Wei Shao

Benefiting from its strong oxidizing properties, the singlet oxygen has garnered serious attentions in physical, chemical, as well as biological studies. However, the photosensitizers for the generation of singlet oxygen bear in low quantum yields, lack of long wavelength absorption band, poor biocompatibility, undegradable in living tissues, and so on. Here we first demonstrate the exfoliated black phosphorus nanosheets to be effective photosensitizers for the generation of singlet oxygen with a high quantum yield of about 0.91, rendering their attractive applications in catalysis and photodynamic therapy. Through in vitro and in vivo studies, the water dispersible black phosphorus nanosheets show notable cancer therapy ability. In addition, the photodegradable character of black phosphorus from element to biocompatible phosphorus oxides further highlights its therapeutic potential against cancer. This study will not only expand the breadth of study in black phosphorus but also offer an efficient catalyst and photodynamic therapy agent.

Excitonic effects mediated by Coulomb interactions between photogenerated electrons and holes play crucial roles in photoinduced processes of semiconductors. In terms of photocatalysis, however, efforts have seldom been devoted to the relevant aspects. For the catalysts with giant excitonic effects, the coexisting, competitive exciton generation serves as a key obstacle to the yield of free charge carriers, and hence, transformation of excitons into free carriers would be beneficial for optimizing the charge-carrier-involved photocatalytic processes. Herein, by taking bismuth oxybromide (BiOBr) as a prototypical model system, we demonstrate that excitons can be effectively dissociated into charge carriers with the incorporation of oxygen vacancy, leading to excellent performances in charge-carrier-involved photocatalytic reactions such as superoxide generation and selective organic syntheses under visible-light illumination. This work not only establishes an in-depth understanding of defective structures in photocatalysts but also paves the way for excitonic regulation via defect engineering.

Experimental data reveal that the incorporation of carbonyl groups into polymer matrix can significantly enhance singlet oxygen (1O2) generation and suppress production of other reactive oxygen species. Excitonic processes investigated by phosphorescence spectroscopy reveal enhanced triplet-exciton generation in the modified g-C3N4, which facilitate 1O2 generation through an energy transfer process. Benefiting from this, the modified g-C3N4 shows excellent conversion and selectivity in organic synthesis. As a service to our authors and readers, this journal provides supporting information supplied by the authors. Such materials are peer reviewed and may be re-organized for online delivery, but are not copy-edited or typeset. Technical support issues arising from supporting information (other than missing files) should be addressed to the authors. Please note: The publisher is not responsible for the content or functionality of any supporting information supplied by the authors. Any queries (other than missing content) should be directed to the corresponding author for the article.

Excitonic effects, arising from the Coulomb interactions between photogenerated electrons and holes, dominate the optical excitation properties of semiconductors, whereas their influences on photocatalytic processes have seldom been discussed. In view of the competitive generation of excitons and hot carriers, exciton dissociation is proposed as an alternative strategy for hot-carrier harvesting in photocatalysts. Herein, by taking heptazine-based melon as an example, we verified that enhanced hot-carrier generation could be obtained in semicrystalline polymeric photocatalysts, which is ascribed to the accelerated exciton dissociation at the abundant order-disorder interfaces. Moreover, driven by the accompanying electron injection toward ordered chains and hole blocking in disordered chains, semicrystalline heptazine-based melon showed an ∼7-fold promotion in electron concentration with respect to its pristine counterpart. Benefiting from these, the semicrystalline sample exhibited dramatic enhancements in electron-involved photocatalytic processes, such as superoxide radical production and selective alcohol oxidation. This work brightens excitonic aspects for the design of advanced photocatalysts.

Numerous efforts have been devoted to understanding the excitation processes of photocatalysts, whereas the potential Coulomb interactions between photogenerated electrons and holes have been long ignored. Once these interactions are considered, excitonic effects will arise that undoubtedly influence the sunlight-driven catalytic processes. Herein, by taking bismuth oxyhalide as examples, we proposed that giant electron-hole interactions would be expected in confined layered structures, and excitons would be the dominating photoexcited species. Photocatalytic molecular oxygen activation tests were performed as a proof of concept, where singlet oxygen generation via energy transfer process was brightened. Further experiments verify that structural confinement is curial to the giant excitonic effects, where the involved catalytic process could be readily regulated via facet-engineering, thus enabling diverse reactive oxygen species generation. This study not only provides an excitonic prospective on photocatalytic processes, but also paves a new approach for pursuing systems with giant electron-hole interactions.

Recently low-dimensional materials hold great potential in the field of photocatalysis, whereas the concomitantly promoted many-body effects have long been ignored. Such Coulomb interaction-mediated effects would lead to some intriguing, nontrivial band structures, thus promising versatile photocatalytic performances and optimized strategies. Here, we demonstrate that ultrathin black phosphorus (BP) nanosheets exhibit an exotic, excitation-energy-dependent, optical switching effect in photocatalytic reactive oxygen species (ROS) generation. It is, for the first time, observed that singlet oxygen (1O2) and hydroxyl radical (•OH) are the dominant ROS products under visible- and ultraviolet-light excitations, respectively. Such an effect can be understood as a result of subband structure, where energy-transfer and charge-transfer processes are feasible under excitations in the first and second subband systems, respectively. This work not only establishes an in-depth understanding on the influence of many-body effects on photocatalysis but also paves the way for optimizing catalytic performances via controllable photoexcitation.

Understanding the photoexcitation processes in semiconductors is critical for the design of advanced photocatalytic materials. Nevertheless, traditional viewpoints focus on photogenerated free charge carriers, which are somehow invalid once the many-body effects are taken into account, especially for polymeric photocatalysts. Here we systematically investigate the photoexcitation processes involved in the polymer matrix of graphitic carbon nitride (g-C3N4) by combining photoluminescence spectroscopy and ultrafast transient absorption spectroscopy, validating the strong excitonic effects in the well-known photocatalyst for the first time. The identification of the robust triplet-triplet annihilation process, in which two triplet excitons collide to produce a singlet exciton, highlights an important nonradiative depopulation pathway of excited species and thereby offers potential strategies to regulate the photocatalytic activities of polymeric g-C3N4. The work establishes a new understanding of the photocatalytic mechanism in the polymeric g-C3N4 matrix, and thus paves the way for designing effective polymeric photocatalysts through excitonic engineering.

Selective photooxidation of amines to biologically important imines is in great demand for industrial applications. The conversion efficiency and selectivity of the process are strongly dependent on the activation of photocatalytic molecular oxygen (O2) into reactive oxygen species. Here, we propose the construction of rich interfaces to boost photocatalytic O2 activation by facilitating the transfer of photocarriers. Taking Bi3O4Br/Bi2O3 heterojunctions as an example, rich interfaces facilitate electron transfer to adsorbed O2 for superoxide (O2·−) generation, thus achieving ≥ 98% conversion efficiency and selectivity for benzylamine and benzylamine derivatives. This study offers a valid method to design advanced photocatalysts for selective oxidation reactions.

Enhanced H2 evolution efficiency is achieved via manipulating the spatial location of oxygen vacancies in niobates. The ultrathin K4Nb6O17 nanosheets which are rich in surface oxygen vacancies show enhanced optical absorption and band gap narrowing. Meanwhile, the fast charge separation effectively reduces the probability of hole-electron recombination, enabling 20 times hydrogen evolution rate compared with the defect-free bulk counterpart. As a service to our authors and readers, this journal provides supporting information supplied by the authors. Such materials are peer reviewed and may be re-organized for online delivery, but are not copy-edited or typeset. Technical support issues arising from supporting information (other than missing files) should be addressed to the authors. Please note: The publisher is not responsible for the content or functionality of any supporting information supplied by the authors. Any queries (other than missing content) should be directed to the corresponding author for the article.

Identification of active sites in an electrocatalyst is essential for understanding of the mechanism of electrocatalytic water splitting. To be one of the most active oxygen evolution reaction catalysts in alkaline media, Ni-Fe based compounds have attracted tremendous attention, while the role of Ni and Fe sites played has still come under debate. Herein, by taking the pyrrhotite Fe7S8 nanosheets with mixed-valence states and metallic conductivity for examples, we illustrate that Fe could be a highly active site for electrocatalytic oxygen evolution. It is shown that the delocalized electrons in the ultrathin Fe7S8 nanosheets could facilitate electron transfer processes of the system, where d orbitals of FeII and FeIII would be overlapped with each other during the catalytic reactions, rendering the ultrathin Fe7S8 nanosheets to be the most efficient Fe-based electrocatalyst for water oxidation. As expected, the ultrathin Fe7S8 nanosheets exhibit promising electrocatalytic oxygen evolution activities, with a low overpotential of 0.27 V and a large current density of 300 mA cm-2 at 0.5 V. This work provides solid evidence that Fe could be an efficient active site for electrocatalytic water splitting.

Abstract As the properties of ultrathin two‐dimensional (2D) crystals are strongly related to their electronic structures, more and more attempts were carried out to tune their electronic structures to meet the high standards for the construction of next‐generation smart electronics. Herein, for the first time, we show that the conductive nature of layered ternary chalcogenide with formula of Cu 2 WS 4 can be switched from semiconducting to metallic by hydrogen incorporation, accompanied by a high increase in electrical conductivity. In detail, the room‐temperature electrical conductivity of hydrogenated‐Cu 2 WS 4 nanosheet film was almost 10 10 times higher than that of pristine bulk sample with a value of about 2.9×10 4 S m −1 , which is among the best values for conductive 2D nanosheets. In addition, the metallicity in the hydrogenated‐Cu 2 WS 4 is robust and can be retained under high‐temperature treatment. The fabricated all‐solid‐state flexible supercapacitor based on the hydrogenated‐Cu 2 WS 4 nanosheet film shows promising electrochemical performances with capacitance of 583.3 F cm −3 at a current density of 0.31 A cm −3 . This work not only offers a prototype material for the study of electronic structure regulation in 2D crystals, but also paves the way in searching for highly conductive electrodes.

The heavy metal inventory and the ecological risk of the tidal flat sediments in Haizhou Bay were investigated. Results show that the average concentrations of heavy metals in the surface sediments exceeded the environment background values of Jiangsu Province coastal soil, suggesting that the surface sediments were mainly polluted by heavy metals (Cd, Cr, Cu, Mn, Pb and Zn). In addition, the profiles of heavy metals fluxes can reflect the socio-economic development of Lianyungang City, and heavy metals inputs were attributed to anthropogenic activities. Cr, Cu, Pb and Zn were mainly present in the non-bioavailable residual form in surface sediments, whereas Cd and Mn were predominantly in the highly mobile acid soluble and reducible fractions. The ecological risk of the polluted sediments stemmed mainly from Cd and Pb. According to the Sediment quality guidelines (SQGs), however, the adverse biological effects caused by the heavy metals occasionally occurred in tidal flat.

