Supramolecular luminescent materials(SLMs)exhibit exceptional luminescence properties and the ability to be intelligently regulated through diverse assembly approaches,making them highly attractive in the field of lum...Supramolecular luminescent materials(SLMs)exhibit exceptional luminescence properties and the ability to be intelligently regulated through diverse assembly approaches,making them highly attractive in the field of luminescent materials.In recent years,the novel macrocyclic arenes characterized by unique electron-rich structures,ease of derivatization,tunable conformations and even inherent luminescence properties afford much opportunities to create such dynamic smart luminescent materials.The incorporation of macrocyclic arenes into SLMs leads to simple preparation process,diverse photophysical phenomena and sophisticated regulatory mechanisms,which is also currently one of the most frontier and hot topics in macrocyclic and supramolecular chemistry and even luminescent materials.In this review,the research advances in construction and applications of SLMs based on macrocyclic arenes in the last several years will be presented from the different assembly strategies,including host-vip complexes,supramolecular polymers,nanoparticles,and other assemblies.Moreover,some insights into future directions for this research area will also be offered.展开更多
Neuroinflammation contributes to a wide range of neurodegenerative diseases including Alzheimer's disease,Parkinson's disease,Huntington's disease,and multiple sclerosis.It is driven by non-neuronal glial ...Neuroinflammation contributes to a wide range of neurodegenerative diseases including Alzheimer's disease,Parkinson's disease,Huntington's disease,and multiple sclerosis.It is driven by non-neuronal glial cells,mainly microglia and astrocytes.Microglia are the resident immune cells of the central nervous system,while astrocytes are the main support cells for neuronal functions but can also participate in neuroimmune responses.Both these glial cell types can become reactive upon detection of certain endogenous intracellular molecules that appear in the extracellular space under specific circumstances;these can be pathology-associated abnormal structures,such as amyloidβproteins,or damage-associated molecular patterns released from injured cells,including their mitochondria.Once in the extracellular space,damage-associated molecular patterns act as ligands for specific pattern recognition receptors expressed by glia inducing their reactivity and neuroimmune responses.This review considers the following mitochondrial damage-associated molecular patterns:heme,cytochrome c,cardiolipin,adenosine triphosphate,mitochondrial DNA,mitochondrial transcription factor A,N-formyl peptides,and the tricarboxylic acid cycle metabolites:succinate,fumarate,and itaconate.We describe their well-established functions as damage-associated molecular patterns of the peripheral tissues before summarizing available evidence indicating these molecules may also play significant roles in the neuroimmune processes of the central nervous system.We highlight the pattern recognition receptors that mitochondrial damage-associated molecular patterns interact with and the cellular signaling mechanisms they modulate.Our review demonstrates that some mitochondrial damage-associated molecular patterns,such as cytochrome c,adenosine triphosphate,and mitochondrial transcription factor A,have already demonstrated significant effects on the central nervous system.In contrast,others including cardiolipin,mitochondrial DNA,N-formyl peptides,succinate,fumarate,and itaconate,will require additional studies corroborating their roles as damageassociated molecular patterns in the central nervous system.For all of the reviewed mitochondrial damage-associated molecular patterns,there is a shortage of studies using human cells and tissues,which is identified as a significant knowledge gap.We also assess the need for targeted research on the effects of mitochondrial damage-associated molecular patterns in the central nervous system pathologies where their roles are understudied.Such studies could identify novel treatment strategies for multiple neurodegenerative diseases,which are characterized by chronic neuroinflammation and currently lack effective therapies.展开更多
Light-driven artificial molecular machines[1,2]are a class of functional small molecules powered by photochemical reactions,broadly divided into molecular motors and molecular photoswitches.Molecular motors[3,4],owing...Light-driven artificial molecular machines[1,2]are a class of functional small molecules powered by photochemical reactions,broadly divided into molecular motors and molecular photoswitches.Molecular motors[3,4],owing to their intrinsic point chirality and dynamic axial chirality,undergo unidirectional rotation about a carbon–carbon double bond when irradiated with light.In nature,biological molecular motors and pumps are ubiquitous:driving vision,intracellular transport,energy conversion,signal transduction,muscle contraction,and locomotion.展开更多
The convergence of materials science and biotechnology has catalyzed the development of innovative platforms,including nanotechnology,smart sensors,and supramolecular materials,significantly advancing the progress in ...The convergence of materials science and biotechnology has catalyzed the development of innovative platforms,including nanotechnology,smart sensors,and supramolecular materials,significantly advancing the progress in the field of life sciences[1−7].Among them,supramolecular materials have garnered increasing attention in life sciences owing to their distinctive self-assembly capabilities and intelligent responsiveness[8−12].展开更多
Circularly polarized luminescence(CPL)-active materials have a wide range of technological applications.Traditionally,creating CPL-active materials relies on the use of chiral luminophores.In contrast,supramolecular a...Circularly polarized luminescence(CPL)-active materials have a wide range of technological applications.Traditionally,creating CPL-active materials relies on the use of chiral luminophores.In contrast,supramolecular assembly introduces an innovative and promising strategy for developing CPL-active materials not only from chiral luminophores but also from achiral species.This approach significantly enriches the diversity of CPL-active materials.It also offers an effective means to optimize the performance of CPL-active materials,such as enhancing the asymmetry factor|glum|.Compared to polymers,the assembly of small molecules is generally easier to control.This review systematically summarizes the recent progress and developments in CPL from small-molecule assemblies,particularly focusing on differences,merits,and demerits of three typical assembly modes.The aim is to provide valuable insights for the future development of chiroptical materials.展开更多
