ABSTRACT
The future application of Li metal batteries (LMBs) at scale demands electrolytes that endow improved performance under fast-charging and low-temperature operating conditions. Recent works indicate that desolvation kinetics of Li+ plays a crucial role in enabling such behavior. However, the modulation of this process has typically been achieved through inducing qualitative degrees of ion pairing into the system. In this work, we find that a more quantitative control of the ion pairing is crucial to minimizing the desolvation penalty at the electrified interface and thus the reversibility of the Li metal anode under kinetic strain. This effect is demonstrated in localized electrolytes based on strongly and weakly bound ether solvents that allow for the deconvolution of solvation chemistry and structure. Unexpectedly, we find that maximum degrees of ion pairing are suboptimal for ultralow temperature and high-rate operation and that reversibility is substantially improved via slight local dilution away from the saturation point. Further, we find that at the optimum degree of ion pairing for each system, weakly bound solvents still produce superior behavior. The impact of these structure and chemistry effects on charge transfer are then explicitly resolved via experimental and computational analyses. Lastly, we demonstrate that the locally optimized diethyl ether-based localized-high-concentration electrolytes supports kinetic strained operating conditions, including cycling down to -60 °C and 20-min fast charging in LMB full cells. This work demonstrates that explicit, quantitative optimization of the Li+ solvation state is necessary for developing LMB electrolytes capable of low-temperature and high-rate operation.
ABSTRACT
Surface fouling poses a significant challenge that restricts the analytical performance of electrochemical sensors in both in vitro and in vivo applications. Biofouling resistance is paramount to guarantee the reliable operation of electrochemical sensors in complex biofluids (e.g., blood, serum, and urine). Seeking efficient strategies for surface fouling and establishing highly sensitive sensing platforms for applications in complex media have received increasing attention in the past. In this review, we provide a comprehensive overview of recent research efforts focused on antifouling electrochemical sensors. Initially, we present a detailed illustration of the concept about biofouling along with an exploration of four key antifouling mechanisms. Subsequently, we delve into the commonly employed antifouling strategies in the fabrication of electrochemical sensors. These encompass physical surface topography (micro/nanostructure coatings and filtration membranes) and chemical surface modifications (PEG and its derivatives, zwitterionic polymers, peptides, proteins, and various other antifouling materials). The progress in antifouling electrochemical sensors is proposed concerning the antifouling mechanisms as well as sensing capability assessments (e.g., sensitivity, stability, and practical application ability). Finally, we summarize the evolving trends in the field and highlight some key remaining limitations.
Subject(s)
Biofouling , Nanostructures , Biofouling/prevention & control , Polymers/chemistry , Proteins , Peptides/chemistry , Nanostructures/chemistryABSTRACT
Nonaqueous fluidic transport and ion solvation properties under nanoscale confinement are poorly understood, especially in ion conduction for energy storage and conversion systems. Herein, metal-organic frameworks (MOFs) and aprotic electrolytes are studied as a robust platform for molecular-level insights into electrolyte behaviors in confined spaces. By employing computer simulations, along with spectroscopic and electrochemical measurements, we demonstrate several phenomena that deviate from the bulk, including modulated solvent molecular configurations, aggregated solvation structures, and tunable transport mechanisms from quasi-solid to quasi-liquid in functionalized MOFs. Technologically, taking advantage of confinement effects may prove useful for addressing stability concerns associated with volatile organic electrolytes while simultaneously endowing ultrafast transport of solvates, resulting in improved battery performance, even at extreme temperatures. The molecular-level insights presented here further our understanding of structure-property relationships of complex fluids at the nanoscale, information that can be exploited for the predictive design of more efficient electrochemical systems.
