Guillermo J. Copello

Removal of dyes from water using chitosan hydrogel/SiO2 and chitin hydrogel/SiO2 hybrid materials obtained by the sol-gel method

This work describes the synthesis of chitosan hydrogel/SiO(2) and chitin hydrogel/SiO(2) hybrid mesoporous materials obtained by the sol-gel method for their use as biosorbents. Their adsorption capabilities against four dyes (Remazol Black B, Erythrosine B, Neutral Red and Gentian Violet) were compared in order to evaluate chitin as a plausible replacement for chitosan considering its efficiency and lower cost. Both chitin and chitosan were used in the form of hydrogels. This allowed full compatibility with the ethanol release from tetraethoxysilane. The hybrid materials were characterized by Attenuated Total Reflectance-Fourier Transform Infrared Spectroscopy (ATR-FTIR), Scanning Electron Microscopy (SEM), Energy Dispersive X-Ray Spectroscopy (EDS), Nitrogen Adsorption Isotherms and (13)C solid-state Nuclear Magnetic Resonance. Adsorption experimental data were analyzed using Langmuir, Freundlich and Dubinin-Radushkevich isotherm models along with the evaluation of adsorption energy and standard free energy (ΔG(0)). The adsorption was observed to be pH dependent. The main mechanism of dye adsorption was found to be a spontaneous charge associated interaction, except for EB adsorption on chitin/SiO(2) matrix, which showed to involve a lower energy physical adsorption interaction. Aside from highly charged dyes the chitin containing matrix has similar or higher adsorption capacity than the chitosan one.

Immobilized chitosan as biosorbent for the removal of Cd(II), Cr(III) and Cr(VI) from aqueous solutions

The generation of layer-by-layer silicate-chitosan composite biosorbent was studied. The films were evaluated on its stability regarding the polymer leakage and its capability in the removal of Cd(II), Cr(III) and Cr(VI) from an aqueous solution. SEM, EDAX and ATR-IR techniques were applied for material characterization. Silicate-chitosan films with a final layer of silicate demonstrated chitosan retention and had better sorption capacities than those without it. For metal species, such as Cd(II) and Cr(III), the greatest adsorption was obtained when the pH of the solution was 7. When Cr(VI) was evaluated, pH 4 was the optimal for its adsorption. Langmuir and Freundlich isotherms were modeled for the equilibrium data. An 80% of the adsorbed metal was recovered by HNO(3) incubation. This non-covalent immobilization method allowed chitosan surface retention and did not affect its adsorption properties. The use of a coated surface would facilitate sorbent removal from medium after adsorption.

Adsorption of Cd(II) and Pb(II) onto a one step-synthesized polyampholyte: kinetics and equilibrium studies.

A one step-synthesized polyampholyte, bearing carboxylate and 2-methylimidazole (2MI) groups, was tested as adsorbent for the removal of Pb(II) and Cd(II) from aqueous solutions. This material combines the benefits of synthetic polymers, such as high adsorption capacity and chemical stability, and the advantages of biosorbents in regard of costs and simplicity of the production. The short time needed to achieve the adsorption equilibrium indicated a chemical-reaction controlled process. A network expansion was predicted as a result of repulsive interaction between the fixed positive charges. Langmuir model presented the best fitting to isotherm equilibrium data, with a maximum adsorption capacity of 182 mg g(-1) for Cd(II) and 202 mg g(-1) for Pb(II). The metal removal was strongly dependent on pH, involving carboxylate and 2MI residues. An ion-exchange process for Pb(II) and Cd(II), combined with coordination for the later, were the most probable mechanism of interaction. The adsorption of 1.35 ppm Cd(II) was 72±6% in well-water, and the adsorption of 0.50 ppm Pb(II) was 62±5% in tap-water. The recovery figures for Cd(II) in 1% HNO(3) were optimal.

