Keratin protein nanofibers from merino wool yarn: a top-down approach for the disintegration of hierarchical wool architecture to extract α-keratin protein nanofibers.

We report the extraction of keratin nanofibers from the medulla of a parent yarn after denaturing the cuticle and cortex microstructures of a merino wool yarn. Controlled alkaline hydrolysis, followed by high-speed blending in acetic acid, allowed for the extraction of keratin protein nanofibers with an average diameter of 25 nm and a length of less than 3 µm. SEM and AFM analyses showed the removal of cuticle cells from the yarn. FT-IR and DSC analyses confirmed the hydrolysis and denaturation of the sheet protein matrix of cuticle cells. XPS analysis provided strong evidence for the gradual removal of the epicuticle, cuticle cells, and cortex of the hierarchical wool structure with an increase in alkaline hydrolysis conditions. It was confirmed that the merino wool yarn subjected to hydrolysis under alkaline conditions exposed its internal fibrillar surface. In an acetic acid medium, these fibrillar surfaces obtained a surface charge, which further supported the defibrillation of the structure into its individual nanofibrils during high-speed blending. The extracted nanostructures constitute mainly α-helical proteins. The morphology of the nanofibers is composed of a uniform circular cross-section based on the images obtained using AFM, TEM, and SEM. The extracted nanofibers were successfully fabricated into transparent sheets that can be used in several applications.

Dielectric behaviour of plasma hydrogenated TiO2/cyanoethylated cellulose nanocomposites.

The interface between the polymer and nanoparticle has a vital role in determining the overall dielectric properties of a dielectric polymer nanocomposite. In this study, a novel dielectric nanocomposite containing a high permittivity polymer, cyanoethylated cellulose (CRS) and TiO2 nanoparticles surface modified by hydrogen plasma treatments was successfully prepared with different weight percentages (10%, 20% and 30%) of hydrogenated TiO2. Internal structure of H plasma treated TiO2 nanoparticles (H-TiO2) and the intermolecular interactions and morphology within the polymer nanocomposites were analysed. H-TiO2/CRS thin films on SiO2/Si wafers were used to form metal-insulator-metal (MIM) type capacitors. Capacitances and loss factors in the frequency range of 1 kHz to 1 MHz were measured. At 1 kHz H-TiO2/CRS nanocomposites exhibited ultra-high dielectric constants of 80, 118 and 131 for nanocomposites with 10%, 20% and 30% weight of hydrogenated TiO2 respectively, significantly higher than values of pure CRS (21) and TiO2 (41). Furthermore, all three H-TiO2 /CRS nanocomposites show a loss factor <0.3 at 1 kHz and low leakage current densities (10-6 A cm-2-10-7 A cm-2). Leakage was studied using conductive atomic force microscopy (C-AFM) and it was observed that the leakage is associated with H-TiO2 nanoparticles embedded in the CRS polymer matrix. Although, modified interface slightly reduces energy densities compared to pristine TiO2/CRS system, the capacitance values for H-TiO2/CRS-in the voltage range of -2 V to 2 V are very stable. Whilst H-TiO2/CRS possesses ultra-high dielectric constants (>100), this study reveals that the polymer nanoparticle interface has a potential influence on dielectric behaviour of the composite.

Gold nanoparticle decorated titania for sustainable environmental remediation: green synthesis, enhanced surface adsorption and synergistic photocatalysis.

Developing materials for efficient environmental remediation via cheap, nontoxic and environmentally benign routes remains a challenge for the scientific community. Here, a novel, facile, and green synthetic approach to prepare gold nanoparticle decorated TiO2 (Au/TiO2) nanocomposites for sustainable environmental remediation is reported. The synthesis involved only TiO2, metal precursor and green tea, obviating the need for any solvents and/or harsh chemical reducing or stabilizing agents, and was efficiently conducted at 50 °C, indicating the prominent sustainability of the novel synthetic approach. The synthesis indicated notable atom economy, akin to that observed in a typical chemical mediated synthesis while high-resolution transmission electron microscopy (HRTEM) findings suggest the presence of a pertinent decoration of spherical and homogeneous gold nanoparticles on the titania surface. Notably, the Au/TiO2 nanocomposite demonstrated appreciable stability during preparation, subsequent processing and prolonged storage. Further, the nanocomposite was found to have a superior adsorption capacity of 8185 mg g-1 towards methylene blue (MB) in solution using the Freundlich isotherm model, while the rate constants for the photocatalytic degradation of MB on the nanocomposite under UV irradiation indicated a 4.2-fold improvement compared to that of bare TiO2. Hence, this novel green synthesized Au/TiO2 nanocomposite shows promising potential for sustainable environmental remediation via efficient contaminant capture and subsequent synergistic photocatalysis.

