Covalent attachment of Candida rugosa lipase on chemically modified hybrid matrix of polysiloxane-polyvinyl alcohol with different activating compounds

Candida rugosa lipase was immobilized by covalent binding on hybrid matrix of polysiloxane-polyvinyl alcohol chemically modified with different activating agents as glutaraldehyde, sodium metaperiodate and carbonyldiimidazole. The experimental results suggested that functional activating agents render different interactions between enzyme and support, producing consequently alterations in the optimal reaction conditions. Properties of the immobilized systems were assessed and their performance on hydrolytic and synthetic reactions were evaluated and compared with the free enzyme. In hydrolytic reactions using p-nitrophenyl palmitate as substrate all immobilized systems showed higher thermal stability and optima pH and temperature values in relation to the free lipase. Among the activating compounds, carbonyldiimidazole resulted in a total recovery of activity on the support and the highest thermal stability. For the butyl butyrate synthesis, the best performance (molar conversion of 95% and volumetric productivity of 2.33 g L-1 h(-1)) was attained with the lipase immobilized on POS-PVA activated with sodium metaperiodate. The properties of the support and immobilized derivatives were also evaluated by scanning electron microscopy (SEM), energy dispersive X-ray spectroscopies and chemical composition (FTIR). (c) 2007 Elsevier B.V. All rights reserved.

Effect of acid or alkaline catalyst and of different capping agents on the optical properties of CdS nanoparticles incorporated within a diureasil hybrid matrix

CdS nanoparticles (NPs) were synthesized using colloidal methods and incorporated within a diureasil hybrid matrix. The surface capping of the CdS NPs by 3-mercaptopropyltrimethoxysilane (MPTMS) and 3-aminopropyltrimethoxysilane (APTMS) organic ligands during the incorporation of the NPs within the hybrid matrix has been investigated. The matrix is based on poly(ethylene oxide)/poly(propylene oxide) chains grafted to a siliceous skeleton through urea bonds and was produced by sol–gel process. Both alkaline and acidic catalysis of the sol–gel reaction were used to evaluate the effect of each organic ligand on the optical properties of the CdS NPs. The hybrid materials were characterized by absorption, steady-state and time-resolved photoluminescence spectroscopy and High Resolution Transmission Electron Microscopy (HR-TEM). The preservation of the optical properties of the CdS NPs within the diureasil hybrids was dependent on the experimental conditions used. Both organic ligands (APTMS and MPTMS) demonstrated to be crucial in avoiding the increase of size distribution and clustering of the NPs within the hybrid matrix. The use of organic ligands was also shown to influence the level of interaction between the hybrid host and the CdS NPs. The CdS NPs showed large Stokes shifts and long average lifetimes, both in colloidal solution and in the xerogels, due to the origin of the PL emission in surface states. The CdS NPs capped with MPTMS have lower PL lifetimes compared to the other xerogel samples but still larger than the CdS NPs in the original colloidal solution. An increase in PL lifetimes of the NPs after their incorporation within the hybrid matrix is related to interaction between the NPs and the hybrid host matrix.

Multi-spectroscopic monitoring of cisplatin-derived species delivery from ureasil polyether hybrid matrix

Driven by the challenges involved in the development of new advanced materials with unusual drug delivery profiles capable of improving the therapeutic and toxicological properties of existing cancer chemotherapy, the one-pot sol-gel synthesis of flexible, transparent and insoluble urea-cross-linked polyether-siloxane hybrids has been recently developed. In this one-pot synthesis, the strong interaction between the antitumor cisplatin (CisPt) molecules and the ureasil-poly(propylene oxide) (PPO) hybrid matrix gives rise to the incorporation and release of an unknown CisPt-derived species, hindering the quantitative determination of the drug release pattern from the conventional UV-Vis absorption technique. In this article, we report the use of an original synchrotron radiation calibration method based on the combination of XAS and UV-Vis for the quantitative determination of the amount of Pt-based molecules released in water. Thanks to the combination of UV-Vis, XAS and Raman techniques, we demonstrated that both the CisPt molecules and the CisPt-derived species are loaded into an ureasil-PPO/ureasil-poly(ethylene oxide) (PEO) hybrid blend matrix. The experimentally determined molar extinction coefficient of the CisPt-derived species loaded into ureasil-PPO hybrid matrix enabled the simultaneous time-resolved monitoring of each Pt species released from this hybrid blend matrix.