In vitro Studies and Preliminary In vivo Evaluation of Silicified Concentrated Collagen Hydrogels

Hybrid and nanocomposite silica-collagen materials derived from concentrated collagen hydrogels were evaluated in vitro and in vivo to establish their potentialities for biological dressings. Silicification significantly improved the mechanical and thermal stability of the collagen network within the hybrid systems. Nanocomposites were found to favor the metabolic activity of immobilized human dermal fibroblasts while decreasing the hydrogel contraction. Cell adhesion experiments suggested that in vitro cell behavior was dictated by mechanical properties and surface structure of the scaffold. First-to-date in vivo implantation of bulk hydrogels in subcutaneous sites of rats was performed over the vascular inflammatory period. These materials were colonized and vascularized without inducing strong inflammatory response. These data raise reasonable hope for the future application of silica-collagen biomaterials as biological dressings.

Antimicrobial Activity of Starch Hydrogel Incorporated with Copper Nanoparticles

In order to obtain an antimicrobial gel, a starch-based hydrogel reinforced with silica-coated copper nanoparticles (Cu NPs) was developed. Cu NPs were synthesized by use of a copper salt and hydrazine as a reducing agent. In order to enhance Cu NP stability over time, they were synthesized in a starch medium followed by a silica coating. The starch hydrogel was prepared by use of urea and water as plasticizers and it was treated with different concentrations of silica-coated copper nanoparticles (Si-Cu NPs). The obtained materials were characterized by Fourier transform infrared (FT-IR) spectroscopy, electron paramagnetic resonance (EPR) spectroscopy, scanning electron microscopy (SEM), and rheometry. FT-IR and EPR spectra were used for characterization of Cu NPs and Si-Cu NPs, confirming that a starch cap was formed around the Cu NP and demonstrating the stability of the copper nanoparticle after the silica coating step. SEM images showed Cu NP, Si-Cu NP, and hydrogel morphology. The particle size was polydisperse and the structure of the gels changed along with particle concentration. Increased NP content led to larger pores in starch structure. These results were in accordance with the rheological behavior, where reinforcement by the Si-Cu NP was seen. Antimicrobial activity was evaluated against Gram-negative (Escherichia coli) and Gram-positive (Staphylococcus aureus) bacterial species. The hydrogels were demonstrated to maintain antimicrobial activity for at least four cycles of use. A dermal acute toxicity test showed that the material could be scored as slightly irritant, proving its biocompatibility. With these advantages, it is believed that the designed Si-Cu NP loaded hydrogel may show high potential for applications in various clinical fields, such as wound dressings and fillers.

Polyphenol–SiO2 hybrid biosorbent for heavy metal removal. Yerba mate waste (Ilex paraguariensis) as polyphenol source: Kinetics and isotherm studies

A low-cost biosorbent hybrid material ready for application was obtained in this work. Yerba mate (Ilex paraguariensis) milling residual dust was used as a polyphenol source by ethanolic extraction. Polyphenols were immobilized within a SiO(2) matrix to form an interpenetrated polymer after glutaraldehyde cross-linking. Pb(II), Cr(III) and Cr(VI) were chosen as model metals for adsorption. The hybrid materials were characterized by Fourier Transform Infrared Spectroscopy (FTIR), Scanning Electron Microscopy (SEM), Energy Dispersive X-Ray Spectroscopy (EDS) and Nitrogen Adsorption Isotherms. Adsorption experimental data were analysed using Langmuir, Freundlich, Dubinin-Radushkevich, Temkin, Redlich-Peterson, Sips and Toth isotherm models along with the evaluation of adsorption energy and standard free energy (ΔG°). The adsorption was observed to be pH dependent. The main mechanism of metal adsorption was found to be a spontaneous charge associated interaction. Electron Spin Resonance (ESR) spectroscopy confirmed that Cr(VI) adsorption was an adsorption-coupled reaction and the adsorbed specie was Cr(V). The hybrid matrix probed its adsorption capacity of Cr(III) in a non-treated tannery wastewater.

