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Iodide‐mediated surface etching can tailor the surface plasmon resonance of gold nanostars through etching of the high‐energy facets of the nanoparticle protrusions in a rapid and sensitive way. By exploring the underlying mechanisms of this etching and the key parameters influencing it (such as iodide, oxygen, pH, and temperature), we show its potential in a sensitive biosensing system. Horseradish peroxidase‐catalyzed oxidation of iodide enables control of the etching of gold nanostars to spherical gold nanoparticles, where the resulting spectral shift in the surface plasmon resonance yields a distinct color change of the solution. We further develop this enzyme‐modulated surface etching of gold nanostars into a versatile platform for plasmonic immunoassays, where a high sensitivity is possible by signal amplification via magnetic beads and click chemistry., We outline a rapid and sensitive nanoparticle etching‐based strategy for biosensing. Iodide modulates the plasmonic features of gold nanostars by etching them into spherical nanoparticles, being a versatile biosensing platform for enzyme detection and plasmonic immunoassays.

Sulfamates and sulfamides are prevalent in biological molecules, but their universal synthetic methods are limited. We herein report a sulfamoylation agent with high solubility and shelf stability. Various sulfamates and sulfamides can be synthesized directly from alcohols or amines by employing this agent with high selectivity and high yields. This protocol was also successfully used for late-stage sulfamoylation of pharmaceuticals containing a hydroxyl or amino group.

The development of monoclonal antibody treatments for successful tumor-targeted therapies took several decades. However, the efficacy of antibody-based therapy is still confined and desperately needs further improvement. Nanobodies are the recombinant variable domains of heavy-chain-only antibodies, with many unique properties such as small size (~15kDa), excellent solubility, superior stability, ease of manufacture, quick clearance from blood, and deep tissue penetration, which gain increasing acceptance as therapeutical tools and are considered also as building blocks for chimeric antigen receptors as well as for targeted drug delivery. Thus, one of the promising novel developments that may address the deficiency of monoclonal antibody-based therapies is the utilization of nanobodies. This article provides readers the significant factors that the structural and biochemical properties of nanobodies and the research progress on nanobodies in the fields of tumor treatment, as well as their application prospect.

Silica aerogel is a typical nanoporous material exhibiting excellent thermal insulation property, and its nanostructure change at high temperature has attracted extensive attention. However, there is a lack of real-time research on the nanostructure evolution of silica aerogel under rapid heating. Here, silica aerogel was rapidly heated and imaged via an in-situ heating TEM to characterize the nanostructure evolution of from 600 °C to 1300 °C. After rapid heating at different temperatures, the silica aerogels were characterized by SEM, BET, TG-DSC, XRD and FT-IR. The nanostructure evolution of the aerogels can be divided into three temperature stages and experimental strategies for inhibiting aerogel shrinkage at high temperature can be provided. In stage Ⅰ (600 °C–1000 °C), the shrinkage of the silica aerogels occurred during the initial time of the heating process (within 2 h), and then the structure of silica aerogel became stable. The shrinkage of silica aerogels is primarily caused by the fusion of secondary particles, and increasing the secondary silica aerogel particle size may contribute to reducing the aerogel shrinkage. In stage Ⅱ (1100 °C), the aerogel shrinkage can be observed all the time with the heating process continues, and finally closed to the dense state. The shrinkage of silica aerogels is caused by the fusion of secondary particles and the macropore collapse, increasing the particle size and reducing the macropore content may slow down aerogel shrinkage. In stage Ⅲ (1200 °C–1300 °C), the aerogel will shrink rapidly and reach a dense state in a very short time (within 0.5 h). The shrinkage of silica aerogels is caused by the rapid pore collapse and the rapid fusion and shrinkage of the secondary particles of the aerogel, and pure silica aerogels cannot be used at this temperature.

SUMMARY The loess from the northern piedmont of the Dabie Mountains is in a transition area between loess from the Chinese Loess Plateau, the Quaternary red soils of southern China and the Xiashu loess. Despite its significant location, the study has been inadequate. In this study, the Guangshan section in the northern piedmont of the Dabie Mountains was selected for investigation. Environmental magnetism, geochemistry, colour reflectance and optical diffuse reflection spectroscopy analyses were applied to detect the magnetic variations in the loess. The results showed that (1) the magnetic minerals consisted mainly of magnetite, maghemite, hematite and goethite, which are the same as those in the Quaternary loess from the Chinese Loess Plateau, the Xiashu loess and the Quaternary red soils of southern China. The average magnetic particles were in the pseudo-single domain, like those of the Chinese Loess Plateau loess. (2) Unit III of the Guangshan section (2.4–4 m), with high chemical index of alteration and low Ba-index, was demonstrated as the most strongly developed palaeosol in the whole section, in agreement with field observations (more Fe-Mn films and weakly vermiculated development). However, it exhibited minimal susceptibility values and the lowest concentration of fine ferrimagnetic minerals. Simultaneously, the unit had low hematite to goethite ratio (Hm/Gt), suggesting that the pedogenic environment was humid; and it also had high values of b* and Gt%, implying that there was more goethite. Therefore, we can conclude that excessive soil moisture and intensive pedogenesis dissolved the fine ferrimagnetic minerals originally produced by pedogenesis and transformed them into goethite. These results could help to trace the palaeoclimatic evolution of the study area and clarify the magnetic variations of loess in different climates throughout China.

