Conformational analysis and molecular modeling of cholesteric liquid-crystal polyesters based on XRD, Raman and transition thermal analysis

Molecular modeling of the cholesteric liquid crystal polyester poly[oxy(1,2 - dodecane)oxycarbonyl-1,4-phenyleneoxycarbonyl-1,4-phenylenecarbonyloxy-1,4-phenylenecarbonyl] (PTOBDME), [C34H36O8] n , synthesized in our laboratory and thermally characterized by differential scanning calorimetry (DSC),...

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Detalles Bibliográficos
Autores: Fayos, José, Pérez Méndez, Mercedes, Sánchez Cortés, Santiago, Marco,Carlos
Tipo de recurso: artículo
Fecha de publicación:2001
País:España
Institución:Consejo Superior de Investigaciones Científicas (CSIC)
Repositorio:DIGITAL.CSIC. Repositorio Institucional del CSIC
OAI Identifier:oai:digital.csic.es:10261/253036
Acceso en línea:http://hdl.handle.net/10261/253036
Access Level:acceso abierto
Palabra clave:Cholesteric LC
FT Raman
Solvent effect
Structure simulation
XRD
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spelling Conformational analysis and molecular modeling of cholesteric liquid-crystal polyesters based on XRD, Raman and transition thermal analysisFayos, JoséPérez Méndez, MercedesSánchez Cortés, SantiagoMarco,CarlosCholesteric LCFT RamanSolvent effectStructure simulationXRDMolecular modeling of the cholesteric liquid crystal polyester poly[oxy(1,2 - dodecane)oxycarbonyl-1,4-phenyleneoxycarbonyl-1,4-phenylenecarbonyloxy-1,4-phenylenecarbonyl] (PTOBDME), [C34H36O8] n , synthesized in our laboratory and thermally characterized by differential scanning calorimetry (DSC), was performed to explain both its cholesteric mesophase and 3D crystalline structure. Conformational analysis (CA) was run for the monomer both by systematic search and with molecular dynamics (MD) simulations. Minima energy conformers were “polymerized” with Cerius2 and helical, cholesteric molecules were obtained in all cases. Our models agree with the chiral behavior observed by X-ray diffraction (XRD), thermooptical analysis (TOA) and circular dichroism (CD) experiments. Crystal packing of the polymer molecules were simulated in cells with parameters a and b obtained from experimental powder X-ray diffraction patterns and c calculated from the translational repetitive unit during the theoretical polymerization. Recalculated X-ray powder diffraction patterns of our models matched the observed ones. Morphology simulation from those crystal models is in good agreement with the crystals observed by optical microscopy. We have also modeled the self-associating nature of those polyesters when dispersed in aqueous media. Simulation of our models surrounded by different solvents, such as water and chloroform, were performed by calculating their interaction energies, coordination numbers, and mixing energies, applying Monte Carlo simulation techniques based on the Flory-Huggins theory. These results were compared with their experimental vibrational Fourier transform (FT)–Raman spectra in the regions in which structural marker bands of the polymer appear.Peer reviewed[0000-0003-1319-6818][0000-0002-9303-2268]Consejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72]202120212001info:eu-repo/semantics/articlehttp://purl.org/coar/resource_type/c_6501http://hdl.handle.net/10261/253036reponame:DIGITAL.CSIC. Repositorio Institucional del CSICinstname:Consejo Superior de Investigaciones Científicas (CSIC)InglésSíinfo:eu-repo/semantics/openAccessoai:digital.csic.es:10261/2530362026-05-22T06:33:51Z
dc.title.none.fl_str_mv Conformational analysis and molecular modeling of cholesteric liquid-crystal polyesters based on XRD, Raman and transition thermal analysis
title Conformational analysis and molecular modeling of cholesteric liquid-crystal polyesters based on XRD, Raman and transition thermal analysis
spellingShingle Conformational analysis and molecular modeling of cholesteric liquid-crystal polyesters based on XRD, Raman and transition thermal analysis
Fayos, José
Cholesteric LC
FT Raman
Solvent effect
