Cells in the body are exposed to physiological and pathophysiological stimuli that encompass both chemical and mechanical factors,which coordinately modulate cellular functions. Compared to the large amount of informa...Cells in the body are exposed to physiological and pathophysiological stimuli that encompass both chemical and mechanical factors,which coordinately modulate cellular functions. Compared to the large amount of information on cellular re-展开更多
Immunogenic cell death(ICD)has been demonstrated as a reliable approach to improve therapeutic effect in cancer treatment by triggering antitumor immunity.However,the trigger of ICD on the basis of chemotherapy and ph...Immunogenic cell death(ICD)has been demonstrated as a reliable approach to improve therapeutic effect in cancer treatment by triggering antitumor immunity.However,the trigger of ICD on the basis of chemotherapy and phototherapy meets the obstacles of serious side effect and poor penetration ability,which seriously impedes the therapeutic effect.The development of sonodynamic immunotherapy with the evoking of ICD presents high promise for cancer treatment with high efficacy.Herein,high performance aggregation-induced emission(AIE)sonosensitizer is constructed on the basis of the engineering structure modulation for sonodynamic-augmented immunotherapy.By regulating the intermolecular interaction and pull-push electronic effect,sonosensitizer bearing AIE feature and amplified sono-sensitizing effect is developed.In addition,in vitro observation demonstrated that thiolate-substituted segment incorporation endows the molecules with enhanced cellular uptake efficiency and improved tumor cell eradication ability.More importantly,the developed sonosensitizer could efficiently evoke ICD upon the trigger of ultrasound,which allows for the efficient tumor eradication both at cellular level and in solid tumor.The inhibition of primary tumor and further boost systemic immunity response with the complete elimination toward the distant tumor is achieved.The investigation highlights the promise of utilizing AIE sonosensitizers in sonodynamic immunotherapy to conquer the current limitation of immunotherapy in solid tumor treatment.展开更多
In the version of article originally published in the volume 68,2025 of Sci China Chem(pages 3675-3688),the article was published in subscription format rather than open access format due to an oversight during the pr...In the version of article originally published in the volume 68,2025 of Sci China Chem(pages 3675-3688),the article was published in subscription format rather than open access format due to an oversight during the production stage.The corrected copyright and open access notes are provided below.The original article has been corrected.展开更多
Highly optical-absorption hybrid perovskites with upgraded stability and superior photoelectronic properties are essential for optoelectronics.However,various defects are generated by the solution-based film quality i...Highly optical-absorption hybrid perovskites with upgraded stability and superior photoelectronic properties are essential for optoelectronics.However,various defects are generated by the solution-based film quality inevitably produces during the crystallization process,which leads to non-radiative recombination and interface mismatch.In this work,polyvinylpyrrolidone(PVP)molecule layer was implemented as the interfacially multifunctional layer and selective transport layer to fabricate an effective photodetector.Interfacial PVP is conductive to the bond coordination between the PVP molecule and the MAPbI_(3)surface,which could lower the work function of the perovskite film and effectively improve its surface morphology so as to isolate it from water and oxygen molecules.The interfacial passivation for the undercoordinated Pb^(2+)defects was also verified via first-principles calculations.The electron injection barrier can be regulated via interfacial molecule engineering,leading to the result that the dark current is suppressed by five orders of magnitude to 1.57310−11 A,and the specific detectivity improved by about three orders of magnitude reaching 2.9310^(12)Jones.These results provide a feasible route to fabricate highly sensitive and stable hybrid perovskite photodetectors.展开更多
Photocatalysis provides a green way to produce hydrogen peroxide(H_(2)O_(2)) from oxygen and water.Although many materials with different structures have been designed for the photocatalytic production of H_(2)O_(2),t...Photocatalysis provides a green way to produce hydrogen peroxide(H_(2)O_(2)) from oxygen and water.Although many materials with different structures have been designed for the photocatalytic production of H_(2)O_(2),the supramolecular porous materials have been rarely reported.Herein,three imine-linked[3+6]type POCs,containing benzoxadiazole units with tunable functional groups(R=H,OMe,OH),named H-POC,OMe-POC,and OH-POC,are rationally fabricated for visible-light-driven generation of H_(2)O_(2) in water and oxygen.The results show that performance is improved by regulating group from H,OMe,to OH,with the H_(2)O_(2) yields of 527,670,and 976μmol h^(-1)g^(-1),respectively.Moreover,under the synergistic effect of light and heat(70℃),the H_(2)O_(2)production rate of OH-POC was further increased to 2748μmol h^(-1)g^(-1).Photophysical and electrochemical studies have shown that functional group regulation enhances hydrophilicity,light absorption,and charge separation/transfer.In addition,the mechanism of the two-step 1e^(-) ORR and direct 2e^(-) WOR pathway for H_(2)O_(2)production.Importantly,OH-POC shows extraordinary potential in the degradation of water environmental pollutants(tetracycline hydrochloride and mercaptobenzothiazole).This study provides a novel idea for the rational design of photocatalysts that rely on the POCs platform from the perspective of molecular structure design.展开更多
Organic semiconductor single-crystal(OSSC)arrays,with superior charge transport and well-aligned properties,are emerging as a fascinating platform for highperformance integrated electronic and optoelectronic applicati...Organic semiconductor single-crystal(OSSC)arrays,with superior charge transport and well-aligned properties,are emerging as a fascinating platform for highperformance integrated electronic and optoelectronic applications.Taking advantage of the solution processability of organic semiconductors,solution self-assembly OSSC arrays hold great potential for achieving cost-effective manufacturing of large-area and flexible electronics.While the rational design of molecular building blocks for regulating crystal growth has been achieved,the fundamental principles of molecular structure design for one-dimensional(1D)crystalline nanostructures and the impact of intermolecular interactions in molecular self-assembly remain unclear,limiting the practical application of the solution self-assembly.Drawing inspiration from the concave-convex packing preferences of bowl-shaped polyaromatic hydrocarbons,we propose an innovative molecular engineering strategy for hetero-buckybowl trichalcogenasumanenes to direct the self-assembly of OSSC arrays.The distinctive molecular architecture of trichalcogenasumanenes promotes the formation of 1D crystal arrays via directional concave-convexπ-πinteractions while effectively suppressing intercolumnar coupling,enhancing structural anisotropy and charge transport properties.Accordingly,the centimeter-sized OSSC arrays are obtained on various substrates via solution self-assembly.Furthermore,high-performance organic field-effect transistors(OFETs)based on these OSSC arrays demonstrate mobility values up to 0.89 cm^(2)V^(-1)s^(-1)with small device-to-device variation,superior to previous buckybowl-based devices.This molecular engineering strategy significantly enhances crystallinity and uniformity,providing a pathway for high-performance,largearea organic electronics.展开更多
