Epoxy resins are widely employed in wind turbine blades,drone rotors,and automotive interiors due to their excel-lent mechani-cal proper-ties and long service life.However,their insoluble and infusible cross-linked ne...Epoxy resins are widely employed in wind turbine blades,drone rotors,and automotive interiors due to their excel-lent mechani-cal proper-ties and long service life.However,their insoluble and infusible cross-linked networks pose a significant re-cycling challenge,particularly with the impending retirement of the first generation of wind turbine blades.In this work,we reported a fully bio-based epoxy Vitrimer(FEP)incorporat-ing a dual-dynamic covalent network design and systematically investigated the influence of the 1,5,7-triazabicyclo[4.4.0]dec-5-ene(TBD)catalyst on its curing kinetics,thermal/mechan-ical properties,dynamic exchange behavior,and degradation performance in a mild alkaline solution.Compared to conventional epoxy resins,FEP exhibited superior tensile strength and elongation at break at an optimal TBD concentration(2 wt%),achieving an excellent strength-toughness balance.The presence of TBD accelerated the exchange rates of both disulfide and ester bonds,endowing FEP with notable stress relaxation at elevated tempera-tures.Moreover,FEP demonstrated complete dissolution in 1 mol/L NaOH within 6 h at 25℃.These results underscored the exceptional strength,toughness,and recyclability of FEP,positioning it as a promising,environmentally friendly matrix resin for next-generation appli-cations in the new energy sector.展开更多
Aqueous Zn-iodine batteries(ZIBs)face the formidable challenges towards practical implementation,including metal corrosion and rampant dendrite growth on the Zn anode side,and shuttle effect of polyiodide species from...Aqueous Zn-iodine batteries(ZIBs)face the formidable challenges towards practical implementation,including metal corrosion and rampant dendrite growth on the Zn anode side,and shuttle effect of polyiodide species from the cathode side.These challenges lead to poor cycle stability and severe self-discharge.From the fabrication and cost point of view,it is technologically more viable to deploy electrolyte engineering than electrode protection strategies.More importantly,a synchronous method for modulation of both cathode and anode is pivotal,which has been often neglected in prior studies.In this work,cationic poly(allylamine hydrochloride)(Pah^(+))is adopted as a low-cost dual-function electrolyte additive for ZIBs.We elaborate the synchronous effect by Pah^(+)in stabilizing Zn anode and immobilizing polyiodide anions.The fabricated Zn-iodine coin cell with Pah^(+)(ZnI_(2) loading:25 mg cm^(−2))stably cycles 1000 times at 1 C,and a single-layered 3.4 cm^(2) pouch cell(N/P ratio~1.5)with the same mass loading cycles over 300 times with insignificant capacity decay.展开更多
Developing green and efficient methods to acquire lignocellulose-based chemicals with high added value is beneficial for facilitating green chemistry and sustainable development.The goal of this study is to demonstrat...Developing green and efficient methods to acquire lignocellulose-based chemicals with high added value is beneficial for facilitating green chemistry and sustainable development.The goal of this study is to demonstrate that bio-based benzaldehyde,a noteworthy high-value chemical,is able to be directionally prepared from lignocellulosic biomass.This new control-lable transformation was materialized by uniting catalytic-pyrolysis of lignocellulose to toluene intermediate and catalytic oxidation of toluene intermediate to bio-based benzalde-hyde.This work also developed a highly active magnetic catalyst(CoFe_(2)O_(4)@Biochar(HTR)),achieving 77.1%benzaldehyde selectivity and 46.7%benzaldehyde yield using this catalyst.It was found that introducing the biochar carrier into the cobalt iron composite metal oxide cat-alyst enhanced hydroxyl radical formation and bio-based benzaldehyde synthesis.Based on catalyst characterizations and hydroxyl radical analysis,potential reaction mechanism for bio-based benzaldehyde synthesis was proposed.This strategy may provide a beneficial pathway for developing high-value bio-based chemical(benzaldehyde)using renewable lignocellulosic biomass.展开更多
The tensile strain in inorganic perovskite films induced by thermal annealing is one of the primary factors contributing to the inefficiency and instability of inorganic perovskite solar cells(IPSCs),which reduces the...The tensile strain in inorganic perovskite films induced by thermal annealing is one of the primary factors contributing to the inefficiency and instability of inorganic perovskite solar cells(IPSCs),which reduces the defect formation energy.Here,a flexible molecule 5-maleimidovaleric acid(5-MVA)was introduced as a strain buffer to release the residual strain of CsPbI_(2.85)Br_(0.15)perovskite.Maleic anhydride and carboxyl groups in 5-MVA interact strongly with the uncoordinated Pb^(2+)through Lewis acid-base reaction,thus tightly“pull”the perovskite lattice.The in-between soft carbon chain increased the structural flexibility of CsPbI_(2.85)Br_(0.15)perovskite materials,which effectively relieved the intrinsic internal strain of CsPbI_(2.85)Br_(0.15),resisted the corrosion of external strain,and also reduced the formation of defects such as VIand Pb0.In addition,the introduction of 5-MVA improved crystal quality,passivated residual defects,and narrowed energy level barriers.Eventually,power conversion efficiency(PCE)of NiOxbased inverted IPSCs increased from 19.25%to 20.82%with the open-circuit voltage enhanced from 1.164 V to 1.230 V.The release of strain also improved the stability of CsPbI_(2.85)Br_(0.15)perovskite films and devices.展开更多
Acceptor-donor-acceptor(A-D-A)type molecules,of which the novel non-fused azacyclic end-group pyrazoli-nones were modified with chlorine substitution on the phenyl ring,were synthesized.The non-fused azacyclic end-gro...Acceptor-donor-acceptor(A-D-A)type molecules,of which the novel non-fused azacyclic end-group pyrazoli-nones were modified with chlorine substitution on the phenyl ring,were synthesized.The non-fused azacyclic end-group py-razolinones have the advantages of simple synthesis steps,low cost and environmental friendliness,compared to the classical end-group dicyanomethyleneindianone.The properties of the synthesized A-D-A type molecules with non-fused azacyclic end groups were characterized by theoretical calculation,UV-vis absorption,cyclic voltammetry,X-ray diffraction and space charge limited current.It is shown that the strong UV-vis absorptions of the synthesized A-D-A type molecules are located in the wavelength range of 500~700 nm,with a moderate band gap of nearly 1.7 eV.At the same time,the influence of end-group chlorination on the properties of A-D-A type molecules was compared and explored.It is proven that this kind of A-D-A type molecule with non-fused azacyclic end groups has the potential to be applied as interfacial modified layer of the active layer in perovskite solar cell devices.展开更多
