3D-structured carbon-coated MnO/graphene nanocomposites with exceptional electrochemical performance for Li-ion battery anodes

MnO has a high theoretical capacity, moderate discharge plateau, and low polarization when it is used as the anode material in lithium battery. However, the issues that limit its application are its poor conductivity and large volume changes, which can easily result in the collapse of electrode structure during long-term cycling. In the present work, a carbon-coated MnO/graphene 3D-network anode material is synthesized by an electrostatic adsorption of dispersed precipitates precipitation method. The MnO nanoparticles coated by carbon are uniformly distributed on the surface of graphene nanosheets and form a 3D sandwich-like nanostructure. A carbon layer is coated on the surface of MnO nanoparticles, which slows down the volume expansion in the process of lithium intercalation. The graphene nanosheets are cross-linked through carbons in this 3D nanostructure, which provides mechanical support and effective electron conduction pathways during the charge-discharge. The electrochemical tests indicate that the prepared 3D carbon-coated MnO/graphene electrode exhibits an excellent rate capacity of 1247.3 and 713.2 mAh g^?1 at 100 and 1000 mA g^?1, respectively. The capacity is 792.2 mAh g^?1 after long cycle at a current density of 1000 mA g^?1. The specific capacity is higher than that of MnO-based composite lithium anode materials currently reported. The superior rate and cycling performances are attributed to the unique 3D-network structure, which provides an effectively conductive network, buffers volume expansion, and prevents falling and aggregation of MnO in the charge and discharge process of the electrode materials. The 3D-structured carbon-coated MnO/graphene anode material will have an excellent application prospect.

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Graphical abstract Cyclic performance at 1 A g^?1 and SEM images (inset) of the 3D-structured carbon-coated MnO/graphene nanocomposite.

     

Facial Synthesis and Bioevaluation of Well-Defined OEGylated Betulinic Acid-Cyclodextrin Conjugates for Inhibition of Influenza Infection

Betulinic acid (BA) and its derivatives exhibit a variety of biological activities, especially their anti-HIV-1 activity, but generally have only modest inhibitory potency against influenza virus. The entry of influenza virus into host cells can be competitively inhibited by multivalent derivatives targeting hemagglutinin. In this study, a series of hexa-, hepta- and octavalent BA derivatives based on α-, β- and γ-cyclodextrin scaffolds, respectively, with varying lengths of flexible oligo(ethylene glycol) linkers was designed and synthesized using a microwave-assisted copper-catalyzed 1,3-dipolar cycloaddition reaction. The generated BA-cyclodextrin conjugates were tested for their in vitro activity against influenza A/WSN/33 (H1N1) virus and cytotoxicity. Among the tested compounds, 58, 80 and 82 showed slight cytotoxicity to Madin-Darby canine kidney cells with viabilities ranging from 64 to 68% at a high concentration of 100 μM. Four conjugates 51 and 69–71 showed significant inhibitory effects on influenza infection with half maximal inhibitory concentration values of 5.20, 9.82, 7.48 and 7.59 μM, respectively. The structure-activity relationships of multivalent BA-cyclodextrin conjugates were discussed, highlighting that multivalent BA derivatives may be potential antiviral agents against influenza infection.     

Deeper Insight into the Volatile Profile of Rosa willmottiae with Headspace Solid-Phase Microextraction and GC–MS Analysis

As the distribution center of Rosa in the world, China has abundant wild germplasm resources, which can contribute to the breeding of modern roses. To explore the potential value of wild roses distributed in the Sichuan–Tibet region, solid phase microextraction (SPME) and gas chromatography–mass spectrometry (GC–MS) were used to determine the volatile organic compounds (VOCs) in Rosa willmottiae flowers at three flowering stages (bud stage, initial flowering stage, full flowering stage). Meanwhile, we compared the VOCs of R. willmottiae with different phenotypes (double flowers and single flowers). A total of 74 volatile compounds were identified. The results show that the essential substances belong to alcohols and terpenoids. The main volatile organic compounds are 2-phenyl ethanol (20.49%), benzyl alcohol (10.69%), β-maaliene (8.66%), geranyl acetate (8.47%), and (+)-α-long pinene (6.127%). Different flowering stages had great influence on the volatile profile, from the bud stage to full flowering stage; the content of terpenoids released decreased by 6.17%, whereas alcohols and esters increased by 8.58% and 11.56%, respectively. The chemical diversity and the content of the main components with a different phenotype were not significantly different. Our result will provide a theoretical basis for the development and utilization of Rosa willmottiae in Sichuan and Tibet.     

