Mature pollen germinates rapidly on the stigma,extending its pollen tube to deliver sperm cells to the ovule for fertilization.The success of this process is an important factor that limits output.The flavonoid conten...Mature pollen germinates rapidly on the stigma,extending its pollen tube to deliver sperm cells to the ovule for fertilization.The success of this process is an important factor that limits output.The flavonoid content increased signi ficantly during pollen germination and pollen tube growth,which suggests it may play an important role in these processes.However,the speci fi c mechanism of this involvement has been little researched.Our previous research found that hyperoside can prolong the flowering period of Abelmoschus esculentus(okra),but its speci fic mechanism is still unclear.Therefore,in this study,we focused on the effect of hyperoside in regulating the actin-depolymerizing factor(ADF),which further affects the germination and growth of pollen.We found that hyperoside can prolong the effective pollination period of okra by 2-3-fold and promote the growth of pollen tubes in the style.Then,we used Nicotiana benthamiana cells as a research system and found that hyperoside accelerates the depolymerization of intercellular micro fi laments.Hyperoside can promote pollen germination and pollen tube elongation in vitro.Moreover,AeADFl was identi fied out of all AeADF genes as being highly expressed in pollen tubes in response to hyperoside.In addition,hyperoside promoted AeADF1-mediated micro filament dissipation according to micro filament severing experiments in vitro.In the pollen tube,the gene expression of AeADFl was reduced to 1/5 by oligonucleotide transfection.The decrease in the expression level of AeADFl partially reduced the promoting effect of hyperoside on pollen germination and pollen tube growth.This research provides new research directions for flavonoids in reproductive development.展开更多
One important subject in the field of all-polymer solar cells (all-PSCs) is the exploration of electron-deficient building blocks with optimized physicochemical properties to promote the performance of polymer accepto...One important subject in the field of all-polymer solar cells (all-PSCs) is the exploration of electron-deficient building blocks with optimized physicochemical properties to promote the performance of polymer acceptors. Here, two ladder-type heteroheptacene-containing small-molecule acceptors with branched 2-octyldodecyl or 2-hexyldecyl side-chains are synthesized and polymerized with the thiophene co-monomer to afford polymer acceptors (PW-OD and PW-HD) with strong near-infrared absorption. Experimental results reveal that the alkyl chain length has a large impact on the molecular packing behavior of the resulting polymers, which in turn affects their light-absorbing and charge transport properties, and thus the photovoltaic performance of the final devices. When blended with the polymer donor PM6, PW-HD-based all-PSCs deliver a higher power conversion efficiency (PCE) of 9.12% compared to the PCE of 6.47% for the PW-OD-based all-PSCs, mainly due to its more ordered inter-chain packing and more favorable blend morphology. This work provides a promising building block for the development of high-performance narrow-bandgap polymer acceptors and highlights the importance of side-chain substitution in optimizing the photovoltaic performance of polymer acceptors.展开更多
Background:Emerging mounts of research support the ancestral theory of cancer,indicating that tumorigenesis and embryogenesis share many similar biological features,yet yield distinct outcomes.Gene co-expression netwo...Background:Emerging mounts of research support the ancestral theory of cancer,indicating that tumorigenesis and embryogenesis share many similar biological features,yet yield distinct outcomes.Gene co-expression networks underlie both embryonic development and tumorigenesis.We hypothesize that deviations in the gene interaction patterns in tumors compared to villi predispose to malignancy and worse prognosis.Methods:By constructing a gene co-expression network of villi and colorectal cancer(CRC)and conducting functional enrichment analysis to identify“off-track genes.”Cox regression assessed prognostic significance,while tissue microarrays evaluated protein expression and progression.Additionally,mRNA sequencing of chondroitin polymerizing factor(CHPF)-knockdown LOVO and SW480 cell lines was conducted and validated via in vitro assays.Results:We found that genes in villi and CRC have similar functions,but the genes that performed corresponding functions were not identical.Then,according to“off-track theory”and linear regression models,we obtained 24 genes whose aberrant expression was significantly associated with poor CRC survival.Notably,CHPF emerged as an adverse prognostic factor.Immunohistochemical analysis confirmed that CHPF is an independent prognostic marker for CRC.Furthermore,cell phenotype assays demonstrated that CHPF enhances proliferation and migration,suppresses apoptosis,and engages in the TNF signaling pathway.Conclusion:These findings validate that villi development can serve as a research model for tumorigenesis,and identify CHPF is an independent oncogenic factor in CRC,suggesting its potential as a prognostic biomarker and a therapeutic target for clinical treatment.展开更多
Among various architectures of polymers,end-group-free rings have attracted growing interests due to their distinct physicochemical performances over the linear counterparts which are exemplified by reduced hydrodynam...Among various architectures of polymers,end-group-free rings have attracted growing interests due to their distinct physicochemical performances over the linear counterparts which are exemplified by reduced hydrodynamic size and slower degradation.It is key to develop facile methods to large-scale synthesis of polymer rings with tunable compositions and microstructures.Recent progresses in large-scale synthesis of polymer rings against single-chain dynamic nanoparticles,and the example applications in synchronous enhancing toughness and strength of polymer nanocomposites are summarized.Once there is the breakthrough in rational design and effective large-scale synthesis of polymer rings and their functional derivatives,a family of cyclic functional hybrids would be available,thus providing a new paradigm in developing polymer science and engineering.展开更多
Four distinct coordination polymers(CPs)were successfully synthesized by altering solvent types and adjusting ligand concentrations,and their crystal structures were investigated.[Co(L)(FDCA)(H_(2)O)_(2)]·0.5H_(2...Four distinct coordination polymers(CPs)were successfully synthesized by altering solvent types and adjusting ligand concentrations,and their crystal structures were investigated.[Co(L)(FDCA)(H_(2)O)_(2)]·0.5H_(2)O(1)was synthesized as a 2D structure using Coas the metal source,methanol‑water(4∶6,V/V)as the solvent,and specific concentrations of 2,5‑furandicarboxylic acid(H_(2)FDCA)and 1,3,5‑triimidazole benzene(L).Adjusting to pure water and lowering the concentration of L yielded the 1D chain structure of[Co(HL)2(H_(2)O)_(2)](FDCA)_(2)·6H_(2)O(2).Using Cu(Ⅱ)as the metal source,methanol/water(9∶1,V/V)as the solvent,and specific concentrations of L and H2FDCA,the 1D chain structure of[Cu(L)(FDCA)(H_(2)O)]·2H_(2)O(3)was synthesized.Upon increasing the concentrations of L and H2FDCA,and switching the solvent to pure water,the 1D chain structure of[Cu(HL)_(2)(H_(2)O)_(2)](FDCA)_(2)·6H_(2)O(4)was obtained.This shows that changing the solvent and ligand concentrations can affect the structural changes of CPs.In addition,the solid‑state photoluminescence of CPs 1‑4 at room temperature was studied,and their morphological changes were observed via scanning electron microscopy.Density functional theory calculations revealed that the negative charge concentrates on the O and N atoms of the ligand,facilitating ligand‑metal ion coordination.CCDC:2403934,1;2403935,2;2403936,3;2403938,4.展开更多
