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The microstructure of primary Mg 2 Si and the interface of Mg 2 Si / α -Mg modified by Sn and Sb elements in an as-cast Mg-5Sn-2Si-1.5Al-1Zn-0.8Sb (wt.%) alloy were investigated. In the primary Mg 2 Si phase not only the Si atoms but also the Mg atoms could be substituted by Sn and Sb atoms, resulting in the slightly reduced lattice constant a of 0.627 nm. An OR of Mg 2 Si phase and α -Mg in the form of [ 001 ] Mg 2 Si ∥ [ 01 1 ¯ 1 ] α , ( 220 ) Mg 2 Si ∥ ( 0 1 ¯ 12 ) α was discovered. Between primary Mg 2 Si phase and α -Mg matrix two transitional nano-particle layers were formed. In the rim region of primary Mg 2 Si particle, Mg 2 Sn precipitates sizing from 5 nm to 50 nm were observed. Adjacent to the boundary of primary Mg 2 Si particle, luxuriant columnar crystals of primary Mg 2 Sn phase with width of about 25 nm and length of about 100 nm were distributed on the α -Mg matrix. The lattice constant of the Mg 2 Sn precipitate in primary Mg 2 Si particle was about 0.756 nm. Three ORs between Mg 2 Sn and Mg 2 Si were found, in which the Mg 2 Sn precipitates had strong bonding interfaces with Mg 2 Si phase. Three new minor ORs between Mg 2 Sn phase and α -Mg were found. The lattice constant of primary Mg 2 Sn phase was enlarged to 0.813 nm owing to the solution of Sn and Sb atoms. Primary Mg 2 Sn had edge-to-edge interfaces with α -Mg. Therefore, the primary Mg 2 Si particle and α -Mg were united and the interfacial adhesion was improved by the two nano-particles layers of Mg 2 Sn phase.

Highly efficient and stable catalysts are among the key factors in industrial ethanol dehydration to ethylene. Among the widely studied catalysts, alumina is the most suitable for industrial application. In this study, novel gamma alumina was synthesized by solvent protection and a hydrothermal procedure. HRTEM, XRD, FT-IR, NH3-TPD, H-D exchange, and 29Si MAS NMR were employed to compare the difference in physicochemical properties between the novel gamma alumina and commercial alumina. Characterization results show that the as-synthesized novel gamma alumina mainly exposes the high-energy crystal plane (111) while the commercial alumina mainly exposes the thermostatically stable (110) crystal plane. The dominating (111) plane, according to the characterizations, endows the novel gamma alumina with a higher density of surface hydroxyl groups, higher acid content, and higher surface energy compared to the commercial alumina. The catalytic performance of the two catalysts for industrial ethanol dehydration to ethylene was studied. The novel (111) plane-exposed alumina showed a higher yield of ethylene than commercial alumina under the same reaction conditions. This could be related to the difference in atomic arrangement and the unsaturated aluminum coordination of different crystal planes. Stability testing under severe reaction conditions (450 °C, 1 MPa, 4 h−1) indicates that novel gamma alumina shows better stability (catalyst life cycle increased by 50%) and produces less acetaldehyde as a byproduct. The effects of steam treatment on the catalytic performance were further investigated. The surface acidity and the catalytic performance of novel gamma alumina present a volcanic curve with the increase in steam treatment temperature. Under the optimal water vapor treatment temperature of 650 °C, the conversion of ethanol and selectivity of ethylene were both higher than 99%.

In aromatic systems with large π-conjugated structures, armchair and zigzag configurations can affect each material’s electronic properties, determining their performance and generating certain quantum effects. Here, we explore the intrinsic effect of armchair and zigzag pathways on charge transport through single hexabenzocoronene molecules. Theoretical calculations and systematic experimental results from static carbon-based single-molecule junctions and dynamic scanning tunneling microscope break junctions show that charge carriers are preferentially transported along the hexabenzocoronene armchair pathway, and thus, the corresponding current through this pathway is approximately one order of magnitude higher than that through the zigzag pathway. In addition, the molecule with the zigzag pathway has a smaller energy gap. In combination with its lower off-state conductance, it shows a better field-effect performance because of its higher on-off ratio in electrical measurements. This study on charge transport pathways offers a useful perspective for understanding the electronic properties of π-conjugated systems and realizing high-performance molecular nanocircuits toward practical applications.

