Fast crystal growth in deeply undercooled ZrTi melts.

We investigate the growth of crystals in Zr50Ti50 melts by classical molecular-dynamics simulations with an embedded atom method and a Stillinger-Weber potential model. Both models display fast solidification rates that can be captured by the transition state theory or the Ginzburg-Landau theory at small undercoolings. Fast crystal-growth rates are found to be affected by the pre-existing ordering in liquids, such as the body-centered cubic-like and icosahedral-like structures. The interface-induced ordering unveiled by the crystal-freezing method can explain the rate difference between these two models. However, these orderings fail to rationalize the temperature evolution of the growth rate at deep undercoolings. We correlate the growth kinetics with the detailed dynamical processes in liquids, finding the decoupling of hierarchic relaxation processes when collective motion emerges in supercooled liquids. We find that the growth kinetics is nondiffusive, but with a lower activation barrier corresponding to the structural relaxation or the cage-relative motion in ZrTi melts. These results explore a new relaxation mechanism for the fast growth rate in deeply undercooled liquids.

Biphasic alcoholysis coupled with high-speed countercurrent chromatography for high performance on separating phorbol from Croton tiglium Linn extracts.

Phorbol is a tetracyclic diterpenoid found in Euphorbia tirucalli, Croton tiglium, and Rehmannia glutinosa, and is nuclear of various phorbol esters. The rapid obtaining of phorbol with high purity highly contributes to its application, such as synthesizing phorbol esters with designable side chains and particular therapeutic efficacy. This study introduced a biphasic alcoholysis method for obtaining phorbol from croton oil by using polarity imparity organic solvents in both phases and established a high-speed countercurrent chromatography method for simultaneous separation and purification of phorbol. The optimized operation conditions of biphasic alcoholysis were a reaction time of 91 min, a temperature of 14°C, and a croton oil-methanol ratio of 1:30 (g:ml). The phorbol during the biphasic alcoholysis was 3.2-fold higher in content than that obtained in conventional monophasic alcoholysis. The optimized high-speed countercurrent chromatography method was using the ethyl acetate/n-butyl alcohol/water at 4.7:0.3:5 (v:v:v) with Na2 SO4 at 0.36 g/10 ml as the solvent system, using the mobile phase flow rate of 2 ml/min, the revolution of 800 r/min, under which the retention of the stationary phase was achieved at 72.83%. The crystallized phorbol following high-speed countercurrent chromatography was obtained as high purity of 94%.

Nonmonotonic Dynamical Correlations beneath the Surface of Glass-Forming Liquids.

Collective motion over increasing length scales is a signature of the vitrification process of liquids. We demonstrate how distinct static and dynamic length scales govern the dynamics of vitrifying films. In contrast to a monotonically growing static correlation length, the dynamical correlation length that measures the extent of surface-dynamics acceleration into the bulk displays a striking nonmonotonic temperature evolution that is robust also against changes in detailed interatomic interaction. This nonmonotonic change defines a crossover temperature T_{*} that is distinct from the critical temperature T_{c} of mode-coupling theory. We connect this nonmonotonic change to a morphological change of cooperative rearrangement regions of fast particles, and to the point where the decoupling of fast-particle motion from the bulk relaxation is most sensitive to fluctuations. We propose a rigorous definition of this new crossover temperature T_{*} within a recent extension of mode-coupling theory, the stochastic ß-relaxation theory.

Orientational wetting and dynamical correlations toward glass transition on the surface of imidazolium-based ionic liquids.

Surface induces many fascinating physical phenomena, such as dynamic acceleration, surface anchoring, and orientational wetting, and, thus, is of great interest to study. Here, we report classic molecular dynamics simulations on the free-standing surface of imidazolium-based ionic liquids (ILs) [C4mim][PF6] and [C10mim][PF6]. On [C10mim][PF6] surface, a significant orientational wetting is observed, with the wetting strength showing a diverging tendency. Depth of the wetting was captured from the density and orientational order profile by a static length, which remarkably increases below the temperature Tstat upon cooling down. The dynamical correlation length that measures the distance of surface-dynamics acceleration into the bulk was characterized via the spatial-dependent mobility. The translational correlation exhibits a similar drastic increment at Tstat, while the rotational correlation drastically increases at a lower temperature Trot. We connect these results to the dynamics in bulk liquids, by finding Tstat and Trot that correspond to the onset temperatures where the liquids become cooperative for translational and rotational relaxation, respectively. This signifies the importance of collective dynamics in the bulk on the orientational wetting and surface dynamics in the ILs.