Among the various strategies for achieving high solar energy utilization, elemental doping has been extensively explored owing to its advantages in regulating light absorption, band positions and charge carrier processes of photocatalysts.

Municipal wastewater treatment plants (WWTPs) are an important reservoir for heavy metal (e.g., Hg and Ag) resistance genes and antibiotic resistance genes (ARGs). However, current knowledge on Hg/Ag resistance genes and their association with ARGs in WWTPs remains largely unknown. In this study, the fates of five Hg/Ag resistance genes (merB, merD, merR, silE, and silR), five ARGs (sulI, sulII, tetO, tetQ, tetW), and class 1 integrase (intI1) in a WWTP were investigated. Results show that the absolute abundances of all target genes were greatly reduced through the treatment systems. The dynamics of merB, merD and silE were significantly correlated with tetW and sulII. Based on network analysis, Hg/Ag resistance genes might share the same microbial hosts with tetQ and tetW, implying the potential importance of Hg/Ag in ARGs evolution and spread. These findings advanced our understanding of the occurrence of Hg/Ag resistance genes and ARGs in WWTPs.

Photocatalytic selective aerobic oxidation reactions are crucial in designing advanced organic intermediates, but suffer from low conversion efficiency. Hence, activating O2 to create suitable reactive oxygen species, such as singlet oxygen (1O2), can significantly increase the yield of desired products. Herein, using ZnIn2S4 nanosheets as a model system, we build a surface-modified theoretical structure, where a surface-covered non-conductive macromolecular chain, polyvinyl pyrrolidone (PVP), is bound to ZnIn2S4 and influences the O2 adsorption process. PVP on the surface significantly changes the electronic structure and suppresses electron conduction of ZnIn2S4 nanosheets. Therefore, abundantly photogenerated and long-lived species transfer their energy to physically absorbed O2 to efficiently generate 1O2, which can oxidize sulphides into their corresponding sulphoxides. For sulphoxidation of different sulphides, surface modification brings a 3-9-fold increase in conversion efficiency and high selectivities ≥98%. This study provides a feasible way of boosting 1O2-generation-related photocatalytic reactions.

The defects in metal-organic frameworks (MOFs) can dramatically alter their pore structure and chemical properties. However, it has been a great challenge to characterize the molecular structure of defects, especially when the defects are distributed irregularly in the lattice. In this work, we applied a characterization strategy based on solid-state nuclear magnetic resonance (NMR) to assess the chemistry of defects. This strategy takes advantage of the coordination-sensitive phosphorus probe molecules, e.g., trimethylphosphine (TMP) and trimethylphosphine oxide (TMPO), that can distinguish the subtle differences in the acidity of defects. A variety of local chemical environments have been identified in defective and ideal MOF lattices. The geometric dimension of defects can also be evaluated by using the homologs of probe molecules with different sizes. In addition, our method provides a reliable way to quantify the density of defect sites, which comes together with the molecular details of local pore environments. The comprehensive solid-state NMR strategy can be of great value for a better understanding of MOF structures and for guiding the design of MOFs with desired catalytic or adsorption properties.

Singlet oxygen (1 O2 ) with electrical neutrality and long lifetime holds great promise in producing high-added-value chemicals via a selective oxidation reaction. However, photocatalytic 1 O2 generation via the charge-transfer mechanism still suffers from low efficiency due to the mismatched redox capacities and low concentration of photogenerated carriers in confined systems. Herein, by taking bismuth oxysilicate (Bi2 O2 SiO3 ) with alternating heterogeneous layered structure as a model, it is shown that iodine doping can facilitate the spatial redistributions of bands on alternated [Bi2 O2 ] and [SiO3 ] layers, which can promote the separation and transfer of photogenerated charge carriers. Meanwhile, the band positions of Bi2 O2 SiO3 are optimized to match the redox potential of 1 O2 generation. Benefiting from these features, iodine-doped Bi2 O2 SiO3 exhibits efficient 1 O2 generation with respect to its pristine counterpart, leading to promoted performance in the selective sulfide oxidation reaction. A new strategy is offered here for optimizing charge-transfer-mediated 1 O2 generation.

The surface-state-mediated trapping process, a dominant consumption pathway of photoinduced charge carriers, sometimes plays a detrimental role in gaining high-efficiency photocatalytic solar energy utilization.

The activity of electrocatalyst is dominant by the spin configuration of active sites, which is strongly related to its local structure. Herein, for the first time, the intrinsic relationships among local structural distortion, spin configuration and oxygen evolution reaction (OER) activity of the sample are systematically studied by taking the solid solution of transition metal tungstates (CoxFe1-xWO4) with tunable degrees of local structural distortions as a platform, and proposed that the local structural distortion induced spin transition is account for its high catalytic activity. Benefiting from the co-presence of high spin and low spin states, the Co0.708Fe0.292WO4 exhibits the best OER activity among all samples with a small overpotential of 327 mV for 10 mA cm−2 and a large current density of 254 mA cm−2 at 1.825 V (vs RHE) in 1 M KOH solution. This work introduces a deeply understanding on the role of local structural distortion played in OER process.

Fish-associated antibiotic resistance genes (ARGs) have attracted increasing attention due to their potential risks to human beings via the food chain. However, data are scarce regarding the antibiotic resistance in fish themselves. Herein, the antibiotic resistance genes (ARGs) were assessed in the gut of four major Chinese freshwater carp (i.e., silver carp, grass carp, bighead carp, and crucian carp) from food retail markets. Results show that the abundances of target ARGs (e.g., tetA, tetO, tetQ, tetW, sulI, sulII, and blaTEM-1) and class 1 integrase (intI1) were in the range 9.4 × 10-6 - 1.6 × 10-1 and 6.7 × 10-5 - 5.2 × 10-2 gene copies per 16S rRNA gene, respectively. The sulI, sulII, and tetQ strongly correlated with silver and mercury resistance genes (e.g., silE and merR). The microbial taxa of fish gut could be partly separated among retail markets based on the PCA analysis. About 15.0% of the OTUs in fish gut were shared and 74.5% of the shared OTUs were identified as Acidobacteria, Bacteroidetes, Chloroflexi, Cyanobacteria, Firmicutes, and Proteobacteria. These phyla may constitute the core microbiota in the guts of the four Chinese freshwater carp. The possible ARG hosts were revealed based on the network analysis, and the presence of pathogen-associated resistant genera in fish gut highlights the need to fully understand their potential human health risks.

Atomic-level engineering strategies in 2D electrocatalysts for the CO₂RR.

Chemical fixation of carbon dioxide (CO2 ) into value-added organics is regarded as a competitive and viable method in large scale industrial production, during which the catalysts with promoting CO2 activation ability are needed. Herein, we proposed an in-plane heterostructure strategy to construct Lewis acid-base sites for efficient CO2 activation. By taking ultrathin in-plane Cu2 O/Cu heterostructures as a prototype, we show that Lewis acid-base sites on heterointerface can facilitate a mixed C and O dual coordination on surface, which not only strengthen CO2 adsorption, but also effectively activate the inert molecules. As revealed by in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) and quasi in situ X-ray photoelectron spectroscopy (XPS), Lewis acid-base sites could readily activate CO2 to . CO2- species, which is the key intermediate radical for CO2 fixation. As a result, abundant Lewis acid-base sites endow Cu2 O/Cu nanosheets with excellent performances for dimethyl carbonate generation, a high conversion yield of 28 % with nearly 100 % selectivity under mild conditions. This study provides a model structure for CO2 fixation reactions.

The cycloaddition of CO2 with epoxides towards cyclic carbonates provides a promising pathway for CO2 utilization. Given the crucial role of epoxide ring opening in determining the reaction rate, designing catalysts with rich active sites for boosting epoxide adsorption and C-O bond cleavage is necessary for gaining efficient cyclic carbonate generation. Herein, by taking two-dimensional FeOCl as a model, we propose the construction of electron-donor and -acceptor units within a confined region via vacancy-cluster engineering to boost epoxide ring opening. By combing theoretical simulations and in situ diffuse reflectance infrared Fourier-transform spectroscopy, we show that the introduction of Fe-Cl vacancy clusters can activate the inert halogen-terminated surface and provide reactive sites containing electron-donor and -acceptor units, leading to strengthened epoxide adsorption and promoted C-O bond cleavage. Benefiting from these, FeOCl nanosheets with Fe-Cl vacancy clusters exhibit enhanced cyclic carbonate generation from CO2 cycloaddition with epoxides.

Incorporation of nanomaterials in the thin film polyamide (PA) is instrumental to overcome the intrinsic trade-off between permeability and selectivity of polymeric nanofiltration (NF) membranes. However, the universal method of preparing thin film nanocomposite (TFN) NF membranes by directly combining the synthesized nanofillers into PA faces a stubborn issue of poor compatibility for filler-PA, which is adverse to membrane separation. Herein, an in-situ interfacial synthetic strategy was induced in interfacial polymerization (IP) process to prepare TFN membranes with metal-organic framework (MOF) in the PA selective layer. The metal ions and ligands constituting the MOF were dissolved individually in the aqueous and organic phases. MOF particles and the PA layer were simultaneously formed at the liquid-liquid interface. The increment of cross-linking degree confirmed the good compatibility between MOF and PA. Compared with the thin film composite (TFC) membrane, the acquired TFN-1 membrane exhibited 100 % enhancement of pure water permeance (from 10.0 to 20.6 L m−2 h−1 bar−1) due to the markedly reduced thin film thickness. Meanwhile, the rejection of rhodamine B (99.9 %) and Na2SO4 (96.5 %) for TFN membrane were higher than those of TFC membrane (97.2 % and 95.6 %), respectively. The TFN membrane exhibited long-term stability without deterioration. The in-situ interfacial synthesis of the MOF/PA layer provides a new avenue in TFN membrane fabrications.

The influence of the gadolinium doping on the structural features and opto-electrical properties of ZnO:Al (ZAO) films deposited by radio frequency (RF) magnetron sputtering method onto glass substrates was investigated. X-ray analysis showed that the films were polycrystalline fitting well with a hexagonal wurtzite structure and have preferred orientation in [0 0 2] direction. The Gd doped ZAO film with a thickness of 140 nm showed a high visible region transmittance of 90%. The optical band gap was found to be 3.38 eV for pure ZnO film and 3.58 eV for ZAO films while a drop in optical band gap of ZAO film was observed by Gd doping. The lowest resistivities of 8.4 × 10−3 and 10.6 × 10−3 Ω cm were observed for Gd doped and undoped ZAO films, respectively, which were deposited at room temperature and annealed at 150 °C.

