Under hydrothermal and solvothermal conditions,two novel cobalt-based complexes,{[Co_(2)(CIA)(OH)(1,4-dtb)]·3.2H_(2)O}n(HU23)and{[Co_(2)(CIA)(OH)(1,4-dib)]·3.5H2O·DMF}n(HU24),were successfully construct...Under hydrothermal and solvothermal conditions,two novel cobalt-based complexes,{[Co_(2)(CIA)(OH)(1,4-dtb)]·3.2H_(2)O}n(HU23)and{[Co_(2)(CIA)(OH)(1,4-dib)]·3.5H2O·DMF}n(HU24),were successfully constructed by coordinatively assembling the semi-rigid multidentate ligand 5-(1-carboxyethoxy)isophthalic acid(H₃CIA)with the Nheterocyclic ligands 1,4-di(4H-1,2,4-triazol-4-yl)benzene(1,4-dtb)and 1,4-di(1H-imidazol-1-yl)benzene(1,4-dib),respectively,around Co^(2+)ions.Single-crystal X-ray diffraction analysis revealed that in both complexes HU23 and HU24,the CIA^(3-)anions adopt aκ^(7)-coordination mode,bridging six Co^(2+)ions via their five carboxylate oxygen atoms and one ether oxygen atom.This linkage forms tetranuclear[Co4(μ3-OH)2]^(6+)units.These Co-oxo cluster units were interconnected by CIA^(3-)anions to assemble into 2D kgd-type structures featuring a 3,6-connected topology.The 2D layers were further connected by 1,4-dtb and 1,4-dib,resulting in 3D pillar-layered frameworks for HU23 and HU24.Notably,despite the similar configurations of 1,4-dtb and 1,4-dib,differences in their coordination spatial orientations lead to topological divergence in the 3D frameworks of HU23 and HU24.Topological analysis indicates that the frameworks of HU23 and HU24 can be simplified into a 3,10-connected net(point symbol:(4^(10).6^(3).8^(2))(4^(3))_(2))and a 3,8-connected tfz-d net(point symbol:(4^(3))_(2)((4^(6).6^(18).8^(4)))),respectively.This structural differentiation confirms the precise regulatory role of ligands on the topology of metal-organic frameworks.Moreover,the ultraviolet-visible absorption spectra confirmed that HU23 and HU24 have strong absorption capabilities for ultraviolet and visible light.According to the Kubelka-Munk method,their bandwidths were 2.15 and 2.08 eV,respectively,which are consistent with those of typical semiconductor materials.Variable-temperature magnetic susceptibility measurements(2-300 K)revealed significant antiferromagnetic coupling in both complexes,with their effective magnetic moments decreasing markedly as the temperature lowered.CCDC:2457554,HU23;2457553,HU24.展开更多
In this study,polyacrylic acid(PAA)films were employed as a model system,and a series of PAA films with tunable water wettability was systematically prepared by varying molecular weight and curing temperature.Using at...In this study,polyacrylic acid(PAA)films were employed as a model system,and a series of PAA films with tunable water wettability was systematically prepared by varying molecular weight and curing temperature.Using attenuated total reflectance Fourier-transform infrared spectroscopy(ATR-FTIR),the molecular configurations of surface carboxyl groups(COOH),free carboxyl(COOH_(f))and hydrogen-bonded carboxyl(COOH_(HB),were directly correlated with the polar component of surface energy(γ^(s,p)).By decomposing theγ^(s,p)values of the PAA thin films as a sum of the contributions of COOH_(f)and COOH_(H B),the intrinsic polar component of surface energy of COOH_(H B)(γ_(H B)^(s,p*))was quantified for the first time as 8.34 mN/m,significantly lower than that of COOH_(f)(γ_(f)^(s,p*)=34 mN/m).This result highlights that hydrogen bonding markedly reduces theγ^(s,p),providing a rational explanation for the relatively large water contact angle observed on PAA thin films.Furthermore,it establishes a thermodynamic basis for estimating the fraction of surface COOH_(H B)groups(f H B)from wettability measurements.Further extension of the model to carboxyl-terminated self-assembled monolayers(COOH-SAMs)revealed that surface COOH density(ΣCOOH)critically regulates wetting behavior:whenΣCOOH ranges from 4.30 to 5.25 nm^(-2),COOH groups predominantly exist in a free state and facilitate effective hydration layers,thereby promoting superhydrophilicity.Overall,this study not only establishes a unified thermodynamic framework linking surface COOH configurations to macroscopic wettability,but also validates its universality by extending it to COOH-SAMs systems,thereby providing a unified theoretical framework for the controllable design of hydrophilicity in various COOH-functionalized surfaces.展开更多
Zn-I_(2) batteries have emerged as promising next-generation energy storage systems owing to their inherent safety,environmental compatibility,rapid reaction kinetics,and small voltage hysteresis.Nevertheless,two crit...Zn-I_(2) batteries have emerged as promising next-generation energy storage systems owing to their inherent safety,environmental compatibility,rapid reaction kinetics,and small voltage hysteresis.Nevertheless,two critical challenges,i.e.,zinc dendrite growth and polyiodide shuttle effect,severely impede their commercial viability.To conquer these limitations,this study develops a multifunctional separator fabricated from straw-derived carboxylated nanocellulose,with its negative charge density further reinforced by anionic polyacrylamide incorporation.This modification simultaneously improves the separator’s mechanical properties,ionic conductivity,and Zn^(2+)ion transfer number.Remarkably,despite its ultrathin 20μm profile,the engineered separator demonstrates exceptional dendrite suppression and parasitic reaction inhibition,enabling Zn//Zn symmetric cells to achieve impressive cycle life(>1800 h at 2 m A cm^(-2)/2 m Ah cm^(-2))while maintaining robust performance even at ultrahigh areal capacities(25 m Ah cm^(-2)).Additionally,the separator’s anionic characteristic effectively blocks polyiodide migration through electrostatic repulsion,yielding Zn-I_(2) batteries with outstanding rate capability(120.7 m Ah g^(-1)at 5 A g^(-1))and excellent cyclability(94.2%capacity retention after 10,000 cycles).And superior cycling stability can still be achieved under zinc-deficient condition and pouch cell configuration.This work establishes a new paradigm for designing high-performance zinc-based energy storage systems through rational separator engineering.展开更多
Achieving heterogeneous photocatalytic activation of sp^(3)C-H bonds and carboxylation of CO_(2)to produce arylacetic acids and alkyl carboxylic acids with increased carbon chains is a highly significant and demanding...Achieving heterogeneous photocatalytic activation of sp^(3)C-H bonds and carboxylation of CO_(2)to produce arylacetic acids and alkyl carboxylic acids with increased carbon chains is a highly significant and demanding research endeavor.In this work,a new method for synthesizing redox centers spatially separated Z-scheme CdS@graphitic carbon nitride(g-C_(3)N_(4))was developed,aiming to achieve photocatalytic benzylic and aliphatic sp^(3)C-H activation as well as CO_(2)carboxylation without sacrificial agent.Notably,both benzylic and aliphatic sp^(3)C-H activation together with CO_(2)carboxylation were achieved in heterogeneous photocatalytic system,resulting in the production of carboxylic acids with increased carbon chains under mild conditions.Various methylbenzene derivatives and cycloalkanes were employed to synthesize carbon-chain increased acids via a process involving K_(3)PO_(4)-assisted photogenerated holes activation for benzyl radical generation,photoinduced CO_(2)reduction,as well as solvent-assisted chemoselective carboxylation.Various characterizations and density functional theory(DFT)results revealed that Z-scheme CdS@g-C_(3)N_(4)not just significantly enhanced separation of charges and accumulation of photoinduced electrons on g-C_(3)N_(4)but also facilitated adsorption along with activation of CO_(2).This research provided novel heterogeneous photocatalytic approach to produce carbon chains increased carboxylic acids via sp^(3)C-H activation and CO_(2)carboxylation.展开更多