With the escalating global emphasis on environmental conservation and sustainable development,enhancing the service quality and durability of road surfaces and facilitating the green development of highways have comma...With the escalating global emphasis on environmental conservation and sustainable development,enhancing the service quality and durability of road surfaces and facilitating the green development of highways have commanded considerable attention.Bio-based polyurethane,on account of its remarkable physical and chemical properties,green,sustainable and renewable capacity,as well as its structural design capabilities,has drawn widespread attention and numerous studies have been carried out.It has gradually started to substitute traditional petroleum-based polyurethane materials in road engineering.Nevertheless,the application of bio-based polyurethane materials in road engineering remains in the exploratory phase.To stimulate the application research of bio-based polyurethane materials in road engineering and offer additional research directions,this paper reviews the research advancements of bio-based polyurethane materials and their applications in road engineering.The fundamental classification of bio-based polyurethane is introduced.The characteristics and challenges associated with various preparation methods for bio-based polyurethane are described.The influence of bio-based polyurethane on road engineering materials are analyzed.The evaluation indicators of bio-based polyurethane within the life cycle of road engineering are investigated.Finally,the development tendency towards in road engineering applications are forecasted.This paper provides a reference for the study of bio-based polyurethane materials in road engineering applications.展开更多
CRISPR-based tran-scription regulators(CRISPR-TRs)have revolutionized the field of synthetic biol-ogy by enabling tar-geted activation or repression of any de-sired gene.However,the majority of exist-ing inducible CRI...CRISPR-based tran-scription regulators(CRISPR-TRs)have revolutionized the field of synthetic biol-ogy by enabling tar-geted activation or repression of any de-sired gene.However,the majority of exist-ing inducible CRISPR-TRs are limited by their dependence on specific sequences,which restricts their flex-ibility and controllability in genetic engineering applications.In this study,we proposed a novel strategy to construct sequence-independent inducible CRISPR-TRs,which is achieved by the design of stem loop 2 in the single guide RNA(sgRNA).Under this strategy,by utiliz-ing toehold-mediated strand displacement(TMSD)reactions between small endogenous molecules(miR-20a and TK1 mRNA)and bridge RNA(bRNA)to link bRNA with sgRNA,we achieved synergistic transcriptional activation of VP64 and p65-HSF1 in response to en-dogenous molecules.To enable response to exogenous molecules,we added response se-quences and bRNA sequences to the 5'end of sgRNA to block sgRNA activity,and achieved activation of sgRNA by shearing the response sequence,called sequential unlimited interlock-ing(SUI).Compared with conventional sequence-restricted interlocking(spacer-blocking hairpin(SBH)),the transcriptional activation ratio between response and non-response to the Cas6A protein using our approach was increased by 2.28-fold.Our work presents a modular and versatile framework for endogenous and exogenous molecule-responsive CRISPR-TRs in mammalian cells,without limitations imposed by sequence dependence.展开更多
The current global shortage of oil resources and the pollution problems caused by traditional barrier materials urgently require the search for new substitutes.Biodegradable bio-based barrier materials possess the cha...The current global shortage of oil resources and the pollution problems caused by traditional barrier materials urgently require the search for new substitutes.Biodegradable bio-based barrier materials possess the characteristics of being renewable,environmentally friendly,and having excellent barrier properties.They have become an important choice in fields such as food packaging,agricultural film covering,and medical protection.This review systematically analyzes the design and research of this type of material,classifying biobased and biodegradable barrier materials based on the sources of raw materials and synthesis pathways.It also provides a detailed introduction to the latest research progress of biobased and biodegradable barrier materials,discussing the synthesis methods and improvement measures of their barrier properties.Subsequently,it analyzes the related technologies for enhancing the barrier properties of biobased and biodegradable barrier materials,and finally looks forward to the directions that future research should focus on,promoting the transition of biobased and biodegradable barrier materials from the laboratory to industrial applications.展开更多
The demand for energy-efficient and environmental-friendly power grid construction has made the exploitation of bio-based electrical epoxy resins with excellent properties increasingly important.This work developed th...The demand for energy-efficient and environmental-friendly power grid construction has made the exploitation of bio-based electrical epoxy resins with excellent properties increasingly important.This work developed the bio-based electrotechnical epoxy resins based on magnolol.High-performance epoxy resin(DGEMT)with a double crosslinked points and its composites(Al_(2)O_(3)/DGEMT)were obtained taking advantages of the two bifunctional groups(allyl and phenolic hydroxyl groups)of magnolol.Benefitting from the distinctive structure of DGEMT,the Al_(2)O_(3)/DGEMT composites exhibited the advantages of intrinsically high thermal conductivity,high insulation,and low dielectric loss.The AC breakdown strength and thermal conductivity of Al_(2)O_(3)/DGEMT composites were 35.5 kV/mm and 1.19 W·m-1·K-1,respectively,which were 15.6%and 52.6%higher than those of petroleum-based composites(Al_(2)O_(3)/DGEBA).And its dielectric loss tanδ=0.0046 was 20.7%lower than that of Al_(2)O_(3)/DGEBA.Furthermore,the mechanical,thermal and processing properties of Al_(2)O_(3)/DGEMT are fully comparable to those of Al_(2)O_(3)/DGEBA.This work confirms the feasibility of manufacturing environmentally friendly power equipment using bio-based epoxy resins,which has excellent engineering applications.展开更多
By investigating the performance characteristics of the bio-based surfactant 8901A,a composite decontamination and injection system was developed using 8901A as the primary agent,tailored for application in low-permea...By investigating the performance characteristics of the bio-based surfactant 8901A,a composite decontamination and injection system was developed using 8901A as the primary agent,tailored for application in low-permeability and heavy oil reservoirs under varying temperature conditions.The results demonstrate that this system effectively reduces oil–water interfacial tension,achieving an ultra-low interfacial tension state.The static oil washing efficiency of oil sands exceeds 85%,the average pressure reduction rate reaches 21.55%,and the oil recovery rate improves by 13.54%.These enhancements significantly increase the system’s ability to dissolve oilbased blockages,thereby lowering water injection pressure caused by organic fouling,increasing the injection volume of injection wells,and ultimately improving oil recovery efficiency.展开更多