Fruit tree species have significant impacts on the physicochemical properties of soil, the soil enzyme activity and the soil microbial community. Analyzing the physicochemical properties, enzyme activity and microbial community of the rhizosphere soil among different species of deciduous fruit trees in northern China is significantly beneficial in clarifying the differences in the rhizosphere environment among different species of fruit trees; this analysis can facilitate the development of specialized fruit tree fertilizers tailored to these characteristics to meet the fruit trees’ demand for nutrients, increasing fruit production and achieving sustainable agricultural development. In this study, we examined the soil physicochemical properties, enzyme activity, CLPP (community level physiological profile) and microbial structure diversity based on tree species. The results showed that the content of soil available minerals, the pH, the soil enzyme activity, the microbial community utilization of six types of carbon substrates and the microbial structure diversity in the rhizosphere were significantly different among the deciduous fruit trees. An RDA (redundancy analysis) showed that the soil pH, ammonia nitrogen content and invertase activity were closely related to the soil microbial community. The Pearson correlation coefficients between the bacterial and fungal genus relative abundances and environmental factors revealed that the soil microbial utilization of the six carbon sources, nitrate nitrogen content, and invertase activity were negatively correlated with Ambiguous and Alternaria; however, they were positively correlated with pH. The ammonia nitrogen content was positively correlated with carbon source utilization and negatively correlated with Ambiguous, Lysobacter, Nitrospira, Alternaria, Fusarium and Colletotrichum. Invertase was positively correlated with carbohydrates, carboxylic acids, amino acids, amines and organic matter content. Interestingly, it was closely related to the fungal community; positively correlated with Mortierella, Geomyces, Lysobacter, and Chaetomium; and negatively correlated with Alternaria, Fusarium and Colletotrichum. In addition, Ambiguous had the most significantly negative correlation with microbial carbon utilization. Hence, the soil physicochemical properties, enzyme activity and microbial community were significantly affected by tree species. Additionally, a variety of environmental factors was closely related to the microbial community in the rhizosphere soil of eight species of deciduous fruit trees.

Earthworms have shown their effectiveness in reducing the abundances of antibiotic resistance genes (ARGs) from solid waste. However, the mechanisms of the reduced ARGs by earthworm and whether the solid waste would affect the ARGs profile in earthworm gut were poorly understood. Herein, the patterns of ARGs and microbial communities in digested sludge-amended soil and earthworm gut after 80-day cultivation were investigated. Results show that the enrichment of ARGs (e.g., tetA, tetQ, and sulII) in soil caused by digested sludge-amendment was temporary and would recover to their original levels before amendment. In addition, earthworms could contribute to the further reduction of ARG abundances, which was mainly attributed to their gut digestion via shifting the microbial community (e.g., attenuating the anaerobes). However, the amended soil could significantly increase ARGs abundance in the earthworm gut, which may enhance the potential risk of ARGs spread via the food chain. These findings may provide a new sight on the control of ARGs occurrence and dissemination in sludge-amended soil ecosystem with consideration of earthworms.

The spatial and temporal variations and sources of polychlorinated biphenyls (PCBs) in sediment of tidal flat from Haizhou Bay, China were investigated. PCBs concentrations in surface sediments ranged from 1.33 to 6.27ngg(-1) dry weight. Low-chlorinated PCBs, dominated by the tri-PCB homologs, were identified as the prevalent contaminate of surface sediments. These results were in agreement with the fact that tri-PCB homologs are the dominant contaminants in China. In surface sediment, the highest level appeared in the estuary, and it decreased with distance from the Linhong River estuary. PCBs concentrations started to rise from the mid-1950s, and reached a maximum in 2005. PCBs in sediment might originate from surface runoff and discharges of local source as well as slight atmospheric deposition, based on PCA. Additionally, the PCBs levels in the sediments were considered to rarely pose hazard to the aquatic and human health, based on Sediment Quality Guidelines (SQGs).

Excitonic effects, originating from the interactions between charge carriers, influence and even dominate the photoresponsive properties of low-dimensional materials. For efficient carrier-related photoresponse, it is imperative to develop appropriate strategies to promote exciton dissociation in these systems. Herein, by taking black phosphorus nanosheets/poly(3-hexylthiophene) (BP/P3HT) as a prototype, we propose that the construction of a heterojunction with a certain band alignment and transport property can facilitate exciton dissociation into free carriers. Analyses on band structures and carrier kinetics confirmed the directional injection of holes from BP to P3HT and the excellent transport property associated with the injected holes in P3HT. Benefiting from these features, the BP/P3HT heterojunction yielded a high photocurrent on–off ratio of ∼18.3, contrasting with the much lower values in pristine BP nanosheets and P3HT. This work provides a feasible scenario for exciton regulation via constructing a heterojunction and establishes an in-depth understanding of exciton dissociation in photoresponsive properties.

ADVERTISEMENT RETURN TO ISSUEPREVAddition/CorrectionNEXTORIGINAL ARTICLEThis notice is a correctionCorrection to "Oxygen-Vacancy-Mediated Exciton Dissociation in BiOBr for Boosting Charge-Carrier-Involved Molecular Oxygen Activation"Hui WangHui WangMore by Hui Wang, Dingyu YongDingyu YongMore by Dingyu Yong, Shichuan ChenShichuan ChenMore by Shichuan Chen, Shenlong JiangShenlong JiangMore by Shenlong Jiang, Xiaodong Zhang*Xiaodong ZhangMore by Xiaodong Zhanghttp://orcid.org/0000-0002-8288-035X, Wei ShaoWei ShaoMore by Wei Shao, Qun Zhang*Qun ZhangMore by Qun Zhanghttp://orcid.org/0000-0002-5777-9276, Wensheng YanWensheng YanMore by Wensheng Yan, Bicai PanBicai PanMore by Bicai Panhttp://orcid.org/0000-0002-5128-7860, and Yi Xie*Yi XieMore by Yi Xiehttp://orcid.org/0000-0002-1416-5557Cite this: J. Am. Chem. Soc. 2018, 140, 15, 5320Publication Date (Web):April 9, 2018Publication History Published online9 April 2018Published inissue 18 April 2018https://doi.org/10.1021/jacs.8b03587Copyright © 2018 American Chemical SocietyRIGHTS & PERMISSIONSArticle Views3131Altmetric-Citations12LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (428 KB) Get e-Alerts Get e-Alerts

The oxygen evolution reaction (OER) occurs at the anode in numerous electrochemical reactions and plays an important role due to the nature of proton-coupled electron transfer. However, the high voltage requirement and low stability of the OER dramatically limits the total energy converting efficiency. Recently, electrocatalysts based on multi-metal oxyhydroxides have been reported as excellent substitutes for commercial noble metal catalysts due to their outstanding OER activities. However, normal synthesis routes lead to either the encapsulation of excessively active sites or aggregation during the electrolysis. To this end, we design a novel core-shell structure integrating CoMoO4 as support frameworks covered with two-dimensional γ-FeOOH nanosheets on the surface. By involving CoMoO4, the electrochemically active surface area is significantly enhanced. Additionally, Co atoms immerge into the γ-FeOOH nanosheet, tuning its electronic structure and providing additional active sites. More importantly, the catalysts exhibit excellent OER catalytic performance, reducing overpotentials to merely 243.1 mV a versus 10 mA cm-2. The current strategy contributes to advancing the frontiers of new types of OER electrocatalysts by applying a proper support as a multi-functional platform.

