Development of natural attapulgite derived ferromanganese spinel oxides as heterogeneous catalysts for persulfate activation of tetracycline degradation.

Ferromanganese spinel oxides (MnFe2O4, MFO) have been proven effective in activating persulfate for pollutants removal. However, their inherent high surface energy often leads to agglomeration, diminishing active sites and consequently restricting catalytic performance. In this study, using Al-MCM-41 (MCM) mesoporous molecular sieves derived from natural attapulgite as a support, the MFO/MCM composite was synthesized through dispersing MnFe2O4 nanoparticles on MCM carrier by a simple hydrothermal method, which can effectively activate persulfate (PS) to degrade Tetracycline (TC). The addition of Al-MCM-41 can effectively improve the specific surface area and adsorption performance of MnFe2O4, but also reduce the leaching amount of metal ions. The MFO/MCM composite exhibited superior catalytic reactivity towards PS and 84.3% removal efficiency and 64.7% mineralization efficiency of TC (20 mg/L) was achieved in 90 min under optimized conditions of 0.05 mg/L catalyst dosage, 5 mM PS concentration, room temperature and no adjustment of initial pH. The effects of various stoichiometric MFO/MCM ratio, catalyst dosage, PS concentration, initial pH value and co-existing ions on the catalytic performance were investigated in detail. Moreover, the possible reaction mechanism in MFO-MCM/PS system was proposed based on the results of quenching tests, electron paramagnetic resonance (EPR) and XPS analyses. Finally, major degradation intermediates of TC were detected by liquid chromatography mass spectrometry technologies (LC-MS) and four possible degradation pathways were proposed. This study enhances the design approach for developing highly efficient, environmentally friendly and low-cost catalysts for the advanced treatment process of antibiotic wastewater.

Recent developments and perspectives of MXene-Based heterostructures in photocatalysis.

Energy crises and environmental degradation are serious in recent years. Inexhaustible solar energy can be used for photocatalytic hydrogen production or CO2 reduction to reduce CO2 emissions. At present, the development of efficient photocatalysts is imminent. MXene as new two-dimensional (2D) layered material, has been used in various fields in recent years. Based on its high conductivity, adjustable band gap structure and sizable specific surface area, the MXene is beneficial to hasten the separation and reduce the combination of photoelectron-hole pairs in photocatalysis. Nevertheless, the re-stacking of layers because of the strong van der Waals force and hydrogen bonding interactions seriously hinder the development of MXene material as photocatalysts. By contrast, the MXene-based heterostructures composed of MXene nanosheets and other materials not only effectively suppress the re-stacking of layers, but also show the superior synergistic effects in photocatalysis. Herein, the recent progress of the MXene-based heterostructures as photocatalysts in energy and environment fields is summarized in this review. Particularly, new synthetic strategies, morphologies, structures, and mechanisms of MXene-based heterostructures are highlighted in hydrogen production, CO2 reduction, and pollutant degradation. In addition, the structure-activity relationship between the synthesis strategy, components, morphology and structure of MXene-based heterostructures, and their photocatalytic properties are elaborated in detail. Finally, a summary and the perspectives on improving the application study of the heterostructures in photocatalysis are presented.

Vacancy pairs regulate BiOBr microstructure for efficient dimethyl phthalate removal under visible light irradiation.

Developing new photocatalysts to achieve efficient removal of phthalate esters (PAEs) in water is an important research task in environmental science. However, existing modification strategies for photocatalysts often focus on enhancing the efficiency of material photogenerated charge separation, neglecting the degradation characteristics of PAEs. In this work, we proposed an effective strategy for the photodegradation process of PAEs: introducing vacancy pair defects. We developed a BiOBr photocatalyst containing "Bi-Br" vacancy pairs, and confirmed that it has an excellent photocatalytic activity in removing phthalate esters (PAEs). Through a combination of experimental and theoretical calculations, it is proved that "Bi-Br" vacancy pairs can not only improve the charge separation efficiency, but also alter the adsorption configuration of O2, thus accelerating the formation and transformation of reactive oxygen species. Moreover, "Bi-Br" vacancy pairs can effectively improve the adsorption and activation of PAEs on the surface of samples, surpassing the effect of O vacancies. This work enriches the design concept of constructing highly active photocatalysts based on defect engineering, and provides a new idea for the treatment of PAEs in water.