To alleviate the wastage of resources and environmental pollution caused by waste luminous polyester fibers, glycolysis was found rapidly to degrade luminescent polyester fibers and assist in recovering luminescent materials from the fibers. However, the luminescent performance of recycled luminescent materials is poor. To improve the performance of recovered luminescent materials, this study employs the recovery rate of luminescent materials, initial brightness, and recovery rate of Bis (2-hydroxyethyl) terephthalate as performance indexes. The present study aims at optimizing the alcoholysis process by influencing factors such as the amount of catalyst, amount of ethylene glycol added, and reaction temperature to improve the luminous performance, and explores the mechanism of alcoholysis reaction in the recovery process of luminescent materials. The results showed that, when the catalyst content is 0.1 g, the mass ratio of polyethylene terephthalate:ethylene glycol is 1:10, the reaction temperature is 170°C for 4 hours, the Bis (2-hydroxyethyl) terephthalate conversion rate reaches 61.92%, the recovery rate of luminescent materials reaches 92.53%, and the initial brightness is as high as 5.607 cd/m2.

The inherent dipole moment and higher polarizability of azulene lead to ambipolar characteristics and good gate controllability of azulene-based single-molecule transistors.

A mechano-sliding strategy for controllable assembly of nanowires was demonstrated by directly transferring chemical vapor deposition grown silicon nanowires to obtain nanoscale electronic devices.

A single-molecule field-effect transistor (FET) is the key building block of future electronic circuits. At the same time, a single-molecule FET is also a unique platform for studying physical mechanisms at the single-molecule level. How to construct single-molecule FETs and how to efficiently control the charge transfer characteristics of the devices are two core issues in the development of single-molecule FETs. In this review, we introduce the research progresses of single-molecule FETs with solid or liquid gates. Strategies to design single-molecule FETs are emphasized, including the design of functional molecules, the construction of gate electrodes and the control of molecule-electrode interface coupling. These single-molecule FETs provide a basis for practical applications and the exploration of physical laws. Specifically, the physical mechanisms of single-molecule FETs, especially those related to interfacial coupling, are explained, such as energy level shift, Coulomb blockade effect, Kondo effect and electron-phonon coupling. The applications of single-molecule FETs are summarized, including the regulation of quantum interference, spin, thermoelectric effect and superconductivity. Finally, the current opportunities and challenges in the field of single-molecule FETs are proposed, aiming to promote the future development of single-molecule electronics.

The study was conducted to investigate the effects of dietary nonfibrous carbohydrate (NFC)/neutral detergent fiber (NDF) ratio on methanogenic archaea and cellulose-degrading bacteria in Karakul sheep by 16S rRNA gene sequencing. Twelve Karakul sheep were randomly divided into four groups, each group with three replicates, and they were fed with four dietary NFC/NDF ratios at 0.54, 0.96, 1.37, and 1.90 as groups 1, 2, 3, and 4, respectively. The experiment lasted for four periods: I (1 to 18 days), II (19 to 36 days), III (37 to 54 days), and IV (55 to 72 days); during each period, rumen contents were collected before morning feeding to investigate on methanogenic archaea and cellulose-degrading bacteria. The results showed that with an increase in dietary NFC/NDF ratio, the number of rumen archaea operational taxonomic units and the diversity of archaea decrease. The most dominant methanogens did not change with dietary NFC/NDF ratio and prolongation of experimental periods.

The electrical detecion data and analyized data have been included in this file.

The choice of axial ligands is of great importance for the construction of high-performance Dy-based single-molecule magnets (SMMs). Here, combining axial ligands Ph

With aging, iron will accumulate in the brain, catalyzing oxidative radicals that damage brain neurons and induceAlzheimer's disease. In this experiment, we observed that in the brains of senile mice, the iron-exporting protein ferriportin was decreased. Further investigation indicated that H3K27 of the slc40a1 gene was methylated and that the methyltransferase Ezh2 was activated. To discharge the excessive iron in the brains of senile mice, we developed the YP peptide, and with it, we demethylated H3K27me of Slc40a1 by phosphorylation, activating the demethylase Kdm6a and inhibiting methyltransferase Ezh2. Consequently, the transcription of Slc40a1 was enhanced,and ferriportin was resumed. Thesenile brain reacquired the function of iron excretion, and as a result, the radicals in the brain weredecreased,and neuron damage was reduced, which finally restored the intelligence of dementia senile mice. Thus, YP could be a potential drug in the prevention of Alzheimer's disease

Intermolecular charge transport plays a vital role in the fields of electronics, as well as biochemical systems. Here, we design supramolecular dimer junctions and investigate the effects of charge state and energy level alignment on charge transport under nanoconfinement. Incoherent tunneling caused by thermally-induced vibrations is enhanced in positively charged systems. The transition between coherent and incoherent tunneling is associated with specific molecular vibration modes. Positively charged systems with smaller torsional barriers and vibrational frequencies result in lower transition temperatures. Multiple thermal effects have a great impact on the conductance in the off-resonant tunneling, while thermally-induced vibron-assisted tunneling contributes more to the transport in the resonant tunneling. These investigations offer a deep mechanism understanding of intermolecular charge transport and facilitate the development of practical functional molecular devices.