MicrobiologyOpenVolume 5, Issue 4 p. 604-615 Original ResearchOpen Access Response of enzyme activities and microbial communities to soil amendment with sugar alcohols Huili Yu, Huili Yu Zhengzhou Fruit Research Institute, Chinese Academy of Agricultural Sciences, Zhengzhou, Henan, 450000 ChinaSearch for more papers by this authorPeng Si, Corresponding Author Peng Si Zhengzhou Fruit Research Institute, Chinese Academy of Agricultural Sciences, Zhengzhou, Henan, 450000 China Correspondence Peng Si, Zhengzhou Fruit Research Institute, Chinese Academy of Agricultural Sciences, Zhengzhou, Henan 450000, China. Tel: 86-371-65330985; Fax: 86-371-65330987; E-mail: sipeng@caas.cnSearch for more papers by this authorWei Shao, Wei Shao Zhengzhou Fruit Research Institute, Chinese Academy of Agricultural Sciences, Zhengzhou, Henan, 450000 ChinaSearch for more papers by this authorXiansheng Qiao, Xiansheng Qiao Zhengzhou Fruit Research Institute, Chinese Academy of Agricultural Sciences, Zhengzhou, Henan, 450000 ChinaSearch for more papers by this authorXiaojing Yang, Xiaojing Yang Zhengzhou Fruit Research Institute, Chinese Academy of Agricultural Sciences, Zhengzhou, Henan, 450000 ChinaSearch for more papers by this authorDengtao Gao, Dengtao Gao Zhengzhou Fruit Research Institute, Chinese Academy of Agricultural Sciences, Zhengzhou, Henan, 450000 ChinaSearch for more papers by this authorZhiqiang Wang, Zhiqiang Wang Zhengzhou Fruit Research Institute, Chinese Academy of Agricultural Sciences, Zhengzhou, Henan, 450000 ChinaSearch for more papers by this author Huili Yu, Huili Yu Zhengzhou Fruit Research Institute, Chinese Academy of Agricultural Sciences, Zhengzhou, Henan, 450000 ChinaSearch for more papers by this authorPeng Si, Corresponding Author Peng Si Zhengzhou Fruit Research Institute, Chinese Academy of Agricultural Sciences, Zhengzhou, Henan, 450000 China Correspondence Peng Si, Zhengzhou Fruit Research Institute, Chinese Academy of Agricultural Sciences, Zhengzhou, Henan 450000, China. Tel: 86-371-65330985; Fax: 86-371-65330987; E-mail: sipeng@caas.cnSearch for more papers by this authorWei Shao, Wei Shao Zhengzhou Fruit Research Institute, Chinese Academy of Agricultural Sciences, Zhengzhou, Henan, 450000 ChinaSearch for more papers by this authorXiansheng Qiao, Xiansheng Qiao Zhengzhou Fruit Research Institute, Chinese Academy of Agricultural Sciences, Zhengzhou, Henan, 450000 ChinaSearch for more papers by this authorXiaojing Yang, Xiaojing Yang Zhengzhou Fruit Research Institute, Chinese Academy of Agricultural Sciences, Zhengzhou, Henan, 450000 ChinaSearch for more papers by this authorDengtao Gao, Dengtao Gao Zhengzhou Fruit Research Institute, Chinese Academy of Agricultural Sciences, Zhengzhou, Henan, 450000 ChinaSearch for more papers by this authorZhiqiang Wang, Zhiqiang Wang Zhengzhou Fruit Research Institute, Chinese Academy of Agricultural Sciences, Zhengzhou, Henan, 450000 ChinaSearch for more papers by this author https://doi.org/10.1002/mbo3.355Citations: 16AboutSectionsPDF ToolsExport citationAdd to favoritesTrack citationReprints ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinkedInRedditWechat Graphical Abstract Our analysis of changes in microbial functional diversity and soil enzyme activities identified different susceptibilities to sorbitol and mannitol, revealing selective pressure on the function of the soil microbial community during the cultivable period. Summary Changes in microbial community structure are widely known to occur after soil amendment with low-molecular-weight organic compounds; however, there is little information on concurrent changes in soil microbial functional diversity and enzyme activities, especially following sorbitol and mannitol amendment. Soil microbial functional diversity and enzyme activities can be impacted by sorbitol and mannitol, which in turn can alter soil fertility and quality. The objective of this study was to investigate the effects of sorbitol and mannitol addition on microbial functional diversity and enzyme activities. The results demonstrated that sorbitol and mannitol addition altered the soil microbial community structure and improved enzyme activities. Specifically, the addition of sorbitol enhanced the community-level physiological profile (CLPP) compared with the control, whereas the CLPP was significantly inhibited by the addition of mannitol. The results of a varimax rotated component matrix demonstrated that carbohydrates, polymers, and carboxylic acids affected the soil microbial functional structure. Additionally, we found that enzyme activities were affected by both the concentration and type of inputs. In the presence of high concentrations of sorbitol, the urease, catalase, alkaline phosphatase, β-glucosidase, and N-acetyl-β-d-glucosaminidase activities were significantly increased, while invertase activity was decreased. Similarly, this increase in invertase, catalase, and alkaline phosphatase and N-acetyl-β-d-glucosaminidase activities was especially evident after mannitol addition, and urease activity was only slightly affected. In contrast, β-glucosidase activity was suppressed at the highest concentration. These results indicate that microbial community diversity and enzyme activities are significantly affected by soil amendment with sorbitol and mannitol. Introduction Amending soil with low-molecular-weight organic compounds, such as amino acids, sugars, and carboxylates can stimulate increases in carbon mineralization, microbial biomass, and the number of culturable bacteria (Nakatsu et al. 2005; Raffa et al. 2005; Chaparro et al. 2013). Broadly, these compounds are associated with root exudation, plant residues, and soil fauna excretes and may be utilized by soil microorganisms and affect the quality of the microbial community. Hopkins et al. (2008) found that soil respiration responded positively to both glucose and NH4Cl additions, along with associated changes in soil microbial community structure. Glucose addition has consistently been shown to cause significant shifts in microbial community structure (Falchini et al. 2003; Hoyle et al. 2008; Dungait et al. 2011), and oxalic acid supplementation has been shown to have similar effects (Landi et al. 2006). The addition of phenol and oxalate led to enhanced degradation of soil organic matter as compared to glucose and glutamate addition (Brant et al. 2006). Sugar alcohols, such as sorbitol and mannitol, are produced by microorganisms and plants, can be present at levels of 0.33 and 0.8 μg·g−1, respectively, in olive tree rhizospheric soil, and in trace amounts in soil (Roser et al. 1994; Mechri et al. 2015), and can serve as carbohydrate reserves, storage of reducing power, translocatory compounds, and osmoprotectants (Wisselink et al. 2002; Akinterinwa et al. 2008; Liebeke et al. 2009). Additionally, sugar alcohols enhance the growth of plants, fungi, yeasts, and bacteria under stress (Stoop et al. 1996; Chaturvedi et al. 1997; Ichimura et al. 2016). However, until now, there have been no investigations of the effects of soil amendment with sugar alcohols on soil microbial functional diversity and enzyme activities. Soil microorganisms are crucial to many ecosystem processes, promoting plant growth, nutrient cycling, soil structure, and energy flow. These functions are of great importance to the productivity of agricultural soils (Juarez et al. 2013). Yet, soil microorganisms are very sensitive to any ecosystem disturbance that rapidly alters community diversity and activity (Vallejo et al. 2010; Berthrong et al. 2013; Ouni et al. 2013). Soil microbial community properties, particularly those related to diversity and functional activity, can serve as useful predictors of the impact of substrate amendment on soil quality. (Kızılkaya et al. 2004; Wu et al. 2014). Soil amendment with low-molecular-weight organic substances can change microbial activity (including microbial biomass C and metabolic quotient, qCO2) (Steinbeiss et al. 2009; Fischer et al. 2010; An et al. 2015) and community structure. These effects have been investigated in a number of studies using molecular profiling or similar methods, such as 13C tracer (Maxfield et al. 2012; Juarez et al. 2013), denaturing gradient gel electrophoresis (DGGE; Tortella et al. 2013), phospholipids fatty acid analysis (PLFA; Dungait et al. 2011; Ai et al. 2015), and quantitative PCR (qPCR; Schauss et al. 2009). Broadly, functional diversity is the representation of various aspects of overall soil microbial diversity. The Biolog-Eco method is a useful tool to evaluate disturbances in soil microbial functional diversity and community due to different stresses (Lupwayi et al. 2009; Wang et al. 2010), and is thought to be one of the quickest and most effective methods available (Staddon et al. 1997). In addition, the activities of soil enzymes are sensitive indicators of the functional diversity of soil microbial communities due to their roles in soil biology (Tian and Shi 2014; Zaccardelli et al. 2013; Bending et al. 2002). Moreover, Unlike the Biolog-Eco method, which relies on the activities of those species that have adapted to rapid growth on simple substrates, soil enzyme activity is cultivated independently and to some extent represents the functioning of the entire microbial community. To date, few studies of the microbial effects of sugar alcohol amendments have employed both methods. Therefore, we utilized a combination of these two methods to compare functional changes induced by soil amendment with sugar alcohols. The objective of this study was to analyze community-level physiological profile (CLPP) using the Biolog-Eco method and enzymatic activities to identify and quantify specific effects of sugar alcohols on soil microbial functional diversity. These results will improve our understanding of the influence of sugar alcohols on soil fertility and quality. Experimental Procedures Experimental design Soil (top 0–25 cm) was collected from the experimental plots of the Zhengzhou Fruit Research Institute, CAAS. The field had not been planted with crops in the last 5 years. The soil was classified as a silty loam, and its properties were as follows: 7.0 g organic matter/kg soil, 47.15 mg available P/kg soil, 127.2 mg available K/kg soil, 10.64 mg NH4+-N/kg soil, 4.17 mg NO3−N/kg soil, and pH 7.62. Mannitol and sorbitol were not detected according to the method previously described by Mechri et al. (2015). After collection, the soil was homogenized, air-dried for 48 h, sieved with a 2-mm mesh to remove any plant tissue, grit, and soil animals, and then used for the experiments described below. A 60-day study was performed, and for each sugar alcohol (sorbitol and mannitol) concentration, a set of three replicate microcosms was prepared by transferring 300 g of soil (dry weight, DW) into jars. Each sample was artificially supplemented by spiking 15 mL of a sugar alcohol solution at calculated concentrations to produce final sugar alcohol concentrations of 0. 25, 0.5, and 1.0 g/kg DW soil (C0.25, C0.5, and C1, respectively). The control soil received an equivalent amount of distilled water. Each treatment was incubated at 25°C, and distilled water was added at regular intervals to maintain a water content of 60% of the maximum water holding capacity. For each microcosm, soil was taken at 60 days of incubation and stored at −20°C, as required for further analysis. Community-level physiological profiles Functional diversity of the soil microbial community was assessed using Biolog Eco Plates™ as described by Garau et al. (2007). The plate was composed of 96 wells containing a triplicate set of 31 carbon sources (ten carbohydrates, seven carboxylic acid (CA), four polymers, six amino acids, two phenolic compounds, and two amines) as well as three control wells with no carbon. Briefly, approximately 5 g of fresh soil was suspended in 50 mL of saline solution (0.85% NaCl, w/v) in a 250-mL flask. After being shaken for 30 min (300 rpm) at 25°C, the suspensions were settled for 10 min. Subsequently, each suspension was diluted 100-fold, and 150 μL of the clear supernatant was inoculated directly into the Biolog plate, which was then incubated in the dark at 25°C for 7 days. Microbial development was monitored by reading the optical density (OD) at 590 nm every 24 h using a Biolog Microstation™ reader (Biolog., Hayward, CA, USA). The data collected were expressed as the following five parameters: average well color development (AWCD) for the metabolic activity of soil bacterial community, Shannon index (H'), Simpson index (D), substrate evenness (E), and substrate richness (S) at 96 h after addition of sugar alcohols. Soil enzyme activities Invertase activity was measured according to the method previously described by Yao and Huang (2006) as follows: in a 150-mL volumetric flask, 2 g of fresh soil was mixed with 15 mL of 8% sucrose, 5 mL of phosphate buffer (pH 5.5), and 5 drops of methylbenzene, followed by incubation at 37°C for 24 h. After filtration, 1 mL of filtrate and 3 mL of 3,5-dinitrosalicylic acid (DNS) were added to react in a 50-mL centrifuge tube, followed by incubation in a boiling bath for 5 min. Finally, the solution was diluted to 100 mL, and absorbance at 508 nm was measured using a spectrophotometer. Urease activity was determined as described by Yao and Huang (2006). Briefly, 5 g of soil and 1 mL of methylbenzene were added to a 150-mL conical flask. After 15 min, 10 mL of 10% urea and 20 mL of citrate buffer (pH 6.7) were mixed with the soil sample and then incubated at 37°C for 24 h. After filtration, 3 mL of filtrate was added to a 50-mL volumetric flask and mixed with 4 mL of sodium phenoxide and 3 mL of sodium hypochlorite. After dilution to 50 mL and within 1 h, the absorbance at 578 nm was measured using a spectrophotometer. Catalase activity was measured according to Li et al. (2008). Briefly, in a 150-mL conical flask, 2 g of soil and 40 mL of distilled water were mixed with 5 mL of 0.3% H2O2. The flask was then sealed and shaken at 120 rpm for 20 min. To terminate the reaction, 5 mL of 1.5 mol/L H2SO4 was added to the flask. After filtration, 25 mL of filtrate was titrated with KMnO4. Alkaline phosphatase activity was measured according to the method previously described by Guan (1986). Briefly, 2 g of soil was mixed with 20 mL of borate saline buffer (pH 9.6) and five drops of methylbenzene in