Controlled Cisplatin Delivery from Ureasil-PEO1900 Hybrid Matrix

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Drug-matrix interaction of sodium diclofenac incorporated into ureasilpoly(ethylene oxide) hybrid materials

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Multi-scale structural description of siloxane-PPO hybrid ionic conductors doped by sodium salts

Alkaline metal doped organic - inorganic hybrids have potential applications in the field of portable energy sources. Attractive sol - gel derived urea cross-linked polyether, siloxane - PPO ( poly( propylene oxide)) hybrids doped with sodium salts ( NaClO4 and NaBF4) were examined by multi-spectroscopic approach that includes complex impedance, X-ray powder diffraction (XRPD), small angle X-ray scattering (SAXS), Si-29 and Na-23 magic-angle spinning nuclear magnetic resonance (NMR/MAS), Na K-edge X-ray absorption near edge structure (XANES) and Raman spectroscopies. The goals of this work were to determine which cation coordinating site of the host matrix ( ether oxygen atoms or carbonyl oxygen atoms) is active in each of the materials analyzed, its influence on the nanostructure of the samples and its relation with the thermal and electrical properties. The main conclusion derived from this study is that the NaBF4 salt has a much lower solubility in the hybrid matrix than the NaClO4 salt. Furthermore, the addition of a large amount of salt plays a major role in the hybrid nanostructure and electrical properties, modifying the PPO chain conformation, weakening or breaking the hydrogen bond of the polyether - urea associations and changing the polycondensation and aggregation processes involving the siloxane species.

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

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White light emission of Eu3+-based hybrid xerogels

The luminescence spectra and extended x-ray-absorption fine-structure (EXAFS) measurements of a series of Eu3+-based organic/inorganic xerogels were reported and related to the local coordination of the lanthanide cations. The hybrid matrix of these organically modified silicates, classed as U(2000) ureasils, is a siliceous network to which short organic chains containing oxyethylene units are covalently grafted by means of urea bridges. The luminescent centers were incorporated as europium triflate, Eu(CF3SO3)3, and europium bromide, EuBr3, with concentrations 200≥n≥20 and n=80, 40, and 30, respectively - where n is the number of ether oxygens in the polymer chains per Eu3+ cation. EXAFS measurements were carried out in some of the U(2000)nEu(CF3SO3)3 xerogels (n=200, 80, 60, and 40). The obtained coordination numbers N ranging from 12.8, n=200, to 9.7, n=40, whereas the average Eu3+ first neighbors distance R is 2.48-2.49 Å. The emission spectra of these multiwavelength phosphors superpose a broad green-blue band to a series of yellow-red narrow 5D0→7F0-4 Eu3+ lines and to the eye the hybrids appeared to be white, even at room temperature. The ability to tune the emission of the xerogels to colors across the chromaticity diagram is achieved by changing the excitation wavelength and the amount of salt incorporated in the hybrid host. The local environment of Eu3+ is described as a continuous distribution of closely similar low-symmetry network sites. The cations are coordinated by the carbonyl groups of the urea moieties, water molecules, and, for U(2000)nEu(CF3SO3)3, by the SO3 end groups of the triflate anions. No spectral evidences have been found for the coordination by the ether oxygens of the polyether chains. A mean radius for the first coordination shell of Eu3+ is calculated on the basis of the emission energy assignments. The results obtained for U(2000)nEu(CF3SO3)3, 2.4 Å for 90 ≥n≥40 and 2.6 and 2.5 Å for n=30 and 20, respectively, are in good agreement with the values calculated from EXAFS measurements. The energy of the intraconfigurational charge-transfer transitions, the redshift of the 5D0→7F0 line, with respect to the value calculated for gaseous Eu3+, and the hypersensitive ratio between the 5D0→7F2 and 5D0→7F1 transitions, point out a rather low covalency nature of the Eu3+ first coordination shell in these xerogels, comparing to the case of analogous polymer electrolytes modified by europium bromide. ©1999 The American Physical Society.

Ureasil-polyether hybrid film-forming materials

The objectives of this work were to study the suitability and highlight the advantages of the use of cross-linked ureasil-polyether hybrid matrices as film-forming systems. The results revealed that ureasil-polyethers are excellent film-forming systems due to specific properties, such as their biocompatibility, their cosmetic attractiveness for being able to form thin and transparent films, their short drying time to form films and their excellent bioadhesion compared to the commercial products known as strong adhesives. Rheological measurements have demonstrated the ability of these hybrid matrices to form a film in only a few seconds and Water Vapor Transmitting Rate (WVTR) showed adequate semi-occlusive properties suggesting that these films could be used as skin and wound protectors. Both the high skin bioadhesion and non-cytotoxic character seems to be improved by the presence of multiple amine groups in the hybrid molecules. © 2012 Elsevier B.V.

