Poly(vinylidene fluoride-trifluoroethylene) porous films: tailoring microstructure and physical properties by solvent casting strategies

A systematic study for the production of porous poly(vinylidene fluoride-trifluoroethylene), P(VDF-TrFE), films using solvent evaporation and non-solvent induced phase separation techniques is presented. Processing parameters such as copolymer volume fraction, solvent, preset exposure time to air before immersion, and non-solvent and temperature of the coagulation bath were varied and the corresponding sample morphology, hydrophobicity, thermal and mechanical properties were determined. Film morphologies including homogeneous pore distributions, micropores, microvoids, spherulites and non-porous films were obtained. The morphology variations strongly influence sample hydrophobicity and mechanical properties. All samples crystallize in the electroactive β-phase with a degree of crystallinity around 30 %.

In vitro mechanical fatigue behavior of poly-ε-caprolactone macroporous scaffolds for cartilage tissue engineering: Influence of pore filling by a poly(vinyl alcohol) gel

Polymeric scaffolds used in regenerative therapies are implanted in the damaged tissue and subjected to repeated loading cycles. In the case of articular cartilage engineering, an implanted scaffold is typically subjected to long term dynamic compression. The evolution of the mechanical properties of the scaffold during bioresorption has been deeply studied in the past, but the possibility of failure due to mechanical fatigue has not been properly addressed. Nevertheless, the macroporous scaffold is susceptible to failure after repeated loading-unloading cycles. In this work fatigue studies of polycaprolactone scaffolds were carried by subjecting the scaffold to repeated compression cycles in conditions simulating the scaffold implanted in the articular cartilage. The behaviour of the polycaprolactone sponge with the pores filled with a poly(vinyl alcohol) gel simulating the new formed tissue within the pores was compared with that of the material immersed in water. Results were analyzed with Morrow’s criteria for failure and accurate fittings are obtained just up to 200 loading cycles. It is also shown that the presence of poly(vinyl alcohol) increases the elastic modulus of the scaffolds, the effect being more pronounced with increasing the number of freeze/thawing cycles.

Erratum: Influence of oxygen plasma treatment parameters on poly(vinylidene fluoride) electrospun fiber mats wettability

Electrospun poly(vinylidene fluoride) (PVDF) fiber mats find applications in an increasing number of areas, such as battery separators, filtration and detection membranes, due to their excellent properties. However, there are limitations due to the hydrophobic nature and low surface energy of PVDF. In this work, oxygen plasma treatment has been applied in order to modify the surface wettability of PVDF fiber mats and superhydrophilic PVDF electrospun membranes have been obtained. Further, plasma treatment does not significantly influences fiber average size (~400 ± 200 nm), morphology, electroactive -phase content (~80-85%) or the degree of crystallinity (Xc of 42 ± 2%), allowing to maintain the excellent physical-chemical characteristics of PVDF. Plasma treatment mainly induces surface chemistry modifications, such as the introduction of oxygen and release of fluorine atoms that significantly changes polymer membrane wettability by a reduction of the contact angle of the polymer fibers and an overall decrease of the surface tension of the membranes.

Poly(2-hydroxyethyl methacrylate): A new star polymer

Multiarm star polymers are attractive materials due to their unusual bulk and solution properties. They are considered analogues of dendrimers with a wide range of applications, such as drug delivery, membranes, coatings and lithography.1 The advent of controlled polymerization made possible the existence of this unique class of organic nanoparticles (ONPs).2 Two major synthetic strategies are usually employed in the preparation of star polymers, the core-first and arm-first approaches. The core-first approach involves a controlled living polymerization using a multiarm initiator core while the arm-first methodology is based in the quenching of living polymers with multifunctional coupling agent or bifunctional vinyl compounds. Herein, we present the synthesis and characterization of a new star polymer, the multiarm star poly(2-hydroxyethyl methacrylate). The tetra-armed star polymer was prepared by reversible addition fragmentation chain-transfer (RAFT) polymerization using the core-first approach. The RAFT chain-transfer agent (RAFT CTA) pentaerythritol tetrakis[2-(dodecylthiocarbonothioylthio)-2-methylpropionate] was used as multiarm initiator core were 2-hydroxyethyl methacrylate (HEMA) was polymerized using AIBN as radical initiator. Structural characterization was performed by 1H NMR and FTIR. The new polymer is able to uptake large quantities of organic solvents, forming gels. The rheological behavior of these gels was also investigated.

