Recent advances in research on extracellular vesicles have significantly enhanced their potential as therapeutic agents for neurological diseases.Owing to their therapeutic properties and ability to cross the blood–b...Recent advances in research on extracellular vesicles have significantly enhanced their potential as therapeutic agents for neurological diseases.Owing to their therapeutic properties and ability to cross the blood–brain barrier,extracellular vesicles are recognized as promising drug delivery vehicles for various neurological conditions,including ischemic stroke,traumatic brain injury,neurodegenerative diseases,glioma,and psychosis.However,the clinical application of natural extracellular vesicles is hindered by their limited targeting ability and short clearance from the body.To address these limitations,multiple engineering strategies have been developed to enhance the targeting capabilities of extracellular vesicles,thereby enabling the delivery of therapeutic contents to specific tissues or cells.Therefore,this review aims to highlight the latest advancements in natural and targeting-engineered extracellular vesicles,exploring their applications in treating traumatic brain injury,ischemic stroke,Parkinson's disease,Alzheimer's disease,amyotrophic lateral sclerosis,glioma,and psychosis.Additionally,we summarized recent clinical trials involving extracellular vesicles and discussed the challenges and future prospects of using targeting-engineered extracellular vesicles for drug delivery in treating neurological diseases.This review offers new insights for developing highly targeted therapies in this field.展开更多
Radiative cooling systems(RCSs)possess the distinctive capability to dissipate heat energy via solar and thermal radiation,making them suitable for thermal regulation and energy conservation applications,essential for...Radiative cooling systems(RCSs)possess the distinctive capability to dissipate heat energy via solar and thermal radiation,making them suitable for thermal regulation and energy conservation applications,essential for mitigating the energy crisis.A comprehensive review connecting the advancements in engineered radiative cooling systems(ERCSs),encompassing material and structural design as well as thermal and energy-related applications,is currently absent.Herein,this review begins with a concise summary of the essential concepts of ERCSs,followed by an introduction to engineered materials and structures,containing nature-inspired designs,chromatic materials,meta-structural configurations,and multilayered constructions.It subsequently encapsulates the primary applications,including thermal-regulating textiles and energy-saving devices.Next,it highlights the challenges of ERCSs,including maximized thermoregulatory effects,environmental adaptability,scalability and sustainability,and interdisciplinary integration.It seeks to offer direction for forthcoming fundamental research and industrial advancement of radiative cooling systems in real-world applications.展开更多
A new manufactured soil product (Turba) was produced using acidified bauxite residue into which 10% green waste compost had been incorporated. A laboratory/greenhouse experiment was carried out to determine if sand co...A new manufactured soil product (Turba) was produced using acidified bauxite residue into which 10% green waste compost had been incorporated. A laboratory/greenhouse experiment was carried out to determine if sand could be used as an ingredient or an amendment for Turba. Sand was added at rates of 0%, 5%, 10%, 25, 50% and 75% (w/w) in two different ways 1) by incorporating it into the Turba during its manufacture (IN) or 2) by mixing it with Turba aggregates after their manufacture (OUT). Incorporation of sand into Turba aggregates (IN) decreased the percentage of sample present as large aggregates (2 - 4 mm dia.) after crushing and sieving (<4 mm) and also reduced the stability of 2 - 4 mm dia. formed aggregates (to dry/wet sieving) and are therefore not recommended. In a 16-week greenhouse study, ryegrass shoot yields were greater in Turba than in sand [and decreased with increasing sand additions (OUT)] while root dry matter showed the opposite trend. The greater grass growth in Turba than sand was attributed to incipit water stress in plants grown in sand and this may have promoted greater allocation of assimilates to roots resulting in a greater root-to-top mass ratio. The much lower macroporosity in Turba coupled with the solid cemented nature of Turba aggregates resulted in production of thinner roots and therefore greater root length than in sand. Turba (manufactured from bauxite residue and compost added at 10% w/w) is a suitable medium for plant growth and there is no advantage in incorporating sand into, or with, the Turba aggregates.展开更多
Chemically engineered extracts represent a promising source of new bioactive semi-synthetic molecules.Prepared through direct derivatization of natural extracts,they can include constituents enriched with elements and...Chemically engineered extracts represent a promising source of new bioactive semi-synthetic molecules.Prepared through direct derivatization of natural extracts,they can include constituents enriched with elements and sub-structures that are less common in natural products compared to drugs.Fourteen such extracts were prepared through sequential reactions with hydrazine and a fluorinating reagent,and their α-glucosidase inhibition properties were compared.For the most bioactive mixture,a chemically modified propolis extract,enzyme inhibition increased 22 times due to the reaction sequence.Bio-guided fractionation led to the isolation of a new fluorinated pyrazole produced within the extract by chemical transformation of the flavonoid chrysin.The inhibitor results from the action of the two reagents used on four common functional groups present in natural products(carbonyl,phenol,aromatic carbon,and a double bond).The reactions led to the opening of a 6-member oxygenated heterocycle to produce a 5-member nitrogenated one,as well as the dehydroxylation and fluorination in two different positions of one of the aromatic rings of the natural starting material,all within a complex mixture of natural products.Overall,these transformations led to an approximately 20-fold increase in the α-glucosidase inhibition by the isolated inhibitor compared to its natural precursor.展开更多
In 1891,a New York surgeon named William Coley injected cancer patients with live bacteria,observing with fascination as some tumors shrank amid raging fevers.His crude experiments-later deemed reckless-nonetheless re...In 1891,a New York surgeon named William Coley injected cancer patients with live bacteria,observing with fascination as some tumors shrank amid raging fevers.His crude experiments-later deemed reckless-nonetheless revealed a tantalizing truth:The immune system,when properly provoked,could attack cancer.Over a century later,researchers have transformed this observation into a precision strike force.展开更多
Up to now,numerous emerging methods of cancer treatment including chemodynamic therapy,photothermal therapy,photodynamic therapy,sonodynamic therapy,immunotherapy and chemotherapy have rapidly entered a new stage of d...Up to now,numerous emerging methods of cancer treatment including chemodynamic therapy,photothermal therapy,photodynamic therapy,sonodynamic therapy,immunotherapy and chemotherapy have rapidly entered a new stage of development.However,the single treatment mode is often constrained by the complex tumor microenvironment.Recently,the nanomaterials and nanomedicine have emerged as promising avenues to overcome the limitation in cancer theranostics.Especially,metal-organic frameworks(MOFs)have gained considerable interests in cancer therapy because of their customizable morphologies,easy functionalization,large specific surface area,and good biocompatibility.Among these MOFs,iron-based MOFs(Fe-MOFs)are particularly promising for cancer treatment due to their properties as nano-photosensitizers,peroxidase-like activity,bioimaging contrast capabilities,and biodegradability.Utilizing their structural regularity and synthetic tunability,Fe-MOFs can be engineered to incorporate organic molecules or other inorganic nanoparticles,thereby creating multifunctional nanoplatforms for single or combined theranostic modes.Herein,the minireview focuses on the recent advancements of the Fe-MOFs-based nanoplatforms for self-enhanced imaging and treatment at tumor sites.Furthermore,the clinical research development of Fe-MOFs-based nanoplatforms is discussed,addressing key challenges and innovations for the future.Our review aims to provide novice researchers with a foundational understanding of advanced cancer theranostic modes and promote their clinical applications through the modification of Fe-MOFs.展开更多
As industrial pollution continues to contaminate ecosystems worldwide,researchers have engineered a breakthrough solution:a single bacterial strain that can tackle five persistent organic pollutants at once.