The E3 ubiquitin ligase,carboxyl terminus of heat shock protein 70(Hsp70)interacting protein(CHIP),also functions as a co-chaperone and plays a crucial role in the protein quality control system.In this study,we aimed...The E3 ubiquitin ligase,carboxyl terminus of heat shock protein 70(Hsp70)interacting protein(CHIP),also functions as a co-chaperone and plays a crucial role in the protein quality control system.In this study,we aimed to investigate the neuroprotective effect of overexpressed CHIP on Alzheimer’s disease.We used an adeno-associated virus vector that can cross the blood-brain barrier to mediate CHIP overexpression in APP/PS1 mouse brain.CHIP overexpression significantly ameliorated the performance of APP/PS1 mice in the Morris water maze and nest building tests,reduced amyloid-βplaques,and decreased the expression of both amyloid-βand phosphorylated tau.CHIP also alleviated the concentration of microglia and astrocytes around plaques.In APP/PS1 mice of a younger age,CHIP overexpression promoted an increase in ADAM10 expression and inhibitedβ-site APP cleaving enzyme 1,insulin degrading enzyme,and neprilysin expression.Levels of HSP70 and HSP40,which have functional relevance to CHIP,were also increased.Single nuclei transcriptome sequencing in the hippocampus of CHIP overexpressed mice showed that the lysosomal pathway and oligodendrocyte-related biological processes were up-regulated,which may also reflect a potential mechanism for the neuroprotective effect of CHIP.Our research shows that CHIP effectively reduces the behavior and pathological manifestations of APP/PS1 mice.Indeed,overexpression of CHIP could be a beneficial approach for the treatment of Alzheimer’s disease.展开更多
Bay-site carboxyl functionalized perylene diimide derivative 1,7-COOH-PDI-C_(12)(PDI-COOH)was synthesized and distinct enhanced fluorescence was observed through combining with calcium ion(Ca^(2+))in THF/H_(2)O soluti...Bay-site carboxyl functionalized perylene diimide derivative 1,7-COOH-PDI-C_(12)(PDI-COOH)was synthesized and distinct enhanced fluorescence was observed through combining with calcium ion(Ca^(2+))in THF/H_(2)O solution.The assembly and fluorescence behavior of PDI-COOH/Ca^(2+)were studied in detail by changing hydration state with different concentrations.Based on the differences in assembly morphology and stoichiometric ratios of PDICOOH/Ca^(2+),we proposed the fluorescence emission mechanism of PDI-COOH/Ca^(2+)in THF/H_(2)O and THF,respectively.This work reveals a novel strategy of aggregated state fluorescence enhancement and reminds us of the important role of water in molecular fluorescence emission and assembly.展开更多
Pore structure engineering has been acknowledged as suitable approach to creating active sites and en-hancing ion transport capabilities of hard carbon anodes.However,conventional porous carbon materials exhibit high ...Pore structure engineering has been acknowledged as suitable approach to creating active sites and en-hancing ion transport capabilities of hard carbon anodes.However,conventional porous carbon materials exhibit high BET and surface defects.Additionally,the sodium storage mechanism predominantly occurs in the slope region.This contradicts practical application requirements because the capacity of the plateau region is crucial for determining the actual capacity of batteries.In our work,we prepared a novel“core-shell”carbon framework(CNA1200).Introducingclosedporesand carboxylgroupsinto coal-basedcarbon materials to enhance its sodium storage performance.The closed pore structure dominates in the“core”structure,which is attributed to the timely removal of sodium hydroxide(NaOH)to prevent further for-mation of active carbon structure.The presence of closed pores is beneficial for increasing sodium ion storage in the low-voltage plateau region.And the“shell”structure originates from coal tar pitch,it not only uniformly connects hard carbon particles together to improve cycling stability,but is also rich in carboxyl groups to enhance the reversible sodium storage performance in slope region.CNA1200 has ex-cellent electrochemical performance,it exhibits a specific capacity of 335.2 mAh g^(−1)at a current density of 20 mA g^(−1)with ICE=51.53%.In addition,CNA1200 has outstanding cycling stability with a capac-ity retention of 91.8%even when cycling over 200 times.When CNA1200 is used as anode paired with Na_(3)V_(2)(PO_(4))_(3)cathode,it demonstrates a capacity of 109.54 mAh g^(−1)at 0.1 C and capacity retention of 94.64%at 0.5 C.This work provides valuable methods for regulating the structure of sodium-ion battery(SIBs)anode and enhances the potential for commercialization.展开更多
Mitochondria and mitochondria-associated endoplasmic reticulum membrane in neurodegenerative diseases:Mitochondria generate most of the chemical energy needed to power the biochemical reactions of cells,and thus are o...Mitochondria and mitochondria-associated endoplasmic reticulum membrane in neurodegenerative diseases:Mitochondria generate most of the chemical energy needed to power the biochemical reactions of cells,and thus are often referred to as the"powerhouse"of the cell.Nevertheless,this organelle is also involved in a pleth,ora of different cellular functions such as calcium(Ca^(2+))homeostasis,apoptosis,oxidative stress,and several metabolic pathways including oxidative phosphorylation,tricarboxylic acid cycle,andβ-oxidation of fatty acids.展开更多
An efficient TfOH-catalyzed O—H insertion reaction of α-aryl diazoesters with carboxylic acids is reported.This metal-free protocol provides an operationally simple method for a one-pot assembly of diverse α-acylox...An efficient TfOH-catalyzed O—H insertion reaction of α-aryl diazoesters with carboxylic acids is reported.This metal-free protocol provides an operationally simple method for a one-pot assembly of diverse α-acyloxy esters in moderate to high yields with a broad substrate scope.All starting materials are readily available,and the reactions can be conducted in the open air at room temperature.展开更多
Four new coordination polymers,{[Cd(mbtx)(4OHphCOO)]NO_(3)}n(1),{[Zn(mbtx)(1,4-bdc)_(0.5)(H_(2)O)_(2)]·(1,4-bdc)_(0.5)·4H_(2)O}n(2),{[Cd2(mbtx)(5NO_(2)-bdc)_(2)(H_(2)O)_(3)]·4.5H_(2)O}n(3),and{[Zn(H_(2)...Four new coordination polymers,{[Cd(mbtx)(4OHphCOO)]NO_(3)}n(1),{[Zn(mbtx)(1,4-bdc)_(0.5)(H_(2)O)_(2)]·(1,4-bdc)_(0.5)·4H_(2)O}n(2),{[Cd2(mbtx)(5NO_(2)-bdc)_(2)(H_(2)O)_(3)]·4.5H_(2)O}n(3),and{[Zn(H_(2)O)6][Zn_(2)(mbtx)_(2)(btc)_(2)(H_(2)O)_(4)]·2H_(2)O}n(4)(mbtx=1,3-bis(4H-1,2,4-triazole)benzene,4OHphCOO-=p-hydroxybenzoate,1,4-bdc2-=1,4-benzenedicarboxylate,5NO_(2)-bdc2-=5-nitro-isophthalate,btc3-=1,3,5-benzenetricarboxylate),were synthesized under room temperature condition and characterized by single-crystal X-ray diffraction,elemental analyses,and powder X-ray diffraction.Single-crystal X-ray structural analysis shows that complexes 1 and 3 are 2D networks.In 1,the adjacent 2D networks are linked to a 3D network byπ-πstacking interaction.2 and 4 exhibit 1D chains,and the 1D chains are connected into a 3D network byπ-πstacking interaction and intermolecular hydrogen bond.Luminescence and thermogravimetric analysis of the four complexes were discussed.CCDC:2416406,1;2416407,2;2416408,3;2416409,4.展开更多
A strategy for copper-catalyzed and biphosphine ligand controlled boracarboxylation of 1,3-dienes and CO_(2) with 3,4-selectivity was developed.The Cu Cl coupled with DPPF(1,1-bis(diphenylphosphino)ferrocene)was assig...A strategy for copper-catalyzed and biphosphine ligand controlled boracarboxylation of 1,3-dienes and CO_(2) with 3,4-selectivity was developed.The Cu Cl coupled with DPPF(1,1-bis(diphenylphosphino)ferrocene)was assigned to be the best catalyst,with 84%yield and exclusive3,4-selectivity.The ligand effect on both catalytic activity and regioselectivity of boracarboxylation was disclosed,which is rarely reported in any copper catalyzed boracarboxylation.The borocupration process is revealed to be a vital step for the biphosphine participated boracarboxylation of 1,3-dienes with CO_(2).The minimal substrate distortion occurring in 3,4-borocupration favors the 3,4-regioselectivity of boracarboxylation.The“pocket”confinement and suitableβ_(n)(92°–106°)of bisphosphine ligands are demonstrated to be in favour of the interaction between LCu-Bpin complex(the catalytic precursor)and1,3-diene substrate to decrease their interaction energyΔE_(int)(ζ)in 3,4-borocupration,thus promoting the 3,4-boracarboxylation.展开更多