ABSTRACT
α-L-rhamnosidase (Rha) is ubiquitous in nature and has high feasibility in the food and biotechnology industries. A green and environmentally friendly method was used to improve the activity of Rha. Here, we show that the effects of ultrasound treatment on the Rha. Ultrasonic treatment at 80 W for 10 min yielded the highest enzyme activity. Treatment increased enzyme activity by 26.3% and half-life by 124 min. Further, treatment increased the catalytic efficiency of Rha and increased the substrate conversion rate by 33.88%. These results demonstrate that ultrasound increases the catalytic activity and stability of Rha. Thus, ultrasonic treatment of Rha is cost-effective on the industrial scale.
ABSTRACT
In this work, an organic-inorganic hybrid crystal, violet-crystal (VC), was used to etch the nickel foam (NF) to fabricate a self-standing electrode for the water oxidation reaction. The efficacy of VC-assisted etching manifests the promising electrochemical performance towards the oxygen evolution reaction (OER), requiring only ~356 and ~376â mV overpotentials to reach 50 and 100â mA cm-2 , respectively. The OER activity improvement is attributed to the collectively exhaustive effects arising from the incorporation of various elements in the NF, and the enhancement of active site density. Furthermore, the self-standing electrode is robust, exhibiting a stable OER activity after 4,000 cyclic voltammetry cycles, and ~50â h. The anodic transfer coefficients (αa ) show that the first electron transfer step is the rate-determining step on the surface of NF-VCs-1.0 (NF etched by 1â g of VCs) electrode, while the chemical step involving dissociation following the first electron transfer step is identified as the rate-limiting step in other electrodes. The lowest Tafel slope value observed in the NF-VCs-1.0 electrode indicates the high surface coverage of oxygen intermediates and more favorable OER reaction kinetics, as confirmed by high interfacial chemical capacitance and low charge transport/interfacial resistance. This work demonstrates the importance of VCs-assisted etching of NF to activate the OER, and the ability to predict reaction kinetics and rate-limiting step based on αa values, which will open new avenues to identify advanced electrocatalysts for the water oxidation reaction.
ABSTRACT
The ß-glucosidases known to improve tea aroma are all mesothermal enzymes, limiting their use under brewing conditions. Based on the properties analysis and molecular docking, the thermostable ß-glucosidase (TPG) from Thermotoga petrophlia showed potential to enhance tea aroma. Treatment by recombinant TPG at 90 °C, the floral, sweet and grassy notes of instant Oolong tea were increased, while the roasted, caramel and woody notes were decreased. The improved floral, sweet and grassy notes were related to increase releasing of benzyl alcohol (floral), geraniol (floral), (Z)-3-hexen-1-ol (grassy), benzaldehyde (sweet) and 1-hexanol (grassy) by TPG hydrolyzing of (Z)-3-hexenyl-ß-D-glucopyranoside, hexanyl-ß-D-glucopyranoside (HGP), benzyl-ß-D-glucopyranoside, prunasin and geranyl-ß-D-glucopyranoside (GGP), respectively. Although the catalytic efficiency of TGP to GGP was about twice that to HGP, HPG was more competitive than GGP when they mixed. Combined with microstructure analysis, the structure-function relationship of TPG-influencing tea aroma were understood. This study provided the method of how to mining new function of characterized ß-glucosidases, as well as a theoretical basis for the development of new tea products.
ABSTRACT
Lung cancer is one of the most prevalent, fatal, and highly heterogeneous diseases that, seriously threaten human health. Lung cancer is primarily caused by the aberrant expression of multiple genes in the cells. Lung cancer treatment options include surgery, radiation, chemotherapy, targeted therapy, and immunotherapy. In recent decades, significant progress has been made in developing therapeutic agents for lung cancer as well as a biomarker for its early diagnosis. Nonetheless, the alternative applications of traditional pre-clinical models (cell line models) for diagnosis and prognosis prediction are constrained by several factors, including the lack of microenvironment components necessary to affect cancer biology and drug response, and the differences between laboratory and clinical results. The leading reason is that substantial shifts accrued to cell biological behaviors, such as cell proliferative, metastatic, invasive, and gene expression capabilities of different cancer cells after decades of growing indefinitely in vitro. Moreover, the introduction of individualized treatment has prompted the development of appropriate experimental models. In recent years, preclinical research on lung cancer has primarily relied on the patient-derived tumor xenograft (PDX) model. The PDX provides stable models with recapitulate characteristics of the parental tumor such as the histopathology and genetic blueprint. Additionally, PDXs offer valuable models for efficacy screening of new cancer drugs, thus, advancing the understanding of tumor biology. Concurrently, with the heightened interest in the PDX models, potential shortcomings have gradually emerged. This review summarizes the significant advantages of PDXs over the previous models, their benefits, potential future uses and interrogating open issues.