Immunotherapy offers the promise of a potential cure for cancer,yet achieving the desired therapeutic effect can be challenging due to the immunosuppressive tumor microenvironments(TMEs) present in some tumors.Therefo...Immunotherapy offers the promise of a potential cure for cancer,yet achieving the desired therapeutic effect can be challenging due to the immunosuppressive tumor microenvironments(TMEs) present in some tumors.Therefore,robust immune system activation is crucial to enhance the efficacy of cancer immunotherapy in clinical applications.Bacteria have shown the ability to target the hypoxic TMEs while activating both innate and adaptive immune responses.Engineered bacteria,modified through chemical or biological methods,can be endowed with specific physiological properties,such as diverse surface antigens,metabolites,and improved biocompatibility.These unique characteristics give engineered bacteria distinct advantages in stimulating anti-cancer immune responses.This review explores the potential regulatory mechanisms of engineered bacteria in modulating both innate and adaptive immunity while also forecasting the future development and challenges of using engineered bacteria in clinical cancer immunotherapy.展开更多
Precancerous lesions of gastric cancer(PLGC)are crucial for the progression to gastric cancer,and early intervention in PLGC is pivotal in preventing its development into gastric cancer.In order to illustrate the mole...Precancerous lesions of gastric cancer(PLGC)are crucial for the progression to gastric cancer,and early intervention in PLGC is pivotal in preventing its development into gastric cancer.In order to illustrate the molecular mechanisms underlying PLGC and the roles of associated genes within these lesions,genetically engineered mouse models(GEMMs)have been developed.We systematically summarize the current GEMMs,and highlight the principal pathological mechanisms involved,including gastrin/gastric acid balance,inflammatory factors,the interplay between cancer-promoting and cancer-suppressing genes,and apoptotic pathways.We further discuss the mechanisms involved in the existing GEMMs of PLGC.展开更多
Practical applications of desulfurization gypsum are limited owing to its brittleness and low strength.To overcome these challenges,researchers have developed engineered desulfurization gypsum composites(EDGCs)by inco...Practical applications of desulfurization gypsum are limited owing to its brittleness and low strength.To overcome these challenges,researchers have developed engineered desulfurization gypsum composites(EDGCs)by incorporating ultrahigh molecular weight polyethylene(UHMWPE)fiber and sulfoaluminate cement(SAC).The mix ratio was optimized using response surface methodology(RSM).Experimental testing of EDGC under compressive and tensile loads led to the creation of a regression model that investigates the influence of variables and their interactions on the material’s compressive and tensile strengths.Additionally,microscopic morphology and hydration product composition were analyzed to explore the influence mechanism.The results indicated that EDGC’s compressive strength increased by up to 38.4%owing to a decreased water-binder ratio and higher SAC content.Similarly,tensile strength increased by up to 38.6%owing to increased SAC and fiber content.Moreover,EDGC demonstrated excellent strain-hardening behavior and multiple cracking characteristics,achieving a maximum tensile strain of nearly 3%.The research findings provide valuable insights for optimizing the performance of desulfurization gypsum.展开更多
Parkinson’s disease is characterized by synucleinopathy-associated neurodegeneration.Previous studies have shown that glucagon-like peptide-1(GLP-1)has beneficial effects in a mouse model of Parkinson’s disease indu...Parkinson’s disease is characterized by synucleinopathy-associated neurodegeneration.Previous studies have shown that glucagon-like peptide-1(GLP-1)has beneficial effects in a mouse model of Parkinson’s disease induced by 1-methyl-4-phenyl-1,2,3,6-tetrahydropyridine.However,the effect of GLP-1 on intrinsic synuclein malfunction remains unclear.In this study,we investigated the effect of Lactococcus lactis MG1363-pMG36e-GLP-1 on parkinsonism in SncaA53T transgenic mice and explored the underlying mechanisms.Our data showed that Lactococcus lactis MG1363-pMG36e-GLP-1 inhibited dopaminergic neuronal death,reduced pathological aggregation ofα-synuclein,and decreased movement disorders in SncaA53T transgenic mice.Furthermore,Lactococcus lactis MG1363-pMG36e-GLP-1 downregulated lipopolysaccharide-related inflammation,reduced cerebral activation of microglia and astrocytes,and promoted cell survival via the GLP-1 receptor/PI3K/Akt pathway in the substantia nigra.Additionally,Lactococcus lactis MG1363-pMG36e-GLP-1 decreased serum levels of pro-inflammatory molecules including lipopolysaccharide,lipopolysaccharide binding protein,interleukin-1β,and interleukin-6.Gut histopathology and western blotting further revealed that Lactococcus lactis MG1363-pMG36e-GLP-1 increased the expression of gut integrity-related proteins and reduced lipopolysaccharide-related inflammation by reversing gut dysbiosis in SncaA53T transgenic mice.Our findings showed that the beneficial effect of Lactococcus lactis MG1363-pMG36e-GLP-1 on parkinsonism traits in SncaA53T transgenic mice is mediated by microglial polarization and the reversal of dysbiosis.Collectively,our findings suggest that Lactococcus lactis MG1363-pMG36e-GLP-1 is a promising therapeutic agent for the treatment of Parkinson’s disease.展开更多
Ischemic stroke is a secondary cause of mortality worldwide,imposing considerable medical and economic burdens on society.Extracellular vesicles,serving as natural nanocarriers for drug delivery,exhibit excellent bioc...Ischemic stroke is a secondary cause of mortality worldwide,imposing considerable medical and economic burdens on society.Extracellular vesicles,serving as natural nanocarriers for drug delivery,exhibit excellent biocompatibility in vivo and have significant advantages in the management of ischemic stroke.However,the uncertain distribution and rapid clearance of extracellular vesicles impede their delivery efficiency.By utilizing membrane decoration or by encapsulating therapeutic cargo within extracellular vesicles,their delivery efficacy may be greatly improved.Furthermore,previous studies have indicated that microvesicles,a subset of large-sized extracellular vesicles,can transport mitochondria to neighboring cells,thereby aiding in the restoration of mitochondrial function post-ischemic stroke.Small extracellular vesicles have also demonstrated the capability to transfer mitochondrial components,such as proteins or deoxyribonucleic acid,or their sub-components,for extracellular vesicle-based ischemic stroke therapy.In this review,we undertake a comparative analysis of the isolation techniques employed for extracellular vesicles and present an overview of the current dominant extracellular vesicle modification methodologies.Given the complex facets of treating ischemic stroke,we also delineate various extracellular vesicle modification approaches which are suited to different facets of the treatment process.Moreover,given the burgeoning interest in mitochondrial delivery,we delved into the feasibility and existing research findings on the transportation of mitochondrial fractions or intact mitochondria through small extracellular vesicles and microvesicles to offer a fresh perspective on ischemic stroke therapy.展开更多