The diagnostic efficacy of contemporary bioimaging technologies remains constrained by inherent limitations of conventional imaging agents,including suboptimal sensitivity,off-target biodistribution,and inherent cytot...The diagnostic efficacy of contemporary bioimaging technologies remains constrained by inherent limitations of conventional imaging agents,including suboptimal sensitivity,off-target biodistribution,and inherent cytotoxicity.These limitations have catalyzed the development of intelligent stimuli-responsive block copolymers-based bioimaging agents,which was engineered to dynamically respond to endogenous biochemical cues(e.g.,p H gradients,redox potential,enzyme activity,hypoxia environment) or exogenous physical triggers(e.g.,photoirradiation,thermal gradients,ultrasound(US)/magnetic stimuli).Through spatiotemporally controlled structural transformations,stimuli-responsive block copolymers enable precise contrast targeting,activatable signal amplification,and theranostic integration,thereby substantially enhancing signal-to-noise ratios of bioimaging and diagnostic specificity.Hence,this mini-review systematically examines molecular engineering principles for designing p H-,redox-,enzyme-,light-,thermo-,and US/magnetic-responsive polymers,with emphasis on structure-property relationships governing imaging performance modulation.Furthermore,we critically analyze emerging strategies for optical imaging,US synergies,and magnetic resonance imaging(MRI).Multimodal bioimaging has also been elaborated,which could overcome the inherent trade-offs between resolution,penetration depth,and functional specificity in single-modal approaches.By elucidating mechanistic insights and translational challenges,this mini-review aims to establish a design framework of stimuli-responsive block copolymersbased for high fidelity bioimaging agents and accelerate their clinical translation in precise diagnosis and therapy.展开更多
Conjugation of antibodies to nanoparticles allows specific cancer targeting,but conventional conjugation methods generate heterogeneous conjugations that cannot guarantee the optimal orientation and functionality of t...Conjugation of antibodies to nanoparticles allows specific cancer targeting,but conventional conjugation methods generate heterogeneous conjugations that cannot guarantee the optimal orientation and functionality of the conjugated antibody.Here,a molecular engineering technique was used for sitespecific conjugation of antibodies to nanoparticles.We designed an anti-claudin 3(CLDN3)antibody containing a single cysteine residue,h4 G3 cys,then linked it to the maleimide group of lipid polydopamine hybrid nanoparticles(LPNs).Because of their negatively charged lipid coating,LPNs showed high colloidal stability and provided a functional surface for site-specific conjugation of h4 G3 cys.The activity of h4 G3 cys was tested by measuring the binding of h4 G3 cys-conjugated LPNs(C-LPNs)to CLDN3-positive tumor cells and assessing its subsequent photothermal effects.C-LPNsspecifically recognized CLDN3-overexpressing T47 D breast cancer cells but not CLDN3-negative Hs578 T breast cancer cells.High binding of C-LPNs to CLDN3-overexpressing T47 D cells resulted in significantly higher temperature generation upon NIR irradiation and potent anticancer photothermal efficacy.Consistent with this,intravenous injection of C-LPNsin a T47 D xenograft mouse model followed by NIR irradiation caused remarkable tumor ablation compared with other treatments through high temperature increases.Our results establish an accurate antibody-linking method and demonstrate the possibility of developing therapeutics using antibody-guided nanoparticles.展开更多
Perovskite quantum dots (PQDs) require ligands on their surfaces to passivate defects and prevent aggregation. However, the ligands construct the interface relationship between the PQDs, which may seriously hinder the...Perovskite quantum dots (PQDs) require ligands on their surfaces to passivate defects and prevent aggregation. However, the ligands construct the interface relationship between the PQDs, which may seriously hinder the carrier transport. Hence, we propose a molecular engineering strategy of using 3,4-ethylenedioxythiophene (EDOT) to perfectly solve this problem, benefiting from its high conjugation and passivation ability to CsPbBr_(3) PQDs. Furthermore, EDOT on the surface of PQDs can be in-situ polymerized under the photocurrent of the photodetector, thus interconnecting the PQDs which enhanced the performance of the photodetectors up to 178% of its initial performance. We have thoroughly investigated the electropolymerization process of EDOT and its passivation effect on PQDs. The simple lateral photodetector based on EDOT PQDs exhibits a high responsivity of 11.96 A/W, which is 104 times higher than that of oleic acid caped PQDs. Due to the protection of poly(3,4-ethylenedioxythiophene) (PEDOT), the photodetector prepared from EDOT PQDs exhibited very high stability, retaining 94% of its performance after six months in air. This strategy provides a solution for the application of PQDs in high performances and stable optoelectronic devices.展开更多
The power conversion efficiencies(PCEs)of single-junction organic solar cells(OSCs)have surpassed 19%,owing to the emerging Y-series nonfullerene acceptors(NFAs).Undoubtedly,the power and flexibility of chemical desig...The power conversion efficiencies(PCEs)of single-junction organic solar cells(OSCs)have surpassed 19%,owing to the emerging Y-series nonfullerene acceptors(NFAs).Undoubtedly,the power and flexibility of chemical design has been a strong driver for this rapid efficiency improvement in the OSC field.Over the course of the past 3 years,a variety of modifications have been made to the structure of the Y6 acceptor,and a large number of Y-series NFAs have been reported to further improve performance.Herein,we present our insights into the rationale behind the Y6 acceptor and discuss the design principles toward high-performance Y-series NFAs.It is clear that structural modifications through choice of heteroatom,soluble chains,πspacers,central cores,and end groups alter the material characteristics and properties,contributing to distinctive photovoltaic performance.Subsequently,we analyze various design strategies of Y-series-containing materials,including polymerized small-molecule acceptors(PSMA),non-fused-ring acceptors(NFRA),and all-fused-ring acceptors(AFRA).This review is expected to be of value in providing effective molecular design strategies for high-performance NFAs in future innovations.展开更多
Fluorophores play a significant role in achieving high-contrast imaging in complex physiological environment.Herein,we present the results of our studies on the development of various fluorophores,such as anti-solvato...Fluorophores play a significant role in achieving high-contrast imaging in complex physiological environment.Herein,we present the results of our studies on the development of various fluorophores,such as anti-solvatochromic fluorophores,long wavelength emission two-photon fluorophores,large Stokes shift fluorophores and solid-state fluorophores,to achieve high-contrast bioimaging in physiological environments.in this study,we have primarily focused on the design,optical performance,imaging mechanisms,and the applications of these fluorophores with respect to complex physiological conditions.展开更多