Mesenchymal stem cells culture on poly(vinylidene fluoride) piezoelectric microspheres

Dissertação de mestrado em Biofísica e Bionanossistemas

Poly lactic acid based biodegradable stents and functionalization techniques: brief review

Commercial stents, especially metallic ones, present several disadvantages, and this gives rise to the necessity of producing or coating stents with different materials, like natural polymers, in order to improve their biocompatibility and minimize the disadvantages of metallic ones. This review paper discusses some applications of natural-based polymers in stents, namely polylactic acid (PLA) for stent development and chitosan for biocompatible coatings of stents . Furthermore, some effective stent functionalization techniques will be discussed, namely Layer by Layer (LBL) technique.

Ultrasound enhances lipase-catalyzed synthesis of poly (ethylene glutarate)

The present work explores the best conditions for the enzymatic synthesis of poly (ethylene glutarate) for the first time. The start-up materials are the liquids; diethyl glutarate and ethylene glycol diacetate, without the need of addition of extra solvent. The reactions are catalyzed by lipase B from Candida antarctica immobilized on glycidyl methacrylate-ter-divinylbenzene-ter-ethylene glycol dimethacrylate at 40 °C during 18 h in water bath with mechanical stirring or 1 h in ultrasonic bath followed by 6 h in vacuum in both the cases for evaporation of ethyl acetate. The application of ultrasound significantly intensified the polyesterification reaction with reduction of the processing time from 24 to 7 h. The same degree of polymerization was obtained for the same enzyme loading in less time of reaction when using the ultrasound treatment. The degree of polymerization for long-term polyesterification was improved approximately 8-fold due to the presence of sonication during the reaction. The highest degree of polymerization achieved was 31, with a monomer conversion of 96.77%. The ultrasound treatment demonstrated to be an effective green approach to intensify the polyesterification reaction with enhanced initial kinetics and high degree of polymerization.

Poly(ester-urethane) scaffolds: effect of structure on properties and osteogenic activity of stem cells

The present study aimed to investigate the effect of structure (design and porosity) on the matrix stiffness and osteogenic activity of stem cells cultured on poly(ester-urethane) (PEU) scaffolds. Different three-dimensional (3D) forms of scaffold were prepared from lysine-based PEU using traditional salt-leaching and advanced bioplotting techniques. The resulting scaffolds were characterized by differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), scanning electron microscopy (SEM), mercury porosimetry and mechanical testing. The scaffolds had various pore sizes with different designs, and all were thermally stable up to 300â °C. In vitrotests, carried out using rat bone marrow stem cells (BMSCs) for bone tissue engineering, demonstrated better viability and higher cell proliferation on bioplotted scaffolds compared to salt-leached ones, most probably due to their larger and interconnected pores and stiffer nature, as shown by higher compressive moduli, which were measured by compression testing. Similarly, SEM, von Kossa staining and EDX analyses indicated higher amounts of calcium deposition on bioplotted scaffolds during cell culture. It was concluded that the design with larger interconnected porosity and stiffness has an effect on the osteogenic activity of the stem cells.

Beta-adrenergic blocking agents in heart failure

Cardiac dysfunction in heart failure is widely recognized as a progressive process, regardless of the clinical signs and symptoms. An increase in cardiac sympathetic drive is one of the earliest neurohormonal responses occurring in patients with heart failure and may be one of the major causes of the progressive remodeling leading to the decline in myocardial function, and responsible for the poor prognosis of patients with heart failure. Therefore, recent data provided by several appropriately designed clinical trials clearly indicate the benefits of beta-adrenoceptor blocking agents, combined with diuretics, ACE inhibitors, and digoxin in chronic heart failure class II to IV due to systolic ventricular dysfunction. The benefits are related to symptoms, functional capacity, remodeling, and improvement in left ventricular function, reduction in cardiovascular hospitalization, a decrease in the overall and sudden cardiac death rate, and are similar in patients with ischemic or nonischemic cardiomyopathy, independent of age, gender, or functional class. In this review we describe the cardiovascular effects of the increase in sympathetic drive, the pharmacological properties of the beta-blockers most evaluated in heart failure therapy (metoprolol, bisoprolol, and carvedilol), the major clinical trials related to these agents in heart failure, the recommendations for their appropriate use in clinical practice, the precautions to be adopted, and how to handle the more common adverse reactions.