In-situ formation of supramolecular aggregates between chitin nanofibers and silver nanoparticles.

Chitin and chitin derivatives have gained significant research interest over the years due to a number of beneficial properties that can be exploited in various application fields. Particularly, interactions between their nanostructures and other nanomaterials are of great interest. In situ photo-reduction of AgCl in chitin nanofiber aqueous dispersions resulted in significant loss of colloidal stability of both chitin nanofibers (CNF) and silver nanoparticles. UV-vis spectroscopy was used to characterize the extinction profiles of in-situ prepared CNF and several silver nanoparticle mixtures over the reaction steps. High resolution TEM characterization of the resulting structures indicated the presence of the aggregated form of nanofiber and nanoparticles. Energy filtered TEM analysis confirmed the existence of both CNF and silver nano particles in the aggregate, with silver in its chemically reduced state (Ag(0)). FT-IR, and 13C solid state NMR revealed the presence of strong interactions between Ag and CNF through hydroxyl and carbonyl moieties of the CNF structure. It was concluded that these interactions led to the formation of a supramolecular aggregate in the in-situ mixture as a result of wrapping of CNF around photo-reduced silver nanoparticles which resulted in the colloidal instability.

Urea-Hydroxyapatite Nanohybrids for Slow Release of Nitrogen.

While slow release of chemicals has been widely applied for drug delivery, little work has been done on using this general nanotechnology-based principle for delivering nutrients to crops. In developing countries, the cost of fertilizers can be significant and is often the limiting factor for food supply. Thus, it is important to develop technologies that minimize the cost of fertilizers through efficient and targeted delivery. Urea is a rich source of nitrogen and therefore a commonly used fertilizer. We focus our work on the synthesis of environmentally benign nanoparticles carrying urea as the crop nutrient that can be released in a programmed manner for use as a nanofertilizer. In this study, the high solubility of urea molecules has been reduced by incorporating it into a matrix of hydroxyapatite nanoparticles. Hydroxyapatite nanoparticles have been selected due to their excellent biocompatibility while acting as a rich phosphorus source. In addition, the high surface area offered by nanoparticles allows binding of a large amount of urea molecules. The method reported here is simple and scalable, allowing the synthesis of a urea-modified hydroxyapatite nanohybrid as fertilizer having a ratio of urea to hydroxyapatite of 6:1 by weight. Specifically, a nanohybrid suspension was synthesized by in situ coating of hydroxyapatite with urea at the nanoscale. In addition to the stabilization imparted due to the high surface area to volume ratio of the nanoparticles, supplementary stabilization leading to high loading of urea was provided by flash drying the suspension to obtain a solid nanohybrid. This nanohybrid with a nitrogen weight of 40% provides a platform for its slow release. Its potential application in agriculture to maintain yield and reduce the amount of urea used is demonstrated.

Alginate nanoparticles protect ferrous from oxidation: Potential iron delivery system.

A novel, efficient delivery system for iron (Fe2+) was developed using the alginate biopolymer. Iron loaded alginate nanoparticles were synthesized by a controlled ionic gelation method and was characterized with respect to particle size, zeta potential, morphology and encapsulation efficiency. Successful loading was confirmed with Fourier Transform Infrared spectroscopy and Thermogravimetric Analysis. Electron energy loss spectroscopy study corroborated the loading of ferrous into the alginate nanoparticles. Iron encapsulation (70%) was optimized at 0.06% Fe (w/v) leading to the formation of iron loaded alginate nanoparticles with a size range of 15-30nm and with a negative zeta potential (-38mV). The in vitro release studies showed a prolonged release profile for 96h. Release of iron was around 65-70% at pH of 6 and 7.4 whereas it was less than 20% at pH 2.The initial burst release upto 8h followed zero order kinetics at all three pH values. All the release profiles beyond 8h best fitted the Korsmeyer-Peppas model of diffusion. Non Fickian diffusion was observed at pH 6 and 7.4 while at pH 2 Fickian diffusion was observed.