Oxygen vacancies assist a facet effect to modulate the microstructure of TiO2 for efficient photocatalytic O2 activation.

Defect engineering is recognized as an effective route to obtaining highly active photocatalytic materials. However, the current understanding of the role of defects in photocatalysts mainly comes from their independent functional analysis, ignoring the synergy between defects and the chemical environment, especially with crystal facets. Herein, oxygen vacancy (VO)-rich TiO2 nanostructures with different dominant exposed facets were prepared, and the microstructural changes induced by the synergy between the VO and facet effect and the performance difference of photocatalytic O2 activation were explored. The results showed that the combination of high concentration VO and the {101} facet is more conducive to improving the photocatalytic performance of TiO2, which is significantly superior to the combination of low concentration VO and the {101} facet as well as the combination of high concentration VO and the {001} facet. The experimental and theoretical results clarified the dependence of each stage of photocatalysis on two factors. Specifically, VO plays a more significant role in energy band regulation, improving the dynamic behavior of photogenerated charges and enhancing the adsorption and activation of O2, while the facet effect made more contributions to reducing the thermodynamic energy barrier of ROS formation and conversion. The excellent ability of O2 activation enables T101-VO to show potential application characteristics in the removal of RhB and bacterial disinfection. This work established a link between defect and facet effects, providing new insights into understanding defect function in photocatalysts.

A composite photocatalytic system based on spent alkaline Zn-Mn batteries for toluene removal under multiple conditions.

The resource utilization of spent alkaline Zn-Mn batteries (S-AZMB) has always been a hot issue in the field of energy regeneration and environmental protection. The cumbersome and complicated purification process is the reason for their limited recycling. Not long ago, we proved that unpurified S-AZMB can be used directly: construct a Z-scheme photocatalytic system by combining with commercial TiO2 through high-temperature calcination. In order for this finding to be truly adopted by the application market, the high energy consumption calcination process needs to be improved urgently. In this work, we explore the temperature dependence of performance for the composite photocatalyst (TiO2@S-AZMB). A series of experimental results confirm that lowering the calcination temperature not only conducive to improving the separation efficiency of photogenerated electron-hole pairs, but also can significantly improve the environmental adaptability of the catalyst. Specifically, the catalyst synthesized by calcination temperature at 200 °C exhibits higher toluene removal efficiency than that at 500 °C under different initial concentration of pollutants, relative humidity, light intensity and oxygen content. This study not only further improves the photocatalytic performance of the composite catalyst, but also accords with the idea of energy saving and emission reduction, which provides more space for the possibility of recycling S-AZMB.

Recycling of spent alkaline Zn-Mn batteries directly: Combination with TiO2 to construct a novel Z-scheme photocatalytic system.

Recycling of spent alkaline Zn-Mn batteries (S-AZMB) has always been a focus of attention in environmental and energy fields. However, the current research mostly concentrated in the recovery of purified materials, and ignores the direct reuse of S-AZMB. Herein, we propose a new concept for the first time that unpurified S-AZMB can be used as raw materials for preparation of Z-scheme photocatalytic system in combination with TiO2. A series of characterizations and experiments confirm that the combination with S-AZMB not only extends the response of TiO2 to visible light, but also significantly enhances the separation ability of photogenerated electron-hole pairs. In the toluene removal experiment, the degradation kinetic rate of Z-scheme TiO2@S-AZMB photocatalyst reaches 21.0 and 10.5 times than that of TiO2 and S-AZMB, respectively. More notably, this S-AZMB based Z-scheme photocatalyst can maintain structural and photocatalytic performance stability in cyclic catalytic reactions. We believe that this work not only expands the research concept of recycling S-AZMB, but also provides a new idea for designing highly efficient Z-scheme photocatalysts.