3D Hierarchical Porous and N-Doped Carbonized Microspheres Derived from Chitin for Remarkable Adsorption of Congo Red in Aqueous Solution.

A novel adsorbent of N-doped carbonized microspheres were developed from chitin (N-doped CM-chitin) for adsorption of Congo red (CR). The N-doped CM-chitin showed spherical shape and consisted of carbon nanofibers with 3D hierarchical architecture. There were many micro/nano-pores existing in N-doped CM-chitin with high surface area (455.703 m2 g-1). The N element was uniformly distributed on the carbon nanofibers and formed with oxidize-N graphitic-N, pyrrolic-N, and pyridinic-N. The N-doped CM-chitin showed excellent adsorption capability for CR and the maximum adsorption amount was approximate 954.47 mg g-1. The π-π/n-π interaction, hydrogen-bond interactions, and pore filling adsorption might be the adsorption mechanisms. The adsorption of N-doped CM-chitin was considered as a spontaneous endothermic adsorption process, and which well conformed to the pseudo-second-order kinetic and Langmuir isotherm model. The N-doped CM-chitin exhibited an effective adsorption performance for dynamic CR water with good reusability. Therefore, this work provides new insights into the fabrication of a novel N-doped adsorbent from low-cost and waste biomasses.

Preparation and Characterization of Protein Molecularly Imprinted Poly (Ionic Liquid)/Calcium Alginate Composite Cryogel Membrane with High Mechanical Strength for the Separation of Bovine Serum Albumin.

In order to improve the mechanical strength and imprinting efficiency, a novel bovine serum albumin (BSA) molecularly imprinted poly(ionic liquid)/calcium alginate composite cryogel membrane (MICM) was prepared. The results of the tensile test indicated that the MICM had excellent mechanical strength which could reach up to 90.00 KPa, 30.30 times higher than the poly (ionic liquid) membrane without calcium alginate; the elongation of it could reach up to 93.70%, 8.28 times higher than the poly (ionic liquid) membrane without calcium alginate. The MICM had a very high welling ratio of 1026.56% and macropore porosity of 62.29%, which can provide effective mass transport of proteins. More remarkably, it had a very high adsorption capacity of 485.87 mg g-1 at 20 °C and 0.66 mg mL-1 of the initial concentration of BSA. Moreover, MICM also had good selective and competitive recognition toward BSA, exhibiting potential utility in protein separation. This work can provide a potential method to prepare the protein-imprinted cryogel membrane with both high mechanical strength and imprinting efficiency.

Molecular-dynamics simulations on the mesophase transition induced by oscillatory shear in imidazolium-based ionic liquid crystals.

Molecular dynamics simulations were performed on a 1-dodecyl-3-methylimidazolium hexafluorophosphate ([C12mim][PF6]) ionic liquid crystal (ILC) with the application of an oscillatory shear. We found that the oscillatory shear can both accelerate and suppress mesophase formation depending on shear amplitude. A small amplitude shear can speed up the mesophase transition dynamics and result in a more ordered mesomorphic structure than that without shear, i.e., an effect of accelerated aging. The mesophase is destabilized when the shear amplitude is large enough, resulting in a smectic A (SmA) to liquid or a smectic B (SmB) to SmA transition, with the mesophase behaviour summarized in an out-of-equilibrium phase diagram. Inside the layer plane a medium-range hexatic order was observed, with the correlation length extending to several nanometres in the shear-induced SmA phase. We rationalize the nonequilibrium mesophase behaviour from the rheology of isotropic liquids, finding a temperature-independent critical relaxation time for the mesophase transition in the translational or rotational dynamics. This finding can be used to predict the mesophase behaviour in the sheared ILCs from the rheology of isotropic liquids.