Organic pollutants,a pivotal factor in water pollution,have persistently menaced the aquatic ecosystem,as well as the sustainable development of human health,economy,and society.Consequently,there is an urgent need fo...Organic pollutants,a pivotal factor in water pollution,have persistently menaced the aquatic ecosystem,as well as the sustainable development of human health,economy,and society.Consequently,there is an urgent need for advanced techniques to efficiently eliminate organic micropollutants from water.Here,we present the synthesis of three nonporous cavitand-crosslinked polymers capable of adsorbing diverse organic pollutants from aqueous solutions.These polymeric adsorbents exhibit outstanding adsorptive performance towards the tested micropollutants,characterized by high apparent adsorption rate constants(kobs)and maximum adsorption capacities(qmax,e).Notably,Compound NCCP-1 demonstrated a remarkable qmax,e of 459 mg/g for bisphenol A(BPA),ranking among the highest values reported for organic polymer adsorbents.In-depth investigation of the adsorption mechanism of the nonporous polymer revealed that it involves the recognition of pollutants by the deep cavities of the cavitand moieties and the interstitial spaces between them,primarily mediated by the hydrophobic effect.Furthermore,NCCP-1 was applied in situ water purification simulations and was proven to maintain its removal efficiency over more than four cycles,highlighting its potential for practical applications in water treatment.展开更多
Submission.Papers appearing in the Journal comprise Editorials,Rapid Communications,Perspectives,Tutorials,Feature Articles,Reviews,Research Articles,which should contain original information,theoretical or experiment...Submission.Papers appearing in the Journal comprise Editorials,Rapid Communications,Perspectives,Tutorials,Feature Articles,Reviews,Research Articles,which should contain original information,theoretical or experimental,on any topics in the field of polymer science and polymer material science.Papers already published or scheduled to be published elsewhere should not be submitted and certainly will not be accepted.展开更多
Polymer-modified bentonite(PMB)is much more effective at containing chemically aggressive liquids than conventional bentonite.The PMB manufacturing process typically utilizes natural,high-quality sodium bentonite(NaB)...Polymer-modified bentonite(PMB)is much more effective at containing chemically aggressive liquids than conventional bentonite.The PMB manufacturing process typically utilizes natural,high-quality sodium bentonite(NaB)owing to its excellent hydrophilicity and swelling capacity.However,calcium bentonite(CaB),which is much more abundant worldwide,is rarely used for containment applications owing to its poor hydrophilicity.This study proposed a polymerization method that transforms sodium-activated calcium bentonite(NCB)into PMB to achieve low hydraulic conductivity(k)to aggressive liquids.The mechanism for its low k was revealed through characterization techniques and analyses(e.g.X-ray diffraction(XRD),Fourier transform infrared spectroscopy(FTIR),scanning electron microscopy(SEM),and Brunauer-Emmett-Teller(BET)).The results showed that the PMB had a small amount of polymer elution(indicating better interface stability)and thus exhibited excellent barrier properties under chemically aggressive conditions,with the k of<10^(-11) m/s for 0.6 mol/L NaCl solution,which is four orders of magnitude lower than that of the NCB(k=3×10^(-7) m/s).Various microscopic analyses indicated that the selected monomers were successfully polymerized,and intercalated into and grafted onto the montmorillonite layers of bentonite.The formed polymer network increased the swelling capability of PMB granules,decreased the pore size,and created narrow and tortuous flow pathways leading to a very low k to aggressive liquids.展开更多
To precisely control intrachain π-electron delocalization and interchain interaction simultaneously is the prerequisite to obtain stable and efficient deep-blue light-emitting p-n polymer semiconductors for the polym...To precisely control intrachain π-electron delocalization and interchain interaction simultaneously is the prerequisite to obtain stable and efficient deep-blue light-emitting p-n polymer semiconductors for the polymer light-emitting diodes(PLEDs).Herein,we introduced the steric carbazole-fluorene nanogrid into light-emitting diphenyl sulfone-based p-n polymer semiconductors(PG and PDG) via metal-free C-N coupling polymerization for the fabrication of deep-blue PLEDs.The steric,rigid and twisted configuration between nanogrid and diphenyl sulfone in PG and PDG present the unique characteristic of large steric hindrance interaction to suppress interchain aggregation in solid state.Due to the different length of electron-deficient diphenyl sulfone monomers,PG showed a deep-blue emission with a maximum peak at 428 nm but red-shifted to 480 nm for the PDG films.Interestingly,similar deep-blue emission behavior of PG in diluted non-polar solution and films suggested the extremely weak interchain aggregation.Finally,PLEDs based on PG are fabricated with a stable deep-blue emission of CIE(0.15,0.10),and corresponding EL spectral profile is also completely identical to PL ones of diluted solution,revealed the intrachain emission without obvious interchain excited state,confirmed effectiveness of the steric hindrance functionalization of nanogrid in p-n polymer semiconductor for deep-blue light-emitting organic optoelectronics.展开更多
Heterogeneous polymerization represents a widely employed method in the polyolefin industry.In recent years,various heterogenization strategies for late transition metal catalysts have been developed,enabling effectiv...Heterogeneous polymerization represents a widely employed method in the polyolefin industry.In recent years,various heterogenization strategies for late transition metal catalysts have been developed,enabling effective control of polymer morphology and optimization of catalytic performance.However,while most studies have focused on designing anchoring groups and advancing support approaches,systematic investigations into how the support influences the catalytic behavior of the late transition metal catalysts.In this work,we fabricated supported α-diimine nickel catalysts by functionalizing the ligand with alkyl alcohol chains of varying lengths and supporting them onto MgCl_(2)supports.The ethylene polymerization behavior of these catalysts was then investigated.By precisely adjusting the alkyl alcohol chain length,the distance between the catalytically active metal center and the support surface was modulated.This approach demonstrates that support-induced steric hindrance effect can be effectively regulated by controlling the separation distance between the metal center and the support surface.展开更多
With the global push for energy conservation and the rapid development of low-power,flexible and wearable optical displays,the demand for electrochromic technology has surged.Gel polymer electrolytes(GPEs),a crucial c...With the global push for energy conservation and the rapid development of low-power,flexible and wearable optical displays,the demand for electrochromic technology has surged.Gel polymer electrolytes(GPEs),a crucial component of electrochromic devices(ECDs),show great promise in applications.This is attributed to their efficient ion-transport capabilities,excellent mechanical properties and strong adhesion.All of these characteristics are conducive to enhancing the safety of the devices,streamlining the packaging process,significantly improving the electrochromic performance of ECDs and boosting their commercial application potential.This review provides a comprehensive overview of GPEs for ECDs,focusing on their basic designs,functional modifications and practical applications.Firstly,this review outlines the fundamental design of GPEs for ECDs,encompassing key performance index,classification,gelation mechanism and preparation methods.Building on this foundation,it provides an in-depth discussion of functionalized GPEs developed to enhance device performance or expand functionality,including electrochromic,temperature-responsive,photo-responsive and stretchable self-healing GPE.Furthermore,the integration of GPEs into various ECD applications,including smart windows,displays,energy storage devices and wearable electronic,are summarized to highlight the advantages that the design of GPEs brings to the practical application of ECDs.Finally,based on the summary of GPEs employed for ECDs,the challenges and development expectations in this direction were indicated.展开更多