Conventional analytic techniques that measure ensemble averages and static disorder provide essential knowledge of the reaction mechanisms of organic and organometallic reactions. However, single-molecule junctions enable the in situ, label-free and non-destructive sensing of molecular reaction processes at the single-event level with an excellent temporal resolution. Here we deciphered the mechanism of Pd-catalysed Suzuki-Miyaura coupling by means of a high-resolution single-molecule platform. Through molecular engineering, we covalently integrated a single molecule Pd catalyst into nanogapped graphene point electrodes. We detected sequential electrical signals that originated from oxidative addition/ligand exchange, pretransmetallation, transmetallation and reductive elimination in a periodic pattern. Our analysis shows that the transmetallation is the rate-determining step of the catalytic cycle and clarifies the controversial transmetallation mechanism. Furthermore, we determined the kinetic and thermodynamic constants of each elementary step and the overall catalytic timescale of this Suzuki-Miyaura coupling. Our work establishes the single-molecule platform as a detection technology for catalytic organochemistry that can monitor transition-metal-catalysed reactions in real time.

The completely selective oxidation of toluene to benzaldehyde with dioxygen, without the need to use H2O2, halogens, or any radical initiators, is a reaction long desired but never previously successful. Here, we demonstrate the enzyme-like mechanism of the reaction over hexadecylphosphate acid (HDPA)-bonded nano-oxides, which appear to interact with toluene through specific recognition. The active sites of the catalyst are related to the ability of HDPA to change its bonding to the oxides between monodentate and bidentate during the reaction cycle. This greatly enhances the mobility of the crystal oxygen or the reactivity of the catalyst, specifically in toluene transformations. The catalytic cycle of the catalyst is similar to that of methane monooxygenase. In the presence of catalyst and through O2 oxidation, the conversion of toluene to benzaldehyde is initiated at 70 dC. We envision that this novel mechanism reveals alternatives for an attractive route to design high-performance catalysts with bioinspired structures.

Summary Conventional mechanistic studies based on detection of species concentration reveal the basic laws of matter conversion, but inherently display ensemble averages. Single-molecule detection provides a solution and direct visualization of reaction pathway rather than only detection of species. Here, we establish an in situ label-free electrical detection platform and report universal single-molecule electrical spectroscopy (SMES) of organocatalysis to decipher the intrinsic mechanism of a benzoin reaction. This SMES is capable of monitoring each event in a simple (homo-condensation) or complex (cross-condensation) system. Both experimental and theoretical results consistently revealed accuracy of the spectroscopic attribution and proved its reliability. Furthermore, the correlation of adjacent events in the spectroscopy indicated the local repeated interaction between a catalyst and a substrate. Through a new thermodynamic and kinetic model, the inventory of substrates around the single-molecule catalyst can be reversely deduced, which enables quantitative analysis of the target single molecule.

Development of high-performance and cost-effective catalysts for electrocatalytic hydrogen evolution reaction (HER) play crucial role in the growing hydrogen economy. Recently, the atomically dispersed metal catalysts have attracted increasing attention due to their ultimate atom utilization and great potential for highly cost-effective and high-efficiency HER electrocatalyst. Herein, we propose a high-temperature treatment strategy to furtherly improve the HER performance of atomically dispersed Pt-based catalyst. Interestingly, after appropriate high-temperature treatment on the atomically dispersed Pt0.8@CN, the Pt species on the designed N-doped porous carbon substrate with rich defect sites can be re-dispersed to single atom state with new coordination environment. The obtained Pt0.8@CN-1000 shows superior HER performance with overpotential of 13 mV at 10 mA cm−2 and mass activity of 11,284 mA/mgPt at −0.1 V, much higher than that of the pristine Pt0.8@CN and commercial Pt/C catalyst. The experimental and theoretical investigations indicate that the high-temperature treatment induces the restructuring of coordination environment and then the optimized Pt electronic state leads to the enhanced HER performances. This work affords new strategy and insights to develop the atomically dispersed high-efficiency catalysts.