Carbon nanotube-reinforced siloxane-PMMA hybrid coatings with high corrosion resistance

Siloxane-polymethyl methacrylate hybrid films containing functionalized multiwall carbon nanotubes (CNTs) were deposited by dip-coating on carbon steel substrates from a sol prepared by radical polymerization of methyl methacrylate and 3-methacryloxy propyl-trimethoxysilane, followed by hydrolytic co-polycondensation of tetraethoxysilane. The correlation between the structural properties and corrosion protection efficiency was studied as a function of the molar ratio of nanotubes carbon to silicon, varied in the range between 0.1% and 5%. 29Si nuclear magnetic resonance and thermogravimetric measurements have shown that hybrids containing carbon nanotubes have a similar degree of polycondensation and thermal stability as the undoped matrix and exhibit and excellent adhesion to the substrate. Microscopy and X-ray photoelectron spectroscopy results revealed a very good dispersion of carbon nanotubes in the hybrid matrix and the presence of carboxylic groups allowing covalent bonding with the end-siloxane nodes. Potentiodynamic polarization curves and electrochemical impedance spectroscopy results demonstrate that CNTs containing coatings maintain the excellent corrosion protection efficiency of the hybrids, showing even a superior performance in acidic solution. The nanocomposite structure acts as efficient corrosion barrier, increasing the total impedance by 4 orders of magnitude and reducing the current densities by more than 3 orders of magnitude, compared to the bare steel electrode. © 2013 Elsevier B.V. All rights reserved.

Ureasil-polyether hybrid blend with tuneable hydrophilic/hydrophobic features based on U-PEO1900 and U-PPO400 mixtures

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Pseudomonas fluorescens lipase immobilization on polysiloxane-polyvinyl alcohol composite chemically modified with epichlorohydrin

The technique based on sol-gel approach was used to generate silica matrices derivatives by hydrolysis of silane compounds. The present work evaluates a hybrid matrix obtained with tetraethoxysilane (TEOS) and polyvinyl alcohol (PVA) on the immobilization yield of lipase from Pseudomonas fluorescens. The resulting polysiloxane-polyvinyl alcohol (POS-PVA) matrix combines the property of PVA as a suitable polymer to retain proteins with an excellent optical, thermal and chemical stability of the host silicon oxide matrix. Aiming to render adequate functional groups to the covalent binding with the enzyme the POS-PVA matrix was chemically modified using epichlorohydrin. The results were compared with immobilized derivative on POS-PVA activated with glutaraldehyde. Immobilization yield based on the recovered lipase activity depended on the activating agent and the highest efficiency (32%) was attained when lipase was immobilized on POS-PVA activated with epichlorohydrin, which, probably, provided more linkage points for the covalent bind of the enzyme on the support. This was confirmed by determining the morphological properties using different techniques as X-ray diffraction and scanning electron microscopy (SEM). Comparative studies were carried out to attain optimal activities for free lipase and immobilized systems. For this purpose, a central composite experimental design with different combinations of pH and temperature was performed. Enzymatic hydrolysis with the immobilized enzyme in the framework of the Michaelis-Menten mechanism was also reported. Under optimum conditions, the immobilized derivative on POS-PVA activated with epichlorohydrin showed to have more affinity for the substrate in the hydrolysis of olive oil, with a Michaelis-Menten constant value (K-m) of 293 mM, compared to the value of 401 mM obtained for the immobilized lipase on support activated with glutaraldehyde. Data generated by DSC showed that both immobilized derivatives have similar thermal stabilities. (C) 2007 Elsevier B.V. All rights reserved.

