Evolution of self-diffusion and local structure in some amines over a wide temperature range at high pressures: a molecular dynamics simulation study

Self-diffusion and structural properties of ammonia, methylamine and trimethylamine have been studied by molecular dynamics simulation in the temperature range between the melting pressure curve and 700 K at pressures up to 400 MPa. The calculation results agree well with the experiment, which suggests that one can use the simulation method as a powerful tool to obtain self-diffusion coefficients over wide range of temperatures and pressures, under which it is rather difficult for experiments. The local structures of such fluids are investigated by calculating radial distribution functions (RDFs), the numbers of hydrogen bonds and coordination numbers. The correlation between self-diffusion and structural properties, and the influence of temperature and pressure on them are discussed. The simulation results demonstrate that the temperature effects are more pronounced than the pressure effects on self-diffusion and structural properties, and the effect of hydrogen bonding on the translational dynamics in any of these systems is a minor factor, while it is mainly affected by the close packing of amine molecules.     

One-pot synthesis of stable NIR tetracene diimides via double cross-coupling

Tetracene tetracarboxylic diimides have been synthesized based on direct double ring extension of electron-deficient naphthalene diimides involving metallacyclopentadienes. Atomic structure and electronic transitions responsible for their NIR absorption spectra are investigated with quantum-chemical calculations. In light of their unique structure and admirable photophysical and electronic properties, this new molecular skeleton is promising candidate for n-type semiconductors.     

A simple and efficient copper oxide-catalyzed Barbier–Grignard reaction of unactivated aryl or alkyl bromides with ester

An efficient one-pot route to synthesize tertiary alcohol compounds using Barbier–Grignard reaction of unactivated alkyl or aryl bromides with ester in THF at 65 °C catalyzed by CuO has been developed and systematically investigated. A wide range of substituted tertiary alcohol compounds were obtained in good to high yields. The reaction is highly chemoselective. The mechanism involving the leaving group of R²O^-group is discussed.     

Low‐Background,Highly Sensitive DNA Biosensor by Using an Electrically Neutral Cobalt(II) Complex as the Redox Hybridization Indicator

An electrically neutral cobalt complex, [Co(GA)₂(phen)] (GA=glycollic acid, phen=1,10‐phenathroline), was synthesized and its interactions with double‐stranded DNA (dsDNA) were studied by using electrochemical methods on a glassy carbon electrode (GCE). We found that [Co(GA)₂(phen)] could intercalate into the DNA duplex through the planar phen ligand with a high binding constant of 6.2(±0.2)×10⁵ M ^?1. Surface studies showed that the cobalt complex could electrochemically accumulate within the modified dsDNA layer, rather than within the single‐stranded DNA (ssDNA) layer. Based on this feature, the complex was applied as a redox‐active hybridization indicator to detect 18‐base oligonucleotides from the CaMV35S promoter gene. This biosensor presented a very low background signal during hybridization detection and could realize the detection over a wide kinetic range from 1.0×10^?14 M to 1.0×10^?8 M , with a low detection limit of 2.0 fM towards the target sequences. The hybridization selectivity experiments further revealed that the complementary sequence, the one‐base‐mismatched sequence, and the non‐complementary sequence could be well‐distinguished by the cobalt‐complex‐based biosensor.     

Highly oxidized graphene with enhanced fluorescence and its direct fluorescence visualization

We prepared hyper-oxidized graphene (HOG) as a form of graphene derivative by additional oxidation of graphene oxide (GO) sheets. HOG, which formed more functional groups and isolated conjugated clusters on the sheets, accordingly showed high solubility in water and alcohols, high transmittance and film transparence, longer fluorescence decay constant time, and enhanced fluorescence in states of solution and solid. By contrast, GO has much weaker fluorescence in solution and its fluorescence is totally quenched in solid. The influences of concentration, metallic ions, and pH on HOG fluorescence in aqueous solution were also investigated in detail. Due to HOG’s strong fluorescence, direct visualization was realized on substrates and in solution. In addition, direct 3D fluorescence visualizations of HOG phase in polymer composites were achieved. These results show the great potential of HOG in a broad range of applications, from biological labeling, probes, and drug carriers to high-performance composites and nanomanipulation.     

分子沉积聚合物膜的制备及其摩擦学性能研究

以聚对磺酸钠苯乙烯(PSS)为聚阴离子、聚烯丙基氯化氨(PAH)为聚阳离子交替沉积制备了多层聚合物纳米复合膜,用热分析仪考察了这两种体相聚合物的热稳定性,采用紫外-可见光谱仪、椭圆偏振光测厚仪、接触角测量仪等分析了复合膜的性能,用DF-PM型动静摩擦系数精密测定装置考察了其摩擦学性能.结果发现,所制备的聚合物复合膜具有一定的减摩作用,原因是单晶硅表面沉积聚合物超薄膜可以降低表面的粘着力,对硅表面具有微观修饰作用,从而降低其同钢对摩时的摩擦系数;单晶硅表面分子沉积聚合物纳米复合膜的摩擦学特性同超薄膜的层数相关,沉积层数较多的超薄膜的耐磨寿命较长,并因加热处理而得到明显改善.     

Fine-tuning the molecular energy levels by incorporating thiophene units onto the π-backbone of core-expanded naphthalene diimides

A series of core-expanded naphthalene diimides (NDI-DTYM) and thiophene-based derivatives (1a-c) were designed and synthesized to investigate the relationship between molecular structures and the highest occupied molecular orbital (HOMO) energy levels but has little impact on the lowest unoccupied molecular orbital (LUMO) energy levels. The results demonstrated that increasing the number of thiophene units can gradually elevate the HOMO energy levels but had little impact on the LUMO energy levels. The n-channel organic field-effect transistors (OFETs) based on 1b and 1c have demonstrated that these almost unchanged LUMO energy levels are proper to transport electrons.     

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.