Recently, enzymatic peptide synthesis has drawn increasing attention due to its eco-friendly reagents and mild conditions, as compared to traditional chemical peptide synthesis. In this study, we successfully produced...Recently, enzymatic peptide synthesis has drawn increasing attention due to its eco-friendly reagents and mild conditions, as compared to traditional chemical peptide synthesis. In this study, we successfully produced an important antioxidant dipeptide precursor, BOC-Tyr-Ala, via a kinetically controlled enzymatic peptide synthesis reaction, catalyzed by the recombinant car- boxypeptidase Y （CPY） expressed in P. pastoris GS 115. In this reaction, the enzyme activity was 95.043 U/mL, and we used t-butyloxycarbonyl-L-tyrosine-methyl ester （BOC-Tyr-OMe） as the acyl donor and L-alanine （L-Ala） was the amino donor. We optimized the reaction conditions to be： 30 ℃, pH 9.5, organic phase （methanol）/aqueous phase = 1：20, BOC-Tyr-OMe 0.05 mol/L, Ala 0.5 mol/L, and a reaction time of 12 h. Under these conditions, the dipeptide yield reached 49.84%. Then, we established the kinetic model of the synthesis reaction in the form of Michaelis-Menten equation according to the con-centration-time curve during the process and the transpeptidation mechanism. We calculated the apparent Michaelis constant K^（app）mand the apparent maximum reaction rate r^（app）max to be 2.9946 x 10^-2 mol/L and 2.0406 x 10.2 mmol/（mL h）, respectively.展开更多
The demand for ^(238)Pu (nuclear battery heat source) drives the separation of its precursor,^(237)Np,from spent nuclear fuel (SNF).However,the co-existence of multi-valence states (Ⅳ/Ⅴ/Ⅵ) of Np and similar redox b...The demand for ^(238)Pu (nuclear battery heat source) drives the separation of its precursor,^(237)Np,from spent nuclear fuel (SNF).However,the co-existence of multi-valence states (Ⅳ/Ⅴ/Ⅵ) of Np and similar redox behavior with Pu(Ⅳ) hinder the effective separation of Np.N-Butyraldehyde (n-C_(3)H_(7)CHO) selectively reduces Np(Ⅵ) to Np(Ⅴ) without reducing Pu(Ⅳ).Herein,we examined the reduction mechanisms of Np(Ⅵ) and Pu(Ⅳ) by n-C3H7CHO using relativistic density functional theory.Based on the results of the potential energy profiles,the reductions of both Np(Ⅵ) and Pu(Ⅳ) by n-C_(3)H_(7)CHO are thermodynamically feasible,whereas only the former is kinetically achievable.It uncovers that n-C_(3)H_(7)CHO can only reduce Np(Ⅵ) to Np(Ⅴ) owing to kinetically controlled selective reduction.The analyses of spin density and bond distance indicate that the reduction nature for the first Np(Ⅵ)/Pu(Ⅳ) belongs to hydrogen atom transfer,whereas that for the second one involves outer-sphere electron transfer.Localized molecular orbitals (LMOs) analysis discloses the bonding evolution during the reduction process of Np(Ⅵ)/Pu(Ⅳ).This study elucidates the reason behind the kinetically controlled selective reduction of Np(Ⅵ)/Pu(Ⅳ) by nC3H7CHO at the molecular level and offers in-depth perspectives on the isolation of specific metal ions from the view of kinetic control.展开更多
In order to improve the oxidation resistance of Ti Al alloy, silicide coatings were prepared by pack cementation method at 1273, 1323, and 1373 K for 1-3 hours. Scanning electron microscopy（SEM）, energy dispersive s...In order to improve the oxidation resistance of Ti Al alloy, silicide coatings were prepared by pack cementation method at 1273, 1323, and 1373 K for 1-3 hours. Scanning electron microscopy（SEM）, energy dispersive spectrometry（EDS） and X-ray diffraction（XRD） were employed to investigate the microstructures and phase constitutions of the coatings. The experimental results show that all silicon deposition coatings have multi-layer structure. The microstructure and composition of silicide coatings strongly depend on siliconizing temperatures. In order to investigate the rate controlling step of pack siliconizing on Ti Al alloy, coating growth kinetics was analyzed by measuring the mass gains per unit area of silicided samples as a function of time and temperature. The results showed that the rate controlling step was gas-phase diffusion step and the growth rate constant（k） ranged from 1.53 mg^2/（cm^4·h^2） to 2.3 mg^2/（cm^4·h^2）. Activation energy（Q） for the process was calculated as 109 k J/mol, determined by Arrhenius＇ equation： k = k0 exp[–Q/（RT）].展开更多
Shape control of nickel sulfide(NiS_(2))catalysts is beneficial for boosting their catalytic performances,which is vital to their practical application as a class of advanced non-noble electro-catalysts.However,precis...Shape control of nickel sulfide(NiS_(2))catalysts is beneficial for boosting their catalytic performances,which is vital to their practical application as a class of advanced non-noble electro-catalysts.However,precisely controlling the formation kinetics and fabricate ultrathin NiS_(2)nanostructures still remains challenge.Herein,we provide an injection rate-mediated method to fabricate ultrathin NiS_(2)nanocages(HNCs)with hierarchical walls,high-density lattice defects and abundant grain boundaries(GBs).Through mechanism analysis,we find the injection rate determines the concentration of S_(2)−in the steady state and thus control the growth pattern,leading to the formation of NiS_(2)HNCs at slow etching kinetics and NiCo PBA@NiS_(2)frames at fast etching kinetics,respectively.Benefiting from the ultrathin and hierarchical walls that minimize the mass transport restrictions,the high-density lattice defects and GBs that offer abundant unsaturated reaction sites,the NiS_(2)HNCs exhibit obviously enhanced electrocatalytic activity and stability toward OER,with overpotential of 255mV to reach 10mA/cm^(2)and a Tafel slope of 27.44mV/dec,surpassing the performances of NiCo PBA@NiS_(2)frames and commercial RuO_(2).展开更多
Photothermal catalysis is a widely researched field in which the reaction mechanism is usually investigated based on the photochemical behavior of the catalytic material.Considering that the adsorption of reactants is...Photothermal catalysis is a widely researched field in which the reaction mechanism is usually investigated based on the photochemical behavior of the catalytic material.Considering that the adsorption of reactants is essential for catalytic reactions to occur,in this study,the synergistic effect of photothermal catalysis is innovatively elucidated in terms of the electron transfer behavior of reactant adsorption.For the H_(2)+O2 or CO+H_(2)reaction systems over a ZnO catalyst,UV irradiation at 25°C or heat without UV irradiation did not cause H_(2)oxidation or CO reduction;only photothermal conditions(100 or 150°C+UV light)initiated the two reactions.This result is related to the electron transfer behavior associated with the adsorption of CO or H_(2)on ZnO,in which H_(2)or CO that lost an electron could be oxidized by O2 or hydroxyls.However,the electron‐accepting CO could be reduced by the electron‐donating H_(2)into CH4 under photothermal conditions.Based on the in‐situ characterization and theoretical calculation results,it was established that the synergistic effect of the photothermal conditions acted on the(002)crystal surface of ZnO to stimulate the growth of zinc vacancies,which resulted in the formation of defect energy levels,adsorption sites,and an adjusted Fermi level.As a result,the electron transfer behavior between adsorbed CO or H_(2)and the crystal surface varied,which further affected the photocatalytic behavior.The results show that the effect of photothermal synergy may not only produce the expected kinetic energy,but more importantly,produce energy that can change the activation mode of the reactant gas.This study provides a new understanding of the CO catalytic oxidation and reduction processes over semiconductor materials.展开更多