Selective catalytic reduction of NO_(x) with CO(CO-SCR)is a process that purifies both NO and CO pollutants through a catalytic reaction.Specifically,the cleavage of NO on the catalyst surface is crucial for promoting...Selective catalytic reduction of NO_(x) with CO(CO-SCR)is a process that purifies both NO and CO pollutants through a catalytic reaction.Specifically,the cleavage of NO on the catalyst surface is crucial for promoting the reaction.During the reaction,the presence of oxygen vacancies can extract oxygen from NO,thereby facilitating the cleavage of NO on the catalyst surface.Thus,the formation of oxygen vacancies is key to accelerating the CO-SCR reaction,with different types of oxygen vacancies being more conducive to their generation.In this study,Rh/CeCuO_(x) catalysts were synthesized using the co-crystallization and impregnation methods,and asymmetric oxygen vacancies were induced through hydrogen thermal treatment.This structuralmodification was aimed at regulating the behavior of NO on the catalyst surface.The Rh/Ce0.95Cu0.05O_(x)-H_(2) catalyst exhibited the best performance in CO-SCR,achieving above 90%NO conversion at 162℃.Various characterization techniques showed that the H_(2) treatment effectively reduced some of the CuO and Rh_(2)O_(3),creating asymmetric oxygen vacancies that accelerated the cleavage of NO on the catalyst surface,rather than forming difficult-to-decompose nitrates.This study offers a novel approach to constructing oxygen vacancies in new CO-SCR catalysts.展开更多
Craniofacial muscles are essential components of the skeletal muscular system that contribute to important physiological processes.Severe trauma can induce craniofacial volumetric muscle loss(VML),which impairs muscle...Craniofacial muscles are essential components of the skeletal muscular system that contribute to important physiological processes.Severe trauma can induce craniofacial volumetric muscle loss(VML),which impairs muscle regeneration,causes facial muscular deformities and functional disability,and leads to psychosocial consequences such as isolation and depression.Conventional therapies involving muscle flap transposition or autologous tissue grafting achieve morphological repair but are ineffective in restoring muscle function,resulting in donor site injury and sensory deficit.In this study,we successfully constructed a biomimetically engineered muscle tissue that integrates myofiber alignment,effective innervation,and blood perfusion to promote multi-tissue regeneration in the masseter area in vivo,enabling functional regeneration.Using light-controlled micropatterning technology,we constructed mature muscle fibers with oriented alignment and established a neuromuscular co-culture system for in vitro neuromuscular junction reconstruction.Furthermore,we designed and fabricated a vascular network structure to promote tissue vascularization using hydrogel as the vehicle for assembling the composite engineered tissue.Using this technology,the shape and dimension of the constructed entity can be customized to address various muscle defects,enabling individualized repair.This study offers a promising novel strategy for tissue regeneration that breaks through the current challenges in the treatment of craniofacial VML.展开更多
N-substituted furfurylamines(FAs)are valuable precursors for producing pharmacologically active compounds and polymers.However,enzymatic synthesis of the type of chemicals is still in its infancy.Here we report an imi...N-substituted furfurylamines(FAs)are valuable precursors for producing pharmacologically active compounds and polymers.However,enzymatic synthesis of the type of chemicals is still in its infancy.Here we report an imine reductase from Streptomyces albidoflavus(SaIRED)for the reductive amination of biobased furans.A simple,fast and interference-resistant high-throughput screening(HTS)method was developed,based on the coloration reaction of carbonyl compounds with 2,4-dinitrophenylhydrazine.The reductive amination activity of IREDs can be directly indicated by a colorimetric assay.With the reductive amination of furfural with allylamine as the model reaction,SaIRED with the activity of 4.8 U mg^(-1) was subjected to three rounds of protein engineering and screening by this HTS method,affording a high-activity tri-variant I127V/D241A/A242T(named M3,20.2 U mg^(-1)).The variant M3 showed broad substrate scope,and enabled efficient reductive amination of biobased furans with a variety of amines including small aliphatic amines and sterically hindered amines,giving the target FAs in yields up to>99%.In addition,other variants were identified for preparative-scale synthesis of commercially interesting amines such as N-2-(methylsulfonyl)ethyl-FA by the screen method,with isolated yields up to 87%and turnover numbers up to 9700 for enzyme.Gram-scale synthesis of N-allyl-FA,a valuable building block and potential polymer monomer,was implemented at 0.25 mol L^(-1) substrate loading by a whole-cell catalyst incorporating variant M3,with 4.7 g L^(-1) h^(-1) space-time yield and 91%isolated yield.展开更多
Heme peroxygenases exhibit remarkable catalytic versatility in facilitating a wide array of oxidative reactions under mild conditions,eliminating the need for coenzymes and intricate electron transport systems.This un...Heme peroxygenases exhibit remarkable catalytic versatility in facilitating a wide array of oxidative reactions under mild conditions,eliminating the need for coenzymes and intricate electron transport systems.This unique character underscores their essentiality and potential as promising tools in synthetic biology.Recent advancements in enzyme engineering have significantly enhanced the catalytic performance of both natural and artificial peroxygenases.Extensive engineering efforts have been directed towards unspecific peroxygenases and fatty acid peroxygenases,aiming to expand their substrate specificities,and enhance reaction selectivities,as well as increase enzyme stability.Furthermore,innovative strategies such as dual-functional small molecule-assisted systems and H_(2)O_(2) tunnel engineering have been harnessed to transform P450 monooxygenases into highly efficient peroxygenases,capable of catalyzing reactions with a variety of unnatural substrates.This review consolidates the latest progress in the engineered and artificial heme peroxygenases,emphasizing their catalytic performances as potent biocatalysts for sustainable organic synthesis.展开更多
Covalent organic frameworks(COFs)play a crucial role in metal-free electrocatalysts for promoting oxygen reduction reaction(ORR)due to their adjustable skeleton structure and catalytic activity.While it is true that n...Covalent organic frameworks(COFs)play a crucial role in metal-free electrocatalysts for promoting oxygen reduction reaction(ORR)due to their adjustable skeleton structure and catalytic activity.While it is true that numerous studies have explored COFs for ORR,the critical gap by providing a systematic framework for ligand-driven electronic state manipulation is essential for designing highly active COF-based ORR catalysts.Herein,a series of COF-based metal-free materials have been conceived and synthesized by linkage-engineered strategy with dicarboxaldehyde(BPC),bipyridine-dicarbaldehyde(BPA)and benzodithiophene(BDA)as electronic linkages.Consequently,by incorporating different linkages into COFs,the surface area,electronic state,hydrophobic properties and affinities towards intermediates are optimized.Notably,the benzodithiophene-linked COF(denoted as BDA-COF)has greater catalytic ability with a half-wave potential of 0.74 V vs.RHE and an onset potential of 0.86 V vs.RHE than dicarboxaldehyde(denoted as BPC-COF)and dicarbaldehyde(denoted as BPA-COF).Relevant characterizations,in situ techniques and theoretical calculations confirm that thiophene-S-based COF promotes the electronic migration and enhances the interaction with the intermediate.The result provides insight into for illustration of a high-performance COF-based electrocatalyst via a linkage-engineered approach.展开更多
