Machine-Learning-Assisted Design of Deep Eutectic Solvents Based on Uncovered Hydrogen Bond Patterns

Non-ionic deep eutectic solvents(DESs)are non-ionic designer solvents with various applications in catalysis,extraction,carbon capture,and pharmaceuticals.However,discovering new DES candidates is challenging due to a lack of efficient tools that accurately predict DES formation.The search for DES relies heavily on intuition or trial-and-error processes,leading to low success rates or missed opportunities.Recognizing that hydrogen bonds(HBs)play a central role in DES formation,we aim to identify HB features that distinguish DES from non-DES systems and use them to develop machine learning(ML)models to discover new DES systems.We first analyze the HB properties of 38 known DES and 111 known non-DES systems using their molecular dynamics(MD)simulation trajectories.The analysis reveals that DES systems have two unique features compared to non-DES systems:The DESs have①more imbalance between the numbers of the two intra-component HBs and②more and stronger inter-component HBs.Based on these results,we develop 30 ML models using ten algorithms and three types of HB-based descriptors.The model performance is first benchmarked using the average and minimal receiver operating characteristic(ROC)-area under the curve(AUC)values.We also analyze the importance of individual features in the models,and the results are consistent with the simulation-based statistical analysis.Finally,we validate the models using the experimental data of 34 systems.The extra trees forest model outperforms the other models in the validation,with an ROC-AUC of 0.88.Our work illustrates the importance of HBs in DES formation and shows the potential of ML in discovering new DESs.

Boosting overall saline water splitting by constructing a strain-engineered high-entropy electrocatalyst

High-entropy materials(HEMs),which are newly manufactured compounds that contain five or more metal cations,can be a platform with desired properties,including improved electrocatalytic performance owing to the inherent complexity.Here,a strain engineering methodology is proposed to design transition-metal-based HEM by Li manipulation(LiTM)with tunable lattice strain,thus tailoring the electronic structure and boosting electrocatalytic performance.As confirmed by the experiments and calculation results,tensile strain in the LiTM after Li manipulation can optimize the d-band center and increase the electrical conductivity.Accordingly,the asprepared LiTM-25 demonstrates optimized oxygen evolution reaction and hydrogen evolution reaction activity in alkaline saline water,requiring ultralow overpotentials of 265 and 42 mV at 10 mA cm−2,respectively.More strikingly,LiTM-25 retains 94.6%activity after 80 h of a durability test when assembled as an anion-exchange membrane water electrolyzer.Finally,in order to show the general efficacy of strain engineering,we incorporate Li into electrocatalysts with higher entropies as well.

Enhanced H_(2) permeation and CO_(2) tolerance of self-assembled ceramic-metal-ceramic BZCYYb-Ni-CeO_(2) hybrid membrane for hydrogen separation

Perovskite-type mixed protonic-electronic conducting membranes have attracted attention because of their ability to separate and purify hydrogen from a mixture of gases generated by industrial-scale steam reforming based on an ion diffusion mechanism.Exploring cost-effective membrane materials that can achieve both high H_(2) permeability and strong CO_(2)-tolerant chemical stability has been a major challenge for industrial applications.Herein,we constructed a triple phase(ceramic-metal-ceramic)membrane composed of a perovskite ceramic phase BaZr_(0.1)Ce_(0.7)Y_(0.1)Yb_(0.1)O_(3-δ)(BZCYYb),Ni metal phase and a fluorite ceramic phase CeO_(2).Under H_(2) atmosphere,Ni metal in-situ exsolved from the oxide grains,and decorated the grain surface and boundary,thus the electronic conductivity and hydrogen separation performance can be promoted.The BZCYYbNi-CeO_(2)hybrid membrane achieved an exceptional hydrogen separation performance of 0.53 mL min^(-1)cm^(-2) at 800℃ under a 10 vol% H_(2) atmosphere,surpassing all other perovskite membranes reported to date.Furthermore,the CeO_(2) phase incorporated into the BZCYYb-Ni effectively improved the CO_(2)-tolerant chemical stability.The BZCYYbNi-CeO_(2) membrane exhibited outstanding long-term stability for at least 80 h at 700℃ under 10 vol%CO_(2)-10 vol%H_(2).The success of hybrid membrane construction creates a new direction for simultaneously improving their hydrogen separation performance and CO_(2) resistance stability.

