Hydrolytic and enzymatic degradation of a poly(å-caprolactone) network

“NOTICE: this is the author’s version of a work that was accepted for publication in Polymer Degradation and Stability. Changes resulting from the publishing process, such as peer review, editing, corrections, structural formatting, and other quality control mechanisms may not be reflected in this document. Changes may have been made to this work since it was submitted for publication. A definitive version was subsequently published in Polymer Degradation and Stability, [Volume 97, Issue 8, August 2012, Pages 1241–1248] DOI 10.1016/j.polymdegradstab.2012.05.038Long-term hydrolytic and enzymatic degradation profiles of poly(å-caprolactone) (PCL) networks were obtained. The hydrolytic degradation studies were performed in water and phosphate buffer solution (PBS) for 65 weeks. In this case, the degradation rate of PCL networks was faster than previous results in the literature on linear PCL, reaching a weight loss of around 20% in 60 weeks after immersing the samples either in water or in PBS conditions. The enzymatic degradation rate in Pseudomonas Lipase for 14 weeks was also studied, with the conclusion that the degradation profile of PCL networks is lower than for linear PCL, also reaching a 20% weight loss. The weight lost, degree of swelling, and calorimetric and mechanical properties were obtained as a function of degradation time. Furthermore, the morphological changes in the samples were studied carefully through electron microscopy and crystal size through X-ray diffraction. The changes in some properties over the degradation period such as crystallinity, crystal size and Young¿s modulus were smaller in the case of enzymatic studies, highlighting differences in the degradation mechanism in the two studies, hydrolytic and enzymatic.The authors would like to acknowledge the support of the Spanish Ministry of Science and Education through the DPI2010-20399-004-03 project. JM Meseguer-Duenas and A Vidaurre also would like to acknowledge the support of the CIBER-BBN, an initiative funded by the VI National R&D&i Plan 2008-2011, Iniciativa Ingenio 2010, Consolider Program, CIBER Actions and financed by the Instituto de Salud Carlos III with assistance from the European Regional Development Fund. The translation of this paper was funded by the Universidad Politecnica de Valencia, SpainCastilla Cortázar, MIC.; Más Estellés, J.; Meseguer Dueñas, JM.; Escobar Ivirico, JL.; Marí Soucase, B.; Vidaurre, A. (2012). Hydrolytic and enzymatic degradation of a poly(å-caprolactone) network. Polymer Degradation and Stability. 97(8):1241-1248. https://doi.org/10.1016/j.polymdegradstab.2012.05.038S1241124897

Surface stiffening and enhanced photoluminescence of ion implanted cellulose - polyvinyl alcohol - silica composite

Novel Cellulose (Cel) reinforced polyvinyl alcohol (PVA)-Silica (Si) composite which has good stability and in vitro degradation was prepared by lyophilization technique and implanted using N3+ ions of energy 24 keV in the fluences of 1 x 10(15), 5 x 10(15) and 1 x 10(16) ions/cm(2). SEM analysis revealed the formation of microstructures, and improved the surface roughness on ion implantation. In addition to these structural changes, the implantation significantly modified the luminescent, thermal and mechanical properties of the samples. The elastic modulus of the implanted samples has increased by about 50 times compared to the pristine which confirms that the stiffness of the sample surface has increased remarkably on ion implantation. The photoluminescence of the native cellulose has improved greatly due to defect site, dangling bonds and hydrogen passivation. Electric conductivity of the ion implanted samples was improved by about 25%. Hence, low energy ion implantation tunes the mechanical property, surface roughness and further induces the formation of nano structures. MG63 cells seeded onto the scaffolds reveals that with the increase in implantation fluence, the cell attachment, viability and proliferation have improved greatly compared to pristine. The enhancement of cell growth of about 59% was observed in the implanted samples compared to pristine. These properties will enable the scaffolds to be ideal for bone tissue engineering and imaging applications.G.M.S. acknowledges CSIR, India (Grant no: 09/468 (0474)/2013-EMR-I) and S.N.K. thanks the award of Erasmus-Mundus Svaagata for providing financial support to carry out this research. G.M.S., N.S. and S.N.K. acknowledge the support of UGC National facility for characterization facility. J.A.G.T. acknowledges the support of the Spanish Ministry of Economy and Competitiveness (MINECO) through the project DPI2015-65401-C3-2-R (including the FEDER financial support). CIBER-BBN, Spain is an initiative funded by the VI National R&D Plan 2008-2011, Iniciativa Ingenio 2010, Consolider Program. CIBER actions are financed by the Instituto de Salud Carlos III with assistance from the European Regional Development Fund. AFM was conducted by the microscopy service of the UPV, whose advice was greatly appreciated.Shanthini, GM.; Sakthivel, N.; Menon, R.; Nabhiraj, PY.; Gómez-Tejedor, JA.; Meseguer Dueñas, JM.; Gómez Ribelles, JL.... (2016). Surface stiffening and enhanced photoluminescence of ion implanted cellulose - polyvinyl alcohol - silica composite. Carbohydrate Polymers. 153:619-630. https://doi.org/10.1016/j.carbpol.2016.08.016S61963015

