Cross-linkedβ-cyclodextrin polymer/Fe3O4 composite nanoparticles with core-shell structures were prepared via cross linking reaction on the surface of carboxymethylβ-cyclodextrin（CM-β-CD） modified Fe3O4 nanoparti...Cross-linkedβ-cyclodextrin polymer/Fe3O4 composite nanoparticles with core-shell structures were prepared via cross linking reaction on the surface of carboxymethylβ-cyclodextrin（CM-β-CD） modified Fe3O4 nanoparticles inβ-cyclodextrin alkaline solution by using epichlorohydrin as crosslinking agent.The morphology,structure and magnetic properties of the prepared composite nanoparticles were investigated by transmission electron microscopy（TEM）,Fourier transform infrared（FTIR） spectrometry,X-ray diffraction（XRD） measurement,thermogravimetric analysis（TGA） and Vibrating sample magnetometry （VSM）,respectively.展开更多
Ionic liquids functionalized β-cyclodextrin polymer, a mono-6-deoxy-6-（1,2-dimethylimida- zolium）-β-cyclodextrin iodide polymer （ILs-β-CDCP）, was synthesized as a solid-phase adsorbent coupled with high-perform...Ionic liquids functionalized β-cyclodextrin polymer, a mono-6-deoxy-6-（1,2-dimethylimida- zolium）-β-cyclodextrin iodide polymer （ILs-β-CDCP）, was synthesized as a solid-phase adsorbent coupled with high-performance liquid chromatography for separating or analyzing magnolol in drug samples. The results showed that magnolol was adsorbed rapidly on ILs-D-CDCP and eluted with methanol. Under the optimum conditions, preconcentration factor of the proposed method was 12. The linear range, limit of detection （LOD）, correlation coefficient （R） and relative standard deviation （RSD） were found to be 0.02-8.00 μg/mL, 1.9 ng/mL, 0.9992 and 2.76% （n=3, c=2.00 pg/mL）, respectively. The interaction between 1Ls-]）-CDCP and magnolol was studied through the inclusion constant, FTIR and TGA analysis. This proposed method has been successfully applied to the determination of magnolol in real samples.展开更多
Insoluble β-cyclodextrin polymers were prepared from β-cyclodextrin(β-CD) using epichlorohydrin(EPI) as crosslinking agent under basic conditions.The polymers were characterized by Fourier Transform Infrared(FTIR),...Insoluble β-cyclodextrin polymers were prepared from β-cyclodextrin(β-CD) using epichlorohydrin(EPI) as crosslinking agent under basic conditions.The polymers were characterized by Fourier Transform Infrared(FTIR),Thermogravimetry(TG),X-ray diffraction(XRD) and TG-FTIR.The results demonstrated that the polym-erization between EPI and β-CD indeed occurred,and a number of CD rings were interconnected to form a three-dimensional network.Moreover,different factors influencing the polymerization,e.g.molar ratio of EPI to β-CD,the concentration of NaOH and reaction temperature,have been investigated.The polymer prepared under the optimal conditions(the molar ratio EPI:β-CD of 44,the NaOH concentration 50% in mass,and the temperature at 65 ℃) showed excellent thermal stability and insolubility in organic solvents or strong acid/base.In addition,the β-cyclodextrin polymers also presented high catalytic activity for aqueous oxidation of benzyl alcohol with hy-pochlorite as oxidant.展开更多
Apurinic/apyrimidinic endonuclease 1（APE1） plays an important role in protecting the fidelity of genetic material and is also a promising biomarker of cancers. Herein, a simple and sensitive fluorescent method for A...Apurinic/apyrimidinic endonuclease 1（APE1） plays an important role in protecting the fidelity of genetic material and is also a promising biomarker of cancers. Herein, a simple and sensitive fluorescent method for APE1 activity detection was designed based on host-vip interaction between β-cyclodextrin polymer（β-CDP） and pyrene. In this method, pyrene-labelled DNA probes（AP-S1 S2） and β-CDP functioned as fluorescent signal producer and enhancer, respectively. When APE1 was absent, pyrene on the AP-S1 S2 could not enter the cavity of β-CDP because of steric hindrance, leading to a weak fluorescence intensity/anisotropy. When APE1 was present, it would recognize and cleave AP site in APS1 S2, thus producing a dissociated pyrene-labelled oligonucleotide segment. Pyrene labelled at the 50 end of oligonucleotide segment could be easily trapped into the cavity of β-CDP via host-vip interaction, leading to a significant enhancement of fluorescence intensity/anisotropy. This assay offered a dynamic range of 0.05 U/m L–5 U/m L and an estimated detection limit of 0.05 U/m L. Furthermore,assessment of APE1 activity in He La cell extracts was successfully implemented, which hold the potential for APE1-related cancer diagnosis and biological researches.展开更多