Microbial consortia that catalyze chain elongation processes have been enriched using different selection strategies,for which the electron donor is an essential one.Propanol is an extraordinarily promising electron d...Microbial consortia that catalyze chain elongation processes have been enriched using different selection strategies,for which the electron donor is an essential one.Propanol is an extraordinarily promising electron donor because it can be generated from renewable resources,including lignocellulosic biomass and protein wastes.Here,propanol was proven in detail to be an efficient electron donor,enhancing the production of odd medium-chain carboxylates during chain elongation.By exploring various electron acceptors,reactor conditions,and electron donor/electron acceptor mol ratios,our study highlights that acetate is the most suitable electron acceptor for the production of both odd-and even-chain carboxylates.The optimal conditions for propanol-based chain elongation were 30℃ and pH 6,achieving 82.8%selectivity for odd-chain carboxylates.Another critical insight from our work is that a propanol/acetate mol ratio of 1:1 can minimize the inhibitory effect of propanol and maximize the yield of medium-chain carboxylates,with the highest concentration of n-heptanoate reaching 124.5 mmol C/L.This was further illustrated by 16S rRNA amplicon sequencing,which elucidated that the community composition and keystone species in a propanol-based reactor closely resembled that of the ethanol one.The dominant phylum of the propanol-based reactor,Firmicutes showed a significant positive correlation with the concentrations of n-caproate and n-valerate.Additionally,the co-occurrence of Clostridium sensu stricto 12 and Oscillibacter,known as typical chain elongators,was identified within the propanol-based reactor.These findings enhance our understanding of propanolbased chain elongation,offer guiding principles for reactor microbiota assembly,and support efficient odd medium-chain carboxylate production.展开更多
Unconventional natural gas has become an important supplement to conventional energy sources,and the process of enrichment and purification of methane from low concentration coalbed methane is crucial.To this end,we r...Unconventional natural gas has become an important supplement to conventional energy sources,and the process of enrichment and purification of methane from low concentration coalbed methane is crucial.To this end,we report a copper-based metal-organic framework(MOF),ZJNU-119Cu,featuring two methane traps constructed with uncoordinated carboxylic acid oxygens and open metal sites.ZJNU-119Cu exhibits a high methane adsorption capacity(58.2 cm^(3)·g^(-1))at 298 K and 0.1 MPa and excellent CH_(4)/N_(2) separation performance under dynamic conditions.Densityfunctional theory calculations combined with grand canonical Monte Carlo simulation theory reveal the interaction mechanism for the uncoordinated carboxylic acid oxygen atoms and open metal sites in ZJNU-119Cu with CH4.The gas adsorption isotherms,heat of adsorption calculations,and breakthrough separation experiments indicate that this MOF is a very promising adsorbent for CH_(4)/N_(2) separation.展开更多
The photocatalytic reduction of CO_(2)is a crucial area of research aimed at addressing the dual challenges of mitigating rising CO_(2)emissions and producing sustainable chemical feedstocks.While multielectron reduct...The photocatalytic reduction of CO_(2)is a crucial area of research aimed at addressing the dual challenges of mitigating rising CO_(2)emissions and producing sustainable chemical feedstocks.While multielectron reduction pathways for CO_(2)are well explored,the single electron reduction to produce the highly reactive carbon dioxide radical anion(CO_(2)^(·-))remains challenging yet promising for green organic transformations.This review contributes to the field by providing a comprehensive analysis of the mechanisms,materials,and reaction pathways involved in CO_(2)^(·-)generation,focusing on the use of visible-lightdriven photocatalytic materials to circumvent the need for high-energy ultraviolet irradiation.Through a systematic examination of CO_(2)^(·-)production,detection methods,and chemical utilization in photocatalytic carboxylation reactions,this review advances understanding of the chemistry of CO_(2)^(·-)and its applications in sustainable chemical synthesis.In addition,it highlights existing key challenges,such as redox potential limitations,and proposes strategies for scaling up photocatalytic systems to enable practical application.By illuminating the pathway to effectively photocatalyze CO_(2)^(·-)generation and its transformative potential in sustainable chemical synthesis,this review equips scientists with critical insights and strategic approaches for overcoming current limitations,driving innovation in photocatalytic materials for solar-to-chemical energy conversion.展开更多
Surfactant sodium alcohol ether carboxylate(AEC-9Na)was added to the magnesium sulfate solution in order to enhance the leaching efficiency of ionic rare earth ore,and the mechanism of action for AEC-9Na was elucidate...Surfactant sodium alcohol ether carboxylate(AEC-9Na)was added to the magnesium sulfate solution in order to enhance the leaching efficiency of ionic rare earth ore,and the mechanism of action for AEC-9Na was elucidated.Under optimal conditions,the addition of AEC-9Na with a mass fraction of 0.03% can enhance the leaching rate by 5.2% and reduce the leaching cycle.Kinetic analysis demonstrates that the leaching process follows the model of internal diffusion control.The analysis of the mass transfer process reveals that the addition of AEC-9Na results in a decrease in the height equivalent to a theoretical plate(HETP)and an improvement in mass transfer efficiency.The addition of AEC-9Na can reduce the thickness of the water layer adsorbed on particles during leaching,which in turn reduces hydration and facilitates penetration of the leaching solution into ore body pores.This improves mass transfer concentration differences during leaching,and facilitates desorption of rare earth ions.Periodic density functional theory(DFT)calculations show that the adsorption of AEC-9Na onto the surface of kaolinite(001)enhances the hydrophilicity of the mineral surface and improves its permeability efficiency.Simultaneously,AEC-9Na forms complexes with hydrated rare earth ions on the kaolinite(001)surface,thereby reducing their adsorption strength on clay minerals.This promotes the exchange and desorption process of magnesium ions to hydrated rare earth ions,ultimately enhancing the mass transfer process for leaching rare earth elements.展开更多
Solar-driven thermo-electric generation(STEG)emerges as a promising solution to mitigate the global en-ergy shortage.However,the practical application of conventional photothermal materials equipped with STEG is limit...Solar-driven thermo-electric generation(STEG)emerges as a promising solution to mitigate the global en-ergy shortage.However,the practical application of conventional photothermal materials equipped with STEG is limited due to low solar thermal conversion efficiency.Herein,we fabricated an epoxy resin(EP)nanocomposite,EP/CCA80,with excellent photo-thermal-electric conversion properties by embedding a vertically aligned aerogel consisting of cellulose nanofibers(CNF)and carboxylated multi-walled carbon nanotubes(CMWCNTs)into a transparent EP matrix.EP/CCA80 composites possessed a broad light ab-sorption range from 200 nm to 2500 nm and excellent photothermal properties.Under illumination of 1.0 kW m^(-2),EP/CCA80 achieved a notable stable temperature of 93.2℃ and a photothermal conversion efficiency of up to 54.35%with only 0.65 wt%CMWCNTs inclusion.Additionally,coupled with thermo-electric(TE)devices,the EP/CCA80 composite facilitated a significant temperature difference and voltage output of up to 25.3℃ and 160.29 mV(1.0 kW m^(-2)),respectively,which could power a small fan to rotate at a speed of 193 min^(-1).Such materials are poised to offer viable solutions for enhancing energy accessibility in remote regions,thereby contributing to the reduction of energy shortages and environ-mental degradation.展开更多