Femtosecond laser direct writing of functional stimulus-responsive structures and applications

Diverse natural organisms possess stimulus-responsive structures to adapt to the surrounding environment.Inspired by nature,researchers have developed various smart stimulus-responsive structures with adjustable properties and functions to address the demands of ever-changing application environments that are becoming more intricate.Among many fabrication methods for stimulus-responsive structures,femtosecond laser direct writing(FsLDW)has received increasing attention because of its high precision,simplicity,true three-dimensional machining ability,and wide applicability to almost all materials.This paper systematically outlines state-of-the-art research on stimulus-responsive structures prepared by FsLDW.Based on the introduction of femtosecond laser-matter interaction and mainstream FsLDW-based manufacturing strategies,different stimulating factors that can trigger structural responses of prepared intelligent structures,such as magnetic field,light,temperature,pH,and humidity,are emphatically summarized.Various applications of functional structures with stimuli-responsive dynamic behaviors fabricated by FsLDW,as well as the present obstacles and forthcoming development opportunities,are discussed.

企业数字化转型对双元创新决策的影响——基于公司治理的调节作用

基于我国2011-2021年A股上市公司的数据,通过CSMAR数据库获取数字化转型指数,采用实证方法检验企业数字化转型对双元创新决策的影响。结果表明:数字化转型能显著提高企业创新投入的水平,相比于利用式创新,企业数字化转型对探索式创新的投入水平的提升作用更大。公司内部治理和外部治理对“企业数字化转型—双元创新决策”的关系也有影响,相比于探索式创新投入,股权集中度、分析师关注度、市场竞争程度高能显著增强数字化转型对利用式创新投入的正向作用。通过对产权性质和经济发达程度分组回归发现,数字化转型对探索式创新的促进作用在国有企业中更大,但数字化转型对利用式创新的促进作用在非国有企业中更大;数字化转型对探索式创新的促进作用在经济发达地区更大,而数字化转型对利用式创新的促进作用在经济不发达地区更大。基于研究结论,本文对企业数字化转型和政府制定相关政策都提出了相应的建议。

Catalysis performance comparison of a Br?nsted acid H_2SO_4 and a Lewis acid Al_2(SO_4)_3 in methyl levulinate production from biomass carbohydrates

An experimental investigation was conducted to understand the roles of the Br？nsted acid H2SO4 and Lewis acid Al2（SO4）3 in methyl levulinate（ML） production from biomass carbohydrates, including glucose,fructose and cellulose. The product distributions with different catalysts revealed that the Lewis acid was responsible for the isomerization of methyl glucoside（MG）, producing a significant amount of the subsequent product 5-methoxymethylfurfural（MMF）, while the Br？nsted acid facilitated the production of ML from MMF. Al2（SO4）3 was efficient for monosaccharide conversion but not for cellulose. Using ball-milled cellulose with Al2（SO4）3 resulted in a desired ML yield within a reasonable reaction time. The significant catalysis performances of two types of acids will guide the design of efficient catalytic processes for the selective conversion of biomass into levulinate esters.

Semi-enclosed experimental system for coal spontaneous combustion for determining regional distribution of high-temperature zone of coal fire

Temperature variation and gas generation at diferent depths and positions in the coal combustion process were studied to determine the propagation and evolution of high temperature regions in the process of coal spontaneous combustion.This study selected coal samples from Mengcun,Shaanxi Province,People’s Republic of China,and developed a semi-enclosed experimental system(furnace)for simulating coal combustion.The thermal mass loss of coal samples under various heating rates(5,10,and 15℃/min)was analyzed through thermogravimetric analysis,and the dynamic characteristics of the coal samples were analyzed;the reliability of the semi-enclosed experimental system was verifed through the equal proportional method of fuzzy response.The results reveal that the high-temperature zone is distributed nonlinearly from the middle to the front end of the furnace,and the temperatures of points in this zone decreased gradually as the layer depth increased.The apparent activation energy of the coal samples during combustion frst increased and then decreased as the conversion degree increased.Furthermore,the proportion of mass loss and the mass loss rate in the coal samples observed in the thermogravimetric experiment is consistent with that observed in the frst and second stages of the experiment conducted using the semi-enclosed system.The research fndings can provide a theoretical basis for the prevention and control of hightemperature zones in coal combustion.