The direct in situ TEM imaging method is adopted to investigate the sintering behavior of SiO2 aerogels during the rapid heating process. The structural evolution of SiO2 aerogels and composites at different times during the heat treatment process are further investigated via SEM, FT-IR, BET and XRD. The results indicate that the shrinkage of the SiO2 aerogels and composites primarily occurs during the initial stage of the heating process (within 20 min) with the shrinkage primarily linked to the fusion of small aerogel particles at high temperatures. The aerogel structure then stabilizes with no further shrinkage observed as the heating process continues. The heat treatment process only promotes the space rearrangement and fusion of small aerogel particles with no observed changes to the amorphous structure of the aerogels, and the small-sized particles fusion was the main causes for the structural evolution of SiO2 aerogels and composites under rapid heating condition.

Currently, arginine-rich cell-penetrating peptides (CPPs), due to their little cytotoxicity and high transmembrane efficiency, are considered as one of the important intracellular carriers. Although the mechanism of the transmembrane process for arginine-rich CPPs was proposed, the quantitative correlations and the key factors involved in this process still deserve further investigation. In this study, all-atom molecular dynamics and the umbrella sampling technique were employed to study the arginine-rich CPPs transmembrane process. In the adsorption process of CPPs from solution to the surface of the lipid bilayer, the adsorption free energy (ΔGA) is found to be linearly related to the interaction energy change (ΔEA): ΔGA = 0.0426ΔEA + 36.7, R2 = 0.92. In the CPPs transmembrane process, the transmembrane free energy barrier (ΔGB) is roughly correlated with the corresponding interaction energy change (ΔEB): ΔGB = 0.108ΔEB +135, R2 = 0.73. The multiple salt bridges of guanidinium-PO4 account for 65% of the overall interaction energy, so the increased negative charges of the lipid bilayer or more salt bridges would facilitate CPPs adsorption and transmembrane processes. Also, the increased negative charges of the lipid bilayer would reduce the amount of water to be carried into the pore and further reduce the ΔGB. The peptide backbone would not have a direct impact on transmembrane efficiency. The ΔGB is also found to be related to the length of the pore (L): ΔGB = 46.2L - 31.3, R2 = 0.92, which makes the transmembrane efficiency estimable. This work is expected to deliver an in-depth understanding and help the optimization of CPPs.

In this paper, Ga2O3 thin films were grown on c-plane sapphire substrates by metal-organic chemical vapor deposition (MOCVD). There was phase transition for samples grown with different flow rates of triethyl-gallium (TEGa) and deionized water (H2O). It is found that ε-Ga2O3 is difficult to coalesce and the phase mixture by β­Ga2O3 takes place if the flow rates of TEGa and H2O are too high. However, by using multiple-step growth method, the film became fully coalesced. High-quality ε-Ga2O3 thin film with atomically flat surface and multilayer morphology was obtained.

Quantum-sized metallic clusters protected by biological ligands represent a new class of luminescent materials; yet the understanding of structural information and photoluminescence origin of these ultrasmall clusters remains a challenge. Herein we systematically study the surface ligand dynamics and ligand–metal core interactions of peptide-protected gold nanoclusters (AuNCs) with combined experimental characterizations and theoretical molecular simulations. We show that the peptide sequence plays an important role in determining the surface peptide structuring, interfacial water dynamics and ligand–Au core interaction, which can be tailored by controlling peptide acetylation, constituent amino acid electron donating/withdrawing capacity, aromaticity/hydrophobicity and by adjusting environmental pH. Specifically, emission enhancement is achieved through increasing the electron density of surface ligands in proximity to the Au core, discouraging photoinduced quenching, and by reducing the amount of surface-bound water molecules. These findings provide key design principles for understanding the surface dynamics of peptide-protected nanoparticles and maximizing the photoluminescence of metallic clusters through the exploitation of biologically relevant ligand properties.

The high-bias and breakdown behavior of suspended mono- and few-layer WS2 was explored by in situ aberration-corrected transmission electron microscopy. The suspended WS2 devices were found to undergo irreversible breakdown at sufficiently high biases due to vaporization of the WS2. Simultaneous to the removal of WS2 was the accompanying formation of few-layer graphene decorated with W and WS2 nanoparticles, with the carbon source attributed to organic residues present on the WS2 surface. The breakdown of few-layer WS2 resulted in the formation of faceted S-depleted WS2 tendrils along the vaporization boundary, which were found to exhibit lattice contraction indicative of S depletion, alongside pure W phases incorporated into the structure, with the interfaces imaged at atomic resolution. The combination of observing the graphitization of the amorphous carbon surface residue, W nanoparticles, and S-depleted WS2 phases following the high-bias WS2 disintegration all indicate a thermal Joule heating breakdown mechanism over an avalanche process, with WS2 destruction promoted by preferential S emission. The observation of graphene formation and the role the thin amorphous carbon layer has in the prebreakdown behavior of the device demonstrate the importance of employing encapsulated heterostructure device architectures that exclude residues.