The application of nanotechnologies in formulation has significantly promoted the development of modern medical and pharmacological science, especially for nanoparticle-based drug delivery, bioimaging, and theranostic...The application of nanotechnologies in formulation has significantly promoted the development of modern medical and pharmacological science, especially for nanoparticle-based drug delivery, bioimaging, and theranostics. The advancement of engineering particle design and fabrication is largely supported by a better understanding of how their apparent characteristics(e.g., size and size distribution, surface morphology, colloidal stability, chemical composition) influence their in vivo biological performance, which raises an urgent need for practical nanoformulation methods. Based on turbulent flow mixing and the self-assembly of molecules in fluids, flash technologies emerged as effective bottom-up fabrication strategies for effective nanoformulation. Among the flash technology family, flash nanocomplexation(FNC) is considered a novel and promising candidate that can promote and optimize formulation processes in a precise spatiotemporal manner, thus obtaining excellent fabrication efficiency, reproducibility and expandability. This review presents an overview of recent advances in fabricating drug-delivery nanoparticles using FNC platforms. Firstly, brief introductions to the basic principles of FNC technology were carried out, followed by descriptions of turbulent microvolume mixers that have significantly promoted the efficiency of FNC-based fabrications. Applications of real formulation cases were then categorized according to the self-assembly-driven interactions(including electrostatic interaction, coordination interaction,hydrogen bonding and hydrophobic interaction) and discussed to reveal the progressiveness of fabricating nanoparticles and discuss how its flexibility will provide advances and replenish the philosophy of nanomedicine formulation. In the end, the commercial potential, current limitations, and prospects of FNC technology for nanoformulation will be summarized and discussed.展开更多
Synthesis of N-benzoyl-argininylglycylasparagine methyl ester（ Bz-Arg-Gly-Asp-OMe）, a precursor tripeptide of Arg-Gly-Asp） was catalyzed by papain under kinetic control, at alkaline pH, in a full aqueous medium. Th...Synthesis of N-benzoyl-argininylglycylasparagine methyl ester（ Bz-Arg-Gly-Asp-OMe）, a precursor tripeptide of Arg-Gly-Asp） was catalyzed by papain under kinetic control, at alkaline pH, in a full aqueous medium. The substrates were N-benzoyl-argininylglycine ethyl ester and asparagine dimethyl ester. An aqueous solution of 0. 1 mol/L KCl/NaOH containing 8 mmol/L EDTA and 2 mmol/L DTT was selected as the reaction medium. The synthesized hydrophilic tripeptide was soluble in the reaction medium during the reaction process, however, the secondary hydro- lysis of the tripeptide product was not considerable. The effects of different factors, including water content, temperature, reaction time, and molar ratio of the substrates, on the yield of Bz-Arg-Gly-Asp-OMe were examined. The optimal reaction conditions were 0. 05 mol/L Bz-Arg-Gly-OEt and 0. 15 mol/L Asp（ -OMe）2·HCl in 0. 1 mol/L KCl/ NaOH solution（pH 8.5）, at 40 ℃, and a reaction time of 60 min, with a maximum conversion yield of 62.4%.展开更多
Chiral superstructures in confined spaces are subtly affected by the complex interplay among various noncovalent interactions,details of which are still in adequately understood.Herein,we report the threedimensional c...Chiral superstructures in confined spaces are subtly affected by the complex interplay among various noncovalent interactions,details of which are still in adequately understood.Herein,we report the threedimensional confined assembly of the chiral block copolymers of polystyrene-block-poly(D-lactide)andits enantiomer in emulsion droplets and demonstrate unprecedented successive microphase transformations from single helices to double helices with inverted helicity,and then to twisted cylinders in the constructedcolloidal particles.Theabovehierarchical structural transformations of chiral microphases are kinetically dependent and can further transform into thermodynamically stable achiral cylinders with saddle-shaped topology upon solvent annealing.The formation and subsequent structural transformations as well as thefinal degeneration of chiral architectures provide guidance to understand the chiral evolution at different length scales within spherical confined space and to fabricate biomimetic systems.展开更多
In this article, we present a facile, direct, synthetic approach of preparing monodisperse [Au2s（SePh）ls]- nanoclusters in high yield. In this synthetic approach, two-phase Brust-Schiffrin method is used. Both PhSeH...In this article, we present a facile, direct, synthetic approach of preparing monodisperse [Au2s（SePh）ls]- nanoclusters in high yield. In this synthetic approach, two-phase Brust-Schiffrin method is used. Both PhSeH and NaBH4 should be added drop-wise to the solution of Au （III） at the same time. The formula and molecular purity of [Au25（SePh）ls] TOA＋ clusters are characterized by MALDI-TOF mass spectrometry, NMR and TGA analysis. Furthermore, some critical parameters to obtain pure [Au25（SePh）18]-TOA＋ are identified, including the NaBH4-to-Au ratio, the selenolate-to-Au ratio and the temperature. The facile, direct, high yield synthetic method can be widely applied in the theoretical research of Au clusters protected by selenol.展开更多