Identification of reversible insertion-type lithium storage reaction of manganese oxide with long cycle lifespan

Recently,MnO2 has gained attention as an electrode material because of its very high theoretical capacity and abundant availability.However,the very high volumetric change caused by its conversion-type reaction results in bad reversibility of charge-discharge.In this study,δ-MnO2 of thickness 8 nm anchored on the surface of carbon nanotubes(CNT)by Mn-O-C chemical bonding is synthesized via a facile hydrothermal method.Numerous ex-situ characterizations of the lithium storage process were performed.Furthermore,density functional theory(DFT)calculations indicated thatδ-MnO2(012)thermodynamically prefers bonding with CNTs.Moreover,the interfacial interaction reinforces the connection of Mn-O and reduces the bond strength of Li-O in lithiated MnO2,which could facilitate an intercalation-type lithium storage reaction.Consequently,the as-synthesizedδ-MnO2 retains an excellent reversible capacity of 577.5 mAh g-1 in 1000 cycles at a high rate of 2 A g-1 between 0.1 V and 3.0 V.The results of this study demonstrate the possibility of employing the cost-effective transition metal oxides as intercalation lithium storage dominant electrodes for advanced rechargeable batteries.

Theoretical and experimental studies on high-power laser-induced thermal blooming effect in chamber with different gases

High-power laser induced thermal blooming effects in a closed chamber with three different gases are investigated theoretically and experimentally in this work. In the theoretical treatment, an incompressible gas turbulent model is adopted.In the numerical simulation the gas refractive index as a function of both the temperature and pressure is taken into consideration. In the experimental study the pump-probe technology is adopted. A high-power 1064-nm fiber laser with maximum output power of 12 k W is used to drive the gas thermal blooming, and a 50-m W high-beam-quality 637-nm laser diode(LD)is used as a probe beam. The influences of the gas thermal blooming in the chamber on the probe beam wavefront and beam quality are analyzed for three different gases of air, nitrogen, and helium, respectively. The results indicate that nitrogen is well suitable for restraining thermal blooming effect for high-power laser. The measured data are in good agreement with the simulated results.

Synthesis of ternary magnetic nanoparticles for enhanced catalytic conversion of biomass-derived methyl levulinate into γ-valerolactone

Conversion of levulinic acid and its esters into versatile y-valerolactone(GVL)is a pivotal and challenging step in biorefineries,limited by high catalyst cost,the use of hydrogen atmosphere,or tedious catalyst preparation and recycling process.Here we have successfully synthesized a ternary magnetic nanoparticle catalyst(Al_(2)O_(3)-ZrO_(2)/Fe_(3)O_(4)(5)),over which biomass-derived methyl levulinate(ML)can be quantitively converted to GVL with an extremely high selectivity of>99%and yield of-98%in the absence of molecular hydrogen.Al_(2)O_(3)-ZrO_(2)/Fe_(3)O_(4)(5)incorporates simultaneously inexpensive alumina and zirconia onto magnetite support by a facile coprecipitation method,giving rise to a core-shell structure,welldistributed acid-base sites,and strong magnetism,as evidenced by the X-ray diffraction(XRD),X-ray photoelectron spectroscopy(XPS),scanning electron microscopy(SEM),transmission electron microscopy(TEM),high-angle annular dark-field scanning-TEM(HAADF-STEM),SEM-energy dispersive Xray spectroscopy(SEM-EDX),temperature-programmed desorption of ammonia(NH3-TPD),temperature-programmed desorption of carbon dioxide(CO_(2)-TPD),pyridine-adsorption infrared spectra(Py-IR),and vibrating sample magnetometry(VSM).Such characteristics enable it to be highly active and easily recycled by a magnet for at least five cycles with a slight loss of its catalytic activity,avoiding a time-consuming and energy-intensive reactivation process.It is found that there was a synergistic effect among the metal oxides,and the high efficiency and selectivity originating from such synergism are evidenced by kinetic studies.Furthermore,a reaction mechanism regarding the hydrogenation of ML to GVL is proposed by these findings,coupled with gas chromatography-mass spectrometry(GC-MS)analysis.Accordingly,this readily synthesized and recovered magnetic nanocatalyst for conversion of biomassderived ML into GVL can provide an eco-friendly and safe way for biomass valorization.

