Publicação
Revisiting the dissolution of cellulose in H3PO4(aq) through cryo-TEM PTssNMR and DWS
| Resumo: | Cellulose can be dissolved in concentrated acidic aqueous solvents forming extremely viscous solutions, and, in some cases, liquid crystalline phases. In this work, the concentrated phosphoric acid aqueous solvent is revisited implementing a set of advanced techniques, such as cryo-transmission electronic microscopy (cryo-TEM), polarization transfer solid-state nuclear magnetic resonance (PTssNMR), and diffusing wave spectroscopy (DWS). Cryo-TEM images confirm that this solvent system is capable to efficiently dissolve cellulose. No cellulose particles, fibrils, or aggregates are visible. Conversely, PTssNMR revealed a dominant CP signal at 25 degrees C, characteristic of C-H bond reorientation with correlation time longer than 100 ns and/or order parameter above 0.5, which was ascribed to a transient gel-like network or an anisotropic liquid crystalline phase. Increasing the temperature leads to a gradual transition from CP to INEPT-dominant signal and a loss of birefringence in optical microscopy, suggesting an anisotropic-to-isotropic phase transition. Finally, an excellent agreement between optical microrheology and conventional mechanical rheometry was also obtained. |
|---|---|
| Autores principais: | Alves, Luis |
| Outros Autores: | Medronho, Bruno; Filipe, Alexandra; Romano, Anabela; Rasteiro, Maria G.; Lindman, Bjorn; Topgaard, Daniel; Davidovich, Irina; Talmon, Yeshayahu |
| Assunto: | Phosphoric acid Cellulose dissolution Anisotropy Liquid crystalline phase PTssNMR DWS cryo-TEM |
| Ano: | 2021 |
| País: | Portugal |
| Tipo de documento: | artigo |
| Tipo de acesso: | acesso restrito |
| Instituição associada: | Universidade do Algarve |
| Idioma: | inglês |
| Origem: | Sapientia - Universidade do Algarve |
| _version_ | 1867050864419536896 |
|---|---|
| author | Alves, Luis |
| author2 | Medronho, Bruno Filipe, Alexandra Romano, Anabela Rasteiro, Maria G. Lindman, Bjorn Topgaard, Daniel Davidovich, Irina Talmon, Yeshayahu |
| author2_role | author author author author author author author author |
| author_facet | Alves, Luis Medronho, Bruno Filipe, Alexandra Romano, Anabela Rasteiro, Maria G. Lindman, Bjorn Topgaard, Daniel Davidovich, Irina Talmon, Yeshayahu |
| author_role | author |
| contributor_name_str_mv | Sapientia |
| country_str | PT |
| creators_json_txt | [{\"Person.name\":\"Alves, Luis\"},{\"Person.name\":\"Medronho, Bruno\",\"Person.identifier.orcid\":\"0000-0003-0972-1739\"},{\"Person.name\":\"Filipe, Alexandra\"},{\"Person.name\":\"Romano, Anabela\",\"Person.identifier.orcid\":\"0000-0002-7204-7428\"},{\"Person.name\":\"Rasteiro, Maria G.\"},{\"Person.name\":\"Lindman, Bjorn\"},{\"Person.name\":\"Topgaard, Daniel\"},{\"Person.name\":\"Davidovich, Irina\"},{\"Person.name\":\"Talmon, Yeshayahu\"}] |
| datacite.contributors.contributor.contributorName.fl_str_mv | Sapientia |
| datacite.creators.creator.creatorName.fl_str_mv | Alves, Luis Medronho, Bruno Filipe, Alexandra Romano, Anabela Rasteiro, Maria G. Lindman, Bjorn Topgaard, Daniel Davidovich, Irina Talmon, Yeshayahu |
| datacite.date.Accepted.fl_str_mv | 2021-01-01T00:00:00Z |
| datacite.date.available.fl_str_mv | 2021-09-08T10:58:11Z |
| datacite.date.embargoed.fl_str_mv | 2021-09-08T10:58:11Z |
| datacite.rights.fl_str_mv | http://purl.org/coar/access_right/c_16ec |
| datacite.subjects.subject.fl_str_mv | Phosphoric acid Cellulose dissolution Anisotropy Liquid crystalline phase PTssNMR DWS cryo-TEM |
| datacite.titles.title.fl_str_mv | Revisiting the dissolution of cellulose in H3PO4(aq) through cryo-TEM PTssNMR and DWS |
| dc.contributor.none.fl_str_mv | Sapientia |
| dc.creator.none.fl_str_mv | Alves, Luis Medronho, Bruno Filipe, Alexandra Romano, Anabela Rasteiro, Maria G. Lindman, Bjorn Topgaard, Daniel Davidovich, Irina Talmon, Yeshayahu |
| dc.date.Accepted.fl_str_mv | 2021-01-01T00:00:00Z |
| dc.date.available.fl_str_mv | 2021-09-08T10:58:11Z |
| dc.date.embargoed.fl_str_mv | 2021-09-08T10:58:11Z |
| dc.format.none.fl_str_mv | application/pdf |