ABSTRACT
This study aims to investigate the evolution patterns of fluidity and rheological properties of AASCM under varying dosages of foaming agent and particle sizes of filling aggregate. The flow characteristics of AASCM are significantly affected by the filling aggregate's size and the foaming agent's dosage. Specifically, an increase in filling aggregate size (D(4,3) ϵ [26 µm, 69 µm]) enhances the fluidity of foamed AASCM, while an increase in foaming agent dosage reduces fluidity. These observed variations can be attributed to the presence of particle voids, the specific surface area of the aggregate, as well as the quantity and spatial distribution of bubbles within the slurry. A bubble-particle packing model is established, and by calibrating the simulation error coefficient to 1.1, the study investigates the evolution of water film thickness (WFT) in foamed AASCM with slurry expansion degree. It is observed that bubbles in the slurry affect the fluidity by altering the overall compactness and specific surface area of the foamed slurry, subsequently modifying the WFT.
ABSTRACT
Scopoletin is a coumarin compound with various biological activities including detumescence and analgesic, insecticidal, antibacterial and acaricidal effects. However, interference with scopolin and other components often leads to difficulties in purification of scopoletin with low extraction rates from plant resource. In this paper, heterologous expression of the gene encoding ß-glucosidase An-bgl3 derived from Aspergillus niger were carried out. The expression product was purified and characterized with further structure-activity relationship between it and ß-glucosidase analyzed. Subsequently, its ability for transforming scopolin from plant extract was studied. The results showed that the specific activity of the purified ß-glucosidase An-bgl3 was 15.22 IU/mg, the apparent molecular weight was about 120 kDa. The optimum reaction temperature and pH were 55 â and 4.0, respectively. Moreover, 10 mmol/L metal ions Fe2+ and Mn2+ increased the enzyme activity by 1.74-fold and 1.20-fold, respectively. A 10 mmol/L solution containing Tween-20, Tween-80 and Triton X-100 all inhibited the enzyme activity by 30%. The enzyme showed affinity towards scopolin and tolerated 10% methanol and 10% ethanol solution, respectively. The enzyme specifically hydrolyzed scopolin into scopoletin from the extract of Erycibe obtusifolia Benth with a 47.8% increase of scopoletin. This demonstrated that the ß-glucosidase An-bgl3 from A. niger shows specificity on scopolin with good activities, thus providing an alternative method for increasing the extraction efficiency of scopoletin from plant material.