Improving Photocatalytic Water Treatment through Nanocrystal Engineering: Mesoporous Nanosheet-Assembled 3D BiOCl Hierarchical Nanostructures That Induce Unprecedented Large Vacancies.

Vacancy control can significantly enhance the performance of photocatalytic semiconductors for water purification. However, little is known about the mechanisms and approaches that could generate stable large vacancies. Here, we report a new mechanism to induce vacancy formation on nanocrystals for enhanced photocatalytic activity: the introduction of mesopores. We synthesized two nanosheet-assembled hierarchical 3D BiOCl mesoporous nanostructures with similar morphology and exposed facets but different nanosheet thickness. Positron annihilation analysis detected unprecedentedly large VBi‴ VO•• VBi‴ VO•• VBi‴ vacancy associates (as well as VBi‴ VO•• VBi‴) on BiOCl assembled from 3-6 nm nanosheets but only VBi‴ VO•• VBi‴ vacancy associates on BiOCl assembled from thicker (10-20 nm) nanosheets. Comparison of vacancy properties with 2D ultrathin 2.7 nm nanosheets (with VBi‴ VO•• VBi‴ and VBi‴) indicates that nanosheet thinness alone cannot explain the formation of such large atom vacancies. On the basis of density functional theory computations of formation energy of isolated Bi vacancy, we show that mesopores facilitate the formation of large vacancies to counterbalance thermodynamic instability caused by incompletely coordinated Bi and O atoms along the mesopore perimeters. We corroborate that the extraordinarily large VBi‴ VO•• VBi‴ VO•• VBi‴ vacancy associates facilitate photoexcitation of electrons and prevent the recombination of electron-hole pairs, which significantly enhances photocatalytic activity. This is demonstrated by the rapid mineralization of bisphenol A (10-5 M) with low photocatalyst loading (1 g L-1), as well as enhanced bacterial disinfection. Improved electron-hole separation is also corroborated by enhanced photocatalytic reduction of nitrate.

A unique semiconductor-carbon-metal hybrid structure design as a counter electrode in dye-sensitized solar cells.

The catalytic activity of counter electrodes (CEs) severely restricts the photovoltaic conversion efficiency of dye-sensitized solar cells. However, electrons trapped by bulk defects greatly reduce the catalytic activity of the CE. In this study, we report a novel In2S3-C-Au hybrid structure designed by simply decorating Au particles on the surface of carbon-coated hierarchical In2S3 flower-like architectures, which could avoid the abovementioned problems. This effect can be attributed to the unique contribution of indium sulfide, carbon, and Au from the hybrid structure, as well as to their synergy. Electrochemical measurements revealed that the hybrid structure possessed high catalytic activity and electrochemical stability for the interconversion of the redox couple I3-/I-. Moreover, this superior performance can be incorporated into the dye-sensitized solar cells system. We used this hybrid structure as a counter electrode by casting it on an FTO substrate to form a film, which displayed better photovoltaic conversion efficiency (8.91%) than the commercial Pt counterpart (7.67%).

Facile Preparation and Lithium Storage Properties of TiO2 @Graphene Composite Electrodes with Low Carbon Content.

Over the past decade, TiO2 /graphene composites as electrodes for lithium ion batteries have attracted a great deal of attention for reasons of safety and environmental friendliness. However, most of the TiO2 /graphene electrodes have large graphene content (9-40 %), which is bound to increase the cost of the battery. Logically, reducing the amount of graphene is a necessary part to achieve a green battery. The synthesis of TiO2 nanosheets under solvothermal conditions without additives is now demonstrated. Through mechanical mixing TiO2 nanosheets with different amount of reduced graphene (rGO), a series of TiO2 @graphene composites was prepared with low graphene content (rGO content 1, 2, 3, and 5 wt %). When these composites were evaluated as anodes for lithium ion batteries, it was found that TiO2 +3 wt % rGO manifested excellent cycling stability and a high specific capacity (243.7 mAh g(-1) at 1 C; 1 C=167.5 mA g(-1) ), and demonstrated superior high-rate discharge/charge capability at 20 C.

