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Photoelectrocatalysis has emerged as a promising technology to degrade recalcitrant pollutants such as textile dyes in wastewater completely. Titanium dioxide is typically used as a photocatalyst, but its wide bandgap constrains its use to the use of ultraviolet light. To extend its use to the visible-light region, we doped titanium dioxide nanotubes with iron and sulfur. We used them as a photoelectrode for the photoelectrocatalytic degradation of a model pollutant – phenol red. Response surface methodology using a Box-Behnken design of experiments was used to investigate the effects of initial dye concentration, applied potential, and dopant loading on phenol red degradation kinetics. Statistical analysis showed that our reduced cubic model adequately correlates these parameters. The fastest dye degradation rate was achieved at the optimized conditions: initial phenol red concentration = 5.0326 mg L-1, applied voltage = 29.9686 V, and dopant loading = 1.2244 wt.%. Complete degradation of phenol red may be achieved after 11.77 hours of treatment under the optimized conditions in a batch reactor. Our model's robustness enables it to be used for process modeling and a basis for designing scaled-up photoelectrocatalytic reactors.

Continuous fixed-bed column studies were performed using nanocomposite beads made up of chitosan, polyethyleneimine, and graphene oxide as adsorbents for the removal of methyl orange (MO) in water. The effects of different operating parameters such as initial MO concentration (5, 10, and 15 ppm), bed height (10, 17.5, and 25 cm), and flow rate (27, 43, and 58 mL/min) were investigated using an upward-flow fixed-bed column set-up. The breakthrough curves generated were fitted with Adams-Bohart, Thomas, Yoon-Nelson, and Yan et al. models. The results showed that Yan et al. model agreed best with the breakthrough curves having an R2 as high as 0.9917. Lastly, design parameters for a large-scale adsorption column were determined via scale-up approach using the parameters obtained from column runs.

Transition metal-based compounds with new two-dimensional, triangle-based topology are rare but are of considerable interest because of their unusual magnetic properties. Here we report the synthes...

Response surface methodology (RSM) was used to determine the optimal blend of alginate (ALG), poly (vinyl alcohol) (PVA) and graphene oxide (GO), as well as glutaraldehyde (GA) crosslinking solution concentration for the synthesis of dual-crosslinked ALG/PVA/GO nanocomposite hydrogel adsorbent beads for methylene blue (MB) removal. Statistical analyses show that PVA concentration contributes the largest effect to the adsorption capacity response, attributed to improved accessibility of MB molecules to adsorption sites. The optimal blend was determined to be 3% polymer with 50% PVA, 383.8384 ppm GO, crosslinked in 1% CaCl2 and 5% GA. These results were validated, and the experimental value of the adsorption capacity deviated by only 1.702% from the RSM model prediction, suggesting good model predictability. Adsorption isotherm models were tested to provide a description of the adsorption process. The Sips isotherm model, suggesting monolayer adsorption over heterogeneous surface with action of cooperative adsorbate-adsorbate interactions, was the best fit to the experimental equilibrium data, with an R2 of 0.9782. Furthermore, the ALG/PVA/GO beads demonstrated a maximum monolayer adsorption capacity of 1081.62 mg/g, showing superior performance compared to known biosorbents of MB.

Photoelectrocatalysis is a rapidly developing technology for degrading recalcitrant organic compounds in wastewater due to its ability to overcome electron-hole recombination. Herein, we synthesized Fe/S co-doped TiO2 nanotubes through an in-situ anodization technique. We developed a simple reduced quadratic model based on response surface modeling which can be used to adequately correlate the operating parameters with the photoelectrocatalytic performance of Fe/S-TiNTs in degrading phenol red. Predicted maximum dye degradation of 54.78% was achieved by the generated model using the optimized parameters: initial phenol red concentration = 5.22 mg L-1, applied voltage = 27.4 V, and dopant loading = 2.97 wt.%. Upon validation, experimental maximum phenol degradation of 53.24% was obtained, which agrees well with the predicted value within statistical significance. Overall, our model can be potentially used for process optimization within the design space studied.

Titanium dioxide is a widely-investigated semiconductor photocatalyst due to its wide availability and low cost. Although it has been successfully used in the photocatalytic treatment of various organics in wastewater, it remains a challenge to modify its structure to achieve enhanced catalytic properties at a wider light spectrum. Doping with transition metals was seen to narrow its optical band gap yet synthesis routes have been largely limited to the use of high-end equipment. Herein we demonstrate the use of a simpler one-pot approach to synthesize nanoporous arrays of silver-doped titanium dioxide nanotubes (Ag-TiNTs) by double anodization of titanium sheets. The synthesized Ag-TiNTs have an average inner diameter of 58.68 nm and a wall thickness of 16.46 nm. ATR-FTIR spectroscopy revealed its characteristic peaks attributed to O-Ti-O bonds. Silver doping increased the lattice volume and crystallite size of anatase with a corresponding decrease in the degree of crystallinity due to the introduction of impurity Ag atoms in its tetragonal structure. Silver was homogeneously distributed across the nanotube surface at an average loading of 1.41 at. %. The synthesized Ag-TiNTs were shown to have a superior photoelectrocatalytic activity in degrading C.I. Basic Blue 9 under UV illumination with a pseudo-first-order kinetic rate of 1.0253 x 10-2 min-1. Most importantly, the Ag-TiNTs are photoelectrocatalytically-active even at a low Ag loading.