Molecular medicine,which delves into the intricacies of biomolecular structure,function,and role,is pivotal for advancing precise diagnostics and personalized treatment.Nucleic acids,a class of star functional molecul...Molecular medicine,which delves into the intricacies of biomolecular structure,function,and role,is pivotal for advancing precise diagnostics and personalized treatment.Nucleic acids,a class of star functional molecules,are notable for their versatile applications in molecular diagnostics,gene therapy,and drug development.Therefore,in this study,we review the extensive use of nucleic acid aptamers in medicinal practice.Furthermore,the expanding field of molecular medicine has catalyzed advancements in traditional Chinese medicine(TCM),as evidenced by scientific endeavors to integrate modern technologies.Therefore,TCM has experienced rapid modernization by leveraging artificial intelligence,nucleic acid molecular medicine,and bioelectronic medicine.展开更多
Pancreatic cancer, particularly pancreatic ductal adenocarcinoma(PDAC), is one of the most lethal malignancies,which is characterized by a complex tumor microenvironment(TME) that fosters immune evasion and treatment ...Pancreatic cancer, particularly pancreatic ductal adenocarcinoma(PDAC), is one of the most lethal malignancies,which is characterized by a complex tumor microenvironment(TME) that fosters immune evasion and treatment resistance. Recent genomic advancements have unveiled diverse molecular subtypes of PDAC, providing insights into targeted therapies and precision medicine. This review synthesizes the current understanding of PDAC's molecular characterization and immunosuppressive TME, as well as emerging therapeutic strategies, including innovative approaches targeting key molecular pathways such as kirsten rat sarcoma viral oncogene homolog(KRAS), epidermal growth factor receptor(EGFR), and immune checkpoints. Despite advances, challenges remain in overcoming treatment resistance and inherent heterogeneity of pancreatic cancer subtypes. We highlight the need for multidisciplinary collaboration to enhance early diagnosis and develop individualized therapeutic protocols, paving the way for improving the outcomes of this aggressive cancer. This integrated perspective underscores the urgency of transforming the innovative research into pancreatic cancer management.展开更多
The bioactive constituents found in natural products(NPs)are crucial in protein-ligand interactions and drug discovery.However,it is difficult to identify ligand molecules from complex NPs that specifically bind to ta...The bioactive constituents found in natural products(NPs)are crucial in protein-ligand interactions and drug discovery.However,it is difficult to identify ligand molecules from complex NPs that specifically bind to target protein,which often requires time-consuming and labor-intensive processes such as isolation and enrichment.To address this issue,in this study we developed a method that combines ultra-high performance liquid chromatography-electrospray ionization-mass spectrometry(UHPLCESI-MS)with molecular dynamics(MD)simulation to identify and observe,rapidly and efficiently,the bioactive components in NPs that bind to specific protein target.In this method,a specific protein target was introduced online using a three-way valve to form a protein-ligand complex.The complex was then detected in real time using high-resolution MS to identify potential ligands.Based on our method,only 10 molecules from green tea(a representative natural product),including the commonly reported epigallocatechin gallate(EGCG)and epicatechin gallate(ECG),as well as the previously unreported eepicatechin(4β→8)-epigallocatechin 3-O-gallate(EC-EGCG)and eepiafzelechin 3-O-gallate-(4β→8)-epigallocatechin 3-O-gallate(EFG-EGCG),were screened out,which could form complexes with Aβ_(1-42)(a representative protein target),and could be potential ligands of Aβ_(1-42).Among of them,EC-EGCG demonstrated the highest binding free energy with Aβ_(1-42)(−68.54±3.82 kcal/mol).On the other side,even though the caffeine had the highest signal among green tea extracts,it was not observed to form a complex with Aβ_(1-42).Compared to other methods such as affinity selection mass spectrometry(ASMS)and native MS,our method is easy to operate and interpret the data.Undoubtedly,it provides a new methodology for potential drug discovery in NPs,and will accelerate the research on screening ligands for specific proteins from complex NPs.展开更多
Although supramolecular transformations have been emerged as a potent strategy for transitioning between various topologies,post-modification induced topological transformations have never been explored in the context...Although supramolecular transformations have been emerged as a potent strategy for transitioning between various topologies,post-modification induced topological transformations have never been explored in the context of[2]catenane topologies.In this study,we present a novel supramolecular transformation between a Hopf link and a macrocycle,induced by the Diels–Alder click reaction.By strategically selecting the half-sandwich ruthenium binuclear fragment B as a rigid capping agent,we successfully integrated tetrazine moieties into the metalla[2]catenane structure.We demonstrated that the introduction of 2,5-norbornadiene(NBD)as an external stimulus allows for the transformation of the novel metalla[2]catenane,featuring reactive tetrazine sites,into the corresponding monomeric ring through postmodification for the first time.The synthetic results are corroborated by single-crystal X-ray diffraction analysis,ESI-TOF/MS,elemental analysis,and detailed solution-state NMR techniques.展开更多
The influences of reaction temperature,duration,pressure,and catalyst concentration on the molecular transformation of residual slurry phase hydrocracking process were investigated.The molecular composition of the het...The influences of reaction temperature,duration,pressure,and catalyst concentration on the molecular transformation of residual slurry phase hydrocracking process were investigated.The molecular composition of the heteroatom compounds in the residue feedstock and its upgrading products were characterized using high-resolution Orbitrap mass spectrometry coupled with multiple ionization methods.The simultaneous promotion of cracking and hydrogenation reactions was observed with increasing of the reaction temperature and time.Specifically,there was a significant increase in the cracking degree of alkyl side chain,while the removal of low-condensation sulfur compounds such as sulfides and benzothiophenes was enhanced.In particular,the cracking reactions were more significantly facilitated by high temperatures,while an appropriately extended reaction time can result in the complete elimination of the aforementioned sulfur compounds with a lower degree of condensation.Under conditions of low hydrogen pressure and catalyst concentration,the products still exhibit a high relative abundance of easily convertible compounds such as sulfoxides,indicating a significant deficiency in the effectiveness of hydrogenation.The hydrogen pressure exhibits an optimal value,beyond which further increments have no effect on the composition and performance of the liquid product but can increase the yield of the liquid product.At significantly high catalyst concentration,the effect of desulfurization and deoxidation slightly diminishes,while the aromatic saturation of highly condensed compounds was notably enhanced.This hydrogenation saturation effect cannot be attained through manipulation of other operational parameters,thereby potentially benefiting subsequent product processing and utilization.This present study demonstrates a profound comprehension of the molecular-level residue slurry phase hydrocracking process,offering not only specific guide for process design and optimization but also valuable fundamental data for constructing reaction models at the molecular level.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
