Carbon-Dot-Sensitized, Nitrogen-Doped TiO2in Mesoporous Silica for Water Decontamination through Nonhydrophobic Enrichment-Degradation Mode

Mesoporous silica synthesized from the co-condensation of tetraethoxysilane and silylated carbon dot containing amide group has been adopted as the carrier for the in-situ growth of TiO2 through an impregnation-hydrothermal crystallization process. Benefitted from the initial complexing between the titania precursor and carbon dot, highly dispersed anatase TiO2 nanoparticles can be formed inside the mesoporous channel. The hybrid material possesses ordered hexagonal mesostructure with a p6mm symmetry, high specific surface area (446.27 m2g-1), large pore volume (0.57 cm3g-1), uniform pore size (5.11 nm) and a wide absorption band between 300-550 nm. TiO2 nanocrystals are anchored to carbon dot through bonds of Ti-O-N and Ti-O-C as revealed by X-ray photoelectron spectroscopy. Moreover, the nitrogen doping of TiO2 is also verified by the formation of Ti-N bond. This composite shows excellent adsorption capability to organic 2, 4-dichlorophenol and acid orange 7 with electron-deficient aromatic ring through the electron donor-acceptor interaction between carbon dot and organics instead of hydrophobic effect as analyzed by the contact angle analysis, which can be photocatalytically recycled through visible light irradiation after the adsorption. The narrowed bandgap by nitrogen doping and the photosensitization effect of carbon dot are revealed to be co-responsible for the visible-light activity of TiO2. The adsorption capacity does not suffer obvious loss after being recycled 3 times

The Mechanism of the Iodination of Phenols

Author Institution: Department of Chemistry, Miami University, Oxfor

Pharmaceutical and personal care products-induced stress symptoms and detoxification mechanisms in cucumber plants.

Contamination of agricultural soils by pharmaceutical and personal care products (PPCPs) resulting from the application of treated wastewater, biosolids and animal wastes constitutes a potential environmental risk in many countries. To date a handful of studies have considered the phytotoxicity of individual PPCPs in crop plants, however, little is known about the effect of PPCPs as mixtures at environmentally relevant levels. This study investigated the uptake and transport, physiological responses and detoxification of a mixture of 17 PPCPs in cucumber seedlings. All PPCPs were detected at higher concentrations in roots compared to leaves, with root activity inhibited in a dose-dependent manner. At 5-50 μg/L, the mature leaves exhibited burnt edges as well as a reduction in photosynthesis pigments. Reactive oxygen species (ROS) production and lipid peroxidation increased with increasing PPCP concentrations; and their contents were greater in roots than in leaves for all PPCP treatments. Enzymes involved in various functions, including oxidative stress (superoxide dismutase and ascorbate peroxidase) and xenobiotic metabolism (peroxidase and glutathione S-transferase), were elevated to different levels depending on the PPCP concentration. Glutathione content gradually increased in leaves, while a maxima occurred at 0.5 μg L-1 PPCPs in roots, followed by a decrease thereafter. This study illustrated the complexity of phytotoxicity after exposure to PPCP mixtures, and provided insights into the molecular mechanisms likely responsible for the detoxification of PPCPs in higher plants

Using Box–Behnken experimental design to optimize the degradation of Basic Blue 41 dye by Fenton reaction

Degradation of a Basic Blue 41 dye using Fenton reagent was examined at laboratory scale in batch experiments using Box-Behnken statistical experiment design. Dyestuff, hydrogen peroxide (H2O2) and ferrous ion (Fe2+) concentrations were selected as independent factors. On the other hand, color and chemical oxygen demand (COD) removal were considered as the response functions. The value of coefficient of determination (R-2) for both color and chemical oxygen demand removal with values 0.98 and 0.99 shows the best agreement between predicted value and experimental values. Perturbation plots indicated that iron dosage has the most effect on both color and COD removal. Normalized plot of residuals also indicated that the models were adequate to predict for both responses. Color and COD removal increased with increasing H2O2 and Fe2+ concentrations up to a certain level. High concentrations of H2O2 and Fe2+ did not result in better removal of color and COD due to hydroxyl radical being gradually consumed by both oxidant and catalyst. Percent color removal was higher than COD removal indicating the production of colorless compounds. The second-order polynomial model revealed optimal process factor ratio. The ratio of H2O2/Fe2+/dyestuff which gives a complete color removal and 95% COD removal was found to be 1195 mg/L/90 mg/L/255 mg/L

Modeling the effect of soil meso- and macropores topology on the biodegradation of a soluble carbon substrate