Subject(s)
Aspergillus niger , beta-Glucosidase , Aspergillus niger/genetics , beta-Glucosidase/genetics , beta-Glucosidase/chemistry , Scopoletin , Polysorbates , CoumarinsABSTRACT
The hydrolysis of xylo-oligosaccharides catalyzed by ß-xylosidase plays an important role in the degradation of lignocellulose. However, the enzyme is easily inhibited by its catalytic product xylose, which severely limits its application. Based on molecular docking, this paper studied the xylose affinity of Aspergillus niger ß-xylosidase An-xyl, which was significantly differentially expressed in the fermentation medium of tea stalks, through cloning, expression and characterization. The synergistic degradation effect of this enzyme and cellulase on lignocellulose in tea stems was investigated. Molecular docking showed that the affinity of An-xyl to xylose was lower than that of Aspergillus oryzae ß-xylosidase with poor xylose tolerance. The Ki value of xylose inhibition constant of recombinant-expressed An-xyl was 433.2 mmol/L, higher than that of most ß-xylosidases of the GH3 family. The Km and Vmax towards pNPX were 3.6 mmol/L and 10 000 µmol/(min·mL), respectively. The optimum temperature of An-xyl was 65 â, the optimum pH was 4.0, 61% of the An-xyl activity could be retained upon treatment at 65 â for 300 min, and 80% of the An-xyl activity could be retained upon treatment at pH 2.0-8.0 for 24 h. The hydrolysis of tea stem by An-xyl and cellulase produced 19.3% and 38.6% higher reducing sugar content at 2 h and 4 h, respectively, than that of using cellulase alone. This study showed that the An-xyl mined from differential expression exhibited high xylose tolerance and higher catalytic activity and stability, and could hydrolyze tea stem lignocellulose synergistically, which enriched the resource of ß-xylosidase with high xylose tolerance, thus may facilitate the advanced experimental research and its application.
Subject(s)
Cellulases , Xylosidases , Aspergillus niger/genetics , Xylose/metabolism , Molecular Docking Simulation , Xylosidases/genetics , Tea , Hydrogen-Ion Concentration , Substrate SpecificityABSTRACT
Sulfurized polyacrylonitrile (SPAN) is considered as a high-value cathode material, which leverages the high energy of S redox while mitigating the negative externalities that limit elemental S cycling. As such, the sulfur content in Li-SPAN batteries plays a critical role. In this work, we demonstrate that high-S loading SPAN cathodes, where the PAN backbone approaches the saturation point without signs of elemental S, are highly dependent on the electrolyte chemistry for long-term reversibility. Specifically, we find that a localized-high-concentration electrolyte (LHCE) further enhances the reversible capacity and cycling stability of SPAN cathode with optimized S content relative to a carbonate control, largely due to the formation of a compatible interphase. With this LHCE as the electrolyte and 43% sulfur ratio of SPAN as the cathode, a full cell applying N/P ratio = 1.82, a cathode loading of 6 mAh cm-2 (9.2 mg cm-2), and an electrolyte loading of 7 µL mg-1 SPAN can be cycled for 100 cycles with 433 mAh g-1 retained capacity and retains much of this reversibility even at 60 °C. This work reveals the molecular origin of optimized sulfur ratio in SPAN cathodes while providing guidance in electrolyte design for Li||SPAN cells with high capacity and cyclability.
ABSTRACT
The noradrenergic and cholinergic modulation of functionally distinct regions of the brain has become one of the primary organizational principles behind understanding the contribution of each system to the diversity of neural computation in the central nervous system. Decades of work has shown that a diverse family of receptors, stratified across different brain regions, and circuit-specific afferent and efferent projections play a critical role in helping such widespread neuromodulatory systems obtain substantial heterogeneity in neural information processing. This review briefly discusses the anatomical layout of both the noradrenergic and cholinergic systems, as well as the types and distributions of relevant receptors for each system. Previous work characterizing the direct and indirect interaction between these two systems is discussed, especially in the context of higher order cognitive functions such as attention, learning, and the decision-making process. Though a substantial amount of work has been done to characterize the role of each neuromodulator, a cohesive understanding of the region-specific cooperation of these two systems is not yet fully realized. For the field to progress, new experiments will need to be conducted that capitalize on the modular subdivisions of the brain and systematically explore the role of norepinephrine and acetylcholine in each of these subunits and across the full range of receptors expressed in different cell types in these regions.
