Enhancing Interfacial Capacitance by Boron Doping in Vertically Porous Carbon Toward High-Performance AC Filtering Electrochemical Capacitors.

Electrochemical capacitors (ECs) show great perspective in alternate current (AC) filtering once they simultaneously reach ultra-fast response and high capacitance density. Nevertheless, the structure-design criteria of the two key properties are often mutually incompatible in electrode construction. Herein, it is proposed that combining vertically oriented porous carbon with enhanced interfacial capacitance (Ci) can efficiently solve this issue. Theoretically, the density function theory calculation shows that the Ci of a carbon electrode can be enhanced by boron doping due to the corresponding compact induced charge layer. Experimentally, the vertical-oriented boron-doped graphene nanowalls (BGNWs) electrodes, whose Ci is enhanced from 4.20 to 10.16 µF cm-2 upon boron doping, are prepared on a large scale (480 cm2) using a hot-filament chemical vapor deposition technique (HFCVD). Owing to the high Ci and vertically oriented porous structure, BGNWs-based EC has a high capacitance density of 996 µF cm-2 with a phase angle of - 79.4° at 120 Hz in aqueous electrolyte and a high energy density of 1953 µFV2 cm-2 in organic electrolyte. As a result, the EC is capable of smoothing 120 Hz ripples for 60 Hz AC filtering. These results provide enlightening insights on designing high-performance ECs for high-frequency applications.

Apigenin Ameliorates Insulin Resistance and Lipid Accumulation by Endoplasmic Reticulum Stress and SREBP-1c/SREBP-2 Pathway in Palmitate-Induced HepG2 Cells and High-Fat Diet-Fed Mice.

Insulin resistance (IR) is the common basis of diabetes and cardiovascular diseases, and its development is closely associated with lipid metabolism disorder. Flavonoids have definite chemical defense effects, including anti-inflammatory effects, anticancer effects, and antimutation effects. However, the function and mechanism of apigenin (AP, a kind of flavonoid) in IR are still unclear. In our study, intracellular fat accumulation model cells and high-fat diet (HFD)-fed model mice were established using palmitate (PA) and HFD. Mechanistically, we first demonstrated that AP could notably downregulate sterol regulatory element-binding protein 1c (SREBP-1c), sterol regulatory element-binding protein 2 (SREBP-2), fatty acid synthase, stearyl-CoA desaturase 1, and 3-hydroxy-3-methyl-glutaryl-CoA reductase in PA-induced hyperlipidemic cells and mice. Functionally, we verified that AP could markedly reduce lipid accumulation in PA-induced hyperlipidemic cells and decrease the body weight, visceral fat weight, IR, and lipid accumulation in HFD-induced hyperlipidemic mice. Besides, we showed that PA could significantly downregulate endoplasmic reticulum stress (ERS)-related proteins and inhibit ERS. Furthermore, we proved that AP could reduce blood lipids by inhibiting ERS in PA-induced hyperlipidemic cells. Meanwhile, 4-phenyl butyric acid (also called ERS alleviator), like AP, could significantly reduce blood lipids and alleviate IR in HFD-fed model mice. Therefore, we concluded that AP could substantially improve the disorder of lipid metabolism, and its mechanism might be related to the decrease of SREBP-1c, SREBP-2, and downstream genes, the inhibition of ERS, and the reduction of blood lipids and IR. SIGNIFICANCE STATEMENT: Apigenin, a nontoxic and naturally sourced flavonoid, has antihyperlipidemic properties in mice and hepatocyte. This study highlights a new mechanism of apigenin and proposes that these hypolipidemic effects are associated with the mitigation of endoplasmic reticulum stress and insulin resistance in diet-induced obesity. This study might provide translational insight into the prevention and treatment of apigenin in hyperlipidemia-related diseases.

Nitrogen-doped carbon nanowalls/diamond films as efficient electrocatalysts toward oxygen reduction reaction.

