Synthesis of TiO2 on different substrates by chemical vapor deposition for photocatalytic reduction of Cr(VI) in water

TiO₂ loaded on several substrates such as carbon fiber, aluminum plate, silica plate, and glass plate was prepared using the chemical vapor deposition (CVD) method for the photocatalytic reduction of Cr(VI) in water with the presence of ethanol under Ultraviolet (UV) illumination. As‐prepared samples were characterized by X‐Ray Diffraction (XRD), X‐ray photoelectron spectroscopy (XPS), Brunauer–Emmett–Teller (BET), and scanning electron microscopy (SEM). The catalyst with TiO₂ loaded on carbon fiber possessed an extremely large surface area (1,463,91 m²/g), while the other catalysts possessed small surface areas (0.05–0.21 m²/g). The photocatalytic activity of TiO₂ loaded on carbon fiber, which was determined by the conversion of Cr(VI) and the degradation of chemical oxygen demand (COD), was much higher than that of other catalysts. The reusability of TiO₂ loaded on carbon fiber catalyst exhibited almost the same activity as the fresh catalyst. The results indicated that TiO₂ loaded on carbon fiber is feasible for practical application.     

Photo‐induced surface transformations of silica nanocomposites

The photo‐induced, physicochemical surface transformations to silica nanoparticle (SiNP) ‐ epoxy composites have been investigated. The silica nanocomposites (SiNCs) were prepared using a two‐part epoxy system with a 10% mass fraction of SiNPs and exposed to varying doses of high intensity, ultraviolet (UV) radiation at wavelengths representative of the solar spectrum at sea level (290 nm to 400 nm) under constant temperature and humidity. Visibly apparent physical modifications to the SiNC surface were imaged with scanning electron microscopy. Surface pitting and cracking became more apparent with increased UV exposure. Elemental and surface chemical characterization of the SiNCs was accomplished through X‐ray energy dispersive spectroscopy and X‐ray photoelectron spectroscopy, while attenuated total reflectance Fourier transform infrared spectroscopy revealed changes to the epoxy's structure. During short UV exposures, there was an increase in the epoxy's overall oxidation, which was accompanied by a slight rise in the silicon and oxygen components and a decrease in overall carbon content. The initial carbon components (e.g. aliphatic, aromatic and alcohol/ether functionalities) decreased and more highly oxidized functional groups increased until sufficiently long exposures at which point the surface composition became nearly constant. At long exposure times, the SiNC's silicon concentration increased to form a surface layer composed of approximately 75% silica (by mass). Published 2012. This article is a U.S. Government work and is in the public domain in the USA.     

Enzymatic‐ and light‐degradable hybrid nanogels: Crosslinking of polyacrylamide with acrylate‐functionalized Dextrans containing photocleavable linkers

Enzymatically cleavable and light‐degradable hybrid nanogels were prepared by free radical inverse miniemulsion copolymerization of acrylamide (AAm) with a newly synthesized functional dextran crosslinker containing acrylate moieties attached to the backbone via a photolabile linker, that is, dextran‐photolabile linker‐acrylate (Dex‐PL‐A). The Dex‐PL‐A/AAm feed ratio was systematically varied to investigate the influence of the particle composition on the gel properties. The resulting hydrogel nanoparticles were examined with regard to their degradation behavior upon the appliance of the two orthogonal stimuli by turbidity measurements in combination with dynamic light scattering. Although continuous photolytic cleavage of the photolabile linkers between polyacrylamide chains and dextran molecules was found to proceed fast and quantitatively yielding completely disintegrated networks, stepwise irradiation resulted in partial degradation of crosslinking points. Thus, nanogels of a desired specific degree of swelling (DGS) can be obtained by adjusting the irradiation time accordingly. Partial enzymatic cleavage of the dextran backbones of the Dex‐PL‐A crosslinking molecules resulted in an increase in the DGS of the nanogels up to a constant value. Subsequent irradiation of those swollen hydrogel particles was used to fully degrade the network structure in a second step. Hence, a two‐step degradation profile was realized by the combination of the two orthogonal stimuli. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Synthetic approaches to constructing proteolysis targeting chimeras (PROTACs)

The development of various heterobifunctional constructs dubbed PRoteolysis-TArgeting Chimeras (PROTACs) has gained a significant impetus in the last few years. A viable alternative to the traditional occupancy-based inhibition of aberrantly hyperactive proteins, PROTACs operate by an event-based catalytic mechanism bringing together the protein of interest (POI, to be degraded) and E3 ubiquitin ligases. The formation of the ternary complex ‘POI–PROTAC–E3 ubiquitin ligase’ is the critical step which leads to the ubiquitination of the POI and its proteasomal degradation. The current Focused Review aims to highlight the syntheses of selected innovative PROTAC-type degraders of the therapeutically important protein targets as well as some notable chemical aspects of PROTAC construction. The overview is focusing on PROTACs aimed at recruiting Cereblon, the most exploited E3 ligase for targeted protein degradation.     