Optically detected magnetic resonance(ODMR)has emerged as a powerful technique for quantum sensing,enabling high-sensitivity detection of physical quantities even at room temperature.Solid-state defects,such as nitrog...Optically detected magnetic resonance(ODMR)has emerged as a powerful technique for quantum sensing,enabling high-sensitivity detection of physical quantities even at room temperature.Solid-state defects,such as nitrogen-vacancy(NV)centers in diamond,have demonstrated remarkable capabilities in this domain[1–4].However,these systems are limited by their rigid lattice structures and lack tunability.展开更多
The concept of liquid-solid hybrid catalyst that featuring a truly homogeneous liquid microenvironment together with insoluble solid characteristics has been established recently by our group,which enables us to conve...The concept of liquid-solid hybrid catalyst that featuring a truly homogeneous liquid microenvironment together with insoluble solid characteristics has been established recently by our group,which enables us to conveniently bridge the gap between homo-and heterogeneous catalysis.In this study,we extend this general concept to the confinement of molecular rhodium phosphine complexes,including Rh-TPPTS,Rh-TPPMS and Rh-SXP,for olefin hydroformylation reactions.A series of hybrid catalyst materials consisting a modulated liquid interior([BMIM]NTf_(2),[BMIM]PF_(6),[BMIM]BF_(4) or H_(2)O)and a permeable silica crust were fabricated through our developed Pickering emulsion-based method,showing 9.4–24.2-fold activity enhancement and significantly improved aldehyde selectivity(from 72.2%,61.8%to 86.6%)compared to their biphasic counterparts or traditional supported liquid phase system in the hydroformylation of 1-dodecene.Interestingly,the catalytic efficiency was demonstrated to be tunable by rationally engineering the thickness of porous crust and dimensions of the liquid pool.The thus-attained hybrid catalyst could also successfully catalyze the hydroformylation of a variety of olefin substrates and be recycled without a significant loss of activity for at least seven times.展开更多
Metal-ceramic composites combine the excellent properties of metals and ceramics,which have high strength,stability,and corrosion re-sistance.Al_(2)O_(3)/FeCo composites have been proven to be useful in ap-plications ...Metal-ceramic composites combine the excellent properties of metals and ceramics,which have high strength,stability,and corrosion re-sistance.Al_(2)O_(3)/FeCo composites have been proven to be useful in ap-plications such as catalysts,mi-crowave absorption materials,and enhanced permeability dielectric.The understanding of the mechani-cal properties and dynamics at the atomic scale of the Al_(2)O_(3)/FeCo in-terface can promote the design and exploitment of metal-ceramic composites.In this work,we have obtained Young’s modulus and diffusion coefficient of the Al_(2)O_(3)/FeCo interface using molecular dynamics simulation,elucidated the structural characteristics of the Al_(2)O_(3)/FeCo interface at the atomic scale,and investigated the impact of atomic magnetism and the exter-nal magnetic field on the interface.Simulated results show that Young’s modulus of the Al_(2)O_(3)/FeCo interface is significantly improved compared with pure Al_(2)O_(3)and FeCo alloy at room and high temperatures.When the atomic magnetism and the external magnetic field are applied,Young’s modulus of the Al_(2)O_(3)/FeCo interface further increases to 612 GPa at 300 K and 602 GPa at 500 K.Moreover,the average density,diffusion coefficient,and radial distri-bution function are found to be modified substantially.This study will shed light on the atom-istic investigations of the metal-ceramic composites.展开更多
Wide-bandgap mixed-halide perovskites,particularly CsPbIBr_(2),hold great promise for multi-junction solar cells due to their well-matched bandgap and all-inorganic material system.However,their inherent susceptibilit...Wide-bandgap mixed-halide perovskites,particularly CsPbIBr_(2),hold great promise for multi-junction solar cells due to their well-matched bandgap and all-inorganic material system.However,their inherent susceptibility to light-induced phase segregation(LIPS)limits efficiency and stability.In this work,we investigate the effect of three organic additives-4-cyclopentene-1,3-dione(CPD),maleimide(HPD),and 3,4-dibromo-1H-pyrrole-2,5(2H,5H)-dione(BrPD)-on LIPS in wide-bandgap CsPbIBr_(2)perovskite films.The additives form various chemical interactions,including coordination bonds,hydrogen bonds,and ionic bonds,with I^(-)and undercoordinated Pb^(2+)ions,among which BrPD has the strongest interaction.This interaction regulates crystallization and improves film morphology.The BrPD-modified films have the largest grain size and the highest light stability,suppressing LIPS,enhancing carrier transfer,and improving device performance.BrPD-modified CsPbIBr_(2)-based solar cells achieve a power conversion efficiency(PCE)of 11.34%,outperforming the control(8.96%)and other additives.Moreover,BrPDmodified devices show excellent stability,retaining 94%of their initial PCE after 60 min of continuous light exposure.This work highlights the potential of strategically selected organic additives to enhance the stability and performance of perovskite solar cells,offering valuable insights for the design of high-efficiency and long-lasting perovskite-based optoelectronic devices.展开更多
Obesity has become a significant global public health issue.Previous studies have found that the Chenpi has the anti-obesity activity.However,the anti-obesity phytochemicals and their mechanisms are still unclear.This...Obesity has become a significant global public health issue.Previous studies have found that the Chenpi has the anti-obesity activity.However,the anti-obesity phytochemicals and their mechanisms are still unclear.This study investigated the anti-obesity phytochemicals and molecular mechanisms involved in treating obesity by Chenpi through network pharmacology and molecular docking.A total of 17 bioactive phytochemicals from Chenpi and its 475 related anti-obesity targets have been identified.The KEGG pathway analysis showed that the PI3K/Akt signaling pathway,MAPK signaling pathway,AMPK signaling pathway,and nuclear factor kappa B signaling pathway are the main signaling pathways involved in the anti-obesity effect of Chenpi.According to molecular docking analysis,the phytochemicals of Chenpi can bind to central anti-obesity targets.Based on the ADMET analysis and network pharmacology results,tangeretin exhibited the lowest predicted toxicity and potential for anti-obesity effects.In the in vitro lipid accumulation model,tangeretin effectively suppressed the free fatty acid-induced lipid in Hep G2 cells by upregulating the PI3K/Akt/GSK3βsignaling pathway based on the result of q-PCR and Western blotting.The outcomes of this research give insights for future research on the anti-obesity phytochemicals and molecular mechanisms derived from Chenpi,also providing the theoretical basis for developing anti-obesity functional foods based on Chenpi.展开更多