The detection of circulating tumor DNA(ctDNA)with high sensitivity and specificity is crucial for the early diagnosis and monitoring of tumors,as well as for drug therapy.In this study,a simple and highly sensitive bi...The detection of circulating tumor DNA(ctDNA)with high sensitivity and specificity is crucial for the early diagnosis and monitoring of tumors,as well as for drug therapy.In this study,a simple and highly sensitive biosensor was specifically designed for the identification of targeted ctDNA.For the first time,a three-dimensional polyvinylidene fluoride-graphene oxide-chitosan(PVDF/CS/GO)nanofiber mesh was fabricated on a polydimethylsiloxane(PDMS)micropillar substrate using electrospinning technology,and the nanofibers were functionalized with peptide nucleic acids probe-gold nanoparticle(PNA-AuNP)complexes,which served as affinity molecules for detecting the methylation of the E542K variant of the phosphatidylinositol-4,5-bisphosphate 3-kinase catalytic subunit α(PIK3CA)gene in the peripheral blood of cancer patients.Additionally,an anti-5-Methylcytosine monoclonal antibody-multi-walled carbon nanotubes-COOH complex(Anti-5-mC-MWCNTs-COOH)complex was incubated to result in significantly amplified electrochemical signals for the accurate quantification of the E542K variant of the PIK3CA gene.Detectable signal responses were observed only when both molecules were simultaneously present,greatly enhancing the accuracy of the analysis.The biosensor exhibits high capture sensitivity for the methylation level of the E542K variant of the PIK3CA gene across a concentration range of 50 to 10000 fmol/L,with the lowest detection limit of 10 fmol/L.The ctDNA nanobiosensor has been shown to be both feasible and valuable for quantifying ctDNA concentrations in clinical blood samples.Consequently,this 3D nanofiber biosensor shows significant potential for clinical applications in cancer diagnosis and personalized medical treatments.展开更多
Oxalic acid salts(oxalate)were recently developed as C1 synthon,potent single-electron-transfer(SET)reductant,and hole scavengers via generation of CO_(2) and CO_(2) radical anion(CO_(2)·^(-))under mild photochem...Oxalic acid salts(oxalate)were recently developed as C1 synthon,potent single-electron-transfer(SET)reductant,and hole scavengers via generation of CO_(2) and CO_(2) radical anion(CO_(2)·^(-))under mild photochemical conditions.A series of challenging reductive transformations were realized with oxalic dianion under catalytic photoredox conditions or through an electron-donor-acceptor(EDA)complex formation process.As a chemical intermediate for carbon capture and utilization(also a cheap and readily available reagent),oxalate salts could release one electron easily(E_(ox)=+0.06 V vs.SCE)via visible-light irradiation to give CO_(2) and CO_(2)·^(-) and therefore opened a new arena for reductive carboxylation reactions with highly expanded reaction diversity and chemical space to realize challenging C-X bond activation,alkenes cross coupling,and reductive carboxylation of unsaturated chemical bonds in a more sustainable and efficient way.This review features the recently developed aspects with oxalate salts and also an outlook for its further application in organic radical transformations.展开更多
Salination of solutions of salinity gradient releases large‐scale clean and renewable energy, which can be directly and efficiently transformed into electrical energy using ion‐selective nanofluidic channel membrane...Salination of solutions of salinity gradient releases large‐scale clean and renewable energy, which can be directly and efficiently transformed into electrical energy using ion‐selective nanofluidic channel membranes. However, conventional ion‐selective membranes are typically either cation‐ or anion‐selective. A pH‐switchable system capable of dual cation and anion transport along with salt gradient energy harvesting properties has not been demonstrated in ion‐selective membranes. Here, we constructed an amphoteric heterolayer metal–organic framework (MOF) membrane with subnanochannels modified with carboxylic and amino functional groups. The amphoteric MOF‐composite membrane, AAO/aUiO‐66‐(COOH)_(2)/UiO‐66‐NH_(2), exhibits pH‐tuneable ion conduction and achieves osmotic energy conversion of 7.4 and 5.7 W/m^(2) in acidic and alkaline conditions, respectively, using a 50‐fold salt gradient. For different anions but the same cation diffusion transport, the amphoteric membrane produces an outstanding I−/CO_(3)^(2−) selectivity of ~4160 and an osmotic energy conversion of ~133.5 W/m^(2). The amphoteric membrane concept introduces a new pathway to explore the development of ion transport and separation technologies and their application in osmotic energy‐conversion devices and flow batteries.展开更多
To improve the low-temperature performances of Li-ion cells, three types of linear carboxylic ester-based electrolyte, such as EC/EMC/EA（1：1：2, mass ratio）, EC/EMC/EP（1：1：2, mass ratio） and EC/EMC/EB（1：1：2,...To improve the low-temperature performances of Li-ion cells, three types of linear carboxylic ester-based electrolyte, such as EC/EMC/EA（1：1：2, mass ratio）, EC/EMC/EP（1：1：2, mass ratio） and EC/EMC/EB（1：1：2, mass ratio）, were prepared to substitute for industrial electrolyte（EC/EMC/DMC）. Then, 18650-type Li Mn2O4-graphite cells（nominal capacity of 1150 mA ·h） were assembled and studied. Results show that the cells containing three types of electrolyte are able to undertake 5C discharging current with above 93% capacity retention at-20 °C. Electrochemical impedance spectra show that the discharge capacity fading of Li-ion cells at low temperature is mainly ascribed to the charge transfer resistance increasing with temperature decreasing. In comparison, the cells containing electrolyte of 1.0 mol/L LiPF6 in EC/EMC/EA（1：1：2, mass ratio） have the highest capacity retention of 90% at-40 °C and 44.41% at-60 °C, due to its lowest charge-transfer resistance.展开更多
文摘Under hydrothermal and solvothermal conditions,two novel cobalt-based complexes,{[Co_(2)(CIA)(OH)(1,4-dtb)]·3.2H_(2)O}n(HU23)and{[Co_(2)(CIA)(OH)(1,4-dib)]·3.5H2O·DMF}n(HU24),were successfully constructed by coordinatively assembling the semi-rigid multidentate ligand 5-(1-carboxyethoxy)isophthalic acid(H₃CIA)with the Nheterocyclic ligands 1,4-di(4H-1,2,4-triazol-4-yl)benzene(1,4-dtb)and 1,4-di(1H-imidazol-1-yl)benzene(1,4-dib),respectively,around Co^(2+)ions.Single-crystal X-ray diffraction analysis revealed that in both complexes HU23 and HU24,the CIA^(3-)anions adopt aκ^(7)-coordination mode,bridging six Co^(2+)ions via their five carboxylate oxygen atoms and one ether oxygen atom.This linkage forms tetranuclear[Co4(μ3-OH)2]^(6+)units.These Co-oxo cluster units were interconnected by CIA^(3-)anions to assemble into 2D kgd-type structures featuring a 3,6-connected topology.The 2D layers were further connected by 1,4-dtb and 1,4-dib,resulting in 3D pillar-layered frameworks for HU23 and HU24.Notably,despite the similar configurations of 1,4-dtb and 1,4-dib,differences in their coordination spatial orientations lead to topological divergence in the 3D frameworks of HU23 and HU24.Topological analysis indicates that the frameworks of HU23 and HU24 can be simplified into a 3,10-connected net(point symbol:(4^(10).6^(3).8^(2))(4^(3))_(2))and a 3,8-connected tfz-d net(point symbol:(4^(3))_(2)((4^(6).6^(18).8^(4)))),respectively.This structural differentiation confirms the precise regulatory role of ligands on the topology of metal-organic frameworks.Moreover,the ultraviolet-visible absorption spectra confirmed that HU23 and HU24 have strong absorption capabilities for ultraviolet and visible light.According to the Kubelka-Munk method,their bandwidths were 2.15 and 2.08 eV,respectively,which are consistent with those of typical semiconductor materials.Variable-temperature magnetic susceptibility measurements(2-300 K)revealed significant antiferromagnetic coupling in both complexes,with their effective magnetic moments decreasing markedly as the temperature lowered.CCDC:2457554,HU23;2457553,HU24.