Aging plays a critical role in determining the durability and long-term performance of asphalt pavements,as it is influenced by both external factors(e.g.,temperature,ultraviolet(UV)radiation,moisture,oxidative gases)...Aging plays a critical role in determining the durability and long-term performance of asphalt pavements,as it is influenced by both external factors(e.g.,temperature,ultraviolet(UV)radiation,moisture,oxidative gases)and internal factors such as binder composition.Although laboratory simulations of aging are well established for conventional bituminous binders,limited attention has been paid to replicating and evaluating aging processes in bio-based binders.This review provides a comprehensive analysis of current laboratory techniques for simulating and assessing binder aging,with a focus on two key areas:aging simulation protocols and evaluation methodologies.The analysis shows that although several efforts have been made to incorporate external aging factors into lab simulations,significant challenges persist,especially in the case of bio-based binders,which are characterized by a high variability in composition and limited understanding of their aging behavior.Current evaluation approaches also exhibit limitations.Improvements are needed in the molecular-level analysis of oxidation(e.g.,through more representative oxidation modelsin molecular dynamicssimulations),in the separation and quantification of binder constituents,and in the application of advanced techniques such as fluorescence microscopy to better characterize polymer dispersion.To enhance the reliability of laboratory simulations,future research should aim to improve the correlation between laboratory and field aging,define robust aging indexes,and refine characterization methods.These advancements are particularly critical for bio-based binders,whose performance is highly sensitive to aging and for which standard test protocols are still underdeveloped.A deeper understanding of aging mechanisms in both polymer-modified and biobased binders,along with improved analytical tools for assessing oxidative degradation and morphological changes,will be essential to support the development of sustainable,high-performance paving materials.展开更多
In the context of transitioning toward more sustainable construction materials,this study explores the impact of incorporating millet husks as an alternative to sand on the physical,mechanical,and thermal performance ...In the context of transitioning toward more sustainable construction materials,this study explores the impact of incorporating millet husks as an alternative to sand on the physical,mechanical,and thermal performance of lightweight concrete.Through a mixture design approach,five formulations were selected and thoroughly characterized.The analysis of iso-response curves enabled an in-depth assessment of the cross-effects between formulation parameters and their interactions on the final properties of the material.The results show that integrating millet husks leads to a significant reduction in density,reaching up to 21%,while maintaining notable mechanical performance.A balanced formulation of sand and fibers achieved a maximum compressive strength of 12.11 MPa,demonstrating that,under specific conditions,plant fibers actively contribute to the structural integrity of the composite.In tensile strength,the positive influence of fibers is even more pronounced,with a maximum resistance of 8.62 MPa,highlighting their role in enhancing material cohesion.From a thermal perspective,millet husks reduce both thermal conductivity and effusivity,thereby limiting heat transfer and accumulation within the composite.Iso-response curve analysis reveals that these effects are directly linked to the proportions of the constituents and that achieving an optimal balance between sand,fibers,and cement is key to maximizing performance.These findings demonstrate that the adopted approach allows moving beyond conventional substitution methods by identifying optimal configurations for the design of lightweight bio-based concretes that are both strong and insulating,thereby confirming the potential of millet husks in developing lightweight concretes suitable for sustainable construction applications.展开更多
Immunotherapy has transformed cancer treatment,marked by the approval of numerous antibody-based drugs.However,the limitations of antibodies in pharmacokinetics including long half-lives,limited oral bioavailability a...Immunotherapy has transformed cancer treatment,marked by the approval of numerous antibody-based drugs.However,the limitations of antibodies in pharmacokinetics including long half-lives,limited oral bioavailability and immunogenicity,have prompted the pursuit of small molecule-based immunotherapy.Traditional drug discovery strategies,which focus on blocking protein activity through inhibitors,face persistent hurdles,such as reliance on accessible binding pockets,poor selectivity,and the emergence of drug resistance.Targeted protein degradation(TPD)technologies have emerged as powerful tools to address these limitations,offering significant therapeutic advantages over conventional inhibition strategies,particularly for historically "undruggable" targets.In recent years,small molecule-based protein degraders have rapidly advanced in cancer immunotherapy.In this review,we highlight recent progress in TPD-driven small-molecule drug discovery and summarize the application of these technologies in cancer immunotherapy,including degraders targeting PD-1/PD-L1,chemokine receptors,IDO1,AhR,and others.展开更多
Molecular high-order harmonic spectroscopy is a significant advancement in ultrafast science, enabling the measurement of multielectron dynamics with attosecond temporal resolution. The fine structures observed in the...Molecular high-order harmonic spectroscopy is a significant advancement in ultrafast science, enabling the measurement of multielectron dynamics with attosecond temporal resolution. The fine structures observed in the molecular harmonic spectrum provide crucial insights into the structural or multielectron dynamical effects induced by intense laser fields. In this study, we measure the high-order harmonic spectrum of aligned CO_(2) molecules contributed from short trajectories. Two distinct groups of minima are identified in the plateau region. Our findings indicate that the deeper-lying molecular orbitals and two-center interference play significant roles in molecular harmonic generation. The results pave the way for advancing the understanding of multielectron dynamics in polyatomic molecules under intense laser fields.展开更多
An in-depth understanding of the hydration mechanism of tricalcium silicate is an important basis for optimizing cement strength development.In this study,the adsorption of water molecules onto the M3-C3S(001)surface ...An in-depth understanding of the hydration mechanism of tricalcium silicate is an important basis for optimizing cement strength development.In this study,the adsorption of water molecules onto the M3-C3S(001)surface at different water coverage levels(θ=1/5,2/5,3/5,4/5,and 1)was investigated using first-principles calculations.The results demonstrate that the conclusions obtained for single water molecule adsorption cannot be fully applied to multiple water molecule adsorption.The total adsorption energies become more negative with increasing water coverage,while the average adsorption energy of each water molecule becomes more positive with increasing water coverage.The water–water interactions reduce the water–surface interactions and are responsible for the anticooperative adsorption of multiple water molecules onto M3-C_(3)S(001).The formation of Ca–OH(–Ca)bonds favors the detachment of Ca from co-valent oxygen,which reveals the significant role of dissociative adsorption.This work aims to extend the water adsorption study on M3-C3S(001)from single water molecule adsorption to multiple water molecule adsorption,providing more detailed insights into the initial water reaction on the C3S surface.展开更多