The tightness of π-π stacking in supramolecular organic semiconductors plays a crucial role in governing the spatial separation and migration dynamics of photogenerated charge carriers,ultimately determining their p...The tightness of π-π stacking in supramolecular organic semiconductors plays a crucial role in governing the spatial separation and migration dynamics of photogenerated charge carriers,ultimately determining their photocatalytic performance.To achieve closeπ-πstacking,the suitable design of molecular structure is essential.Therefore,two isomers of pyridine carboxylic acid-modified perylene monoimide(PMI)were designed and synthesized,namely PM5A and PM6A.In aqueous solution,these molecules self-assemble into aggregates,which exhibit distinct stacking properties and optical characteristics.Upon photoexcitation,the looseπ-πstacking of PM5A favors the generation of charge-transfer excitons(CTEs)over charge-separation excitons(CSEs).In contrast,PM6A,stabilized by intermolecular hydrogen bonds and possessing closeπ-πstacking,undergoes efficient charge separation(CS)to produce CSEs within 4.5 picoseconds.When incorporated into metal-insulatorsemiconductor(MIS)photosystems with polyvinylpyrrolidone(PVP)-capped Pt,the Pt/PVP/PM6A system demonstrates a hydrogen evolution rate(HER)of 8100μmol g^(-1)h^(-1),nearly five times higher than that of the Pt/PVP/PM5A system.Additionally,the maximum apparent quantum efficiency(AQE)reaches approximately 2.1%under irradiation with light of a single wavelength of λ=425 nm.展开更多
Since 2009,perovskite solar cells(PSCs)have advanced significantly,achieving over 26%efficiency for single-junction devices and exceeding 34%for silicon-perovskite tandem cells.Despite these successes,the weak adhesio...Since 2009,perovskite solar cells(PSCs)have advanced significantly,achieving over 26%efficiency for single-junction devices and exceeding 34%for silicon-perovskite tandem cells.Despite these successes,the weak adhesion of C_(60)to perovskite layers,due to van der Waals interactions,hinders long-term stability.In this study,we introduce electron-deficient intermolecular adhesives(EDIAs)as a novel interlayer material to enhance adhesion between perovskite and C_(60)layers.Comprehensive analyses,including density functional theory calculations,microscopy,and spectroscopy,demonstrate that EDIAs,particularly NDI-C9-Ace comprising of three key functionalities:aπ-electron-deficient arene core,a hydrophobic passivation core,and a secondary-bond anchoring core,significantly improve bonding strength and recombination passivation.This leads to enhanced efficiency as well as enhanced mechanical and photochemical stability in PSCs.Long-term stability tests further confirm the superior durability of EDIA-enhanced devices.This study highlights EDIA as a promising strategy for enhancing the robustness and efficiency of PSCs.展开更多
Sonic Hedgehog Medulloblastoma(SHH-MB)is one of the four primary molecular subgroups of Medulloblastoma.It is estimated to be responsible for nearly one-third of allMB cases.Using transcriptomic and DNA methylation pr...Sonic Hedgehog Medulloblastoma(SHH-MB)is one of the four primary molecular subgroups of Medulloblastoma.It is estimated to be responsible for nearly one-third of allMB cases.Using transcriptomic and DNA methylation profiling techniques,new developments in this field determined four molecular subtypes for SHH-MB.SHH-MB subtypes show distinct DNAmethylation patterns that allow their discrimination fromoverlapping subtypes and predict clinical outcomes.Class overlapping occurs when two or more classes share common features,making it difficult to distinguish them as separate.Using the DNA methylation dataset,a novel classification technique is presented to address the issue of overlapping SHH-MBsubtypes.Penalizedmultinomial regression(PMR),Tomek links(TL),and singular value decomposition(SVD)were all smoothly integrated into a single framework.SVD and group lasso improve computational efficiency,address the problem of high-dimensional datasets,and clarify class distinctions by removing redundant or irrelevant features that might lead to class overlap.As a method to eliminate the issues of decision boundary overlap and class imbalance in the classification task,TL enhances dataset balance and increases the clarity of decision boundaries through the elimination of overlapping samples.Using fivefold cross-validation,our proposed method(TL-SVDPMR)achieved a remarkable overall accuracy of almost 95%in the classification of SHH-MB molecular subtypes.The results demonstrate the strong performance of the proposed classification model among the various SHH-MB subtypes given a high average of the area under the curve(AUC)values.Additionally,the statistical significance test indicates that TL-SVDPMR is more accurate than both SVM and random forest algorithms in classifying the overlapping SHH-MB subtypes,highlighting its importance for precision medicine applications.Our findings emphasized the success of combining SVD,TL,and PMRtechniques to improve the classification performance for biomedical applications with many features and overlapping subtypes.展开更多
基金the National Natural Science Foundation of China(Nos.22171272,22031010)the Strategic Priority Research Program of the Chinese Academy of Sciences(No.XDB0520302)the Youth Innovation Promotion Association CAS(No.2021035)for financial support。
文摘Supramolecular luminescent materials(SLMs)exhibit exceptional luminescence properties and the ability to be intelligently regulated through diverse assembly approaches,making them highly attractive in the field of luminescent materials.In recent years,the novel macrocyclic arenes characterized by unique electron-rich structures,ease of derivatization,tunable conformations and even inherent luminescence properties afford much opportunities to create such dynamic smart luminescent materials.The incorporation of macrocyclic arenes into SLMs leads to simple preparation process,diverse photophysical phenomena and sophisticated regulatory mechanisms,which is also currently one of the most frontier and hot topics in macrocyclic and supramolecular chemistry and even luminescent materials.In this review,the research advances in construction and applications of SLMs based on macrocyclic arenes in the last several years will be presented from the different assembly strategies,including host-vip complexes,supramolecular polymers,nanoparticles,and other assemblies.Moreover,some insights into future directions for this research area will also be offered.