文摘In this study,polyacrylic acid(PAA)films were employed as a model system,and a series of PAA films with tunable water wettability was systematically prepared by varying molecular weight and curing temperature.Using attenuated total reflectance Fourier-transform infrared spectroscopy(ATR-FTIR),the molecular configurations of surface carboxyl groups(COOH),free carboxyl(COOH_(f))and hydrogen-bonded carboxyl(COOH_(HB),were directly correlated with the polar component of surface energy(γ^(s,p)).By decomposing theγ^(s,p)values of the PAA thin films as a sum of the contributions of COOH_(f)and COOH_(H B),the intrinsic polar component of surface energy of COOH_(H B)(γ_(H B)^(s,p*))was quantified for the first time as 8.34 mN/m,significantly lower than that of COOH_(f)(γ_(f)^(s,p*)=34 mN/m).This result highlights that hydrogen bonding markedly reduces theγ^(s,p),providing a rational explanation for the relatively large water contact angle observed on PAA thin films.Furthermore,it establishes a thermodynamic basis for estimating the fraction of surface COOH_(H B)groups(f H B)from wettability measurements.Further extension of the model to carboxyl-terminated self-assembled monolayers(COOH-SAMs)revealed that surface COOH density(ΣCOOH)critically regulates wetting behavior:whenΣCOOH ranges from 4.30 to 5.25 nm^(-2),COOH groups predominantly exist in a free state and facilitate effective hydration layers,thereby promoting superhydrophilicity.Overall,this study not only establishes a unified thermodynamic framework linking surface COOH configurations to macroscopic wettability,but also validates its universality by extending it to COOH-SAMs systems,thereby providing a unified theoretical framework for the controllable design of hydrophilicity in various COOH-functionalized surfaces.
基金the financial support from the Natural Science Foundation of Jiangsu Province(BK20231292)the Jiangsu Agricultural Science and Technology Innovation Fund(CX(24)3091)+6 种基金the Postgraduate Research&Practice Innovation Program of Jiangsu Province(KYCX25_1429)the National Key R&D Program of China(2024YFE0109200)the Fundamental Research Funds for the Central Universities(No.2024300440)Guangdong Basic and Applied Basic Research Foundation(2025A1515011098)the National Natural Science Foundation of China(12464032)the Natural Science Foundation of Jiangxi Province(20232BAB201032)Ji'an Science and Technology Plan Project(2024H-100301)。
文摘Zn-I_(2) batteries have emerged as promising next-generation energy storage systems owing to their inherent safety,environmental compatibility,rapid reaction kinetics,and small voltage hysteresis.Nevertheless,two critical challenges,i.e.,zinc dendrite growth and polyiodide shuttle effect,severely impede their commercial viability.To conquer these limitations,this study develops a multifunctional separator fabricated from straw-derived carboxylated nanocellulose,with its negative charge density further reinforced by anionic polyacrylamide incorporation.This modification simultaneously improves the separator’s mechanical properties,ionic conductivity,and Zn^(2+)ion transfer number.Remarkably,despite its ultrathin 20μm profile,the engineered separator demonstrates exceptional dendrite suppression and parasitic reaction inhibition,enabling Zn//Zn symmetric cells to achieve impressive cycle life(>1800 h at 2 m A cm^(-2)/2 m Ah cm^(-2))while maintaining robust performance even at ultrahigh areal capacities(25 m Ah cm^(-2)).Additionally,the separator’s anionic characteristic effectively blocks polyiodide migration through electrostatic repulsion,yielding Zn-I_(2) batteries with outstanding rate capability(120.7 m Ah g^(-1)at 5 A g^(-1))and excellent cyclability(94.2%capacity retention after 10,000 cycles).And superior cycling stability can still be achieved under zinc-deficient condition and pouch cell configuration.This work establishes a new paradigm for designing high-performance zinc-based energy storage systems through rational separator engineering.
基金financially supported by Natural Science Foundation Project of CQ(No.CSTB2023NSCQ-LZX0067)Science and Technology Research Program of Chongqing Municipal Education Commission(No.KJZD-K202200804)+1 种基金Venture&Innovation Support Program for Chongqing Overseas Returnees(No.cx2020113)National Natural Science Foundation of China(No.21201184).
文摘Achieving heterogeneous photocatalytic activation of sp^(3)C-H bonds and carboxylation of CO_(2)to produce arylacetic acids and alkyl carboxylic acids with increased carbon chains is a highly significant and demanding research endeavor.In this work,a new method for synthesizing redox centers spatially separated Z-scheme CdS@graphitic carbon nitride(g-C_(3)N_(4))was developed,aiming to achieve photocatalytic benzylic and aliphatic sp^(3)C-H activation as well as CO_(2)carboxylation without sacrificial agent.Notably,both benzylic and aliphatic sp^(3)C-H activation together with CO_(2)carboxylation were achieved in heterogeneous photocatalytic system,resulting in the production of carboxylic acids with increased carbon chains under mild conditions.Various methylbenzene derivatives and cycloalkanes were employed to synthesize carbon-chain increased acids via a process involving K_(3)PO_(4)-assisted photogenerated holes activation for benzyl radical generation,photoinduced CO_(2)reduction,as well as solvent-assisted chemoselective carboxylation.Various characterizations and density functional theory(DFT)results revealed that Z-scheme CdS@g-C_(3)N_(4)not just significantly enhanced separation of charges and accumulation of photoinduced electrons on g-C_(3)N_(4)but also facilitated adsorption along with activation of CO_(2).This research provided novel heterogeneous photocatalytic approach to produce carbon chains increased carboxylic acids via sp^(3)C-H activation and CO_(2)carboxylation.