a 150-mL conical flask, and the mixture was incubated at 37°C for 24 h. Then, 40 mL of 3% aluminum sulfate solution was added to the flask. After filtration, 3 mL of filtrate and four drops of 2,6-dibromoquinone-4-chloroimide were transferred to a 50-mL volumetric flask and then diluted to 50 mL. The absorbance at 660 nm was determined using a spectrophotometer. β-Glucosidase activity was measured according to the method previously described by Eivazi and Tabatabai (1988). Briefly, 1 g of soil was weighed into 50-mL glass vials, and 4 mL of phosphate buffer (pH = 6.0) and 1 mL of substrate (p-nitrophenyl-β-d-glucopyranoside) were added. The soil sample was then mixed thoroughly and incubated at 37°C for 1 h, after which 1 mL of 0.5-mol/L CaCl2 and 4 mL Tris buffer (pH 12) were added. The resulting suspensions were filtered immediately and the absorbance at 400 nm was measured using a spectrophotometer. N-acetyl-β-d-glucosaminidase activity was assayed using the method described by Ekenler and Tabatabai (2002). Briefly, 1 g of soil was weighed into 50-mL glass vials, treated with 4 mL of 0.1 mol/L acetate buffer (pH 5.5) and 1 mL of 10-mmol/L p-nitrophenyl-N-acetyl-β-d-glucosaminide as a substrate. The flask was stoppered, swirled to mix the contents, and incubated at 37°C. After 1 h of incubation, 1 mL of 0.5-mol/L CaCl2 and 4 mL of 0.5-mol/L NaOH were added to stop the reaction. The samples were filtered and the color intensity of the filtrate at 405 nm was measured using a spectrophotometer. Data analysis The values in the figures and tables correspond to the average of triplicate data ± standard error (SE). The significance of differences between concentrations was tested by one-way ANOVA using SPSS ver. 17 software (SPSS Inc., Chicago, IL, USA). Varimax rotated component matrix of carbon sources was conducted using SPSS ver. 17. Principal component analysis (PCA) of soil microbial CLPPs was performed with the Canoco software ver. 4.5 (Biometris., Wageningen, The Netherlands). Enzyme activities were calculated and the AWCD growth curve generated using SigmaPlot ver. 10 software (Systat Software Inc., San Jose, CA, USA). Results Sugar alcohols affect CLPPs Average well color development (AWCD) was used as an indicator of soil microbial activity. Variation in AWCD with incubation time and addition of sugar alcohols was evaluated (Fig. 1). AWCD of the soil was almost zero after the first 24-h incubation period, but gradually increased with incubation time. The addition of sorbitol caused an obvious increase in AWCD as compared to the control (Fig. 1A). In particular, the highest sorbitol concentration condition (C1) had the higher carbon utilization rate compared to other concentrations. However, as mannitol concentrations increased, the AWCD of all samples decreased; particularly, when the concentration of mannitol was 1.0 g/kg (C1), AWCD dropped to near zero during the incubation (Fig. 1B). The distinct AWCD decrease with mannitol addition revealed that mannitol has a suppressive effect on AWCD. Figure 1Open in figure viewerPowerPoint Variation in the average well color development of substrate utilization profiles of soil treated with (A) sorbitol and (B) mannitol. C0.25, C0.5, and C1 represent concentrations of 0.25, 0.5, and 1.0 g/kg dry weight soil after addition of sorbitol and mannitol, respectively. Vertical bars represent the standard error. The effects of different concentrations of sugar alcohols on microbial functional diversity, as reflected by the Shannon diversity index, Simpson index, and substrate evenness and richness, were evaluated (Table 1). The Shannon diversity and Simpson indices of soils following sorbitol addition were slightly higher than the control, indicating few significant differences among the treatments. However, the Shannon diversity and Simpson indices of soils following mannitol addition (C1) were significantly lower than those for other treatments. Conversely, the substrate evenness for mannitol (C1) amendment showed a dramatic increase that was significantly higher than that with other treatments, whereas no significant differences were observed between the control and sorbitol. The substrate richness in the sorbitol addition treatments was higher than that for the control. Moreover, the increase was significantly higher with C1 treatment. Although the substrate richness was found to be significantly lower in mannitol treatment relative to the control, differences were also observed among different concentrations of the mannitol treatment. Table 1. Shannon diversity index (H'), Simpson index (D), Substrate evenness (E), and Substrate richness (S) of the microbial functional diversity in sandy soils in relation to sugar alcohol treatment at 96 h after addition of sugar alcohols Treatment Shannon diversity index (H') Simpson index (D) Substrate evenness (E) Substrate richness (S) Control 2.73 ± 0.08ab 0.92 ± 0.01ab 1.05 ± 0.01b 13.67 ± 1.2abc Sorbitol C0.25 2.85 ± 0.08a 0.93 ± 0.01ab 1.02 ± 0.01b 16.67 ± 1.45ab C0.5 2.84 ± 0.02a 0.93 ± 0ab 1.00 ± 0.01b 17.33 ± 0.88ab C1 3.04 ± 0.03a 0.94 ± 0a 1.02 ± 0.01b 19.67 ± 0.33a Mannitol C0.25 2.58 ± 0.22abc 0.90 ± 0.02ab 1.04 ± 0.04b 13.33 ± 3.28bc C0.5 2.31 ± 0.32bc 0.86 ± 0.05bc 1.15 ± 0.07b 8.67 ± 2.91 cd C1 2.16 ± 0.06c 0.81 ± 0.03c 1.68 ± 0.22a 3.00 ± 1.15d Data represent the mean of three replicates ± standard error. Different letters indicate significant difference within a column (P < 0.05). The use of six types of substrates (carbohydrates, amino acids, polymers, amines, phenolic compounds, and CAs) with sugar alcohol supplementation is listed in Table 2. Addition of sorbitol had positive effect on utilization of the substrate categories. Compared to the control, C0.5 and C1 significantly increased utilization of CAs by 112% and 128%, respectively. There was no significant difference in the utilization of substrates between mannitol addition and the control, except for C0.25 using amino acids. Table 2. Average optical density of six types of substrates at 96 h after addition of sugar alcohols for 60 days Treatment Carbohydrates Amino acids Carboxylic acids Polymers Amines Phenolic compounds Control 0.35 ± 0.04a 0.35 ± 0.01bc 0.25 ± 0.02bc 0.51 ± 0.14ab 0.02 ± 0.02a 0.29 ± 0.12ab Sorbitol C0.25 0.35 ± 0.03a 0.57 ± 0.12ab 0.34 ± 0.08b 0.6 ± 0.06a 0.06 ± 0.03a 0.20 ± 0.03ab C0.5 0.39 ± 0.02a 0.38 ± 0.04abc 0.53 ± 0.04a 0.4 ± 0.03ab 0.05 ± 0.03a 0.48 ± 0.13a C1 0.41 ± 0.02a 0.52 ± 0.03ab 0.63 ± 0.05a 0.39 ± 0.02ab 0.08 ± 0.07a 0.35 ± 0.05a Mannitol C0.25 0.30 ± 0.08a 0.6 ± 0.1a 0.33 ± 0.04b 0.43 ± 0.07ab 0.00 ± 0a 0.37 ± 0.13a C0.5 0.41 ± 0.05a 0.23 ± 0.08c 0.29 ± 0.09b 0.31 ± 0.06b 0.02 ± 0.01a 0.05 ± 0.02b C1 0.09 ± 0.05b 0.2 ± 0.07c 0.10 ± 0.04c 0.05 ± 0.03c 0.01 ± 0.01a 0.01 ± 0.00b Different letters indicate significant differences within a column (P < 0.05). Data represent the mean of three replicates ± standard error. Principal component analysis (PCA) of soil microbial CLPP revealed that addition of sugar alcohols changed the soil microbial community functional structure (Fig. 2). Applying PCA, we identified two principle components (PC1 and PC2) that accounted for 51.0% and 21.4% of the variation, respectively. PC1 and PC2 were plotted (Fig. 2), together accounting for 72.4% of the total variance. The principle component plot of the treatments showed clear separation, with the differences along the PC1 axis caused by sugar alcohols being larger than those along the PC2 axis. The substrate utilization patterns from medium and highest concentrations of mannitol amendment (C0.5 and C1) were located at the positive end of the PC1 axis, whereas most other treatments were located at the negative end. Moreover, the effects of medium and highest concentrations (C0.5 and C1) of sorbitol amendment were clearly different from the control along the PC2 axis. Meanwhile, the rotated component matrix (Table 3) identified the types of carbon sources with high loading (>0.75) for PC1 and PC2 as carbohydrates (CH), polymers (PM), and CA, along with sorbitol and mannitol (Yin et al. 2014; Dong et al. 2013). Figure 2Open in figure viewerPowerPoint Principal component analysis of the soil microbial community-level physiological profiles of the soils treated with sorbitol and mannitol. Triangle represents sorbitol treatment; diamond represents mannitol treatment; circle represents control. Table 3. Varimax rotated component matrix of carbon sources Carbon sources Sort PC1 PC2 β-Methyl-d-Glucoside CH 0.85 −0.18 d-Galactonic Acid γ-Lactone CH 0.46 0.53 d-Xylose CH 0.57 0.59 i-Erythritol CH 0.91 −0.15 d-Mannose CH 0.33 0.53 N-Acetyl-d-Glucosamine CH 0.93 0.18 d-Cellobiose CH 0.85 −0.19 Glucose-1-Phosphate CH 0.69 0.71 α-d-Lactose CH 0.90 −0.25 d,l- α-Glycerol CH −0.51 0.84 l-Arginine AA 0.57 −0.55 l-Asparagine AA 0.76 −0.53 l-Phenylalanine AA 0.72 −0.41 l-Serine AA 0.42 0.06 l-Threonine AA 0.80 0.11 Glycyl-l-Glutamic Acid AA −0.34 0.86 Pyruvic Acid Methyl Ester CA 0.89 −0.19 d-Galacturonic Acid CA 0.56 0.13 γ-Hydroxybutyric Acid CA −0.31 0.88 d-Glucosaminic Acid CA 0.58 0.26 Itaconic Acid CA 0.94 −0.80 α-Ketobutyric Acid CA 0.84 0.46 d-Malic Acid CA 0.49 0.66 Tween 40 PM 0.90 0.04 Tween 80 PM 0.76 −0.31 α-Cyclodextrin PM 0.11 −0.31 Glycogen PM 0.75 −0.15 Phenylethyl-amine AN 0.31 0.91 Putrescine AN 0.62 0.14 2-Hydroxy Benzoic Acid PC 0.14 0.45 4-Hydroxy Benzoic PC 0.71 0.54 CH, carbohydrates; AA, amino acids; CA, carboxylic acids; PM, polymers; AN, amines; PC, phenolic compounds. Effects of sugar alcohols on soil enzyme activities The activities at 60 days of incubation were determined in the control and sugar- alcohol-treated soils (Fig. 3). Invertase activity increased after the addition of sugar alcohols (Fig. 3A). However, invertase activity in sorbitol-treated samples was slightly higher than that in the control, but no significant differences were found between the concentrations evaluated. Mannitol addition increased invertase activity significantly compared to the control. Figure 3Open in figure viewerPowerPoint Soil enzyme activities of sorbitol- and mannitol-treated soils. Soil (A) invertase, (B) calatase, (C) alkaline phosphatase, (D) urease, (E) β-glucosidase and (F) N-acetyl-β-d-glucosaminidase activities. Values are mean ± SE, and letters denote significant differences among sugar alcohol concentrations (P < 0.05). The addition of sugar alcohols also caused significant effects on catalase activity (Fig. 3B). The average catalase activity in sorbitol and mannitol treatments increased by 44.44% and 36.78%, respectively, with maximum, significantly increased values of 56.85% and 53.75% at the highest concentration (C1), respectively. Furthermore, catalase stimulation was dependent on the sugar alcohol concentration, with the greatest stimulation during sorbitol and mannitol treatments observed at the highest treatment concentrations. Similar to catalase activity, the activity of alkaline phosphatase was positively affected during treatments with sugar alcohols (Fig. 3C). When compared with the control, sorbitol and mannitol treatments on average increased alkaline phosphatase activity by 26.42% and 59.93%, respectively. The most pronounced increase in catalase activity in the sorbitol and mannitol treatments was observed primarily at the highest concentrations. Moreover, there were significant differences between the treatments and control. The urease activity in the sorbitol-treated samples was higher than that in the control, indicating that urease activity was stimulated by sorbitol addition (Fig. 3D). Moreover, the maximum urease activity occurred at the highest sorbitol concentrations, suggesting that stimulation was more pronounced at the highest sorbitol concentrations. However, urease activity was scarcely influenced by mannitol addition. β-Glucosidase activity was affected to some extent by sugar alcohols (Fig. 3E). When compared with the control, the β-glucosidase activity in the sorbitol-treated samples increased significantly by 16.37% and 28.84% at the medium and highest concentrations, respectively. However, compared with the control, addition of the highest concentration of mannitol significantly inhibited β-glucosidase activity. The addition of sugar alcohols exerted positive effects on N-acetyl-β-d-glucosaminidase activity (Fig. 3F). Compared with the control, treatment with the highest concentration of sorbitol significantly increased N-acetyl-β-d-glucosaminidase activity by 17.12%. The greatest increase in N-acetyl-β-d-glucosaminidase activity occurred following addition of the medium concentration of mannitol. The correlation analysis (Table 4) showed that CAE, ALP, and URE activities were positively correlated with AWCD, S, and CA. There were also significant positive correlations of INE with S following sorbitol treatment. However, INE activities were negatively correlated with AWCD, H, D, S, and CH, and CAE was negatively correlated with S, PM, and PC after mannitol treatment. Table 4. Correlation of enzyme activities with CLPP and carbon sources Sorbitol Mannitol INE CAE ALP URE GLU NAG INE CAE ALP URE GLU NAG AWCD 0.494 0.776a 0.632b 0.593b 0.407 −0.713a −0.630b −0.566 −0.386 −0.402 0.303 0.655b H 0.484 0.712a 0.555 0.546 0.342 −0.690b −0.577b −0.498 −0.482 −0.512 0.174 0.546 D 0.356 0.717a 0.527 0.406 0.507 −0.655b −0.612b −0.565 −0.508 −0.527 0.263 0.648b S 0.596a 0.816a 0.657a 0.584b 0.427 −0.643b −0.667b −0.637b −0.5 −0.348 0.274 0.657b E −0.515 −0.61 0.548 −0.34 −0.478 0.175 0.676b 0.695b 0.426 0.167 −0.423 −0.792a CH 0.055 0.51 0.43 0.332 0.221 −0.643b −0.668b −0.396 −0.276 −0.466 0.507 0.725a AA 0.284 0.406 0.242 0.212 0.354 −0.533 −0.24 −0.445 −0.153 0.124 0.114 0.235 PM −0.356 −0.378 −0.368 −0.169 −0.086 0.142 −0.722a −0.77a −0.538 −0.097 0.292 0.781a AN 0.023 0.365 0.44 0.227 0.343 −0.376 −0.198 −0.014 −0.095 −0.15 0.21 0.085 PC 0.41 0.224 0.281 0.026 0.257 0.177 −0.377 −0.581b −0.478 −0.16 0.111 0.315 CA 0.379 0.839a 0.826a 0.687b 0.446 −0.525 0.748a 0.822a 0.734a 0.1 −0.081 −0.638b Enzyme activities: INE, invertase; CAE, catalase; ALP, alkaline phosphatase; URE, urease; GLU, β-glucosidase; NAG, N-acetyl-β-d-glucosaminidase. a Correlation is significant at the 0.01 level. b Correlation is significant at the 0.05 level. Discussion Soil amendment with organic substances is a major driving force for changes in soil microbial community composition (Ai et al. 2012; Bowles et al. 2014), and these change

