Recent trends in the transfer of graphene films.

Recent years have witnessed advances in chemical vapor deposition growth of graphene films on metal foils with fine scalability and thickness controllability. However, challenges for obtaining wrinkle-free, defect-free and large-area uniformity remain to be tackled. In addition, the real commercial applications of graphene films still require industrially compatible transfer techniques with reliable performance of transferred graphene, excellent production capacity, and suitable cost. Transferred graphene films, particularly with a large area, still suffer from the presence of transfer-related cracks, wrinkles and contaminants, which would strongly deteriorate the quality and uniformity of transferred graphene films. Potential applications of graphene films include moisture barrier films, transparent conductive films, electromagnetic shielding films, and optical communications; such applications call different requirements for the performance of transferred graphene, which, in turn, determine the suitable transfer techniques. Besides the reliable transfer process, automatic machines should be well developed for the future batch transfer of graphene films, ensuring the repeatability and scalability. This mini-review provides a summary of recent advances in the transfer of graphene films and offers a perspective for future directions of transfer techniques that are compatible for industrial batch transfer.

Defects-Induced Single-Atom Anchoring on Metal-Organic Frameworks for High-Efficiency Photocatalytic Nitrogen Reduction.

Aiming to improve the photocatalytic activity in N2 fixation to produce ammonia, herein, we proposed a photochemical strategy to fabricate defects, and further deposition of Ru single atoms onto UiO-66 (Zr) framework. Electron-metal-support interactions (EMSI) were built between Ru single atoms and the support via a covalently bonding. EMSI were capable of accelerating charge transfer between Ru SAs and UiO-66, which was favorable for highly-efficiently photocatalytic activity. The photocatalytic production rate of ammonia improved from 4.57 µmol g-1 h-1 to 16.28 µmol g-1 h-1 with the fabrication of defects onto UiO-66, and further to 53.28 µmol g-1 h-1 with Ru-single atoms loading. From the DFT results, it was found that d-orbital electrons of Ru were donated to N2 π✶-antibonding orbital, facilitating the activation of the N≡N triple bond. A distal reaction pathway was probably occurred for the photocatalytic N2 reduction to ammonia on Ru1 /d-UiO-66 (single Ru sites decorated onto the nodes of defective UiO-66), and the first step of hydrogenation of N2 was the reaction determination step. This work shed a light on improving the photocatalytic activity via feasibly anchoring single atoms on MOF, and provided more evidences to understand the reaction mechanism in photocatalytic reduction of N2 .

Population impact of fine particulate matter on tuberculosis risk in China: a causal inference.

BACKGROUND: Previous studies have suggested the potential association between air pollution and tuberculosis incidence, but this association remains inconclusive and evidence to assess causality is particularly lacking. We aimed to draw causal inference between fine particulate matter less than 2.5 µm in diameter (PM2.5) and tuberculosis in China. METHODS: Granger causality (GC) inference was performed within vector autoregressive models at levels and/or first-differences using annual national aggregated data during 1982-2019, annual provincial aggregated data during 1982-2019 and monthly provincial aggregated data during 2004-2018. Convergent cross-mapping (CCM) approach was used to determine the backbone nonlinear causal association based on the monthly provincial aggregated data during 2004-2018. Moreover, distributed lag nonlinear model (DLNM) was applied to quantify the causal effects. RESULTS: GC tests identified PM2.5 driving tuberculosis dynamics at national and provincial levels in Granger sense. Empirical dynamic modeling provided the CCM causal intensity of PM2.5 effect on tuberculosis at provincial level and demonstrated that PM2.5 had a positive effect on tuberculosis incidence. Then, DLNM estimation demonstrated that the PM2.5 exposure driven tuberculosis risk was concentration- and time-dependent in a nonlinear manner. This result still held in the multi-pollutant model. CONCLUSIONS: Causal inference showed that PM2.5 exposure driving tuberculosis, which showing a concentration gradient change. Air pollutant control may have potential public health benefit of decreasing tuberculosis burden.