Colloidal molecules exhibit unique electronic,optical,and magnetic properties owing to their molecular-like configurations and coupling effects,making them promising building blocks for multifunctional materials.Howev...Colloidal molecules exhibit unique electronic,optical,and magnetic properties owing to their molecular-like configurations and coupling effects,making them promising building blocks for multifunctional materials.However,achieving precise and controllable assembly of isotropic nanoparticles with high yields remains a great challenge.In this study,we present a synergistic strategy that integrates molecular dynamics simulations with interpretable machine learning to develop a programmable assembly system based on block copolymers and DNA-functionalized nanoparticles.Our simulation results reveal that block copolymer modification facilitates stepwise control over surface phase separation and nanoparticle coassembly,thereby enhancing structural stability and efficiently suppressing disordered aggregation of atom-like nanoparticles.Furthermore,we demonstrated that precise,controllable,and programmable assembly of colloidal molecules can be achieved through rational DNA sequence design.SHapley Additive exPlanations(SHAP)analysis identified key structural descriptors that govern assembly outcomes and elucidated their underlying mechanistic roles.This work not only deepens the understanding of colloidal molecule assembly mechanisms but also lays a theoretical foundation for the rational design of functional colloidal architectures in nanomaterial science.展开更多
Exploring multifunctional interfacial modifiers is an effective approach to addressing interface issues in perovskite solar cells(PSCs)and improving device performance and stability.While most interfacial modifiers fo...Exploring multifunctional interfacial modifiers is an effective approach to addressing interface issues in perovskite solar cells(PSCs)and improving device performance and stability.While most interfacial modifiers focus on passivating defects at the interfaces,there has been limited investigation into the relationship between molecular design and interfacial charge dynamics.This work introduces resonance molecules with a push-pull effect for interfacial modification,allowing for synergistic regulation of passivation effects and charge dynamics.Specifically,FCz-PO,which includes an electron-withdrawing fluorine atom,exhibits superior passivation but poor molecular stacking and charge extraction.In contrast,MCz-PO,featuring an electron-donating methoxy group,provides effective passivation,wellordered molecular packing,and efficient charge extraction and transport.Consequently,PSCs using MCz-PO achieve high power conversion efficiency(PCE)of 24.74%and excellent operational stability.This study suggests that resonance structures can be an effective molecular design strategy for developing interfacial modifiers with both strong passivation capabilities and well-regulated charge dynamics.展开更多
Spiral patterns widely exist in both macroscopic and microscopic systems such as hearts,bacteria,and active matters but have never been reported at molecular length scale.The emergence of spiral patterns has considera...Spiral patterns widely exist in both macroscopic and microscopic systems such as hearts,bacteria,and active matters but have never been reported at molecular length scale.The emergence of spiral patterns has considerable impacts on the trajectories of the objects and thus usually relates to various physical,chemical,biological and physiological processes.In this paper,we show that,down to the length scale of only several Angstroms,asymmetric molecules exhibit spiral patterns in their trajectories within finite time based on the under-damped Langevin equation and demonstrated by molecular dynamics simulation.The key to this observation lies in the asymmetric molecular architecture that leads to a translation-rotation coupling.This finding enriches the knowledge of spiral patterns to the molecular length scale,provides a new insight into the understanding of various processes at the molecular level,and may evoke new ideas on the understanding of the vortices in turbulence.展开更多
Soliton molecules(SMs),bounded and self-assembled of particle-like dissipative solitons,exist with versatile mutual interactions and manifest substantial potential in soliton communication and optical data storage.How...Soliton molecules(SMs),bounded and self-assembled of particle-like dissipative solitons,exist with versatile mutual interactions and manifest substantial potential in soliton communication and optical data storage.However,controllable manipulation of the bounded molecular patterns remains challenging,as reaching a specific operation regime in lasers generally involves adjusting multiple control parameters in connection with a wide range of accessible pulse dynamics.An evolutionary algorithm is implemented for intelligent control of SMs in a 2μm ultrafast fiber laser mode locked through nonlinear polarization rotation.Depending on the specifications of the merit function used for the optimization procedure,various SM operations are obtained,including spectra shape programming and controllable deterministic switching of doublet and triplet SMs operating in stationary or pulsation states with reconfigurable temporal separations,frequency locking of pulsation SMs,doublet and SM complexes with controllable pulsation ratio,etc.Digital encoding is further demonstrated in this platform by employing the self-assembled characteristics of SMs.Our work opens up an avenue for active SM control beyond conventional telecom bands and brings useful insights into nonlinear science and applications.展开更多
An efficient and novel approach is proposed for oxidative arylation of bio-based furfuryl alcohol(FA)to aryl furans(AFs),a versatile monomer of photoelectric materials,in the presence of UiO-67-Pd(F)with phenanthrolin...An efficient and novel approach is proposed for oxidative arylation of bio-based furfuryl alcohol(FA)to aryl furans(AFs),a versatile monomer of photoelectric materials,in the presence of UiO-67-Pd(F)with phenanthroline/bipyridine,and poly-F substituted phenyl ligands as the mixture linkers.The results of control experiments and theoretical calculations reveal that the–F on the phenyl linkers efficiently tunes the electron-deficient nature of Pd through the Zr_(6) clusters bridges,which favors the adsorption and activation of the furan ring.Furthermore,the conjugation of different nitrogen-containing ligands facilitates Pd coordination for the Heck-type insertion and subsequent electrophilic palladation,respectively.As a result,the oxidative arylation of FA derivatives is substantially enhanced because of these electronic and steric synergistic effects.Under the optimized conditions,72.2%FA conversion and 74.8%mono aryl furan(MAF)selectivity are shown in the Heck-type insertion.Meanwhile,85.3%of MAF is converted,affording 74.8%selectivity of final product(AFs)in the subsequent electrophilic palladation reaction.This process efficiency is remarkably higher than that with homogeneous catalysts.In addition,furan-benzene polymer obtained from the halogen-free synthesis catalyzed by UiO-67-Pd(F)show significantly better properties than that from conventional Suzuki coupling method.Therefore,the present work provides a new insight for useful AFs synthesis by oxidative arylation of bio-furan via rational tunning the metal center micro-environment of heterogeneous catalyst.展开更多
基金support from the National Natural Science Foundation of China(Nos.22293011,T2341001)the Major Science and Technology Project of Anhui Province(202203a06020010).