The feasibility of using gene therapy to treat full-thickness articular cartilage defects was investigated with respect to the transfection and expression of exogenous transforming growth factor(TGF)-β_(1)genes in bo...The feasibility of using gene therapy to treat full-thickness articular cartilage defects was investigated with respect to the transfection and expression of exogenous transforming growth factor(TGF)-β_(1)genes in bone marrow-derived mesenchymal stem cells(MSCs)in vitro.The full-length rat TGF-β_(1)cDNA was transfected to MSCs mediated by lipofectamine and then selected with G418,a synthetic neomycin analog.The transient and stable expression of TGF-β_(1)by MSCs was detected by using immunohistochemical staining.The lipofectamine-mediated gene therapy efficiently transfected MSCs in vitro with the TGF-β_(1)gene causing a marked up-regulation in TGF-β_(1)expression as compared with the vector-transfected control groups,and the increased expression persisted for at least 4 weeks after selected with G418.It was suggested that bone marrow-derived MSCs were susceptible to in vitro lipofectamine mediated TGF-β_(1)gene transfer and that transgene expression persisted for at least 4 weeks.Having successfully combined the existing techniques of tissue engineering with the novel possibilities offered by modern gene transfer technology,an innovative concept,i.e.molecular tissue engineering,are put forward for the first time.As a new branch of tissue engineering,it represents both a new area and an important trend in research.Using this technique,we have a new powerful tool with which:(1)to modify the functional biology of articular tissue repair along defined pathways of growth and differentiation and(2)to affect a better repair of full-thickness articular cartilage defects that occur as a result of injury and osteoarthritis.展开更多
The effect of transforming growth factor β 1 (TGF β 1 ) gene transfection on the proliferation of bone marrow derived mesenchymal stem cells (MSC S ) and the mechanism was investigated to provide basi...The effect of transforming growth factor β 1 (TGF β 1 ) gene transfection on the proliferation of bone marrow derived mesenchymal stem cells (MSC S ) and the mechanism was investigated to provide basis for accelerating articular cartilage repairing using molecular tissue engineering technology. TGF β 1 gene at different doses was transduced into the rat bone marrow derived MSCs to examine the effects of TGF β 1 gene transfection on MSCs DNA synthesis, cell cycle kinetics and the expression of proliferating cell nuclear antigen (PCNA). The results showed that 3 μl lipofectamine mediated 1 μg TGF β 1 gene transfection could effectively promote the proliferation of MSCs best; Under this condition (DNA/Lipofectamine=1μg/3μl), flow cytometry and immunohistochemical analyses revealed a significant increase in the 3 H incorporation, DNA content in S phase and the expression of PCNA. Transfection of gene encoding TGF β 1 could induce the cells at G0/G1 phase to S1 phase, modulate the replication of DNA through the enhancement of the PCNA expression, increase the content of DNA at S1 phase and promote the proliferation of MSCs. This new molecular tissue engineering approach could be of potential benefit to enhance the repair of damaged articular cartilage, especially those caused by degenerative joint diseases.展开更多
Tissue engineering has confronted many difficulties mainly as follows:1)How to modulate the adherence,proliferation,and oriented differentiation of seed cells, especially that of stemcells. 2) Massive preparation and ...Tissue engineering has confronted many difficulties mainly as follows:1)How to modulate the adherence,proliferation,and oriented differentiation of seed cells, especially that of stemcells. 2) Massive preparation and sustained controllable delivery of tissue inducing factors or plasmid DNA, such as growth factors, angiogenesis stimulators,and so on. 3) Development of 'intelligent biomimetic materials' as extracellular matrix with a good superficial and structural compatibility as well as biological activity to stimulate predictable, controllable and desirable responses under defined conditions.Molecular biology is currently one of the most exciting fields of research across life sciences,and the advances in it also bring a bright future for tissue engineering to overcome these difficulties.In recent years,tissue engineering benefits a lot from molecular biology.Only a comprehensive understanding of the involved ingredients of tissue engineering (cells,tissue inducing factors,genes,biomaterials) and the subtle relationships between them at molecular level can lead to a successful manipulation of reparative processes and a better biological substitute.Molecular tissue engineering,the offspring of the tissue engineering and molecular biology,has gained an increasing importance in recent years.It offers the promise of not simply replacing tissue,but improving the restoration.The studies presented in this article put forward this new concept for the first time and provide an insight into the basic principles,status and challenges of this emerging technology.展开更多
Thermodynamic properties of complex systems play an essential role in developing chemical engineering processes.It remains a challenge to predict the thermodynamic properties of complex systems in a wide range and des...Thermodynamic properties of complex systems play an essential role in developing chemical engineering processes.It remains a challenge to predict the thermodynamic properties of complex systems in a wide range and describe the behavior of ions and molecules in complex systems.Machine learning emerges as a powerful tool to resolve this issue because it can describe complex relationships beyond the capacity of traditional mathematical functions.This minireview will summarize some fundamental concepts of machine learning methods and their applications in three aspects of the molecular thermodynamics using several examples.The first aspect is to apply machine learning methods to predict the thermodynamic properties of a broad spectrum of systems based on known data.The second aspect is to integer machine learning and molecular simulations to accelerate the discovery of materials.The third aspect is to develop machine learning force field that can eliminate the barrier between quantum mechanics and all-atom molecular dynamics simulations.The applications in these three aspects illustrate the potential of machine learning in molecular thermodynamics of chemical engineering.We will also discuss the perspective of the broad applications of machine learning in chemical engineering.展开更多