The inherent complexities of excitable cardiac,nervous,and skeletal muscle tissues pose great challenges in constructing artificial counterparts that closely resemble their natural bioelectrical,structural,and mechani...The inherent complexities of excitable cardiac,nervous,and skeletal muscle tissues pose great challenges in constructing artificial counterparts that closely resemble their natural bioelectrical,structural,and mechanical properties.Recent advances have increasingly revealed the beneficial impact of bioelectrical microenvironments on cellular behaviors,tissue regeneration,and therapeutic efficacy for excitable tissues.This review aims to unveil the mechanisms by which electrical microenvironments enhance the regeneration and functionality of excitable cells and tissues,considering both endogenous electrical cues from electroactive biomaterials and exogenous electrical stimuli from external electronic systems.We explore the synergistic effects of these electrical microenvironments,combined with structural and mechanical guidance,on the regeneration of excitable tissues using tissue engineering scaffolds.Additionally,the emergence of micro/nanoscale bioelectronics has significantly broadened this field,facilitating intimate interactions between implantable bioelectronics and excitable tissues across cellular,tissue,and organ levels.These interactions enable precise data acquisition and localized modulation of cell and tissue functionalities through intricately designed electronic components according to physiological needs.The integration of tissue engineering and bioelectronics promises optimal outcomes,highlighting a growing trend in developing living tissue construct-bioelectronic hybrids for restoring and monitoring damaged excitable tissues.Furthermore,we envision critical challenges in engineering the next-generation hybrids,focusing on integrated fabrication strategies,the development of ionic conductive biomaterials,and their convergence with biosensors.展开更多
The atomic-level exploration of structure-property correlations poses significant challenges in establishing precise design principles for electrocatalysts targeting efficient CO_(2)conversion.This study demonstrates ...The atomic-level exploration of structure-property correlations poses significant challenges in establishing precise design principles for electrocatalysts targeting efficient CO_(2)conversion.This study demonstrates how controlled exposure of metal sites governs CO_(2)electroreduction performance through two octanuclear bismuth-oxo clusters with distinct architectures.The Bi_(8)-DMF cluster,constructed using tert–butylthiacalix[4]arene(TC4A)as the sole ligand,features two surface-exposed Bi active sites,while the dual-ligand Bi_(8)-Fc(with TC4A/ferrocene carboxylate)forms a fully encapsulated structure.Electrocatalytic tests reveal Bi_(8)-DMF achieves exceptional formate selectivity(>90%Faradaic efficiency)across a broad potential window(-0.9 V to-1.6 V vs.RHE)with 20 h stability,outperforming Bi_(8)-Fc(60%efficiency at-1.5 V).Theoretical calculations attribute Bi_(8)-DMF's superiority to exposed Bi sites that stabilize the critical*OCHO intermediate via optimized orbital interactions.This work provides crucial guidance for polynuclear catalyst design:moderate exposure of metal active sites significantly enhances CO_(2)reduction performance.展开更多
Engineering a phosphide-based multifunctional heterostructure with high redox activity,stability,and efficient charge kinetics for both supercapacitors and water splitting remains challenging due to sluggish reaction ...Engineering a phosphide-based multifunctional heterostructure with high redox activity,stability,and efficient charge kinetics for both supercapacitors and water splitting remains challenging due to sluggish reaction kinetics and structural instability.This study overcomes these challenges by implementing a rapid,energy-efficient approach to develop a MOF-modulated MnP@Cu_(3)P heterostructure via a hydrothermal process followed by high-temperature phosphorization.The heterostructure demonstrates superior redox activity with enhanced stability and improved charge kinetics achieving a high specific capacity of 1131 C g^(-1)as supported by density functional theory findings of increased DOS near the Fermi level.The flexible supercapacitor achieves a peak energy density of 99.20 Wh kg^(-1)and power density of 15.40 kW kg^(-1).Simultaneously,it shows exceptional hydrogen evolution reaction performance with an overpotential of η_(10)=44 mV and η_(1000)=225 mV,attributed to electron transfer from Cu to Mn via P bridging,which shifts the active centers from Mn and Cu sites to the P site,confirmed by lowestΔG_(H)^(*)value of-0.16 eV.The overall water-splitting in full-cell electrocatalyzer delivers cell voltage of E_(20)=1.48 V and E_(1000)=1.88 V and setting a new standard in solar-to-hydrogen efficiency of 20.02%.The electrolyzer cell maintained prolonged stability at industrial-scale current densities of 1.0 A cm^(-2)under alkaline electrolysis achieving an estimated hydrogen production cost of INR 146.7 or US$1.67per kilogram aligning with the cost target of $2/kg by 2026 established by the Clean Hydrogen Electrolysis Program,U.S.department of energy.Furthermore,real-phase demonstration highlights the uninterrupted hydrogen production till 6-minutes via connecting this electrocatalyzer with photovoltaic-charged supercapacitors effectively addressing solar intermittency and gas fluctuations challenges in water-electrolysis.展开更多
基金supported by the National Natural Science Foundation of China,Nos.82171363,82371381(to PL),82171458(to XJ)Key Research and Development Project of Shaa nxi Province,Nos.2024SF-YBXM-404(to KY)。
文摘Recent advances in research on extracellular vesicles have significantly enhanced their potential as therapeutic agents for neurological diseases.Owing to their therapeutic properties and ability to cross the blood–brain barrier,extracellular vesicles are recognized as promising drug delivery vehicles for various neurological conditions,including ischemic stroke,traumatic brain injury,neurodegenerative diseases,glioma,and psychosis.However,the clinical application of natural extracellular vesicles is hindered by their limited targeting ability and short clearance from the body.To address these limitations,multiple engineering strategies have been developed to enhance the targeting capabilities of extracellular vesicles,thereby enabling the delivery of therapeutic contents to specific tissues or cells.Therefore,this review aims to highlight the latest advancements in natural and targeting-engineered extracellular vesicles,exploring their applications in treating traumatic brain injury,ischemic stroke,Parkinson's disease,Alzheimer's disease,amyotrophic lateral sclerosis,glioma,and psychosis.Additionally,we summarized recent clinical trials involving extracellular vesicles and discussed the challenges and future prospects of using targeting-engineered extracellular vesicles for drug delivery in treating neurological diseases.This review offers new insights for developing highly targeted therapies in this field.