基金supported by the National Natural Science Foundation of China,Nos.91849115 and U1904207(to YX),81974211 and 82171247(to CS)Non-profit Central Research Institute Fund of Chinese Academy of Medical Sciences,No.2020-PT310-01(to YX).
文摘The E3 ubiquitin ligase,carboxyl terminus of heat shock protein 70(Hsp70)interacting protein(CHIP),also functions as a co-chaperone and plays a crucial role in the protein quality control system.In this study,we aimed to investigate the neuroprotective effect of overexpressed CHIP on Alzheimer’s disease.We used an adeno-associated virus vector that can cross the blood-brain barrier to mediate CHIP overexpression in APP/PS1 mouse brain.CHIP overexpression significantly ameliorated the performance of APP/PS1 mice in the Morris water maze and nest building tests,reduced amyloid-βplaques,and decreased the expression of both amyloid-βand phosphorylated tau.CHIP also alleviated the concentration of microglia and astrocytes around plaques.In APP/PS1 mice of a younger age,CHIP overexpression promoted an increase in ADAM10 expression and inhibitedβ-site APP cleaving enzyme 1,insulin degrading enzyme,and neprilysin expression.Levels of HSP70 and HSP40,which have functional relevance to CHIP,were also increased.Single nuclei transcriptome sequencing in the hippocampus of CHIP overexpressed mice showed that the lysosomal pathway and oligodendrocyte-related biological processes were up-regulated,which may also reflect a potential mechanism for the neuroprotective effect of CHIP.Our research shows that CHIP effectively reduces the behavior and pathological manifestations of APP/PS1 mice.Indeed,overexpression of CHIP could be a beneficial approach for the treatment of Alzheimer’s disease.
文摘Bay-site carboxyl functionalized perylene diimide derivative 1,7-COOH-PDI-C_(12)(PDI-COOH)was synthesized and distinct enhanced fluorescence was observed through combining with calcium ion(Ca^(2+))in THF/H_(2)O solution.The assembly and fluorescence behavior of PDI-COOH/Ca^(2+)were studied in detail by changing hydration state with different concentrations.Based on the differences in assembly morphology and stoichiometric ratios of PDICOOH/Ca^(2+),we proposed the fluorescence emission mechanism of PDI-COOH/Ca^(2+)in THF/H_(2)O and THF,respectively.This work reveals a novel strategy of aggregated state fluorescence enhancement and reminds us of the important role of water in molecular fluorescence emission and assembly.
基金the National Natural Science Foundation of China(No.21978164,22078189 and 22105120)the Outstanding Youth Science Fund of Shaanxi Province(No.2021JC-046)and the Special Support Program for high level talents of Shaanxi Province+3 种基金the Innovation Support Program of Shaanxi Province(2021JZY-001)the Key Research and Development Program of Shaanxi Province(No.2020GY-243)the Special Research Fund of Education Department of Shaanxi(No.20JK0535)the National High-end Foreign Expert Project(No.GDW20186100428).
文摘Pore structure engineering has been acknowledged as suitable approach to creating active sites and en-hancing ion transport capabilities of hard carbon anodes.However,conventional porous carbon materials exhibit high BET and surface defects.Additionally,the sodium storage mechanism predominantly occurs in the slope region.This contradicts practical application requirements because the capacity of the plateau region is crucial for determining the actual capacity of batteries.In our work,we prepared a novel“core-shell”carbon framework(CNA1200).Introducingclosedporesand carboxylgroupsinto coal-basedcarbon materials to enhance its sodium storage performance.The closed pore structure dominates in the“core”structure,which is attributed to the timely removal of sodium hydroxide(NaOH)to prevent further for-mation of active carbon structure.The presence of closed pores is beneficial for increasing sodium ion storage in the low-voltage plateau region.And the“shell”structure originates from coal tar pitch,it not only uniformly connects hard carbon particles together to improve cycling stability,but is also rich in carboxyl groups to enhance the reversible sodium storage performance in slope region.CNA1200 has ex-cellent electrochemical performance,it exhibits a specific capacity of 335.2 mAh g^(−1)at a current density of 20 mA g^(−1)with ICE=51.53%.In addition,CNA1200 has outstanding cycling stability with a capac-ity retention of 91.8%even when cycling over 200 times.When CNA1200 is used as anode paired with Na_(3)V_(2)(PO_(4))_(3)cathode,it demonstrates a capacity of 109.54 mAh g^(−1)at 0.1 C and capacity retention of 94.64%at 0.5 C.This work provides valuable methods for regulating the structure of sodium-ion battery(SIBs)anode and enhances the potential for commercialization.
基金supported by LifeArc Philanthropic Fund(P2019-0004)LifeArc Pathfinder Award+7 种基金along with Wellcome Trust Seed Award(109626/Z/15/Z)FA PESP-UoB Strategic Collaboration FundBirmingham Fellowship(to SS)grants from Laboratoire d'Excellence Revive(Investissement d'AvenirANR-10-LABX-73)the Region lle-de-France via doctoral school Innovation Therapeutique,du Fondamentalàl'Appliqué(ED569)from Universite Paris-Saclay(to LA)Medical Research Council(MRC)Developmental Pathway Funding Scheme(DPFS)grant(MR/P007732/1)(to TB)supported by the Association Fran?aise contre les Myopathies(AFM-Téléthon)。
文摘Mitochondria and mitochondria-associated endoplasmic reticulum membrane in neurodegenerative diseases:Mitochondria generate most of the chemical energy needed to power the biochemical reactions of cells,and thus are often referred to as the"powerhouse"of the cell.Nevertheless,this organelle is also involved in a pleth,ora of different cellular functions such as calcium(Ca^(2+))homeostasis,apoptosis,oxidative stress,and several metabolic pathways including oxidative phosphorylation,tricarboxylic acid cycle,andβ-oxidation of fatty acids.
文摘An efficient TfOH-catalyzed O—H insertion reaction of α-aryl diazoesters with carboxylic acids is reported.This metal-free protocol provides an operationally simple method for a one-pot assembly of diverse α-acyloxy esters in moderate to high yields with a broad substrate scope.All starting materials are readily available,and the reactions can be conducted in the open air at room temperature.
文摘Four new coordination polymers,{[Cd(mbtx)(4OHphCOO)]NO_(3)}n(1),{[Zn(mbtx)(1,4-bdc)_(0.5)(H_(2)O)_(2)]·(1,4-bdc)_(0.5)·4H_(2)O}n(2),{[Cd2(mbtx)(5NO_(2)-bdc)_(2)(H_(2)O)_(3)]·4.5H_(2)O}n(3),and{[Zn(H_(2)O)6][Zn_(2)(mbtx)_(2)(btc)_(2)(H_(2)O)_(4)]·2H_(2)O}n(4)(mbtx=1,3-bis(4H-1,2,4-triazole)benzene,4OHphCOO-=p-hydroxybenzoate,1,4-bdc2-=1,4-benzenedicarboxylate,5NO_(2)-bdc2-=5-nitro-isophthalate,btc3-=1,3,5-benzenetricarboxylate),were synthesized under room temperature condition and characterized by single-crystal X-ray diffraction,elemental analyses,and powder X-ray diffraction.Single-crystal X-ray structural analysis shows that complexes 1 and 3 are 2D networks.In 1,the adjacent 2D networks are linked to a 3D network byπ-πstacking interaction.2 and 4 exhibit 1D chains,and the 1D chains are connected into a 3D network byπ-πstacking interaction and intermolecular hydrogen bond.Luminescence and thermogravimetric analysis of the four complexes were discussed.CCDC:2416406,1;2416407,2;2416408,3;2416409,4.