Geomaterials are known to be non-associated materials. Granular soils therefore exhibit a variety of failure modes, with diffuse or localized kinematical patterns. In fact, the notion of failure itself can be confusin...Geomaterials are known to be non-associated materials. Granular soils therefore exhibit a variety of failure modes, with diffuse or localized kinematical patterns. In fact, the notion of failure itself can be confusing with regard to granular soils, because it is not associated with an obvious phenomenology. In this study, we built a proper framework, using the second-order work theory, to describe some failure modes in geomaterials based on energy conservation. The occurrence of failure is defined by an abrupt increase in kinetic energy. The increase in kinetic energy from an equilibrium state, under incremental loading, is shown to be equal to the difference between the external second-order work,involving the external loading parameters, and the internal second-order work, involving the constitutive properties of the material. When a stress limit state is reached, a certain stress component passes through a maximum value and then may decrease. Under such a condition, if a certain additional external loading is applied, the system fails, sharply increasing the strain rate. The internal stress is no longer able to balance the external stress, leading to a dynamic response of the specimen. As an illustration, the theoretical framework was applied to the well-known undrained triaxial test for loose soils. The influence of the loading control mode was clearly highlighted. It is shown that the plastic limit theory appears to be a particular case of this more general second-order work theory. When the plastic limit condition is met, the internal second-order work is nil. A class of incremental external loadings causes the kinetic energy to increase dramatically, leading to the sudden collapse of the specimen, as observed in laboratory.展开更多
Modulation of the morphology of nanostructures is often a rewarding but challenging task. We have employed the seeded growth method and induced kinetic control to synthesize Bi2Se3 nanoplates with modifiable morpholog...Modulation of the morphology of nanostructures is often a rewarding but challenging task. We have employed the seeded growth method and induced kinetic control to synthesize Bi2Se3 nanoplates with modifiable morphology. By manipulating the rate at which precursor solutions were injected into seeds solution with syringe pumps, two distinctive growth modes could be realized. With a fast injection, the thickness of Bi2Se3 nanoplates slightly increased from N7.5 nm （seeds） to -9.5 nm while the edge length grew up from ~160 nm （seeds） to N12 ~tm, after 6 successive rounds of seeded growth. With a slow injection, the thickness and edge length increased simultaneously to -35 nm and -6 b^m after 6 rounds of growth, respectively. These two modes could be viewed as a competition between atomic deposition and surface migration. The products showed interesting, thickness-dependent Raman properties. In addition, NIR transparent, highly conductive and flexible Bi2Se3 thin films with different thicknesses were constructed by the assembly of the as-synthesized Bi2Se3 nanoplates. This approach based on seeded growth and kinetic control can significantly promote the development of versatile nanostructures with diverse morphology.展开更多
Zinc and its alloys provide a scalable alternative to the list of biodegradable metals due to its moderate degradation rates and biocompatible degradation products.However,one of the challenges impeding their clinical...Zinc and its alloys provide a scalable alternative to the list of biodegradable metals due to its moderate degradation rates and biocompatible degradation products.However,one of the challenges impeding their clinical applications is the uncontrollable and unstable interfacial reactions between zinc implants and the corrosive media.In this study,we report a facile synthesis of metal-organic framework(MOF)nanocrystal coating with tunable thickness on the high-strength Zn-0.8Li alloy matrix for controlled corrosion.The as-obtained dense and uniform MOF nanocrystals form a strong connection with the zinc matrix via coordination bond so as to maintain the mechanical properties,and meantime provide highly rough surfaces exhibiting tunable wettability.The varied MOF coating thus regulate the interface structure between the zinc matrix and corrosive media to control the degradation behavior.Excellent antibacterial activity and biocompatibility are also achieved because of the unique topology morphologies,surface superhydrophilicity,as well as the dynamic Zn^(2+)release.This study sheds valuable lights on the design of MOF-functionalized metal implants for practical use and also triggers extensive applications of MOF in biomaterials.展开更多
Pathway selection in a complex chemical reaction network(CRN)enables organisms to adapt,evolve,and even learn in response to changing environments.Inspired by this,herein we report an artificial system,where light sig...Pathway selection in a complex chemical reaction network(CRN)enables organisms to adapt,evolve,and even learn in response to changing environments.Inspired by this,herein we report an artificial system,where light signal was used to manipulate the reaction pathways in a disulfide-based nonequilibrium CRN.By changing the photon energy and irradiation window,the anion or new radical-mediated pathways were selectively triggered,resulting in a user-defined evolution pathway.Additional photodissipative cycles were achieved by UV(365 nm)irradiation,increasing the total number of reactions from 3 to 7.The emerging pathway selection of the CRN is accurately predictable and controllable even in complex organo-hydrogel materials.We demonstrate up to five-state autonomous sol-gel transitions and the formation of fuel-driven dissipative organo-hydrogel through both chemical and light input.This work represents a new approach to allowing CRNs to communicate with the environment that can be used in the development of materials with lifelike behaviors.展开更多
A reasonable discrimination method for ablative control mechanism in solid-propellant rocket nozzle can improve the calculation accuracy of ablation rate.Based on the different rate constants for reactions of C with H...A reasonable discrimination method for ablative control mechanism in solid-propellant rocket nozzle can improve the calculation accuracy of ablation rate.Based on the different rate constants for reactions of C with H2O and CO_(2),a new discrimination method for ablative control mechanism,which comprehensively considers the influence of nozzle surface temperature and gas component concentration,is presented.Using this new discrimination method,calculations were performed to simulate the nozzle throat insert ablation.The numerical results showed that the calculated ablation rate,which was more close to the measured values,was less than the value calculated by diffusion control mechanisms or by double control mechanisms.And H2O was proved to be the most detrimental oxidizing species in nozzle ablation.展开更多