Association between long-term exposure to ambient air pollutants and the risk of tuberculosis: A time-series study in Nantong, China.

Background: Increasing evidence has shown that the risk of tuberculosis (TB) might be related to the exposure to air pollutants; however, the findings are inconsistent and studies on long-term air pollutant exposure and TB risk are scarce. This study aime to assess the relationship between monthly exposure to air pollution and TB risk in Nantong, China. Methods: We collected the time series data on the number of TB cases, as well as environmental and socioeconomic covariates from January 2005 to December 2020. The impact of air pollutant exposure on TB risk was evaluated using the distributed lag nonlinear model (DLNM). Stratified analyses were conducted to examine the effect modifications of sex and age on the association between air pollutants and TB risk. Sensitivity analyses were applied to test the stability of the model. Results: There were a total of 54,096 cases of TB in Nantong during the study period. In the single-pollutant model, for each 10 µg/m3 increase in concentration, the pooled relative risks (RRs) of TB reached the maximum to 1.10 (95% confidence interval (CI): 1.04-1.16, lag 10 months) for particulate matter with aerodynamic diameter less than 2.5 µm (PM2.5), 1.05 (95% CI: 1.01-1.10, lag 9 months) for particulate matter with aerodynamic diameter less than 10 µm (PM10), and 1.11 (95%CI: 1.04-1.19, lag 10 months) for nitrogen dioxide (NO2). Ozone (O3) did not show significant effect on TB risk. Effect modifications of sex and age on the association between air pollutants and TB risk were not observed. The multi-pollutant model results showed no significant variation compared with the single-pollutant model. Conclusions: Our study suggests that air pollutants pose a substantial threat to the TB risk. Reducing air pollution might be crucial for TB prevention and control.

Combined impacts of environmental and socioeconomic covariates on HFMD risk in China: A spatiotemporal heterogeneous perspective.

BACKGROUND: Understanding geospatial impacts of multi-sourced influencing factors on the epidemic of hand-foot-and-mouth disease (HFMD) is of great significance for formulating disease control policies tailored to regional-specific needs, yet the knowledge is very limited. We aim to identify and further quantify the spatiotemporal heterogeneous effects of environmental and socioeconomic factors on HFMD dynamics. METHODS: We collected monthly province-level HFMD incidence and related environmental and socioeconomic data in China during 2009-2018. Hierarchical Bayesian models were constructed to investigate the spatiotemporal relationships between regional HFMD and various covariates: linear and nonlinear effects for environmental covariates, and linear effects for socioeconomic covariates. RESULTS: The spatiotemporal distribution of HFMD cases was highly heterogeneous, indicated by the Lorenz curves and the corresponding Gini indices. The peak time (R2 = 0.65, P = 0.009), annual amplitude (R2 = 0.94, P<0.001), and semi-annual periodicity contribution (R2 = 0.88, P<0.001) displayed marked latitudinal gradients in Central China region. The most likely cluster areas for HFMD were located in south China (Guangdong, Guangxi, Hunan, Hainan) from April 2013 to October 2017. The Bayesian models achieved the best predictive performance (R2 = 0.87, P<0.001). We found significant nonlinear associations between monthly average temperature, relative humidity, normalized difference vegetation index and HFMD transmission. Besides, population density (RR = 1.261; 95%CI, 1.169-1.353), birth rate (RR = 1.058; 95%CI, 1.025-1.090), real GDP per capita (RR = 1.163; 95%CI, 1.033-1.310) and school vacation (RR = 0.507; 95%CI, 0.459-0.559) were identified to have positive or negative effects on HFMD respectively. Our model could successfully predict months with HFMD outbreaks versus non-outbreaks in provinces of China from Jan 2009 to Dec 2018. CONCLUSIONS: Our study highlights the importance of refined spatial and temporal data, as well as environmental and socioeconomic information, on HFMD transmission dynamics. The spatiotemporal analysis framework may provide insights into adjusting regional interventions to local conditions and temporal variations in broader natural and social sciences.