Ultralong In2S3 Nanotubes on Graphene Substrate with Enhanced Electrocatalytic Activity.

Ultralong one-dimensional (1D) nanostructures including nanowires or nanotubes have been extensively studied because of their widespread applications in many fields. Although a lot of methods have been reported to prepare In2S3 nanotubes, approaching these nanotubes through one-pot solution synthesis is still extremely difficult, probably because of the intrinsic isotropic crystal growth characteristic of In2S3. In this article, we demonstrated a self-assembly approach for hydrothermal synthesis of In2S3 nanotubes/graphene composites, which contain ultralong (up to 10 µm) In2S3 nanotubes on graphene substrate. The influence of several important synthetic parameters on the final products has been systematically investigated. Importantly, the as-prepared In2S3 nanotubes/graphene composites can be easily cast on FTO to form a film, which can be used as a counter electrode. Our research indicates that the as-fabricated counter electrode exhibits excellent electrocatalytic activity toward the iodide species (I-/I3-) reduction reaction and very high energy conversion efficiency (8.01%) in dye-sensitized solar cells.

Mesoporous Bi2S3 nanorods with graphene-assistance as low-cost counter-electrode materials in dye-sensitized solar cells.

In this work, we report the synthesis of mesoporous Bi2S3 nanorods under hydrothermal conditions without additives, and investigated their catalytic activities as the CE in DSCs by I-V curves and tested conversion efficiency. To further improve their power conversion efficiency, we added different amounts of reduced graphene by simple physical mixing. With the addition of 9 wt% reduced graphene (rGO), the short-circuit current density, open-circuit voltage and fill factor were Jsc = 15.33 mA cm(-2), Voc = 0.74 V and FF = 0.609. More importantly, the conversion efficiency reached 6.91%, which is slightly inferior to the commercial Pt counter electrode (7.44%). Compared to the conventional Pt counter electrodes of solar cells, this new material has the advantages of low-cost, facile synthesis and high efficiency with graphene assistance. To the best of our knowledge, this Bi2S3 + 9 wt% rGO system has the best performance ever recorded in all Bi2S3-based CEs in the DSCs system.

A novel differential expression system for gene modulation in Mycobacteria.

Tuberculosis (TB) remains a major global health problem, and successful genetic manipulation of mycobacteria is crucial for developing new approaches to study the mechanism of pathogenesis of Mycobacterium tuberculosis (M.tb) and to combat TB. In this study, a series of M.tb furA gene operator/promoter (pfurA) mutants were generated aiming at optimization of the promoter activities in mycobacterial strains. Measured by the lacZ gene-fusion reporter system, change of the initial codon GTG to the preferred ATG resulted in a double increase of beta-galactosidase activity, while a 6-bp substitution in the conserved FurA binding AT-rich region upstream of furA gene led to 4-6 folds increase of the activity. It is significant that combination of both mutations showed about 10 folds of beta-galactosidase activity higher than that of the prototype pfurA. Furthermore, all of the furA promoters were expressed continuously in vivo during intracellular growth of Mycobacterium bovis BCG, and were induced early upon infection in macrophages. Employing the series of pfurA-based differential expression vectors, M.tb chimeric antigen Ag856A2 known for its excellent immunogenicity, was shown to be expressed at different levels in the recombinant Mycobacterium smegmatis and BCG strains. These results indicated that this differential expression system is feasible to express any target antigen of interest in a modular fashion for the study of gene regulation in mycobacterial strains, and also for the development of different recombinant BCG vaccine candidates against TB or other infectious diseases, which would be beneficial for elicitation of optimal immune response.

