Responses of the structure and function of microbes in Yellow River Estuary sediments to different levels of mercury.

The health and stability of the estuary of the Yellow River ecosystem have come under increasing pressure from land-based inputs of heavy metals. While it is known that heavy metals affect the function and health of the microbial community, there remains little knowledge on the responses of the microbial community to heavy metals, particularly highly toxic mercury. The research aimed to characterize the responses of the sediment microbial community of the estuary of the Yellow River to different levels of mercury stress. Estuary sediment samples were collected for microbial community analysis, measurement of mercury [including total mercury (THg) and methylmercury (MeHg)], and measurement of other physicochemical factors, including pH, total organic carbon (TOC), sulfide, iron ratio (Fe3+/Fe2+), ammonium salt (NH4+), and biochemical oxygen demand (BOD). The application of 16S rRNA sequencing identified 60 phyla of bacteria, dominated by Proteobacteria, Firmicutes, and Bacteroidetes. Stations with higher THg or MeHg and lower microbial abundance and diversity were generally distributed further outside of the estuary. Besides mercury, the measured physicochemical factors had impacts on microbial diversities and distribution. Metagenomics assessment of three stations, representative of low, moderate, and high mercury concentrations and measured physicochemical factors, revealed the abundances and functions of predicted genes. The most abundant genes regulating the metabolic pathways were categorized as metabolic, environmental information processing, and genetic information processing, genes. At stations with high levels of mercury, the dominant genes were related to energy metabolism, signal transport, and membrane transport. Functional genes with a mercury-resistance function were generally in the mer system (merA, merC, merT, merR), alkylmercury lyase, and metal-transporting ATPase. These results offer insight into the microbial community structure of the sediments in the Yellow River Estuary and the microbial function of mercury resistance under mercury stress.

Thermal Decomposition Kinetics of the Indenyl Radical: A Theoretical Study.

Quantum chemistry and statistical reaction rate theory calculations have been performed to investigate the products and kinetics of indenyl radical decomposition. Three competitive product sets are identified, including formation of a cyclopentadienyl radical (c-C5H5) and diacetylene (C4H2), which has not been included in prior theoretical kinetics investigations. Rate coefficients for indenyl decomposition are determined from master equation simulations at 1800-2400 K and 0.01-100 atm, and temperature- and pressure-dependent rate coefficient expressions are incorporated into a detailed chemical kinetic model for indene pyrolysis. Indenyl is found to predominantly decompose to o-benzyne (o-C6H4) + propargyl (C3H3), with lesser amounts of fulvenallenyl (C7H5) + C2H2 and c-C5H5 + C4H2.

Graphene/MoS2/FeCoNi(OH)x and Graphene/MoS2/FeCoNiPx multilayer-stacked vertical nanosheets on carbon fibers for highly efficient overall water splitting.

Development of excellent and cheap electrocatalysts for water electrolysis is of great significance for application of hydrogen energy. Here, we show a highly efficient and stable oxygen evolution reaction (OER) catalyst with multilayer-stacked hybrid structure, in which vertical graphene nanosheets (VGSs), MoS2 nanosheets, and layered FeCoNi hydroxides (FeCoNi(OH)x) are successively grown on carbon fibers (CF/VGSs/MoS2/FeCoNi(OH)x). The catalyst exhibits excellent OER performance with a low overpotential of 225 and 241 mV to attain 500 and 1000 mA cm-2 and small Tafel slope of 29.2 mV dec-1. Theoretical calculation indicates that compositing of FeCoNi(OH)x with MoS2 could generate favorable electronic structure and decrease the OER overpotential, promoting the electrocatalytic activity. An alkaline water electrolyzer is established using CF/VGSs/MoS2/FeCoNi(OH)x anode for overall water splitting, which generates a current density of 100 mA cm-2 at 1.59 V with excellent stability over 100 h. Our highly efficient catalysts have great prospect for water electrolysis.

Porous Cu Film Enables Thick Slurry-Cast Anodes with Enhanced Charge Transfer Efficiency for High-Performance Li-Ion Batteries.