Crystal morphology is known to be of great importance to the end-use properties of crystal products, and to affect down-stream processing such as filtration and drying. However, it has been previously regarded as too ...Crystal morphology is known to be of great importance to the end-use properties of crystal products, and to affect down-stream processing such as filtration and drying. However, it has been previously regarded as too challenging to achieve automatic closed-loop control. Previous work has focused on controlling the crystal size distribution, where the size of a crystal is often defined as the diameter of a sphere that has the same volume as the crystal. This paper reviews the new advances in morphological population balance models for modelling and simulating the crystal shape distribution （CShD）, measuring and estimating crystal facet growth kinetics, and two- and three-dimensional imaging for on-line characterisation of the crystal morphology and CShD. A framework is presented that integrates the various components to achieve the ultimate objective of model-based closed-loop control of the CShD. The knowledge gaps and challenges that require further research are also identified.展开更多
Rational control on the D(donor)–A(acceptor)system of photocatalyst for boosting sacrificial-agentfree photosynthesis of hydrogen peroxide(H_(2)O_(2))from open air and water is highly desirable for H_(2)O_(2) product...Rational control on the D(donor)–A(acceptor)system of photocatalyst for boosting sacrificial-agentfree photosynthesis of hydrogen peroxide(H_(2)O_(2))from open air and water is highly desirable for H_(2)O_(2) production but remains a challenging issue.To this end,we developed a novel conversion strategy by controlling the reaction dynamics to rationally construct a three-component D–A–D isomer.Without any sacrificial agent,this three-component D–A–D isomer was found to enable an H_(2)O_(2) production rate of 4463μmol g^(−1) h^(−1) in open air and water,which was 1.9-and 1.5-fold higher,respectively,than the corresponding two-component D–A isomers.Accompanied is the O_(2) utilization and conversion efficiency of 99.8%,exceeding all established photocatalysts for such usage.The catalytic mechanism stemmed from a dual-channel pathway from both oxygen reduction reaction(ORR)and water oxidation reaction(WOR).The construction of a threecomponent D–A–D isomer was found to not only enhance the efficiency in the generation,transmission,and separation of photogenerated carriers but also optimize the O_(2) fixing site relative to the two-component D–A isomers.In addition,we further confirmed the application of this three-component D–A–D isomerization for real-time H_(2)O_(2) production from various real-life environments in open air and sunlight.展开更多
The crucial component,bulky spacers,in two-dimensional Ruddlesden-Popper(2 DRP)layered tin(Sn)perovskites are highly limited by halide ammonium salts,leading to the insufficient control of complex crystallization proc...The crucial component,bulky spacers,in two-dimensional Ruddlesden-Popper(2 DRP)layered tin(Sn)perovskites are highly limited by halide ammonium salts,leading to the insufficient control of complex crystallization process due to the limited interaction between bulky spacers and 2 DRP perovskite frameworks.Here,we report an ionic liquid-bulky spacer,butylammounium acetate(BAAc O),for constructing efficient and stable 2 DRP Sn-based perovskite solar cells(PSCs).In contrast to the traditional halide ammonium bulky spacer,butylammounium iodide(BAI),the Ac O^(-)-functional group in BAAc O has a strong interaction with formamidine ions(FA^(+))and Sn2+.The inter-component interaction allows the formation of controllable intermediates for the favorable growth of smooth,dense,and highly oriented perovskite films.A PSC with power conversion efficiency of 10.36%(7.16%for BAI)is achieved,which is the highest report,along with improved stability with~90%retained after~600 h storage in N_(2) atmosphere without any encapsulation.展开更多
Noble-metal nanocrystals enclosed by high-index facets are of growing interest due to their enhanced catalytic performance in a variety of reactions.Herein,we report the deterministic synthesis of Pd nanocrystals enca...Noble-metal nanocrystals enclosed by high-index facets are of growing interest due to their enhanced catalytic performance in a variety of reactions.Herein,we report the deterministic synthesis of Pd nanocrystals encased by high-index facets by controlling the rate of deposition(V_(deposition))relative to that of surface diffusion(V_(diffusion)).For octahedral seeds with truncated corners,a reduction rate(and thus deposition rate)faster than that of surface diffusion(i.e.,V_(deposition)/V_(diffusion)>1)led to the formation of concave trisoctahedra(TOH)with high-index facets.When the reduction was slowed down,in contrast,surface diffusion dominated the growth pathway.In the case of V_(deposition)/V_(diffusion)≈1,truncated octahedra with enlarged sizes were produced.When the reduction rate was between these two extremes,we obtained concave tetrahexahedra(THH)without or with truncation.Similar growth patterns were also observed for the cuboctahedral seeds.When the Pd octahedra,concave TOH,and concave THH were tested for electrocatalyzing the formic acid oxidation(FAO)reaction,those with high-index facets were advantageous over the conventional Pd octahedra enclosed by{111}facets.This work not only contributes to the understanding of surface diffusion and its role in nanocrystal growth but also offers a general protocol for the synthesis of nanocrystals enclosed by high-index facets.展开更多
基金supported by Ministry of Science and Technology of China(No.2012YQ090194 and No.2013AA102204)the National Natural Science Foundation of China(No.21676191,No.21476165,and No.21621004)
文摘Recently, enzymatic peptide synthesis has drawn increasing attention due to its eco-friendly reagents and mild conditions, as compared to traditional chemical peptide synthesis. In this study, we successfully produced an important antioxidant dipeptide precursor, BOC-Tyr-Ala, via a kinetically controlled enzymatic peptide synthesis reaction, catalyzed by the recombinant car- boxypeptidase Y （CPY） expressed in P. pastoris GS 115. In this reaction, the enzyme activity was 95.043 U/mL, and we used t-butyloxycarbonyl-L-tyrosine-methyl ester （BOC-Tyr-OMe） as the acyl donor and L-alanine （L-Ala） was the amino donor. We optimized the reaction conditions to be： 30 ℃, pH 9.5, organic phase （methanol）/aqueous phase = 1：20, BOC-Tyr-OMe 0.05 mol/L, Ala 0.5 mol/L, and a reaction time of 12 h. Under these conditions, the dipeptide yield reached 49.84%. Then, we established the kinetic model of the synthesis reaction in the form of Michaelis-Menten equation according to the con-centration-time curve during the process and the transpeptidation mechanism. We calculated the apparent Michaelis constant K^（app）mand the apparent maximum reaction rate r^（app）max to be 2.9946 x 10^-2 mol/L and 2.0406 x 10.2 mmol/（mL h）, respectively.