基金the National Key R&D Program of China(No.2022YFB4101900)National Natural Science Foundation of China(Nos.22278305,U21B2096)Natural Science Foundation of Tianjin City(No.23JCZDJC00040)。
文摘A strategy for copper-catalyzed and biphosphine ligand controlled boracarboxylation of 1,3-dienes and CO_(2) with 3,4-selectivity was developed.The Cu Cl coupled with DPPF(1,1-bis(diphenylphosphino)ferrocene)was assigned to be the best catalyst,with 84%yield and exclusive3,4-selectivity.The ligand effect on both catalytic activity and regioselectivity of boracarboxylation was disclosed,which is rarely reported in any copper catalyzed boracarboxylation.The borocupration process is revealed to be a vital step for the biphosphine participated boracarboxylation of 1,3-dienes with CO_(2).The minimal substrate distortion occurring in 3,4-borocupration favors the 3,4-regioselectivity of boracarboxylation.The“pocket”confinement and suitableβ_(n)(92°–106°)of bisphosphine ligands are demonstrated to be in favour of the interaction between LCu-Bpin complex(the catalytic precursor)and1,3-diene substrate to decrease their interaction energyΔE_(int)(ζ)in 3,4-borocupration,thus promoting the 3,4-boracarboxylation.
基金supported by the National Key R&D Program of China(No.2022YFC2105301)the National Natural Science Foundation of China(No.52270096).
文摘Microbial consortia that catalyze chain elongation processes have been enriched using different selection strategies,for which the electron donor is an essential one.Propanol is an extraordinarily promising electron donor because it can be generated from renewable resources,including lignocellulosic biomass and protein wastes.Here,propanol was proven in detail to be an efficient electron donor,enhancing the production of odd medium-chain carboxylates during chain elongation.By exploring various electron acceptors,reactor conditions,and electron donor/electron acceptor mol ratios,our study highlights that acetate is the most suitable electron acceptor for the production of both odd-and even-chain carboxylates.The optimal conditions for propanol-based chain elongation were 30℃ and pH 6,achieving 82.8%selectivity for odd-chain carboxylates.Another critical insight from our work is that a propanol/acetate mol ratio of 1:1 can minimize the inhibitory effect of propanol and maximize the yield of medium-chain carboxylates,with the highest concentration of n-heptanoate reaching 124.5 mmol C/L.This was further illustrated by 16S rRNA amplicon sequencing,which elucidated that the community composition and keystone species in a propanol-based reactor closely resembled that of the ethanol one.The dominant phylum of the propanol-based reactor,Firmicutes showed a significant positive correlation with the concentrations of n-caproate and n-valerate.Additionally,the co-occurrence of Clostridium sensu stricto 12 and Oscillibacter,known as typical chain elongators,was identified within the propanol-based reactor.These findings enhance our understanding of propanolbased chain elongation,offer guiding principles for reactor microbiota assembly,and support efficient odd medium-chain carboxylate production.
基金financial support from the National Natural Science Foundation of China(22408258 and 22378287)the Joint Founds of the National Natural Science Foundation of China(U20B6004)the Natural Science Foundation of Shanxi Province(202303021222012).
文摘Unconventional natural gas has become an important supplement to conventional energy sources,and the process of enrichment and purification of methane from low concentration coalbed methane is crucial.To this end,we report a copper-based metal-organic framework(MOF),ZJNU-119Cu,featuring two methane traps constructed with uncoordinated carboxylic acid oxygens and open metal sites.ZJNU-119Cu exhibits a high methane adsorption capacity(58.2 cm^(3)·g^(-1))at 298 K and 0.1 MPa and excellent CH_(4)/N_(2) separation performance under dynamic conditions.Densityfunctional theory calculations combined with grand canonical Monte Carlo simulation theory reveal the interaction mechanism for the uncoordinated carboxylic acid oxygen atoms and open metal sites in ZJNU-119Cu with CH4.The gas adsorption isotherms,heat of adsorption calculations,and breakthrough separation experiments indicate that this MOF is a very promising adsorbent for CH_(4)/N_(2) separation.
基金funding programs,the Walter Benjamin Programme(DFG,German Research Foundation,project number:530742479)the ProChancecareer Programme for the Promotion of Equal Opportunities in Academia for providing the financial support+1 种基金financial support by the Deutsche Forschungsgemeinschaft via the TRR 234 Cata Light(DFG,German Research Foundation)-Projektnummer 364549901-TRR 234[B6]the financial support taken from the CSIR and UGC,Delhi,India。
文摘The photocatalytic reduction of CO_(2)is a crucial area of research aimed at addressing the dual challenges of mitigating rising CO_(2)emissions and producing sustainable chemical feedstocks.While multielectron reduction pathways for CO_(2)are well explored,the single electron reduction to produce the highly reactive carbon dioxide radical anion(CO_(2)^(·-))remains challenging yet promising for green organic transformations.This review contributes to the field by providing a comprehensive analysis of the mechanisms,materials,and reaction pathways involved in CO_(2)^(·-)generation,focusing on the use of visible-lightdriven photocatalytic materials to circumvent the need for high-energy ultraviolet irradiation.Through a systematic examination of CO_(2)^(·-)production,detection methods,and chemical utilization in photocatalytic carboxylation reactions,this review advances understanding of the chemistry of CO_(2)^(·-)and its applications in sustainable chemical synthesis.In addition,it highlights existing key challenges,such as redox potential limitations,and proposes strategies for scaling up photocatalytic systems to enable practical application.By illuminating the pathway to effectively photocatalyze CO_(2)^(·-)generation and its transformative potential in sustainable chemical synthesis,this review equips scientists with critical insights and strategic approaches for overcoming current limitations,driving innovation in photocatalytic materials for solar-to-chemical energy conversion.
基金Project supported by the National Natural Science Foundation Regional Innovation Development Joint Fund(U24A2096)。
文摘Surfactant sodium alcohol ether carboxylate(AEC-9Na)was added to the magnesium sulfate solution in order to enhance the leaching efficiency of ionic rare earth ore,and the mechanism of action for AEC-9Na was elucidated.Under optimal conditions,the addition of AEC-9Na with a mass fraction of 0.03% can enhance the leaching rate by 5.2% and reduce the leaching cycle.Kinetic analysis demonstrates that the leaching process follows the model of internal diffusion control.The analysis of the mass transfer process reveals that the addition of AEC-9Na results in a decrease in the height equivalent to a theoretical plate(HETP)and an improvement in mass transfer efficiency.The addition of AEC-9Na can reduce the thickness of the water layer adsorbed on particles during leaching,which in turn reduces hydration and facilitates penetration of the leaching solution into ore body pores.This improves mass transfer concentration differences during leaching,and facilitates desorption of rare earth ions.Periodic density functional theory(DFT)calculations show that the adsorption of AEC-9Na onto the surface of kaolinite(001)enhances the hydrophilicity of the mineral surface and improves its permeability efficiency.Simultaneously,AEC-9Na forms complexes with hydrated rare earth ions on the kaolinite(001)surface,thereby reducing their adsorption strength on clay minerals.This promotes the exchange and desorption process of magnesium ions to hydrated rare earth ions,ultimately enhancing the mass transfer process for leaching rare earth elements.