Abstract As the properties of ultrathin two‐dimensional (2D) crystals are strongly related to their electronic structures, more and more attempts were carried out to tune their electronic structures to meet the high standards for the construction of next‐generation smart electronics. Herein, for the first time, we show that the conductive nature of layered ternary chalcogenide with formula of Cu 2 WS 4 can be switched from semiconducting to metallic by hydrogen incorporation, accompanied by a high increase in electrical conductivity. In detail, the room‐temperature electrical conductivity of hydrogenated‐Cu 2 WS 4 nanosheet film was almost 10 10 times higher than that of pristine bulk sample with a value of about 2.9×10 4 S m −1 , which is among the best values for conductive 2D nanosheets. In addition, the metallicity in the hydrogenated‐Cu 2 WS 4 is robust and can be retained under high‐temperature treatment. The fabricated all‐solid‐state flexible supercapacitor based on the hydrogenated‐Cu 2 WS 4 nanosheet film shows promising electrochemical performances with capacitance of 583.3 F cm −3 at a current density of 0.31 A cm −3 . This work not only offers a prototype material for the study of electronic structure regulation in 2D crystals, but also paves the way in searching for highly conductive electrodes.

<h2>Abstract</h2> The direct synthesis of dimethyl carbonate (DMC) from CO₂ possesses both theoretical and practical value, deserving attention in the pursuit of minimizing CO₂ emissions and securing carbon neutrality. In this review, we summarize the recent progress in the chemical fixing of CO₂ into DMC, including the advantages and disadvantages of various catalytic routes, and the design of active sites, such as Lewis acid-base sites, for promoted activity and selectivity. We also highlight the disclosure of catalytic processes by <i>in situ</i> characterization and theoretical studies and discuss the structure–activity correlations of catalysts. We end this review with an outlook on the future challenges and opportunities in CO₂ chemical fixation into DMC.

OER reaction is a key process in water electrolysis systems, while it’s extremely challenging to develop the cheap and highly active OER electrocatalysts with earth-abundant material through facile methods. Here, FeCo oxides and its fluorides were prepared using one-step synthesis at room temperature and fluorination with fluorine gas. The OER performance of Fe, Co, and FeCo oxides was compared, and investigated the effect of fluorine doping on their physical properties and OER performance. The results showed that the overpotential of FeCo-O bimetallic oxide was 370 mV in alkaline electrolyte at a current density of 10 mA/cm2, which was much better than that of monometallic Fe-O (1 V) and Co-O (467 mV) OER performance. The fluorine modification of the three materials significantly improved their OER performance of (Fe-OF (570 mV), Co-OF (330 mV) and FeCo-OF (285 mV)), in which, FeCo-OF, in a continuous OER test for 12 h, showed a stable lower overpotential value than that of commercial RuO2 (289 mV). Electrochemical analysis and spectral characterization indicated that with the help of fluorine ion electronic regulation, the spent catalyst FeCo-OF can provide efficient electrocatalytic active sites after in situ self-reconstruction, and thus showed stable and excellent OER performance. DFT calculations showed that the modification of bimetallic oxides by fluorine could reduce the O⁎ Gibbs free energy from 4.86 to 2.44 eV, and thus promote the OER reaction kinetics.

Abstract Traumatic brain injury (TBI) is recognised as a leading cause of disability and death. As such, timely and effective secondary brain injury intervention is crucial, given its potential to enhance the prognosis of TBI. Oxidative stress represents one of the factors that contribute to post-traumatic secondary cognitive impairment. Reducing post-traumatic oxidative stress can effectively enhance cognitive function. PGAM5, a member of the phosphoglycerate transporter enzyme family, is upregulated in TBI and induces mitochondrial autophagy. This exacerbates the damage further after TBI. Our focus is on the recently discovered small molecule drug, LFHP-1c, a novel PGAM5 inhibitor. The investigation utilized an in vivo model incorporating a controlled cortical impact-induced traumatic brain injury in mice to examine the impact of LFHP-1c on oxidative stress and cognitive function. The primary aim was to discern the influence of LFHP-1c on the PGAM5-KEAP1-NRF2 ternary complex within the TBI context. Our data indicates that LFHP-1c suppresses PGAM5 expression and diminishes the development of the PGAM5-KEAP1-NRF2 ternary complex, prompting the discharge of NRF2 and KEAP1. The occurrence subsequently allowed NRF2 to enter the nucleus following a traumatic brain injury, thereby resulting in amplified expression of HO-1, GPX1 and SOD1. Furthermore, LFHP-1c diminishes the accumulation of external mitochondria in the nucleus, which limits oxidative stress and improves cognitive capability after TBI.

The recognition of pathogen effectors through the nucleotide-binding leucine-rich repeat receptor (NLR) family is an important component of plant immunity. In addition to typical domains such as TIR, CC, NBS, and LRR, NLR proteins also contain some atypical integrated domains (IDs), the roles of which are rarely investigated. Here, we carefully screened the soybean (Glycine max) genome and identified the IDs that appeared in the soybean TNL-like proteins. Our results show that multiple IDs (36) are widely present in soybean TNL-like proteins. A total of 27 Gm-TNL-ID genes (soybean TNL-like gene encoding ID) were cloned and their antiviral activity towards the soybean mosaic virus (SMV)/tobacco mosaic virus (TMV) was verified. Two resistance (R) genes, SRA2 (SMV resistance gene contains AAA_22 domain) and SRZ4 (SMV resistance gene contains zf-RVT domain), were identified to possess broad-spectrum resistance characteristics towards six viruses including SMV, TMV, plum pox virus (PPV), cabbage leaf curl virus (CaLCuV), barley stripe mosaic virus (BSMV), and tobacco rattle virus (TRV). The effects of Gm-TNL-IDX (the domain of the Gm-TNL-ID gene after the TN domain) on the antiviral activity of a R protein SRC7TN (we previously reported the TN domain of the soybean broad-spectrum resistance gene SRC7) were validated, and most of Gm-TNL-IDX inhibits antiviral activity mediated by SRC7TN, possibly through intramolecular interactions. Yeast-two-hybrid (Y2H) and bimolecular fluorescence complementation (BiFC) assays showed that seven Gm-TNL-IDX interacted with SMV-component proteins. Truncation analysis on a broad-spectrum antiviral protein SRZ4 indicated that SRZ4TIR is sufficient to mediate antiviral activity against SMV. Soybean cDNA library screening on SRZ4 identified 48 interacting proteins. In summary, our results indicate that the integration of IDs in soybean is widespread and frequent. The NLR-ID toolkit we provide is expected to be valuable for elucidating the functions of atypical NLR proteins in the plant immune system and lay the foundation for the development of engineering NLR for plant-disease control in the future.