Succinonitrile(SN)-based polymer plastic crystal electrolytes(PPCEs)are regarded as promising candidates for lithium metal batteries but suffer from serious side reactions with Li metal.Herein,we propose a multi-dimen...Succinonitrile(SN)-based polymer plastic crystal electrolytes(PPCEs)are regarded as promising candidates for lithium metal batteries but suffer from serious side reactions with Li metal.Herein,we propose a multi-dimensional optimization strategy to alleviate the side reactions between SN and Li metal,and develop a highly stable poly-vinylethylene carbonate-based PPCE(PPCE-VEC).Moreover,we identify the intrinsic factors of multi-dimensional polymer structures on the electrolyte stability by three typical classes of polyesters.The PPCE-VEC constructed by in situ polymerization exhibits much better stability than poly-vinylene carbonate-based PPCE(PPCE-VCA)and poly-trifluoroethyl acrylate-based PPCE(PPCE-TFA),which is verified by its fewer SN-decomposition species in X-ray photoelectron spectroscopy(XPS)and outstanding full cell performance.The PPCE-VEC-enabled LiNi_(0.6)Co_(0.2)Mn_(0.2)O_(2)full cell achieve 73.7%capacity retention after 1400 cycles,which outperforms PPCE-VCA-and PPCE-TFA-enabled full cells(61.9%and 46.9%).Spectral analysis and theoretical calculation reveal that the high solvation ability of the carbonyl site,flexible polymer chain,and homogeneous electrolyte phase of PPCE-VEC are favorable to maximizing competition coordination with Li^(+)to weaken the Li^(+)–SN binding and shape an anion-rich solvation structure.This optimized polymer-involved Li^(+)solvation enhances SN stability and facilitates the formation of B/F enriched solid-electrolyte interphase(SEI),thus significantly improving PPCE stability.展开更多
In 2024,the MOE Key Laboratory of Macromolecular Synthesis and Functionalization at Zhejiang University continued its impactful researches across five core areas.In controllable catalytic polymerization,organoboron ca...In 2024,the MOE Key Laboratory of Macromolecular Synthesis and Functionalization at Zhejiang University continued its impactful researches across five core areas.In controllable catalytic polymerization,organoboron catalysts were developed for CO₂copolymerization and novel photoresist materials.Studies in microstructure and rheology elucidated universal deformation modes in graphene-based 2D membranes and improved graphene fiber properties through shear alignment engineering,defect control,and enhanced interlayer entanglement.For separating functional polymers,Janus membranes and channels were created for multiphase separation,liquid-phase molecular layer-by-layer deposition technique was developed to fabricate aromatic polyamide nanofilms,and the harmonic amide bond density was established as a valuable parameter for polyamide structural analysis.In biomedical functional polymers,a sustainable carboxyl-ester transesterification strategy was proposed for upcycling poly(ethylene terephthalate)(PET)waste into biodegradable plastics.Additionally,immunocompatible biomaterials were designed utilizing zwitterionic polypeptides and albumin-derived coatings,and Cu2+-phenolic nanoflower was designed to combat fungal infections by combining cuproptosis and cell wall digestion.Further,the researchers developed a gelatin-DOPA-knob/fibrinogen hydrogel to achieve rapid and robust hemostatic sealing,utilized a double-network polyelectrolyte-coated hydrogel for enhancing endothelialization of left atrial appendage(LAA)occluders,and the researchers also demonstrated that image-guided high-intensity focused ultrasound enables manipulation of shape-memory polymers.Finally,in the realm of photo-electro-magnetic functional polymers,precise control of through-space conjugation was shown to enhance organic luminescence.Topologically structured hydrogels were revealed to exhibit autonomous actuation.Also,solar-driven photothermal ion pumps were developed for selective lithium extraction from seawater,and high-performance non-solvated C60 single-crystal films were prepared via facile bar coating.Lastly,the researchers demonstrated outstanding dielectric properties of polyethylene(PE)lamellar single crystals.The relevant works are reviewed in this paper.展开更多
Chinese Journal of Polymer Science(CJPS)is a monthly journal published in English and sponsored by the Chinese Chemical Society and the Institute of Chemistry,Chinese Academy of Sciences.CJPS is edited by a distinguis...Chinese Journal of Polymer Science(CJPS)is a monthly journal published in English and sponsored by the Chinese Chemical Society and the Institute of Chemistry,Chinese Academy of Sciences.CJPS is edited by a distinguished Editorial Board headed by Professor Qi-Feng Zhou and supported by an International Advisory Board in which many famous active polymer scientists all over the world are included.展开更多
Conductive polymers have recently drawn tremendous attention due to their promising applications in electronic and energy-related devices.While p-type conductive polymers such as poly(3,4-ethylenedioxythiophene):poly(...Conductive polymers have recently drawn tremendous attention due to their promising applications in electronic and energy-related devices.While p-type conductive polymers such as poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate)(PEDOT:PSS)have achieved commercialization,the development of stable,high-performance n-type polymers has lagged.Recently,the discovery of n-type polymer poly(benzodifurandione)(PBFDO)has greatly promoted the development and application of n-type conductive polymers.However,the synthesis process involves cumbersome post-processing,which greatly increases the cost and difficulty of mass production.Herein,a novel synthesis method for PBFDO has been developed,which was promoted by the combination of solvent dimethyl sulfoxide(DMSO)and acetic anhydride(Ac_(2)O).This method exploits the oxidative capability of DMSO,activated by Ac_(2)O,which can promote the keto-enol tautomerism of 3,7-dihydrobenzo[1,2-b:4,5-b′]difuran-2,6-dione(BFDO)and induce the rapid polymerization.The resulting PBFDO ink exhibits a high electronic conductivity of more than 2000 S cm^(-1)and excellent ambient stability.Significantly,the additives and by-products remain in a liquid state during the polymerization process and possess low boiling points,allowing for the production of pure PBFDO films through straightforward heating and drying.Furthermore,this approach holds considerable promise for in situ polymerization,as functional conductive films can be prepared by merely combining the monomers with the DMSO/Ac_(2)O mixture and applying heat.This efficient,purification-free strategy represents a significant step toward the industrial application of the highperformance n-type conductive polymer PBFDO.展开更多