Stacking interactions are of significant importance in the fields of chemistry, biology, and material optoelectronics because they determine the efficiency of charge transfer between molecules and their quantum states. Previous studies have proven that when two monomers are π-stacked in series to form a dimer, the electrical conductance of the dimer is significantly lower than that of the monomer. Here, we present a strong opposite case that when two anthanthrene monomers are π-stacked to form a dimer in a scanning tunneling microscopic break junction, the conductance increases by as much as 25 in comparison with a monomer, which originates from a room-temperature quantum interference. Remarkably, both theory and experiment consistently reveal that this effect can be reversed by changing the connectivity of external electrodes to the monomer core. These results demonstrate that synthetic control of connectivity to molecular cores can be combined with stacking interactions between their π systems to modify and optimize charge transfer between molecules, opening up a wide variety of potential applications ranging from organic optoelectronics and photovoltaics to nanoelectronics and single-molecule electronics.

In recent years, natural polymer-based electrospun fibers (EFs) with huge specific surface area, good biocompatibility, and biological activity obtained from electrospinning process exhibit tremendous vitality in the field of biomedical areas. Herein, the parameters of electrospinning from two perspectives, polymer solution such as solvent, polymeric relative molecular mass, concentration, viscosity, and conductivity of the solution, and electrospinning process such as spinning voltage, spinning flow rate, needle tip to collector distance, temperature, and humidity are first detailed. Next, the raw materials consisting of polysaccharides such as cellulose, hyaluronic acid, alginate, and chitosan as well as proteins such as collagen, gelatin, silk fibroin, and keratin are summarized. The preparation method and related characteristics of EFs with multistage structures such as porous, core-shell, Janus, bamboo-like and other structures are introduced. The biomedical applications of these natural polymer-based EFs mainly including tissue engineering, drug sustained release, wound dressings, and biomedical sensors are systematically recapitulated. Finally, the outlook on natural EFs is further proposed.

Charge transport in a single-molecule junction is extraordinarily sensitive to both the internal electronic structure of a molecule and its microscopic environment. Two distinct conductance states of a prototype terphenyl molecule are observed, which correspond to the bistability of outer phenyl rings at each end. An azobenzene unit is intentionally introduced through atomically precise side-functionalization at the central ring of the terphenyl, which is reversibly isomerized between trans and cis forms by either electric or optical stimuli. Both experiment and theory demonstrate that the azobenzene side-group delicately modulates charge transport in the backbone via a single-molecule stereoelectronic effect. We reveal that the dihedral angle between the central and outer phenyl ring, as well as the corresponding rotation barrier, is subtly controlled by isomerization, while the behaviors of the phenyl ring away from the azobenzene are hardly affected. This tunability offers a new route to precisely engineer multiconfigurational single-molecule memories, switches, and sensors.

High energy density and enhanced rate capability are highly sought-after for supercapacitors in today’s mobile world. In this work, polyaniline/titanium carbide (MXene) (PANI/Ti3C2Tx) nanohybrid is synthesized through a facile and cost-effective self-assembly of one-dimensional (1D) PANI nanofibers and two-dimensional (2D) Ti3C2Tx nanosheets. PANI/Ti3C2Tx delivers greatly improved specific capacitance, ultrahigh rate capability (67% capacitance retention from 1 to 100 A·g−1) as well as good cycle stability. Electrochemical kinetic analysis reveals that PANI/Ti3C2Tx is featured with surface capacitance-dominated process and has a quasi-reversible kinetics at high scan rates, giving rise to an ultrahigh rate capability. By using PANI/Ti3C2Tx as positive electrode, an 1.8 V aqueous asymmetric supercapacitor (ASC) is successfully assembled, showing a maximum energy density of 50.8 Wh·kg−1 (at 0.9 kW·kg−1) and a power density of 18 kW·kg−1 (at 26 Wh·kg−1). Moreover, an 3.0 V organic ASC is also elaborately fabricated by using PANI/Ti3C2Tx, achieving an ultrahigh energy density of 67.2 Wh·kg−1 (at 1.5 kW·kg−1) and a power density of 30 kW·kg−1 (at 26.8 Wh·kg−1). The present work not only improves fundamental understanding of the structure-property relationship towards ultrahigh rate capability electrode materials, but also provides valuable guideline for the rational design of high-performance energy storage devices with both high energy and power densities.

The function of proteins depends on their structural flexibility and conformational change. By utilizing silicon-nanowire-based single-molecule electrical circuits, here we present a label-free real-time measurement method that can directly monitor conformational changes of a photosynthetic LH1-RC complex, reaching the ultimate goal of analytic chemistry. These results manifest that the conformation of the LH1-RC complex vibrates among four conformations with strong temperature dependence. At the optimal temperature, States 2 and 3 occupy the main conformations of the LH1-RC complex, and its conformational variation mostly emerges as anharmonic vibration modes, which contributes to photon acquisition and heat transmission. The influence of light activation on occurrence percentage is observed, resulting from light-driven quivering of pigments. Therefore, this avenue proves to be an efficient platform for revealing the fundamental mechanisms of various biological processes in vitro.