The Carboxyl Functionalized UiO-66-(COOH)2 for Selective Adsorption of Sr2+

Efficient and selective removal of ⁹⁰Sr is an important process for the safe use of nuclear energy. Herein, we investigate and assess the Sr²⁺ adsorption properties of a metal-organic framework UiO-66-(COOH)₂ functionalized by non-bonded carboxylic groups. This MOF is an exciting class of free carboxylic functionalized MOFs that combine chemical stability with gas sorption, dye elimination, and conductivity. Specifically, we show that uniformly distributed carboxyl and water stability make it accessible for loading Sr²⁺ without structural changes. The FTIR spectroscopy, PXRD analysis, XPS, and SEM-EDS studies show excellent stability as well as the strong affinity between -COOH active site and Sr²⁺. This strong coordination interaction guarantees a high adsorption capacity of 114 mg g⁻¹ within 5 h (pH 5 and 298 K). Combined kinetic and thermodynamic studies show that the surface complexation is strong chemisorption and cost-effective spontaneous process (ΔG = −5.49 kJ mol⁻¹~−2.16 kJ mol⁻¹). The fact that UiO-66-(COOH)₂ not only possesses a high adsorption capacity, but also enables selectivity to Sr²⁺ in the presence of similar radius ions Na⁺ and K⁺, prefigures its great potential for the practical treatment of radioactive Sr²⁺ in polluted water.     

Zinc-Guided 3D Graphene for Thermally Chargeable Supercapacitors to Harvest Low-Grade Heat

Low-grade heat energy recycling is the key technology of waste-heat utilization, which needs to be improved. Here, we use a zinc-assisted solid-state pyrolysis route to prepare zinc-guided 3D graphene (ZnG), a 3D porous graphene with the interconnected structure. The obtained ZnG, with a high specific surface area of 1817 m²·g⁻¹ and abundant micropores and mesopores, gives a specific capacitance of 139 F·g⁻¹ in a neutral electrolyte when used as electrode material for supercapacitors. At a high current density of 8 A·g⁻¹, the capacitance retention is 93% after 10,000 cycles. When ZnG is used for thermally chargeable supercapacitors, the thermoelectric conversion of the low-grade heat energy is successfully realized. This work thus provides a demonstration for low-grade heat energy conversion.     

Energy-Efficient Optimization for Energy-Harvesting-Enabled mmWave-UAV Heterogeneous Networks

Energy Harvesting (EH) is a promising paradigm for 5G heterogeneous communication. EH-enabled Device-to-Device (D2D) communication can assist devices in overcoming the disadvantage of limited battery capacity and improving the Energy Efficiency (EE) by performing EH from ambient wireless signals. Although numerous research works have been conducted on EH-based D2D communication scenarios, the feature of EH-based D2D communication underlying Air-to-Ground (A2G) millimeter-Wave (mmWave) networks has not been fully studied. In this paper, we considered a scenario where multiple Unmanned Aerial Vehicles (UAVs) are deployed to provide energy for D2D Users (DUs) and data transmission for Cellular Users (CUs). We aimed to improve the network EE of EH-enabled D2D communications while reducing the time complexity of beam alignment for mmWave-enabled D2D Users (DUs). We considered a scenario where multiple EH-enabled DUs and CUs coexist, sharing the full mmWave frequency band and adopting high-directive beams for transmitting. To improve the network EE, we propose a joint beamwidth selection, power control, and EH time ratio optimization algorithm for DUs based on alternating optimization. We iteratively optimized one of the three variables, fixing the other two. During each iteration, we first used a game-theoretic approach to adjust the beamwidths of DUs to achieve the sub-optimal EE. Then, the problem with regard to power optimization was solved by the Dinkelbach method and Successive Convex Approximation (SCA). Finally, we performed the optimization of the EH time ratio using linear fractional programming to further increase the EE. By performing extensive simulation experiments, we validated the convergence and effectiveness of our algorithm. The results showed that our proposed algorithm outperformed the fixed beamwidth and fixed power strategy and could closely approach the performance of exhaustive search, particle swarm optimization, and the genetic algorithm, but with a much reduced time complexity.     

