Ligand Exchange Inducing Efficient Incorporation of CisPt Derivatives into Ureasil-PPO Hybrid and Their Interactions with the Multifunctional Hybrid Network

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dc.contributor.authorMolina, Eduardo F. [UNESP]
dc.contributor.authorPulcinelli, Sandra Helena [UNESP]
dc.contributor.authorSantilli, Celso Valentim [UNESP]
dc.contributor.authorBriois, Valerie
dc.contributor.institutionUniversidade Estadual Paulista (Unesp)
dc.contributor.institutionSynchrotron SOLEIL LOrme Merisiers
dc.date.accessioned2014-05-20T15:33:41Z
dc.date.available2014-05-20T15:33:41Z
dc.date.issued2012-07-12
dc.description.abstractEfficient incorporation of (PtCl3EtOH)(-) anion derived from CisPt moiety into ureasil-PPO (poly(propylene oxide)) network was achieved from one-pot sol-gel synthesis carried out in the presence of water, HCl, and ethanol. Reactant proportion was adequately chosen to lead the sol-gel formation of siloxane nodes at the end of short PPO chains, to prevent the CisPt hydrolysis, and to induce platinum ligand exchange. The efficient dissolution of Pt species and the formation of a homogeneous liquid like solution on the transparent and elastomeric ureasil-PPO hybrid were evidenced by differential scanning calorimetry and small-angle X-ray scattering. The CisPt ligand exchange and the formation of a Zeise-type salt Y+(PtCl3R)(-) were demonstrated by Raman spectroscopy and Pt L-3-edge EXAFS analysis. In light of these results and in agreement with the proportion of reactants introduced in the media for synthesis and those self produced by hydrolysis and condensation processes, we proposed for R the ethanol moiety and for Y the ammonium cation. The Raman spectroscopy studies indicated also that the ammonium cations are coordinated by the ether type oxygen atoms of the PPO chains backbone, whereas the amine groups of the urea linkage participate in the (PtCl3EtOH)(-) anion coordination. In situ Raman monitoring of Pt species decomplexation induced by immersion of hybrid matrix in water highlighted the specific participation of Pt ligands in interaction with the urea group and of NH4+ cations coordinated by ether type oxygen atoms in the formation of supramolecular interactions between the PPO chains. The electrospray mass spectrometry analysis of the Pt species released in water from the ureasil-PPO hybrid evidenced that the structure of the complex, NH4 (PtCl3 EtOH), incorporated in the matrix is totally preserved after delivery. Due to both well-known antitumoral and catalytic activities of Pt species, the results reported herein are of prime importance for further applications as drug delivery systems with optimized release pattern or as potential materials for new conceptual development of in situ catalyst delivery in homogeneous catalysis.en
dc.description.affiliationUNESP, Inst Quim, BR-14800900 Araraquara, SP, Brazil
dc.description.affiliationSynchrotron SOLEIL LOrme Merisiers, F-91192 Gif Sur Yvette, France
dc.description.affiliationUnespUNESP, Inst Quim, BR-14800900 Araraquara, SP, Brazil
dc.description.sponsorshipCoordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)
dc.description.sponsorshipConselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)
dc.description.sponsorshipFundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)
dc.description.sponsorshipFrench COFECUB agency
dc.description.sponsorshipSOLEIL (France)
dc.description.sponsorshipLaboratório Nacional de Luz Síncrotron (LNLS)
dc.description.sponsorshipIdFrench COFECUB agency: Ph 564/07
dc.format.extent7931-7939
dc.identifierhttp://dx.doi.org/10.1021/jp302606b
dc.identifier.citationJournal of Physical Chemistry B. Washington: Amer Chemical Soc, v. 116, n. 27, p. 7931-7939, 2012.
dc.identifier.doi10.1021/jp302606b
dc.identifier.issn1520-6106
dc.identifier.lattes9971202585286967
dc.identifier.lattes5584298681870865
dc.identifier.orcid0000-0002-8356-8093
dc.identifier.urihttp://hdl.handle.net/11449/42245
dc.identifier.wosWOS:000306264200020
dc.language.isoeng
dc.publisherAmer Chemical Soc
dc.relation.ispartofJournal of Physical Chemistry B
dc.relation.ispartofjcr3.146
dc.relation.ispartofsjr1,331
dc.rights.accessRightsAcesso restrito
dc.sourceWeb of Science
dc.titleLigand Exchange Inducing Efficient Incorporation of CisPt Derivatives into Ureasil-PPO Hybrid and Their Interactions with the Multifunctional Hybrid Networken
dc.typeArtigo
dcterms.licensehttp://pubs.acs.org/page/copyright/journals/faqs.html
dcterms.rightsHolderAmer Chemical Soc
unesp.author.lattes9971202585286967
unesp.author.lattes5584298681870865[3]
unesp.author.orcid0000-0002-8356-8093[3]
unesp.campusUniversidade Estadual Paulista (Unesp), Instituto de Química, Araraquarapt

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