文摘Epoxy resins are widely employed in wind turbine blades,drone rotors,and automotive interiors due to their excel-lent mechani-cal proper-ties and long service life.However,their insoluble and infusible cross-linked networks pose a significant re-cycling challenge,particularly with the impending retirement of the first generation of wind turbine blades.In this work,we reported a fully bio-based epoxy Vitrimer(FEP)incorporat-ing a dual-dynamic covalent network design and systematically investigated the influence of the 1,5,7-triazabicyclo[4.4.0]dec-5-ene(TBD)catalyst on its curing kinetics,thermal/mechan-ical properties,dynamic exchange behavior,and degradation performance in a mild alkaline solution.Compared to conventional epoxy resins,FEP exhibited superior tensile strength and elongation at break at an optimal TBD concentration(2 wt%),achieving an excellent strength-toughness balance.The presence of TBD accelerated the exchange rates of both disulfide and ester bonds,endowing FEP with notable stress relaxation at elevated tempera-tures.Moreover,FEP demonstrated complete dissolution in 1 mol/L NaOH within 6 h at 25℃.These results underscored the exceptional strength,toughness,and recyclability of FEP,positioning it as a promising,environmentally friendly matrix resin for next-generation appli-cations in the new energy sector.
基金supported by the financial support from the National Research Foundation,Singapore,under its Singapore-China Joint Flagship Project(Clean Energy).
文摘Aqueous Zn-iodine batteries(ZIBs)face the formidable challenges towards practical implementation,including metal corrosion and rampant dendrite growth on the Zn anode side,and shuttle effect of polyiodide species from the cathode side.These challenges lead to poor cycle stability and severe self-discharge.From the fabrication and cost point of view,it is technologically more viable to deploy electrolyte engineering than electrode protection strategies.More importantly,a synchronous method for modulation of both cathode and anode is pivotal,which has been often neglected in prior studies.In this work,cationic poly(allylamine hydrochloride)(Pah^(+))is adopted as a low-cost dual-function electrolyte additive for ZIBs.We elaborate the synchronous effect by Pah^(+)in stabilizing Zn anode and immobilizing polyiodide anions.The fabricated Zn-iodine coin cell with Pah^(+)(ZnI_(2) loading:25 mg cm^(−2))stably cycles 1000 times at 1 C,and a single-layered 3.4 cm^(2) pouch cell(N/P ratio~1.5)with the same mass loading cycles over 300 times with insignificant capacity decay.
基金supported by the National Natural Sci-ence Foundation of China(Nos.U21A20288 and 21978280).
文摘Developing green and efficient methods to acquire lignocellulose-based chemicals with high added value is beneficial for facilitating green chemistry and sustainable development.The goal of this study is to demonstrate that bio-based benzaldehyde,a noteworthy high-value chemical,is able to be directionally prepared from lignocellulosic biomass.This new control-lable transformation was materialized by uniting catalytic-pyrolysis of lignocellulose to toluene intermediate and catalytic oxidation of toluene intermediate to bio-based benzalde-hyde.This work also developed a highly active magnetic catalyst(CoFe_(2)O_(4)@Biochar(HTR)),achieving 77.1%benzaldehyde selectivity and 46.7%benzaldehyde yield using this catalyst.It was found that introducing the biochar carrier into the cobalt iron composite metal oxide cat-alyst enhanced hydroxyl radical formation and bio-based benzaldehyde synthesis.Based on catalyst characterizations and hydroxyl radical analysis,potential reaction mechanism for bio-based benzaldehyde synthesis was proposed.This strategy may provide a beneficial pathway for developing high-value bio-based chemical(benzaldehyde)using renewable lignocellulosic biomass.
基金financial support of National Key Research and Development Program of China(Grant No.2022YFB04200302)joint funds of National Natural Science Foundation of China(Grant No.62104115)+5 种基金National Natural Science Foundation of China(Grant No.U21A2072)Overseas Expertise Introduction Project for Discipline Innovation of Higher Education of China(Grant No.B16027)Key R&D Program of Hebei Province(No.19214301D)Yunnan Provincial Science and Technology Project at Southwest United Graduate School(No.202302A0370009)Haihe Laboratory of Sustainable Chemical TransformationsFundamental Research Funds for the Central Universities,Nankai University。
文摘The tensile strain in inorganic perovskite films induced by thermal annealing is one of the primary factors contributing to the inefficiency and instability of inorganic perovskite solar cells(IPSCs),which reduces the defect formation energy.Here,a flexible molecule 5-maleimidovaleric acid(5-MVA)was introduced as a strain buffer to release the residual strain of CsPbI_(2.85)Br_(0.15)perovskite.Maleic anhydride and carboxyl groups in 5-MVA interact strongly with the uncoordinated Pb^(2+)through Lewis acid-base reaction,thus tightly“pull”the perovskite lattice.The in-between soft carbon chain increased the structural flexibility of CsPbI_(2.85)Br_(0.15)perovskite materials,which effectively relieved the intrinsic internal strain of CsPbI_(2.85)Br_(0.15),resisted the corrosion of external strain,and also reduced the formation of defects such as VIand Pb0.In addition,the introduction of 5-MVA improved crystal quality,passivated residual defects,and narrowed energy level barriers.Eventually,power conversion efficiency(PCE)of NiOxbased inverted IPSCs increased from 19.25%to 20.82%with the open-circuit voltage enhanced from 1.164 V to 1.230 V.The release of strain also improved the stability of CsPbI_(2.85)Br_(0.15)perovskite films and devices.
文摘Acceptor-donor-acceptor(A-D-A)type molecules,of which the novel non-fused azacyclic end-group pyrazoli-nones were modified with chlorine substitution on the phenyl ring,were synthesized.The non-fused azacyclic end-group py-razolinones have the advantages of simple synthesis steps,low cost and environmental friendliness,compared to the classical end-group dicyanomethyleneindianone.The properties of the synthesized A-D-A type molecules with non-fused azacyclic end groups were characterized by theoretical calculation,UV-vis absorption,cyclic voltammetry,X-ray diffraction and space charge limited current.It is shown that the strong UV-vis absorptions of the synthesized A-D-A type molecules are located in the wavelength range of 500~700 nm,with a moderate band gap of nearly 1.7 eV.At the same time,the influence of end-group chlorination on the properties of A-D-A type molecules was compared and explored.It is proven that this kind of A-D-A type molecule with non-fused azacyclic end groups has the potential to be applied as interfacial modified layer of the active layer in perovskite solar cell devices.