基金supported by the National Natural Science Foundation of China(Nos.22376197,U2441225,22076188).
文摘The demand for ^(238)Pu (nuclear battery heat source) drives the separation of its precursor,^(237)Np,from spent nuclear fuel (SNF).However,the co-existence of multi-valence states (Ⅳ/Ⅴ/Ⅵ) of Np and similar redox behavior with Pu(Ⅳ) hinder the effective separation of Np.N-Butyraldehyde (n-C_(3)H_(7)CHO) selectively reduces Np(Ⅵ) to Np(Ⅴ) without reducing Pu(Ⅳ).Herein,we examined the reduction mechanisms of Np(Ⅵ) and Pu(Ⅳ) by n-C3H7CHO using relativistic density functional theory.Based on the results of the potential energy profiles,the reductions of both Np(Ⅵ) and Pu(Ⅳ) by n-C_(3)H_(7)CHO are thermodynamically feasible,whereas only the former is kinetically achievable.It uncovers that n-C_(3)H_(7)CHO can only reduce Np(Ⅵ) to Np(Ⅴ) owing to kinetically controlled selective reduction.The analyses of spin density and bond distance indicate that the reduction nature for the first Np(Ⅵ)/Pu(Ⅳ) belongs to hydrogen atom transfer,whereas that for the second one involves outer-sphere electron transfer.Localized molecular orbitals (LMOs) analysis discloses the bonding evolution during the reduction process of Np(Ⅵ)/Pu(Ⅳ).This study elucidates the reason behind the kinetically controlled selective reduction of Np(Ⅵ)/Pu(Ⅳ) by nC3H7CHO at the molecular level and offers in-depth perspectives on the isolation of specific metal ions from the view of kinetic control.
基金Funded by the Natural Science Program for Basic Research in Key Areas of Shaanxi Province(2014JZ012)
文摘In order to improve the oxidation resistance of Ti Al alloy, silicide coatings were prepared by pack cementation method at 1273, 1323, and 1373 K for 1-3 hours. Scanning electron microscopy（SEM）, energy dispersive spectrometry（EDS） and X-ray diffraction（XRD） were employed to investigate the microstructures and phase constitutions of the coatings. The experimental results show that all silicon deposition coatings have multi-layer structure. The microstructure and composition of silicide coatings strongly depend on siliconizing temperatures. In order to investigate the rate controlling step of pack siliconizing on Ti Al alloy, coating growth kinetics was analyzed by measuring the mass gains per unit area of silicided samples as a function of time and temperature. The results showed that the rate controlling step was gas-phase diffusion step and the growth rate constant（k） ranged from 1.53 mg^2/（cm^4·h^2） to 2.3 mg^2/（cm^4·h^2）. Activation energy（Q） for the process was calculated as 109 k J/mol, determined by Arrhenius＇ equation： k = k0 exp[–Q/（RT）].
基金financially supported by National Natural Science Foundation of China (Nos. 21902078, 22279062, 22232004,22072067)the supports from National and Local Joint Engineering Research Center of Biomedical Functional Materialsa project sponsored by the Priority Academic Program Development of Jiangsu Higher Education Institutions
文摘Shape control of nickel sulfide(NiS_(2))catalysts is beneficial for boosting their catalytic performances,which is vital to their practical application as a class of advanced non-noble electro-catalysts.However,precisely controlling the formation kinetics and fabricate ultrathin NiS_(2)nanostructures still remains challenge.Herein,we provide an injection rate-mediated method to fabricate ultrathin NiS_(2)nanocages(HNCs)with hierarchical walls,high-density lattice defects and abundant grain boundaries(GBs).Through mechanism analysis,we find the injection rate determines the concentration of S_(2)−in the steady state and thus control the growth pattern,leading to the formation of NiS_(2)HNCs at slow etching kinetics and NiCo PBA@NiS_(2)frames at fast etching kinetics,respectively.Benefiting from the ultrathin and hierarchical walls that minimize the mass transport restrictions,the high-density lattice defects and GBs that offer abundant unsaturated reaction sites,the NiS_(2)HNCs exhibit obviously enhanced electrocatalytic activity and stability toward OER,with overpotential of 255mV to reach 10mA/cm^(2)and a Tafel slope of 27.44mV/dec,surpassing the performances of NiCo PBA@NiS_(2)frames and commercial RuO_(2).