The ever-growing demand for energy in the consumer market has put higher requirements on the energy density of Li-ion batteries. Many researchers have strived to discover new electrode materials with higher capacity, while little attention has been focused on improving the cell structure. How to increase the thickness of conventional slurry-cast electrodes as well as decrease the charge transfer resistance by improving the electrode structure is an urgent problem for enhancing the energy density of Li-ion batteries. Here, a porous Cu film is developed to replace the conventional Cu foil current collector, and a thick graphite anode (300 µm) is engineered by two-side slurry casting. The anode delivers a maximum capacity of 18 mAh cm-2 or 301.3 mAh g-1 under a highly active mass loading of 60 mg cm-2, much higher than that fabricated on Cu foil. The assembled full cell with the graphite anode and the LiFePO4 cathode achieves high energy densities of 36.2 mWh cm-2 and 283.3 Wh kg-1. Systematic experimental and simulation investigations reveal the enhanced performance benefits from the facilitated charge transfer efficiency by the porous Cu current collector. This work provides a new strategy for engineering thick electrodes for high-energy Li-ion batteries by improving the conventional electrode structure.

Tissue-Specific Accumulation and Antioxidant Defenses in Flounder (Paralichthys olivaceus) Juveniles Experimentally Exposed to Methylmercury.

Methylmercury (MeHg) is the most toxic form of mercury and can accumulate in the cells of marine organisms, such as fish, causing adverse effects on various physiological functions. This study examined MeHg accumulation and its toxicological role in antioxidant defenses in tissues, including the liver, gills, and muscle of flounder (Paralichthys olivaceus) juveniles. After 30 d of MeHg exposure (0, 0.1, 1.0, 10.0, and 20.0 µg L-1), the accumulation of MeHg in the three tissues correlated positively with the concentration of MeHg and exhibited tissue specificity in the order of liver > gills > muscle. Among the antioxidant markers, the activities of SOD (superoxide dismutase) and GST (glutathione S-transferase) as well as the content of glutathione (GSH) in the liver and gills were induced at 0.1-10.0 µg L-1 but repressed at 20.0 µg L-1. The activities of SOD and GST and the content of GSH in the muscle significantly increased with increasing MeHg concentration. Catalase (CAT) activity in the liver was induced at 0.1-1.0 µg L-1 but inhibited at 10.0-20.0 µg L-1, whereas exposure to MeHg did not remarkably affect CAT activity in the gills and muscle. The levels of lipid peroxidation (LPO) increased dose dependently, showing tissue specificity with the highest level in the liver, then the gills, followed by muscles. Overall, higher sensitivity to oxidative stress induced by MeHg was detected in the liver than the gills and muscle. These findings improve our understanding of the tissue-specific accumulation of heavy metals and their roles in antioxidant responses in marine fish subjected to MeHg exposure.

Auto-Oxidation of a Volatile Silicon Compound: A Theoretical Study of the Atmospheric Chemistry of Tetramethylsilane.

Volatile silicon compounds (VOSiCs) are air pollutants present in both indoor and outdoor environments. Here, tetramethylsilane (TMS) is selected as a model to study the photochemical oxidation mechanisms for VOSiCs using ab initio and RRKM theory/master equation kinetic modeling. Under tropospheric conditions, the radical (CH3)3SiCH2• reacts with O2 to produce a stabilized peroxyl radical, which is expected to ultimately yield the alkoxyl radical (CH3)3SiCH2O•. At combustion-relevant temperatures, however, a well-skipping reaction to (CH3)3SiO• + HCHO dominates. Importantly, the (CH3)3SiCH2O• radical is predicted to rearrange to (CH3)3SiOCH2• with a very low reaction barrier, enabling an auto-oxidation process involving addition of a second O2. Subsequent oxidation reaction mechanisms of (CH3)3SiOCH2• have been developed, with the major product predicted to be the trimethylsilyl formate (CH3)3SiOCHO, an experimentally observed TMS oxidation product. The production of substantially oxygenated compounds following a single radical initiation reaction has implications for the ability of VOSiCs to contribute to ozone and particle formation in both outdoor and indoor environments.

Effects of seawater acidification and cadmium on the antioxidant defense of flounder Paralichthys olivaceus larvae.