Proteomic analysis of nitrate-dependent acetone degradation by Alicycliphilus denitrificans strain BC

Alicycliphilus denitrificans strain BC grows anaerobically on acetone with nitrate as electron acceptor. Comparative proteomics of cultures of A. denitrificans strain BC grown on either acetone or acetate with nitrate was performed to study the enzymes involved in the acetone degradation pathway. In the proposed acetone degradation pathway, an acetone carboxylase converts acetone to acetoacetate, an AMP-dependent synthetase/ligase converts acetoacetate to acetoacetyl-CoA, and an acetyl-CoA acetyltransferase cleaves acetoacetyl-CoA to two acetyl-CoA. We also found a putative aldehyde dehydrogenase associated with acetone degradation. This enzyme functioned as a -hydroxybutyrate dehydrogenase catalyzing the conversion of surplus acetoacetate to -hydroxybutyrate that may be converted to the energy and carbon storage compound, poly--hydroxybutyrate. Accordingly, we confirmed the formation of poly-?-hydroxybutyrate in acetone-grown cells of strain BC. Our findings provide insight in nitrate-dependent acetone degradation that is activated by carboxylation of acetone. This will aid studies of similar pathways found in other microorganisms degrading acetone with nitrate or sulfate as electron acceptor.

Endothelium-dependent relaxation in response to poly-L-arginine in canine coronary arteries: implications about hyperpolarization as a mechanism of vasodilatation

OBJECTIVE: To study the mechanism by which poly-L-arginine mediates endothelium-dependent relaxation. METHODS: Vascular segments with and without endothelium were suspended in organ chambers filled with control solution maintained at 37ºC and bubbled with 95% O2 / 5% CO2. Used drugs: indomethacin, acetycholine, EGTA, glybenclamide, ouabain, poly-L-arginine, methylene blue, N G-nitro-L-arginine, and verapamil and N G-monomethyl-L-arginine. Prostaglandin F2á and potassium chloride were used to contract the vascular rings. RESULTS: Poly-L-arginine (10-11 to 10-7 M) induced concentration-dependent relaxation in coronary artery segments with endothelium. The relaxation to poly-L-arginine was attenuated by ouabain, but was unaffected by glybenclamide. L-NOARG and oxyhemoglobin caused attenuation, but did not abolish this relaxation. Also, the relaxations was unaffected by methylene blue, verapamil, or the presence of a calcium-free bathing medium. The endothelium-dependent to poly-L-arginine relaxation was abolished only in vessels contracted with potassium chloride (40 mM) in the presence of L-NOARG and indomethacin. CONCLUSION: These experiments indicate that poly-L-arginine induces relaxation independent of nitric oxide.

Braquiterapia intracoronariana. Tratamento da reestenose intra-stent com o sistema Beta-Cath: experiência inicial na América Latina