Fluorescence-guided surgery calls for development of near-infrared fluorophores.Despite the wide-spread application and a safe clinical record of Indocyanine Green(ICG),its maximal absorption wavelength at780 nm is ra...Fluorescence-guided surgery calls for development of near-infrared fluorophores.Despite the wide-spread application and a safe clinical record of Indocyanine Green(ICG),its maximal absorption wavelength at780 nm is rather short and longer-wavelength dyes are desired to exploit such benefits as low phototoxicity and deep penetration depth.Here,we report ECY,a stable deep near-infrared(NIR)fluorochromic scaffold absorbing/emitting at 836/871 nm with a fluorescence quantum yield of 16%in CH_(2)Cl_(2).ECY was further rationally engineered for biological distribution specificity.Analogous bearing different numbers of sulfonate group or a polyethylene glycol chain were synthesized.By screening this focused library upon intravenous injection to BALB/c mice,ECYS2 was identified to be a suitable candidate for bioimaging of organs involved in hepatobiliary excretion,and ECYPEG was found to be a superior candidate for vasculature imaging.They have potentials in intraoperative imaging.展开更多
In this work,a molecular-level kinetic model was built to simulate the vacuum residue(VR)coking process in a semi-batch laboratory-scale reaction kettle.A series of reaction rules for heavy oil coking were summarized ...In this work,a molecular-level kinetic model was built to simulate the vacuum residue(VR)coking process in a semi-batch laboratory-scale reaction kettle.A series of reaction rules for heavy oil coking were summarized and formulated based on the free radical reaction mechanism.Then,a large-scale molecularlevel reaction network was automatically generated by applying the reaction rules on the vacuum residue molecules.In order to accurately describe the physical change of each molecule in the reactor,we coupled the molecular-level kinetic model with a vapor–liquid phase separation model.The vapor–liquid phase separation model adopted the Peng-Robinson equation of state to calculate vapor–liquid equilibrium.A separation efficiency coefficient was introduced to represent the mass transfer during the phase separation.We used six sets of experimental data under various reaction conditions to regress the model parameters.The tuned model showed that there was an excellent agreement between the calculated values and experimental data.Moreover,we investigated the effect of reaction temperature and reaction time on the product yields.After a comprehensive evaluation of the reaction temperature and reaction time,the optimal reaction condition for the vacuum residue coking was also obtained.展开更多
Fe single-atom catalysts(Fe-SACs)have been extensively studied as a highly efficient electrocatalyst toward the oxygen reduction reaction(ORR).Nonetheless,they suffer from stability issue induced by dissolution of Fe ...Fe single-atom catalysts(Fe-SACs)have been extensively studied as a highly efficient electrocatalyst toward the oxygen reduction reaction(ORR).Nonetheless,they suffer from stability issue induced by dissolution of Fe metal center and the OH^(−)blocking.Herein,a surface molecular engineering strategy is developed by usingβ-cyclodextrins(CDs)as a localized molecular encapsulation.The CD-modified Fe-SAC(Fe-SNC-β-CD)shows obviously improved activity toward the ORR with 0.90 V,4.10 and 4.09 mA cm^(-2)for E_(1/2),J_(0)and Jk0.9,respectively.Meanwhile,the Fe-SNC-β-CD shows the excellent long-term stability against aggressive stress and the poisoning.It is confirmed through electrochemical investigation that modification ofβ-CD can,on one hand,regulate the atomic Fe coordination chemistry through the interaction between the CD and FeN_(x) moiety,while on the other mitigate the strong adsorption of OH^(−)and function as protective barrier against the poisoning molecules leading to enhanced ORR activity and stability for the Fe-SACs.The molecular encapsulation strategy demonstrates the uniqueness of post-pyrolysis surface molecular engineering for the design of single-atom catalyst.展开更多
H_(2)O_(2)is an environmentally friendly oxidant and a promising energy-containing molecule widely applied in industrial production,environmental remediation,and as a potential carrier for energy storage.Solar-driven ...H_(2)O_(2)is an environmentally friendly oxidant and a promising energy-containing molecule widely applied in industrial production,environmental remediation,and as a potential carrier for energy storage.Solar-driven conversion of earth-abundant H_(2)O and O_(2)is the most ideal method for producing H_(2)O_(2).Due to poor separation of photogenerated charge carriers in semiconductors,sacrificial reagents such as ethanol are typically added to consume photogenerated holes,but this is not an energy storage process.Therefore,developing efficient photocatalysts for direct H_(2)O_(2)production from H_(2)O and O_(2)without sacrificial agents is crucial for sustainable energy conversion.Organic framework materials,due to their customizable structures,have gained traction in the photosynthesis of H_(2)O_(2)from pure H_(2)O and O_(2).A series of functionalized molecules have been introduced as building blocks into organic frameworks to enhance the H_(2)O_(2)production performance,but their key roles in performance and reaction pathways have not been summarized in detail so far.This review aims to address this gap and elucidate the relationship between the structure and performance of organic framework photocatalysts,providing insights and guidance for the development of efficient photocatalysts.展开更多
Reversible control of surface wettability has wide applications in lab-on-chip systems, tunable optical lenses, and microfluidic tools. Using a graphene sheet as a sam- ple material and molecular dynamic simulations, ...Reversible control of surface wettability has wide applications in lab-on-chip systems, tunable optical lenses, and microfluidic tools. Using a graphene sheet as a sam- ple material and molecular dynamic simulations, we demon- strate that strain engineering can serve as an effective way to control the surface wettability. The contact angles 0 of water droplets on a graphene vary from 72.5° to 106° under biaxial strains ranging from -10% to 10% that are applied on the graphene layer. For an intrinsic hydrophilic surface （at zero strain）, the variation of 0 upon the applied strains is more sensitive, i.e., from 0° to 74.8°. Overall the cosines of the contact angles exhibit a linear relation with respect to the strains. In light of the inherent dependence of the contact an- gle on liquid-solid interfacial energy, we develop an analytic model to show the cos 0 as a linear function of the adsorption energy Eads of a single water molecule over the substrate sur- face. This model agrees with our molecular dynamic results very well. Together with the linear dependence of Eads on bi- axial strains, we can thus understand the effect of strains on the surface wettability. Thanks to the ease of reversibly ap- plying mechanical strains in micro/nano-electromechanical systems, we believe that strain engineering can be a promis- ing means to achieve the reversibly control of surface wetta- bility.展开更多
基金supported in part by grants from NIH HL098472, CA139272, NS063405NSF CBET0846429,CMMI0800870the Wallace H Coulter Foundation,and the Beckman Laser Institute Inc
文摘Cells in the body are exposed to physiological and pathophysiological stimuli that encompass both chemical and mechanical factors,which coordinately modulate cellular functions. Compared to the large amount of information on cellular re-
基金financially supported by the Hunan Provincial Natural Science Foundation(Grants 2024RC3206,2022JJ40375,2021JJ304060,LINC00475,and 2023JJ40552)the Scientific Research Fund of Hunan Provincial Education Department(Grants 22A0287 and 22B0404)the Open Fund of Guangdong Provincial Key Laboratory of Luminescence from Molecular Aggregates,Guangzhou 510640,China(South China University of Technology)(Grant 2023B1212060003).