Population-level health and economic impacts of introducing Vaccae vaccination in China: a modelling study.

INTRODUCTION: Given the ageing epidemic of tuberculosis (TB), China is facing an unprecedented opportunity provided by the first clinically approved next-generation TB vaccine Vaccae, which demonstrated 54.7% efficacy for preventing reactivation from latent infection in a phase III trial. We aim to assess the population-level health and economic impacts of introducing Vaccae vaccination to inform policy-makers. METHODS: We evaluated a potential national Vaccae vaccination programme in China initiated in 2024, assuming 20 years of protection, 90% coverage and US$30/dose government contract price. An age-structured compartmental model was adapted to simulate three strategies: (1) no Vaccae; (2) mass vaccination among people aged 15-74 years and (3) targeted vaccination among older adults (60 years). Cost analyses were conducted from the healthcare sector perspective, discounted at 3%. RESULTS: Considering postinfection efficacy, targeted vaccination modestly reduced TB burden (~20%), preventing cumulative 8.01 (95% CI 5.82 to 11.8) million TB cases and 0.20 (0.17 to 0.26) million deaths over 2024-2050, at incremental cost-effectiveness ratio of US$4387 (2218 to 10 085) per disability adjusted life year averted. The implementation would require a total budget of US$22.5 (17.6 to 43.4) billion. In contrast, mass vaccination had a larger bigger impact on the TB epidemic, but the overall costs remained high. Although both preinfection and postinfection vaccine efficacy type might have a maximum impact (>40% incidence rate reduction in 2050), it is important that the vaccine price does not exceed US$5/dose. CONCLUSION: Vaccae represents a robust and cost-effective choice for TB epidemic control in China. This study may facilitate the practice of evidence-based strategy plans for TB vaccination and reimbursement decision making.

Ti3C2 MXene supporting platinum nanoparticles as rapid electrons transfer channel and active sites for boosted photocatalytic water splitting over g-C3N4.

Two-dimension (2D) MXene materials have increasingly attracted attentions in improving the photocatalytic conversion of solar-to-chemical energy over graphitic carbon nitride (g-C3N4). In this work, Pt nanoparticles modified few-layer Ti3C2 MXene sheet (MXene@Pt) was successfully prepared by chemical reduction, which was used as efficient co-catalysts to enhance the photocatalytic hydrogen evolution over porous g-C3N4 (PCN). The high work function of MXene@Pt and the tight 2D/2D interfacial contact between MXene@Pt and PCN significantly promoted the transfer and separation of photogenerated electron-hole. Besides, the MXene@Pt could enhance the light-harvesting of PCN and provide plentiful active sites for hydrogen evolution reaction. The hydrogen evolution activity of optimum 2D/2D MXene@Pt modified PCN (PCN/MPt-5) composite was dramatically enhanced, even higher than that of equal Pt mass modified PCN. Besides, overall water splitting was realized via a two-electron pathway with H2O2 and H2 generation. This work may provide the fabrication strategy for developing MXene-based co-catalyst in photocatalysis.

Study the interactions between multiple flavonoids and bovine serum albumin by the developed equilibrium dialysis.