基金support from the Contract Research(“Development of Breathable Fabrics with Nano-Electrospun Membrane”,CityU ref.:9231419“Research and application of antibacterial and healing-promoting smart nanofiber dressing for children’s burn wounds”,CityU ref:PJ9240111)+1 种基金the National Natural Science Foundation of China(“Study of Multi-Responsive Shape Memory Polyurethane Nanocomposites Inspired by Natural Fibers”,Grant No.51673162)Startup Grant of CityU(“Laboratory of Wearable Materials for Healthcare”,Grant No.9380116).
文摘Radiative cooling systems(RCSs)possess the distinctive capability to dissipate heat energy via solar and thermal radiation,making them suitable for thermal regulation and energy conservation applications,essential for mitigating the energy crisis.A comprehensive review connecting the advancements in engineered radiative cooling systems(ERCSs),encompassing material and structural design as well as thermal and energy-related applications,is currently absent.Herein,this review begins with a concise summary of the essential concepts of ERCSs,followed by an introduction to engineered materials and structures,containing nature-inspired designs,chromatic materials,meta-structural configurations,and multilayered constructions.It subsequently encapsulates the primary applications,including thermal-regulating textiles and energy-saving devices.Next,it highlights the challenges of ERCSs,including maximized thermoregulatory effects,environmental adaptability,scalability and sustainability,and interdisciplinary integration.It seeks to offer direction for forthcoming fundamental research and industrial advancement of radiative cooling systems in real-world applications.
文摘A new manufactured soil product (Turba) was produced using acidified bauxite residue into which 10% green waste compost had been incorporated. A laboratory/greenhouse experiment was carried out to determine if sand could be used as an ingredient or an amendment for Turba. Sand was added at rates of 0%, 5%, 10%, 25, 50% and 75% (w/w) in two different ways 1) by incorporating it into the Turba during its manufacture (IN) or 2) by mixing it with Turba aggregates after their manufacture (OUT). Incorporation of sand into Turba aggregates (IN) decreased the percentage of sample present as large aggregates (2 - 4 mm dia.) after crushing and sieving (<4 mm) and also reduced the stability of 2 - 4 mm dia. formed aggregates (to dry/wet sieving) and are therefore not recommended. In a 16-week greenhouse study, ryegrass shoot yields were greater in Turba than in sand [and decreased with increasing sand additions (OUT)] while root dry matter showed the opposite trend. The greater grass growth in Turba than sand was attributed to incipit water stress in plants grown in sand and this may have promoted greater allocation of assimilates to roots resulting in a greater root-to-top mass ratio. The much lower macroporosity in Turba coupled with the solid cemented nature of Turba aggregates resulted in production of thinner roots and therefore greater root length than in sand. Turba (manufactured from bauxite residue and compost added at 10% w/w) is a suitable medium for plant growth and there is no advantage in incorporating sand into, or with, the Turba aggregates.
基金support by Universidad Nacional de Rosario(80020180300114UR and 80020180100128UR)CONICET(PIP No 11220200102423)FONCYT(PICT2019-02232 and PICT2021-1034)for the development of this work.
文摘Chemically engineered extracts represent a promising source of new bioactive semi-synthetic molecules.Prepared through direct derivatization of natural extracts,they can include constituents enriched with elements and sub-structures that are less common in natural products compared to drugs.Fourteen such extracts were prepared through sequential reactions with hydrazine and a fluorinating reagent,and their α-glucosidase inhibition properties were compared.For the most bioactive mixture,a chemically modified propolis extract,enzyme inhibition increased 22 times due to the reaction sequence.Bio-guided fractionation led to the isolation of a new fluorinated pyrazole produced within the extract by chemical transformation of the flavonoid chrysin.The inhibitor results from the action of the two reagents used on four common functional groups present in natural products(carbonyl,phenol,aromatic carbon,and a double bond).The reactions led to the opening of a 6-member oxygenated heterocycle to produce a 5-member nitrogenated one,as well as the dehydroxylation and fluorination in two different positions of one of the aromatic rings of the natural starting material,all within a complex mixture of natural products.Overall,these transformations led to an approximately 20-fold increase in the α-glucosidase inhibition by the isolated inhibitor compared to its natural precursor.
文摘In 1891,a New York surgeon named William Coley injected cancer patients with live bacteria,observing with fascination as some tumors shrank amid raging fevers.His crude experiments-later deemed reckless-nonetheless revealed a tantalizing truth:The immune system,when properly provoked,could attack cancer.Over a century later,researchers have transformed this observation into a precision strike force.
基金National Key Research and Development Program of China(No.2022YFD2200602)111 Project(No.B20088)+1 种基金National Natural Science Foundation of China(Nos.52202345 and 31930076)the Heilongjiang Touyan Innovation Team Program(Tree Genetics and Breeding Innovation Team)。
文摘Up to now,numerous emerging methods of cancer treatment including chemodynamic therapy,photothermal therapy,photodynamic therapy,sonodynamic therapy,immunotherapy and chemotherapy have rapidly entered a new stage of development.However,the single treatment mode is often constrained by the complex tumor microenvironment.Recently,the nanomaterials and nanomedicine have emerged as promising avenues to overcome the limitation in cancer theranostics.Especially,metal-organic frameworks(MOFs)have gained considerable interests in cancer therapy because of their customizable morphologies,easy functionalization,large specific surface area,and good biocompatibility.Among these MOFs,iron-based MOFs(Fe-MOFs)are particularly promising for cancer treatment due to their properties as nano-photosensitizers,peroxidase-like activity,bioimaging contrast capabilities,and biodegradability.Utilizing their structural regularity and synthetic tunability,Fe-MOFs can be engineered to incorporate organic molecules or other inorganic nanoparticles,thereby creating multifunctional nanoplatforms for single or combined theranostic modes.Herein,the minireview focuses on the recent advancements of the Fe-MOFs-based nanoplatforms for self-enhanced imaging and treatment at tumor sites.Furthermore,the clinical research development of Fe-MOFs-based nanoplatforms is discussed,addressing key challenges and innovations for the future.Our review aims to provide novice researchers with a foundational understanding of advanced cancer theranostic modes and promote their clinical applications through the modification of Fe-MOFs.