文摘Photothermal catalysis is a widely researched field in which the reaction mechanism is usually investigated based on the photochemical behavior of the catalytic material.Considering that the adsorption of reactants is essential for catalytic reactions to occur,in this study,the synergistic effect of photothermal catalysis is innovatively elucidated in terms of the electron transfer behavior of reactant adsorption.For the H_(2)+O2 or CO+H_(2)reaction systems over a ZnO catalyst,UV irradiation at 25°C or heat without UV irradiation did not cause H_(2)oxidation or CO reduction;only photothermal conditions(100 or 150°C+UV light)initiated the two reactions.This result is related to the electron transfer behavior associated with the adsorption of CO or H_(2)on ZnO,in which H_(2)or CO that lost an electron could be oxidized by O2 or hydroxyls.However,the electron‐accepting CO could be reduced by the electron‐donating H_(2)into CH4 under photothermal conditions.Based on the in‐situ characterization and theoretical calculation results,it was established that the synergistic effect of the photothermal conditions acted on the(002)crystal surface of ZnO to stimulate the growth of zinc vacancies,which resulted in the formation of defect energy levels,adsorption sites,and an adjusted Fermi level.As a result,the electron transfer behavior between adsorbed CO or H_(2)and the crystal surface varied,which further affected the photocatalytic behavior.The results show that the effect of photothermal synergy may not only produce the expected kinetic energy,but more importantly,produce energy that can change the activation mode of the reactant gas.This study provides a new understanding of the CO catalytic oxidation and reduction processes over semiconductor materials.
基金supported by the Sanya Yazhou Bay Science and Technology City (No. 2021JJLH0037)Taishan Scholar Foundation of Shandong Province (No. tsqn202211065)+2 种基金Natural Science Foundation of China (No. 82003673)Yangcheng Scholars Research Project of Guangzhou (No. 20183197)Guangzhou Science and Technology Plan (No. 201901010170)
文摘The application of nanotechnologies in formulation has significantly promoted the development of modern medical and pharmacological science, especially for nanoparticle-based drug delivery, bioimaging, and theranostics. The advancement of engineering particle design and fabrication is largely supported by a better understanding of how their apparent characteristics(e.g., size and size distribution, surface morphology, colloidal stability, chemical composition) influence their in vivo biological performance, which raises an urgent need for practical nanoformulation methods. Based on turbulent flow mixing and the self-assembly of molecules in fluids, flash technologies emerged as effective bottom-up fabrication strategies for effective nanoformulation. Among the flash technology family, flash nanocomplexation(FNC) is considered a novel and promising candidate that can promote and optimize formulation processes in a precise spatiotemporal manner, thus obtaining excellent fabrication efficiency, reproducibility and expandability. This review presents an overview of recent advances in fabricating drug-delivery nanoparticles using FNC platforms. Firstly, brief introductions to the basic principles of FNC technology were carried out, followed by descriptions of turbulent microvolume mixers that have significantly promoted the efficiency of FNC-based fabrications. Applications of real formulation cases were then categorized according to the self-assembly-driven interactions(including electrostatic interaction, coordination interaction,hydrogen bonding and hydrophobic interaction) and discussed to reveal the progressiveness of fabricating nanoparticles and discuss how its flexibility will provide advances and replenish the philosophy of nanomedicine formulation. In the end, the commercial potential, current limitations, and prospects of FNC technology for nanoformulation will be summarized and discussed.
基金Supported by the Scientific Research Foundation for the Returned Overseas Chinese Scholars of Ministry of Education,China.
文摘Synthesis of N-benzoyl-argininylglycylasparagine methyl ester（ Bz-Arg-Gly-Asp-OMe）, a precursor tripeptide of Arg-Gly-Asp） was catalyzed by papain under kinetic control, at alkaline pH, in a full aqueous medium. The substrates were N-benzoyl-argininylglycine ethyl ester and asparagine dimethyl ester. An aqueous solution of 0. 1 mol/L KCl/NaOH containing 8 mmol/L EDTA and 2 mmol/L DTT was selected as the reaction medium. The synthesized hydrophilic tripeptide was soluble in the reaction medium during the reaction process, however, the secondary hydro- lysis of the tripeptide product was not considerable. The effects of different factors, including water content, temperature, reaction time, and molar ratio of the substrates, on the yield of Bz-Arg-Gly-Asp-OMe were examined. The optimal reaction conditions were 0. 05 mol/L Bz-Arg-Gly-OEt and 0. 15 mol/L Asp（ -OMe）2·HCl in 0. 1 mol/L KCl/ NaOH solution（pH 8.5）, at 40 ℃, and a reaction time of 60 min, with a maximum conversion yield of 62.4%.
基金the National Natural Science Foundation of China(nos.51525302 and 21802049)the China Postdoctoral Science Foundation(no.2017M622403)the Innovation and Talent Recruitment Base of New Energy Chemistry and Devices(no.B21003).
文摘Chiral superstructures in confined spaces are subtly affected by the complex interplay among various noncovalent interactions,details of which are still in adequately understood.Herein,we report the threedimensional confined assembly of the chiral block copolymers of polystyrene-block-poly(D-lactide)andits enantiomer in emulsion droplets and demonstrate unprecedented successive microphase transformations from single helices to double helices with inverted helicity,and then to twisted cylinders in the constructedcolloidal particles.Theabovehierarchical structural transformations of chiral microphases are kinetically dependent and can further transform into thermodynamically stable achiral cylinders with saddle-shaped topology upon solvent annealing.The formation and subsequent structural transformations as well as thefinal degeneration of chiral architectures provide guidance to understand the chiral evolution at different length scales within spherical confined space and to fabricate biomimetic systems.
基金the financial support by the National Natural Science Foundation of China (20871112, 21072001, 21372006)Changjiang Scholars Program+1 种基金the Scientific Research Foundation for Returning Overseas Chinese Scholars, State Education Ministry, Ministry of Human Resources and Social Security, Anhui Province International Scientific and Technological Cooperation Project211 Project of Anhui University
文摘In this article, we present a facile, direct, synthetic approach of preparing monodisperse [Au2s（SePh）ls]- nanoclusters in high yield. In this synthetic approach, two-phase Brust-Schiffrin method is used. Both PhSeH and NaBH4 should be added drop-wise to the solution of Au （III） at the same time. The formula and molecular purity of [Au25（SePh）ls] TOA＋ clusters are characterized by MALDI-TOF mass spectrometry, NMR and TGA analysis. Furthermore, some critical parameters to obtain pure [Au25（SePh）18]-TOA＋ are identified, including the NaBH4-to-Au ratio, the selenolate-to-Au ratio and the temperature. The facile, direct, high yield synthetic method can be widely applied in the theoretical research of Au clusters protected by selenol.