Structure simulation
XRD
title_short Conformational analysis and molecular modeling of cholesteric liquid-crystal polyesters based on XRD, Raman and transition thermal analysis
title_full Conformational analysis and molecular modeling of cholesteric liquid-crystal polyesters based on XRD, Raman and transition thermal analysis
title_fullStr Conformational analysis and molecular modeling of cholesteric liquid-crystal polyesters based on XRD, Raman and transition thermal analysis
title_full_unstemmed Conformational analysis and molecular modeling of cholesteric liquid-crystal polyesters based on XRD, Raman and transition thermal analysis
title_sort Conformational analysis and molecular modeling of cholesteric liquid-crystal polyesters based on XRD, Raman and transition thermal analysis
dc.creator.none.fl_str_mv Fayos, José
Pérez Méndez, Mercedes
Sánchez Cortés, Santiago
Marco,Carlos
author Fayos, José
author_facet Fayos, José
Pérez Méndez, Mercedes
Sánchez Cortés, Santiago
Marco,Carlos
author_role author
author2 Pérez Méndez, Mercedes
Sánchez Cortés, Santiago
Marco,Carlos
author2_role author
author
author
dc.contributor.none.fl_str_mv [0000-0003-1319-6818]
[0000-0002-9303-2268]
Consejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72]
dc.subject.none.fl_str_mv Cholesteric LC
FT Raman
Solvent effect
Structure simulation
XRD
topic Cholesteric LC
FT Raman
Solvent effect
Structure simulation
XRD
description Molecular modeling of the cholesteric liquid crystal polyester poly[oxy(1,2 - dodecane)oxycarbonyl-1,4-phenyleneoxycarbonyl-1,4-phenylenecarbonyloxy-1,4-phenylenecarbonyl] (PTOBDME), [C34H36O8] n , synthesized in our laboratory and thermally characterized by differential scanning calorimetry (DSC), was performed to explain both its cholesteric mesophase and 3D crystalline structure. Conformational analysis (CA) was run for the monomer both by systematic search and with molecular dynamics (MD) simulations. Minima energy conformers were “polymerized” with Cerius2 and helical, cholesteric molecules were obtained in all cases. Our models agree with the chiral behavior observed by X-ray diffraction (XRD), thermooptical analysis (TOA) and circular dichroism (CD) experiments. Crystal packing of the polymer molecules were simulated in cells with parameters a and b obtained from experimental powder X-ray diffraction patterns and c calculated from the translational repetitive unit during the theoretical polymerization. Recalculated X-ray powder diffraction patterns of our models matched the observed ones. Morphology simulation from those crystal models is in good agreement with the crystals observed by optical microscopy. We have also modeled the self-associating nature of those polyesters when dispersed in aqueous media. Simulation of our models surrounded by different solvents, such as water and chloroform, were performed by calculating their interaction energies, coordination numbers, and mixing energies, applying Monte Carlo simulation techniques based on the Flory-Huggins theory. These results were compared with their experimental vibrational Fourier transform (FT)–Raman spectra in the regions in which structural marker bands of the polymer appear.
publishDate 2001
dc.date.none.fl_str_mv 2001
2021
2021
dc.type.none.fl_str_mv info:eu-repo/semantics/article
http://purl.org/coar/resource_type/c_6501
format article
dc.identifier.none.fl_str_mv http://hdl.handle.net/10261/253036
url http://hdl.handle.net/10261/253036
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.relation.none.fl_str_mv Sí
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
eu_rights_str_mv openAccess
dc.source.none.fl_str_mv reponame:DIGITAL.CSIC. Repositorio Institucional del CSIC
instname:Consejo Superior de Investigaciones Científicas (CSIC)
instname_str Consejo Superior de Investigaciones Científicas (CSIC)
reponame_str DIGITAL.CSIC. Repositorio Institucional del CSIC
collection DIGITAL.CSIC. Repositorio Institucional del CSIC
repository.name.fl_str_mv
repository.mail.fl_str_mv
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