Substitution of commercial Pt/C electrocatalysts with efficient carbon-based ones for oxygen reduction reaction (ORR) still remains a huge challenge. For practical ORR applications it is significant to design robust 3D network nanostructures in that they do not require polymer binders. For conventional powder catalysts, they must be combined with substrate, leading to their shedding and degradation. In this work, vertically-aligned N-doped carbon nanowalls/diamond (N-CNWs/D) films are synthesized by means of a microwave plasma chemical vapor deposition technique, where nitrogen doping is conducted during the growth process and a subsequent facile annealing treatment under Ar atmosphere. The obtained Ar treated N-CNWs/D film exhibits an ORR onset potential of 835 mV (versus reversible hydrogen electrode) in 0.1 mol l-1KOH solution in a four-electron reaction pathway. It also displays excellent tolerance toward methanol crossover and long-term stability (e.g. a current density loss of only 10% even after 16 h measurement). The boosting ORR performance can be attributed to the activated pyridinic N dopant at abundant edge sites and enlarged electrochemical surface areas of N-CNWs/D films. This work not only develops a controllable strategy to fabricate binder-free carbon-based ORR electrocatalysts, but also paves a way to in-depth understand actual active sites in terms of ORR pathway mechanisms.

Rational Construction of 3D-Networked Carbon Nanowalls/Diamond Supporting CuO Architecture for High-Performance Electrochemical Biosensors.

Tremendous demands for highly sensitive and selective nonenzymatic electrochemical biosensors have motivated intensive research on advanced electrode materials with high electrocatalytic activity. Herein, the 3D-networked CuO@carbon nanowalls/diamond (C/D) architecture is rationally designed, and it demonstrates wide linear range (0.5 × 10-6 -4 × 10-3 m), high sensitivity (1650 µA cm-2 mm-1 ), and low detection limit (0.5 × 10-6 m), together with high selectivity, great long-term stability, and good reproducibility in glucose determination. The outstanding performance of the CuO@C/D electrode can be ascribed to the synergistic effect coming from high-electrocatalytic-activity CuO nanoparticles and 3D-networked conductive C/D film. The C/D film is composed of carbon nanowalls and diamond nanoplatelets; and owing to the large surface area, accessible open surfaces, and high electrical conduction, it works as an excellent transducer, greatly accelerating the mass- and charge-transport kinetics of electrocatalytic reaction on the CuO biorecognition element. Besides, the vertical aligned diamond nanoplatelet scaffolds could improve structural and mechanical stability of the designed electrode in long-term performance. The excellent CuO@C/D electrode promises potential application in practical glucose detection, and the strategy proposed here can also be extended to construct other biorecognition elements on the 3D-networked conductive C/D transducer for various high-performance nonenzymatic electrochemical biosensors.

A Highly Active Porous Mo2C-Mo2N Heterostructure on Carbon Nanowalls/Diamond for a High-Current Hydrogen Evolution Reaction.

Developing non-precious metal-based electrocatalysts operating in high-current densities is highly demanded for the industry-level electrochemical hydrogen evolution reaction (HER). Here, we report the facile preparation of binder-free Mo2C-Mo2N heterostructures on carbon nanowalls/diamond (CNWs/D) via ultrasonic soaking followed by an annealing treatment. The experimental investigations and density functional theory calculations reveal the downshift of the d-band center caused by the heterojunction between Mo2C/Mo2N triggering highly active interfacial sites with a nearly zero ∆GH* value. Furthermore, the 3D-networked CNWs/D, as the current collector, features high electrical conductivity and large surface area, greatly boosting the electron transfer rate of HER occurring on the interfacial sites of Mo2C-Mo2N. Consequently, the self-supporting Mo2C-Mo2N@CNWs/D exhibits significantly low overpotentials of 137.8 and 194.4 mV at high current densities of 500 and 1000 mA/cm2, respectively, in an alkaline solution, which far surpass the benchmark Pt/C (228.5 and 359.3 mV) and are superior to most transition-metal-based materials. This work presents a cost-effective and high-efficiency non-precious metal-based electrocatalyst candidate for the electrochemical hydrogen production industry.