基金the French Research Network Me Ge (Multiscale and Multiphysics Couplings in Geo-environmental Mechanics GDR CNRS 3176/2340, 2008e2015) for having supported this work
文摘Geomaterials are known to be non-associated materials. Granular soils therefore exhibit a variety of failure modes, with diffuse or localized kinematical patterns. In fact, the notion of failure itself can be confusing with regard to granular soils, because it is not associated with an obvious phenomenology. In this study, we built a proper framework, using the second-order work theory, to describe some failure modes in geomaterials based on energy conservation. The occurrence of failure is defined by an abrupt increase in kinetic energy. The increase in kinetic energy from an equilibrium state, under incremental loading, is shown to be equal to the difference between the external second-order work,involving the external loading parameters, and the internal second-order work, involving the constitutive properties of the material. When a stress limit state is reached, a certain stress component passes through a maximum value and then may decrease. Under such a condition, if a certain additional external loading is applied, the system fails, sharply increasing the strain rate. The internal stress is no longer able to balance the external stress, leading to a dynamic response of the specimen. As an illustration, the theoretical framework was applied to the well-known undrained triaxial test for loose soils. The influence of the loading control mode was clearly highlighted. It is shown that the plastic limit theory appears to be a particular case of this more general second-order work theory. When the plastic limit condition is met, the internal second-order work is nil. A class of incremental external loadings causes the kinetic energy to increase dramatically, leading to the sudden collapse of the specimen, as observed in laboratory.
文摘Modulation of the morphology of nanostructures is often a rewarding but challenging task. We have employed the seeded growth method and induced kinetic control to synthesize Bi2Se3 nanoplates with modifiable morphology. By manipulating the rate at which precursor solutions were injected into seeds solution with syringe pumps, two distinctive growth modes could be realized. With a fast injection, the thickness of Bi2Se3 nanoplates slightly increased from N7.5 nm （seeds） to -9.5 nm while the edge length grew up from ~160 nm （seeds） to N12 ~tm, after 6 successive rounds of seeded growth. With a slow injection, the thickness and edge length increased simultaneously to -35 nm and -6 b^m after 6 rounds of growth, respectively. These two modes could be viewed as a competition between atomic deposition and surface migration. The products showed interesting, thickness-dependent Raman properties. In addition, NIR transparent, highly conductive and flexible Bi2Se3 thin films with different thicknesses were constructed by the assembly of the as-synthesized Bi2Se3 nanoplates. This approach based on seeded growth and kinetic control can significantly promote the development of versatile nanostructures with diverse morphology.
基金financially supported by the National Natural Science Foundation of China(52371248,52373273)National Key R&D Program of China(2021YFB3802200)+1 种基金Guangdong Basic and Applied Basic Research Foundation(2023A1515010905)Fundamental Research Funds for the Central Universities(FRF-EYIT-23-05)。
文摘Zinc and its alloys provide a scalable alternative to the list of biodegradable metals due to its moderate degradation rates and biocompatible degradation products.However,one of the challenges impeding their clinical applications is the uncontrollable and unstable interfacial reactions between zinc implants and the corrosive media.In this study,we report a facile synthesis of metal-organic framework(MOF)nanocrystal coating with tunable thickness on the high-strength Zn-0.8Li alloy matrix for controlled corrosion.The as-obtained dense and uniform MOF nanocrystals form a strong connection with the zinc matrix via coordination bond so as to maintain the mechanical properties,and meantime provide highly rough surfaces exhibiting tunable wettability.The varied MOF coating thus regulate the interface structure between the zinc matrix and corrosive media to control the degradation behavior.Excellent antibacterial activity and biocompatibility are also achieved because of the unique topology morphologies,surface superhydrophilicity,as well as the dynamic Zn^(2+)release.This study sheds valuable lights on the design of MOF-functionalized metal implants for practical use and also triggers extensive applications of MOF in biomaterials.
基金supported by the National Natural Science Foundation of China(grant no.52073175)National Natural Science Foundation of Shanghai(grant no.23ZR1442700)。
文摘Pathway selection in a complex chemical reaction network(CRN)enables organisms to adapt,evolve,and even learn in response to changing environments.Inspired by this,herein we report an artificial system,where light signal was used to manipulate the reaction pathways in a disulfide-based nonequilibrium CRN.By changing the photon energy and irradiation window,the anion or new radical-mediated pathways were selectively triggered,resulting in a user-defined evolution pathway.Additional photodissipative cycles were achieved by UV(365 nm)irradiation,increasing the total number of reactions from 3 to 7.The emerging pathway selection of the CRN is accurately predictable and controllable even in complex organo-hydrogel materials.We demonstrate up to five-state autonomous sol-gel transitions and the formation of fuel-driven dissipative organo-hydrogel through both chemical and light input.This work represents a new approach to allowing CRNs to communicate with the environment that can be used in the development of materials with lifelike behaviors.
基金supported by the National Hi-Tech Research and Development Program of China("863"Project)(Grant No.2008AA7020508).
文摘A reasonable discrimination method for ablative control mechanism in solid-propellant rocket nozzle can improve the calculation accuracy of ablation rate.Based on the different rate constants for reactions of C with H2O and CO_(2),a new discrimination method for ablative control mechanism,which comprehensively considers the influence of nozzle surface temperature and gas component concentration,is presented.Using this new discrimination method,calculations were performed to simulate the nozzle throat insert ablation.The numerical results showed that the calculated ablation rate,which was more close to the measured values,was less than the value calculated by diffusion control mechanisms or by double control mechanisms.And H2O was proved to be the most detrimental oxidizing species in nozzle ablation.