Thermoelectric(TE)materials,being capable of converting waste heat into electricity,are pivotal for sustainable energy solutions.Among emerging TE materials,organic TE materials,particularly conjugated polymers,are ga...Thermoelectric(TE)materials,being capable of converting waste heat into electricity,are pivotal for sustainable energy solutions.Among emerging TE materials,organic TE materials,particularly conjugated polymers,are gaining prominence due to their unique combination of mechanical flexibility,environmental compatibility,and solution-processable fabrication.A notable candidate in this field is poly(2,5-bis(3-alkylthiophen-2-yl)thieno[3,2-b]thiophene)(PBTTT),a liquid-crystalline conjugated polymer,with high charge carrier mobility and adaptability to melt-processing techniques.Recent advancements have propelled PBTTT’s figure of merit from below 0.1 to a remarkable 1.28 at 368 K,showcasing its potential for practical applications.This review systematically examines strategies to enhance PBTTT’s TE performance through doping(solution,vapor,and anion exchange doping),composite engineering,and aggregation state controlling.Recent key breakthroughs include ion exchange doping for stable charge modulation,multi-heterojunction architectures reducing thermal conductivity,and proton-coupled electron transfer doping for precise Fermi-level tuning.Despite great progress,challenges still persist in enhancing TE conversion efficiency,balancing or decoupling electrical conductivity,Seebeck coefficient and thermal conductivity,and leveraging melt-processing scalability of PBTTT.By bridging fundamental insights with applied research,this work provides a roadmap for advancing PBTTT-based TE materials toward efficient energy harvesting and wearable electronics.展开更多
Catalysts are key for olefin polymerization reactions and are also ubiquitous in catalysis science.Multinuclear metal catalysts have witnessed enhanced performances in catalytic reactions relative to mononuclear catal...Catalysts are key for olefin polymerization reactions and are also ubiquitous in catalysis science.Multinuclear metal catalysts have witnessed enhanced performances in catalytic reactions relative to mononuclear catalysts,but which substantially involve multi-step,tedious,and difficult synthesis.Herein,this study reports an intriguing approach to construct multi-nuclear catalysts for the milestoneα-diimine nickel catalysts using an oligomeric strategy.A polymerizable norbornene unit is incorporated into theα-diimine ligand backbone,leading to the formation of the monomeric nickel catalyst Ni_(1)and its corresponding oligomeric nickel catalysts(Ni_(3)and Ni_(5))with varying degrees of polymerization(DP=3 and 5).Notably,the oligomeric catalyst Ni_(5)was facilely scaled up(50 g-level),showed enhanced thermal stability,exhibited 4.6 times higher activity,and yielded polyethylene elastomer with a 379%increased molecular weight in ethylene polymerization,compared to the monomeric catalyst Ni_(1).Catalytic performance enhancements of oligomeric catalysts were found to be DP-dependent.The kilogram-scale polyethylene,produced using Ni_(5)in a 20 L reactor,presented a highly branched all-hydrocarbon structure,which demonstrated typical elastic properties(tensile strength:4 MPa,elastic recovery:SR=72%)along with great processability(MFI=3.0 g/10 min),insulating characteristics(volume resistivity=2×10^(16)Ω/m),and hydrophobicity(water vapor permeability:0.03 g/m^(2)/day),suggesting potentially practical applications.展开更多
The extraction of uranium from seawater via membrane adsorption is a promising strategy for ensuring a long-term supply of uranium and the sustainability of nuclear energy.However,this approach has been hindered by th...The extraction of uranium from seawater via membrane adsorption is a promising strategy for ensuring a long-term supply of uranium and the sustainability of nuclear energy.However,this approach has been hindered by the longstanding challenge of identifying sustainable membrane materials.In response,we propose a prototypal hybridization strategy to design a novel series of aminated conjugated microporous polymer(CMPN)@collagen fiber membrane(COLM).These sustainable and low-cost membrane materials allow a rapid and high-affinity kinetic to capture 90%of the uranium in just 30 min from 50 ppm with a high selectivity of Kd>105 mL·g^(−1).They also afford a robustly reusable adsorption capacity as high as 345 mg·g^(−1)that could harvest 1.61 mg·g^(−1)of uranium in a short 7-day real marine engineering in Fujian Province,even though suffered from very low uranium concentration of 3.29μg·L^(−1)and tough influence of salts such as 10.77 g·L^(−1)of Na^(+),1.75μg·L^(−1)of VO_(3)^(−)etc.in the rough seas.The structural evidence from both experimental and theoretical studies confirmed the formation of favorable chelating motifs from the amino group on CMPN-COLM,and the intensification by the synergistic effect from the size-sieving action of CMPN and the capillary inflow effect of COLM.展开更多
Recent advances in geoscience have underscored the critical role of abiogenic processes in petroleum formation,especially the formation and polymerization of methane.However,whether a direct carbon-H_(2) reaction can ...Recent advances in geoscience have underscored the critical role of abiogenic processes in petroleum formation,especially the formation and polymerization of methane.However,whether a direct carbon-H_(2) reaction can produce C_(2+)hydrocarbons(e.g.,ethane and propane)beyond methane remains an open question.Here,we demonstrate the direct synthesis of ethane and propane via reactions between amorphous carbon and H_(2) under upper mantle conditions(2-10 GPa and 800-1200℃).A systematic investigation reveals that increasing structural disorder in carbon precursors,from graphite to glassy carbon-Ⅱ and carbon black,enhances the production of C_(2)-C_(3) hydrocarbons.Through integrated X-ray diffraction and reverse Monte Carlo simulations,we establish that the continuous random atomic network structures in amorphous carbon enable one-step synthesis of heavy hydrocarbons with H_(2).These models establish a direct link between atomic-scale carbon structures and the one-step synthesis of C_(2+) hydrocarbons under H_(2)-rich,high-pressure,and high-temperature conditions—potentially revealing an efficient mechanism for the abiotic production of C_(2+) hydrocarbons in the upper mantle.展开更多
Smart pesticide delivery systems based on stimuli-responsive nanocarriers have attracted considerable attention because of their potential to enhance pesticide efficiency while reducing environmental risks.In this stu...Smart pesticide delivery systems based on stimuli-responsive nanocarriers have attracted considerable attention because of their potential to enhance pesticide efficiency while reducing environmental risks.In this study,a novel p H/glutathione dual-responsive pesticide delivery system was constructed through the synthesis of disulfide-bridged hollow mesoporous organosilica nanospheres(HMONs)via the St??ber method,followed by poly(acrylic acid)(PAA)coating through distillation-precipitation polymerization to form HMONs@PAA nanocomposites.The resulting abamectin-loaded system(Abamectin-HMONs@PAA)demonstrated a 12.73% pesticide loading capacity and significantly improved photostability,retaining twice as much active ingredient as free abamectin after 250 h of UV irradiation(36 W).Release studies revealed p H-and glutathione-dependent characteristics,with cumulative releases in acidic conditions exceeding those in neutral and alkaline environments by 18.66% and 40.98%,respectively,and a 14.2% increase in glutathione-containing solution(0.2 mmol·L^(-1) in 70% ethanol)after 97 h.Bioassays showed superior performance against Plutella xylostella,with a 13.33% reduction in survival rate compared to conventional suspension at equivalent dosage(40 mg·L^(-1)),while maintaining efficacy after extensive rainfall simulation(20 events over 10 days).This study provides a promising approach for developing environmentally responsive nanopesticides with enhanced durability and controlled-release properties,offering significant potential for sustainable crop protection.展开更多
基金The auth ors gratefully ack no wledge the fi nan cial supp ort of the"Nati onal Key R&D Program of China"(2019YFD1000605-1)"The National Natural Science Foun dati on of Ch ina"(31922058)+3 种基金"Outsta nding Young Tale nt Fund in Beij ing Forestry University"(2019JQ03009)"The National Natural Science Foundation of China"(31800509),(31901281),(31930076)"The 111 Project"(B20088)"Heilongjiang Touyan Innovation Team Program"(Tree Genetics and Breeding Innovation Team).
