dc.contributor.author | Aboudzadeh, Ali | |
dc.contributor.author | Dolz, Mikel | |
dc.contributor.author | Monnier, Xavier | |
dc.contributor.author | González de San Román, Estibaliz | |
dc.contributor.author | Cangialosi, Daniele | |
dc.contributor.author | Grzelczak, Marek | |
dc.contributor.author | Barroso Bujans, Fabienne | |
dc.date.accessioned | 2020-04-02T11:09:37Z | |
dc.date.available | 2020-04-02T11:09:37Z | |
dc.date.issued | 2019-12-21 | |
dc.identifier.citation | Polymer Chemistry 10(47) : 6495-6504 (2019) | es_ES |
dc.identifier.issn | 1759-9954 | |
dc.identifier.issn | 1759-9962 | |
dc.identifier.uri | http://hdl.handle.net/10810/42583 | |
dc.description.abstract | We introduce an approach to synthesize macrocyclic poly(ethylene oxide)s containing a pendant protected thiol group (pSH-CPEO), which is demonstrated to be able to attach to gold surfaces without prior deprotection. Our strategy is based on a bimolecular approach by which a di-alkyne molecule derived from thiol-protected 3-mercapto-1,2-propanediol and a series of PEO bis(azides) of M-n = 2, 6, and 11 kg mol(-1) are coupled via copper-catalyzed azide-alkyne cycloaddition. The cyclization reaction was verified by size exclusion chromatography and matrix-assisted laser desorption ionization time of flight mass spectrometry. In addition, we used fast scanning calorimetry to evaluate the glass transition temperature (T-g) of the synthesized pSH-CPEOs. Thanks to the extremely rapid cooling power of this technique, PEO crystallization can be circumvented and, therefore, its fully amorphous state can be investigated. The results confirmed higher T-g values for macrocycles compared to their chemically equivalent linear precursors. This result highlights the importance of the chain end in affecting the T-g of polymers. Finally, to demonstrate the ability of pSH-CPEO to covalently attach to gold surfaces, pSH-CPEO samples were allowed to react with gold-coated glass slides and the surface properties were compared with those of the samples obtained by the reaction of linear alpha-thiol, omega-methoxy PEO (with and without protection of the thiol group) and gold-coated glass slides. X-ray photoelectron spectroscopy data confirmed the formation of Au-S linkages as well as the removal of the thiol protector group through the quantitative analysis of the chemical composition at the surface. The contact angle data of pSH-CPEO/gold exhibited increased hydrophilicity compared to bare gold and topological effects at the interface. A reaction mechanism between the 2,4-dinitrobenzene-protected thiol group and the gold surface is also proposed. | es_ES |
dc.description.sponsorship | We thank Dr Farihah M. Haque for helpful discussions on MALDI-TOF MS and Dr. J. I. Miranda for experiments and helpful discussions on NMR. We also gratefully acknowledge support from the Spanish Ministry "Ministerio de Ciencia, Innovacion y Universidades" (PGC2018-094548-B-I00, MICINN/FEDER, UE), Basque Government (IT-1175-19 and PIBA 2018-34), and Diputacion Foral de Guipuzcoa (RED 2018). | es_ES |
dc.language.iso | eng | es_ES |
dc.publisher | Royal Society of Chemistry | es_ES |
dc.rights | info:eu-repo/semantics/openAccess | es_ES |
dc.rights.uri | http://creativecommons.org/licenses/by-nc/3.0/es/ | * |
dc.subject | glass-transition temperatures | es_ES |
dc.subject | dynamics | es_ES |
dc.subject | topology | es_ES |
dc.subject | glycol) | es_ES |
dc.subject | poly(oxyethylene) | es_ES |
dc.subject | nanoparticles | es_ES |
dc.subject | stability | es_ES |
dc.subject | route | es_ES |
dc.subject | well | es_ES |
dc.title | Synthesis of macrocyclic poly(ethylene oxide)s containing a protected thiol group: a strategy for decorating gold surfaces with ring polymers | es_ES |
dc.type | info:eu-repo/semantics/article | es_ES |
dc.rights.holder | This article is licensed under a Creative Commons Attribution-NonCommercial 3.0 Unported Licence. | es_ES |
dc.rights.holder | Atribución-NoComercial 3.0 España | * |
dc.relation.publisherversion | https://pubs.rsc.org/en/content/articlelanding/2019/PY/C9PY01394F#!divAbstract | es_ES |
dc.identifier.doi | 10.1039/c9py01394f | |
dc.departamentoes | Física de materiales | es_ES |
dc.departamentoeu | Materialen fisika | es_ES |