文摘As industrial pollution continues to contaminate ecosystems worldwide,researchers have engineered a breakthrough solution:a single bacterial strain that can tackle five persistent organic pollutants at once.
基金supported by the Science and Technology Research Project of Jilin Education Bureau(No.JJKH20230804KJ)。
文摘Immunotherapy offers the promise of a potential cure for cancer,yet achieving the desired therapeutic effect can be challenging due to the immunosuppressive tumor microenvironments(TMEs) present in some tumors.Therefore,robust immune system activation is crucial to enhance the efficacy of cancer immunotherapy in clinical applications.Bacteria have shown the ability to target the hypoxic TMEs while activating both innate and adaptive immune responses.Engineered bacteria,modified through chemical or biological methods,can be endowed with specific physiological properties,such as diverse surface antigens,metabolites,and improved biocompatibility.These unique characteristics give engineered bacteria distinct advantages in stimulating anti-cancer immune responses.This review explores the potential regulatory mechanisms of engineered bacteria in modulating both innate and adaptive immunity while also forecasting the future development and challenges of using engineered bacteria in clinical cancer immunotherapy.
基金Supported by the National Administration of Traditional Chinese Medicine National Superior Specialty Project of Traditional Chinese Medicine,No.[2024]90Shanghai Municipal Administrator of Traditional Chinese Medicine Policy Letter[2024],No.20+1 种基金Science and Technology Development Fund of Shanghai University of Traditional Chinese Medicine,No.23KFL102Shuguang Hospital Siming Foundation Research Special Project,No.SGKJ-202304。
文摘Precancerous lesions of gastric cancer(PLGC)are crucial for the progression to gastric cancer,and early intervention in PLGC is pivotal in preventing its development into gastric cancer.In order to illustrate the molecular mechanisms underlying PLGC and the roles of associated genes within these lesions,genetically engineered mouse models(GEMMs)have been developed.We systematically summarize the current GEMMs,and highlight the principal pathological mechanisms involved,including gastrin/gastric acid balance,inflammatory factors,the interplay between cancer-promoting and cancer-suppressing genes,and apoptotic pathways.We further discuss the mechanisms involved in the existing GEMMs of PLGC.
基金The National Natural Science Foundation of China(No.51978504).
文摘Practical applications of desulfurization gypsum are limited owing to its brittleness and low strength.To overcome these challenges,researchers have developed engineered desulfurization gypsum composites(EDGCs)by incorporating ultrahigh molecular weight polyethylene(UHMWPE)fiber and sulfoaluminate cement(SAC).The mix ratio was optimized using response surface methodology(RSM).Experimental testing of EDGC under compressive and tensile loads led to the creation of a regression model that investigates the influence of variables and their interactions on the material’s compressive and tensile strengths.Additionally,microscopic morphology and hydration product composition were analyzed to explore the influence mechanism.The results indicated that EDGC’s compressive strength increased by up to 38.4%owing to a decreased water-binder ratio and higher SAC content.Similarly,tensile strength increased by up to 38.6%owing to increased SAC and fiber content.Moreover,EDGC demonstrated excellent strain-hardening behavior and multiple cracking characteristics,achieving a maximum tensile strain of nearly 3%.The research findings provide valuable insights for optimizing the performance of desulfurization gypsum.
基金supported by grants from the Jiangxi Provincial Natural Science Foundation,No.20242BAB26134(to XF)the National Natural Science Foundation of China,Nos.82060638(to TC),82060222(to XF),82460237(to XF)+1 种基金the Major Disciplines of Academic and Technical Leaders Project of Jiangxi Province,Nos.20194BCJ22032(to TC),20213BCJL22049(to XF)Science and Technology Plan of Jiangxi Health Planning Committee,No.202210390(to XF).
文摘Parkinson’s disease is characterized by synucleinopathy-associated neurodegeneration.Previous studies have shown that glucagon-like peptide-1(GLP-1)has beneficial effects in a mouse model of Parkinson’s disease induced by 1-methyl-4-phenyl-1,2,3,6-tetrahydropyridine.However,the effect of GLP-1 on intrinsic synuclein malfunction remains unclear.In this study,we investigated the effect of Lactococcus lactis MG1363-pMG36e-GLP-1 on parkinsonism in SncaA53T transgenic mice and explored the underlying mechanisms.Our data showed that Lactococcus lactis MG1363-pMG36e-GLP-1 inhibited dopaminergic neuronal death,reduced pathological aggregation ofα-synuclein,and decreased movement disorders in SncaA53T transgenic mice.Furthermore,Lactococcus lactis MG1363-pMG36e-GLP-1 downregulated lipopolysaccharide-related inflammation,reduced cerebral activation of microglia and astrocytes,and promoted cell survival via the GLP-1 receptor/PI3K/Akt pathway in the substantia nigra.Additionally,Lactococcus lactis MG1363-pMG36e-GLP-1 decreased serum levels of pro-inflammatory molecules including lipopolysaccharide,lipopolysaccharide binding protein,interleukin-1β,and interleukin-6.Gut histopathology and western blotting further revealed that Lactococcus lactis MG1363-pMG36e-GLP-1 increased the expression of gut integrity-related proteins and reduced lipopolysaccharide-related inflammation by reversing gut dysbiosis in SncaA53T transgenic mice.Our findings showed that the beneficial effect of Lactococcus lactis MG1363-pMG36e-GLP-1 on parkinsonism traits in SncaA53T transgenic mice is mediated by microglial polarization and the reversal of dysbiosis.Collectively,our findings suggest that Lactococcus lactis MG1363-pMG36e-GLP-1 is a promising therapeutic agent for the treatment of Parkinson’s disease.
基金supported by the grants from University of Macao,China,Nos.MYRG2022-00221-ICMS(to YZ)and MYRG-CRG2022-00011-ICMS(to RW)the Natural Science Foundation of Guangdong Province,No.2023A1515010034(to YZ)。
文摘Ischemic stroke is a secondary cause of mortality worldwide,imposing considerable medical and economic burdens on society.Extracellular vesicles,serving as natural nanocarriers for drug delivery,exhibit excellent biocompatibility in vivo and have significant advantages in the management of ischemic stroke.However,the uncertain distribution and rapid clearance of extracellular vesicles impede their delivery efficiency.By utilizing membrane decoration or by encapsulating therapeutic cargo within extracellular vesicles,their delivery efficacy may be greatly improved.Furthermore,previous studies have indicated that microvesicles,a subset of large-sized extracellular vesicles,can transport mitochondria to neighboring cells,thereby aiding in the restoration of mitochondrial function post-ischemic stroke.Small extracellular vesicles have also demonstrated the capability to transfer mitochondrial components,such as proteins or deoxyribonucleic acid,or their sub-components,for extracellular vesicle-based ischemic stroke therapy.In this review,we undertake a comparative analysis of the isolation techniques employed for extracellular vesicles and present an overview of the current dominant extracellular vesicle modification methodologies.Given the complex facets of treating ischemic stroke,we also delineate various extracellular vesicle modification approaches which are suited to different facets of the treatment process.Moreover,given the burgeoning interest in mitochondrial delivery,we delved into the feasibility and existing research findings on the transportation of mitochondrial fractions or intact mitochondria through small extracellular vesicles and microvesicles to offer a fresh perspective on ischemic stroke therapy.