文摘Mature pollen germinates rapidly on the stigma,extending its pollen tube to deliver sperm cells to the ovule for fertilization.The success of this process is an important factor that limits output.The flavonoid content increased signi ficantly during pollen germination and pollen tube growth,which suggests it may play an important role in these processes.However,the speci fi c mechanism of this involvement has been little researched.Our previous research found that hyperoside can prolong the flowering period of Abelmoschus esculentus(okra),but its speci fic mechanism is still unclear.Therefore,in this study,we focused on the effect of hyperoside in regulating the actin-depolymerizing factor(ADF),which further affects the germination and growth of pollen.We found that hyperoside can prolong the effective pollination period of okra by 2-3-fold and promote the growth of pollen tubes in the style.Then,we used Nicotiana benthamiana cells as a research system and found that hyperoside accelerates the depolymerization of intercellular micro fi laments.Hyperoside can promote pollen germination and pollen tube elongation in vitro.Moreover,AeADFl was identi fied out of all AeADF genes as being highly expressed in pollen tubes in response to hyperoside.In addition,hyperoside promoted AeADF1-mediated micro filament dissipation according to micro filament severing experiments in vitro.In the pollen tube,the gene expression of AeADFl was reduced to 1/5 by oligonucleotide transfection.The decrease in the expression level of AeADFl partially reduced the promoting effect of hyperoside on pollen germination and pollen tube growth.This research provides new research directions for flavonoids in reproductive development.
基金supported by the National Natural Science Foundation of China(Nos.52130306,22075287 and 22101285)the Nature Science Foundation of Fujian Province(No.2021J01515)the Program of Youth Innovation Promotion Association CAS(No.2021299).
文摘One important subject in the field of all-polymer solar cells (all-PSCs) is the exploration of electron-deficient building blocks with optimized physicochemical properties to promote the performance of polymer acceptors. Here, two ladder-type heteroheptacene-containing small-molecule acceptors with branched 2-octyldodecyl or 2-hexyldecyl side-chains are synthesized and polymerized with the thiophene co-monomer to afford polymer acceptors (PW-OD and PW-HD) with strong near-infrared absorption. Experimental results reveal that the alkyl chain length has a large impact on the molecular packing behavior of the resulting polymers, which in turn affects their light-absorbing and charge transport properties, and thus the photovoltaic performance of the final devices. When blended with the polymer donor PM6, PW-HD-based all-PSCs deliver a higher power conversion efficiency (PCE) of 9.12% compared to the PCE of 6.47% for the PW-OD-based all-PSCs, mainly due to its more ordered inter-chain packing and more favorable blend morphology. This work provides a promising building block for the development of high-performance narrow-bandgap polymer acceptors and highlights the importance of side-chain substitution in optimizing the photovoltaic performance of polymer acceptors.
基金supported by the CAMS Innovation Fund for Medical Sciences(CIFMS2016-I2M-3-005)the National and Provincial Clinical Key Specialty Capacity Building Project of 2020(No.2-1-2-038).
文摘Background:Emerging mounts of research support the ancestral theory of cancer,indicating that tumorigenesis and embryogenesis share many similar biological features,yet yield distinct outcomes.Gene co-expression networks underlie both embryonic development and tumorigenesis.We hypothesize that deviations in the gene interaction patterns in tumors compared to villi predispose to malignancy and worse prognosis.Methods:By constructing a gene co-expression network of villi and colorectal cancer(CRC)and conducting functional enrichment analysis to identify“off-track genes.”Cox regression assessed prognostic significance,while tissue microarrays evaluated protein expression and progression.Additionally,mRNA sequencing of chondroitin polymerizing factor(CHPF)-knockdown LOVO and SW480 cell lines was conducted and validated via in vitro assays.Results:We found that genes in villi and CRC have similar functions,but the genes that performed corresponding functions were not identical.Then,according to“off-track theory”and linear regression models,we obtained 24 genes whose aberrant expression was significantly associated with poor CRC survival.Notably,CHPF emerged as an adverse prognostic factor.Immunohistochemical analysis confirmed that CHPF is an independent prognostic marker for CRC.Furthermore,cell phenotype assays demonstrated that CHPF enhances proliferation and migration,suppresses apoptosis,and engages in the TNF signaling pathway.Conclusion:These findings validate that villi development can serve as a research model for tumorigenesis,and identify CHPF is an independent oncogenic factor in CRC,suggesting its potential as a prognostic biomarker and a therapeutic target for clinical treatment.
基金Supported by the National Natural Science Foundation of China(Nos.52293472,22473096 and 22471164)。
文摘Among various architectures of polymers,end-group-free rings have attracted growing interests due to their distinct physicochemical performances over the linear counterparts which are exemplified by reduced hydrodynamic size and slower degradation.It is key to develop facile methods to large-scale synthesis of polymer rings with tunable compositions and microstructures.Recent progresses in large-scale synthesis of polymer rings against single-chain dynamic nanoparticles,and the example applications in synchronous enhancing toughness and strength of polymer nanocomposites are summarized.Once there is the breakthrough in rational design and effective large-scale synthesis of polymer rings and their functional derivatives,a family of cyclic functional hybrids would be available,thus providing a new paradigm in developing polymer science and engineering.
文摘Four distinct coordination polymers(CPs)were successfully synthesized by altering solvent types and adjusting ligand concentrations,and their crystal structures were investigated.[Co(L)(FDCA)(H_(2)O)_(2)]·0.5H_(2)O(1)was synthesized as a 2D structure using Coas the metal source,methanol‑water(4∶6,V/V)as the solvent,and specific concentrations of 2,5‑furandicarboxylic acid(H_(2)FDCA)and 1,3,5‑triimidazole benzene(L).Adjusting to pure water and lowering the concentration of L yielded the 1D chain structure of[Co(HL)2(H_(2)O)_(2)](FDCA)_(2)·6H_(2)O(2).Using Cu(Ⅱ)as the metal source,methanol/water(9∶1,V/V)as the solvent,and specific concentrations of L and H2FDCA,the 1D chain structure of[Cu(L)(FDCA)(H_(2)O)]·2H_(2)O(3)was synthesized.Upon increasing the concentrations of L and H2FDCA,and switching the solvent to pure water,the 1D chain structure of[Cu(HL)_(2)(H_(2)O)_(2)](FDCA)_(2)·6H_(2)O(4)was obtained.This shows that changing the solvent and ligand concentrations can affect the structural changes of CPs.In addition,the solid‑state photoluminescence of CPs 1‑4 at room temperature was studied,and their morphological changes were observed via scanning electron microscopy.Density functional theory calculations revealed that the negative charge concentrates on the O and N atoms of the ligand,facilitating ligand‑metal ion coordination.CCDC:2403934,1;2403935,2;2403936,3;2403938,4.