Bond fluctuation model to describe physical aging in polymeric materials

International audienc

Bond fluctuation model to describe physical aging in polymeric materials

International audienc

Forced compatibility in poly(methyl acrylate)/poly(methyl methacrylate) sequential interpenetrating polymer networks

The aim of this work is to study the miscibility of poly(methyl acrylate)/poly(methyl methacrylate), (PMA/PMMA), sequential interpenetrating networks, (IPNs), as a function of the crosslink density using dielectric and dynamic-mechanical techniques. The PMA/PMMA system is immiscible and so, for low crosslink densities, phase separation appears, as detected by the occurrence of two clearly differentiated main dynamic-mechanical relaxation processes corresponding to the two components. If crosslink density is high enough, a homogeneous IPN can be obtained, achieving a forced compatibilization of both networks. The IPN crosslinked with 10% ethyleneglycol dimethacrylate shows a single main dynamic-mechanical relaxation process. Only the α main relaxation process appears in the PMA networks within the temperature range (−60 to 200°C) of the experiments conducted in this work. The dielectric relaxation spectrum of PMMA networks shows the secondary β relaxation followed by a small α relaxation partially overlapped with it. In the IPNs, both the main relaxation processes tend to merge into a single one and the dielectric spectrum shows a single peak that mainly corresponds to the secondary relaxation of the PMMA

Structure and properties of poly(ɛ-caprolactone) networks with modulated water uptake

A PCL macromonomer was obtained by the reaction of PCL diol with methacrylic anhydride. The effective incorporation of the polymerizable end groups was assessed by FT-IR and 1H NMR spectroscopy. PCL networks were then prepared by photopolymerization of the PCL macromonomer. Furthermore, the macromonomer was copolymerized with HEA, with the aim of tailoring the hydrophilicity of the system. A set of hydrophilic semicrystalline copolymer networks were obtained. The phase microstructure of the new system and the network architecture was investigated by DSC, IR, DMS, TG, dielectric spectroscopy and water sorption studies. The presence of the hydrophilic units in the system prevented PCL crystallization on cooling; yet there was no effect on the glass transition process. The copolymer networks showed microphase separation and the α relaxation of the HEA units moved to lower temperatures as the amount of PCL in the system increased

Analysis of the biological response of endothelial and fibroblast cells cultured on synthetic scaffolds with various hydrophilic/hydrophobic ratios: influence of fibronectin adsorption and conformation