Metal-Organic Framework (MOF) membranes act as selective layers have offered unprecedented opportunities for energy-efficient and cost-effective gas separation. Searching for the green and sustainable synthesis method of dense MOF membrane has received huge attention in both academia and industry. In this work, we demonstrate an in situ electrochemical potential-induced synthesis strategy to aqueously fabricate Metal Azolate Framework-4 (MAF-4) membranes on polypropylene (PP) support. The constant potential can induce the heterogeneous nucleation and growth of MAF-4, resulting an ultrathin membrane with the thickness of only 390 nm. This high-quality membrane exhibits a high H2/CO2 separation performance with the H2 permeance as high as 1565.75 GPU and selectivity of 11.6. The deployment of this environment friendly one-step fabrication method under mild reaction conditions, such as low-cost polymer substrate, water instead of organic solvent, room temperature and ambient pressure shows great promise for the scale-up of MOF membranes.

Based on the density functional theory method, the ab initio calculation with GGA+U was performed to investigate the electronic structure and properties of W-doped TiO2. The results indicated that W-doping induced ferromagnetism and shifted the absorption spectra to visible light region. The ferromagnetism derived from the spin-split of O 2p and W 5d caused by p–d orbit hybridization. Several impurity bands under the conduction band decreased the band gap. The experiment results illustrated that the ferromagnetism had occurred and the absorption spectra had a shift to visible light region in W-doped TiO2 samples. The experiment results are consistent with the calculation ones.

The reductive capacity of microbial extracellular polymeric substances (EPS) plays important roles in environmental processes involved in heavy metal detoxification and organic contaminant degradation. However, the crucial parameter to evaluate the reductive capacity of EPS, electron donating capacity (EDC) lacks a quantitative approach. In this study, a novel mediated electrochemical oxidation (MEO) method was developed to investigate the EDCs of microbial EPS extracted from Shewanella oneidensis MR-1 (S. oneidensis MR-1), Escherichia coli (E. coli) and activated sludge. The results indicate that the MEO approach rapidly and accurately quantifies the EDCs of microbial EPS. S. oneidensis MR-1 EPS possessed the highest EDC value ascribed to their specific redox proteins components. EDCs of S. oneidensis MR-1 EPS were dependent on measurement conditions and increased with growing solution pH and applied potential. EDCs of S. oneidensis MR-1 EPS were depleted gradually during the redox reaction with irreversible oxidation of EPS. The reductive property of microbial EPS was accurately evaluated by quantifying the EDCs of EPS using the MEO approach, as well as their potential in environmental remediation.

Fe2O3@CdS photocatalyst has been successfully prepared by photo-deposition of Fe2O3 on the surface of CdS. The as-synthesized samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS). The results revealed that the Fe2O3@CdS samples consisted of CdS and Fe2O3. The deposited amount of Fe2O3 has an remarkable influence on the photodegradation of tetracycline. The degradation rate of tetracycline was 94.1% under the optimized conditions. The enhanced photocatalytic activity is mainly due to the high dispersion of Fe2O3 deposited on the surface of CdS. The migration path of photocatalytic holes and electrons follows the Z-scheme heterogeneous junction mechanism, which is useful to improve the separation ability of photogenerated electrons-holes pairs. This work provides a new way to construct a photocatalyst with high photocatalytic performance for the photodegradation of tetracycline.

Malic acid is a component of the rhizosphere exudate and is vital for crop growth. However, little information is available about the effects of external applications of malic acid on the nutrient absorption and quality of grape fruit, and few studies have been performed on the relationship between the changes in the rhizosphere microbial community and nutrient absorption and fruit quality of grapes after adding malic acid. Here, the LM (low concentration of malic acid) and HM (high concentration of malic acid) treatments comprised 5% and 10% malic acid (the ratio of acid to the total weight of the fertilizer) combined with NPK fertilizer, respectively. Applying malic acid changed the grape rhizosphere microbial community structure and community-level physiological profile (CLPP) significantly, and HM had a positive effect on the utilization of substrates. The microbial community structure in the rhizosphere of the grapes with added malic acid was closely related to the CLPP. The N and P content in the leaves and fruits increased after applying malic acid compared to the control, while K content in the fruits increased significantly. In addition, malic acid significantly reduced the weight per fruit, significantly increased soluble sugar content (SSC) and vitamin C content of the fruit, and significantly improved the fruit sugar-acid ratio and grape tasting score. Moreover, the principal component analysis and grape nutrient and fruit quality scores showed that grape nutrients and fruit quality were significantly affected by malic acid and ranked as 5% malic acid > 10% malic acid > control. Pearson's correlation heatmap of microbial composition, nutrient absorption and fruit quality of the grapes showed that the grape microbial community was closely related to grape nutrients and fruit quality. Adding malic acid was positively correlated to Planococcaceae, Bacillaceae, Woeseiaceae and Rhodobacteraceae. Furthermore, Planococcaceae, Bacillaceae, Woeseiaceae and Rhodobacteraceae were closely related to grape nutrient absorption and fruit quality. Bacillaceae and Woeseiaceae were positively correlated with total soluble sugar, while Planococcaceae and Rhodobacteraceae were positively correlated with titratable acid. Hence, Bacillaceae and Woeseiaceae were the key bacteria that played a major role in grape fruit quality and nutrient absorption after applying malic acid water-soluble fertilizer.

The oxygen evolution reaction (OER) is a crucial reaction in water splitting, metal-air batteries, and other electrochemical conversion technologies. Rationally designed catalysts with rich active sites and high intrinsic activity have been considered as a hopeful strategy to address the sluggish kinetics for OER. However, constructing such active sites in non-noble catalysts still faces grand challenges. To this end, we fabricate a Ni2P@Fe2P core-shell structure with outperforming performance toward OER via chemical transformation of rationally designed Ni-MOF hybrid nanosheets. Specifically, the Ni-MOF nanosheets and their supported Fe-based nanomaterials were in situ transformed into porous Ni2P@Fe2P core-shell nanosheets composed of Ni2P and Fe2P nanodomains in homogenous dispersion via a phosphorization process. When employed as the OER electrocatalyst, the Ni2P@Fe2P core-shell nanosheets exhibits excellent OER performance, with a low overpotential of 238/247 mV to drive 50/100 mA cm-2, a small Tafel slope of 32.91 mV dec-1, as well as outstanding durability, which could be mainly ascribed to the strong electronic interaction between Ni2P and Fe2P nanodomains stabilizing more Ni and Fe atoms with higher valence. These high-valence metal sites promote the generation of high-active Ni/FeOOH to enhance OER activity.

Cycloaddition of epoxides with CO2 to synthesis cyclic carbonates is an atom-economic pathway for CO2 utilization with promising industry application value, while its efficiency was greatly inhibited for the lack of highly active catalytic sites. Herein, by taking BiOX (X = Cl, Br) with layered structure for example, we proposed a facet engineering strategy to construct Lewis acid-base pairs for CO2 cycloaddition, where the typical BiOBr with (010) facets expose surface Lewis acid Bi sites and Lewis base Br sites simultaneously. By the combination of in-situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) and theoretical calculations, the oxygen atom of the epoxide is interacted with the Lewis acid Bi site to activate the ternary ring, then facilitates the attack of the carbon atom by the Lewis base Br site for the ring-opening of the epoxide, which is the rate-determining step in the cycloaddition reaction. As a result, the BiOBr-(010) with rich surface Lewis acid-base pairs showed a high conversion of 85% with 100% atomic economy in the synthesis of cyclic-carbonates without any cocatalyst. This study provides a model structure for CO2 cycloaddition to high value-added long chain chemicals.

Plant growth can be promoted by the application of apple fruit fermentation (AFF), despite unclear of the underlying mechanisms, the effects involved in AFF on rhizosphere microorganisms have been hypothesized. We investigated the consequences of applying AFF alone or in combination with Bacillus licheniformis to strawberry tissue culture seedlings in vitro, the analyses of Denaturing Gradient Gel Electrophoresis (DGGE) and 16S rDNA were performed to determine AFF effects on rhizosphere. Moreover, the growth index and antioxidant enzyme activities were determined 30 days after treatments. We identified five dominant bacteria in AFF: Coprinus atramentarius, Bacillus megaterium, Bacillus licheniformis, Weissella and B. subtilis. The greatest number of bacterial species were observed in the rhizosphere of control matrix (water treated), and the lowest diversity appeared in the rhizosphere soil treated with 108 cfu/mL B. licheniformis alone. Combining AFF plus B. licheniformis in one treatment resulted in the largest leaf area, plant height, root length, plant weight, and the markedly higher activities of antioxidant enzymes. We conclude that a combination of AFF plus B. licheniformis treatment to matrix can increase antioxidant enzymes activities in strawberry seedlings, optimize the status of rhizosphere microbial, and promote plant growth.

Aluminum-doped zinc oxide (ZnO: Al), abbreviated as ZAO, is a novel and widely used transparent conductive material. The ZAO powder was synthesized by chemical coprecipitation. The ZAO ceramic sputtering target materials were fabricated by sintering in air, and ZAO transparent conductive films were prepared by RF magnetron sputtering on glass substrates. XRD proved that such films had an orientation of (002) crystal panel paralleled to the surface of the glass substrate. The average transmittance of the films in the visible region exceeded 80%.

Nanocrystalline W-doped TiO 2 powders with different initial W/Ti ratio in starting materials have been prepared by hydrothermal method. The phase composition, morphologies, specific surface areas and the photocatalytic activities under visible light irradiation of the synthesized powders have been characterized. XRD identification reveals that the synthesized powders were composed of anatase. No rutile has been detected in the products. The specific surface area of the powders was ranged from 185 to 210 m 2 /g by BET measurement. The averaged grain size of the powders was calculated as about 12 nm by Scheller's method. Uniform size distribution and good crystallinity have been confirmed by TEM. UV-Vis spectra show that the absorption edges of the synthesized W-doped TiO 2 powders with different nominal doping concentration of W ions have been red-shifted into visible light region, which suggests that the W ions have been doped into the lattice of TiO 2 . In our case, W-doped TiO 2 with initial W/Ti atomic ratio of 1% in starting materials has the best photocatalytic activities when decompose the Methylblue in its aqueous solution, which is consistent with that of the theoretical results from our previous work.