Humic acid - functionalized silver nanoparticles (HA-AgNPs) were successfully synthesized and used to detect Cu (II) ions in aqueous solutions. The HA-AgNPs was shown to have an average hydrodynamic diameter of 101.4 nm and a polydispersity index of 0.447. The absorbance spectra of HA-AgNPs showed the characteristic local surface plasmon resonance (LSPR) peak of AgNPs at 408.3 nm. Addition of Cu (II) in the HA-AgNPs led to their agglomeration as evidenced by the change in their surface morphology and their corresponding optical absorbance spectra. The synthesized HA-AgNPs showed a strong linear response for Cu (II) concentrations in the range of 0.00 – 1.25 mM with a limit of detection (LoD) of 4.4428 ± 0.1091 mg L-1, a limit of quantification (LoQ) of 14.8094 ± 0.3636 mg L-1, and a limit of blank (LoB) of 0.1214 ± 0.0065 mg L-1. Statistical analysis showed that this calibration curve could be used to quantify Cu (II) concentrations within a 95% confidence level. Furthermore, HA-AgNPs was found to be selective for Cu (II) detection based on the selectivity study against common metal ions found in drinking water. This shows that the synthesized HA-AgNPs can be used as an environment-friendly colorimetric nanosensor for rapid and point-of-need quantification of Cu (II) ions in aqueous media.

Nanocomposite beads containing 2% chitosan (CS), 2% polyethyleneimine (PEI), and 1,500 ppm graphene oxide (GO) were synthesized for the removal of methyl orange (MO) from water. Characterization of the CS-PEI-GO beads using Fourier transform infrared spectroscopy (FTIR) and scanning electron microscopy (SEM) showed favorable adsorbent properties as given by the presence of numerous surface functional groups and a porous structure. Effects of different parameters such as pH, contact time, and initial concentration on the percentage removal of MO and adsorption capacity of the beads were investigated by performing batch adsorption experiments. MO removal of more than 85% was achieved by the beads across a wide pH range. Kinetic studies were performed and a pseudo-second order kinetic equation with R2 of 0.9999 was obtained. Furthermore, adsorption equilibrium data for MO were best described by the Toth isotherm model (R2 = 0.9644), suggesting multilayer adsorption on heterogeneous adsorption sites with a maximum adsorption capacity of 421.51 mg/g. Finally, FTIR and SEM analyses after adsorption confirmed the presence of MO on the surface of the beads and revealed an intact and stable structure. Overall, the excellent adsorption capability and multi-functionality demonstrated in this study show great potential of the synthesized material for wastewater treatment applications.

Highly-organized one-dimensional arrays of copper-doped titanium dioxide nanotubes (Cu-TiNTs) were synthesized in a one-pot approach by double anodization of titanium sheets. Field-emission scanning electron microscopy showed that Cu-TiNTs have an average inner diameter of 52.13 nm, a wall thickness of 14.28 nm, and a tube length of 0.6401 μm. Fourier-transform infrared spectroscopy confirmed the presence of characteristic O-Ti-O bond of TiO2. X-ray fluorescence spectroscopy confirmed copper-doping with an average dopant loading of 0.0248%. Even at this low dopant loading, Cu-TiNTs were shown to be photo-active in degrading Acid Orange 52 (AO 52) under UV light illumination. The kinetic profiles of AO 52 photoelectrochemical degradation were best described by the pseudo-first-order kinetic model (R2 ≥ 0.991) with kinetic constants 9.42 x 10-3 min-1 for Cu-TiNTs as compared to 6.04 x 10-3 min-1 for pristine TiNTs. Overall, doping pristine TiNTs with Cu was shown to enhance its photoelectrocatalytic properties in degrading textile dyes such as AO 52.

Silver-doped TiO2 nanotubes (Ag-TiNTs) were synthesized in a top-down approach by single-step anodization of titanium sheets. The highly-ordered array of Ag-TiNTs was confirmed by scanning electron microscopy with an average inner diameter of 41.28 nm and a wall thickness of 35.38 nm. Infrared spectroscopy confirmed the presence of O-Ti-O bonds. Analysis of the X-ray powder diffraction profiles showed the characteristic peaks for anatase and titanium for both pristine TiNTs and Ag-TiNTs. Ag-doping caused no observed changes in the crystalline structure of pristine TiNTs. High-definition X-ray fluorescence spectroscopy revealed that the synthesized Ag-TiNTs have 0.05 wt% Ag-loading. Even at low Ag-loading, the Ag-TiNTs were shown to be photo-active, achieving 10.13% degradation of Acid Orange 52 under UV illumination after 120 min.