ABSTRACT
With the constant increase in communication requirements in modern society, the number and type of antennas on communication platforms have been increasing at an accelerating rate. This has led to a continuous increase in platform volume and weight, and the electromagnetic environment of antenna operating has increasingly worsened, seriously restricting the further development of communication systems. As a new communication system antenna type, a reconfigurable microstrip antenna can reconstruct operating frequencies, beam directions, etc., by changing the antenna structure to provide the good multifunction characteristics of a single antenna, avoiding the electromagnetic compatibility issues caused by numerous system antennas. At present, most of the research on reconfigurable antennas judges the influence of structural characteristics on electromagnetic characteristics by simulation, which has imposed restrictions on their development and application. Therefore, a reconfigurable antenna with a resonant frequency of 8.66 GHz and 15.26 GHz and a reconfigurable antenna with maximum radiation directions of 36.2° and -36.5° are designed in this paper, and the electromechanical coupling theory of the reconfigurable antennas is studied. The resonance frequency coupling model and the pattern function coupling model considering the structural deformation of a reconfigurable microstrip antenna are established. Within the applicable range of antenna structural parameters, the relative error between the resonance frequency coupling model and the pattern function coupling model is less than 5%, which meets practical engineering application requirements. Finally, the method is shown by experimentation to verify the accuracy and validity of the proposed electromechanical coupling model.
ABSTRACT
With the development of miniaturization and integration of electronic devices, the conventional manifold microchannels (MMCs) structure has been unable to meet the heat dissipation requirements caused by the rapid growth of internal heat flux. There is an urgent need to design a new heat dissipation structure with higher heat dissipation capacity to ensure the working stability and life of electronic devices. In this paper, we designed a novel manifold dual-microchannel (MDMC) cooling system that embedded the microchannel structure into the manifold microchannel structure. The MDMC not only has good heat dissipation performance that can meet the development needs of electronic equipment to miniaturization and integration, but also has a compact structure that does not increase the overall thickness and volume compared with MMC. The high temperature uniformity and heat transfer performance of MDMC are significantly improved compared to MMC. The Tmax is reduced by 13.6% and 17.5% at the heat flux density of 300 W/cm2 and 700 W/cm2, respectively. In addition, the influence of the inlet-2 velocity and the total microchannels number on the heat transfer performance of the MDMC structure are numerically investigated. The results show that the decrease rate of Tmax and ΔT is about 6.69% and 16% with the increase of inlet-2 velocity from 1.2 m/s to 2.4 m/s and microchannels number from 10 to 48, respectively. At the same time, the best temperature uniformity is obtained when the number of microchannels is 16.
ABSTRACT
Surface mount technology (SMT) plays an important role in integrated circuits, but due to thermal stress alternation caused by temperature cycling, it tends to have thermo-mechanical reliability problems. At the same time, considering the environmental and health problems of lead (Pb)-based solders, the electronics industry has turned to lead-free solders, such as ternary alloy Sn-3Ag-0.5Cu (SAC305). As lead-free solders exhibit visco-plastic mechanical properties significantly affected by temperature, their thermo-mechanical reliability has received considerable attention. In this study, the interface delamination of an SMT solder joint using a SAC305 alloy under temperature cycling has been analyzed by the nonlinear finite element method. The results indicate that the highest contact pressure at the four corners of the termination/solder horizontal interface means that delamination is most likely to occur, followed by the y-direction side region of the solder/land interface and the top arc region of the termination/solder vertical interface. It should be noted that in order to keep the shape of the solder joint in the finite element model consistent with the actual situation after the reflow process, a minimum energy-based morphology evolution method has been incorporated into the established finite element model. Eventually, an Improved Efficient Global Optimization (IEGO) method was used to optimize the geometry of the SMT solder joint in order to reduce the contact pressure at critical points and critical regions. The optimization result shows that the contact pressure at the critical points and at the critical regions decreases significantly, which also means that the probability of thermal-induced delamination decreases.