Pt-nanocrystal:MoS2 hybrid materials have promising catalytic properties for hydrogen evolution, and understanding their detailed structures at the atomic scale is crucial to further development. Here, we use an in situ heating holder in an aberration-corrected transmission electron microscope to study the formation of Pt nanocrystals directly on the surface of monolayer MoS2 from a precursor on heating to 800 °C. Isolated single Pt atoms and small nanoclusters are observed after in situ heating, with two types of preferential alignment between the Pt nanocrystals and the underlying monolayer MoS2. Strain effects and thickness variations of the ultrasmall Pt nanocrystal supported on MoS2 are studied, revealing that single atomic planes are formed from a nonlayered face-centered cubic bulk Pt configuration with a lattice expansion of 7-10% compared to that of bulk Pt. The Pt nanocrystals are surrounded by an amorphous carbon layer and in some cases have etched the local surrounding MoS2 material after heating. Electron beam irradiation also initiates Pt nanocrystal etching of the local MoS2, and we study this process in real time at atomic resolution. These results show that the presence of carbon around the Pt nanocrystals does not affect their epitaxial relationship with the MoS2 lattice. Single Pt atoms within the carbon layer are also immobilized at high temperature. These results provide important insights into the formation of Pt:MoS2 hybrid materials.

The edges of 2D materials show novel electronic, magnetic, and optical properties, especially when reduced to nanoribbon widths. Therefore, methods to create atomically flat edges in 2D materials are essential for future exploitation. Atomically flat edges in 2D materials are found after brittle fracture or when electrically biasing, but a simple scalable approach for creating atomically flat periodic edges in monolayer 2D transition metal dichalcogenides has yet to be realized. Here, we show how heating monolayer MoS2 to 800 °C in vacuum produces atomically flat Mo terminated zigzag edges in nanoribbons. We study this at the atomic level using an ultrastable in situ heating holder in an aberration-corrected transmission electron microscope and discriminating Mo from S at the edge, revealing unique Mo terminations for all zigzag orientations that remain stable and atomically flat when cooling back to room temperature. Highly faceted MoS2 nanoribbon constrictions are produced with Mo rich edge structures that have theoretically predicted spin separated transport channels, which are promising for spin logic applications.

A long-standing controversy exists concerning the spatial and temporal characteristics of Holocene climate change in China. Zhejiang is located in the southeast of China, where the East Asian monsoon dominates the climate and a Neolithic culture flourished. In recent years, geographers have debated the climatic conditions existing at the time of the Neolithic cultures. This study reconstructed the sedimentary environment between 11.30 and 4.17 cal ka BP based on a multi-proxy analysis of a 14.3 meter sediment core, drilled in Beihuqiao, Zhejiang Province, China. The results show: (1) The climate was getting warm between 11.50 and 8.77 cal ka BP. Grain size became finer from the bottom to the top layer, accompanied by an increase in the chemical index of alteration (CIA), Mg/Sr ratio, the percentage of clay, pollen concentrations, and a decrease in SiO2/Al2O3 ratio, and the value of bases–alumina (ba), as well as other trace elements. (2) Between 8.77 and 7.99 cal ka BP, the sediment is composed of gray-yellow and gray silt. The percentage of CaO and the ratio of CaO + Na2O + K2O to Al2O3 is much higher. The pollen concentration sharply decreases. The climate was cold and dry in the early stages of this period, but became relatively warmer and wetter in the later stages. (3) The Holocene Climatic Optimum occurred at 7.99–5.68 cal ka BP. Higher contents of clay, total Fe2O3, Al2O3, CIA, the chemical proxy of alteration, pollen concentration, evergreen pollens, and high values of Mg/Sr are observed at this stage, coinciding with a lower SiO2/Al2O3 value, (CaO + Na2O + K2O)/Al2O3 ratio, and an obvious reduction in silt/clay, and SiO2 and CaO concentrations. (4) During the period 5.68–4.17 cal ka BP, the temperature in the study area declined in a stepwise fashion. The grain size became finer, and the Mg/Sr ratio decreased gradually.

The structures and working principles of a piezoelectric pump with dual vibrators are described in this paper. The output performance of the pump was analyses under different working modes. The experimental results demonstrate that changing the driving strategy can vary the performance. When the driving voltage is 60 V at 160 Hz, the maximum output pressure of the pump in the asynchronous mode is 2.18 kPa. The performance of the upper actuator working alone is better than the lower actuator working alone, and the maximum output pressure in this case is 1.3 kPa. Taking the piezoelectric pump with a single vibrator as a typical example, an optimal design method has been applied on the check valves. The performance of the pump with wheel valves is better than that with cantilever valves; the optimum thickness of the check valves is 0.188 mm.

A useful enantioselective Friedel-Crafts reaction of 3,5-dimethoxylphenol with nitroolefins catalyzed by a bifunctional quinine derived thiourea catalyst 9 was developed. The Michael addition products could be obtained in good to high yields (68-92%) and with excellent enantioselectivities (89-98% ee). Such a reaction is exceptionally attractive in virtue of its simple protocol, ready availability of the starting materials, and practical applications of the products.