基金supported by the support of the National Natural Science Foundation of China(Nos.22072141,22176185 and 52304429)the National Key Research and Development Program of China(Nos.2022YFB3504200,2021YFB3501900)+4 种基金the Natural Science Foundation of Jiangxi Province for Distinguished Young Scholars(No.20232ACB213004)Jiangxi Provincial Key Research and Development Program(No.20232BBG70012)Jiangxi Provincial Natural Science Foundation(No.20212BAB213032)the Youth Innovation Promotion Association of Chinese Academy of Sciences(No.2018263)the Research Projects of Ganjiang Innovation Academy,Chinese Academy of Sciences(No.E355C001).
文摘Selective catalytic reduction of NO_(x) with CO(CO-SCR)is a process that purifies both NO and CO pollutants through a catalytic reaction.Specifically,the cleavage of NO on the catalyst surface is crucial for promoting the reaction.During the reaction,the presence of oxygen vacancies can extract oxygen from NO,thereby facilitating the cleavage of NO on the catalyst surface.Thus,the formation of oxygen vacancies is key to accelerating the CO-SCR reaction,with different types of oxygen vacancies being more conducive to their generation.In this study,Rh/CeCuO_(x) catalysts were synthesized using the co-crystallization and impregnation methods,and asymmetric oxygen vacancies were induced through hydrogen thermal treatment.This structuralmodification was aimed at regulating the behavior of NO on the catalyst surface.The Rh/Ce0.95Cu0.05O_(x)-H_(2) catalyst exhibited the best performance in CO-SCR,achieving above 90%NO conversion at 162℃.Various characterization techniques showed that the H_(2) treatment effectively reduced some of the CuO and Rh_(2)O_(3),creating asymmetric oxygen vacancies that accelerated the cleavage of NO on the catalyst surface,rather than forming difficult-to-decompose nitrates.This study offers a novel approach to constructing oxygen vacancies in new CO-SCR catalysts.
基金supported by the National Natural Science Foundation of China(Nos.82122014,82071085,82020108011,and 82301031)the Zhejiang Provincial Natural Science Foundation of China(No.LR21H140001)+2 种基金the National Key Research and Development Program of China(No.2018YFA0703000)the Medical Technology and Education of Zhejiang Province of China(No.2018KY501)the Fundamental Research Funds for the Central Universities(No.2022QZJH55).
文摘Craniofacial muscles are essential components of the skeletal muscular system that contribute to important physiological processes.Severe trauma can induce craniofacial volumetric muscle loss(VML),which impairs muscle regeneration,causes facial muscular deformities and functional disability,and leads to psychosocial consequences such as isolation and depression.Conventional therapies involving muscle flap transposition or autologous tissue grafting achieve morphological repair but are ineffective in restoring muscle function,resulting in donor site injury and sensory deficit.In this study,we successfully constructed a biomimetically engineered muscle tissue that integrates myofiber alignment,effective innervation,and blood perfusion to promote multi-tissue regeneration in the masseter area in vivo,enabling functional regeneration.Using light-controlled micropatterning technology,we constructed mature muscle fibers with oriented alignment and established a neuromuscular co-culture system for in vitro neuromuscular junction reconstruction.Furthermore,we designed and fabricated a vascular network structure to promote tissue vascularization using hydrogel as the vehicle for assembling the composite engineered tissue.Using this technology,the shape and dimension of the constructed entity can be customized to address various muscle defects,enabling individualized repair.This study offers a promising novel strategy for tissue regeneration that breaks through the current challenges in the treatment of craniofacial VML.
文摘N-substituted furfurylamines(FAs)are valuable precursors for producing pharmacologically active compounds and polymers.However,enzymatic synthesis of the type of chemicals is still in its infancy.Here we report an imine reductase from Streptomyces albidoflavus(SaIRED)for the reductive amination of biobased furans.A simple,fast and interference-resistant high-throughput screening(HTS)method was developed,based on the coloration reaction of carbonyl compounds with 2,4-dinitrophenylhydrazine.The reductive amination activity of IREDs can be directly indicated by a colorimetric assay.With the reductive amination of furfural with allylamine as the model reaction,SaIRED with the activity of 4.8 U mg^(-1) was subjected to three rounds of protein engineering and screening by this HTS method,affording a high-activity tri-variant I127V/D241A/A242T(named M3,20.2 U mg^(-1)).The variant M3 showed broad substrate scope,and enabled efficient reductive amination of biobased furans with a variety of amines including small aliphatic amines and sterically hindered amines,giving the target FAs in yields up to>99%.In addition,other variants were identified for preparative-scale synthesis of commercially interesting amines such as N-2-(methylsulfonyl)ethyl-FA by the screen method,with isolated yields up to 87%and turnover numbers up to 9700 for enzyme.Gram-scale synthesis of N-allyl-FA,a valuable building block and potential polymer monomer,was implemented at 0.25 mol L^(-1) substrate loading by a whole-cell catalyst incorporating variant M3,with 4.7 g L^(-1) h^(-1) space-time yield and 91%isolated yield.
文摘Heme peroxygenases exhibit remarkable catalytic versatility in facilitating a wide array of oxidative reactions under mild conditions,eliminating the need for coenzymes and intricate electron transport systems.This unique character underscores their essentiality and potential as promising tools in synthetic biology.Recent advancements in enzyme engineering have significantly enhanced the catalytic performance of both natural and artificial peroxygenases.Extensive engineering efforts have been directed towards unspecific peroxygenases and fatty acid peroxygenases,aiming to expand their substrate specificities,and enhance reaction selectivities,as well as increase enzyme stability.Furthermore,innovative strategies such as dual-functional small molecule-assisted systems and H_(2)O_(2) tunnel engineering have been harnessed to transform P450 monooxygenases into highly efficient peroxygenases,capable of catalyzing reactions with a variety of unnatural substrates.This review consolidates the latest progress in the engineered and artificial heme peroxygenases,emphasizing their catalytic performances as potent biocatalysts for sustainable organic synthesis.