Efficient microwave-assisted production of biofuel ethyl levulinate from corn stover in ethanol medium

Levulinate esters are versatile chemicals that have been used in various fields. Herein, the production of ethyl levulinate（EL） from corn stover was investigated under microwave irradiation. Several reaction parameters, including acid concentration, reaction temperature, reaction time, and liquid-to-solid mass ratio, were investigated to evaluate the reaction conditions. Response surface methodology（RSM） was employed to optimize the reaction conditions for the production of EL. A quadratic polynomial model was fitted to the data with an R2 value of 0.93. The model validation results reflected a good fit between the experimental and predicted values. A high conversion yield（58.1 mol%） was obtained at the optimum conditions of 190℃, 30.4 min, 2.84 wt% acid, and 15 g/g liquid-to-solid mass ratio. Compared with conventional heating, microwave irradiation facilitated the conversion of corn stover to EL by dramatically shortening the reaction time from several hours to ～30 min. Thus, microwave-assisted conversion of corn stover to EL is an efficient way of utilizing a renewable biomass resource.

Tributyltin causes generational neurodevelopmental toxicity and the protective effect of folic acid in zebrafish

Tributyltin(TBT),a common organotin environmental pollutant,may pose a threat to human development during critical early-life periods.We aimed to assess the neurodevelopmental intergenerational toxicity of early-life exposure to TBT and the protective effect of DNA methyl donor folic acid(FA).Specifically,after early-life exposure(1–21 days postfertilization,dpf)to TBT(0,1,10 and 100 ng/L),zebrafish(Danio rerio)were cultured in clean medium until sexual maturity.The exposed females were mated with unexposed males to produce embryos(F1).The F1 generation were cultured(4–120 hours post-fertilization,hpf)with and without 1 mmol/L FA.The neurotoxic effects of early-life TBT exposure for zebrafish and their offspring(F1)were significantly enhanced anxiety and reduced aggression,decreased gene expression of DNA methyltransferase in the brain and increased serotonin levels in the body.Moreover,the intergenerational neurodevelopmental toxicity,as manifested in the F1 generation,was attenuated by FA supplementation.In summary,early-life TBT exposure led to intergenerational neurodevelopmental deficits in zebrafish,and DNA methyl donors had a protective effect on F1 neurodevelopment,which can inform the prevention and treatment of intergenerational neurotoxicity due to organotin pollutants.

Fe_(3)O_(4) nanoparticles encapsulated in graphitized and inplane porous carbon nanocages derived from emulsified asphalt for a high-performance lithium-ion battery anode

In this work,C@Fe_(3)O_(4) composites were prepared through a typical template method with emulsified asphalt as carbon source,ammonium ferric citrate as transition metal oxide precursor,and NaCl as template.As an anode for lithium-ion batteries,the optimized C@Fe_(3)O_(4)-1:2 composite exhibits an excellent reversible capacity of 856.6 mA·h·g^(-1)after 100 cycles at 0.1A·g^(-1)and a high capacity of 531.1mA·h·g^(-1)after 300 cycles at 1 A·g^(-1),much better than those of bulk carbon/Fe_(3)O_(4) prepared without NaCl.Such remarkable cycling performance mainly benefits from its well-designed structure:Fe_(3)O_(4) nanoparticles generated from ammonium ferric citrate during pyrolysis are homogenously encapsulated in graphitized and in-plane porous carbon nanocages derived from petroleum asphalt.The carbon nanocages not only improve the conductivity of Fe_(3)O_(4),but also suppress the volume expansion of FesO4 effectively during the charge discharge cycle,thus delivering a robust electrochemical stability.This work realizes the high value-added utilization of low-cost petroleum asphalt,and can be extended to application of other transition-metal oxides-based anodes.