Two major challenges of 3D bioprinting are the retention of structural fidelity and efficient endothelialization for tissue vascularization. We address both of these issues by introducing a versatile 3D bioprinting strategy, in which a templating bioink is deposited layer-by-layer alongside a matrix bioink to establish void-free multimaterial structures. After crosslinking the matrix phase, the templating phase is sacrificed to create a well-defined 3D network of interconnected tubular channels. This void-free 3D printing (VF-3DP) approach circumvents the traditional concerns of structural collapse, deformation and oxygen inhibition, moreover, it can be readily used to print materials that are widely considered "unprintable". By pre-loading endothelial cells into the templating bioink, the inner surface of the channels can be efficiently cellularized with a confluent endothelial layer. This in-situ endothelialization method can be used to produce endothelium with a far greater uniformity than can be achieved using the conventional post-seeding approach. This VF-3DP approach can also be extended beyond tissue fabrication and towards customized hydrogel-based microfluidics and self-supported perfusable hydrogel constructs.

Ultrasmall gold nanoclusters (AuNCs) have emerged as agile probes for in vivo imaging, as they exhibit exceptional tumour accumulation and efficient renal clearance properties. However, their intrinsic catalytic activity, which can enable an increased detection sensitivity, has yet to be explored for in vivo sensing. By exploiting the peroxidase-mimicking activity of AuNCs and the precise nanometre-size filtration of the kidney, we designed multifunctional protease nanosensors that respond to disease microenvironments to produce a direct colorimetric urinary readout of the disease state in less than one hour. We monitored the catalytic activity of AuNCs in the collected urine of a mouse model of colorectal cancer in which tumour-bearing mice showed a 13-fold increase in colorimetric signal compared to healthy mice. The nanosensors were eliminated completely through hepatic and renal excretion within four weeks of injection with no evidence of toxicity. We envision that this modular approach will enable the rapid detection of a diverse range of diseases by exploiting their specific enzymatic signatures. Catalytic gold nanoclusters that respond to protease activity in vivo and are excreted in urine can offer a quick colorimetric tool for disease detection in resource-limited settings.

The performance of underwater acoustic (UWA) communication is heavily dependent on channel estimation, which is predominantly researched by simulating UWA channels modelled in complex and dynamic underwater environments. In UWA channels modelling, the measurement-based approach provides an accurate method. However, acquirement of environment data and simulation processes are scenario-specific and thus not cost-effective. To overcome such restraints, this article proposes a comprehensive simulation platform that combines UWA channel modelling with orthogonal frequency division multiplexing (OFDM) channel estimation, allowing users to model UWA channels for different ocean environments and simulate channel estimation with configurable input parameters. Based on the simulation platform, three independent simulations are conducted to determine the impacts of receiving depth, sea bottom boundary, and sea surface boundary on channel estimation. The simulations show that UWA channel estimation is greatly affected by underwater environments. The effect can be mainly attributed to changing acoustic rays tracing which result in fluctuating time delay and amplitude. With 10 m receiving depth and flat sea bottom, the channel estimation achieves optimal performance. Further study indicates that the sea surface has stochastic effects on channel estimation. As the significant wave height (SWH) increases, the average performance of channel estimation shows improvements.

The Upper Miocene–Pliocene red clay deposits of the Chinese Loess Plateau (CLP), like the overlying Quaternary loess, have recorded abundant paleoclimatic evolution information. In this study, we found that the variation in the magnetic susceptibility of seven sections across a north–south climate gradient in the eastern CLP exhibited an oscillatory upward trend. Prior to this research, much less was known about the causation and mechanism of this trend. Among the seven sections, the Jiaxian and Duanjiapo sections are located in the northernmost and southernmost of the climatic gradient, respectively. These representative sections were therefore selected to investigate the causation and mechanism of the aforementioned trend using magnetic measurements. The results were as follows. (1) The absolute and relative content of fine-grained ferrimagnetic minerals displayed an oscillatory upward increasing trend in both of the red clay sequences, which was the primary reason for the susceptibility increase in fluctuations. (2) The absolute content of antiferrimagnetic minerals was nearly equivalent in each red clay sequence. (3) Based on the combination of the results of present study and previous study findings, we found that the weathering and pedogenesis intensity of the red clay sequence showed an oscillatory upward trend during 7–2.6 Ma, which was closely linked with the strengthened East Asian summer monsoon in oscillations. These findings are probably the main cause for the oscillatory upward increasing fine-grained ferrimagnetic minerals in Upper Miocene–Pliocene red clay sequence. Further, this is likely the mechanism for the oscillatory upward increase of χ in the red clay sequence.

We conducted hydraulic fracturing (HF) experiments on 170 mm cubic granite specimens with a 20 mm diameter central hole to investigate how fluid viscosity affects HF process and crack properties. In experiments using supercritical carbon dioxide (SC-CO2), liquid carbon dioxide (L-CO2), water, and viscous oil with viscosity of 0.051–336.6 mPa · s, we compared the results for breakdown pressure, the distribution and fracturing mechanism of acoustic emission (AE), and the microstructure of induced cracks revealed by using an acrylic resin containing a fluorescent compound. Fracturing with low-viscosity fluid induced three-dimensionally sinuous cracks with many secondary branches, which seem to be desirable pathways for enhanced geothermal system (EGS), shale gas recovery and other processes.