In this study we developed polymer scaffolds intended as anchorage rings for cornea prostheses among other applications, and examined their cell compatibility. In particular, a series of interconnected porous polymer scaffolds with pore sizes from 80 to 110 microns were manufactured varying the ratio of hydrophobic to hydrophilic monomeric units along the polymer chains. Further, the effects of fibronectin precoating, a physiological adhesion molecule, were tested. The interactions between the normal human fibroblast cell line MRC-5 and primary human umbilical vein endothelial cells (HUVECs) with the scaffold surfaces were evaluated. Adhesion and growth of the cells was examined by confocal laser scanning microscopy. Whereas MRC-5 fibroblasts showed adhesion and spreading to the scaffolds without any precoating, HUVECs required a fibronectin precoating for adhesion and spreading. Although both cell types attached and spread on scaffold surfaces with a content of up to a 20% hydrophilic monomers, cell adhesion, spreading, and proliferation increased with increasing hydrophobicity of the substrate. This effect is likely due to better adsorption of serum proteins to hydrophobic substrates, which then facilitate cell adhesion. In fact, atomic force microscopy measurements of fibronectin on surfaces representative of our scaffolds revealed that the amount of fibronectin adsorption correlated directly with the hydrophobicity of the surface. Besides cell adhesion we also examined the inflammatory state of HUVECs in contact with the scaffolds. Typical patterns of platelet/endothelial cell adhesion molecule-1 expression were observed at intercellular boarders. HUVECs adhering on the scaffolds retained their proinflammatory response potential as shown by E-selectin mRNA expression after stimulation with lipopolyssacharide (LPS). The proinflammatory activation occurred in most of the cells, thus confirming the presence of a functionally intact endothelium. Little or no expression of the proinflammatory activation markers in the absence of LPS stimulation was observed for HUVECs growing on scaffolds with up to a 20% of hydrophilic component, whereas activation of these markers was observed after stimulation. In conclusion, scaffolds containing up to 20% hydrophilic monomers exhibited excellent cell compatibility toward human fibroblast cell line MRC-5 and human endothelial cells. Atomic force microscopy confirmed that adsorbed serum proteins such as fibronectin probably accounted for the positive correlation of HUVEC adhesion and surface hydrophobicity

A simple model for cooperative and non-exponential processes in non-crystalline polymers

A quite simple Markov chain model is presented in an attempt to understand several characteristic properties of the structural relaxation in glass-former materials. A second order Markov model is proposed for a small region of the material. Only a few parameters are necessary for the definition of the material in the model equations namely the energy levels accessible to that small region and the transition probabilities between them. The later are considered dependent on the energy levels and the potential barrier heights between them, on temperature, on a reference transition rate parameter and on a cooperativity or memory parameter related to the interaction with the neighbour regions. Isothermal relaxations at different temperatures were simulated with selected values of the model parameters. As a result, non-exponentiality of energy relaxations and its temperature dependence appears directly related to the cooperativity parameter. Markov chain model shows also non-linearity and memory effects, and a transition between two different regimes in the dependence of the relaxation times with temperature. © 2010 Elsevier B.V.All rights reserved.The authors would like to acknowledge the support provided by the Vicerectorado de Investigacion, Desarrollo e Innovacion of the Universitat Politecnica de Valencia through the PAID07-20080021 project and by the Conselleria d'Educacio de la Generalitat Valenciana through the GV/2009/033 project.Torregrosa Cabanilles, C.; Molina Mateo, J.; Meseguer Dueñas, JM.; Gómez Ribelles, JL. (2011). A simple model for cooperative and non-exponential processes in non-crystalline polymers. Journal of Non-Crystalline Solids. 357(2):367-370. https://doi.org/10.1016/j.jnoncrysol.2010.06.040S367370357

Phenomenological theory of structural relaxation based on a thermorheologically complex relaxation time distribution

he aim of this work is to explore the consequences on the kinetics of structural relaxation of considering a glass-forming system to consist of a series of small but macroscopic relaxing regions that evolve independently from each other towards equilibrium in the glassy state. The result of this assumption is a thermorheologically complex model. In this approach each relaxing zone has been assumed to follow the Scherer-Hodge model for structural relaxation (with the small modification of taking a linear dependence of configurational heat capacity with temperature). The model thus developed contains four fitting parameters. A least-squares search routine has been used to find the set of model parameters that fit simultaneously four DSC thermograms in PVAc after different thermal histories. The computersimulated curves are compared with those obtained with Scherer-Hodge model and the model proposed by Gómez and Monleón. The evolution of the relaxation times during cooling or heating scans and also during isothermal annealing below the glass transition has been analysed. It has been shown that the relaxation times distribution narrows in the glassy state with respect to equilibrium. Isothermal annealing causes this distribution to broaden during the process to finally attain in equilibrium the shape defined at temperatures above T<sub>g</sub>