文摘Immunogenic cell death(ICD)has been demonstrated as a reliable approach to improve therapeutic effect in cancer treatment by triggering antitumor immunity.However,the trigger of ICD on the basis of chemotherapy and phototherapy meets the obstacles of serious side effect and poor penetration ability,which seriously impedes the therapeutic effect.The development of sonodynamic immunotherapy with the evoking of ICD presents high promise for cancer treatment with high efficacy.Herein,high performance aggregation-induced emission(AIE)sonosensitizer is constructed on the basis of the engineering structure modulation for sonodynamic-augmented immunotherapy.By regulating the intermolecular interaction and pull-push electronic effect,sonosensitizer bearing AIE feature and amplified sono-sensitizing effect is developed.In addition,in vitro observation demonstrated that thiolate-substituted segment incorporation endows the molecules with enhanced cellular uptake efficiency and improved tumor cell eradication ability.More importantly,the developed sonosensitizer could efficiently evoke ICD upon the trigger of ultrasound,which allows for the efficient tumor eradication both at cellular level and in solid tumor.The inhibition of primary tumor and further boost systemic immunity response with the complete elimination toward the distant tumor is achieved.The investigation highlights the promise of utilizing AIE sonosensitizers in sonodynamic immunotherapy to conquer the current limitation of immunotherapy in solid tumor treatment.
文摘In the version of article originally published in the volume 68,2025 of Sci China Chem(pages 3675-3688),the article was published in subscription format rather than open access format due to an oversight during the production stage.The corrected copyright and open access notes are provided below.The original article has been corrected.
基金supported by the National Natural Science Foundation of China(Nos.12064047 and 11864044)the Key Programme of Yunnan Fundamental Research Projects(No.202201AS070010)the Major Science and Technology Projects in Yunnan Province(No.202202AB080019).
文摘Highly optical-absorption hybrid perovskites with upgraded stability and superior photoelectronic properties are essential for optoelectronics.However,various defects are generated by the solution-based film quality inevitably produces during the crystallization process,which leads to non-radiative recombination and interface mismatch.In this work,polyvinylpyrrolidone(PVP)molecule layer was implemented as the interfacially multifunctional layer and selective transport layer to fabricate an effective photodetector.Interfacial PVP is conductive to the bond coordination between the PVP molecule and the MAPbI_(3)surface,which could lower the work function of the perovskite film and effectively improve its surface morphology so as to isolate it from water and oxygen molecules.The interfacial passivation for the undercoordinated Pb^(2+)defects was also verified via first-principles calculations.The electron injection barrier can be regulated via interfacial molecule engineering,leading to the result that the dark current is suppressed by five orders of magnitude to 1.57310−11 A,and the specific detectivity improved by about three orders of magnitude reaching 2.9310^(12)Jones.These results provide a feasible route to fabricate highly sensitive and stable hybrid perovskite photodetectors.
基金supported by the Natural Science Foundation of Hebei Province(B2024201002)the Science Research Project of Hebei Education Department(QN2025151)+3 种基金the Hebei University High-level Talent Research Program(521100223007)the Excellent Youth Research Innovation Team of Hebei University(QNTD202410)Hebei UniversityUniversity of Science and Technology Beijing are gratefully acknowledged for the support。
文摘Photocatalysis provides a green way to produce hydrogen peroxide(H_(2)O_(2)) from oxygen and water.Although many materials with different structures have been designed for the photocatalytic production of H_(2)O_(2),the supramolecular porous materials have been rarely reported.Herein,three imine-linked[3+6]type POCs,containing benzoxadiazole units with tunable functional groups(R=H,OMe,OH),named H-POC,OMe-POC,and OH-POC,are rationally fabricated for visible-light-driven generation of H_(2)O_(2) in water and oxygen.The results show that performance is improved by regulating group from H,OMe,to OH,with the H_(2)O_(2) yields of 527,670,and 976μmol h^(-1)g^(-1),respectively.Moreover,under the synergistic effect of light and heat(70℃),the H_(2)O_(2)production rate of OH-POC was further increased to 2748μmol h^(-1)g^(-1).Photophysical and electrochemical studies have shown that functional group regulation enhances hydrophilicity,light absorption,and charge separation/transfer.In addition,the mechanism of the two-step 1e^(-) ORR and direct 2e^(-) WOR pathway for H_(2)O_(2)production.Importantly,OH-POC shows extraordinary potential in the degradation of water environmental pollutants(tetracycline hydrochloride and mercaptobenzothiazole).This study provides a novel idea for the rational design of photocatalysts that rely on the POCs platform from the perspective of molecular structure design.
基金supported by the National Natural Science Foundation of China(NSFC,52303318 and 22301304)the Natural Science Foundation of Shandong Province(ZR2023QF079)the 2024 Shandong Province Higher Education“Youth Innovation Team Plan”team(2024KJN034)。
文摘Organic semiconductor single-crystal(OSSC)arrays,with superior charge transport and well-aligned properties,are emerging as a fascinating platform for highperformance integrated electronic and optoelectronic applications.Taking advantage of the solution processability of organic semiconductors,solution self-assembly OSSC arrays hold great potential for achieving cost-effective manufacturing of large-area and flexible electronics.While the rational design of molecular building blocks for regulating crystal growth has been achieved,the fundamental principles of molecular structure design for one-dimensional(1D)crystalline nanostructures and the impact of intermolecular interactions in molecular self-assembly remain unclear,limiting the practical application of the solution self-assembly.Drawing inspiration from the concave-convex packing preferences of bowl-shaped polyaromatic hydrocarbons,we propose an innovative molecular engineering strategy for hetero-buckybowl trichalcogenasumanenes to direct the self-assembly of OSSC arrays.The distinctive molecular architecture of trichalcogenasumanenes promotes the formation of 1D crystal arrays via directional concave-convexπ-πinteractions while effectively suppressing intercolumnar coupling,enhancing structural anisotropy and charge transport properties.Accordingly,the centimeter-sized OSSC arrays are obtained on various substrates via solution self-assembly.Furthermore,high-performance organic field-effect transistors(OFETs)based on these OSSC arrays demonstrate mobility values up to 0.89 cm^(2)V^(-1)s^(-1)with small device-to-device variation,superior to previous buckybowl-based devices.This molecular engineering strategy significantly enhances crystallinity and uniformity,providing a pathway for high-performance,largearea organic electronics.