Magnetic susceptibility (MS) of aeolian deposits on the Chinese Loess Plateau is high in paleosol and low in loess. The MS of paleosols is mainly enhanced by ferromagnetic minerals formed during post-depositional soil development. In central Alaska, aeolian deposits, MS is high in loess and low in paleosol. The wind vigor model has been proposed to interpret such MS enhancement for the central Alaskan loess. This model suggests that the MS variations are determined by pre-depositional wind strength. The wind vigor model has been introduced to the Siberian Kurtak section where MS is also high in loess and low in paleosol. Additionally to the wind vigor model, low MS in paleosols could be triggered by post-depositional soil development and gleying when the pedogenesis and gleying transforms the ferromagnetic minerals to weak and non-magnetic minerals. In our study of the most continuous Kurtak section in western Siberia, we found that paleosols have substantially more ferruginous mottles due to water-saturated conditions. Magnetic analysis demonstrates that paleosols contain greater content of hard magnetic minerals compared to the loess. Temperature analysis of the MS in the ferruginous mottles shows that magnetic susceptibility increases 37 times after heating and cooling; half of the MS enhancements are contributed due to the heating in between 600 and 700 °C, being caused by the decomposition of non-magnetic chlorite. This suggests that pedogenesis and gleying at the Kurtak section produces weak and non-magnetic minerals in water-saturated anaerobic conditions, which deplete the MS in paleosols after deposition of loess.

A new kind of piezoelectric pump with triple vibrators was presented. The pump adopted circular piezoelectric vibrator with a hole in the middle, and a check valve was adhered to the hole to cut off air. The working principle of the pump was analyzed. A prototype of piezoelectric pump was fabricated and measured. The experimental results show: (1) The maximum flow rate of the piezoelectric pump under the working mode of vibrators 1, and 3 driven synchronously and vibrator 2 driven asynchronously reached to 1513.2 mL/min when driving frequency was 220 Hz, and the maximum pressure reached to 4.08 kPa when that was 140 Hz. (2) The output performance of the piezoelectric pump with triple vibrators was the best under the working mode of vibrators 1, and 3 driven synchronously and vibrator 2 driven asynchronously. (3) When only two vibrators participate in working, the best connection method was vibrator 1 not driven and vibrators 2, and 3 driven asynchronously. (4) When only one vibrator participates in working, the best connection method was vibrator 3 driven solely.

The influence of the functional groups in MIL-101(Cr)-X metal–organic frameworks (MOFs) with X = H, NH2, and NO2 on the adsorption properties of N/S-heteroaromatic compounds from model fuels was investigated. Benzothiophene (BT), dibenzothiophene (DBT), quinoline, and indole were selected as representative organosulfur and organonitrogen contaminants in liquid fuels. Their adsorption on four MIL-101 materials from model fuels was evaluated in a batch adsorption system. Introducing amino or nitro group into MIL-101(Cr) leads to decreased adsorption capacities of BT and DBT from isooctane, especially the bulkier nitro group. The adsorption capacities of indole and quinoline from isooctane also decrease when introducing nitro group. However, the adsorption capacities of quinoline and indole on amino-MIL-101(Cr) increase by about 25% and 10% even through the porosity is 30% lower than that of the parent. The improved adsorption capacities of amino-MIL-101(Cr) for quinoline and indole are attributed to hydroge...

Computing bubble-points of multicomponent mixtures using Monte Carlo simulations is a non-trivial task. A new method is used to compute gas compositions from a known temperature, bubble-point pressure, and liquid composition. Monte Carlo simulations are used to calculate the bubble-points of carbon dioxide (CO2) and methane (CH4) mixtures in the ionic liquids (ILs) 1-n-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide [bmim][Tf2N] and 1-ethyl-3-methylimidazolium diethylphosphate [emim][dep]. The Continuous Fractional Component Monte Carlo (CFCMC) method in the osmotic ensemble has been used to compute the solubility of CO2/CH4 gas mixtures at different temperatures (T), pressures (P), and gas compositions (yi). The effect of T, P, and yi on the real CO2/CH4 selectivity (i.e., the selectivity of CO2 in the presence of CH4) is investigated. The real selectivity will differ from the ideal selectivity, which is defined as the ratio of the Henry's constants, if the solubility of CO2 is influenced by the presence of CH4. The computed real selectivities are compared with the experimentally obtained real and ideal selectivities. The real CO2/CH4 selectivity decreases with increasing temperature and pressure, while the gas phase composition has a minor effect. The real selectivity is approximately identical to the ideal selectivity for relatively low pressures and low solute concentrations in the liquid phase. The real selectivity deviates from the ideal selectivity as the solute concentration in the liquid phase increases.