Per- and polyfluoroalkyl substances in ambient fine particulate matter in the Pearl River Delta, China: Levels, distribution and health implications.

Per- and polyfluoroalkyl substances (PFAS) have attracted worldwide attention as one of persistent organic pollutants; however, there is limited knowledge about the exposure concentrations of PFAS-contained ambient particulate matter and the related health risks. This study investigated the abundance and distribution of 32 PFAS in fine particulate matter (PM2.5) collected from 93 primary or secondary schools across the Pearl River Delta region (PRD), China. These chemicals comprise four PFAS categories which includes perfluoroalkyl carboxylic acids (PFCAs), perfluoroalkyl sulfonic acids (PFSAs), perfluoroalkyl acid (PFAA) precursors and PFAS alternatives. In general, concentrations of target PFAS ranged from 11.52 to 419.72 pg/m3 (median: 57.29 pg/m3) across sites. By categories, concentrations of PFSAs (median: 26.05 pg/m3) were the dominant PFAS categories, followed by PFCAs (14.25 pg/m3), PFAS alternatives (2.75 pg/m3) and PFAA precursors (1.10 pg/m3). By individual PFAS, PFOS and PFOA were the dominant PFAS, which average concentration were 24.18 pg/m3 and 6.05 pg/m3, respectively. Seasonal variation showed that the concentrations of PFCAs and PFSAs were higher in winter than in summer, whereas opposite seasonal trends were observed in PFAA precursors and PFAS alternatives. Estimated daily intake (EDI) and hazard quotient (HQ) were used to assess human inhalation-based exposure risks to PFAS. Although the health risks of PFAS via inhalation were insignificant (HQ far less than one), sufficient attention should be levied to ascertain the human exposure risks through inhalation, given that exposure to PFAS through air inhalation is a long term and cumulative process.

Cold Laser Micro-Machining of PDMS as an Encapsulation Layer for Soft Implantable Neural Interface.

PDMS (polydimethylsiloxane) is an important soft biocompatible material, which has various applications such as an implantable neural interface, a microfluidic chip, a wearable brain-computer interface, etc. However, the selective removal of the PDMS encapsulation layer is still a big challenge due to its chemical inertness and soft mechanical properties. Here, we use an excimer laser as a cold micro-machining tool for the precise removal of the PDMS encapsulation layer which can expose the electrode sites in an implantable neural interface. This study investigated and optimized the effect of excimer laser cutting parameters on the electrochemical impedance of a neural electrode by using orthogonal experiment design. Electrochemical impedance at the representative frequencies is discussed, which helps to construct the equivalent circuit model. Furthermore, the parameters of the equivalent circuit model are fitted, which reveals details about the electrochemical property of neural electrode using PDMS as an encapsulation layer. Our experimental findings suggest the promising application of excimer lasers in the micro-machining of implantable neural interface.

Quantitative phosphoproteomic analysis provides insights into the aluminum-responsiveness of Tamba black soybean.

Aluminum (Al3+) toxicity is one of the most important limitations to agricultural production worldwide. The overall response of plants to Al3+ stress has been documented, but the contribution of protein phosphorylation to Al3+ detoxicity and tolerance in plants is unclear. Using a combination of tandem mass tag (TMT) labeling, immobilized metal affinity chromatography (IMAC) enrichment and liquid chromatography-tandem mass spectrometry (LC-MS/MS), Al3+-induced phosphoproteomic changes in roots of Tamba black soybean (TBS) were investigated in this study. The Data collected in this study are available via ProteomeXchange with the identifier PXD019807. After the Al3+ treatment, 189 proteins harboring 278 phosphosites were significantly changed (fold change > 1.2 or < 0.83, p < 0.05), with 88 upregulated, 96 downregulated and 5 up-/downregulated. Enrichment and protein interaction analyses revealed that differentially phosphorylated proteins (DPPs) under the Al3+ treatment were mainly related to G-protein-mediated signaling, transcription and translation, transporters and carbohydrate metabolism. Particularly, DPPs associated with root growth inhibition or citric acid synthesis were identified. The results of this study provide novel insights into the molecular mechanisms of TBS post-translational modifications in response to Al3+ stress.

