Potential Use of Chitosan-TiO2 Nanocomposites for the Electroanalytical Detection of Imidacloprid.

The detection of toxic insecticides is a major scientific and technological challenge. In this regard, imidacloprid is a neonicotinoid that is a systemic insecticide that can accumulate in agricultural products and affect human health. This work aims to study the properties of chitosan-TiO2 nanocomposites in which nanoparticles with high surface area serve as molecular recognition sites for electroanalytical imidacloprid detection. We show that the best sensitivity to imidacloprid was obtained using a modified electrode with a chitosan-TiO2 nanocomposite with a 40 wt.% of TiO2 nanoparticles. By using a three-phase effective permittivity model which includes chitosan, TiO2, an interface layer between nanoparticles and a matrix, we showed that nanocomposites with 40 wt.% of TiO2 the interface volume fraction reaches a maximum. At higher nanoparticle concentration, the sensitivity of the sensor decreases due to the decreasing of the interface volume fraction, agglomeration of nanoparticles and a decrease in their effective surface area. The methodology presented can be helpful in the design and optimization of polymer-based nanocomposites for a variety of applications.

Tuning HAuCl4/Sodium Citrate Stoichiometry to Fabricate Chitosan-Au Nanocomposites.

Nanocomposite engineering of biosensors, biomaterials, and flexible electronics demand a highly tunable synthesis of precursor materials to achieve enhanced or desired properties. However, this process remains limited due to the need for proper synthesis-property strategies. Herein, we report on the ability to synthesize chitosan-gold nanocomposite thin films (CS/AuNP) with tunable properties by chemically reducing HAuCl4 in chitosan solutions and different HAuCl4/sodium citrate molar relationships. The structure, electrical, and relaxation properties of nanocomposites have been investigated as a function of HAuCl4/sodium citrate molar relation. It was shown that gold particle size, conductivity, Vogel temperature (glass transition), and water content strongly depend upon HAuCl4/sodium citrate relationships. Two relaxation processes have been observed in nanocomposites; the α-relaxation process, related to a glass transition in wet CS/AuNP films, and the σ-relaxation related to the local diffusion process of ions in a disordered system. The ability to fine-tune both α- and σ-relaxations may be exploited in the proper design of functional materials for biosensors, biomaterials, and flexible electronics applications.

Relaxation Phenomena in Chitosan-Au Nanoparticle Thin Films.

Chitosan-gold nanoparticle (CS/AuNP) thin films were synthesized through the chemical reduction of HAuCl4 in sodium citrate/chitosan solutions. The dielectric and dynamic mechanical behaviors of CS/AuNP films have been investigated as a function of moisture and HAuCl4 content. Two relaxation processes in the nanocomposites have been observed. The α-relaxation process is related to a glass transition in wet CS/AuNP films. However, in dry composites (with 0.2 wt% of moisture content), the glass transition vanished. A second relaxation process was observed from 70 °C to the onset of thermal degradation (160 °C) in wet films and from 33 °C to the onset of degradation in dry films. This relaxation is identified as the σ-relaxation and may be related to the local diffusion process of ions between high potential barriers in disordered systems. The α- and σ-relaxation processes are affected by the HAuCl4 content of the solutions from which films were obtained because of the interaction between CS, sodium succinate, and gold nanoparticles. With about 0.6 mM of HAuCl4, the conductivity of both wet and dry films sharply increased by six orders, corresponding to the percolation effect, which may be related to the appearance of a conductivity pathway between AuNPs, HAuCl4, and NaCl.

Chitosan-ZnO Nanocomposites Assessed by Dielectric, Mechanical, and Piezoelectric Properties.

The aim of this work is to structurally characterize chitosan-zinc oxide nanoparticles (CS-ZnO NPs) films in a wide range of NPs concentration (0-20 wt.%). Dielectric, conductivity, mechanical, and piezoelectric properties are assessed by using thermogravimetry, FTIR, XRD, mechanical, and dielectric spectroscopy measurements. These analyses reveal that the dielectric constant, Young's modulus, and piezoelectric constant (d33) exhibit a strong dependence on nanoparticle concentration such that maximum values of referred properties are obtained at 15 wt.% of ZnO NPs. The piezoelectric coefficient d33 in CS-ZnO nanocomposite films with 15 wt.% of NPs (d33 = 65.9 pC/N) is higher than most of polymer-ZnO nanocomposites because of the synergistic effect of piezoelectricity of NPs, elastic properties of CS, and optimum NPs concentration. A three-phase model is used to include the chitosan matrix, ZnO NPs, and interfacial layer with dielectric constant higher than that of neat chitosan and ZnO. This layer between nanoparticles and matrix is due to strong interactions between chitosan's side groups with ZnO NPs. The understanding of nanoscale properties of CS-ZnO nanocomposites is important in the development of biocompatible sensors, actuators, nanogenerators for flexible electronics and biomedical applications.