基金supported by the National Natural Science Foundation of China (Nos.22208218,22078196,and 22278268)the Natural Science Foundation of Shanghai (No.22ZR1460400)Collaborative Innovation Center of Fragrance Flavour and Cosmetics,and Collaborative Innovation Project of Shanghai Institute of Technology (No.XTCX2023-07)。
文摘The diagnostic efficacy of contemporary bioimaging technologies remains constrained by inherent limitations of conventional imaging agents,including suboptimal sensitivity,off-target biodistribution,and inherent cytotoxicity.These limitations have catalyzed the development of intelligent stimuli-responsive block copolymers-based bioimaging agents,which was engineered to dynamically respond to endogenous biochemical cues(e.g.,p H gradients,redox potential,enzyme activity,hypoxia environment) or exogenous physical triggers(e.g.,photoirradiation,thermal gradients,ultrasound(US)/magnetic stimuli).Through spatiotemporally controlled structural transformations,stimuli-responsive block copolymers enable precise contrast targeting,activatable signal amplification,and theranostic integration,thereby substantially enhancing signal-to-noise ratios of bioimaging and diagnostic specificity.Hence,this mini-review systematically examines molecular engineering principles for designing p H-,redox-,enzyme-,light-,thermo-,and US/magnetic-responsive polymers,with emphasis on structure-property relationships governing imaging performance modulation.Furthermore,we critically analyze emerging strategies for optical imaging,US synergies,and magnetic resonance imaging(MRI).Multimodal bioimaging has also been elaborated,which could overcome the inherent trade-offs between resolution,penetration depth,and functional specificity in single-modal approaches.By elucidating mechanistic insights and translational challenges,this mini-review aims to establish a design framework of stimuli-responsive block copolymersbased for high fidelity bioimaging agents and accelerate their clinical translation in precise diagnosis and therapy.
基金funded by grants from the Global Core Research Center(GCRC,Grant No.2011-0030001)of the National Research Foundation(NRF),Ministry of Science and ICT(MSIT),Republic of Koreathe MSIT,Republic of Korea(NRF-2018R1A2A1A05019203+1 种基金NRF-2018R1A5A2024425)the Korean Health Technology R&D Project(No.HI19C0664),Ministry of Health&Welfare,Republic of Korea
文摘Conjugation of antibodies to nanoparticles allows specific cancer targeting,but conventional conjugation methods generate heterogeneous conjugations that cannot guarantee the optimal orientation and functionality of the conjugated antibody.Here,a molecular engineering technique was used for sitespecific conjugation of antibodies to nanoparticles.We designed an anti-claudin 3(CLDN3)antibody containing a single cysteine residue,h4 G3 cys,then linked it to the maleimide group of lipid polydopamine hybrid nanoparticles(LPNs).Because of their negatively charged lipid coating,LPNs showed high colloidal stability and provided a functional surface for site-specific conjugation of h4 G3 cys.The activity of h4 G3 cys was tested by measuring the binding of h4 G3 cys-conjugated LPNs(C-LPNs)to CLDN3-positive tumor cells and assessing its subsequent photothermal effects.C-LPNsspecifically recognized CLDN3-overexpressing T47 D breast cancer cells but not CLDN3-negative Hs578 T breast cancer cells.High binding of C-LPNs to CLDN3-overexpressing T47 D cells resulted in significantly higher temperature generation upon NIR irradiation and potent anticancer photothermal efficacy.Consistent with this,intravenous injection of C-LPNsin a T47 D xenograft mouse model followed by NIR irradiation caused remarkable tumor ablation compared with other treatments through high temperature increases.Our results establish an accurate antibody-linking method and demonstrate the possibility of developing therapeutics using antibody-guided nanoparticles.
基金This work was supported by the National Natural Science Foundation of China(Nos.21676093,21776092,21978087,21838003,and 91834301)the Shanghai Scientific and Technological Innovation Project(Nos.19JC1410400 and 18JC1410600)+2 种基金Shanghai Rising-Star Program(No.18QA1401500)the Innovation Program of Shanghai Municipal Education Commission,Program for Professor of Special Appointment(Eastern Scholar)at Shanghai Institutes of High Learning,Shanghai Rising-Star Program(No.18QA1401500)the Fundamental Research Funds for the Central Universities(No.222201718002).
文摘Perovskite quantum dots (PQDs) require ligands on their surfaces to passivate defects and prevent aggregation. However, the ligands construct the interface relationship between the PQDs, which may seriously hinder the carrier transport. Hence, we propose a molecular engineering strategy of using 3,4-ethylenedioxythiophene (EDOT) to perfectly solve this problem, benefiting from its high conjugation and passivation ability to CsPbBr_(3) PQDs. Furthermore, EDOT on the surface of PQDs can be in-situ polymerized under the photocurrent of the photodetector, thus interconnecting the PQDs which enhanced the performance of the photodetectors up to 178% of its initial performance. We have thoroughly investigated the electropolymerization process of EDOT and its passivation effect on PQDs. The simple lateral photodetector based on EDOT PQDs exhibits a high responsivity of 11.96 A/W, which is 104 times higher than that of oleic acid caped PQDs. Due to the protection of poly(3,4-ethylenedioxythiophene) (PEDOT), the photodetector prepared from EDOT PQDs exhibited very high stability, retaining 94% of its performance after six months in air. This strategy provides a solution for the application of PQDs in high performances and stable optoelectronic devices.