Increasing atmospheric carbon dioxide has led to a decrease in the pH of the ocean, which influences the speciation of heavy metals and consequently affects metal toxicity in marine organisms. To investigate the effects of seawater acidification and metals on the antioxidant defenses of marine fishes, the flounder Paralichthys olivaceus, was continuously exposed to cadmium (Cd; control, 0.01 and 0.15 mg L-1) and acidified seawater (control (pH 8.10), 7.70 and 7.30) for 49 days from embryogenesis to settlement. The results demonstrated that both Cd and acidified seawater could induce oxidative stress and consequently cause lipid peroxidation (LPO) in the larvae. Antioxidants (i.e., superoxide dismutase, SOD; catalase, CAT; reduced glutathione, GSH; glutathione S-transferase, GST; glutathione peroxidase, GPx; and glutathione reductase, GR) functioned to defend the larvae against oxidative damage. Overall, Cd induced (SOD, GST and GSH) or inhibited (CAT and GPx) the enzymatic activities or contents of all the selected antioxidants except for GR. The antioxidants responded differently to seawater acidification, depending on their interaction with the metal. Similarly, the mRNA expressions of the antioxidant-related genes were upregulated (sod, gr and gst) or downregulated (cat and gpx) in response to increasing Cd exposure. Seawater acidification did not necessarily affect all of the biomarkers; in some cases (e.g., SOD and sod, GR and gr), Cd stress may have exceeded and masked the stress from seawater acidification in regulating the antioxidant defense of the larvae. The integrated biomarker response (IBR) was enhanced with increasing levels of the stressors. These findings support the hypothesis that seawater acidification not only directly affects the antioxidant defense in flounder larvae but also interacts with Cd to further regulate this defense. This study has ecological significance for assessing the long-term impacts of ocean acidification and metal pollution on the recruitment of fish populations in the wild.

Experimental and DFT Studies on the Identity Exchange Reactions between Phenyl Chalcogen Iranium Ions and Alkenes.

The gas-phase ion-molecule identity exchange reactions of phenyl chalcogen iranium ions with alkenes have been examined experimentally in a linear ion trap mass spectrometer by isotope labeling experiments. The nature of both the alkene and the chalcogen play crucial roles, with the bimolecular rates for π-ligand exchange following the order: [PhTe(c-C6H10)]+ + c-C6D10 > [PhTe(C2D4)]+ + C2H4 > [PhSe(c-C6H10)]+ + c-C6D10, with no reaction being observed for [PhSe(C2D4)]+ + C2H4, [PhS(C2D4)]+ + C2H4, and [PhS(c-C6H10)]+ + c-C6D10. The experimental results correlate with RRKM modeling and density functional theory (DFT) calculations, which also demonstrates that these reactions proceed via associative mechanisms. Natural bond orbital (NBO) analysis reveals a shift in the association complexes from a σ-hole interaction to ones mirroring the π-p+ and n-π* at the transition state in accordance with the rates of reaction.

Antioxidant defenses and immune responses of flounder Paralichthys olivaceus larvae under methylmercury exposure.

Methylmercury (MeHg) is a highly toxic contaminant in coastal environments and poses threats to marine fish in early life stages (ELSs). However, MeHg toxicity to fish embryos and larvae is not well investigated. This study investigated the antioxidant defenses and immune responses of flounder Paralichthys olivaceus larvae exposed to waterborne MeHg (0, 0.1, 1.0 and 10.0 µg L-1) for 35 days, from embryogenesis to settlement. The results revealed that metal accumulation in the larvae was positively correlated with MeHg concentration, reduced larval growth and survival. The activities of catalase and glutathione reductase were significantly increased at 10.0 µg L-1, while glutathione peroxidase activity and lipid peroxidation level were significantly increased at concentrations over 1.0 µg L-1. The corresponding antioxidant-related genes were upregulated under MeHg exposure (cat and gpx at 10.0 µg L-1; gr over 1.0 µg L-1). Lysozyme content was significantly increased, but immunoglobulin M content was significantly decreased at 10.0 µg L-1. The immune-related genes were significantly upregulated (hsp70 at 0.1 and 10.0 µg L-1; lzm and il-1ß over 1.0 µg L-1; tnf-α and il-6 at 10.0 µg L-1) or downregulated (igm, over 0.1 µg L-1). Overall, MeHg exposure induced oxidative stress and caused immunotoxicity at concentrations over 1.0 µg L-1 and 10.0 µg L-1, respectively. The transcription of selected genes correlated with the corresponding biochemical markers in response to MeHg toxicity. These findings improve our knowledge to better understand the mechanisms by which marine fish at ELSs cope with oxidative stress and immunotoxicity induced by MeHg.