Soil structure and interactions between biotic and abiotic processes are increasingly recognized as important for explaining the large uncertainties in the outputs of macroscopic SOM decomposition models. We present a numerical analysis to assess the role of meso- and macropore topology on the biodegradation of a soluble carbon substrate in variably water saturated and pure diffusion conditions . Our analysis was built as a complete factorial design and used a new 3D pore-scale model, LBioS, that couples a diffusion Lattice-Boltzmann model and a compartmental biodegradation model. The scenarios combined contrasted modalities of four factors: meso- and macropore space geometry, water saturation, bacterial distribution and physiology. A global sensitivity analysis of these factors highlighted the role of physical factors in the biodegradation kinetics of our scenarios. Bacteria location explained 28% of the total variance in substrate concentration in all scenarios, while the interactions among location, saturation and geometry explained up to 51% of it

Supramolecular Composite Materials from Cellulose, Chitosan, and Cyclodextrin: Facile Preparation and Their Selective Inclusion Complex Formation with Endocrine Disruptors

We have successfully developed a simple one-step method of preparing high-performance supramolecular polysaccharide composites from cellulose (CEL), chitosan (CS), and (2,3,6-tri-O-acetyl)-α-, β-, and γ-cyclodextrin (α-, β-, and γ-TCD). In this method, [BMIm+Cl–], an ionic liquid (IL), was used as a solvent to dissolve and prepare the composites. Because a majority (\u3e88%) of the IL used was recovered for reuse, the method is recyclable. XRD, FT-IR, NIR, and SEM were used to monitor the dissolution process and to confirm that the polysaccharides were regenerated without any chemical modifications. It was found that unique properties of each component including superior mechanical properties (from CEL), excellent adsorption for pollutants and toxins (from CS), and size/structure selectivity through inclusion complex formation (from TCDs) remain intact in the composites. Specifically, the results from kinetics and adsorption isotherms show that whereas CS-based composites can effectively adsorb the endocrine disruptors (polychlrophenols, bisphenol A), their adsorption is independent of the size and structure of the analytes. Conversely, the adsorption by γ-TCD-based composites exhibits a strong dependence on the size and structure of the analytes. For example, whereas all three TCD-based composites (i.e., α-, β-, and γ-TCD) can effectively adsorb 2-, 3-, and 4-chlorophenol, only the γ-TCD-based composite can adsorb analytes with bulky groups including 3,4-dichloro- and 2,4,5-trichlorophenol. Furthermore, the equilibrium sorption capacities for the analytes with bulky groups by the γ-TCD-based composite are much higher than those by CS-based composites. Together, these results indicate that the γ-TCD-based composite with its relatively larger cavity size can readily form inclusion complexes with analytes with bulky groups, and through inclusion complex formation, it can strongly adsorb many more analytes and has a size/structure selectivity compared to that of CS-based composites that can adsorb the analyte only by surface adsorption

Removal of organic compounds by a biofilm supported on GAC : modelling of batch and column data

The performance of a biofilm of Arthrobacter viscosus supported on granular activated carbon on the retention of organic compounds was evaluated. The presence of functional groups on the cell wall surface of the biomass that may interact with the organic compounds was confirmed by Fourier transform infrared spectroscopy, to assess the applicability of this system to the removal of those compounds. The batch assays showed that the removal percentage decreases with the increasing initial concentration. The removal of phenol ranged from 99.5 to 93.4%, the chlorophenol removal ranged from 99.3 to 61.6% and the o-cresol removal ranged from 98.7 to 73.5%, for initial concentrations between 100 and 1,700 mg/L. The batch data were described by Freundlich, Langmuir, Redlich–Peterson, Dubinin-Radushkevich, Sips and Toth model isotherms and the best fit for the retention of phenol and for the retention of o-cresol was obtained with the Sips model, while for chlorophenol, the best fit was obtained with the Freundlich model. The column tests showed that the retention performance followed the order: phenol > chlorophenol > o-cresol, and increased with the increasing initial organic compound concentration. Data from column runs were described by Adams–Bohart, Wolborska and Yoon and Nelson models with good fitting for all the models.POCTI/FEDER - POCTI/CTA/44449/2002Fundação para a Ciência e a Tecnologia (FCT

Biomimetic sulfide oxidation by the means of immobilized Fe(III)-5,10,15,20-tetrakis(pentafluorophenyl)porphin under mild experimental conditions

This paper describes the oxidation of inorganic sulfide to sulfate, minimizing the formation of elemental sulfur. The described catalytic reaction uses dilute hydrogen peroxide at nearly neutral pH values in the presence of a bioinspired, heterogenized, and commercial ferriporphin. A substantial increase of the percentage of sulfide converted to sulfate is obtained in comparison with the yields obtained when working with hydrogen peroxide alone. The biomimetic catalyst also proved to be a much more efficient catalyst than horseradish peroxidase. Accordingly, it could be suitable for large-scale applications. Further studies are in progress to drive sulfate yields up to nearly quantitative