基金Financial support from the following projects and organisa- tions are acknowledged： the China One Thousand Talent Scheme, the National Natural Science Foundation of China （NNSFC） under its Major Research Scheme of Meso-scale Mechanism and Control in Multi-phase Reaction Processes （project reference： 91434126）, the Natural Science Foundation of Guangdong Province （project reference： 2014A030313228）, the UK Engineering and Physical Sciences Research Council （EPSRC） for the projects of Shape （EP/C009541） and StereoVision （EP/E045707）, and the Technology Strategy Board （TSB） for the project of High Value Manufacturing CGM （TP/BD059E）.
文摘Crystal morphology is known to be of great importance to the end-use properties of crystal products, and to affect down-stream processing such as filtration and drying. However, it has been previously regarded as too challenging to achieve automatic closed-loop control. Previous work has focused on controlling the crystal size distribution, where the size of a crystal is often defined as the diameter of a sphere that has the same volume as the crystal. This paper reviews the new advances in morphological population balance models for modelling and simulating the crystal shape distribution （CShD）, measuring and estimating crystal facet growth kinetics, and two- and three-dimensional imaging for on-line characterisation of the crystal morphology and CShD. A framework is presented that integrates the various components to achieve the ultimate objective of model-based closed-loop control of the CShD. The knowledge gaps and challenges that require further research are also identified.
基金supported financially by the Open Project Program of the National Key Laboratory of Uranium Resources Exploration-Mining and Nuclear Remote Sensing,China(grant no.2024QZ-TD-18)the National Natural Science Foundations of China(NSFC+1 种基金grant no.22376024)the Jiangxi project,China(grant no.DHSQT22021007).The authors would also like to thank Wenqian Liu from Shiyanjia Lab,China(www.Shiyanjia.com)for help with X-ray diffraction(XRD)and SEM analysis.
文摘Rational control on the D(donor)–A(acceptor)system of photocatalyst for boosting sacrificial-agentfree photosynthesis of hydrogen peroxide(H_(2)O_(2))from open air and water is highly desirable for H_(2)O_(2) production but remains a challenging issue.To this end,we developed a novel conversion strategy by controlling the reaction dynamics to rationally construct a three-component D–A–D isomer.Without any sacrificial agent,this three-component D–A–D isomer was found to enable an H_(2)O_(2) production rate of 4463μmol g^(−1) h^(−1) in open air and water,which was 1.9-and 1.5-fold higher,respectively,than the corresponding two-component D–A isomers.Accompanied is the O_(2) utilization and conversion efficiency of 99.8%,exceeding all established photocatalysts for such usage.The catalytic mechanism stemmed from a dual-channel pathway from both oxygen reduction reaction(ORR)and water oxidation reaction(WOR).The construction of a threecomponent D–A–D isomer was found to not only enhance the efficiency in the generation,transmission,and separation of photogenerated carriers but also optimize the O_(2) fixing site relative to the two-component D–A isomers.In addition,we further confirmed the application of this three-component D–A–D isomerization for real-time H_(2)O_(2) production from various real-life environments in open air and sunlight.
基金financially supported by the Natural Science Foundation of China(51972172,61705102,61605073,61935017,91833304,91733302)the National Key R&D Program of China(2017YFB1002900)+3 种基金Projects of International Cooperation and Exchanges NSFC(51811530018)Young 1000 Talents Global Recruitment Program of ChinaJiangsu Specially-Appointed Professor program“Six talent peaks”Project in Jiangsu Province,China。
文摘The crucial component,bulky spacers,in two-dimensional Ruddlesden-Popper(2 DRP)layered tin(Sn)perovskites are highly limited by halide ammonium salts,leading to the insufficient control of complex crystallization process due to the limited interaction between bulky spacers and 2 DRP perovskite frameworks.Here,we report an ionic liquid-bulky spacer,butylammounium acetate(BAAc O),for constructing efficient and stable 2 DRP Sn-based perovskite solar cells(PSCs).In contrast to the traditional halide ammonium bulky spacer,butylammounium iodide(BAI),the Ac O^(-)-functional group in BAAc O has a strong interaction with formamidine ions(FA^(+))and Sn2+.The inter-component interaction allows the formation of controllable intermediates for the favorable growth of smooth,dense,and highly oriented perovskite films.A PSC with power conversion efficiency of 10.36%(7.16%for BAI)is achieved,which is the highest report,along with improved stability with~90%retained after~600 h storage in N_(2) atmosphere without any encapsulation.
基金the NSF(CBET-2219546)and startup funds from the Georgia Institute of Technology.
文摘Noble-metal nanocrystals enclosed by high-index facets are of growing interest due to their enhanced catalytic performance in a variety of reactions.Herein,we report the deterministic synthesis of Pd nanocrystals encased by high-index facets by controlling the rate of deposition(V_(deposition))relative to that of surface diffusion(V_(diffusion)).For octahedral seeds with truncated corners,a reduction rate(and thus deposition rate)faster than that of surface diffusion(i.e.,V_(deposition)/V_(diffusion)>1)led to the formation of concave trisoctahedra(TOH)with high-index facets.When the reduction was slowed down,in contrast,surface diffusion dominated the growth pathway.In the case of V_(deposition)/V_(diffusion)≈1,truncated octahedra with enlarged sizes were produced.When the reduction rate was between these two extremes,we obtained concave tetrahexahedra(THH)without or with truncation.Similar growth patterns were also observed for the cuboctahedral seeds.When the Pd octahedra,concave TOH,and concave THH were tested for electrocatalyzing the formic acid oxidation(FAO)reaction,those with high-index facets were advantageous over the conventional Pd octahedra enclosed by{111}facets.This work not only contributes to the understanding of surface diffusion and its role in nanocrystal growth but also offers a general protocol for the synthesis of nanocrystals enclosed by high-index facets.