基金supported by the Key R&D Project in Shaanxi Province(No.2024GX-YBXM-371)Shaanxi Qinchuangyuan Scientists+Engineers Team Construction Project(2025QCY-KXJ-141).
文摘With the escalating global emphasis on environmental conservation and sustainable development,enhancing the service quality and durability of road surfaces and facilitating the green development of highways have commanded considerable attention.Bio-based polyurethane,on account of its remarkable physical and chemical properties,green,sustainable and renewable capacity,as well as its structural design capabilities,has drawn widespread attention and numerous studies have been carried out.It has gradually started to substitute traditional petroleum-based polyurethane materials in road engineering.Nevertheless,the application of bio-based polyurethane materials in road engineering remains in the exploratory phase.To stimulate the application research of bio-based polyurethane materials in road engineering and offer additional research directions,this paper reviews the research advancements of bio-based polyurethane materials and their applications in road engineering.The fundamental classification of bio-based polyurethane is introduced.The characteristics and challenges associated with various preparation methods for bio-based polyurethane are described.The influence of bio-based polyurethane on road engineering materials are analyzed.The evaluation indicators of bio-based polyurethane within the life cycle of road engineering are investigated.Finally,the development tendency towards in road engineering applications are forecasted.This paper provides a reference for the study of bio-based polyurethane materials in road engineering applications.
基金supported by the National Natural Science Foundation of China(No.22073090,No.21991132,No.52021002)the National Key R&D Program of China(No.2020YFA0710700)the Funds of Youth Innovation Promotion Association,and the Fundamental Research Funds for the Central Universities(WK3450000009).
文摘CRISPR-based tran-scription regulators(CRISPR-TRs)have revolutionized the field of synthetic biol-ogy by enabling tar-geted activation or repression of any de-sired gene.However,the majority of exist-ing inducible CRISPR-TRs are limited by their dependence on specific sequences,which restricts their flex-ibility and controllability in genetic engineering applications.In this study,we proposed a novel strategy to construct sequence-independent inducible CRISPR-TRs,which is achieved by the design of stem loop 2 in the single guide RNA(sgRNA).Under this strategy,by utiliz-ing toehold-mediated strand displacement(TMSD)reactions between small endogenous molecules(miR-20a and TK1 mRNA)and bridge RNA(bRNA)to link bRNA with sgRNA,we achieved synergistic transcriptional activation of VP64 and p65-HSF1 in response to en-dogenous molecules.To enable response to exogenous molecules,we added response se-quences and bRNA sequences to the 5'end of sgRNA to block sgRNA activity,and achieved activation of sgRNA by shearing the response sequence,called sequential unlimited interlock-ing(SUI).Compared with conventional sequence-restricted interlocking(spacer-blocking hairpin(SBH)),the transcriptional activation ratio between response and non-response to the Cas6A protein using our approach was increased by 2.28-fold.Our work presents a modular and versatile framework for endogenous and exogenous molecule-responsive CRISPR-TRs in mammalian cells,without limitations imposed by sequence dependence.
基金supported by the Science and Technology Research Project of Henan Province(222102230031)Key Scientific Research Projects of Colleges and Universities in Henan Province(23A430018)Natural Science Foundation of Henan(252300420267).
文摘The current global shortage of oil resources and the pollution problems caused by traditional barrier materials urgently require the search for new substitutes.Biodegradable bio-based barrier materials possess the characteristics of being renewable,environmentally friendly,and having excellent barrier properties.They have become an important choice in fields such as food packaging,agricultural film covering,and medical protection.This review systematically analyzes the design and research of this type of material,classifying biobased and biodegradable barrier materials based on the sources of raw materials and synthesis pathways.It also provides a detailed introduction to the latest research progress of biobased and biodegradable barrier materials,discussing the synthesis methods and improvement measures of their barrier properties.Subsequently,it analyzes the related technologies for enhancing the barrier properties of biobased and biodegradable barrier materials,and finally looks forward to the directions that future research should focus on,promoting the transition of biobased and biodegradable barrier materials from the laboratory to industrial applications.
基金supported by the China Postdoctoral Science Foundation(No.2023M743622)Natural Science Foundation of Ningbo City(No.2024J109)+2 种基金National Natural Science Foundation of China(Nos.E52307038 and U23A20589)Ningbo 2025 Key Scientific Research Programs(Nos.2022Z111,2022Z160 and 2022Z198)the Leading Innovativeand Entrepreneur Team Introduction Program of Zhejiang(No.2021R01005).
文摘The demand for energy-efficient and environmental-friendly power grid construction has made the exploitation of bio-based electrical epoxy resins with excellent properties increasingly important.This work developed the bio-based electrotechnical epoxy resins based on magnolol.High-performance epoxy resin(DGEMT)with a double crosslinked points and its composites(Al_(2)O_(3)/DGEMT)were obtained taking advantages of the two bifunctional groups(allyl and phenolic hydroxyl groups)of magnolol.Benefitting from the distinctive structure of DGEMT,the Al_(2)O_(3)/DGEMT composites exhibited the advantages of intrinsically high thermal conductivity,high insulation,and low dielectric loss.The AC breakdown strength and thermal conductivity of Al_(2)O_(3)/DGEMT composites were 35.5 kV/mm and 1.19 W·m-1·K-1,respectively,which were 15.6%and 52.6%higher than those of petroleum-based composites(Al_(2)O_(3)/DGEBA).And its dielectric loss tanδ=0.0046 was 20.7%lower than that of Al_(2)O_(3)/DGEBA.Furthermore,the mechanical,thermal and processing properties of Al_(2)O_(3)/DGEMT are fully comparable to those of Al_(2)O_(3)/DGEBA.This work confirms the feasibility of manufacturing environmentally friendly power equipment using bio-based epoxy resins,which has excellent engineering applications.
文摘By investigating the performance characteristics of the bio-based surfactant 8901A,a composite decontamination and injection system was developed using 8901A as the primary agent,tailored for application in low-permeability and heavy oil reservoirs under varying temperature conditions.The results demonstrate that this system effectively reduces oil–water interfacial tension,achieving an ultra-low interfacial tension state.The static oil washing efficiency of oil sands exceeds 85%,the average pressure reduction rate reaches 21.55%,and the oil recovery rate improves by 13.54%.These enhancements significantly increase the system’s ability to dissolve oilbased blockages,thereby lowering water injection pressure caused by organic fouling,increasing the injection volume of injection wells,and ultimately improving oil recovery efficiency.