Defect engineered nickel hydroxide nanosheets for advanced pseudocapacitor electrodes

While the past years have witnessed great achievement in pseudocapacitors,the inauguration of electrode materials of high-performance still remains a formidable challenge.Moreover,the capacity and rate capability of the electrode depends largely on its electrical conductivity,which ensures fast charge transfer kinetics in both the grain bulk and grain boundaries.Here,nickel hydroxides with oxygen vacancies are facilely fabricated via a hydrothermal method.The active materials exhibit a high specific capacitance of 3250 F·g^(−1)and a high areal of capacitance of 14.98 F·cm^(−2)at 4.6 mA·cm^(−2).The asymmetric supercapacitor device based on our material delivers a high energy density of~71.6 Wh·kg^(−1)and a power density of~17,300 W·kg^(−1)and could retain~95%of their initial capacitance even after 30,000 cycles.In addition,the defect-rich hydroxides demonstrate higher electrical conductivity as well as dielectric constant,which is responsible for the superior pseudocapacitive performance.Our new scientific strategy in terms of taking the advantages of oxygen vacancies might open up new opportunities for qualified pseudocapacitive materials of overall high performances not only for nickel hydroxides but also for other metal hydroxides/oxides.

Appropriate supply of irrigation and nitrogen produced higher yields of cherry tomatoes

Accurate irrigation and nitrogen application are essential for promoting the growth and yield of cherry tomatoes.In investigating the effects of irrigation and nitrogen on the growth,photosynthesis,and yield of cherry tomatoes,nine treatments including three levels of both irrigation and nitrogen were conducted over two growing seasons.Transverse stem diameter and horizontal stem diameter had the best performance at the irrigation level of 75%evaporation(E_(p)),although their responses to nitrogen were different for the two years.Plant height increased with the increase of irrigation and nitrogen.Plant dry matter(PDM)was significantly affected by irrigation and nitrogen interaction.The lowest PDM was found in the highest proportion of root dry matter,which occurred under low nitrogen level.The net photosynthetic rate(Pn)and transpiration rate enhanced with the increase of irrigation.Medium nitrogen showed promotion effect on all photosynthetic parameters in both growing seasons.Six of all fourteen indicators showed significant correlations with yield.Especially,single plant fruit number and PDM in 2018 Fall had significant positive direct effects on yield with the path coefficients of 0.648 and 1.159,while the significant direct path coefficients were 0.362 and 0.294 in Fruit dry matter and Pn for 2019 Spring,respectively.Based on the comprehensive evaluation of growth and yield by TOPSIS,the irrigation level of 75%E_(p) combined with medium nitrogen application produced higher yields by promoting the growth and photosynthesis of cherry tomatoes.It provides a strategy for water and nitrogen management of cherry tomatoes in Northwest China.

Photocatalytic degradation of enrofloxacin with CoAl-LDH mediated persulfate system:Efficiency evaluations and reaction pathways

Residual enrofloxacin(ENR)exposed in aqueous environments is challenging to the ecosphere.In this work,a layered double hydroxide CoAl-LDH was used to activate the common oxidizing agent persulfate(PS)for photodegradation of ENR,and the degradation pathways of ENR were scrutinized and elucidated.The results indicated that,under the optimal conditions obtained through orthogonal experiments,even though the degradation rate of ENR was as high as 97.72%,the removal of total organic carbon(TOC)from the system was only about 30%.Eleven probable reaction pathways were categorized,and thirty-one types of intermediates were identified in participating in the complex degradation process.The major products of ENR were P4(C_(17)H_(20)FN_(3)O_(3)),P22(C_(19)H_(22)FN_(3)O_(4)),P19(C_(17)H_(18)FN_(3)O_(3)),which are mainly derived from the cleavage of the piperazine groups and quinolone rings.Density functional theory(DFT)calculations of the Fukui index for ENR revealed that the two N atoms in the piperazine ring were the core reactive sites in triggering the degradation chains,which were sensitive for electrophilic attack by the dominant radicals(·OH and SO_(4)·^(-))generated from the composite PS-UV-CoAl-LDH system.