Crystal growth in deeply undercooled Ni50Al50: Signature of the ordering sequence at the interface.

Crystal growth of the intermetallic alloy, Ni50Al50, is investigated by molecular dynamics simulations with two different interatomic potentials. The calculated growth rate can be captured by the Wilson-Frenkel or Broughton-Gilmer-Jackson model at small undercoolings but deviates from the theory at deep undercoolings. Failure of the theory is found to be correlated with the dynamic processes that emerged at the interface, but not apparently with the static interface structure. The chemical segregation of Ni and Al atoms occurs before the geometrical ordering upon crystallization at small undercoolings. In contrast, the geometrical ordering precedes the chemical one at deep undercoolings. These two ordering processes show a collapsed time evolution at the crossover temperature consistent with the onset of the theoretical deviation. We rationalize the delayed chemical segregation behavior by the collective atomic motion, which is characterized by the super-Arrhenius transition of the temperature-dependent diffusivity and structural relaxation time at the crossover point.

Structural origin for vibration-induced accelerated aging and rejuvenation in metallic glasses.

Glassy materials are nonequilibrium and their energy states have crucial influences on properties. Recent studies have shown that oscillating deformations (vibrations) can cause either accelerated aging (lowering energy) or rejuvenation (elevating energy); however, the underlying atomic mechanisms remain elusive. Using metallic glasses (MGs) as model systems, we show that the vibration-induced accelerated aging is correlated with the strain field of the stringlike atomic motions stemming from the Johari-Goldstein (ß) relaxation, whereas the rejuvenation is associated with nonlinear response and the formation of nanoscale shear bands attributing to the activation of α relaxation. Both processes are affected by thermal fluctuations, which result in an optimal temperature for accelerated aging. These results suggest intrinsic correlations among relaxation dynamics, mechanical properties, and the vibration induced structural rearrangements in MGs.

Voltage-Gated Na+ Channels are Modulated by Glucose and Involved in Regulating Cellular Insulin Content of INS-1 Cells.

BACKGROUND/AIMS: Islet beta cells (ß-cells) are unique cells that play a critical role in glucose homeostasis by secreting insulin in response to increased glucose levels. Voltage-gated ion channels in ß-cells, such as K+ and Ca2+ channels, contribute to insulin secretion. The response of voltage-gated Na+ channels (VGSCs) in ß-cells to the changes in glucose levels remains unknown. This work aims to determine the role of extracellular glucose on the regulation of VGSC. METHODS: The effect of glucose on VGSC currents (INa) was investigated in insulin-secreting ß-cell line (INS-1) cells of rats using whole-cell patch clamp techniques, and the effects of glucose on insulin content and cell viability were determined using Enzyme-Linked Immunosorbent Assay (ELISA) and Methylthiazolyldiphenyl-tetrazolium Bromide (MTT) assay methods respectively. RESULTS: Our results show that extracellular glucose application can inhibit the peak of INa in a concentration-dependent manner. Glucose concentration of 18 mM reduced the amplitude of INa, suppressed the INa of steady-state activation, shifted the steady-state inactivation curves of INa to negative potentials, and prolonged the time course of INa recovery from inactivation. Glucose also enhanced the activity-dependent attenuation of INa and reduced the fraction of activated channels. Furthermore, 18 mM glucose or low concentration of tetrodotoxin (TTX, a VGSC-specific blocker) partially inhibited the activity of VGSC and also improved insulin synthesis. CONCLUSION: These results revealed that extracellular glucose application enhances the insulin synthesis in INS-1 cells and the mechanism through the partial inhibition on INa channel is involved. Our results innovatively suggest that VGSC plays a vital role in modulating glucose homeostasis.

Molecular dynamics study of mesophase transitions upon annealing of imidazolium-based ionic liquids with long-alkyl chains.