基金EPSRC project ATIP,Grant/Award Number:EP/TO28513/1China Scholarship Council(CSC)via the CSC Imperial Scholarship。
文摘The power conversion efficiencies(PCEs)of single-junction organic solar cells(OSCs)have surpassed 19%,owing to the emerging Y-series nonfullerene acceptors(NFAs).Undoubtedly,the power and flexibility of chemical design has been a strong driver for this rapid efficiency improvement in the OSC field.Over the course of the past 3 years,a variety of modifications have been made to the structure of the Y6 acceptor,and a large number of Y-series NFAs have been reported to further improve performance.Herein,we present our insights into the rationale behind the Y6 acceptor and discuss the design principles toward high-performance Y-series NFAs.It is clear that structural modifications through choice of heteroatom,soluble chains,πspacers,central cores,and end groups alter the material characteristics and properties,contributing to distinctive photovoltaic performance.Subsequently,we analyze various design strategies of Y-series-containing materials,including polymerized small-molecule acceptors(PSMA),non-fused-ring acceptors(NFRA),and all-fused-ring acceptors(AFRA).This review is expected to be of value in providing effective molecular design strategies for high-performance NFAs in future innovations.
基金This work was supported by the National Key R&D Program of China(Grant 2019YFA0210100)the National Natural Science Foundation of China(Grants 21890744,21977027,21877029,22004033)the China Postdoctoral Science Foundation(2019TQ0085,2020M682538).
文摘Fluorophores play a significant role in achieving high-contrast imaging in complex physiological environment.Herein,we present the results of our studies on the development of various fluorophores,such as anti-solvatochromic fluorophores,long wavelength emission two-photon fluorophores,large Stokes shift fluorophores and solid-state fluorophores,to achieve high-contrast bioimaging in physiological environments.in this study,we have primarily focused on the design,optical performance,imaging mechanisms,and the applications of these fluorophores with respect to complex physiological conditions.
文摘The feasibility of using gene therapy to treat full-thickness articular cartilage defects was investigated with respect to the transfection and expression of exogenous transforming growth factor(TGF)-β_(1)genes in bone marrow-derived mesenchymal stem cells(MSCs)in vitro.The full-length rat TGF-β_(1)cDNA was transfected to MSCs mediated by lipofectamine and then selected with G418,a synthetic neomycin analog.The transient and stable expression of TGF-β_(1)by MSCs was detected by using immunohistochemical staining.The lipofectamine-mediated gene therapy efficiently transfected MSCs in vitro with the TGF-β_(1)gene causing a marked up-regulation in TGF-β_(1)expression as compared with the vector-transfected control groups,and the increased expression persisted for at least 4 weeks after selected with G418.It was suggested that bone marrow-derived MSCs were susceptible to in vitro lipofectamine mediated TGF-β_(1)gene transfer and that transgene expression persisted for at least 4 weeks.Having successfully combined the existing techniques of tissue engineering with the novel possibilities offered by modern gene transfer technology,an innovative concept,i.e.molecular tissue engineering,are put forward for the first time.As a new branch of tissue engineering,it represents both a new area and an important trend in research.Using this technique,we have a new powerful tool with which:(1)to modify the functional biology of articular tissue repair along defined pathways of growth and differentiation and(2)to affect a better repair of full-thickness articular cartilage defects that occur as a result of injury and osteoarthritis.
基金This project was supported by a grant from NationalNatural Science Foundation of China (No. 30 170 2 70 )
文摘The effect of transforming growth factor β 1 (TGF β 1 ) gene transfection on the proliferation of bone marrow derived mesenchymal stem cells (MSC S ) and the mechanism was investigated to provide basis for accelerating articular cartilage repairing using molecular tissue engineering technology. TGF β 1 gene at different doses was transduced into the rat bone marrow derived MSCs to examine the effects of TGF β 1 gene transfection on MSCs DNA synthesis, cell cycle kinetics and the expression of proliferating cell nuclear antigen (PCNA). The results showed that 3 μl lipofectamine mediated 1 μg TGF β 1 gene transfection could effectively promote the proliferation of MSCs best; Under this condition (DNA/Lipofectamine=1μg/3μl), flow cytometry and immunohistochemical analyses revealed a significant increase in the 3 H incorporation, DNA content in S phase and the expression of PCNA. Transfection of gene encoding TGF β 1 could induce the cells at G0/G1 phase to S1 phase, modulate the replication of DNA through the enhancement of the PCNA expression, increase the content of DNA at S1 phase and promote the proliferation of MSCs. This new molecular tissue engineering approach could be of potential benefit to enhance the repair of damaged articular cartilage, especially those caused by degenerative joint diseases.
文摘Tissue engineering has confronted many difficulties mainly as follows:1)How to modulate the adherence,proliferation,and oriented differentiation of seed cells, especially that of stemcells. 2) Massive preparation and sustained controllable delivery of tissue inducing factors or plasmid DNA, such as growth factors, angiogenesis stimulators,and so on. 3) Development of 'intelligent biomimetic materials' as extracellular matrix with a good superficial and structural compatibility as well as biological activity to stimulate predictable, controllable and desirable responses under defined conditions.Molecular biology is currently one of the most exciting fields of research across life sciences,and the advances in it also bring a bright future for tissue engineering to overcome these difficulties.In recent years,tissue engineering benefits a lot from molecular biology.Only a comprehensive understanding of the involved ingredients of tissue engineering (cells,tissue inducing factors,genes,biomaterials) and the subtle relationships between them at molecular level can lead to a successful manipulation of reparative processes and a better biological substitute.Molecular tissue engineering,the offspring of the tissue engineering and molecular biology,has gained an increasing importance in recent years.It offers the promise of not simply replacing tissue,but improving the restoration.The studies presented in this article put forward this new concept for the first time and provide an insight into the basic principles,status and challenges of this emerging technology.
基金financial supports from the National Natural Science Foundation of China(21676245 and 51933009)the National Key Research and Development Program of China(2017YFB0702502)+1 种基金the Leading Innovative and Entrepreneur Team Introduction Program of Zhejiang(2019R01006)financial support provided by the Startup Funds of the University of Kentucky。
文摘Thermodynamic properties of complex systems play an essential role in developing chemical engineering processes.It remains a challenge to predict the thermodynamic properties of complex systems in a wide range and describe the behavior of ions and molecules in complex systems.Machine learning emerges as a powerful tool to resolve this issue because it can describe complex relationships beyond the capacity of traditional mathematical functions.This minireview will summarize some fundamental concepts of machine learning methods and their applications in three aspects of the molecular thermodynamics using several examples.The first aspect is to apply machine learning methods to predict the thermodynamic properties of a broad spectrum of systems based on known data.The second aspect is to integer machine learning and molecular simulations to accelerate the discovery of materials.The third aspect is to develop machine learning force field that can eliminate the barrier between quantum mechanics and all-atom molecular dynamics simulations.The applications in these three aspects illustrate the potential of machine learning in molecular thermodynamics of chemical engineering.We will also discuss the perspective of the broad applications of machine learning in chemical engineering.
