Metal doped carbon nanoneedles and effect of carbon organization with activity for hydrogen evolution reaction (HER)

AbstractCellulose nanowhiskers (CNW) from cotton, was prepared by acid hydrolysis and purified using a size selection process to obtain homogeneous samples with average particle size of 270nm and 85.5% crystallinity. Purified CNW was used as precursor to carbon nanoneedles (CNN) synthesis. The synthesis of CNN loaded with different metals dopants were carried out by a nanoreactor method and the obtained CNNs applied as electrocatalysts for hydrogen evolution reaction (HER). In the carbon nanoneedles synthesis, Ni, Cu, or Fe worked as graphitization catalyst and the metal were found present as dopants in the final material. The used metal appeared to have direct influence on the degree of organization of the particles and also in the surface density of polar groups. It was evaluated the influence of the graphitic organization on the general properties and nickel was found as the more appropriate metal since it leads to a more organized material and also to a high activity toward HER

Drug release mechanisms of chemically cross-linked albumin microparticles: effect of the matrix erosion

Albumin (BSA) microparticles were developed as a biotechnological alternative for drug delivery. Vitamin B12 (Vit-B12) was used as a model drug. The microparticles were obtained from maleic anhydride-functionalized BSA and N′,N′-dimethylacrylamide (DMAAm) in a W/O emulsion without and with PVA. The microparticles produced at 15 min of stirring without PVA showed the best results in terms of size, homogeneity, and sphericity. In such a case, BSA played a role as a surface active agent, replacing PVA. For longer stirring times, BSA was unable to act as an emulsifier. These microparticles showed an uncommon release profile, consisting of a two-step release mechanism, at the pH range studied. Considering that a two-step release mechanism is occurring, the experimental data were adjusted by applying modified power law and Weibull equations in order to describe release mechanism n and release rate constant k, respectively. Each one of the release stages was related to a specific value of n and k. The second stage was driven by a super case II transport mechanism, as a result of diffusion, macromolecular relaxation, and erosion. A third model, described by Hixson–Crowell, confirmed the erosion mechanism. Vit-B12 diffusion kinetics in aqueous solutions (i.e., without the microparticles) follows a one-step process, being k dependent on the pH, confirming that the two-step release mechanism is a characteristic profile of the developed microparticles. The microparticles released only 2.70% of their initial drug load at pH 2, and 58.53% at pH 10

Morphology of temperature-sensitive and ph-responsive ipn-hydrogels for application as biomaterial for cell growth

In the present investigation, hydrogels with pH-responsive and temperature-sensitive properties were obtained by formation of alginate-Ca network inside the PNIPAAm network resulting in an interpenetrated network system (IPN). From scanning electron microscopy (SEM) images and water uptake (WU) tests one observed that IPN hydrogels exhibited a drastic shrinking when heated above 30-35 ºC. The shrinking resulted in decreased average pore size, thus affect the hydrogel morphology significantly. In the pH range studied, IPN hydrogels showed significant pH dependence, which was attributed to the charged alginate groups. The results indicated that the pH-responsiveness and temperature-dependence of alginate and PNIPAAm, respectively, were preserved in IPN hydrogels. In addition, such hydrogels become less deformable when subjected to compressive stress. These hydrogels presented porous morphology that may be tuned by controlling the temperature, and this makes them attractive for applications as biomaterial in cell growth.No presente trabalho, foram sintetizados hidrogéis com ambas as propriedades, termo-sensíveis e pH-responsivos, pela formação de redes de alginato de cálcio (alginato-Ca) dentro de redes de poli(N-Isopropil Acrilamida) (PNIPAAm), resultando em um sistema IPN (sistema de redes poliméricas interpenetradas). Através das análises por microscopia de varredura eletrônica (MEV) e ensaios de intumescimento foi possível observar que os hidrogéis IPN exibiram forte contração quando aquecidos acima da LCST (temperatura critica inferior de solubilização) da PNIPAAm, ou seja, acima de temperaturas de 30-35 ºC. Observou-se ainda que devido à contração do hidrogel, houve uma diminuição significativa nos tamanhos de poros os quais foram observados pelas micrografias. Observou-se também que no intervalo de pH estudado os hidrogéis de IPN sofreram significativa variação da estrutura com a variação desse parâmetro. Tal efeito foi atribuído à presença de grupos químicos carregados com alginato, os quais possuem carga elétrica negativa. Os resultados indicaram que o hidrogel formado por alginato-Ca e PNIPAAm possuíram características especificas após variação de pH e temperatura, e que tais características são derivadas dos compostos individuais envolvidos na síntese. Nesse caso, as propriedades de alginato-Ca e PNIPAAm livres foram preservadas dentro do hidrogel. Tal hidrogel ficou mais resistente à aplicação de uma tensão de compressão. Como conclusão, observou-se que os hidrogéis apresentaram morfologia característica para variações controladas de pH e temperatura, podendo ser eficientemente aplicados como biomaterial na cultura de células.105110Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES

Hydrogels Based on Chitosan and Chitosan Derivatives for Biomedical Applications

Chitosan (CS) is a polymer obtained from chitin, being this, after the cellulose, the most abundant polysaccharide. The fact of (i) CS being obtained from renewable sources; (ii) CS to possess capability for doing interactions with different moieties being such capability dependent of pH; (iii) plenty of possibilities for chemical modification of CS; and (iv) tuning the final properties of CS derivatives makes this polymer very interesting in academic and technological points of view. In this way, hydrogels based on CS and on CS derivatives have been widely used for biomedical applications. Other important technological applications can be also cited, such as adsorbent of metals and dyes in wastewater from industrial effluents. In pharmaceutical field, hydrogels based on CS are often used as drugs’ and proteins’ carrier formulations due to the inherent characteristics such as the biocompatibility, nontoxicity, hydrophilicity, etc. This chapter is an attempt for updating and joining the plenty of available information regarding the preparation, characterization, and biomedical application of hydrogels based on chitosan and chitosan derivatives. More than 260 references are provided, being the majority of them published in the last 10 years

Chitosan/TPP microparticles obtained by microemulsion method applied in controlled release of heparin

AbstractThis work deals with the preparation of chitosan/tripolyphosphate microparticles (CHT/TPP) using microemulsion system based on water/benzyl alcohol. The morphology of the microparticles was evaluated by scanning electron microscopy (SEM). The microparticles were also characterized through infrared spectroscopy (FTIR) and wide-angle X-ray scattering (WAXS). The morphology and crystallinity of microparticles depended mainly on CHT/TPP ratio. Studies of controlled release of HP were evaluated in distilled water and in simulated gastric fluid. Besides, the profile of HP releasing could be tailored by tuning the CHT/TPP molar ratio. Finally, these prospective results allow the particles to be employed as site-specific HP controlled release system

Hidrogéis semi-IPN baseados em rede de alginato-Ca2+ com PNIPAAm entrelaçado: propriedades hidrofílicas, morfológicas e mecânicas Semi-IPN hydrogels based on alginate-Ca2+ network and PNIPAAm: hydrophilic, morphological and mechanical properties