Catalytic hydrolysis of methyl glycolate is a promising way to produce glycolic acid with high purity. The hydrolysis of methyl glycolate was investigated both in a stirred-batch reactor and in a reactive distillation column. Batch hydrolysis distillation was found to be rather effective in improving the conversion of methyl glycolate. A mechanism model including the cooperative catalysis of sulfuric acid and the generated glycolic acid was developed based on the acid-catalyzed hydrolysis mechanism and the protolysis equilibrium; then, the model was further simplified according to the relationship between the concentrations of hydroxonium ions and their providers. This simplified model could be easily introduced to Aspen Plus and applied to simulating the homogeneous hydrolysis process of methyl glycolate with or without sulfuric acid as catalyst via the reactive distillation technique.

Red Clay underlying the loess-palaeosol sequences on the Chinese Loess Plateau is an eolian deposit. There is a controversy over whether magnetic susceptibility (chi) variations in Red Clay sequence can be used as an indicator of summer palaeomonsoon intensity. This study investigates the magnetic mineralogy, magnetic concentration and magnetic grain size distribution of Jiaxian Red Clay with multimagnetic methods. Our results indicate that the magnetic properties of Jiaxian Red Clay are similar to those of the Quaternary loess-palaeosol sequences, and ultrafine ferrimagnetic grains produced during pedogenesis are responsible for an increase in susceptibility, therefore the chi enhancement mechanism of Red Clay is similar to that of the overlying loess-palaeosol sequences. This paper explores chi variations in the Red Clay sequence through spatial and temporal analysis. The susceptibility variation of six sites along a NNE to SSW transect correlate to palaeoclimatic cycles, so chi can be used to trace the summer palaeomonsoon intensity from a spatial perspective. However, a simple loess-derived calibration function cannot be used to quantitative reconstruct the palaeomonsoon intensity variations thought time. An adjusted calibration function for palaeosols from Red Clay sequence needs to be developed, so that chi can be used to quantitative reconstruct palaeomonsoon intensity. Further study is necessary to develop such a transfer function.

High-energy irradiation of materials can lead to void formation due to the aggregation of vacancies, reducing the local stress in the system. Studying void formation and its interplay with vacancy clusters in bulk materials at the atomic level has been challenging due to the thick volume of 3D materials, which generally limits high-resolution transmission electron microscopy. The thin nature of 2D materials is ideal for studying fundamental material defects such as dislocations and crack tips and has potential to reveal void formation by vacancy aggregation in detail. Here, using atomic-resolution in situ transmission electron microscopy of 2D monolayer MoS2, we capture rapid thermal diffusion of S vacancies into ultralong (∼60 nm) 1D S vacancy channels that initiate void formation at high vacancy densities. Strong interactions are observed between the 1D channels and void growth, whereby Mo and S atoms are funneled back and forth between the void edge and the crystal surface to enable void enlargement. Preferential void growth up to 100 nm is shown to occur by rapid digestion of 1D S vacancy channels as they make contact. These results reveal the atomistic mechanisms behind void enlargement in 2D materials under intense high-energy irradiation at high temperatures and the existence of ultralong 1D vacancy channels. This knowledge may also help improve the understanding of void formation in other systems such as nuclear materials, where direct visualization is challenging due to 3D bulk volume.

Direct synthesis of graphene with well-defined nanoscale pores over large areas can transform the fabrication of nanoporous atomically thin membranes (NATMs) and greatly enhance their potential for practical applications. However, scalable bottom-up synthesis of continuous sheets of nanoporous graphene that maintain integrity over large areas has not been demonstrated. Here, it is shown that a simple reduction in temperature during chemical vapor deposition (CVD) on Cu induces in-situ formation of nanoscale defects (≤2-3 nm) in the graphene lattice, enabling direct and scalable synthesis of nanoporous monolayer graphene. By solution-casting of hierarchically porous polyether sulfone supports on the as-grown nanoporous CVD graphene, large-area (>5 cm2 ) NATMs for dialysis applications are demonstrated. The synthesized NATMs show size-selective diffusive transport and effective separation of small molecules and salts from a model protein, with ≈2-100× increase in permeance along with selectivity better than or comparable to state-of-the-art commercially available polymeric dialysis membranes. The membranes constitute the largest fully functional NATMs fabricated via bottom-up nanopore formation, and can be easily scaled up to larger sizes permitted by CVD synthesis. The results highlight synergistic benefits in blending traditional membrane casting with bottom-up pore creation during graphene CVD for advancing NATMs toward practical applications.

The initial cluster centers of traditional K-means algorithm are randomly selected from spatially distributed data samples. This procedure may significantly affect the final clustering outputs and is unable to ensure a high-quality solution. This paper attempts to improve the quality of solution and the efficiency of clustering through selecting initial cluster centers based on hotspot analysis. An algorithm is developed to identify $K$ hotspots as initial cluster centers. The proposed algorithm is compared to three existing methods in our experiments. Our results demonstrate that our method can generate similar but more stable clustering results with less number of iterations than others.

A demonstration is presented of how significant improvements in all-2D photodetectors can be achieved by exploiting the type-II band alignment of vertically stacked WS2 /MoS2 semiconducting heterobilayers and finite density of states of graphene electrodes. The photoresponsivity of WS2 /MoS2 heterobilayer devices is increased by more than an order of magnitude compared to homobilayer devices and two orders of magnitude compared to monolayer devices of WS2 and MoS2 , reaching 103 A W-1 under an illumination power density of 1.7 × 102 mW cm-2 . The massive improvement in performance is due to the strong Coulomb interaction between WS2 and MoS2 layers. The efficient charge transfer at the WS2 /MoS2 heterointerface and long trapping time of photogenerated charges contribute to the observed large photoconductive gain of ≈3 × 104 . Laterally spaced graphene electrodes with vertically stacked 2D van der Waals heterostructures are employed for making high-performing ultrathin photodetectors.