基金supported by grants from the Jack Brown and Family Alzheimer’s Disease Research Foundationthe Natural Sciences and Engineering Research Council of Canada(No.2020-04407)+1 种基金the University of British Columbia Okanagan CampusThe authors also thank Gentmed SIA for financial assistance。
文摘Neuroinflammation contributes to a wide range of neurodegenerative diseases including Alzheimer's disease,Parkinson's disease,Huntington's disease,and multiple sclerosis.It is driven by non-neuronal glial cells,mainly microglia and astrocytes.Microglia are the resident immune cells of the central nervous system,while astrocytes are the main support cells for neuronal functions but can also participate in neuroimmune responses.Both these glial cell types can become reactive upon detection of certain endogenous intracellular molecules that appear in the extracellular space under specific circumstances;these can be pathology-associated abnormal structures,such as amyloidβproteins,or damage-associated molecular patterns released from injured cells,including their mitochondria.Once in the extracellular space,damage-associated molecular patterns act as ligands for specific pattern recognition receptors expressed by glia inducing their reactivity and neuroimmune responses.This review considers the following mitochondrial damage-associated molecular patterns:heme,cytochrome c,cardiolipin,adenosine triphosphate,mitochondrial DNA,mitochondrial transcription factor A,N-formyl peptides,and the tricarboxylic acid cycle metabolites:succinate,fumarate,and itaconate.We describe their well-established functions as damage-associated molecular patterns of the peripheral tissues before summarizing available evidence indicating these molecules may also play significant roles in the neuroimmune processes of the central nervous system.We highlight the pattern recognition receptors that mitochondrial damage-associated molecular patterns interact with and the cellular signaling mechanisms they modulate.Our review demonstrates that some mitochondrial damage-associated molecular patterns,such as cytochrome c,adenosine triphosphate,and mitochondrial transcription factor A,have already demonstrated significant effects on the central nervous system.In contrast,others including cardiolipin,mitochondrial DNA,N-formyl peptides,succinate,fumarate,and itaconate,will require additional studies corroborating their roles as damageassociated molecular patterns in the central nervous system.For all of the reviewed mitochondrial damage-associated molecular patterns,there is a shortage of studies using human cells and tissues,which is identified as a significant knowledge gap.We also assess the need for targeted research on the effects of mitochondrial damage-associated molecular patterns in the central nervous system pathologies where their roles are understudied.Such studies could identify novel treatment strategies for multiple neurodegenerative diseases,which are characterized by chronic neuroinflammation and currently lack effective therapies.
文摘Light-driven artificial molecular machines[1,2]are a class of functional small molecules powered by photochemical reactions,broadly divided into molecular motors and molecular photoswitches.Molecular motors[3,4],owing to their intrinsic point chirality and dynamic axial chirality,undergo unidirectional rotation about a carbon–carbon double bond when irradiated with light.In nature,biological molecular motors and pumps are ubiquitous:driving vision,intracellular transport,energy conversion,signal transduction,muscle contraction,and locomotion.
基金supported by the National Natural Science Foundation of China(22101043)the Fundamental Research Funds for the Central Universities(N2205013,N232410019,N2405013)+3 种基金Natural Science Foundation of Liaoning Province(2023-MSBA-068)the Opening Fund of State Key Laboratory of Heavy Oil Processing(SKLHOP202203006)the Key Laboratory of Functional Molecular Solids,Ministry of Education(FMS2023005)Northeastern University。
文摘The convergence of materials science and biotechnology has catalyzed the development of innovative platforms,including nanotechnology,smart sensors,and supramolecular materials,significantly advancing the progress in the field of life sciences[1−7].Among them,supramolecular materials have garnered increasing attention in life sciences owing to their distinctive self-assembly capabilities and intelligent responsiveness[8−12].
基金support from the National Natural Science Foundation of China(52473192)。
文摘Circularly polarized luminescence(CPL)-active materials have a wide range of technological applications.Traditionally,creating CPL-active materials relies on the use of chiral luminophores.In contrast,supramolecular assembly introduces an innovative and promising strategy for developing CPL-active materials not only from chiral luminophores but also from achiral species.This approach significantly enriches the diversity of CPL-active materials.It also offers an effective means to optimize the performance of CPL-active materials,such as enhancing the asymmetry factor|glum|.Compared to polymers,the assembly of small molecules is generally easier to control.This review systematically summarizes the recent progress and developments in CPL from small-molecule assemblies,particularly focusing on differences,merits,and demerits of three typical assembly modes.The aim is to provide valuable insights for the future development of chiroptical materials.
基金supported by the National Natural Science Foundation of China(T2188102)Hangzhou Institute of Medicine(2024ZZBS02,Hangzhou,China).