基金supported by the National Natural Science Foundation of China(Nos.21908065,22078098,and 22278138)the Shanghai Academic Technology Research Leader(No.22XD1421000)+1 种基金the Research Funds of Happiness Flower ECNU(No.2020JK2103)the Open Funding Project of the State Key Laboratory of Bioreactor Engineering。
文摘Fluorescence-guided surgery calls for development of near-infrared fluorophores.Despite the wide-spread application and a safe clinical record of Indocyanine Green(ICG),its maximal absorption wavelength at780 nm is rather short and longer-wavelength dyes are desired to exploit such benefits as low phototoxicity and deep penetration depth.Here,we report ECY,a stable deep near-infrared(NIR)fluorochromic scaffold absorbing/emitting at 836/871 nm with a fluorescence quantum yield of 16%in CH_(2)Cl_(2).ECY was further rationally engineered for biological distribution specificity.Analogous bearing different numbers of sulfonate group or a polyethylene glycol chain were synthesized.By screening this focused library upon intravenous injection to BALB/c mice,ECYS2 was identified to be a suitable candidate for bioimaging of organs involved in hepatobiliary excretion,and ECYPEG was found to be a superior candidate for vasculature imaging.They have potentials in intraoperative imaging.
基金supported by the National Natural Science Foun-dation of China(22021004 and U19B2002).
文摘In this work,a molecular-level kinetic model was built to simulate the vacuum residue(VR)coking process in a semi-batch laboratory-scale reaction kettle.A series of reaction rules for heavy oil coking were summarized and formulated based on the free radical reaction mechanism.Then,a large-scale molecularlevel reaction network was automatically generated by applying the reaction rules on the vacuum residue molecules.In order to accurately describe the physical change of each molecule in the reactor,we coupled the molecular-level kinetic model with a vapor–liquid phase separation model.The vapor–liquid phase separation model adopted the Peng-Robinson equation of state to calculate vapor–liquid equilibrium.A separation efficiency coefficient was introduced to represent the mass transfer during the phase separation.We used six sets of experimental data under various reaction conditions to regress the model parameters.The tuned model showed that there was an excellent agreement between the calculated values and experimental data.Moreover,we investigated the effect of reaction temperature and reaction time on the product yields.After a comprehensive evaluation of the reaction temperature and reaction time,the optimal reaction condition for the vacuum residue coking was also obtained.
基金the National Natural Science Foundation of China(52171199)for the financial support.
文摘Fe single-atom catalysts(Fe-SACs)have been extensively studied as a highly efficient electrocatalyst toward the oxygen reduction reaction(ORR).Nonetheless,they suffer from stability issue induced by dissolution of Fe metal center and the OH^(−)blocking.Herein,a surface molecular engineering strategy is developed by usingβ-cyclodextrins(CDs)as a localized molecular encapsulation.The CD-modified Fe-SAC(Fe-SNC-β-CD)shows obviously improved activity toward the ORR with 0.90 V,4.10 and 4.09 mA cm^(-2)for E_(1/2),J_(0)and Jk0.9,respectively.Meanwhile,the Fe-SNC-β-CD shows the excellent long-term stability against aggressive stress and the poisoning.It is confirmed through electrochemical investigation that modification ofβ-CD can,on one hand,regulate the atomic Fe coordination chemistry through the interaction between the CD and FeN_(x) moiety,while on the other mitigate the strong adsorption of OH^(−)and function as protective barrier against the poisoning molecules leading to enhanced ORR activity and stability for the Fe-SACs.The molecular encapsulation strategy demonstrates the uniqueness of post-pyrolysis surface molecular engineering for the design of single-atom catalyst.
文摘H_(2)O_(2)is an environmentally friendly oxidant and a promising energy-containing molecule widely applied in industrial production,environmental remediation,and as a potential carrier for energy storage.Solar-driven conversion of earth-abundant H_(2)O and O_(2)is the most ideal method for producing H_(2)O_(2).Due to poor separation of photogenerated charge carriers in semiconductors,sacrificial reagents such as ethanol are typically added to consume photogenerated holes,but this is not an energy storage process.Therefore,developing efficient photocatalysts for direct H_(2)O_(2)production from H_(2)O and O_(2)without sacrificial agents is crucial for sustainable energy conversion.Organic framework materials,due to their customizable structures,have gained traction in the photosynthesis of H_(2)O_(2)from pure H_(2)O and O_(2).A series of functionalized molecules have been introduced as building blocks into organic frameworks to enhance the H_(2)O_(2)production performance,but their key roles in performance and reaction pathways have not been summarized in detail so far.This review aims to address this gap and elucidate the relationship between the structure and performance of organic framework photocatalysts,providing insights and guidance for the development of efficient photocatalysts.
基金supported by the National Natural Science Foundation of China(11172149)the financial support from the IBM World Community Grid project "Computing for Clean Water"+2 种基金the Boeing-Tsinghua Joint Research Project "New Air Filtration Materials"grant 2012 from engineering faculty of Monash Universitysupported by an award under the Merit Allocation Scheme on the Australia NCI National Facility at the ANU
文摘Reversible control of surface wettability has wide applications in lab-on-chip systems, tunable optical lenses, and microfluidic tools. Using a graphene sheet as a sam- ple material and molecular dynamic simulations, we demon- strate that strain engineering can serve as an effective way to control the surface wettability. The contact angles 0 of water droplets on a graphene vary from 72.5° to 106° under biaxial strains ranging from -10% to 10% that are applied on the graphene layer. For an intrinsic hydrophilic surface （at zero strain）, the variation of 0 upon the applied strains is more sensitive, i.e., from 0° to 74.8°. Overall the cosines of the contact angles exhibit a linear relation with respect to the strains. In light of the inherent dependence of the contact an- gle on liquid-solid interfacial energy, we develop an analytic model to show the cos 0 as a linear function of the adsorption energy Eads of a single water molecule over the substrate sur- face. This model agrees with our molecular dynamic results very well. Together with the linear dependence of Eads on bi- axial strains, we can thus understand the effect of strains on the surface wettability. Thanks to the ease of reversibly ap- plying mechanical strains in micro/nano-electromechanical systems, we believe that strain engineering can be a promis- ing means to achieve the reversibly control of surface wetta- bility.