In this report, graphene (Gr) is used as a 2D electrode and monolayer WS2 as the active semiconductor in ultrathin photodetector devices. All of the 2D materials are grown by chemical vapor deposition (CVD) and thus pose as a viable route to scalability. The monolayer thickness of both electrode and semiconductor gives these photodetectors ∼2 nm thickness. We show that graphene is different to conventional metal (Au) electrodes due to the finite density of states from the Dirac cones of the valence and conduction bands, which enables the photoresponsivity to be modulated by electrostatic gating and light input control. We demonstrate lateral Gr-WS2-Gr photodetectors with photoresponsivities reaching 3.5 A/W under illumination power densities of 2.5 × 10(7) mW/cm(2). The performance of monolayer WS2 is compared to bilayer WS2 in photodetectors and we show that increased photoresponsivity is achieved in the thicker bilayer WS2 crystals due to increased optical absorption. This approach of incorporating graphene electrodes in lateral TMD based devices provides insights on the contact engineering in 2D optoelectronics, which is crucial for the development of high performing ultrathin photodetector arrays for versatile applications.

The atomic level dynamics of gold on graphene is studied at temperatures up to 800 °C using an in situ heating holder within an aberration-corrected transmission electron microscope. At this high temperature, individual gold atoms and nanoclusters are mobile across the surface of graphene and attach to defect sites and migrate along the edges of holes in graphene. Gold nanoclusters on clean graphene show crystallinity at temperatures above their predicted melting point for equivalent sized clusters due to strong epitaxial interactions with the underlying graphene lattice. Gold nanoclusters anchored to defect sites in graphene exhibit discrete rotations between fixed orientations while maintaining epitaxial correlations to the graphene. We show that gold nanoclusters can be two-dimensional with monolayer thickness and switch their crystal structure between two different phases. These results have important implications on the use of gold nanoclusters on graphene at elevated temperatures for applications, such as catalysis and plasmonics.

Dopants in two-dimensional dichalcogenides have a significant role in affecting electronic, mechanical, and interfacial properties. Controllable doping is desired for the intentional modification of such properties to enhance performance, however unwanted defects and impurity dopants also have a detrimental impact, as often found for chemical vapor deposition (CVD) grown films. The reliable identification, and subsequent characterization, of dopants is therefore of significant importance. Here, we show that Cr and V impurity atoms are found in CVD grown MoS2 monolayer 2D crystals as single atom substitutional dopants in place of Mo. We attribute these impurities to trace elements present in the MoO3 CVD precursor. Simultaneous annular dark field scanning transmission electron microscopy (ADF-STEM) and electron energy loss spectroscopy (EELS) is used to map the location of metal atom substitutions of Cr and V in MoS2 monolayers with single atom precision. The Cr and V are stable under electron irradiation at 60 to 80 kV, when incorporated into line defects, and when heated to elevated temperatures. The combined ADF-STEM and EELS differentiates these Cr and V dopants from other similar contrast defect structures, such as 2S self-interstitials at the Mo site, preventing misidentification. Density functional theory calculations reveal that the presence of Cr or V causes changes to the density of states, indicating doping of the MoS2 material. These transferred precursor impurities could help explain the presence of trapped charges in CVD prepared MoS2.

An in situ heating holder inside an aberration-corrected transmission electron microscope (AC-TEM) is used to investigate the real-time atomic level dynamics associated with heterogeneous nucleation and growth of graphene from Au nanoparticle seeds. Heating monolayer graphene to an elevated temperature of 800 °C removes the majority of amorphous carbon adsorbates and leaves a clean surface. The aggregation of Au impurity atoms into nanoparticle clusters that are bound to the surface of monolayer graphene causes nucleation of secondary graphene layers from carbon feedstock present within the microscope chamber. This enables the in situ study of heterogeneous nucleation and growth of graphene at the atomic level. We show that the growth mechanism consists of alternating C cluster attachment and indentation filling to maintain a uniform growth front of lowest energy. Back-folding of the graphene growth front is observed, followed by a process that involves flipping back and attaching to the surrounding region. We show how the highly polycrystalline graphene seed evolves with time into a higher order crystalline structure using a combination of AC-TEM and tight-binding molecular dynamics (TBMD) simulations. This helps understand the detailed lowest-energy step-by-step pathways associated with grain boundaries (GB) migration and crystallization processes. We find the motion of the GB is discontinuous and mediated by both bond rotation and atom evaporation, supported by density functional theory calculations and TBMD. These results provide insights into the formation of crystalline seed domains that are generated during bottom-up graphene synthesis.