基金financial support provided by the National Natural Science Foundation of Yunnan Province(202301AS070040)Major Science and Technology Projects of Yunnan Province(202302AB080019-3)。
文摘Covalent organic frameworks(COFs)play a crucial role in metal-free electrocatalysts for promoting oxygen reduction reaction(ORR)due to their adjustable skeleton structure and catalytic activity.While it is true that numerous studies have explored COFs for ORR,the critical gap by providing a systematic framework for ligand-driven electronic state manipulation is essential for designing highly active COF-based ORR catalysts.Herein,a series of COF-based metal-free materials have been conceived and synthesized by linkage-engineered strategy with dicarboxaldehyde(BPC),bipyridine-dicarbaldehyde(BPA)and benzodithiophene(BDA)as electronic linkages.Consequently,by incorporating different linkages into COFs,the surface area,electronic state,hydrophobic properties and affinities towards intermediates are optimized.Notably,the benzodithiophene-linked COF(denoted as BDA-COF)has greater catalytic ability with a half-wave potential of 0.74 V vs.RHE and an onset potential of 0.86 V vs.RHE than dicarboxaldehyde(denoted as BPC-COF)and dicarbaldehyde(denoted as BPA-COF).Relevant characterizations,in situ techniques and theoretical calculations confirm that thiophene-S-based COF promotes the electronic migration and enhances the interaction with the intermediate.The result provides insight into for illustration of a high-performance COF-based electrocatalyst via a linkage-engineered approach.
基金financially supported by the National Natural Science Foundation of China(Nos.52125501,52405325)the Key Research Project of Shaanxi Province(Nos.2021LLRH-08,2024SF2-GJHX-34)+5 种基金the Program for Innovation Team of Shaanxi Province(No.2023-CX-TD17)the Postdoctoral Fellowship Program of CPSF(No.GZB20230573)the Postdoctoral Project of Shaanxi Province(No.2023BSHYDZZ30)the Basic Research Program of Natural Science in Shaanxi Province(No.2021JQ-906)the China Postdoctoral Science Foundationthe Fundamental Research Funds for the Central Universities。
文摘The inherent complexities of excitable cardiac,nervous,and skeletal muscle tissues pose great challenges in constructing artificial counterparts that closely resemble their natural bioelectrical,structural,and mechanical properties.Recent advances have increasingly revealed the beneficial impact of bioelectrical microenvironments on cellular behaviors,tissue regeneration,and therapeutic efficacy for excitable tissues.This review aims to unveil the mechanisms by which electrical microenvironments enhance the regeneration and functionality of excitable cells and tissues,considering both endogenous electrical cues from electroactive biomaterials and exogenous electrical stimuli from external electronic systems.We explore the synergistic effects of these electrical microenvironments,combined with structural and mechanical guidance,on the regeneration of excitable tissues using tissue engineering scaffolds.Additionally,the emergence of micro/nanoscale bioelectronics has significantly broadened this field,facilitating intimate interactions between implantable bioelectronics and excitable tissues across cellular,tissue,and organ levels.These interactions enable precise data acquisition and localized modulation of cell and tissue functionalities through intricately designed electronic components according to physiological needs.The integration of tissue engineering and bioelectronics promises optimal outcomes,highlighting a growing trend in developing living tissue construct-bioelectronic hybrids for restoring and monitoring damaged excitable tissues.Furthermore,we envision critical challenges in engineering the next-generation hybrids,focusing on integrated fabrication strategies,the development of ionic conductive biomaterials,and their convergence with biosensors.
基金supported by the Natural Science Foundation of Hunan Province(No.2023JJ30650)the Central South University Innovation-Driven Research Programme(No.2023CXQD061)。
文摘The atomic-level exploration of structure-property correlations poses significant challenges in establishing precise design principles for electrocatalysts targeting efficient CO_(2)conversion.This study demonstrates how controlled exposure of metal sites governs CO_(2)electroreduction performance through two octanuclear bismuth-oxo clusters with distinct architectures.The Bi_(8)-DMF cluster,constructed using tert–butylthiacalix[4]arene(TC4A)as the sole ligand,features two surface-exposed Bi active sites,while the dual-ligand Bi_(8)-Fc(with TC4A/ferrocene carboxylate)forms a fully encapsulated structure.Electrocatalytic tests reveal Bi_(8)-DMF achieves exceptional formate selectivity(>90%Faradaic efficiency)across a broad potential window(-0.9 V to-1.6 V vs.RHE)with 20 h stability,outperforming Bi_(8)-Fc(60%efficiency at-1.5 V).Theoretical calculations attribute Bi_(8)-DMF's superiority to exposed Bi sites that stabilize the critical*OCHO intermediate via optimized orbital interactions.This work provides crucial guidance for polynuclear catalyst design:moderate exposure of metal active sites significantly enhances CO_(2)reduction performance.
基金supported financially by the Ministry of Textiles(Grant No-2/3/2021-NTTM(Pt.)),Govt.of India。
文摘Engineering a phosphide-based multifunctional heterostructure with high redox activity,stability,and efficient charge kinetics for both supercapacitors and water splitting remains challenging due to sluggish reaction kinetics and structural instability.This study overcomes these challenges by implementing a rapid,energy-efficient approach to develop a MOF-modulated MnP@Cu_(3)P heterostructure via a hydrothermal process followed by high-temperature phosphorization.The heterostructure demonstrates superior redox activity with enhanced stability and improved charge kinetics achieving a high specific capacity of 1131 C g^(-1)as supported by density functional theory findings of increased DOS near the Fermi level.The flexible supercapacitor achieves a peak energy density of 99.20 Wh kg^(-1)and power density of 15.40 kW kg^(-1).Simultaneously,it shows exceptional hydrogen evolution reaction performance with an overpotential of η_(10)=44 mV and η_(1000)=225 mV,attributed to electron transfer from Cu to Mn via P bridging,which shifts the active centers from Mn and Cu sites to the P site,confirmed by lowestΔG_(H)^(*)value of-0.16 eV.The overall water-splitting in full-cell electrocatalyzer delivers cell voltage of E_(20)=1.48 V and E_(1000)=1.88 V and setting a new standard in solar-to-hydrogen efficiency of 20.02%.The electrolyzer cell maintained prolonged stability at industrial-scale current densities of 1.0 A cm^(-2)under alkaline electrolysis achieving an estimated hydrogen production cost of INR 146.7 or US$1.67per kilogram aligning with the cost target of $2/kg by 2026 established by the Clean Hydrogen Electrolysis Program,U.S.department of energy.Furthermore,real-phase demonstration highlights the uninterrupted hydrogen production till 6-minutes via connecting this electrocatalyzer with photovoltaic-charged supercapacitors effectively addressing solar intermittency and gas fluctuations challenges in water-electrolysis.