| dc.identifier.none.fl_str_mv | http://hdl.handle.net/10400.1/17054 |
| dc.language.none.fl_str_mv | eng |
| dc.publisher.none.fl_str_mv | Elsevier |
| dc.rights.none.fl_str_mv | http://purl.org/coar/access_right/c_16ec |
| dc.subject.none.fl_str_mv | Phosphoric acid Cellulose dissolution Anisotropy Liquid crystalline phase PTssNMR DWS cryo-TEM |
| dc.title.fl_str_mv | Revisiting the dissolution of cellulose in H3PO4(aq) through cryo-TEM PTssNMR and DWS |
| dc.type.none.fl_str_mv | http://purl.org/coar/resource_type/c_6501 |
| description | Cellulose can be dissolved in concentrated acidic aqueous solvents forming extremely viscous solutions, and, in some cases, liquid crystalline phases. In this work, the concentrated phosphoric acid aqueous solvent is revisited implementing a set of advanced techniques, such as cryo-transmission electronic microscopy (cryo-TEM), polarization transfer solid-state nuclear magnetic resonance (PTssNMR), and diffusing wave spectroscopy (DWS). Cryo-TEM images confirm that this solvent system is capable to efficiently dissolve cellulose. No cellulose particles, fibrils, or aggregates are visible. Conversely, PTssNMR revealed a dominant CP signal at 25 degrees C, characteristic of C-H bond reorientation with correlation time longer than 100 ns and/or order parameter above 0.5, which was ascribed to a transient gel-like network or an anisotropic liquid crystalline phase. Increasing the temperature leads to a gradual transition from CP to INEPT-dominant signal and a loss of birefringence in optical microscopy, suggesting an anisotropic-to-isotropic phase transition. Finally, an excellent agreement between optical microrheology and conventional mechanical rheometry was also obtained. |
| dirty | 0 |
| eu_rights_str_mv | restrictedAccess |
| format | article |
| fulltext.url.fl_str_mv | https://sapientia.ualg.pt/bitstreams/7462a9f5-7b40-4a34-9271-c0a3c406c3bc/download |
| funding.funder.alternateName_str_mv | FCT FCT FCT FCT |
| funding.funder.identifier_str_mv | http://doi.org/10.13039/501100001871 http://doi.org/10.13039/501100001871 http://doi.org/10.13039/501100001871 http://doi.org/10.13039/501100001871 |
| funding.funder.name_str_mv | Fundação para a Ciência e a Tecnologia Fundação para a Ciência e a Tecnologia Fundação para a Ciência e a Tecnologia Fundação para a Ciência e a Tecnologia |
| funding.name_str_mv | 6817 - DCRRNI ID Investigador FCT CEEC IND 2018 6817 - DCRRNI ID |
| id | sapientia_fdaec2b692c0cc577fc4e981eb3e8112 |
| identifier.url.fl_str_mv | http://hdl.handle.net/10400.1/17054 |
| instacron_str | ualg |
| institution | Universidade do Algarve |
| instname_str | Universidade do Algarve |
| language | eng |
| network_acronym_str | sapientia |
| network_name_str | Sapientia - Universidade do Algarve |
| oai_identifier_str | oai:sapientia.ualg.pt:10400.1/17054 |
| organization_str_mv | urn:organizationAcronym:ualg |
| person_str_mv | Alves, Luis Medronho, Bruno Medronho, Bruno https://www.ciencia-id.pt/6918-9AB3-8D22 6918-9AB3-8D22 http://orcid.org/0000-0003-0972-1739 0000-0003-0972-1739 Filipe, Alexandra Romano, Anabela Romano, Anabela https://www.ciencia-id.pt/8A18-7E9A-3B0E 8A18-7E9A-3B0E http://orcid.org/0000-0002-7204-7428 0000-0002-7204-7428 Rasteiro, Maria G. Lindman, Bjorn Topgaard, Daniel Davidovich, Irina Talmon, Yeshayahu |
| publishDate | 2021 |
| publisher.none.fl_str_mv | Elsevier |
| reponame_str | Sapientia - Universidade do Algarve |
| repository_id_str | urn:repositoryAcronym:sapientia |
| service_str_mv | urn:repositoryAcronym:sapientia |