The nuclear reaction network is usually studied via precise calculation of differential equation sets, and much research interest has been focused on the characteristics of nuclides, such as half-life and size limit. In this paper, however, we adopt the methods from both multilayer and reaction networks, and obtain a distinctive view by mapping all the nuclear reactions in JINA REACLIB database into a directed network with 4 layers: neutron, proton, $^4$He and the remainder. The layer names correspond to reaction types decided by the currency particles consumed. This combined approach reveals that, in the remainder layer, the $\beta$-stability has high correlation with node degree difference and overlapping coefficient. Moreover, when reaction rates are considered as node strength, we find that, at lower temperatures, nuclide half-life scales reciprocally with its out-strength. The connection between physical properties and topological characteristics may help to explore the boundary of the nuclide chart., Comment: 11 pages, 7 figures

The time-order of interactions, which is regulated by some intrinsic activity, surely plays a crucial role regarding the transport efficiency of transportation systems. Here we study the optimal transport structure by measure of the length of time-respecting paths. Our network is built from a two-dimensional regular lattice, and long-range connections are allocated with probability P(ij)∼r(ij)(-α), where r(ij) is the Manhattan distance. By assigning each shortcut an activity rate subjected to its geometric distance τ(ij)∼r(ij)(-C), long-range links become active intermittently, leading to the time-varying dynamics. We show that for 0

Monte Carlo simulations are used to calculate the solubility of natural gas components in ionic liquids (ILs) and Selexol, which is a mixture of poly(ethylene glycol) dimethyl ethers. The solubility of the pure gases carbon dioxide (CO2), methane (CH4), ethane (C2H6), and sulfur dioxide (SO2) in the ILs 1-alkyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([Cnmim][Tf2N], n = 4, 6), 1-ethyl-3-methylimidazolium diethylphosphate ([emim][dep]), and Selexol (CH3O[CH2CH2O]nCH3, n = 4, 6) have been computed at 313.15 K and several pressures. The gas solubility trend observed in the experiments and simulations is: SO2 > CO2 > C2H6 > CH4. Overall, the Monte Carlo simulation results are in quantitative agreement with existing experimental data. Molecular simulation is an excellent tool to predict gas solubilities in solvents and may be used as a screening tool to navigate through the large number of theoretically possible ILs.

We study the bond lengths of silicon (Si) atoms attached to both armchair and zigzag edges using aberration corrected transmission electron microscopy with monochromation of the electron beam. An in situ heating holder is used to perform imaging of samples at 800 °C in order to reduce chemical etching effects that cause rapid structure changes of graphene edges at room temperature under the electron beam. We provide detailed bond length measurements for Si atoms both attached to edges and also as near edge substitutional dopants. Edge reconstruction is also involved with the addition of Si dopants. Si atoms bonded to the edge of graphene are compared to substitutional dopants in the bulk lattice and reveal reduced out-of-plane distortion and bond elongation. An extended linear array of Si atoms at the edge is found to be energy-favorable due to inter-Si interactions. These results provide detailed structural information about the Si-C bonds in graphene, which may have importance in future catalytic and electronic applications.

Baryscapus dioryctriae Yang & Song sp. nov. (Hymenoptera: Eulophidae), a gregarious pupal and larval endo-parasitoid of Dioryctria pryeri Ragonot and Dioryctria abietella Denis & Schiffermuller (Lepidoptera: Pyralidae) is described and illustrated. The hosts are serious pests of the cones, seeds, and twigs of Pinus koraiensis Sieb. & Zucc., a predominant forest tree species in the northeastern China. The parasitoid has potential as a biocontrol agent for the pests, as an average parasitism rate of 19.5% has been observed and 87.7 parasitoid adults (range 41–138) emerge from a single host. Detailed photographs of the key characters of the female and male of the new species are provided. Type specimens were deposited in Insect Museum, Chinese Academy of Forestry, Beijing, and the Insect Collection of Jilin Provincial Academy of Forestry, Changchun, Jilin Province, China, as well as China National Insect Collection at Institute of Zoology, Chinese Academy of Sciences, Beijing.

We introduce temporal effect to the classical Kleinberg model and study how it affects the spatial structure of optimal transport network. The initial network is built from a regular d-dimensional lattice added by shortcuts with probability p(rij) ∼ rij-α, where rij is the geometric distance between node i and j. By assigning each shortcut an energy E=r·τ, a link with length r survives within period τ, which leads the network to a decaying dynamics of constantly losing long-range links. We find new optimal transport in the dynamical system for α=3/4 d, in contrast to any other result in static systems. The conclusion does not depend on the information used for navigation, being based on local or global knowledge of the network, which indicates the possibility of the optimal design for general transport dynamics in the time-varying network.

We use an in situ heating holder within an aberration corrected transmission electron microscope (AC-TEM) to study the structure and dynamics of large closed grain boundary (GB) loops in graphene at the atomic level. Temperatures up to 800 °C are used to accelerate dynamic evolution of the defect clusters, increasing bond rotation and atomic addition/loss. Our results show that the large closed GB loops relax under electron beam irradiation into several isolated dislocations far apart from each other. Line defects composed of several adjacent excess-atom clusters can be found during the reconfiguration process. Dislocation ejection from the closed GB loops are seen in real time and are shown to help the reduction in loop size. These results show detailed information about the stability and behavior of large GB loops in 2D materials that have importance in the high temperature processing of these materials.