Evaluation of the catalytic properties of Burkholderia cepacia lipase immobilized on non-commercial matrices to be used in biodiesel synthesis from different feedstocks

The objective of this work was to produce an immobilized form of lipase from Burkholderia cepacia (lipase PS) with advantageous catalytic properties and stability to be used in the ethanolysis of different feedstocks, mainly babassu oil and tallow beef. For this purpose lipase PS was immobilized on two different non-commercial matrices, such as inorganic matrix (niobium oxide, Nb(2)O(5)) and a hybrid matrix (polysiloxane-polyvinyl alcohol, SiO(2)-PVA) by covalent binding. The properties of free and immobilized enzymes were searched and compared. The best performance regarding all the analyzed parameters (biochemical properties, kinetic constants and thermal stability) were obtained when the lipase was immobilized on SiO(2)-PVA. The superiority of this immobilized system was also confirmed in the transe-sterification of both feedstocks, attained higher yields and productivities. (C) 2010 Elsevier Ltd. All rights reserved.

Screening of Food Grade Lipases to be Used in Esterification and Interesterification Reactions of Industrial Interest

Seven food grade commercially available lipases were immobilized by covalent binding on polysiloxane-polyvinyl alcohol (POS-PVA) hybrid composite and screened to mediate reactions of industrial interest. The synthesis of butyl butyrate and the interesterification of tripalmitin with triolein were chosen as model reactions. The highest esterification activity (240.63 mu M/g min) was achieved by Candida rugosa lipase, while the highest interesterification yield (31%, in 72 h) was achieved by lipase from Rhizopus oryzae, with the production of about 15 mM of the triglycerides C(50) and C(52). This lipase also showed a good performance in butyl butyrate synthesis, with an esterification activity of 171.14 mu M/g min. The results demonstrated the feasibility of using lipases from C. rugosa for esterification and R. oryzae lipase for both esterification and interesterification reactions.

As autarquias e a educação. Centro e periferia na construção das políticas educativas (1998-2008)