基金supported by the National Natural Science Foundation of China(Nos.22322107,22101169 and 22071144)by Shanghai Scientific and Technological Committee(No.22010500300).
文摘Organic pollutants,a pivotal factor in water pollution,have persistently menaced the aquatic ecosystem,as well as the sustainable development of human health,economy,and society.Consequently,there is an urgent need for advanced techniques to efficiently eliminate organic micropollutants from water.Here,we present the synthesis of three nonporous cavitand-crosslinked polymers capable of adsorbing diverse organic pollutants from aqueous solutions.These polymeric adsorbents exhibit outstanding adsorptive performance towards the tested micropollutants,characterized by high apparent adsorption rate constants(kobs)and maximum adsorption capacities(qmax,e).Notably,Compound NCCP-1 demonstrated a remarkable qmax,e of 459 mg/g for bisphenol A(BPA),ranking among the highest values reported for organic polymer adsorbents.In-depth investigation of the adsorption mechanism of the nonporous polymer revealed that it involves the recognition of pollutants by the deep cavities of the cavitand moieties and the interstitial spaces between them,primarily mediated by the hydrophobic effect.Furthermore,NCCP-1 was applied in situ water purification simulations and was proven to maintain its removal efficiency over more than four cycles,highlighting its potential for practical applications in water treatment.
文摘Submission.Papers appearing in the Journal comprise Editorials,Rapid Communications,Perspectives,Tutorials,Feature Articles,Reviews,Research Articles,which should contain original information,theoretical or experimental,on any topics in the field of polymer science and polymer material science.Papers already published or scheduled to be published elsewhere should not be submitted and certainly will not be accepted.
基金supported by the National Natural Science Foundation of China(Grant Nos.52478351,52208329)the Shenzhen Science and Technology Innovation Commission(Grant No.JCYJ20240813143306009)support is gratefully acknowledged.
文摘Polymer-modified bentonite(PMB)is much more effective at containing chemically aggressive liquids than conventional bentonite.The PMB manufacturing process typically utilizes natural,high-quality sodium bentonite(NaB)owing to its excellent hydrophilicity and swelling capacity.However,calcium bentonite(CaB),which is much more abundant worldwide,is rarely used for containment applications owing to its poor hydrophilicity.This study proposed a polymerization method that transforms sodium-activated calcium bentonite(NCB)into PMB to achieve low hydraulic conductivity(k)to aggressive liquids.The mechanism for its low k was revealed through characterization techniques and analyses(e.g.X-ray diffraction(XRD),Fourier transform infrared spectroscopy(FTIR),scanning electron microscopy(SEM),and Brunauer-Emmett-Teller(BET)).The results showed that the PMB had a small amount of polymer elution(indicating better interface stability)and thus exhibited excellent barrier properties under chemically aggressive conditions,with the k of<10^(-11) m/s for 0.6 mol/L NaCl solution,which is four orders of magnitude lower than that of the NCB(k=3×10^(-7) m/s).Various microscopic analyses indicated that the selected monomers were successfully polymerized,and intercalated into and grafted onto the montmorillonite layers of bentonite.The formed polymer network increased the swelling capability of PMB granules,decreased the pore size,and created narrow and tortuous flow pathways leading to a very low k to aggressive liquids.
基金the support from the Jiangsu Provincial Senior Talent Program (Dengfeng,Jiangsu University)the support from the National Key R&D Program of China (No.2024YFB3612600)+3 种基金the National Natural Science Foundation of China (Nos.22275098,62288102)Basic Research Program of Jiangsu (No.BK20243057)the Natural Science Research Start-up Foundation of Recruiting Talents of Nanjing University of Posts and Telecommunications (No.NY222097)the National Natural Science Foundation of China (No.62205035)。
文摘To precisely control intrachain π-electron delocalization and interchain interaction simultaneously is the prerequisite to obtain stable and efficient deep-blue light-emitting p-n polymer semiconductors for the polymer light-emitting diodes(PLEDs).Herein,we introduced the steric carbazole-fluorene nanogrid into light-emitting diphenyl sulfone-based p-n polymer semiconductors(PG and PDG) via metal-free C-N coupling polymerization for the fabrication of deep-blue PLEDs.The steric,rigid and twisted configuration between nanogrid and diphenyl sulfone in PG and PDG present the unique characteristic of large steric hindrance interaction to suppress interchain aggregation in solid state.Due to the different length of electron-deficient diphenyl sulfone monomers,PG showed a deep-blue emission with a maximum peak at 428 nm but red-shifted to 480 nm for the PDG films.Interestingly,similar deep-blue emission behavior of PG in diluted non-polar solution and films suggested the extremely weak interchain aggregation.Finally,PLEDs based on PG are fabricated with a stable deep-blue emission of CIE(0.15,0.10),and corresponding EL spectral profile is also completely identical to PL ones of diluted solution,revealed the intrachain emission without obvious interchain excited state,confirmed effectiveness of the steric hindrance functionalization of nanogrid in p-n polymer semiconductor for deep-blue light-emitting organic optoelectronics.
基金financially supported by the National Natural Science Foundation of China(No.52473338)the National Natural Science Foundation of China(Nos.52173004 and 51873055)+3 种基金Strategic Priority Research Program of the Chinese Academy of Sciences(No.XDA0540000)Advanced Materials-National Science and Technology Major Project(No.2025ZD0614000)Hebei Natural Science Foundation(No.E2022202015)Anhui Province Science and Technology Innovation Tackling Key Project(No.202423i08050025)。
文摘Heterogeneous polymerization represents a widely employed method in the polyolefin industry.In recent years,various heterogenization strategies for late transition metal catalysts have been developed,enabling effective control of polymer morphology and optimization of catalytic performance.However,while most studies have focused on designing anchoring groups and advancing support approaches,systematic investigations into how the support influences the catalytic behavior of the late transition metal catalysts.In this work,we fabricated supported α-diimine nickel catalysts by functionalizing the ligand with alkyl alcohol chains of varying lengths and supporting them onto MgCl_(2)supports.The ethylene polymerization behavior of these catalysts was then investigated.By precisely adjusting the alkyl alcohol chain length,the distance between the catalytically active metal center and the support surface was modulated.This approach demonstrates that support-induced steric hindrance effect can be effectively regulated by controlling the separation distance between the metal center and the support surface.
基金supported by the National Natural Science Foundation of China(52103299)。
文摘With the global push for energy conservation and the rapid development of low-power,flexible and wearable optical displays,the demand for electrochromic technology has surged.Gel polymer electrolytes(GPEs),a crucial component of electrochromic devices(ECDs),show great promise in applications.This is attributed to their efficient ion-transport capabilities,excellent mechanical properties and strong adhesion.All of these characteristics are conducive to enhancing the safety of the devices,streamlining the packaging process,significantly improving the electrochromic performance of ECDs and boosting their commercial application potential.This review provides a comprehensive overview of GPEs for ECDs,focusing on their basic designs,functional modifications and practical applications.Firstly,this review outlines the fundamental design of GPEs for ECDs,encompassing key performance index,classification,gelation mechanism and preparation methods.Building on this foundation,it provides an in-depth discussion of functionalized GPEs developed to enhance device performance or expand functionality,including electrochromic,temperature-responsive,photo-responsive and stretchable self-healing GPE.Furthermore,the integration of GPEs into various ECD applications,including smart windows,displays,energy storage devices and wearable electronic,are summarized to highlight the advantages that the design of GPEs brings to the practical application of ECDs.Finally,based on the summary of GPEs employed for ECDs,the challenges and development expectations in this direction were indicated.