OBJETIVO: Avaliar a segurança e eficácia da braquiterapia intracoronariana usando o sistema Beta-CathTM na prevenção da recorrência de restenose intra-stent (RIS), por meio da análise dos resultados clínicos, angiográficos e pelo ultra-som intracoronariano (USIC). MÉTODO: Foram submetidos à angioplastia com cateter-balão, seguida de beta-radiação intracoronariana com o sistema Beta-CathTM (90Sr/Y) 30 pacientes com RIS em artérias coronárias nativas e, posteriormente, avaliados. RESULTADOS: Incluíram-se lesões reestenóticas complexas (77% do tipo difuso-proliferativo) com extensão elevada (18,66±4,15 mm). O sucesso da braquiterapia foi de 100%. A dose média utilizada foi de 20,7±2,3 Gy, liberada em um período médio de 3,8±2,1 min. No seguimento tardio, o diâmetro luminal mínimo (DLM) intra-stent diminuiu discretamente (1,98±0,30mm para 1,84±0,39 aos 6 meses, p=0,13), com uma perda tardia de 0,14±0,18 mm. O DLM intra-segmentar foi significativamente menor do que o intra-stent (1,55±0,40mm vs.1,84±0,39mm, p=0,008), associando-se à perda tardia (0,40±0,29mm vs. 0,14±0,18mm; p=0,0001). No USIC, observou-se discreto incremento do tecido neointimal em 6,8±14,3 mm³ aos 6 meses (p=0,19) e a percentagem de obstrução volumétrica aumentou em 4,7±7,5%. A reestenose binária e a revascularização do vaso-alvo recorreram em 17% dos casos; houve 1 caso (3%) de oclusão tardia, associada a infarto do miocárdio. A sobrevida livre de eventos foi de 80%. CONCLUSÃO: O manejo da reestenose intra-stent com a beta-radiação intracoronariana mostrou-se procedimento seguro e eficaz, com alta taxa de sucesso imediato, representando uma opção terapêutica para a inibição da hiperplasia neointimal.

Pesquisa de marcadores para os genes da cadeia pesada da beta-miosina cardíaca e da proteína C de ligação à miosina em familiares de pacientes com cardiomiopatia hipertrófica

OBJETIVO: Estudar os marcadores moleculares para os genes da cadeia pesada da beta-miosina cardíaca e da proteína-C de ligação à miosina em familiares de portadores de cardiomiopatia hipertrófica. MÉTODOS: Foram estudadas 12 famílias que realizaram anamnese, exame físico, eletrocardiograma, ecocardiograma e coleta de sangue para o estudo genético através da reação em cadeia da polimerasse. RESULTADOS: Dos 227 familiares 25% eram acometidos, sendo 51% do sexo masculino com idade média de 35±19 (2 a 95) anos. A análise genética mostrou ligação com o gene da b-miosina cardíaca em uma família e, em outra, ligação com o gene da proteína C de ligação à miosina. Em cinco famílias foram excluídas ligações com os dois genes; em duas, a ligação com o gene da proteína C de ligação à miosina, porém para o gene da b-miosina os resultados foram inconclusivos; em duas famílias os resultados foram inconclusivos para os dois genes e em uma foi excluída ligação para o gene da b-miosina mas ficou inconclusivo para o gene da proteína C de ligação à miosina. CONCLUSÃO: Em nosso meio, talvez predominem outros genes que não aqueles descritos na literatura, ou que existam outras diferenças genéticas relacionadas com a origem de nossa população e/ou fatores ambientais.

Estudio de receptores beta cardíacos en la enfermedad de Chagas experimental

Hasta el momento no hay una explicación definitiva sobre los mecanismos etiopatogénicos de la miocardiopatía chagásica. A partir de las alteraciones farmacológicas y lesiones histopatológicas descriptas en trabajos anteriores y coincidiendo con otros autores, pensamos que el compromiso de la perfusión vascular y las reacciones de autoinmunidad podrían involucrar modificaciones en los receptores beta cardíacos. Hemos realizado un seguimiento evolutivo de estos receptores desde los 35 días a los 135 días post inoculación con tripomastigotes cepa Tulahuen y comprobamos que las alteraciones histológicas y farmacológicas se correlacionan con los cambios de afinidad y densidad de dichos receptores de acuerdo a la etapa en estudio (aguda, indeterminada y crónica). Asimismo se demostró que la cantidad de Trypanosoma cruzi que ingresa al huésped determina y acelera la evolución de la miocardiopatía chagásica. Continuando con la línea de estudio de los receptores beta cardíacos en los distintos estadíos de la enfermedad chagásica experimental, nos proponemos estudiar las características dinámicas de las membranas miocárdicas determinando su composición en fosfolípidos y otros componentes polares. A la vez se plantea estudiar si el tratamiento con beta bloqueante incide en los desórdenes que se producen en los receptores beta cardíacos de animales inoculados con T. cruzi , cepa Tulahuen. Por lo antes mencionado, se intenta lograr un aporte que desde el área básica se podría dar para esclarecer la fisiopatogenia de la miocarditis chagásica y colaborar en el enfoque de nuevas acciones terapéuticas.