文摘Molecular medicine,which delves into the intricacies of biomolecular structure,function,and role,is pivotal for advancing precise diagnostics and personalized treatment.Nucleic acids,a class of star functional molecules,are notable for their versatile applications in molecular diagnostics,gene therapy,and drug development.Therefore,in this study,we review the extensive use of nucleic acid aptamers in medicinal practice.Furthermore,the expanding field of molecular medicine has catalyzed advancements in traditional Chinese medicine(TCM),as evidenced by scientific endeavors to integrate modern technologies.Therefore,TCM has experienced rapid modernization by leveraging artificial intelligence,nucleic acid molecular medicine,and bioelectronic medicine.
文摘Pancreatic cancer, particularly pancreatic ductal adenocarcinoma(PDAC), is one of the most lethal malignancies,which is characterized by a complex tumor microenvironment(TME) that fosters immune evasion and treatment resistance. Recent genomic advancements have unveiled diverse molecular subtypes of PDAC, providing insights into targeted therapies and precision medicine. This review synthesizes the current understanding of PDAC's molecular characterization and immunosuppressive TME, as well as emerging therapeutic strategies, including innovative approaches targeting key molecular pathways such as kirsten rat sarcoma viral oncogene homolog(KRAS), epidermal growth factor receptor(EGFR), and immune checkpoints. Despite advances, challenges remain in overcoming treatment resistance and inherent heterogeneity of pancreatic cancer subtypes. We highlight the need for multidisciplinary collaboration to enhance early diagnosis and develop individualized therapeutic protocols, paving the way for improving the outcomes of this aggressive cancer. This integrated perspective underscores the urgency of transforming the innovative research into pancreatic cancer management.
基金supported by the National Key R&D Program of China(No.2018YFA0800900).
文摘The bioactive constituents found in natural products(NPs)are crucial in protein-ligand interactions and drug discovery.However,it is difficult to identify ligand molecules from complex NPs that specifically bind to target protein,which often requires time-consuming and labor-intensive processes such as isolation and enrichment.To address this issue,in this study we developed a method that combines ultra-high performance liquid chromatography-electrospray ionization-mass spectrometry(UHPLCESI-MS)with molecular dynamics(MD)simulation to identify and observe,rapidly and efficiently,the bioactive components in NPs that bind to specific protein target.In this method,a specific protein target was introduced online using a three-way valve to form a protein-ligand complex.The complex was then detected in real time using high-resolution MS to identify potential ligands.Based on our method,only 10 molecules from green tea(a representative natural product),including the commonly reported epigallocatechin gallate(EGCG)and epicatechin gallate(ECG),as well as the previously unreported eepicatechin(4β→8)-epigallocatechin 3-O-gallate(EC-EGCG)and eepiafzelechin 3-O-gallate-(4β→8)-epigallocatechin 3-O-gallate(EFG-EGCG),were screened out,which could form complexes with Aβ_(1-42)(a representative protein target),and could be potential ligands of Aβ_(1-42).Among of them,EC-EGCG demonstrated the highest binding free energy with Aβ_(1-42)(−68.54±3.82 kcal/mol).On the other side,even though the caffeine had the highest signal among green tea extracts,it was not observed to form a complex with Aβ_(1-42).Compared to other methods such as affinity selection mass spectrometry(ASMS)and native MS,our method is easy to operate and interpret the data.Undoubtedly,it provides a new methodology for potential drug discovery in NPs,and will accelerate the research on screening ligands for specific proteins from complex NPs.
基金the Shanxi Province Science Foundation for Youth(No.202203021212408)the Shanxi Normal University Quality Curriculum(No.2019YZKC-13)the 1331 Project of Shanxi Province。
文摘Although supramolecular transformations have been emerged as a potent strategy for transitioning between various topologies,post-modification induced topological transformations have never been explored in the context of[2]catenane topologies.In this study,we present a novel supramolecular transformation between a Hopf link and a macrocycle,induced by the Diels–Alder click reaction.By strategically selecting the half-sandwich ruthenium binuclear fragment B as a rigid capping agent,we successfully integrated tetrazine moieties into the metalla[2]catenane structure.We demonstrated that the introduction of 2,5-norbornadiene(NBD)as an external stimulus allows for the transformation of the novel metalla[2]catenane,featuring reactive tetrazine sites,into the corresponding monomeric ring through postmodification for the first time.The synthetic results are corroborated by single-crystal X-ray diffraction analysis,ESI-TOF/MS,elemental analysis,and detailed solution-state NMR techniques.
基金supported by the National Key R&D Program of China(2021YFA1501200)the National Natural Science Foundation of China(NSFC U23B20169 and 22021004)the Project of R&D Department of CNPC(2020B-2011)。
文摘The influences of reaction temperature,duration,pressure,and catalyst concentration on the molecular transformation of residual slurry phase hydrocracking process were investigated.The molecular composition of the heteroatom compounds in the residue feedstock and its upgrading products were characterized using high-resolution Orbitrap mass spectrometry coupled with multiple ionization methods.The simultaneous promotion of cracking and hydrogenation reactions was observed with increasing of the reaction temperature and time.Specifically,there was a significant increase in the cracking degree of alkyl side chain,while the removal of low-condensation sulfur compounds such as sulfides and benzothiophenes was enhanced.In particular,the cracking reactions were more significantly facilitated by high temperatures,while an appropriately extended reaction time can result in the complete elimination of the aforementioned sulfur compounds with a lower degree of condensation.Under conditions of low hydrogen pressure and catalyst concentration,the products still exhibit a high relative abundance of easily convertible compounds such as sulfoxides,indicating a significant deficiency in the effectiveness of hydrogenation.The hydrogen pressure exhibits an optimal value,beyond which further increments have no effect on the composition and performance of the liquid product but can increase the yield of the liquid product.At significantly high catalyst concentration,the effect of desulfurization and deoxidation slightly diminishes,while the aromatic saturation of highly condensed compounds was notably enhanced.This hydrogenation saturation effect cannot be attained through manipulation of other operational parameters,thereby potentially benefiting subsequent product processing and utilization.This present study demonstrates a profound comprehension of the molecular-level residue slurry phase hydrocracking process,offering not only specific guide for process design and optimization but also valuable fundamental data for constructing reaction models at the molecular level.