基金supported by the National Natural Science Foundation of China(22072048)the Guangdong Provincial Department of Science and Technology(2021A1515010128 and 2022A0505050013).
文摘Succinonitrile(SN)-based polymer plastic crystal electrolytes(PPCEs)are regarded as promising candidates for lithium metal batteries but suffer from serious side reactions with Li metal.Herein,we propose a multi-dimensional optimization strategy to alleviate the side reactions between SN and Li metal,and develop a highly stable poly-vinylethylene carbonate-based PPCE(PPCE-VEC).Moreover,we identify the intrinsic factors of multi-dimensional polymer structures on the electrolyte stability by three typical classes of polyesters.The PPCE-VEC constructed by in situ polymerization exhibits much better stability than poly-vinylene carbonate-based PPCE(PPCE-VCA)and poly-trifluoroethyl acrylate-based PPCE(PPCE-TFA),which is verified by its fewer SN-decomposition species in X-ray photoelectron spectroscopy(XPS)and outstanding full cell performance.The PPCE-VEC-enabled LiNi_(0.6)Co_(0.2)Mn_(0.2)O_(2)full cell achieve 73.7%capacity retention after 1400 cycles,which outperforms PPCE-VCA-and PPCE-TFA-enabled full cells(61.9%and 46.9%).Spectral analysis and theoretical calculation reveal that the high solvation ability of the carbonyl site,flexible polymer chain,and homogeneous electrolyte phase of PPCE-VEC are favorable to maximizing competition coordination with Li^(+)to weaken the Li^(+)–SN binding and shape an anion-rich solvation structure.This optimized polymer-involved Li^(+)solvation enhances SN stability and facilitates the formation of B/F enriched solid-electrolyte interphase(SEI),thus significantly improving PPCE stability.
基金supported by the Fundamental Research Funds for the Central Universities(No.226-2025-00031).
文摘In 2024,the MOE Key Laboratory of Macromolecular Synthesis and Functionalization at Zhejiang University continued its impactful researches across five core areas.In controllable catalytic polymerization,organoboron catalysts were developed for CO₂copolymerization and novel photoresist materials.Studies in microstructure and rheology elucidated universal deformation modes in graphene-based 2D membranes and improved graphene fiber properties through shear alignment engineering,defect control,and enhanced interlayer entanglement.For separating functional polymers,Janus membranes and channels were created for multiphase separation,liquid-phase molecular layer-by-layer deposition technique was developed to fabricate aromatic polyamide nanofilms,and the harmonic amide bond density was established as a valuable parameter for polyamide structural analysis.In biomedical functional polymers,a sustainable carboxyl-ester transesterification strategy was proposed for upcycling poly(ethylene terephthalate)(PET)waste into biodegradable plastics.Additionally,immunocompatible biomaterials were designed utilizing zwitterionic polypeptides and albumin-derived coatings,and Cu2+-phenolic nanoflower was designed to combat fungal infections by combining cuproptosis and cell wall digestion.Further,the researchers developed a gelatin-DOPA-knob/fibrinogen hydrogel to achieve rapid and robust hemostatic sealing,utilized a double-network polyelectrolyte-coated hydrogel for enhancing endothelialization of left atrial appendage(LAA)occluders,and the researchers also demonstrated that image-guided high-intensity focused ultrasound enables manipulation of shape-memory polymers.Finally,in the realm of photo-electro-magnetic functional polymers,precise control of through-space conjugation was shown to enhance organic luminescence.Topologically structured hydrogels were revealed to exhibit autonomous actuation.Also,solar-driven photothermal ion pumps were developed for selective lithium extraction from seawater,and high-performance non-solvated C60 single-crystal films were prepared via facile bar coating.Lastly,the researchers demonstrated outstanding dielectric properties of polyethylene(PE)lamellar single crystals.The relevant works are reviewed in this paper.
文摘Chinese Journal of Polymer Science(CJPS)is a monthly journal published in English and sponsored by the Chinese Chemical Society and the Institute of Chemistry,Chinese Academy of Sciences.CJPS is edited by a distinguished Editorial Board headed by Professor Qi-Feng Zhou and supported by an International Advisory Board in which many famous active polymer scientists all over the world are included.
基金supported by the National Natural Science Foundation of China(52433012)the National Key R&D Program of China(2024YFF1500300)the China Postdoctoral Science Foundation(2023M741201,2024T170286)。
文摘Conductive polymers have recently drawn tremendous attention due to their promising applications in electronic and energy-related devices.While p-type conductive polymers such as poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate)(PEDOT:PSS)have achieved commercialization,the development of stable,high-performance n-type polymers has lagged.Recently,the discovery of n-type polymer poly(benzodifurandione)(PBFDO)has greatly promoted the development and application of n-type conductive polymers.However,the synthesis process involves cumbersome post-processing,which greatly increases the cost and difficulty of mass production.Herein,a novel synthesis method for PBFDO has been developed,which was promoted by the combination of solvent dimethyl sulfoxide(DMSO)and acetic anhydride(Ac_(2)O).This method exploits the oxidative capability of DMSO,activated by Ac_(2)O,which can promote the keto-enol tautomerism of 3,7-dihydrobenzo[1,2-b:4,5-b′]difuran-2,6-dione(BFDO)and induce the rapid polymerization.The resulting PBFDO ink exhibits a high electronic conductivity of more than 2000 S cm^(-1)and excellent ambient stability.Significantly,the additives and by-products remain in a liquid state during the polymerization process and possess low boiling points,allowing for the production of pure PBFDO films through straightforward heating and drying.Furthermore,this approach holds considerable promise for in situ polymerization,as functional conductive films can be prepared by merely combining the monomers with the DMSO/Ac_(2)O mixture and applying heat.This efficient,purification-free strategy represents a significant step toward the industrial application of the highperformance n-type conductive polymer PBFDO.
基金financial support by Guangdong Basic and Applied Basic Research Foundation(2025A1515012415)National Natural Science Foundation of China(52242305)the Stable Support Project of Shenzhen(Project No.20231122125728001).
