Thiago B. Taketa

Removal of glyphosate herbicide from water using biopolymer membranes

Enormous amounts of pesticides are manufactured and used worldwide, some of which reach soils and aquatic systems. Glyphosate is a non-selective herbicide that is effective against all types of weeds and has been used for many years. It can therefore be found as a contaminant in water, and procedures are required for its removal. This work investigates the use of biopolymeric membranes prepared with chitosan (CS), alginate (AG), and a chitosan/alginate combination (CS/AG) for the adsorption of glyphosate present in water samples. The adsorption of glyphosate by the different membranes was investigated using the pseudo-first order and pseudo-second order kinetic models, as well as the Langmuir and Freundlich isotherm models. The membranes were characterized regarding membrane solubility, swelling, mechanical, chemical and morphological properties. The results of kinetics experiments showed that adsorption equilibrium was reached within 4 h and that the CS membrane presented the best adsorption (10.88 mg of glyphosate/g of membrane), followed by the CS/AG bilayer (8.70 mg of glyphosate/g of membrane). The AG membrane did not show any adsorption capacity for this herbicide. The pseudo-second order model provided good fits to the glyphosate adsorption data on CS and CS/AG membranes, with high correlation coefficient values. Glyphosate adsorption by the membranes could be fitted by the Freundlich isotherm model. There was a high affinity between glyphosate and the CS membrane and moderate affinity in the case of the CS/AG membrane. Physico-chemical characterization of the membranes showed low values of solubility in water, indicating that the membranes are stable and not soluble in water. The SEM and AFM analysis showed evidence of the presence of glyphosate on CS membranes and on chitosan face on CS/AG membranes. The results showed that the glyphosate herbicide can be adsorbed by chitosan membranes and the proposed membrane-based methodology was successfully used to treat a water sample contaminated with glyphosate. Biopolymer membranes therefore potentially offer a versatile method to eliminate agricultural chemicals from water supplies.

Nanofilms of hyaluronan/chitosan assembled layer-by-layer: An antibacterial surface for Xylella fastidiosa

In this work, nanofilms of hyaluronan/chitosan (HA/CHI) assembled layer by layer were synthesized; their application as a potential antimicrobial material was demonstrated for the phytopathogen Xylella fastidiosa, a gram-negative bacterium, here used as a model. For the synthesis, the influence of pH and ionic strength of these natural polymer stem-solutions on final characteristics of the HA/CHI nanofilms was studied in detail. The antibacterial effect was evaluated using widefield fluorescence microscopy. These results were correlated with the chemical properties of the nanofilms, studied by FTIR and Raman spectroscopy, as well as with their morphology and surface properties characterized using SEM and AFM. The present findings can be extended to design and optimize HA/CHI nanofilms with enhanced antimicrobial behavior for other type of phytopathogenic gram-negative bacteria species, such as Xanthomonas citri, Xanthomas campestri and Ralstonia solanacearum.

Roughness dynamic in surface growth: Layer-by-layer thin films of carboxymethyl cellulose/chitosan for biomedical applications

Surfaces are responsible for important interactions of biomaterials since they create the interface with the biological environment and affect the response that the body will have to the material. Surface roughness and morphology have great impact on the material performance, affecting cell, bacterial, and biomolecular adhesion. Thin films of chitosan and carboxymethyl cellulose were produced by layer-by-layer deposition at different pH values and had their surface growth process studied throughout roughness measurements. Both polymers are nontoxic and biocompatible to the human biological system, with biomedical applications from tissue engineering to drug delivery. Growth exponents are presented, and it is suggested that fractal-based growth models are suitable for describing surface evolution and morphology of carboxymethyl cellulose/chitosan layer-by-layer thin film growth during deposition, primarily nonlinear models.

Investigation of the Internal Chemical Composition of Chitosan-Based LbL Films by Depth-Profiling X-ray Photoelectron Spectroscopy (XPS) Analysis

Chitosan-based thin films were assembled using the layer-by-layer technique, and the axial composition was accessed using X-ray photoelectron spectroscopy with depth profiling. Chitosan (CHI) samples possessing different degrees of acetylation ([Formula: see text]) and molecular weight ([Formula: see text]) produced via the ultrasound-assisted deacetylation reaction were used in this study along with two different polyanions, namely, sodium polystyrenesulfonate (PSS) and carboxymethylcellulose (CMC). When chitosan, a positively charged polymer in aqueous acid medium, was combined with a strong polyanion (PSS), the total positive charge of chitosan, directly related to its [Formula: see text], was the key factor affecting the film formation. However, for CMC/CHI films, the pH of the medium and [Formula: see text] of chitosan strongly affected the film structure and composition. Consequently, the structure and the axial composition of chitosan-based films can be finely adjusted by choosing the polyanion and defining the chitosan to be used according to its DA and [Formula: see text] for the desired application, as demonstrated by the antibacterial tests.

Layer-by-Layer Thin Films of Alginate/Chitosan and Hyaluronic Acid/Chitosan with Tunable Thickness and Surface Roughness

Layer-by-layer (LbL) is a bottom-up technique used for construction of films with self-assembly and self-organizing properties. In most cases, the fundamental driving force for the formation of these films is originated from the electrostatic interaction between oppositely charged species. The charged segments of polyelectrolytes behave as small building units and their orientation and position can be designed to target structures of great complexity. Furthermore, the technique enables the use of various materials, including natural polymers. In this work, we chose the cationic biopolymer chitosan (CHI) and the negative polyelectrolytes sodium alginate (ALG) and hyaluronic acid (HA). The aim of this study was to evaluate the effect of ionic strength (0 versus 200 mM) and pH (3 versus 5) on ALG/CHI and HA/CHI nanostructured multilayered thin films properties. From profilometry and atomic force microscopy (AFM) analyses, changes in thickness and roughness of the coatings were monitored. The presence of salt in polyelectrolyte solutions induced the polymer chains to adopt conformations with more loops and tails and this arrangement in solution was transmitted to films, resulting in rougher surfaces. Furthermore, the film thickness can be precisely controlled by adjusting the pH of the polyelectrolyte solution. The variation of these parameters shows that it is possible to molecularly control chemical and structural properties of nanostructured coatings, thus opening up new possibilities of application (e.g. cell adhesion).