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.
文摘Optically detected magnetic resonance(ODMR)has emerged as a powerful technique for quantum sensing,enabling high-sensitivity detection of physical quantities even at room temperature.Solid-state defects,such as nitrogen-vacancy(NV)centers in diamond,have demonstrated remarkable capabilities in this domain[1–4].However,these systems are limited by their rigid lattice structures and lack tunability.
文摘The concept of liquid-solid hybrid catalyst that featuring a truly homogeneous liquid microenvironment together with insoluble solid characteristics has been established recently by our group,which enables us to conveniently bridge the gap between homo-and heterogeneous catalysis.In this study,we extend this general concept to the confinement of molecular rhodium phosphine complexes,including Rh-TPPTS,Rh-TPPMS and Rh-SXP,for olefin hydroformylation reactions.A series of hybrid catalyst materials consisting a modulated liquid interior([BMIM]NTf_(2),[BMIM]PF_(6),[BMIM]BF_(4) or H_(2)O)and a permeable silica crust were fabricated through our developed Pickering emulsion-based method,showing 9.4–24.2-fold activity enhancement and significantly improved aldehyde selectivity(from 72.2%,61.8%to 86.6%)compared to their biphasic counterparts or traditional supported liquid phase system in the hydroformylation of 1-dodecene.Interestingly,the catalytic efficiency was demonstrated to be tunable by rationally engineering the thickness of porous crust and dimensions of the liquid pool.The thus-attained hybrid catalyst could also successfully catalyze the hydroformylation of a variety of olefin substrates and be recycled without a significant loss of activity for at least seven times.
基金supported by the National Natural Science Foundation of China(Nos.22173057,52130204,12074241,11929401,12311530675)Science and Technology Commission of Shanghai Municipality(Nos.21JC1402700,22XD1400900,20501130600,21JC1402600)High-Performance Computing Center,Shanghai Technical Service Center of Science and Engineering Computing,Shanghai University。
文摘Metal-ceramic composites combine the excellent properties of metals and ceramics,which have high strength,stability,and corrosion re-sistance.Al_(2)O_(3)/FeCo composites have been proven to be useful in ap-plications such as catalysts,mi-crowave absorption materials,and enhanced permeability dielectric.The understanding of the mechani-cal properties and dynamics at the atomic scale of the Al_(2)O_(3)/FeCo in-terface can promote the design and exploitment of metal-ceramic composites.In this work,we have obtained Young’s modulus and diffusion coefficient of the Al_(2)O_(3)/FeCo interface using molecular dynamics simulation,elucidated the structural characteristics of the Al_(2)O_(3)/FeCo interface at the atomic scale,and investigated the impact of atomic magnetism and the exter-nal magnetic field on the interface.Simulated results show that Young’s modulus of the Al_(2)O_(3)/FeCo interface is significantly improved compared with pure Al_(2)O_(3)and FeCo alloy at room and high temperatures.When the atomic magnetism and the external magnetic field are applied,Young’s modulus of the Al_(2)O_(3)/FeCo interface further increases to 612 GPa at 300 K and 602 GPa at 500 K.Moreover,the average density,diffusion coefficient,and radial distri-bution function are found to be modified substantially.This study will shed light on the atom-istic investigations of the metal-ceramic composites.
基金supported financially by the National Key R&D Program of China(Grant No.2023YFE0111500)the National Natural Science Foundation of China(Grant Nos.52321006,T2394480,T2394484,22109143,22475196,22479131)+11 种基金the Research Grants Council of Hong Kong(CRF C4005-22YRGC Senior Research Fellowship Scheme(SRFS2223-5S01))the Joint Fund for Provincial Science and Technology R&D Program of Henan(grant no.242301420051)the Opening Project of the State Key Laboratory of Advanced Technology for Float Glass(grant no.2022KF04)the China Postdoctoral Innovative Talent Support Program(grant no.BX2021271)the China Postdoctoral Science Foundation(grant no.2022M712851)the Graduate Education Reform Project of Henan Province(Grant No.2023SJGLX136Y)the Key R&D Special Program of Henan Province(Grant No.241111242000)the Program for Science&Technology Innovation Talents in Universities of Henan Province(Grant No.25HASTIT005)the Training Plan for Young Backbone Teachers of Zhengzhou University(Grant No.2023ZDGGJS017)the Joint Research Project of Puyang ShengtongJuyuan New Materials Co.Ltd.(Grant No.20230128A)。
文摘Wide-bandgap mixed-halide perovskites,particularly CsPbIBr_(2),hold great promise for multi-junction solar cells due to their well-matched bandgap and all-inorganic material system.However,their inherent susceptibility to light-induced phase segregation(LIPS)limits efficiency and stability.In this work,we investigate the effect of three organic additives-4-cyclopentene-1,3-dione(CPD),maleimide(HPD),and 3,4-dibromo-1H-pyrrole-2,5(2H,5H)-dione(BrPD)-on LIPS in wide-bandgap CsPbIBr_(2)perovskite films.The additives form various chemical interactions,including coordination bonds,hydrogen bonds,and ionic bonds,with I^(-)and undercoordinated Pb^(2+)ions,among which BrPD has the strongest interaction.This interaction regulates crystallization and improves film morphology.The BrPD-modified films have the largest grain size and the highest light stability,suppressing LIPS,enhancing carrier transfer,and improving device performance.BrPD-modified CsPbIBr_(2)-based solar cells achieve a power conversion efficiency(PCE)of 11.34%,outperforming the control(8.96%)and other additives.Moreover,BrPDmodified devices show excellent stability,retaining 94%of their initial PCE after 60 min of continuous light exposure.This work highlights the potential of strategically selected organic additives to enhance the stability and performance of perovskite solar cells,offering valuable insights for the design of high-efficiency and long-lasting perovskite-based optoelectronic devices.
