André R. Fajardo

Reaction of Glycidyl Methacrylate at the Hydroxyl and Carboxylic Groups of Poly(vinyl alcohol) and Poly(acrylic acid): Is This Reaction Mechanism Still Unclear?

Transesterification and epoxide ring-opening reactions are two mechanism routes that explain chemical modifications of macromolecules by glycidyl methacrylate (GMA). Although the coupling reaction of the GMA with macromolecules has widely been investigated, there are still mechanisms that remain to be explained when GMA is processed in an aqueous solution at different pH conditions. To this end, reaction mechanisms of poly(vinyl alcohol) (PVA) and poly(acrylic acid) (PAAc) by GMA in water in acidic and basic conditions were investigated thoroughly. The presence of hydroxyl groups in PVA and carboxyl groups in PAAc allowed for a better evaluation of the reaction mechanisms. The analysis of the (1)H and (13)C NMR spectra clearly demonstrated that the chemical reactions of GMA with carboxyl groups and alcohols of the macromolecules in an aqueous solution are dependent on pH conditions. At pH 3.5, the GMA reacts with both the carboxylic and the hydroxyl groups through an epoxide ring-opening mechanism. At pH 10.5, the GMA undergoes a hydrolysis process and reacts with hydroxyl groups by way of both the transesterification and the epoxide ring-opening mechanisms, whereas the ring-opening reaction is the preferential pathway.

Superabsorbent hydrogel nanocomposites based on starch-g-poly(sodium acrylate) matrix filled with cellulose nanowhiskers

Superabsorbents hydrogel nanocomposites based on starch-g-poly(sodium acrylate) and cellulose nanowhiskers (CNWs) were synthesized. A set of experiments was performed to evaluate the influence of some factors such as NaAc/starch mass ratio, crosslinker, and nanowhiskers amount in the swelling capacity and swelling kinetics. Increasing the NaAc/starch mass ratio up to 7 leads to an increase in the water uptake at a maximum value, however, higher ratios decreased that value due to the increase of crosslinking points. Similarly, the incorporation of CNWs up to 10 wt% provided an improvement in the swelling due to the hydrophilic groups from cellobiose units. Further, the incorporation of CNWs diminishes the water uptake. Besides, the CNWs improved the mechanical properties. SEM images showed that CNWs increase the average porous size of composites. The composites presented good responsive behavior in relation to pH and salt presence allowing those materials suitable for many potential applications.

Fast dye removal from water by starch-based nanocomposites.

Robust and efficient methylene blue (MB) adsorbent was prepared based on starch/cellulose nanowhiskers hydrogel composite. Maximum MB adsorption capacity of ∼2050mgperg of dried hydrogel was obtained with the composite at 5wt.% of cellulose nanowhiskers and at pH 5. Adsorption capacity varied from 1450mg/g to 2050mg/g with increasing the initial MB concentration from 1500mg/L to 2500mg/L, respectively. For all the concentrations studied ca. 90% of MB was removed by the adsorbent. Optimal conditions were obtained at pH⩾5 due to the generation of negatively charged groups (COO(-)) in the adsorbent, which can strongly interact with the positive charges from MB. The main advantage of this system over other reported adsorbents, besides the fact of being synthesized from biodegradable polymers (starch and cellulose), is its fast adsorption kinetics that follows the pseudo-second order model, which is based on chimisorption phenomenon. Saturation condition was reached as fast as 1h of experiments owing to the formation of an adsorbed MB monolayer as suggested by the Langmuir isotherm model. Desorption experiments showed 60wt.% of MB loaded can be removed from the adsorbent by immersing it in a pH 1 solution, showing its feasibility to be reused. Therefore, starch/cellulose nanowhiskers hydrogel composite presents outstanding capacity to be employed in the remediation of MB contaminated wastewaters.

Preparation and characterization of Zein and Zein-Chitosan microspheres with great prospective of application in controlled drug release

Biomaterials applied as carriers for controlled drug delivery offer many advantages over the conventional systems. Among them, the increase of treatment effectiveness and also a significant reduction of toxicity, due to their biodegradability property, are some special features. In this work, microspheres based on the protein Zein (ZN) and ZN associated to the natural polymer Chitosan (CHI) were prepared and characterized. The microspheres of ZN and ZN/CHI were characterized by FT-IR spectroscopy and thermal analysis, and the morphology was analyzed by SEM images. The results confirmed the incorporation of CHI within the ZN-based microspheres. The morphological analysis showed that the CHI added increased the microspheres porosity when compared to the ZN microspheres. The chemical and physical characterization and the morphological analysis allow inferring that ZN/CHI microspheres are good candidates to act as a carrier for controlled drug release.

Hydrogel based on an alginate–Ca2+/chondroitin sulfate matrix as a potential colon-specific drug delivery system

This work reports on the formation and characterization of a novel hydrogel based on the polysaccharide alginate physically crosslinked by calcium ions (Ca2+) in the presence of chondroitin sulfate (CS). Swelling data and morphological analysis showed that the alginate–Ca2+/CS hydrogel has a clear pH-dependent behavior. Compression tests revealed a gradual decrease in the elastic moduli (E) as the pH of hydrogel-immersed solution is raised but a pronounced decrease for the samples swelled at pH 8 was observed. This fact was attributed to a complete disruption of the polymer network. On the other hand, the hydrogel matrix remains stable when immersed in acidic media. In vitro drug release studies were performed in simulated gastric and intestinal fluids and the collected data showed that the hydrogels formed in this work respond to external stimuli (changes in pH) and, thus, present great potential to be applied in a colon-specific drug delivery system.