Degradation of hazardous organic dyes with solar‐driven advanced oxidation process catalyzed by the mixed metal–organic frameworks

phosphonate‐based bimetallic metal‐ organic frameworks, namely STA‐12(M₁, M₂) (M₁, M₂ = Mn, Fe, Co), show photocatalytic activity for the degradation of Rhodamine B (RhB) and Methylene blue (MB) from aqueous solution under natural sunlight irradiation. The degradation of the dyes, appears to be faster with STA‐12(Fe, Mn) than other synthesized MOFs. Thus, photo‐Fenton oxidative discoloration of dyes has been studied by H₂O₂ catalyzed with the STA‐12(Fe, Mn). The process is first order with respect to dyes and the synergistic index in the STA‐12(Fe, Mn)/sunlight/H₂O₂system reached as high as 472%. Mineralization of dyes was discussed by spectroscopic and TOC measurement. Besides, the efficiency of STA‐12(Fe, Mn) used in photocatalytic process was attentively investigated through the characterization of reactive radicals, the stability and reusability of the photocatalyst, also the effect of operational parameters such as H₂O₂ dosage, solution pH and initial dye concentration. This work demonstrates the first example of facilitating photo‐Fenton‐like excitation of H₂O₂ via phosphonate based mixed metal organic frameworks as photocatalysts and explained a new opportunity for solar‐induced AOP environmental remediation and protection.     

The challenges in reliable determination of degradation rates and lifetime in polymer electrolyte membrane fuel cells

The durability of polymer electrolyte membrane fuel cells (PEMFCs) needs to be further improved to cope with application requirements and economic competitiveness. This article highlights the challenges in the reliable determination of degradation rates and lifetime. The reliable evaluation of performance degradation rates is fundamental to quantify and benchmark durability and to allow comparisons between PEMFC durability tests performed using different materials or in different laboratories. The use of efficient recovery procedures enables the discrimination of reversible and irreversible voltage losses and facilitates the understanding of recovery mechanisms. In the end, recent contributions about lifetime diagnoses and prediction are presented, which are promising to be implemented in PEMFC applications.     

Thermal Degradation Kinetics of Plasticized Poly (Vinyl Chloride) with Six Different Plasticizers

Plasticized PVC formulated with different kinds of normally used plasticizers, including bis(2-ethylhexyl) phthalate (DOP), dioctyl terephthalate (DOTP), acetyl tri-n-butyl citrate (ATBC), acetyl trioctyl citrate (ATOC), trioctyl trimellitate (TOTM), and a new vegetable devived plasticizer, isosorbide ester (ID-37), were prepared by a melt blending method. The effect of plasticizer on the thermal degradation behavior of plasticized PVC was investigated by thermal gravimetric analysis (TGA). The activation energies were calculated by three well known methods, developed by Flynn-Wall-Ozawa (FWO), Friedman and Kissinger, respectively. The TGA conducted in N₂ atmosphere showed that the type of plasticizer had an obvious influence on the thermal stability of plasticized PVC. It was found that the peak temperatures (T_P) of the thermal degradation processes shifted to higher temperature with the increase of the heating rate, with two processes being shown. The activation energy of the first thermal decomposition process (E₁), calculated by the Kissinger method, was between 118 and 130 kJ/mol, while the activation energy of the second thermal decomposition process (E₂) was between 261 and 305 kJ/mol, except 499 kJ/mol for the PVC/TOTM formulation. The corresponding values of E₁ and E₂ obtained by the Flynn-Wall-Ozawa method were similar to the above data. E of the sample with TOTM also showed a higher value than the others; the results demonstrated that the PVC plasticized with TOTM was more thermally stable than with the others. The activation energies for certain conversion degrees were calculated by the Friedman method and the FWO method. The value of activation energy for 20%, 50%, and 80% conversion calculated by the Friedman method, exhibited an apparent difference from that calculated by the Flynn-Wall-Ozawa method; the results showed that the value of E obtained by the Friedman method was much more reasonable than that obtained by the Flynn-Wall-Ozawa method.     

Thermal degradation behaviour of radiation grafted FEP-g-polystyrene sulfonic acid membranes

The thermal degradation behaviour and the gaseous products of FEP-g-polystyrene sulfonic acid membranes prepared by radiation-induced grafting of styrene onto poly(tetrafluoroethylene-co-hexafluoropropylene) (FEP) films and the subsequent sulfonation were studied using thermal gravimetric analysis coupled with Fourier transform infrared spectrometry (TGA/FTIR). The membranes were found to have a three-step degradation behaviour due to water removal, elimination of sulfonic acid groups and decomposition of the FEP matrix. The evolving gaseous products were identified using FTIR analysis. The degree of grafting was found to have a strong effect on the weight loss in the membranes, whilst the degradation temperatures of the individual membrane components were shown to be independent of the degree of grafting.     

Distribution and Degradation of 14C-Ethyl Prothiofos in a Potato Plant and the Effect of Processing

Prothiofos and some of its degradation products have been synthesized in our laboratory for investigation purposes. The residual fate of ¹⁴ C-ethyl prothiofos in different parts of potato plant was studied. The highest level of insecticide residues was detected in and on the leaves of potato plants. The residues of prothiofos insecticide were mainly located in the peels of potato tubers (peeling process removed 85% of the total residue after one month of the treatment), small amount penetrated into the pulp of potato tubers. The degradation products in the extracts of both peel and pulp of potato tubers were identified as prothiofos, prothiofos oxon, desethyl prothiofos, O-ethyl-S-propyl phosphorodithioate, O-ethyl phosphorothioate, O-ethyl-S-propyl phosphoric acid, O-ethyl phosphoric acid, despropylthio prothiofos, and prothiofos oxon sulfoxide. In addition 2,4-dichlorophenol was identified as such and in conjugated metabolites.

Potatoes are processed in three ways: frying, boiling, and baking, which is simulated in home preparation. The amount of prothiofos residues was found to decrease on boiling (70%) and further on baking (82%) and frying (100%). The results indicated that frying process is the most effective method for reducing the amount of pesticide residues. Detectable residues were found in boiled potatoes (2.64 ppm), in the boiling water (0.24 ppm), and in the frying oil (0.71 ppm). From these results we concluded that the processed potatoes are safely used for human consumption.