| spelling | engElsevierCellulose can be dissolved in concentrated acidic aqueous solvents forming extremely viscous solutions, and, in some cases, liquid crystalline phases. In this work, the concentrated phosphoric acid aqueous solvent is revisited implementing a set of advanced techniques, such as cryo-transmission electronic microscopy (cryo-TEM), polarization transfer solid-state nuclear magnetic resonance (PTssNMR), and diffusing wave spectroscopy (DWS). Cryo-TEM images confirm that this solvent system is capable to efficiently dissolve cellulose. No cellulose particles, fibrils, or aggregates are visible. Conversely, PTssNMR revealed a dominant CP signal at 25 degrees C, characteristic of C-H bond reorientation with correlation time longer than 100 ns and/or order parameter above 0.5, which was ascribed to a transient gel-like network or an anisotropic liquid crystalline phase. Increasing the temperature leads to a gradual transition from CP to INEPT-dominant signal and a loss of birefringence in optical microscopy, suggesting an anisotropic-to-isotropic phase transition. Finally, an excellent agreement between optical microrheology and conventional mechanical rheometry was also obtained.application/pdfRevisiting the dissolution of cellulose in H3PO4(aq) through cryo-TEM PTssNMR and DWSAlves, LuisPersonalMedronho, BrunoDSpacehttp://dspace.org/items/4c03571a-93da-4504-8acf-c74326449852DSpacehttp://dspace.org/items/4c03571a-93da-4504-8acf-c74326449852MedronhoBrunoCiência IDhttps://www.ciencia-id.pt6918-9AB3-8D22ORCIDhttp://orcid.org0000-0003-0972-1739Researcher IDhttps://www.researcherid.comP-5927-2014Scopus Author IDhttps://www.scopus.com9940656700Filipe, AlexandraPersonalRomano, AnabelaDSpacehttp://dspace.org/items/e3343b60-17d3-4f5e-a2bf-06f26da69206DSpacehttp://dspace.org/items/e3343b60-17d3-4f5e-a2bf-06f26da69206RomanoAnabelaCiência IDhttps://www.ciencia-id.pt8A18-7E9A-3B0EORCIDhttp://orcid.org0000-0002-7204-7428Scopus Author IDhttps://www.scopus.com56249997600Rasteiro, Maria G.Lindman, BjornTopgaard, DanielDavidovich, IrinaTalmon, YeshayahuHostingInstitutionOrganizationalSapientiae-mailmailto:repositorio@ualg.ptrepositorio@ualg.ptISSNIsPartOf0144-8617DOIIsPartOf10.1016/j.carbpol.2020.1171222021-09-08T10:58:11Z2021-012021-01-01T00:00:00ZHandlehttp://hdl.handle.net/10400.1/17054http://purl.org/coar/access_right/c_16ecrestricted accessPhosphoric acidCellulose dissolutionAnisotropyLiquid crystalline phasePTssNMRDWScryo-TEM2152572 bytesFundação para a Ciência e a TecnologiaMediterranean Institute for Agriculture, Environment and Development6817 - DCRRNI IDCrossref Funder IDhttp://doi.org/10.13039/501100001871Fundação para a Ciência e a TecnologiaFrom Forest to Textiles: Development of Sustainable Processes for the Production of Ecological Man-made Cellulose FibresInvestigador FCTCrossref Funder IDhttp://doi.org/10.13039/501100001871Fundação para a Ciência e a TecnologiaNot AvailableCEEC IND 2018Crossref Funder IDhttp://doi.org/10.13039/501100001871Fundação para a Ciência e a TecnologiaChemical Process Engineering and Forest Products Research Centre6817 - DCRRNI IDCrossref Funder IDhttp://doi.org/10.13039/501100001871literaturehttp://purl.org/coar/resource_type/c_6501journal articlehttp://purl.org/coar/access_right/c_16ecapplication/pdffulltexthttps://sapientia.ualg.pt/bitstreams/7462a9f5-7b40-4a34-9271-c0a3c406c3bc/downloadCarbohydrate Polymers252117122 |
| spellingShingle | Revisiting the dissolution of cellulose in H3PO4(aq) through cryo-TEM PTssNMR and DWS Alves, Luis Phosphoric acid Cellulose dissolution Anisotropy Liquid crystalline phase PTssNMR DWS cryo-TEM |
| status | SINGLETON |
| subject.fl_str_mv | Phosphoric acid Cellulose dissolution Anisotropy Liquid crystalline phase PTssNMR DWS cryo-TEM |
| title | Revisiting the dissolution of cellulose in H3PO4(aq) through cryo-TEM PTssNMR and DWS |
| title_full | Revisiting the dissolution of cellulose in H3PO4(aq) through cryo-TEM PTssNMR and DWS |
| title_fullStr | Revisiting the dissolution of cellulose in H3PO4(aq) through cryo-TEM PTssNMR and DWS |
| title_full_unstemmed | Revisiting the dissolution of cellulose in H3PO4(aq) through cryo-TEM PTssNMR and DWS |
| title_short | Revisiting the dissolution of cellulose in H3PO4(aq) through cryo-TEM PTssNMR and DWS |
| title_sort | Revisiting the dissolution of cellulose in H3PO4(aq) through cryo-TEM PTssNMR and DWS |
| topic | Phosphoric acid Cellulose dissolution Anisotropy Liquid crystalline phase PTssNMR DWS cryo-TEM |
| topic_facet | Phosphoric acid Cellulose dissolution Anisotropy Liquid crystalline phase PTssNMR DWS cryo-TEM |
| url | http://hdl.handle.net/10400.1/17054 |
| visible | 1 |