Molecular dynamics simulations are performed on a 1-dodecyl-3-methylimidazolium hexafluorophosphate ([C12mim][PF6]) ionic liquid using a united-atom model. The ionic liquid exhibits second step relaxation at temperatures below a crossover point, where the diffusion coefficient shows an Arrhenius to non-Arrhenius transition. Annealing below this crossover temperature makes an isotropic to mesophase transition, where the smectic A (SmA) phase or crystal-like smectic B (SmB) phase forms. Hundreds of nanoseconds are required for completing these transitions. A normal diffusion process is found for anions along the layer-normal and -lateral directions in the SmA phase, but only in the lateral directions in the SmB phase. We find a preserved orientational order for the imidazolium-ring rotational and the alkyl-chain reorientational dynamics in both of the smectic phases.

Pt/ZnO@C Nanocable with Dual-Enhanced Photocatalytic Performance and Superior Photostability.

To improve the photocatalytic activity and photostability of ZnO, a novel cable-like Pt/ZnO@C composite is successfully fabricated by coating a 3-5 nm hydrothermal carbon (HTC) layer on the surface of the Pt nanoparticle-modified ZnO nanowire. After investigating the optical and photoelectrochemical performance in detail, it is found that the Pt/ZnO@C nanocable shows a dual-enhanced migration efficiency for the photoinduced surface electrons, distributing to the modified Pt nanoparticles and the coated HTC layer. Consequently, the Pt/ZnO@C nanocable exhibits a dual-enhanced photocatalytic activity for the degradation of various organic pollutants under the UV light irradiation. The coated HTC layer can also play a role in suspending the ZnO photocorrosion and significantly improves the photostability of the Pt/ZnO@C nanocable. Furthermore, the photocatalysis and photocorrosion mechanism of the Pt/ZnO@C nanocable is proposed and discussed in terms of its structural feature and photoelectrochemical property. The resultant Pt/ZnO@C nanocable with the unique HTC layer-coated structure will probably stimulate to design and synthesize more HTC-hybridized composites with a superior photocatalytic or photoelectrocatalytic performance.

Iron-driven self-assembly of dopamine into dumbbell-shaped nanozyme for visual and rapid detection of norfloxacin on a smartphone-assisted platform.

Antibiotics in aquatic environments raise health concerns. Therefore, the rapid, on-site, and accurate detection of antibiotic residues is crucial for protecting the environment and human health. Herein, a dumbbell-shaped iron (Fe3+)-dopamine coordination nanozyme (Fe-DCzyme) was developed via an iron-driven self-assembly strategy. It exhibited excellent peroxidase-like activity, which can be quenched by adding l-cysteine to prevent Fe3+/Fe2+ electron transfer but restored by adding norfloxacin. Given the 'On-Off-On' effect of peroxidase-like activity, Fe-DCzyme was used as a colourimetric sensor for norfloxacin detection, and showed a wide linear range from 0.05 to 6.00 µM (R2 = 0.9950) and LOD of 27.0 nM. A portable smartphone-assisted detection platform using Fe-DCzyme was also designed to convert norfloxacin-induced color changes into RGB values as well as to realise the rapid, on-site and quantitative detection of norfloxacin. A good linear relation (0.10-6.00 µM) and high sensitivity (LOD = 79.3 nM) were achieved for the smartphone-assisted Fe-DCzyme detection platform. Its application was verified using norfloxacin spiking methods with satisfactory recoveries (92.66%-119.65%). Therefore, the portable smartphone-assisted Fe-DCzyme detection platform with low cost and easy operation can be used for the rapid, on-site and visual quantitative detection of antibiotic residues in water samples.

Experimental Study on the Chemical Reaction Characteristics in the Calcination Process of an 811 Ternary Cathode Material.