基金supported by the Guangdong Provincial Key Laboratory IRADS(2022B1212010006,R0400001-22)。
文摘Obesity has become a significant global public health issue.Previous studies have found that the Chenpi has the anti-obesity activity.However,the anti-obesity phytochemicals and their mechanisms are still unclear.This study investigated the anti-obesity phytochemicals and molecular mechanisms involved in treating obesity by Chenpi through network pharmacology and molecular docking.A total of 17 bioactive phytochemicals from Chenpi and its 475 related anti-obesity targets have been identified.The KEGG pathway analysis showed that the PI3K/Akt signaling pathway,MAPK signaling pathway,AMPK signaling pathway,and nuclear factor kappa B signaling pathway are the main signaling pathways involved in the anti-obesity effect of Chenpi.According to molecular docking analysis,the phytochemicals of Chenpi can bind to central anti-obesity targets.Based on the ADMET analysis and network pharmacology results,tangeretin exhibited the lowest predicted toxicity and potential for anti-obesity effects.In the in vitro lipid accumulation model,tangeretin effectively suppressed the free fatty acid-induced lipid in Hep G2 cells by upregulating the PI3K/Akt/GSK3βsignaling pathway based on the result of q-PCR and Western blotting.The outcomes of this research give insights for future research on the anti-obesity phytochemicals and molecular mechanisms derived from Chenpi,also providing the theoretical basis for developing anti-obesity functional foods based on Chenpi.
基金supported from the NSFC(Nos.22302038 and 22406027).
文摘The tightness of π-π stacking in supramolecular organic semiconductors plays a crucial role in governing the spatial separation and migration dynamics of photogenerated charge carriers,ultimately determining their photocatalytic performance.To achieve closeπ-πstacking,the suitable design of molecular structure is essential.Therefore,two isomers of pyridine carboxylic acid-modified perylene monoimide(PMI)were designed and synthesized,namely PM5A and PM6A.In aqueous solution,these molecules self-assemble into aggregates,which exhibit distinct stacking properties and optical characteristics.Upon photoexcitation,the looseπ-πstacking of PM5A favors the generation of charge-transfer excitons(CTEs)over charge-separation excitons(CSEs).In contrast,PM6A,stabilized by intermolecular hydrogen bonds and possessing closeπ-πstacking,undergoes efficient charge separation(CS)to produce CSEs within 4.5 picoseconds.When incorporated into metal-insulatorsemiconductor(MIS)photosystems with polyvinylpyrrolidone(PVP)-capped Pt,the Pt/PVP/PM6A system demonstrates a hydrogen evolution rate(HER)of 8100μmol g^(-1)h^(-1),nearly five times higher than that of the Pt/PVP/PM5A system.Additionally,the maximum apparent quantum efficiency(AQE)reaches approximately 2.1%under irradiation with light of a single wavelength of λ=425 nm.
基金supported by National Research Foundation of Korea(NRF)(RS-2024-00336766 and RS-2023-00301974)support of the National Research Foundation of Korea(NRF)grant funded by the Korea government(MSIT)(RS-2023-00220748)。
文摘Since 2009,perovskite solar cells(PSCs)have advanced significantly,achieving over 26%efficiency for single-junction devices and exceeding 34%for silicon-perovskite tandem cells.Despite these successes,the weak adhesion of C_(60)to perovskite layers,due to van der Waals interactions,hinders long-term stability.In this study,we introduce electron-deficient intermolecular adhesives(EDIAs)as a novel interlayer material to enhance adhesion between perovskite and C_(60)layers.Comprehensive analyses,including density functional theory calculations,microscopy,and spectroscopy,demonstrate that EDIAs,particularly NDI-C9-Ace comprising of three key functionalities:aπ-electron-deficient arene core,a hydrophobic passivation core,and a secondary-bond anchoring core,significantly improve bonding strength and recombination passivation.This leads to enhanced efficiency as well as enhanced mechanical and photochemical stability in PSCs.Long-term stability tests further confirm the superior durability of EDIA-enhanced devices.This study highlights EDIA as a promising strategy for enhancing the robustness and efficiency of PSCs.
基金funded by the Deanship of Graduate Studies and Scientific Research at Jouf University under grant No.(DGSSR-2024-02-01137).
文摘Sonic Hedgehog Medulloblastoma(SHH-MB)is one of the four primary molecular subgroups of Medulloblastoma.It is estimated to be responsible for nearly one-third of allMB cases.Using transcriptomic and DNA methylation profiling techniques,new developments in this field determined four molecular subtypes for SHH-MB.SHH-MB subtypes show distinct DNAmethylation patterns that allow their discrimination fromoverlapping subtypes and predict clinical outcomes.Class overlapping occurs when two or more classes share common features,making it difficult to distinguish them as separate.Using the DNA methylation dataset,a novel classification technique is presented to address the issue of overlapping SHH-MBsubtypes.Penalizedmultinomial regression(PMR),Tomek links(TL),and singular value decomposition(SVD)were all smoothly integrated into a single framework.SVD and group lasso improve computational efficiency,address the problem of high-dimensional datasets,and clarify class distinctions by removing redundant or irrelevant features that might lead to class overlap.As a method to eliminate the issues of decision boundary overlap and class imbalance in the classification task,TL enhances dataset balance and increases the clarity of decision boundaries through the elimination of overlapping samples.Using fivefold cross-validation,our proposed method(TL-SVDPMR)achieved a remarkable overall accuracy of almost 95%in the classification of SHH-MB molecular subtypes.The results demonstrate the strong performance of the proposed classification model among the various SHH-MB subtypes given a high average of the area under the curve(AUC)values.Additionally,the statistical significance test indicates that TL-SVDPMR is more accurate than both SVM and random forest algorithms in classifying the overlapping SHH-MB subtypes,highlighting its importance for precision medicine applications.Our findings emphasized the success of combining SVD,TL,and PMRtechniques to improve the classification performance for biomedical applications with many features and overlapping subtypes.