QUADRATURE METHODS FOR HIGHLY OSCILLATORY SINGULAR INTEGRALS

We address the evaluation of highly oscillatory integrals,with power-law and logarithmic singularities.Such problems arise in numerical methods in engineering.Notably,the evaluation of oscillatory integrals dominates the run-time for wave-enriched boundary integral formulations for wave scattering,and many of these exhibit singularities.We show that the asymptotic behaviour of the integral depends on the integrand and its derivatives at the singular point of the integrand,the stationary points and the endpoints of the integral.A truncated asymptotic expansion achieves an error that decays faster for increasing frequency.Based on the asymptotic analysis,a Filon-type method is constructed to approximate the integral.Unlike an asymptotic expansion,the Filon method achieves high accuracy for both small and large frequency.Complex-valued quadrature involves interpolation at the zeros of polynomials orthogonal to a complex weight function.Numerical results indicate that the complex-valued Gaussian quadrature achieves the highest accuracy when the three methods are compared.However,while it achieves higher accuracy for the same number of function evaluations,it requires signi cant additional cost of computation of orthogonal polynomials and their zeros.     

Sensitive electrochemical determination of α-fetoprotein using a glassy carbon electrode modified with in-situ grown gold nanoparticles,graphene oxide and MWCNTs acting as signal amplifiers

The authors describe an electrochemical immunoassay for α-fetoprotein (α-FP) using a glassy carbon electrode (GCE) modified with a nanocomposite made from gold nanoparticles, graphene oxide and multi-walled carbon nanotubes (AuNPs/GO-MWCNTs) and acting as a signal amplification matrix. The nanocomposite was synthesized in a one-pot redox reaction between GO and HAuCl₄ without using an additional reductant. The stepwise assembly of the immunoelectrode was characterized by means of cyclic voltammetry and electrochemical impedance spectroscopy. The interaction of antigen and antibody on the surface of the electrode creates a barrier for electrons and causes retarded electron transfer, this resulting in decreased signals in differential pulse voltammetry of hexacyanoferrate which is added as an electrochemical probe. Using this strategy and by working at a potential of 0.2 V (vs. SCE), a wide analytical range (0.01 - 100 ng∙mL‾¹) is covered. The correlation coefficient is 0.9929, and the limit of detection is as low as 3 pg∙mL‾¹ at a signal-to-noise ratio of 3. This electrochemical immunoassay combines the specificity of an immunological detection scheme with the sensitivity of an electrode modified with AuNPs and GO-MWCNTs.

Schematic illustration of the fabrication procedure of the immunosensor

     

集值逆上鞅的收敛定理及应用

研究了取值于Ｂａｎａｃｈ空间的集值逆上鞅的收敛性，给出了集值逆上鞅在集列Ｗｉｊｓｍａｎ收敛，弱收敛及Ｋｕｒａｔｏｗｓｋｉ－Ｍｏｓｃｏ收敛意义下的收敛定理，并给出了它们在连续参数集值鞅中的应用。     

Molecular Simulation on Competitive Adsorption Differences of Gas with Different Pore Sizes in Coal

Micropores are the primary sites for methane occurrence in coal. Studying the regularity of methane occurrence in micropores is significant for targeted displacement and other yield-increasing measures in the future. This study used simplified graphene sheets as pore walls to construct coal-structural models with pore sizes of 1 nm, 2 nm, and 4 nm. Based on the Grand Canonical Monte Carlo (GCMC) and molecular dynamics theory, we simulated the adsorption characteristics of methane in pores of different sizes. The results showed that the adsorption capacity was positively correlated with the pore size for pure gas adsorption. The adsorption capacity increased with pressure and pore size for competitive adsorption of binary mixtures in pores. As the average isosteric heat decreased, the interaction between the gas and the pore wall weakened, and the desorption amount of CH₄ decreased. In ultramicropores, the high concentration of CO₂ (50–70%) is more conducive to CH₄ desorption; however, when the CO₂ concentration is greater than 70%, the corresponding CH₄ adsorption amount is meager, and the selected adsorption coefficient S_CO2/CH4 is small. Therefore, to achieve effective desorption of methane in coal micropores, relatively low pressure (4–6 MPa) and a relatively low CO₂ concentration (50–70%) should be selected in the process of increasing methane production by CO₂ injection in later stages. These research results provide theoretical support for gas injection to promote CH₄ desorption in coal pores and to increase yield.