Sulfated glycosaminoglycan-based block copolymer: preparation of biocompatible chondroitin sulfate-b-poly(lactic acid) micelles.

Despite a growing interest in amphiphilic polysaccharide-based diblock copolymers as functional polymeric drug delivery nanosystems, biologically relevant sulfated glycosaminoglycan systems were not yet investigated. Here, we report the synthesis and the self-assembly properties in water of chondroitin sulfate-b-poly(lactic acid) (CS-b-PLA(n)). The CS-b-PLA(n) were synthesized using click-grafting onto method implying reducing-end alkynation of low-molecular weight depolymerized CS (M(w) = 5000 g·mol(-1)) and azide-terminated functionalization of PLAn (M(w) = 6500 g·mol(-1) (n = 46) and M(w) = 1700 g·mol(-1) (n = 20)). The diblock copolymer self-assembled in water giving rise to spherical micelles that were characterized in solution using dynamic/static light scattering and at dry state by TEM technique. In vitro assays on healthy cells showed that at high concentrations, up to 10 μg·mL(-1), CS-b-PLA(n) were noncytotoxic. Those preliminary studies are promising in the perspective to use them as biocompatible nanovehicles for anticancer drug delivery.

Orange waste: A valuable carbohydrate source for the development of beads with enhanced adsorption properties for cationic dyes

Eco-friendly pectin and pectin/cellulose microfibers beads (PB and PB-CF) were synthesized using compounds extracted from orange bagasse, a solid waste from the food industry. PB-CF beads showed remarkable differences regarding several properties as compared to the beads without CF. The adsorption capability of PB and PB-CF was tested towards the removal of methylene blue (MB) from aqueous solution. The effect of various parameters on the MB adsorption was investigated. The kinetics and mechanism of adsorption were explained by the pseudo-second-order kinetics and intra-particle diffusion models. Equilibrium adsorption data are explained by the Langmuir isotherm model, which revealed a maximum adsorption capacity of 1550.3mg/g for PB and 2307.9mg/g for PB-CF5. Thermodynamic analysis suggests that the adsorption of MB on the beads is spontaneous and favorable. Recycling study demonstrated that both PB and PB-CF5 can be implemented in 6 consecutive adsorption/desorption cycles without losing their adsorption capacity. These results enable the use of PB and PB-CF as potentially low-cost adsorbents for wastewater treatments.

Cellulose nanowhiskers improve the methylene blue adsorption capacity of chitosan- g -poly(acrylic acid) hydrogel

Cellulose nanowhiskers (CNWs, 90% crystalline) were used to enhance the adsorption capacity of chitosan-g-poly(acrylic acid) hydrogel. The composites up to 20w/w-% CNWs showed improved adsorption capacity towards methylene blue (MB) as compared to the pristine hydrogel. At 5w/w-% CNWs the composite presented the highest adsorption capacity (1968mg/g). The maximum removal of MB (>98% of initial concentration 2000mg/L) was achieved quickly (60min) at room temperature, pH 6, and at low ionic strength (0.1M). Adsorption mechanism was explained with the Langmuir type I model suggesting the formation of a MB monolayer on the adsorbent surface. The interaction between the adsorbent and MB molecules was explained by chemisorption, as suggested by the pseudo-second-order kinetic model. Desorption experiments showed that 75% of loaded-MB could be recovered from the adsorbent by its immersion in a pH 1 solution. Additional experiments showed the post-utilized composite could be regenerated and reused for at least 5 consecutive adsorption/desorption cycles with minimum efficiency loss (∼2%).

Chitosan/poly(vinyl alcohol)/bovine bone powder biocomposites: A potential biomaterial for the treatment of atopic dermatitis-like skin lesions.

Atopic dermatitis (AD) is a chronic inflammatory skin disease that affects a large percent of the world́s population. This long-lasting skin disease has been treated by different approaches according to its causative agent and severity. Nonetheless, the use of advanced biomaterials to treat AD is poorly explored. The present study assessed the protective effectiveness of biocomposites films based on chitosan (Cs), poly(vinyl alcohol) (PVA) and bovine bone powder (BBP) on AD-like skin lesions. These original biocomposites were fully characterized and in vivo biological assays concerning the AD treatment were performed using a mouse model induced by 2,4-dinitrochlorobenzene (DNCB). The dorsal skin and ear of Balb/c female mice were challenging cutaneously with DNCB. Our findings demonstrate BBP-based biocomposite attenuated and treated considerably the DNCB-induced skin lesions in an AD-like model. In this sense, this study suggests that this original biocomposite may be applied as an active biomaterial for AD treatment.

Chitosan-based film supported copper nanoparticles: A potential and reusable catalyst for the reduction of aromatic nitro compounds

In this study, copper nanoparticles (CuNPs) were synthesized and stabilized into a chitosan/poly(vinyl alcohol) (CP) based film using a simple protocol under mild conditions. The polymeric matrix utilized in this study allows synthesizing stable nanoparticle with narrow size distribution within the film matrix. Further, this system showed very attractive properties, such as good mechanical properties, chemical resistance, easy handling during use and recovery, relatively low-cost as compared to other similar systems, among others. The catalytic performance of CP-Cu film was tested in the reduction reaction of nitrobenzene (NB) to aniline (AN). Our findings reveal that CP-Cu film catalyzes the reaction efficiently and also decreases the energy of activation (Ea) as compared to other catalysts. The catalytic efficiency of CP-Cu regarding this reaction was kept even after 6 consecutive reuse cycles. All these results rank this novel system as a promising catalyst in the reduction of aromatic nitro compounds to aromatic amines.