The research on 811 ternary cathode materials is mainly based on synthesis and modification. However, the preparation process of these materials is accompanied by complex chemical reactions, and the reaction process and corresponding kinetic analysis have not been widely explored. Under different oxygen concentrations, this study analyzed the chemical reaction mechanism of the raw material's (namely, Ni0.8Co0. 1Mn0. 1(OH)2 and LiOH·H2O mixture, which is referred to as the raw material hereinafter) calcination process by non-isothermal thermogravimetry, differential scanning calorimetry, and in situ X-ray diffraction. Based on the obtained data, multiple heating rate methods were used to calculate the reaction mechanism functions and kinetic parameters at each stage as well as the corresponding activation energy and pre-exponential factor. Results showed that four chemical reactions occurred successively during the calcination process of the raw materials with each corresponding to a different kinetic function, pre-exponential factor, and activation energy. Comparing the calcination characteristics under different oxygen concentrations showed that the activation energy was the smallest when the oxygen concentration was 60%.

High strength chitin/chitosan-based aerogel with 3D hierarchically macro-meso-microporous structure for high-efficiency adsorption of Cu(II) ions and Congo red.

A high-strength aerogel with a 3D hierarchically macro-meso-microporous structure (HPS-aerogel) was designed based on biological macromolecules of chitin and chitosan. The macropores can be created within HPS-aerogel after CaCO3 removal, and meso-micropores resulting from water sublimation during freeze-drying. The macro-meso-microporous structure endowed HPS-aerogel with high porosity, good mechanical properties, and excellent compression strength (1472 kPa at strain of 80 %). The HPS-aerogel exposed many adsorption sites and was used as an adsorbent to simultaneously remove Cu(II) and Congo red (CR) from water for the first time. The adsorption capability for Cu(II) and CR was 59.21 mg/g and 2074 mg/g at 303 K, respectively, and the adsorption processes matched Pseudo-second-order and Langmuir models with spontaneous and endothermic nature. Additionally, HPS-aerogel showed good anti-interference ability for coexisting pollutant. Importantly, HPS-aerogel exhibited an effective fixed-bed column adsorption performance for dynamic Cu(II) and CR with superior reusability and stability. Furthermore, HPS-aerogel showed outstanding adsorption efficiencies for Cu(II) and CR in real samples. The main adsorption mechanism for Cu(II) was attributed to the electrostatic attraction and chelation, and which was electrostatic attraction, Schiff base, and hydrogen bonding for CR. Therefore, HPS-aerogel should to be a promising adsorbent for removing both heavy-metal ions and dyes from wastewater.

Ultrahigh Permeability at High Frequencies via A Magnetic-Heterogeneous Nanocrystallization Mechanism in an Iron-Based Amorphous Alloy.

The prevalence of wide-bandgap (WBG) semiconductors allows modern electronic devices to operate at much higher frequencies. However, development of soft magnetic materials with high-frequency properties matching the WBG-based devices remains challenging. Here, a promising nanocrystalline-amorphous composite alloy with a normal composition Fe75.5 Co0.5 Mo0.5 Cu1 Nb1.5 Si13 B8 in atomic percent is reported, which is producible under industrial conditions, and which shows an exceptionally high permeability at high frequencies up to 36 000 at 100 kHz, an increase of 44% compared with commercial FeSiBCuNb nanocrystalline alloy (25 000 ± 2000 at 100 kHz), outperforming all existing nanocrystalline alloy systems and commercial soft magnetic materials. The alloy is obtained by a unique magnetic-heterogeneous nanocrystallization mechanism in an iron-based amorphous alloy, which is different from the traditional strategy of nanocrystallization by doping nonmagnetic elements (e.g., Cu and Nb). The induced magnetic inhomogeneity by adding Co atoms locally promotes the formation of highly ordered structures acting as the nuclei of nanocrystals, and Mo atoms agglomerate around the interfaces of the nanocrystals, inhibiting nanocrystal growth, resulting in an ultrafine nanocrystalline-amorphous dual-phase structure in the alloy. The exceptional soft magnetic properties are shown to be closely related to the low magnetic anisotropy and the unique spin rotation mechanism under alternating magnetic fields.

Optimization of the biological processing of rice dregs into nutritional peptides with the aid of trypsin.