Advancing Toxicity Predictions:A Review on in Vitro to in Vivo Extrapolation in Next-Generation Risk Assessment

As a key step in next-generation risk assessment(NGRA),in vitro to in vivo extrapolation(IVIVE)aims to mobilize a mechanism-based understanding of toxicology to translate bioactive chemical concentrations obtained from in vitro assays to corresponding exposures likely to induce bioactivity in vivo.This conversion can be achieved via physiologically-based toxicokinetic(PBTK)models and machine learning(ML)algorithms.The last 5 years have witnessed a period of rapid development in IVIVE,with the number of IVIVE-related publications increasing annually.This Review aims to(1)provide a comprehensive overview of the origin of IVIVE and initiatives undertaken by multiple national agencies to promote its development;(2)compile and sort out IVIVE-related publications and perform a clustering analysis of their high-frequency keywords to capture key research hotspots;(3)comprehensively review PBTK and ML model-based IVIVE studies published in the last 5 years to understand the research directions and methodology developments;and(4)propose future perspectives for IVIVE from two aspects:expanding the scope of application and integrating new technologies.The former includes focusing on metabolite toxicity,conducting IVIVE studies on susceptible populations,advancing ML-based quantitative IVIVE models,and extending research to ecological effects.The latter includes combining systems biology,multiomics,and adverse outcome networks with IVIVE,aiming at a more microscopic,mechanistic,and comprehensive toxicity prediction.This Review highlights the important value of IVIVE in NGRA,with the goal of providing confidence for its routine use in chemical prioritization,hazard assessment,and regulatory decision making.

光固化生物3D打印研究进展及其在生物医药领域的应用

生物3D打印是一种利用活细胞、生物分子和生物材料打印生物医学结构的增材制造方法.光固化生物3D打印利用光对生物墨水进行时空控制实现3D结构的精确构筑,具有高效、副产物少的特点,被广泛用于组织工程和再生医学领域.本文对光固化反应的化学原理、常用于光固化生物3D打印的天然、合成生物材料和光固化生物3D打印的工艺、前沿方法进行了总结,并介绍了各工艺在生物医药领域的相关应用,最后展望了光固化生物3D打印面临的问题和未来的发展方向.

Achieving highest Young’s modulus in Al-Li by tracing the size and bonding evolution of Li-rich precipitates

For decades,it has been well accepted that every 1 wt.%Li addition to Al will reduce Al alloy’s density by 3%and increase its Young’s modulus by 6%.However,the fundamental mechanism of modulus improve-ments stays controversial though all studies agreed that the contribution of such a substantial boosting comes from Li-rich clusters either in solid solution or precipitations.In this study,we experimentally produce nano-sized Li-rich clusters by non-equilibrium solidification using centrifugal casting and trace their evolutions as a function of subsequent heat treatments.High-resolution transmission electron mi-croscopy(HRTEM)reveals a further decrease in the lattice constants of Li-rich regions from the as-cast(0.406 nm),solid solution(0.405 nm)to the aged state(0.401 nm),while Young’s modulus of the Al-Li al-loy reaches 89.16 GPa.Small-angle neutron scattering(SANS)experiments and first-principle calculations based on density functional theory have shown both the bond strength around precipitates and the size of those Li-rich region dominate Young’s modulus.At the beginning,it is volumetric compression due to Li addition that increases modulus,tightening the Al-Al potential curves.In the end,it is the Al-Al and Al-Li valence bonds in Al 3 Li at large size and high-volume fraction which increase its second derivative of internal energy and thus Young’s modulus.

Response of organic aerosol characteristics to emission reduction in Yangtze River Delta region

Organic aerosol(OA)is a major component of atmospheric particulate matter(PM)with complex composition and formation processes influenced by various factors.Emission reduction can alter both precursors and oxidants which further affects secondary OA formation.Here we provide an observational analysis of secondary OA(SOA)variation properties in Yangtze River Delta(YRD)of eastern China in response to large scale of emission reduction during Chinese New Year(CNY)holidays from 2015 to 2020,and the COVID-19 pandemic period from January to March,2020.We found a 17%increase of SOA proportion during the COVID lockdown.The relative enrichment of SOA is also found during multi-year CNY holidays with dramatic reduction of anthropogenic emissions.Two types of oxygenated OA(OOA)influenced by mixed emissions and SOA formation were found to be the dominant components during the lockdown in YRD region.Our results highlight that these emission-reduction-induced changes in organic aerosol need to be considered in the future to optimize air pollution control measures.