The therapeutic function of traditional Chinese medicine (TCM) is based on the combination effect of multiple active ingredients. However, the current pharmacological studies mainly focus on the protein binding of the single component from TCM, which is difficult to explain the overall therapeutic mechanism. Thus in this work the equilibrium dialysis method combined with high performance liquid chromatography (HPLC) and ultra-performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) was developed to study the interactions between multi-components and protein. Firstly, the binding constants of seven different structural types of flavonoids with bovine serum albumin (BSA) were determined. The results showed that the binding affinity of flavones and flavonols with BSA was stronger than that of dihydroflavonoids, and the substitution of glycosides would reduce the binding affinity with BSA. The results of competitive displacement experiment showed that there existed competitive interactions among the four flavonoids (rutin, luteolin, hesperetin and kaempferol). The binding constants of flavonoids to BSA were significantly changed under the condition of multi-components coexistence. Especially, the binding constant of hesperetin to BSA increased from 9.46 × 104 L/mol to 1.49 × 106 L/mol under the coexistence of rutin. The results of fluorescence spectroscopy showed that the reason for competitive binding was that the four flavonoids were mainly bound to the IIA region of BSA. Finally, the method was successfully applied to study the binding of multiple components in Radix Scutellariae (RS) extract with BSA. Five flavonoids in RS extract were identified by UPLC-MS/MS, they had different degrees of binding to BSA, among which oroxylin A had the strongest binding degree. In conclusion, the equilibrium dialysis was reliable and sufficiently accurate for study of the interaction between multi-components or TCM extract and protein, which can provided a theoretical basis for the scientific explanation of the overall treatment mechanism of TCM.

Preliminary screening of the potential active ingredients in traditional Chinese medicines using the Ussing chamber model combined with HPLC-PDA-MS.

An in vitro intestinal absorption model combined with high-performance liquid chromatography-photo diode array-tandem mass spectrometry (HPLC-PDA-MS) was used for preliminary screening of potential active ingredients from complex multi-component traditional Chinese medicine (TCM) system. Oral administration is one of the main administration methods for TCMs. Only the ingredients that could be absorbed have the opportunity to play a role. Thus, these were defined as potential active ingredients. Studying of intestinal absorption can provide a theoretical basis for the mechanism of TCMs. The Caco-2 cell model, the everted rat gut sac model, and the Ussing chamber model were established for TCMs. The degree of anastomosis between the in vitro intestinal model and the actual intestinal absorption of TCMs were evaluated by the gavage method in rats. The Ussing chamber model was best fit for oral experiments in rats and was selected as the research means to preliminarily screen potential active ingredients from eight TCMs, including Salvia miltiorrhiza Bunge, Astragalus propinquus Schischkin, Plantago asiatica L, Fallopia multiflora (Thunb.) Harald, Epimedium brevicornu Maxim, Moutan Cortex, Citrus reticulata Blanco, and Panax notoginseng (Burkill) F. H. Chen ex C. H. Chow. A total of 44 components were absorbed and screened as the potential active ingredients from the 80 components identified in eight TCMs by HPLC-PDA-MS.

Selective reduction of nitrate into N2 by novel Z-scheme NH2-MIL-101(Fe)/BiVO4 heterojunction with enhanced photocatalytic activity.

Nitrate and its metabolites as common pollutants in water had attracted widespread attentions. Converting nitrate to nontoxic and harmless nitrogen via photocatalysis was a promising approach. In this study, a novel Z-scheme NH2-MIL-101(Fe)/BiVO4 heterojunction was successfully prepared. As-prepared Z-scheme heterojunction along with built-in electric field facilitated the charge separation and enhanced the photocatalytic activity in nitrate reduction. The results showed that 0.10-MBiVO photocatalyst exhibited the highest nitrate removal rate of 94.8% (initial concentration 100 mgN/L) and final selectivity to N2 of 93.4% in 50 min under ultraviolet irradiation. Moreover, formic acid was proved as better hole scavenger compared with methanol and oxalic acid. And the concentration of formic acid had significant influence on the process of nitrate photocatalytic reduction. 0.10-MBiVO photocatalyst exhibited excellent reusability in the recycling tests, indicating its great potential in practical application of nitrate photocatalytic removal. The mechanism of the enhancement as well as reaction pathways for nitrate photocatalytic reduction on NH2-MIL-101(Fe)/BiVO4 were comprehensively explored and described at the end.

Effects of Different Biological Carriers in Microbial Fuel Cells.

