 and at 150 K, above and below Tc. At 293 K our results are similar to those reported before. The low-temperature data show disorder in the water molecules. We interpret the experimental results with a model where the copper atoms hop randomly between different states. This dynamics is related to the fluctuating disorder in the lattice and produces steep changes on the EPR spectra of copper ion dopants. The role of dynamic Jahn−Teller distortions is discussed. A bonding scheme for the copper ions in Zn(d,l-histidine)2 is proposed, and it is compared with that encountered in type 1 blue copper proteins.
Fil: Dalosto, Sergio Daniel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Desarrollo Tecnológico para la Industria Química. Universidad Nacional del Litoral. Instituto de Desarrollo Tecnológico para la Industria Química; Argentina
Fil: Calvo, Rafael. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Desarrollo Tecnológico para la Industria Química. Universidad Nacional del Litoral. Instituto de Desarrollo Tecnológico para la Industria Química; Argentina
Fil: Pizarro, José. Universidad del País Vasco; España
Fil: Arriortua, María. Universidad del País Vasco; España
description We report EPR, X-ray crystallographic, and calorimetric measurements in copper-doped and pure Zn(II) bis(d,l-histidino)pentahydrate (C12H26N6O9Zn), to be called Zn(d,l-histidine)2. EPR data in copper-doped single crystals were obtained at 9.8 GHz as a function of the orientation of the magnetic field B at 298 and 80 K, and as a function of temperature (T) for fixed orientations of B. Powder samples were studied at 9.8 and 35 GHz. Steep changes of the EPR spectra with temperature occur around Tc = 268 K. Above Tc we observe spectra arising from a single copper with rhombic g and copper hyperfine A tensors. The resonances display a strong dependence of the line width with the hyperfine component. Below Tc the spectra can be assigned to two different copper ions displaying axial symmetry and related by a C2 rotation. As T increases approaching Tc, they collapse into the high-temperature spectrum. A peak in the differential specific heat of pure Zn(d,l-histidine)2 between 235 and 270 K indicates a transition intrinsic to the host material. Full X-ray structural studies were performed at 293 and at 150 K, above and below Tc. At 293 K our results are similar to those reported before. The low-temperature data show disorder in the water molecules. We interpret the experimental results with a model where the copper atoms hop randomly between different states. This dynamics is related to the fluctuating disorder in the lattice and produces steep changes on the EPR spectra of copper ion dopants. The role of dynamic Jahn−Teller distortions is discussed. A bonding scheme for the copper ions in Zn(d,l-histidine)2 is proposed, and it is compared with that encountered in type 1 blue copper proteins.
publishDate 2001
dc.date.none.fl_str_mv 2001-01
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/11336/27790
Dalosto, Sergio Daniel; Calvo, Rafael; Pizarro, José; Arriortua, María; Structure, Disorder, and Molecular Dynamics in Zn(d,l-histidine)2:  EPR of Copper Ion Dopants, X-ray Diffraction, and Calorimetric Studies; American Chemical Society; Journal of Physical Chemistry A; 105; 1-2001; 1074-1085
1089-5639
CONICET Digital
CONICET
url http://hdl.handle.net/11336/27790
identifier_str_mv Dalosto, Sergio Daniel; Calvo, Rafael; Pizarro, José; Arriortua, María; Structure, Disorder, and Molecular Dynamics in Zn(d,l-histidine)2:  EPR of Copper Ion Dopants, X-ray Diffraction, and Calorimetric Studies; American Chemical Society; Journal of Physical Chemistry A; 105; 1-2001; 1074-1085
1089-5639
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/doi/10.1021/jp003167n
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
dc.publisher.none.fl_str_mv American Chemical Society
publisher.none.fl_str_mv American Chemical Society
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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