Toxicity Test Assay of Waterborne Methylmercury on the Japanese Flounder (Paralichthys olivaceus) at Embryonic-Larval Stages.

Methylmercury (MeHg) is a widespread pollutant in aquatic ecosystems, but its toxicity to the early life stages of marine fish has not been adequately investigated. This study used acute toxicity tests on embryonic-larval stages of a marine flounder Paralichthys olivaceus to determine the LC50 values for embryos and larvae and evaluate the responses of several biological endpoints to subacute MeHg exposure. Under exposures (0-15 µg L-1) below LC50 values ( < 15.3 µg L-1 for embryos and 16.3 µg L-1 for larvae), embryos were more sensitive to MeHg than were the larvae. MeHg exposures at ≥ 13 µg L-1 increased morphological deformities and mortality, reduced growth and yolk absorption rate of the embryonic-larval flounder. These endpoints were sensitive to MeHg and their responses were dose-dependent. They could be used as bioindicators for assessing MeHg toxicity to the ELS of the flounder. Embryonic-larval flounder could be a useful fish for ecotoxicological assessment of MeHg in marine ecosystems.

A Flexible Supercapacitor with High True Performance.

The demand for better "true performance" of supercapacitors, which is defined as the energy density based on the packaged cell with high active mass loading, is spurred by the ever-increasing energy storage market. The true performance of present supercapacitors is unsatisfactory, greatly limited by the currently used current collectors. Here, we develop a through-pore structured nickel current collector with excellent flexibility by electrodepositing nickel on laser-drilled stainless steel sheets filled with epoxy resin. Based on the new current collector, the electrodes possess higher performance than those fabricated by employing conventional current collectors. At a high active mass loading, the assembled supercapacitors show superior flexibility and high energy densities of 50.4 W hr L-1 and 30.1 W hr kg-1, respectively, based on the packaged cell, outperforming the present supercapacitors. Our strategy provides a new opportunity for promoting the further development of supercapacitors by enhancing the true performance.

3D Graphene Fibers Grown by Thermal Chemical Vapor Deposition.

3D assembly of graphene sheets (GSs) is important for preserving the merits of the single-atomic-layered structure. Simultaneously, vertical growth of GSs has long been a challenge for thermal chemical vapor deposition (CVD). Here, vertical growth of the GSs is achieved in a thermal CVD reactor and a novel 3D graphene structure, 3D graphene fibers (3DGFs), is developed. The 3DGFs are prepared by carbonizing electrospun polyacrylonitrile fibers in NH3 and subsequently in situ growing the radially oriented GSs using thermal CVD. The GSs on the 3DGFs are densely arranged and interconnected with the edges fully exposed on the surface, resulting in high performances in multiple aspects such as electrical conductivity (3.4 × 104 -1.2 × 105 S m-1 ), electromagnetic shielding (60 932 dB cm2 g-1 ), and superhydrophobicity and superoleophilicity, which are far superior to the existing 3D graphene materials. With the extraordinary properties along with the easy scalability of the simple thermal CVD, the novel 3DGFs are highly promising for many applications such as high-strength and conducting composites, flexible conductors, electromagnetic shielding, energy storage, catalysis, and separation and purification. Furthermore, this strategy can be widely used to grow the vertical GSs on many other substrates by thermal CVD.

Large-scale synthesis of hybrid metal oxides through metal redox mechanism for high-performance pseudocapacitors.