Natural rubber latex was chemically modified by enzymatic deproteinization, degradation, and epoxidation to produce deproteinized liquid epoxidized natural rubber (DP-LENR). Polyvinylidene difluoride (PVDF) was blended with DP-LENR and then electrospun to produce nanofibers. Scanning electron microscopy shows reduction in the fiber diameter and beading formation with increasing concentration of DP-LENR. Smooth surface of nanofibers suggests miscibility and chemical compatibility of PVDF with low concentration of DP-LENR. Infrared spectroscopy and X-ray diffraction analysis show the addition of DP-LENR has no effect on chemical structure and crystallinity of electrospun PVDF.

Despite extensive research and development, new nano-based diagnostic contrast agents have faced major barriers in gaining regulatory approval due to their potential systemic toxicity and prolonged retention in vital organs. Here we use five independent biodistribution techniques to demonstrate that oral ingestion of one such agent, gold-silica Raman nanoparticles, results in complete clearance with no systemic toxicity in living mice. The oral delivery mimics topical administration to the oral cavity and gastrointestinal (GI) tract as an alternative to intravenous injection. Biodistribution and clearance profiles of orally (OR) vs. intravenously (IV) administered Raman nanoparticles were assayed over the course of 48 h. Mice given either an IV or oral dose of Raman nanoparticles radiolabeled with approximately 100 μCi (3.7MBq) of 64Cu were imaged with dynamic microPET immediately post nanoparticle administration. Static microPET images were also acquired at 2 h, 5 h, 24 h and 48 h. Mice were sacrificed post imaging and various analyses were performed on the excised organs to determine nanoparticle localization. The results from microPET imaging, gamma counting, Raman imaging, ICP-MS, and hyperspectral imaging of tissue sections all correlated to reveal no evidence of systemic distribution of Raman nanoparticles after oral administration and complete clearance from the GI tract within 24 h. Paired with the unique signals and multiplexing potential of Raman nanoparticles, this approach holds great promise for realizing targeted imaging of tumors and dysplastic tissues within the oral cavity and GI-tract. Moreover, these results suggest a viable path for the first translation of high-sensitivity Raman contrast imaging into clinical practice.

Nanocomposites containing graphene oxide (GO), polyethyleneimine (PEI), and chitosan (CS) were synthesized for chromium(VI) and copper(II) removal from water. Response surface methodology (RSM) was used for the optimization of the synthesis of the CS–PEI–GO beads to achieve simultaneous maximum Cr(VI) and Cu(II) removals. The RSM experimental design involved investigating different concentrations of PEI (1.0–2.0%), GO (500–1500 ppm), and glutaraldehyde (GLA) (0.5–2.5%), simultaneously. Batch adsorption experiments were performed to obtain responses in terms of percent removal for both Cr(VI) and Cu(II) ions. A second-order polynomial equation was used to model the relationship between the synthesis conditions and the adsorption responses. High R2 values of 0.9848 and 0.8327 for Cr(VI) and Cu(II) removal, respectively, were obtained from the regression analyses, suggesting good correlation between observed experimental values and predicted values by the model. The optimum bead composition contained 2.0% PEI, 1500 ppm GO, and 2.08% GLA, and allowed Cr(VI) and Cu(II) removals of up to 91.10% and 78.18%, respectively. Finally, characterization of the structure and surface properties of the optimized CS–PEI–GO beads was carried out using X-ray diffraction (XRD), porosity and BET surface area analysis, scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), and X-ray photoelectron spectroscopy (XPS), which showed favorable adsorbent characteristics as given by a mesoporous structure with high surface area (358 m2 g−1) and plenty of surface functional groups. Overall, the synthesized CS–PEI–GO beads were proven to be effective in removing both cationic and anionic heavy metal pollutants.

Tauopathies are neurodegenerative diseases characterized by intracellular amyloid deposits of tau protein. Missense mutations in the tau gene (MAPT) correlate with aggregation propensity and cause dominantly inherited tauopathies, but their biophysical mechanism driving amyloid formation is poorly understood. Many disease-associated mutations localize within tau’s repeat domain at inter-repeat interfaces proximal to amyloidogenic sequences, such as 306VQIVYK311. We use cross-linking mass spectrometry, recombinant protein and synthetic peptide systems, in silico modeling, and cell models to conclude that the aggregation-prone 306VQIVYK311 motif forms metastable compact structures with its upstream sequence that modulates aggregation propensity. We report that disease-associated mutations, isomerization of a critical proline, or alternative splicing are all sufficient to destabilize this local structure and trigger spontaneous aggregation. These findings provide a biophysical framework to explain the basis of early conformational changes that may underlie genetic and sporadic tau pathogenesis., The biophysical mechanisms of how disease-associated tau mutations drive amyloid formation are not well understood. Here the authors use biophysical approaches, cell models and MD simulations and find that the intrinsically disordered repeat domain of tau encodes a metastable local structure and perturbations through mutations and proline isomerization cause an aggregation phenotype in vitro and in cells.