In this study, to investigate their effects on battery power generation performance and wastewater treatment capacity, coal semicoke granular-activated carbon, granular graphite, and walnut shell-activated carbon were added to the anode compartment of a microbial fuel cell. As revealed from the experimental results, adding activated carbon and graphite can significantly decrease the startup time of microbial fuel cells as well as provide the shortest startup time of coal semicoke-activated carbon fluidized bed microbial fuel cells (MGAC-MFCs). The activated carbon particle diameter did not increase from 0.275 to 0.55 mm, and the voltage changed the chemical oxygen demand (COD) degradation efficiency. However, the 0.275 mm activated carbon exhibited a maximum open-circuit voltage of 935 mV as well as a COD degradation efficiency of 95%, and the operation cycle was shortened. After running a cycle, the COD removals of different systems were 85, 93, and 89%, and the maximum value was obtained by the MGAC-MFC system. After the activated carbon and graphite particles were added, the electrical performance and production capacity of the sewage treatment microbial fuel cells were significantly enhanced.

In-situ construction of ternary Ti3C2 MXene@TiO2/ZnIn2S4 composites for highly efficient photocatalytic hydrogen evolution.

Facing the demand of cleaning energy, the development of efficient photocatalysts for hydrogen evolution is a promising way to realize solar-to-chemical energy conversion for solving energy crisis. Hence, a novel hierarchical Ti3C2 MXene@TiO2/ZnIn2S4 photocatalyst with rapid charge transfer channels was constructed by two-step hydrothermal for efficient hydrogen production, adopting hydrothermal oxidation to in-situ synthesize Ti3C2 MXene embedded with TiO2 nanosheets (M@TiO2), which was applied to load ZnIn2S4 (ZIS). The hybridized photocatalyst with optimized ZIS amount had a hydrogen generation rate of 1185.8 µmol/g/h, which was higher than that of M@TiO2 and pure ZIS. That was originated from the outstanding light harvesting of ZIS and Ti3C2, sufficient active sites of Ti3C2, intimate interfacial contact, and efficient separation and transfer of photogenerated charges via heterojunction. The favorable and rapid charge transfer routes included type-II heterojunction between ZIS and TiO2 nanosheets, Schottky junction of Ti3C2/semiconductor, and metallic Ti3C2 with high conductivity. This work revealed the Schottky junction forming between ZIS and Ti3C2, and hierarchical M@TiO2 could be served as advantageous platform and efficient cocatalyst to construct MXene-based photocatalyst.

Chlorella to fuel conversion on amphiphilic SO3H-SBA-15 catalysts: Pyrolysis characteristics and kinetics.

The aim of this work was to propose a novel process to make Chlorella pyrolyzed and in situ upgraded to fuel over amphiphilic SO3H-SBA-15 catalysts. This strategy is developed to build a Pickering emulsion system through the w/o (water/decalin) droplets. Chlorella catalytic pyrolysis has been conducted under the different heating rates to get the activation energy 166 kJ/mol (α = 0.5) according to the kinetic-free model. Palmitic acid, as a model compound, was employed for TG and DRIFTS analysis to elucidate the pyrolysis and deoxygenation reaction pathway. n-hexadecane pyrolysis at 3 MPa N2 illustrated the peak cracking temperature declining from thermally 422 °C to catalytically 413 °C. N2 physisorption of the fresh and post-reaction catalysts indicated that there is little catalyst decay. With improved thermal stability and hydrophobicity, the SO3H-SBA-15 catalysts showed enhanced performance for Chlorella pyrolysis, and revealed the promising application for better fuel production in aqueous conversion.

Microalgae hydrothermal liquefaction and derived biocrude upgrading with modified SBA-15 catalysts.