RESUMO: Com o actual quadro de descentralização de atribuições e competências da administração central para as autarquias locais, na área da educação, os municípios passam a investir cada vez mais na acção educativa ao liderarem e planearem políticas educativas locais mais ou menos explícitas, e, nalguns casos, tentando superar carências que o sistema educativo apresenta. Esta pesquisa tem como problemática compreender o papel do Estado na (re)configuração das políticas de educação, quando a tendência para a mudança, de um Estado-educador para um Estado-regulador, tem por pressuposto o discurso neoliberal de que com ‗menos‘ Estado mas maior accountability se obtêm melhores resultados. Este processo origina uma redefinição no papel e funções do Estado no plano social e económico, provocando constrangimentos e conflitos de poder no que respeita ao seu controlo político, com a redistribuição de poderes entre o Estado e a comunidade, entre o central e o local. É neste contexto de mudança que a presente investigação, que se situa no âmbito da análise das políticas educativas, procura averiguar como e com que meios as autarquias locais concretizam as suas competências na área da educação. A estratégia de investigação concentra-se em uma metodologia qualitativa, com a utilização de um estudo exploratório, em três municípios da Região de Lisboa e Vale do Tejo. As actuais políticas educativas derivam da nova visão na gestão da coisa pública – res publica –, como resultado da nova concepção para o próprio Estado, e dos processos de elaboração das decisões político-educativas. Nesta perspectiva, a descentralização passa a ser um instrumento do poder local que favorece o aumento da autoridade democrática dos actores. Todavia, a governação – governance – supõe uma dinâmica de negociação, até mesmo de regulação entre o Estado, a região, o local, a escola e o mercado, feita para atender à construção do interesse geral, que já não é totalmente definido pelo Estado, mas construído em conjunto com as diversas forças políticas, económicas, educativas e sociais. O estudo permitiu evidenciar que a descentralização é posta em causa pelo Estado central, quando este ‗recentraliza‘ decisões e condiciona o poder local, com o fecho da maioria das escolas do primeiro ciclo e a verticalização dos agrupamentos escolares. Por sua vez, algumas políticas educativas como a ‗Escola a Tempo Inteiro‘ fomentam a desregulação dos vínculos laborais, forçando os municípios a aumentar os seus meios técnicos e humanos e a construírem novas infra-estruturas educativas. As políticas educativas passaram a ser concebidas segundo uma matriz híbrida, que visam a municipalização da educação – do pré-escolar e de todo o ensino básico –, por um lado; e fomentam a situação de ‗quase-mercado‘ com a privatização de sectores e o financiamento de várias instituições – que fornecem serviços na área da educação –, por outro lado. ABSTRACT: With the current framework of decentralization of functions and powers from central government to local authorities, in education, the municipalities are investing each more in educational work in leading educational policies and planning places more or less explicit and in some cases, trying to overcome shortcomings that education system. This research aims to understand the role of the state in the (re) configuration of education policies, when the tendency for the change in a State-Educator for a State-regulator, is the assumption that neo-liberal speech that with 'less' State but with more accountability we achieve better results. This process leads to a redefinition of the role and State functions in socio-economic constraints, resulting in power struggles with regard to its political control, with the redistribution of powers between the state and community, between the central and local. It is in this changing context that the present investigation, which lies in the examination of education policy addresses the question how and by what means the local, materialized their skills in education. The strategy focuses on a qualitative methodology, with the use of an exploratory study in three municipalities of Lisbon and Tagus Valley. The current education policies come from the new vision in the management of public affairs - res publica - as a result of the new design for the State itself, and the process of preparation of educational policy decisions. In this perspective, decentralization becomes an instrument of local government that favours the increase of democratic authority of the actors. However, the governance assumes a dynamic negotiation, even in regulation between the State, region, local authorities, school and market, made to suit the construction of general interest, which is not anymore fully defined by the State, but constructed together with the various political, economic, educational and social forces. The study indicates that decentralization is undermined by the central government when it ‗re-centralize‘ decisions and the local conditions, with the closure of most primary schools and with vertical groupings of schools. In turn, some educational policies such as 'Full Time School' forced the municipalities to increase their technical and human resources, to build new educational infrastructure. The educative policies began to be designed according to a hybrid matrix, which aims the decentralization of education - from pre-school and all the primary school - on one hand, and promote the situation of 'quasi-market' with privatization of sectors and the financing of several institutions - that provide services in education -, on the other hand. RÉSUMÉ: Avec le cadre actuel de décentralisation des fonctions et pouvoirs du gouvernement central aux autorités locales, dans l'éducation, les municipalités investissent de plus en plus dans le travail éducatif dans la conduite des politiques éducatives en mener et en faisant la planification des lieux plus ou moins explicites et, dans certains cas, essayer de remédier aux lacunes que présente l'éducation. Donc, nous voulons avec cette recherche comprendre le rôle de l'Etat dans la (re) configuration des politiques d'éducation, alors que la tendance au changement d‘un État-éducateur pour un État-régulateur, a comme l'hypothèse le discours néo-libéral de que avec «moins» État, mais plus d‘accountability on a des meilleurs résultats. Ce processus conduit à une redéfinition du rôle et des fonctions de l'Etat au plan social et économique, en donnant lieu à des luttes de pouvoir à l'égard de son contrôle politique, avec la redistribution des compétences entre l'État et la collectivité, entre les niveaux central et local. C‘est dans ce contexte changeant que la présente enquête, qui réside dans l‘examen de la politique de l‘éducation aborde la question de savoir comment et par quels moyens le local matérialisé leurs compétences dans l‘éducation. La stratégie est axée sur une méthodologie qualitative, avec l'utilisation d'une étude exploratoire dans trois municipalités de Lisbonne et Vallée du Tage. Les politiques actuelles d'éducation sont tirées de la nouvelle vision dans la gestion des affaires publiques - res publica – à la suite de la nouvelle conception de l'État lui-même, et le processus de préparation des décisions politique-éducatives. Dans cette perspective, la décentralisation devient un instrument de gouvernement local qui favorise l'augmentation de l'autorité démocratique des acteurs. Toutefois, la gouvernance assume une dynamique de négociation, même en matière de réglementation entre l'État, la région, le local, l'école et le marché, faite pour répondre à la construction d'intérêt général, qui n'est pas plus entièrement défini par l'Etat, mais construit en ensemble avec les divers forces politiques, économiques, éducatives et sociales. L‘étude indique que la décentralisation est minée par le gouvernement central quand il ‗re-centralise‘ les décisions et les conditions locales, avec la fermeture de la plupart des écoles du premier cycle et avec des groupements verticaux d‘écoles. À leur tour, certaines politiques éducatives telles que ‗l'école à temps plein‘ forcé les municipalités à accroître leurs ressources techniques et humaines, de construire de nouvelles infrastructures éducatives. Les politiques éducatives ont commencé à être conçues selon une matrice hybride, qui vise à la municipalisation de l'éducation - de l'école maternelle et de toute l'école basique - d'une part ; et de promouvoir la situation de «quasi-marché» avec la privatisation de secteurs et le financement de plusieurs institutions - qui offrent des services dans l'éducation -, d‘autre part.