A modified single-tube one-step product-enhanced reverse transcriptase (mSTOS-PERT) assay with heparin as DNA polymerase inhibitor for specific detection of RTase activity.

BACKGROUND: Current regulations and recommendations proposed for the production of vaccines in continuous cell lines of any origin demand that these be free of exogenous viruses, particularly retroviruses. Recently, the ultra-sensitive product-enhanced reverse transcriptase (PERT) assay can be used to detect minute of reverse transcriptase (RTase) in single retroviral particle and is 10(6) times more sensitive than the conventional RTase assays. However, coincidental with this increase in sensitivity is an increase in false-positive reactions derived from contaminating cellular DNA polymerases, which are known to have RTase-like activities. OBJECTIVES: To develop a modified single-tube one-step PERT (mSTOS-PERT) assay with improvements on decreasing significantly the level of false-positive reactions, and to evaluate the mSTOS-PERT assay for sensitivity and specificity. STUDY DESIGN: Ampliwaxtrade mark was used to compartmentalize the reverse transcription (RT) and PCR step in the same micro-tube with more efficiency and reproducibility, while maintaining the high sensitivity. The DNA amplification products were separated by 2% agarose gel electrophoresis, and then analyzed by non-isotopic Southern blot hybridization. A wide variety of cell lines used in biologicals production were detected to validate the improved mSTOS-PERT assay. RESULTS: The detection limit for the mSTOS-PERT assay was at least 10(-9)U, when using AMV-RTase as a positive control. Furthermore, heparin involvement in the RT step can eliminate completely the false-positive PERT signals which are exhibited by cellular polymerases such as DNA-dependent DNA polymerase alpha, gamma released by cell death. Most mammalian cells (MRC-5, Vero, WISH, 2BS, RK-13, MDCK, etc.) are PERT-negative in cell supernatants. Some PERT-positive signals in cell lysates were found to be introduced by the cellular DNA polymerases and could be inhibited specifically by heparin. Chick cells derived from either chick embryo fibroblasts (CEF) or allantoic fluid from SPF embryonated eggs, murine hybridoma cell SP2/0, etc., contained authentic RTase activities, which could not be inactivated by heparin. CONCLUSIONS: The improved mSTOS-PERT assay described here may distinguish the genuine RTase activity from cellular polymerases with high sensitivity and specificity, and is rapid and easy to perform to screen for the possible contamination of minute retroviruses in the cell substrates used in vaccine production.

Rapid detection of rpoB gene mutations in rifampin-resistant Mycobacterium tuberculosis isolates in shanghai by using the amplification refractory mutation system.

Rapid detection of drug resistance in Mycobacterium tuberculosis is essential for efficient treatment and control of this pathogen. The amplification refractory mutation system (ARMS) was used to detect mutations in the rifampin resistance-determining region of the rpoB gene. A total of 39 rifampin-resistant M. tuberculosis isolates in Shanghai were analyzed by this assay, resulting in 92.3% sensitivity (36 of 39) and 87.2% concordance (34 of 39) relative to DNA sequencing, by which 41 mutations of 11 different types, including 9 point mutations and 2 deletions, were identified in the rpoB gene. The most frequent mutations were those associated with codon 531 (21 of 39 [53.8%]) and codon 526 (9 of 39 [23.1%]). The results suggest that the ARMS assay is rapid and simple to implement and could be performed for detection of rifampin resistance in M. tuberculosis to complement conventional culture-based methods.

Molecular Cloning of Human beta-arrestin1 cDNA, Expression and Functional Study.

Complete coding sequences of beta-arrestin1 (1A and 1B) were cloned through application of bioinformatics analysis to the dbEST database. beta-arrestin1A was overexpressed in E.coli with partial expression products as inclusion body. Anti-beta-arrestin1 antibodies were prepared by using purified inclusion body. Results also demonstrate that activation of inhibitory G protein mediated by delta and kappa pioid receptors was strongly attenuated by overexpression of beta-arrestin1A in co-transfected 293 cells.