In this study, a novel route was proposed for microalgae biofuel production by catalytic upgrading of Chlorella hydrothermal liquefaction (HTL) derived biocrude. Al-SBA-15, CuO/Al-SBA-15, ZuO/Al-SBA-15, and CuO-ZnO/Al-SBA-15 catalysts were synthesized in a facile, one-pot way, and tested for methyl palmitate decarboxylation and biocrude upgrading without H2 addition. These modified SBA-15 catalysts enhanced alkane selectivity of methyl palmitate decarboxylation from 7.6 wt% up to 79.6 wt% at 340-350 °C. FT-IR, TG and GC-MS characterizations were employed to identify the composition and properties of the upgraded bio-oils. Compared with thermal upgrading, modified SBA-15 catalysts enriched the yield of low boiling point compounds, and the content of heavy bio-oil (>400 °C) declined from 9.57 wt% to 1.89 wt%. Hydrocarbon yield was greatly enriched on the catalysts, and aromatics predominant on Al-SBA-15 while aliphatics abundant on metal oxide(s) supported catalysts. The hydrocarbon yield was increased from 25.1 wt% (thermal) to 65.7 wt% on the CuO/Al-SBA-15.

Iridium nanoparticles supported on hierarchical porous N-doped carbon: an efficient water-tolerant catalyst for bio-alcohol condensation in water.

Nitrogen-doped hierarchical porous carbons were synthesized successfully by a controllable one-pot method using glucose and dicyandiamide as carbon source and nitrogen source via hydrothermal carbonization process. The nitrogen-doped materials, possessing high nitrogen content (up to 7 wt%), large surface area (>320 m(2) g(-1)) and excellent hierarchical nanostructure, were employed as catalyst supports for immobilization of iridium nanoparticles for bio-alcohol condensation in water. The introduction of nitrogen atoms into the carbon framework significantly improved iridium nanoparticles dispersion and stabilization. The novel iridium catalysts exhibited superior catalytic activity in the aqueous phase condensation of butanol, offering high butanol conversion of 45% with impressive 2-ethylhexanol selectivity of 97%. The heterogeneous catalysts had great advantages of easy recovery and high catalytic stability. The outstanding catalytic performance could be attributed to excellent dispersion of iridium nanoparticles, stronger iridium-support interactions and interaction of nitrogen species with alcohol substrates.

Acidic resin-catalysed conversion of fructose into furan derivatives in low boiling point solvents.

Conversion of fructose into furan derivatives 5-hydroxymethylfurfural (HMF) and 5-methoxymethylfurfural (MMF) is performed in tetrahydrofuran (THF) and methanol-organic solvent systems, catalysed by an acidic resin Amberlyst-15. The melted fructose can be converted into HMF on the surface of the solid resin catalyst in the presence of THF as an extracting phase, which is a good solvent for HMF and other by-products. The solid resin catalyst can be reused eleven times without losing its catalytic ability, with an average HMF yield of approximately 50%. Upon the addition of methanol, the generated HMF can further react with methanol to form MMF, and the total yield of HMF and MMF could be promoted to 65%. GC-MS analysis confirms the formation of a small amount of methyl levulinate in methanolorganic solvent system.

Investigation on activated semi-coke desulfurization.

An activated semi-coke with industrial-scale size was prepared by high-pressure hydrothermal chemistry activation, HNO3 oxidation and calcination activation in proper order from Inner Mongolia Zhalainuoer semi-coke, which is rich in resource and cheap in sale. SO2 adsorption capacity on this activated semi-coke was assessed in the fixed bed in the temperature range of 60-170 degrees C, space velocity range of 500-1300 h(-1), SO2 concentration of 1000-3000 ppmv, and N2 as balance. The surface area, elemental and proximate analysis for both raw semi-coke and activated semi-cokes were measured. The experimental results showed that the activated semi-coke has a high adsorption capacity for sulfur dioxide than the untreated semi-coke. This may be the result of increase of surface area on activated semi-coke and surface oxygen functional groups with basicity characteristics. Comparison to result of FTIR, it is known that group of -C-O-C- may be active center of SO2 catalytic adsorption on activated semi-coke.