文摘Thermoelectric(TE)materials,being capable of converting waste heat into electricity,are pivotal for sustainable energy solutions.Among emerging TE materials,organic TE materials,particularly conjugated polymers,are gaining prominence due to their unique combination of mechanical flexibility,environmental compatibility,and solution-processable fabrication.A notable candidate in this field is poly(2,5-bis(3-alkylthiophen-2-yl)thieno[3,2-b]thiophene)(PBTTT),a liquid-crystalline conjugated polymer,with high charge carrier mobility and adaptability to melt-processing techniques.Recent advancements have propelled PBTTT’s figure of merit from below 0.1 to a remarkable 1.28 at 368 K,showcasing its potential for practical applications.This review systematically examines strategies to enhance PBTTT’s TE performance through doping(solution,vapor,and anion exchange doping),composite engineering,and aggregation state controlling.Recent key breakthroughs include ion exchange doping for stable charge modulation,multi-heterojunction architectures reducing thermal conductivity,and proton-coupled electron transfer doping for precise Fermi-level tuning.Despite great progress,challenges still persist in enhancing TE conversion efficiency,balancing or decoupling electrical conductivity,Seebeck coefficient and thermal conductivity,and leveraging melt-processing scalability of PBTTT.By bridging fundamental insights with applied research,this work provides a roadmap for advancing PBTTT-based TE materials toward efficient energy harvesting and wearable electronics.
基金financial support from the National Natural Science Foundation of China(Nos.22401274,U23B6011)the Jilin Provincial Science and Technology Department Program(No.20250102070JC)。
文摘Catalysts are key for olefin polymerization reactions and are also ubiquitous in catalysis science.Multinuclear metal catalysts have witnessed enhanced performances in catalytic reactions relative to mononuclear catalysts,but which substantially involve multi-step,tedious,and difficult synthesis.Herein,this study reports an intriguing approach to construct multi-nuclear catalysts for the milestoneα-diimine nickel catalysts using an oligomeric strategy.A polymerizable norbornene unit is incorporated into theα-diimine ligand backbone,leading to the formation of the monomeric nickel catalyst Ni_(1)and its corresponding oligomeric nickel catalysts(Ni_(3)and Ni_(5))with varying degrees of polymerization(DP=3 and 5).Notably,the oligomeric catalyst Ni_(5)was facilely scaled up(50 g-level),showed enhanced thermal stability,exhibited 4.6 times higher activity,and yielded polyethylene elastomer with a 379%increased molecular weight in ethylene polymerization,compared to the monomeric catalyst Ni_(1).Catalytic performance enhancements of oligomeric catalysts were found to be DP-dependent.The kilogram-scale polyethylene,produced using Ni_(5)in a 20 L reactor,presented a highly branched all-hydrocarbon structure,which demonstrated typical elastic properties(tensile strength:4 MPa,elastic recovery:SR=72%)along with great processability(MFI=3.0 g/10 min),insulating characteristics(volume resistivity=2×10^(16)Ω/m),and hydrophobicity(water vapor permeability:0.03 g/m^(2)/day),suggesting potentially practical applications.
基金supported by National Natural Science Foundation of China(Grant No.22378066,22108040)Collaboration&Innovation Platform Project of National Independent Innovation Demonstration Zone(Fuzhou,Xiamen&Quanzhou)(Project No:3502ZCQXT2023004).
文摘The extraction of uranium from seawater via membrane adsorption is a promising strategy for ensuring a long-term supply of uranium and the sustainability of nuclear energy.However,this approach has been hindered by the longstanding challenge of identifying sustainable membrane materials.In response,we propose a prototypal hybridization strategy to design a novel series of aminated conjugated microporous polymer(CMPN)@collagen fiber membrane(COLM).These sustainable and low-cost membrane materials allow a rapid and high-affinity kinetic to capture 90%of the uranium in just 30 min from 50 ppm with a high selectivity of Kd>105 mL·g^(−1).They also afford a robustly reusable adsorption capacity as high as 345 mg·g^(−1)that could harvest 1.61 mg·g^(−1)of uranium in a short 7-day real marine engineering in Fujian Province,even though suffered from very low uranium concentration of 3.29μg·L^(−1)and tough influence of salts such as 10.77 g·L^(−1)of Na^(+),1.75μg·L^(−1)of VO_(3)^(−)etc.in the rough seas.The structural evidence from both experimental and theoretical studies confirmed the formation of favorable chelating motifs from the amino group on CMPN-COLM,and the intensification by the synergistic effect from the size-sieving action of CMPN and the capillary inflow effect of COLM.
基金mainly supported by the Natural Science Foundation of China (Grant Nos. 52288102, 52090020, and 52372261)the Natural Science Foundation of Hebei Province (Grant No. E202403045)+1 种基金the S&T Program of Hebei (Grant No. 225A1102D)the Ministry of Education Chang Jiang Scholar Professor Program (Grant No. T2022241)
文摘Recent advances in geoscience have underscored the critical role of abiogenic processes in petroleum formation,especially the formation and polymerization of methane.However,whether a direct carbon-H_(2) reaction can produce C_(2+)hydrocarbons(e.g.,ethane and propane)beyond methane remains an open question.Here,we demonstrate the direct synthesis of ethane and propane via reactions between amorphous carbon and H_(2) under upper mantle conditions(2-10 GPa and 800-1200℃).A systematic investigation reveals that increasing structural disorder in carbon precursors,from graphite to glassy carbon-Ⅱ and carbon black,enhances the production of C_(2)-C_(3) hydrocarbons.Through integrated X-ray diffraction and reverse Monte Carlo simulations,we establish that the continuous random atomic network structures in amorphous carbon enable one-step synthesis of heavy hydrocarbons with H_(2).These models establish a direct link between atomic-scale carbon structures and the one-step synthesis of C_(2+) hydrocarbons under H_(2)-rich,high-pressure,and high-temperature conditions—potentially revealing an efficient mechanism for the abiotic production of C_(2+) hydrocarbons in the upper mantle.
基金financially supported by the Jiangsu Forestry Science and Technology Innovation and Promotion Project(No.LYKJ-Nanjing[2022]02)the Jiangsu Agricultural Science and Technology Innovation Fund(No.CX(23)3090)。
文摘Smart pesticide delivery systems based on stimuli-responsive nanocarriers have attracted considerable attention because of their potential to enhance pesticide efficiency while reducing environmental risks.In this study,a novel p H/glutathione dual-responsive pesticide delivery system was constructed through the synthesis of disulfide-bridged hollow mesoporous organosilica nanospheres(HMONs)via the St??ber method,followed by poly(acrylic acid)(PAA)coating through distillation-precipitation polymerization to form HMONs@PAA nanocomposites.The resulting abamectin-loaded system(Abamectin-HMONs@PAA)demonstrated a 12.73% pesticide loading capacity and significantly improved photostability,retaining twice as much active ingredient as free abamectin after 250 h of UV irradiation(36 W).Release studies revealed p H-and glutathione-dependent characteristics,with cumulative releases in acidic conditions exceeding those in neutral and alkaline environments by 18.66% and 40.98%,respectively,and a 14.2% increase in glutathione-containing solution(0.2 mmol·L^(-1) in 70% ethanol)after 97 h.Bioassays showed superior performance against Plutella xylostella,with a 13.33% reduction in survival rate compared to conventional suspension at equivalent dosage(40 mg·L^(-1)),while maintaining efficacy after extensive rainfall simulation(20 events over 10 days).This study provides a promising approach for developing environmentally responsive nanopesticides with enhanced durability and controlled-release properties,offering significant potential for sustainable crop protection.