ABSTRACT
This work reports an efficient [(C6)2Ir(dppz)]+PF6- (C6 = coumarin 6 and dppz = dipyridophenazine)-sensitized NiO photocathode and its application in photoelectrochemical (PEC) bioanalysis field for the first time. This dye-sensitized NiO photocathode was found to exhibit a markedly enhanced cathodic photocurrent. A sensitive cathodic PEC platform was proposed integrating the as-prepared photocathode with enzyme-free cascaded amplification strategies of the catalytic hairpin assembly (CHA) and the hybridization chain reaction (HCR) for DNA methyltransferase (MTase) assay. A hairpin DNA(HDam) with specific recognition site of Dam MTase in its stem was designed. The site of HDam was methylated in the presence of Dam MTase and then cut by endonuclease DpnI. The released loop fragment, as an initiator, triggered the CHA circuit and the follow-up HCR circuit, resulting in long dsDNA concatemers on the ITO electrode. Numerous [(C6)2Ir(dppz)]+PF6- were intercalated into dsDNA, and highly efficient signal amplification was realized. Benefiting from the superior iridium(III) complex-sensitized NiO photocathode and effective amplification strategy, a detection limit of 0.0028 U/mL for the determination of Dam MTase was achieved. Moreover, this work further demonstrated that these proposed tactics could be applied to screen Dam MTase activity inhibitors.
Subject(s)
Biosensing Techniques , Iridium , Biosensing Techniques/methods , DNA , Electrodes , Nucleic Acid HybridizationABSTRACT
Effective determination of trends in sulfur dioxide emissions facilitates national efforts to draft an appropriate policy that aims to lower sulfur dioxide emissions, which is essential for reducing atmospheric pollution. However, to reflect the current situation, a favorable emission reduction policy should be based on updated information. Various forecasting methods have been developed, but their applications are often limited by insufficient data. Grey system theory is one potential approach for analyzing small data sets. In this study, an improved modeling procedure based on the grey system theory and the mega-trend-diffusion technique is proposed to forecast sulfur dioxide emissions in China. Compared with the results obtained by the support vector regression and the radial basis function network, the experimental results indicate that the proposed procedure can effectively handle forecasting problems involving small data sets. In addition, the forecast predicts a steady decline in China's sulfur dioxide emissions. These findings can be used by the Chinese government to determine whether its current policy to reduce sulfur dioxide emissions is appropriate.
Subject(s)
Air Pollutants/analysis , Fuzzy Logic , Sulfur Dioxide/analysis , China , Forecasting , Models, TheoreticalABSTRACT
The weak interlayer refers to the filling material in shear belts or large-scale structural planes, which is usually composed of soil, fine sand and gravels. It is prone to argillization when encountering water and its mechanical strength and stiffness are generally low, which has adverse effects on the stability of underground structures. In recent years, research on reinforcement techniques for weak interlayers has been a hot topic in geotechnical field. As a new reinforcement method for structural planes, the microbial healing technique has attracted a lot of attention. In this paper, a study on the healing technique for weak interlayer based on microbially induced calcium carbonate precipitation (MICP) and related mechanical properties was conducted for the interlayer shear belt at Baihetan Hydropower Station in China. First, Sporosarcina pasteurii was activated in laboratory. Reinforcement of the weak interlayer was realized by utilizing calcium carbonate precipitation on the weak interlayer. Continuous monitoring of the precipitates on the weak interlayer by XRD and SEM indicated that the precipitates on the weak layer were microbially induced calcium carbonate. Its crystals were irregular fish scale-shaped cubes with size in the range of 5~20µm. With favorable crystal growth, the crystals and the particles of the weak interlayer were cemented together. Finally, the mechanical properties of the healed weak interlayer were tested and the variations of uniaxial compressive strength, shear strength and triaxial compressive strength with bacteria concentration were discussed. The test results indicated that the maximum uniaxial compressive strength, peak shear strength and triaxial compressive strength can be increased by 149%, 162% and 119%, respectively, which subsequently improve the overall strength of the shear zone or structural plane. This can provide a new idea for soft ground reinforcement in underground projects.