Electrochemical performance and production cost are the main concerns for the practical application of supercapacitors. Here we report a simple and universally applicable method to prepare hybrid metal oxides by metal redox reaction utilizing the inherent reducibility of metals and oxidbility of for the first time. As an example, Ni(OH)2/MnO2 hybrid nanosheets (NMNSs) are grown for supercapacitor application by self-reaction of Ni foam substrates in KMnO4 solution at room temperature. The obtained hybrid nanosheets exhibit high specific capacitance (2,937 F g(-1)). The assembled solid-state asymmetric pseudocapacitors possess ultrahigh energy density of 91.13 Wh kg(-1) (at the power density of 750 W kg(-1)) and extraordinary cycling stability with 92.28% capacitance retention after 25,000 cycles. Co(OH)2/MnO2 and Fe2O3/MnO2 hybrid oxides are also synthesized through this metal redox mechanism. This green and low-cost method is capable of large-scale production and one-step preparation of the electrodes, holding promise for practical application of high-performance pseudocapacitors.

Single nanoporous gold nanowire as a tunable one-dimensional platform for plasmon-enhanced fluorescence.

We introduce individual nanoporous Au nanowire (AuNW) as a tunable one-dimensional platform for plasmon-enhanced fluorescence, with an enhancement factor of ∼62, which is ∼8-fold higher than that of smooth AuNWs. Besides, nanoporous AuNWs have much lower background emission than smooth AuNWs. These results indicate that nanoporous AuNWs are an excellent optical sensing platform.

Microplasma-assisted rapid synthesis of luminescent nitrogen-doped carbon dots and their application in pH sensing and uranium detection.

Developing a simple synthesis method and expanding the application of carbon dots have attracted increasing attention. In this report, we have developed a facile method to synthesize fluorescent carbon dots (CDs) with the assistance of atmospheric-pressure microplasma. The CDs could be produced within a few minutes with no need of high temperature, external energy input, and multistep procedures. The as-prepared CDs had a relatively uniform size of approximately 2.3 nm. The FTIR spectrum and the XPS analysis showed that carbonyl groups and amide groups exist on the surface of CDs. The CDs showed bright blue luminescence and high stability in high salt concentration and low pH without further modification. A pH-dependent PL behavior was observed and could be applied for pH sensing in the range of 3-14. Moreover, the CDs could be utilized as a reagent capable of detecting U(vi) with a low detection limit and high selectivity.

[Primary study of relationship between lumbar degenerative disease and morbidity of primary knee osteoarthritis].

OBJECTIVE: To study the relationship between lumbar degenerative disease and morbidity of primary unilateral knee osteoarthritis. METHODS: The clinical data of 115 unilateral knee osteoarthritis patients and 119 bilateral knee osteoarthritis patients undergoing TKR (total knee replacement) at our hospital in 2008 were retrospectively analyzed. According to clinical signs of lumbar degenerative disease and radiological changes, these patients were divided into upper/lower/whole/none lumbar degenerative disease group respectively. chi(2) test was performed to compare the difference of lumbar degenerative conditions between unilateral knee osteoarthritis and bilateral knee osteoarthritis patients. RESULTS: The morbidity side of lumbar intervertebral disc protrusion or nerve root canal stenosis in primary unilateral osteoarthritis patients was the same as the morbidity side of primary unilateral osteoarthritis. Lumbar degenerative disease morbidity [(34 + 20 + 15)/115 = 60%] of primary unilateral knee osteoarthritis was higher than that [(3 + 5 + 4 + 6 + 19)/119 = 31.1%] of primary bilateral knee osteoarthritis (chi(2) = 19.723, P = 0.000);Upper lumbar degenerative disease morbidity (34/115 = 29.6%)of primary unilateral knee osteoarthritis was higher than that [(3 + 5)/119 = 6.7%] of primary bilateral knee osteoarthritis, (chi(2) = 20.720, P = 0.000); lower lumbar degenerative disease morbidity (20/115 = 17.4%)of primary unilateral knee osteoarthritis was higher than that [(4 + 6)/119 = 8.4%] of primary bilateral knee osteoarthritis (chi(2) = 4.227, P = 0.040); there was no difference for whole lumbar degenerative disease morbidity between primary unilateral and bilateral knee osteoarthritis patients (chi(2) = 0.402, P = 0.526). CONCLUSION: The primary unilateral knee osteoarthritis morbidity is correlated with lumbar degenerative disease for the same elder patient. Upper lumbar degenerative disease can induce the incidence and aggravation of primary unilateral knee osteoarthritis; the flexion deformity of primary knee osteoarthritis may cause the aggravation of lower lumbar degenerative disease, even upper lumbar degenerative disease.