文摘Aging plays a critical role in determining the durability and long-term performance of asphalt pavements,as it is influenced by both external factors(e.g.,temperature,ultraviolet(UV)radiation,moisture,oxidative gases)and internal factors such as binder composition.Although laboratory simulations of aging are well established for conventional bituminous binders,limited attention has been paid to replicating and evaluating aging processes in bio-based binders.This review provides a comprehensive analysis of current laboratory techniques for simulating and assessing binder aging,with a focus on two key areas:aging simulation protocols and evaluation methodologies.The analysis shows that although several efforts have been made to incorporate external aging factors into lab simulations,significant challenges persist,especially in the case of bio-based binders,which are characterized by a high variability in composition and limited understanding of their aging behavior.Current evaluation approaches also exhibit limitations.Improvements are needed in the molecular-level analysis of oxidation(e.g.,through more representative oxidation modelsin molecular dynamicssimulations),in the separation and quantification of binder constituents,and in the application of advanced techniques such as fluorescence microscopy to better characterize polymer dispersion.To enhance the reliability of laboratory simulations,future research should aim to improve the correlation between laboratory and field aging,define robust aging indexes,and refine characterization methods.These advancements are particularly critical for bio-based binders,whose performance is highly sensitive to aging and for which standard test protocols are still underdeveloped.A deeper understanding of aging mechanisms in both polymer-modified and biobased binders,along with improved analytical tools for assessing oxidative degradation and morphological changes,will be essential to support the development of sustainable,high-performance paving materials.
文摘In the context of transitioning toward more sustainable construction materials,this study explores the impact of incorporating millet husks as an alternative to sand on the physical,mechanical,and thermal performance of lightweight concrete.Through a mixture design approach,five formulations were selected and thoroughly characterized.The analysis of iso-response curves enabled an in-depth assessment of the cross-effects between formulation parameters and their interactions on the final properties of the material.The results show that integrating millet husks leads to a significant reduction in density,reaching up to 21%,while maintaining notable mechanical performance.A balanced formulation of sand and fibers achieved a maximum compressive strength of 12.11 MPa,demonstrating that,under specific conditions,plant fibers actively contribute to the structural integrity of the composite.In tensile strength,the positive influence of fibers is even more pronounced,with a maximum resistance of 8.62 MPa,highlighting their role in enhancing material cohesion.From a thermal perspective,millet husks reduce both thermal conductivity and effusivity,thereby limiting heat transfer and accumulation within the composite.Iso-response curve analysis reveals that these effects are directly linked to the proportions of the constituents and that achieving an optimal balance between sand,fibers,and cement is key to maximizing performance.These findings demonstrate that the adopted approach allows moving beyond conventional substitution methods by identifying optimal configurations for the design of lightweight bio-based concretes that are both strong and insulating,thereby confirming the potential of millet husks in developing lightweight concretes suitable for sustainable construction applications.
基金supported by the National Natural Science Foundation of China(No.82173668,82373706).
文摘Immunotherapy has transformed cancer treatment,marked by the approval of numerous antibody-based drugs.However,the limitations of antibodies in pharmacokinetics including long half-lives,limited oral bioavailability and immunogenicity,have prompted the pursuit of small molecule-based immunotherapy.Traditional drug discovery strategies,which focus on blocking protein activity through inhibitors,face persistent hurdles,such as reliance on accessible binding pockets,poor selectivity,and the emergence of drug resistance.Targeted protein degradation(TPD)technologies have emerged as powerful tools to address these limitations,offering significant therapeutic advantages over conventional inhibition strategies,particularly for historically "undruggable" targets.In recent years,small molecule-based protein degraders have rapidly advanced in cancer immunotherapy.In this review,we highlight recent progress in TPD-driven small-molecule drug discovery and summarize the application of these technologies in cancer immunotherapy,including degraders targeting PD-1/PD-L1,chemokine receptors,IDO1,AhR,and others.
基金Project supported by the National Natural Science Foundation of China (Grant Nos. 92250306 and 12304302)the Natural Science Foundation of Jilin Province, China (Grant Nos. YDZJ202101ZYTS157 and YDZJ202201ZYTS314)the Scientific Research Foundation of Jilin Province Education Department, China (Grant No. JJKH20230283KJ)。
文摘Molecular high-order harmonic spectroscopy is a significant advancement in ultrafast science, enabling the measurement of multielectron dynamics with attosecond temporal resolution. The fine structures observed in the molecular harmonic spectrum provide crucial insights into the structural or multielectron dynamical effects induced by intense laser fields. In this study, we measure the high-order harmonic spectrum of aligned CO_(2) molecules contributed from short trajectories. Two distinct groups of minima are identified in the plateau region. Our findings indicate that the deeper-lying molecular orbitals and two-center interference play significant roles in molecular harmonic generation. The results pave the way for advancing the understanding of multielectron dynamics in polyatomic molecules under intense laser fields.
基金supported by the Young Elite Scientists Sponsorship Program by CAST(No.2023QNRC001)Natural Science Foundation of Hunan Province,China(No.2024JJ2074)supported in part by the High Performance Computing Center of Central South University,China and the Pawsey Supercomputing Centre with funding from the Australian Government and the Government of Western Australia.
文摘An in-depth understanding of the hydration mechanism of tricalcium silicate is an important basis for optimizing cement strength development.In this study,the adsorption of water molecules onto the M3-C3S(001)surface at different water coverage levels(θ=1/5,2/5,3/5,4/5,and 1)was investigated using first-principles calculations.The results demonstrate that the conclusions obtained for single water molecule adsorption cannot be fully applied to multiple water molecule adsorption.The total adsorption energies become more negative with increasing water coverage,while the average adsorption energy of each water molecule becomes more positive with increasing water coverage.The water–water interactions reduce the water–surface interactions and are responsible for the anticooperative adsorption of multiple water molecules onto M3-C_(3)S(001).The formation of Ca–OH(–Ca)bonds favors the detachment of Ca from co-valent oxygen,which reveals the significant role of dissociative adsorption.This work aims to extend the water adsorption study on M3-C3S(001)from single water molecule adsorption to multiple water molecule adsorption,providing more detailed insights into the initial water reaction on the C3S surface.