A protein hydrolysate was prepared from rice dregs (RD) using trypsin as a suitable protease. The hydrolysis conditions were optimized with response surface methodology, and then a mathematical model was developed to demonstrate the effect of each process parameter on the degree of hydrolysis (DH) and recovery of protein (RP). A hydrolysate with relatively high RP (75.81%) and low DH (6.95) was obtained from RD by hydrolyzing for 2.4 h at pH 7.6 52.8°C with a enzyme/RD ratio of 0.89:1000 (w/w) and RD/water level of 0.22 g/mL. The dried hydrolysate was low molecular weight peptides (predominantly <1,000 Da) and it possessed good solubility at various pH levels. Result of amino acid analysis revealed that the hydrolysate was considerably enriched in essential amino acids. Thus, the protein hydrolysate has a potential to be an excellent protein ingredient as a balanced milk replacer.

Anisotropic correlations of plasticity on the yielding of metallic glasses.

We report computer simulations on the shear deformation of CuZr metallic glasses at zero and room temperatures. Shear bands emerge in athermal alloys at strain γ_{c}, with a finite-size effect found. The correlation of nonaffine displacement exhibits an exponential decay even after yielding in thermal alloys, but transits to a power law at γ>γ_{c} in athermal ones. The algebraic exponent is around -1 for the decay inside shear bands, consistent with the theoretical prediction in random elastic media. We quantify the anisotropic correlation with harmonic projection, finding the spectrum is weak in the exponential-decay regime, while it displays a strong polar and quadrupolar symmetry in the power-law regime. The nonvanishing quadrupolar symmetry at long distance signifies the nonlocality of plastic correlation in the athermal alloys. In contrast, the plastic correlation was found to be isotropic and localized at the yielding in the thermal alloys without shear bands.

A Camel Nose-Inspired Highly Durable Neuromorphic Humidity Sensor with Water Source Locating Capability.

Numerous emerging applications in modern society require humidity sensors that are not only sensitive and specific but also durable and intelligent. However, conventional humidity sensors do not have all of these simultaneously because they require very different or even contradictory design principles. Here, inspired by camel noses, we develop a porous zwitterionic capacitive humidity sensor. Relying on the synergistic effect of a porous structure and good chemical and thermal stabilities of hygroscopic zwitterions, this sensor simultaneously exhibits high sensitivity, discriminability, excellent durability, and, in particular, the highest respond speed among reported capacitive humidity sensors, with demonstrated applications in the fast discrimination between fresh, stale, and dry leaves, high-resolution touchless human-machine interactive input devices, and the real-time monitoring humidity level of a hot industrial exhaust. More importantly, this sensor exhibits typical synapse behaviors such as paired-pulse facilitation due to the strong binding interactions between water and zwitterions. This leads to learning and forgetting features with a tunable memory, thus giving the sensor artificial intelligence and enabling the location of water sources. This work offers a general design principle expected to be applied to develop other high-performance biochemical sensors and the next-generation intelligent sensors with much broader applications.

Rapid detection of melamine with 4-mercaptopyridine-modified gold nanoparticles by surface-enhanced Raman scattering.

A surface-enhanced Raman scattering (SERS) strategy based on 4-mercaptopyridine (MPY)-modified gold nanoparticles (AuNPs) was developed for the rapid and sensitive detection of melamine in milk powder. The SERS measurement of melamine strongly relied on the "hotspot" effect, in which AuNPs immediately aggregated upon the addition of melamine, leading to significantly enhanced Raman intensity of the reporter molecule MPY and a color change for the solution from red to blue-gray. The limit of detection based on a signal to noise of 3 (S/N = 3) was found to be as low as 0.1 ppb of melamine, with an excellent linearity of 0.5-100 ppb, demonstrating a higher sensitivity and a wider quantitation range than direct SERS sensing methods based on enhanced substrate. An impressive specificity for melamine detection over various common metal ions and excipients in dairy products, even at concentrations of 100-fold higher than melamine, was achieved. Good recoveries of 88.5% and 111.7% were obtained from milk samples spiked to 20 and 100 ppb levels, respectively. The proposed method is potentially applicable for the rapid in situ determination of melamine in complex matrices.