Coastal zone could be considered as an important sink of regional source to sink and preserve historical records of environmental evolution. Four sediment cores, collected from tidal flat at Haizhou Bay near Lianyungang City, were examined for concentrations of heavy metals including Cd, Cr, Cu, Mn, Pb and Zn in core sediments to investigate the historical input of trace metals. In addition, sediment rates of cores LH3 and LH4 were determined based on radionuclide 210Pb. The results showed that grain size control effect was not the main factor that influenced the distribution of heavy metals. Heavy metals concentrations in the surface sediments were higher than these regional background values. Furthermore, Al element as a proxy of grain size was selected for normalization and calculation of metal enrichment factor (EF) and anthropogenic heavy metal fluxes. The results revealed that heavy metals in tidal flats were continuously enriched in the past decades, meanwhile, tidal flats have been significantly subjected to contaminations due to anthropogenic activities. Moreover, the depth profiles of heavy metals fluxes correspond to scenario of social-economy development of Lianyungang, which is an important urban area near Haizhou Bay. From 1950s to 2005, anthropogenic fluxes of metals increased with fluctuations, whereas, since 2005 anthropogenic fluxes declined, which may be correlated to the adjustment of industrial structure as well as the strengthened environmental regulation.

2D heterostructure Fe 2 P–CoP 2 /MoO x nanosheets on NF were synthesized by simple hydrothermal and phosphorization methods and exhibit remarkable OER performance.

The crystalline sponge method allows for direct and precise molecular structure determination of liquid and gaseous targets and thus has been recognized as a revolutionary breakthrough in crystallography. To expose undergraduates to this cutting-edge technique, we have developed a comprehensive laboratory experiment with reaction conditions and characterizations systematically tailored for students to perform in a mild and accessible way. In this experiment, students investigate the preparation of networked complexes {[(ZnI2)3(TPT)2]·x(solvate)}n as crystalline sponges with benzonitrile, methyl salicylate, and (trifluoromethyoxy)benzene as solvent, respectively. Crystalline sponges obtained in benzonitrile were exposed to solvent exchange in cyclohexane to afford {[(ZnI2)3(TPT)2]·x(cyclohexane)}n, and the progress was monitored by IR and GC-MS. All four crystals were evaluated under a microscope and subjected to single crystal X-ray diffraction (SC-XRD) analysis. The students are provided with the opportunity to learn about scientific software, such as SHELX, Olex2, and Mercury, and carry out structure analysis and visual representation of the sponges and liquid molecules. Moreover, hierarchical experiments have been designed to provide flexibility to students and best fit their individual needs and resources. The experiment has been carried out for three semesters in our school. It may refresh students’ understanding of crystallography and help them excel in future endeavors especially like synthetic chemistry, pharmaceutical R&D, etc.

Abstract Chemical fixation of carbon dioxide (CO 2 ) into value‐added organics is regarded as a competitive and viable method in large scale industrial production, during which the catalysts with promoting CO 2 activation ability are needed. Herein, we proposed an in‐plane heterostructure strategy to construct Lewis acid–base sites for efficient CO 2 activation. By taking ultrathin in‐plane Cu 2 O/Cu heterostructures as a prototype, we show that Lewis acid‐base sites on heterointerface can facilitate a mixed C and O dual coordination on surface, which not only strengthen CO 2 adsorption, but also effectively activate the inert molecules. As revealed by in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) and quasi in situ X‐ray photoelectron spectroscopy (XPS), Lewis acid‐base sites could readily activate CO 2 to . CO 2 − species, which is the key intermediate radical for CO 2 fixation. As a result, abundant Lewis acid–base sites endow Cu 2 O/Cu nanosheets with excellent performances for dimethyl carbonate generation, a high conversion yield of 28 % with nearly 100 % selectivity under mild conditions. This study provides a model structure for CO 2 fixation reactions.

Copy number variations (CNVs) are associated with complex diseases and particular tumor types; thus, reliable CNV identification has substantial potential value. Several different high-throughput technologies can be used to identify CNV sites. One commonly used approach to detect CNVs is array-based comparative genomic hybridization (aCGH). Recent advances in sequencing technology make it affordable to obtain aCGH data for multiple samples, and an increasing number of methods have become available for detecting recurrent CNV regions across samples. However, copy number is highly dynamic in cancer cells and thus individually specific. In contrast, researchers anticipate that detecting recurrent CNVs in samples is an indication that the tumors share the same origin and thus possibly also have common oncogene drivers and tumor insurgence. Therefore, accurate discrimination of recurrent from individual CNVs is vital to explain various phenotype differences and genetic diseases.

Based on the density functional theory method, the ab initio calculation with GGA+U was performed to investigate the electronic structure and properties of W-doped TiO 2 . The results indicated that W-doping induced ferromagnetism and shifted the absorption spectra to visible light region. The ferromagnetism derived from the spin-split of O 2p and W 5d caused by p–d orbit hybridization. Several impurity bands under the conduction band decreased the band gap.

Finely modulating the morphology of bimetallic nanomaterials plays a vital role in enhancing their catalytic activities. Among the various morphologies, concave structures have received considerable attention due to the three advantageous features of high-index facets, high surface areas, and high curvatures, which contribute greatly to enhancing the catalytic performance. However, concave morphologies are not the products generated from thermodynamically controlled growth with minimized surface energy. Additionally, most nanocrystals with concave shapes are currently in the state of mono-metals or alloys with disordered arrangements of atoms. The synthesis of alloy structures with ordered atom arrangements, intermetallic compounds, which tend to display superior catalytic performance on account of their optimal geometric and electronic effects, has rarely been reported as high-temperature annealing is usually needed, which constrains the modulation of morphology and surface structure. In this work, concave one-dimensional Au-Cu nanorods with a partially ordered intermetallic structure were synthesized via a facile wet chemical method. By simply adjusting the reaction kinetics via the concentrations of the corresponding metal precursors, the degree of concavity of the one-dimensional Au-Cu nanorods could be regulated. In both the p-nitrophenol reduction and CO2 electro-reduction reactions, the concave-shaped Au-Cu nanorods demonstrated superior catalytic activity compared to corresponding non-concave samples with the same structure due to the morphological advantages provided by the concave structure.

Dramatic change has overtaken the media industries, which in turn has aroused serious concerns from both academia and industry about the economics and management of those industries. This book expl...

Recently, great effort has been devoted to the exploration of two-dimensional (2D) materials with atomic thickness, for their extraordinary electronic structures with respect to corresponding bulk counterparts, giving promising applications in various fields such as electronics, optoelectronics, catalysis, and energy storage. Nevertheless, relatively limited synthetic methods for preparing these 2D nanosheets undoubtedly restrict further progress, especially for materials with non-layered structures or quasi-layered structures containing relatively strong bonds and van der Waals forces between layers. Therefore, developing novel synthetic methods for 2D nanosheet preparation will not only enrich the family of 2D crystals with atomic thickness, but also bring us unprecedented surprises. Liquid-phase synthetic methods show great potential for preparing 2D crystals with atomic thickness when compared with traditional methods, especially for non-layered and quasi-layered materials. In this chapter, we focus on advances in liquid-phase synthetic strategies for preparing atomically-thick 2D crystals using top-down and bottom-up strategies.

Additional file 6: Table S5. 6713 sequences differentially expressed during the oviposition stage compared with the initial pairing stage (FCÂ â ĽÂ 2).

Additional file 5: Table S4. 43,870 sequences differentially expressed during the oviposition stage compared with the pre-pairing stage (FCÂ â ĽÂ 2).

The invention of air conditioner (AC) has undoubtedly saved the world from the heat of summer.The development of AC is an important embodiment of continuous development and perfection of science and technology.This article explains the mechanism of freon pollution from the perspective of chemistry, and enumerates the important role of fluoride in daily life, to eliminates people's misunderstanding of fluorine element.The hardships of extracting fluorine reflect the chemists' research experience of collecting experience from failure and the scientific spirit of pursuing the truth.

Abstract Background Digested sewage sludge has been widely applied as soil amendment for enhanced crop production. However, given that digested sludge is abundant with antibiotic resistance genes (ARGs) and antibiotic resistant bacteria, the impact of digested sludge amendment on the abundances of ARGs and microbial communities in soil and soil fauna (e.g., earthworms) remains largely unknown. In this study, the patterns of ARGs and microbial communities in soil and gut of earthworms after 80-days cultivation with digested sewage sludge amendment were investigated to gain insights into this impact. Results The results show that the digested sludge amendment increased the initial abundances of ARGs (e.g., tetA, tetQ, and sulII) in soil. However, after 80-days cultivation, the absolute abundances of target ARGs decreased by 62.3–95.4%. The reduction in ARGs absolute abundances was further enhanced by 31.4–84.7% in the presence of earthworms. In contrast, the relative abundances of some ARGs (e.g., tetA, sulI, and bla TEM−1 ) in the gut of earthworms increased by 41–130 folds. The microbial community structure of soil was greatly altered because of the introduction of digested sewage sludge at initial, but it recovered to its original pattern after 80-days cultivation. This could be attributed to the gradual attenuation of anaerobic microorganisms under aerobic conditions in soil. In particular, the presence of earthworms further enhanced this phenomenon. The reduction of ARGs in the amended soils was likely attributed to microbial community shift based on redundancy analysis. Several bacterial families (e.g., Saprospiraceae , Chitinophagaceae , and Rhodanobacteraceae ) were significantly correlated with the target ARGs. Conclusions Our results reveal that the enrichment of ARGs in soil caused by digested sludge-amendment would recover to their original levels before amendment, highlighting the contribution of earthworms to reducing the ARG abundances in amended soil via shifting the microbial community. However, we also found that the amended soil could increase ARGs abundance in the earthworm gut, which may enhance the potential risk of ARGs spread via food chain. These results may provide a new sight on the control of ARGs occurrence and dissemination in sludge-amended soil ecosystem with consideration of the impact of earthworms.

Nanometer TiO2 is a new kind of inorganic functional material, its preparation and application have been paid more and more attention. This article has introduced several methods of preparing nanometer TiO2, focusing on description of preparation technologies and technical characteristics of precipitation method with TiOSO4 as raw material , which is the semifinished product from the production of titanium dioxide by sulfate method.

Topic Selection is essential to the reviews of journalism. Problem-seeking is an effective way to it. That is: ⑴ to raise the new problems timely. ⑵ add news ideas to the old problems. ⑶ to focus on hotly-issued problems. ⑷ to aim to find a positive solution to these problems.