基金financially supported by the National Natural Science Foundation of China(Nos.92477118 and 22173045)the Postgraduate Research and Practice Innovation Program of Jiangsu Province(No.KYCX25_0188)。
文摘Colloidal molecules exhibit unique electronic,optical,and magnetic properties owing to their molecular-like configurations and coupling effects,making them promising building blocks for multifunctional materials.However,achieving precise and controllable assembly of isotropic nanoparticles with high yields remains a great challenge.In this study,we present a synergistic strategy that integrates molecular dynamics simulations with interpretable machine learning to develop a programmable assembly system based on block copolymers and DNA-functionalized nanoparticles.Our simulation results reveal that block copolymer modification facilitates stepwise control over surface phase separation and nanoparticle coassembly,thereby enhancing structural stability and efficiently suppressing disordered aggregation of atom-like nanoparticles.Furthermore,we demonstrated that precise,controllable,and programmable assembly of colloidal molecules can be achieved through rational DNA sequence design.SHapley Additive exPlanations(SHAP)analysis identified key structural descriptors that govern assembly outcomes and elucidated their underlying mechanistic roles.This work not only deepens the understanding of colloidal molecule assembly mechanisms but also lays a theoretical foundation for the rational design of functional colloidal architectures in nanomaterial science.
基金the financial support from the Natural Science Foundation of Xiamen,China(3502Z202373075)the National Natural Science Foundation of China(Grant nos.22175180,52311530673,22103013)+1 种基金the Natural Science Foundation of Fujian Province(No.2023J01527,2021J01184,2024J01189)the Start-up funding from Fujian Normal University(Y0720312K13)。
文摘Exploring multifunctional interfacial modifiers is an effective approach to addressing interface issues in perovskite solar cells(PSCs)and improving device performance and stability.While most interfacial modifiers focus on passivating defects at the interfaces,there has been limited investigation into the relationship between molecular design and interfacial charge dynamics.This work introduces resonance molecules with a push-pull effect for interfacial modification,allowing for synergistic regulation of passivation effects and charge dynamics.Specifically,FCz-PO,which includes an electron-withdrawing fluorine atom,exhibits superior passivation but poor molecular stacking and charge extraction.In contrast,MCz-PO,featuring an electron-donating methoxy group,provides effective passivation,wellordered molecular packing,and efficient charge extraction and transport.Consequently,PSCs using MCz-PO achieve high power conversion efficiency(PCE)of 24.74%and excellent operational stability.This study suggests that resonance structures can be an effective molecular design strategy for developing interfacial modifiers with both strong passivation capabilities and well-regulated charge dynamics.
基金supported by the National Natural Science Foun-dation of China(Grant Nos.12475032 and 12005062)the Supercomputing Center of the Chinese Academy of Sciences,Shanghai Snowlake Technology Co.,Ltd.,and the Shanghai Super-Computer Center of China。
文摘Spiral patterns widely exist in both macroscopic and microscopic systems such as hearts,bacteria,and active matters but have never been reported at molecular length scale.The emergence of spiral patterns has considerable impacts on the trajectories of the objects and thus usually relates to various physical,chemical,biological and physiological processes.In this paper,we show that,down to the length scale of only several Angstroms,asymmetric molecules exhibit spiral patterns in their trajectories within finite time based on the under-damped Langevin equation and demonstrated by molecular dynamics simulation.The key to this observation lies in the asymmetric molecular architecture that leads to a translation-rotation coupling.This finding enriches the knowledge of spiral patterns to the molecular length scale,provides a new insight into the understanding of various processes at the molecular level,and may evoke new ideas on the understanding of the vortices in turbulence.
基金supported by the Research Grants Council of the Hong Kong Special Administrative Region of China(Grant Nos.HKU 17212824,HKU 17210522,HKU C7074-21G,HKU R7003-21,and HKU 17205321)the Innovation and Technology Commission of the Hong Kong SAR Government(Grant Nos.MHP/073/20 and MHP/057/21),and the Health@InnoHK program.
文摘Soliton molecules(SMs),bounded and self-assembled of particle-like dissipative solitons,exist with versatile mutual interactions and manifest substantial potential in soliton communication and optical data storage.However,controllable manipulation of the bounded molecular patterns remains challenging,as reaching a specific operation regime in lasers generally involves adjusting multiple control parameters in connection with a wide range of accessible pulse dynamics.An evolutionary algorithm is implemented for intelligent control of SMs in a 2μm ultrafast fiber laser mode locked through nonlinear polarization rotation.Depending on the specifications of the merit function used for the optimization procedure,various SM operations are obtained,including spectra shape programming and controllable deterministic switching of doublet and triplet SMs operating in stationary or pulsation states with reconfigurable temporal separations,frequency locking of pulsation SMs,doublet and SM complexes with controllable pulsation ratio,etc.Digital encoding is further demonstrated in this platform by employing the self-assembled characteristics of SMs.Our work opens up an avenue for active SM control beyond conventional telecom bands and brings useful insights into nonlinear science and applications.
文摘An efficient and novel approach is proposed for oxidative arylation of bio-based furfuryl alcohol(FA)to aryl furans(AFs),a versatile monomer of photoelectric materials,in the presence of UiO-67-Pd(F)with phenanthroline/bipyridine,and poly-F substituted phenyl ligands as the mixture linkers.The results of control experiments and theoretical calculations reveal that the–F on the phenyl linkers efficiently tunes the electron-deficient nature of Pd through the Zr_(6) clusters bridges,which favors the adsorption and activation of the furan ring.Furthermore,the conjugation of different nitrogen-containing ligands facilitates Pd coordination for the Heck-type insertion and subsequent electrophilic palladation,respectively.As a result,the oxidative arylation of FA derivatives is substantially enhanced because of these electronic and steric synergistic effects.Under the optimized conditions,72.2%FA conversion and 74.8%mono aryl furan(MAF)selectivity are shown in the Heck-type insertion.Meanwhile,85.3%of MAF is converted,affording 74.8%selectivity of final product(AFs)in the subsequent electrophilic palladation reaction.This process efficiency is remarkably higher than that with homogeneous catalysts.In addition,furan-benzene polymer obtained from the halogen-free synthesis catalyzed by UiO-67-Pd(F)show significantly better properties than that from conventional Suzuki coupling method.Therefore,the present work provides a new insight for useful AFs synthesis by oxidative arylation of bio-furan via rational tunning the metal center micro-environment of heterogeneous catalyst.