Chitin hybrid materials reinforced with graphene oxide nanosheets: chemical and mechanical characterisation

Chitin hybrid materials reinforced with graphene oxide nanosheets (nGO) have been prepared. The chitin : nGO ratio ranged from proportions where chitin was the main component to ones where nGO exceeded chitin. SEM and TEM images showed that high proportions of nGO may result in nanosheet association. FTIR, 13C solid-state NMR and DSC analyses showed that the interaction among the components would not involve the formation of new molecular bonds. nGO was shown to act as a filler that induces structural rearrangements in chitin which lead to new hydrogen bonds among the chains. The mechanical stability proved to be higher when the nGO content in the hybrid was similar to or higher than that of chitin. The rheological behaviour of the material was shown to become more solid-like with increasing nGO content. The nGO did not interfere with lysozyme activity on chitin chains, indicating that these materials would be biodegradable.

Chitin nanowhiskers as alternative antimicrobial controlled release carriers

Antimicrobial finishings protect users from pathogenic and odor-generating microorganisms, which are of medical and hygiene concerns. Controlled release is a useful approach to obtain antimicrobial finishings in several materials because it provides a gradual and persistent antibiotic release from the surface into the surroundings. Such a property has been taken into account in this work, using chitin nano-whiskers (CNWs) as carriers of methylparaben to prepare durable antimicrobial cotton textiles. This durability has been endowed with fixing CNWs in a silicon oxide matrix. Antimicrobial activity has been determined using Pseudomonas aeruginosa, Staphylococcus aureus, Escherichia coli, Acinetobacter baumanii and Salmonella choleraesuis. Treated textiles have shown antimicrobial activity with laundering durability up to 20 washing cycles. Methylparaben leaching from the textile has been assessed by liquid chromatography showing a methylparaben controlled release which could be responsible for the obtained antimicrobial laundry durability. Textile mechanical properties have not been altered by the finishing.

Antibody detection employing sol-gel immobilized parasites

Immunofluorescence assay (IFA) and immunoperoxidase assay (IPA) are useful diagnostic techniques for specific antibody detection for different diseases. Both involve several alternatives for immobilization of cells, such as solvent or heat fixation. Non-covalent immobilization implies rigorous storage conditions at -20 degrees C to preserve the slides, and usually numerous cells are detached during the washing steps, which can lead to inconsistencies in the results. Sol-gel chemistry is usually used for coating different materials because of the mild conditions of the polymerization reaction and the ability to introduce functional groups to a wide variety of surfaces. We have developed a novel procedure for the attachment of Trypanosoma cruzi epimastigotes and Leishmania guyanensis promastigotes to a silicon oxide polymer covered glass surface. The film was prepared using standard microscope slides with tetraethoxysilane and 3-aminopropyl triethoxysilane as polymeric precursors. When acetone was used as the major coating solvent, the IFA showed the fluorescence of the attached parasites without matrix background interference. Similar results were observed when the IPA was evaluated. The sensitivity and specificity of the sol-gel immobilized parasite slides were comparable with the heat fixation technique. The performance of the coated slides was maintained for at least 2 months at 4 degrees C storage temperature. This immobilization method does not affect the molecular epitopes of the attached cells. Thus, homogeneous, ready to use, long lasting coated slides were obtained, which are appropriate for field conditions.

Antimicrobial surface functionalization of PVC by a guanidine based antimicrobial polymer.

Abstract Antimicrobial polyvinyl chloride (PVC) plastic was obtained by covalent bonding of poly hexamethylenediamine guanidine hydrochloride (PHMG), a guanidine based antimicrobial polymer. This was achieved by grafting mercaptopropyltrimethoxysilane onto PVC, followed by aminopropyltriethoxysilane. Glutaraldehyde is a bifunctional crosslinker that was bonded to the free amine groups found in the treated PVC on one side and PHMG on the other. The treated PVC samples were characterized by FT-IR and XPS, showing that the PVC samples were successfully modified. Energy Dispersive X-ray spectroscopy showed the spatial distribution of the elements Si and S, indicating that the coatings were homogeneous. The resulting PVC samples showed high antimicrobial activity against Gram-positive and Gram-negative bacteria. Furthermore, the biofilm formation was negligible in comparison with the untreated material. The coating elusion assay indicated that its antimicrobial ability was achieved via direct contact rather than a controlled release mechanism.