Plasma membrane proteomic analysis by TMT-PRM provides insight into mechanisms of aluminum resistance in tamba black soybean roots tips.

Aluminum (Al) toxicity in acid soil is a worldwide agricultural problem that inhibits crop growth and productivity. However, the signal pathways associated with Al tolerance in plants remain largely unclear. In this study, tandem mass tag (TMT)-based quantitative proteomic methods were used to identify the differentially expressed plasma membrane (PM) proteins in Tamba black soybean (TBS) root tips under Al stress. Data are available via ProteomeXchange with identifier PXD017160. In addition, parallel reaction monitoring (PRM) was used to verify the protein quantitative data. The results showed that 907 PM proteins were identified in Al-treated plants. Among them, compared to untreated plants, 90 proteins were differentially expressed (DEPs) with 46 up-regulated and 44 down-regulated (fold change > 1.3 or < 0.77, p < 0.05). Functional enrichment based on GO, KEGG and protein domain revealed that the DEPs were associated with membrane trafficking and transporters, modifying cell wall composition, defense response and signal transduction. In conclusion, our results highlight the involvement of GmMATE13, GmMATE75, GmMATE87 and H+-ATPase in Al-induced citrate secretion in PM of TBS roots, and ABC transporters and Ca2+ have been implicated in internal detoxification and signaling of Al, respectively. Importantly, our data provides six receptor-like protein kinases (RLKs) as candidate proteins for further investigating Al signal transmembrane mechanisms.

In Situ Construction of Hierarchical Diamond Supported on Carbon Nanowalls/Diamond for Enhanced Electron Field Emission.

The integration of sp2-/sp3-bonded carbon has aroused increasing attention on attaining a great electron field emission (EFE) performance. Herein, a novel hierarchical diamond@carbon nanowalls/diamond (D@C/D) architecture is facilely prepared through the growth of the hybrid carbon nanowalls/diamond (C/D) film followed by the in situ hydrogen plasma treatment using microwave plasma chemical vapor deposition. The hierarchical D@C/D architecture is composed of thin diamond nanoplatelets sandwiched into carbon nanowalls (CNWs) as the bottom layer and the thickened nanoplatelets constituted by diamond nanograins as the upper layer. The hydrogen plasma plays an effective role in the transformation of sacrificial sp2-bonded CNWs to sp3-bonded diamond, eventually leading to the template thickening of diamond nanoplatelets in the upper layer. Impressively, the D@C/D-90 film demonstrates much better EFE behaviors of low turn-on potential (Eo = 4.3 V µm-1), high current density (Je@8 V µm-1 = 20.81 mA cm-1), and superior long-term stability, in comparison with the pristine C/D film (Eo = 6 V µm-1, Je@8 V µm-1 = 0.33 mA cm-1). The enhanced EFE performance of the hierarchical D@C/D film is ascribed to the well-established graphite pathway for electrons transported from the bottom to the top and the increased diamond emitting sites with negative electron-affinity and robust nature at the top. This work will promote the development of the high-performance cathode EFE material based on hybrid sp2/sp3-bonded carbon, and the method proposed here also provides an effective strategy to construct a diamond nanostructure for various applications.

Insights into aluminum-tolerance pathways in Stylosanthes as revealed by RNA-Seq analysis.