基金financially supported by the National Natural Science Foundation of China(Grant Nos.52073043 and 52173069)the Fundamental Research Funds for the Central Universities(Grant No.2572022CG03)+1 种基金the Key Research and Development Projects in Heilongjiang Province(Grant No.GZ20210089)the Australian Research Council(Grant Nos.LP220100278,DP240102628,and DP240102728).
文摘Solar-driven thermo-electric generation(STEG)emerges as a promising solution to mitigate the global en-ergy shortage.However,the practical application of conventional photothermal materials equipped with STEG is limited due to low solar thermal conversion efficiency.Herein,we fabricated an epoxy resin(EP)nanocomposite,EP/CCA80,with excellent photo-thermal-electric conversion properties by embedding a vertically aligned aerogel consisting of cellulose nanofibers(CNF)and carboxylated multi-walled carbon nanotubes(CMWCNTs)into a transparent EP matrix.EP/CCA80 composites possessed a broad light ab-sorption range from 200 nm to 2500 nm and excellent photothermal properties.Under illumination of 1.0 kW m^(-2),EP/CCA80 achieved a notable stable temperature of 93.2℃ and a photothermal conversion efficiency of up to 54.35%with only 0.65 wt%CMWCNTs inclusion.Additionally,coupled with thermo-electric(TE)devices,the EP/CCA80 composite facilitated a significant temperature difference and voltage output of up to 25.3℃ and 160.29 mV(1.0 kW m^(-2)),respectively,which could power a small fan to rotate at a speed of 193 min^(-1).Such materials are poised to offer viable solutions for enhancing energy accessibility in remote regions,thereby contributing to the reduction of energy shortages and environ-mental degradation.
基金Funded by the National Natural Science Foundation of China(No.11804121)Special Funds for Central Guiding Local Scientific and Technological Development Project(No.2016ZYYD049)。
文摘The detection of circulating tumor DNA(ctDNA)with high sensitivity and specificity is crucial for the early diagnosis and monitoring of tumors,as well as for drug therapy.In this study,a simple and highly sensitive biosensor was specifically designed for the identification of targeted ctDNA.For the first time,a three-dimensional polyvinylidene fluoride-graphene oxide-chitosan(PVDF/CS/GO)nanofiber mesh was fabricated on a polydimethylsiloxane(PDMS)micropillar substrate using electrospinning technology,and the nanofibers were functionalized with peptide nucleic acids probe-gold nanoparticle(PNA-AuNP)complexes,which served as affinity molecules for detecting the methylation of the E542K variant of the phosphatidylinositol-4,5-bisphosphate 3-kinase catalytic subunit α(PIK3CA)gene in the peripheral blood of cancer patients.Additionally,an anti-5-Methylcytosine monoclonal antibody-multi-walled carbon nanotubes-COOH complex(Anti-5-mC-MWCNTs-COOH)complex was incubated to result in significantly amplified electrochemical signals for the accurate quantification of the E542K variant of the PIK3CA gene.Detectable signal responses were observed only when both molecules were simultaneously present,greatly enhancing the accuracy of the analysis.The biosensor exhibits high capture sensitivity for the methylation level of the E542K variant of the PIK3CA gene across a concentration range of 50 to 10000 fmol/L,with the lowest detection limit of 10 fmol/L.The ctDNA nanobiosensor has been shown to be both feasible and valuable for quantifying ctDNA concentrations in clinical blood samples.Consequently,this 3D nanofiber biosensor shows significant potential for clinical applications in cancer diagnosis and personalized medical treatments.
基金financially supported by the Jiangsu Province Shuangchuang Ph.D.award(No.JSSCBS20211267,Pei Xu)the Natural Science Research Project of Jiangsu Universities(No.23KJB150037,Pei Xu)+2 种基金sponsored by the Jiangsu Specially-Appointed Professor Program(Xu Zhu)the Start-up Funding provided by Xuzhou Medical UniversityThe Public Experimental Research Center of Xuzhou Medical University is also acknowledged。
文摘Oxalic acid salts(oxalate)were recently developed as C1 synthon,potent single-electron-transfer(SET)reductant,and hole scavengers via generation of CO_(2) and CO_(2) radical anion(CO_(2)·^(-))under mild photochemical conditions.A series of challenging reductive transformations were realized with oxalic dianion under catalytic photoredox conditions or through an electron-donor-acceptor(EDA)complex formation process.As a chemical intermediate for carbon capture and utilization(also a cheap and readily available reagent),oxalate salts could release one electron easily(E_(ox)=+0.06 V vs.SCE)via visible-light irradiation to give CO_(2) and CO_(2)·^(-) and therefore opened a new arena for reductive carboxylation reactions with highly expanded reaction diversity and chemical space to realize challenging C-X bond activation,alkenes cross coupling,and reductive carboxylation of unsaturated chemical bonds in a more sustainable and efficient way.This review features the recently developed aspects with oxalate salts and also an outlook for its further application in organic radical transformations.
基金the support provided by the Surface Analysis Laboratory, Solid State and Elemental Analysis Unit, Mark Wainwright Analytical Centre of the University of New South Walesthe support of the Iranian Research Organization for Science and Technology (IROST), contract no. 034592
文摘Salination of solutions of salinity gradient releases large‐scale clean and renewable energy, which can be directly and efficiently transformed into electrical energy using ion‐selective nanofluidic channel membranes. However, conventional ion‐selective membranes are typically either cation‐ or anion‐selective. A pH‐switchable system capable of dual cation and anion transport along with salt gradient energy harvesting properties has not been demonstrated in ion‐selective membranes. Here, we constructed an amphoteric heterolayer metal–organic framework (MOF) membrane with subnanochannels modified with carboxylic and amino functional groups. The amphoteric MOF‐composite membrane, AAO/aUiO‐66‐(COOH)_(2)/UiO‐66‐NH_(2), exhibits pH‐tuneable ion conduction and achieves osmotic energy conversion of 7.4 and 5.7 W/m^(2) in acidic and alkaline conditions, respectively, using a 50‐fold salt gradient. For different anions but the same cation diffusion transport, the amphoteric membrane produces an outstanding I−/CO_(3)^(2−) selectivity of ~4160 and an osmotic energy conversion of ~133.5 W/m^(2). The amphoteric membrane concept introduces a new pathway to explore the development of ion transport and separation technologies and their application in osmotic energy‐conversion devices and flow batteries.
基金Project(2007BAE12B01)supported by the National Key Technology Research and Development Program of ChinaProject(20803095)supported by the National Natural Science Foundation of China
文摘To improve the low-temperature performances of Li-ion cells, three types of linear carboxylic ester-based electrolyte, such as EC/EMC/EA（1：1：2, mass ratio）, EC/EMC/EP（1：1：2, mass ratio） and EC/EMC/EB（1：1：2, mass ratio）, were prepared to substitute for industrial electrolyte（EC/EMC/DMC）. Then, 18650-type Li Mn2O4-graphite cells（nominal capacity of 1150 mA ·h） were assembled and studied. Results show that the cells containing three types of electrolyte are able to undertake 5C discharging current with above 93% capacity retention at-20 °C. Electrochemical impedance spectra show that the discharge capacity fading of Li-ion cells at low temperature is mainly ascribed to the charge transfer resistance increasing with temperature decreasing. In comparison, the cells containing electrolyte of 1.0 mol/L LiPF6 in EC/EMC/EA（1：1：2, mass ratio） have the highest capacity retention of 90% at-40 °C and 44.41% at-60 °C, due to its lowest charge-transfer resistance.