Neste trabalho, a termossensibilidade dos hidrogéis do tipo semi-IPN baseados em rede de alginato-Ca2+com poli(N-isopropil acrilamida) (PNIPAAm) entrelaçado, com diferentes teores de alginato e de PNIPAAm, foi caracterizada por meio de medidas de grau de intumescimento (Q), microscopia eletrônica de varredura (MEV) e propriedades mecânicas [tensão máxima de compressão (&#963;), densidade aparente de reticulação (&#957;e) e módulo de elasticidade (E)]. Os valores de Q variam inversamente com &#957;e. Para o parâmetro &#957;e contribuem as concentrações de retículos alginato-Ca2+ e de cadeias de PNIPAAm. Hidrogéis com maiores valores de Q possuem maiores poros. Resultados de propriedades mecânicas demonstraram que hidrogéis com maior &#957;e apresentam maior rigidez e resistência à compressão, sendo este efeito mais intenso acima da LCST do PNIPAAm. O controle dessas propriedades nesses hidrogéis termos-sensíveis torna esses materiais potencialmente viáveis para aplicação em sistemas carreadores para liberação controlada e/ou prolongada de fármacos e substratos para crescimento e cultura de célula.<br>In this study, the thermosensitivity of semi-IPN hydrogels based on alginate-Ca2+ network and having PNIPAAm entangled was characterized by swelling degree (Q), scanning electron microscopy (SEM) and mechanical properties [compressive stress (&#963;), apparent cross-linking density (&#957;e) and modulus of elasticity (E)]. The Q values change inversely to the &#957;e ones. The concentrations of the alginate-Ca2+ cross-linking and of the PNIPAAm chains contribute to the &#957;e parameter. Higher values of Q correlate to larger pores size in the hydrogel. Hydrogels richer in alginate and PNIPAAm were more rigid, highly resistant to deformation because of their higher compressive modulus of elasticity. This is more intense at temperatures above the LCST of PNIPAAm in water (32-35 °C). The control of thermosensitive properties by tailoring the alginate-Ca2+/PNIPAAm ratio and temperature allows the hydrogels studied in this paper to be applied as drug delivery devices and/or as substrate for cell growth

Miscibility influence in the thermal stability and kinetic parameters of poly (3-hydroxybutyrate)/poly (ethylene terephthalate) sulphonated blends

The thermal degradation of miscible and immiscible poly (3-hidroxy butyrate) PHB/ poly (ethylene terephthalate) sulphonated (PETs) blends was investigated using thermogravimetric analyses. Model-free kinetic analysis, Vyazovkin and Flynn-Wall-Ozawa's methods, were used to determine the apparent activation energy in the whole interval of degradation of the pure polymers, immiscible blends, and miscible blends. The thermal stability of both polymers in their blends is higher when compared to the pure polymers. The synergistic effect in the thermal stability in the blends is higher for the miscible blend where the formation of the specific interaction between PHB and PETs occurs. The apparent activation energy of the individual polymers is higher in PETs/PHB blends, and this effect is potentiated by the miscibility of the blend

Aplicações de fibras lignocelulósicas na química de polímeros e em compósitos

The use of lignocellulosic fibers and their constituents, as raw materials in the production of polymeric and composite materials, represent an exceptional opportunity of sustainable technological development. In the present report works that discuss promising alternatives of obtaining and use of materials such as cellulose, hemicellulose, lignin, cellulose nanocrystals and biocomposites were revised. The advance in the use of biomass can be, in a near future, capable of going beyond the application difficulties of these vast materials, especially in relation to the economical unviability, by the production of high performance polymeric and composite materials. This advance would represent a higher profitability to some areas of agrobusiness, especially the sector of biofuels, which produces elevated amounts of biomass waste

Release of vitamin B12 and diclofenac potassium from N, N-dimethylacrylamide-modified arabic gum hydrogels - the partition-diffusion model

Recently, a model predicting whole profile solute release from a hydrogel was developed. In such model, the partition activity, &#945;, and release kinetic constant, kR, can be obtained. Although &#945; and kR depend on many factors, the hypothesis that &#945;/kR ratio does not depend on external fluid volume was tested in the present study. Thus, &#945;/kR values for two distinct solutes, vitamin B12 (VitB12) and diclofenac potassium (DFK), were obtained at 25, 35 and 45 ºC using 250, 350 and 450 mL of external fluid. The hydrogel used in the experiments was obtained by the copolymerization of N, N-dimethylacrylamide-modified Arabic gum (AGm-DMAAm), at wt% ratio of 60-40. It was verified that &#945;/kR ratio is not volume dependent, at a certain temperature, but the temperature strongly influences the &#945;/kR ratio for both solutes. Changing temperature from 25 to 35 ºC affected DFK release much more than VitB12 release. This was attributed mainly to electrostatic interactions between (R-COO-) from DFK and the positively charged groups in the GAm-DMAAm matrix. Additionally, the values for the half-life time release, t1/2, equilibrium time release, t eq, as well as the activation energy for releasing, EaR, were determined and discussed in light of the partition-diffusion model