Stylo has a great potential for Al3+ resistance in acidic soils through secretion of citrate from the roots. To get insight into the molecular mechanisms responsible, transcriptomic changes were investigated in the roots after treatment with T01 (-Al3+, pH6.0), T02 (-Al3+, pH4.3) and T03 (50 µM AlCl3, pH4.3). In total, 83,197 unigenes generated from 130,933 contigs were obtained. Of them, 282, 148 and 816 differentially expressed unigenes (DEGs) were revealed in T01_vs_T02, T02_vs_T03 and T01_vs_T03 comparison, respectively (FDR < 0.001, log2FC > 2). DEGs by Al3+ were related to G-proteins, diacyglycerol and inositol metabolism, calcium-signaling, transcription regulation, protein modification and transporters for detoxification of Al3+. Additionally, Al3+ facilitates citrate synthesis via modifying gene expression of pathways responsible for citrate metabolism. Overall, Al3+ resistance in stylo involves multiple strategies and enhancement of citrate anabolism. The Al3+ signal transmits through heterotrimeric G-proteins, phospholipase C, inositol triphosphate, diacylglycerol, Ca2+ and protein kinases, thereby activating transcription and anion channels in plasma membrane, and resulting in citrate secretion from stylo roots.

Band-gap tailoring and visible-light-driven photocatalytic performance of porous (GaN)1-x(ZnO)x solid solution.

(GaN)1-x(ZnO)x solid solution has attracted extensive attention due to its feasible band-gap tunability and excellent photocatalytic performance in overall water splitting. However, its potential application in the photodegradation of organic pollutants and environmental processing has rarely been reported. In this study, we developed a rapid synthesis process to fabricate porous (GaN)1-x(ZnO)x solid solution with a tunable band gap in the range of 2.38-2.76 eV for phenol photodegradation. Under visible-light irradiation, (GaN)0.75(ZnO)0.25 solid solution achieved the highest photocatalytic performance compared to other (GaN)1-x(ZnO)x solid solutions with x = 0.45, 0.65 and 0.85 due to its higher redox capability and lower lattice deformation. Slight Ag decoration with a content of 1 wt% on the surface of the (GaN)0.75(ZnO)0.25 solid solution leads to a significant enhancement in phenol degradation, with a reaction rate eight times faster than that of pristine (GaN)0.75(ZnO)0.25. Interestingly, phenol in aqueous solution (10 mg L-1) can also be completely degraded within 60 min, even under the direct exposure of sunlight irradiation. The photocurrent response indicates that the enhanced photocatalytic activity of (GaN)0.75(ZnO)0.25/Ag is directly induced by the improved transfer efficiency of the photogenerated electrons at the interface. The excellent phenol degradation performance of (GaN)1-x(ZnO)x/Ag further broadens their promising photocatalytic utilization in environmental processing, besides in overall water splitting for hydrogen production.

Correction: Band-gap tailoring and visible-light-driven photocatalytic performance of porous (GaN)1-x(ZnO)x solid solution.

Correction for 'Band-gap tailoring and visible-light-driven photocatalytic performance of porous (GaN)1-x(ZnO)x solid solution' by Aimin Wu et al., Dalton Trans., 2017, 46, 2643-2652.

Size-controllable Ni5TiO7 nanowires as promising catalysts for CO oxidation.

Ni5TiO7 nanowires with controllable sizes are synthesized using PEO method combined with impregnation and annealing at 1050(o)C in air, with adjustment of different concentrations of impregnating solution to control the dimension of nanowires. The resulting nanowires are characterized in details using X-ray diffraction, scanning electron microscopy, transmission electron microscopy and energy dispersive X-ray analysis. In addition, the CO catalytic oxidation performance of the Ni5TiO7 nanowires is investigated using a fixed-bed quartz tubular reactor and an on-line gas chromatography system, indicating that the activity of this catalytic system for CO oxidation is a strong dependency upon the nanocrystal size.When the size of the Ni5TiO7 nanowires is induced from 4 µm to 50 nm, the corresponding maximum conversion temperature is lowered by ~100 (o)C.