Adsorptive recovery of valuable components from industrial wastewater is highly desirable for avoiding resource wastage but remains a challenge.Herein,we develop an efficient continuous adsorption process for recoveri...Adsorptive recovery of valuable components from industrial wastewater is highly desirable for avoiding resource wastage but remains a challenge.Herein,we develop an efficient continuous adsorption process for recovering aromatic compounds in wastewater from styrene monomer and propylene oxide coproduction(SMPO)plant.Based on our insight into the potential of bio-based porous materials for adsorption application,starch-graft-polystyrene(SPS)and aryl-modifiedβ-cyclodextrin(ACD)were prepared,and novel hypercrosslinked porous polymers combined SPS with ACD(HSPS-ACDs)were synthesized through external crosslinking approach.In a binary-component system,the best-performing one HSPS-ACD(H)with high ACD content and large specific surface area possessed superior capacities for the representative aromatic compounds,acetophenone(AP,2.81 mmol·g^(-1))and 1-phenylethanol(1-PE,1.35 mmol·g^(-1))compared with the previously reported materials.Further,the adsorption properties of aromatic compounds on HSPS-ACD(H)were investigated in batch mode.For practical application,continuous adsorption experiments were conducted in a HSPS-ACD(H)-packed fixed bed,where the target aromatic components in wastewater were effectively retained and further released by elution.Besides showing the reversible adsorption and efficient enrichment effect,the HSPS-ACD(H)-packed fixed bed also maintained great stability in multiple cycles.Moreover,quantum chemical calculations were performed to elucidate the potential mechanism of adsorption of AP and 1-PE onto HSPS-ACD(H).展开更多
Adenosine triphosphate plays a crucial role in regulation of many biological pathways and has been used as an indicator for many diseases.In this pape r,based on the fact that β-cyclodextrin polymer(polyβ-CD)could s...Adenosine triphosphate plays a crucial role in regulation of many biological pathways and has been used as an indicator for many diseases.In this pape r,based on the fact that β-cyclodextrin polymer(polyβ-CD)could significantly enhance pyrene fluorescence through supramolecular assembly(host-gest interaction),a sensitive and facile method for adenosine triphosphate detection has been developed.A 3’-pyrene-labelled ATP-binding aptamer was employed as the fluorescence probe,which could be digested by exonuclease I to obtain mononucleotides,with pyrene attached on.The pyrene attached on mononucleotides could easily enter the hydrophobic cavity of polyβ-CD,accompanied with prominent fluo rescence enhancement.While ATP was introduced,ATP and its aptamer could combine together and the obtained hairpin complex could not be cleaved by exonuclease Ⅰ,The pyrene labelled on the probe could not enter the cavity of polyβ-CD belong to the complex’steric hindrance,accompanied with the weak pyrene’fluorescence.So we could quantify the concentration of adenosine triphosphate facilely by measuring the fluorescence intensity of the system.The detection limit of this method for adenosine triphosphate was 11 μmol/L(S/N=3),The developed method showed sufficient selectivity and could successfully assay adenosine triphosphate in biological samples.The developed method provides a potential platform for biological micromoles assay.展开更多
Enantiomer of n-pyrrolidinyl phenylpropanol was studied by capillary electrophoresis using b-cyclodextrin polymer as chiral selector. We determined the enantiomeric excess value of n-pyrrolidinyl phenylpropanol with R...Enantiomer of n-pyrrolidinyl phenylpropanol was studied by capillary electrophoresis using b-cyclodextrin polymer as chiral selector. We determined the enantiomeric excess value of n-pyrrolidinyl phenylpropanol with RSD 0.48%.展开更多
As a member of the curcuminoid compound family,curcumin(Cur)has many interesting therapeutic properties.However,its low aqueous solubility and stability have resulted in poor bioavailability and restricted clinical ef...As a member of the curcuminoid compound family,curcumin(Cur)has many interesting therapeutic properties.However,its low aqueous solubility and stability have resulted in poor bioavailability and restricted clinical efficacy.Based on size matching,β-cyclodextrin polymer(β-CDP),with its hydrophilic polymer chains and hydrophobic cavities,can form an inclusion complex with Cur.To improve the water solubility and stability of Cur,a simple and eco-friendly grinding method was designed to formβ-CDP inclusion complexes.According to the Boltzmann-Hamel's method and Job's method,the molar ratio of theβ-CD unit inβ-CDP to Cur was determined to be 1:1.The diffusion coefficient and diffusion activation energy of Cur-β-CDP were calculated in an electrochemical study.This supramolecular complex worked well in vitro to inhibit the proliferation of hepatoma carcinoma cells HepG2.Remarkably,this method visibly reduced the undesirable side effects on normal cells,without weakening the anti-cancer activity of the drugs.We expect that the obtained host-vip complex will provide a new approach for delivering natural drug molecules,having low water solubility.展开更多
Under solvothermal conditions,1,4‑naphthalenedicarboxylic acid(H_(2)ndc)and 9,9′‑dihexyl‑2,7‑di(pyridin‑4‑yl)fluorene(hfdp)reacted with Co^(2+)ions and Cd^(2+)ions to form two coordination polymers,[Co(hfdp)(ndc)(H2O...Under solvothermal conditions,1,4‑naphthalenedicarboxylic acid(H_(2)ndc)and 9,9′‑dihexyl‑2,7‑di(pyridin‑4‑yl)fluorene(hfdp)reacted with Co^(2+)ions and Cd^(2+)ions to form two coordination polymers,[Co(hfdp)(ndc)(H2O)]·DMA}n(1)and{[Cd(hfdp)(ndc)(H_(2)O)]·DMA}_(n)(2),respectively(DMA=N,N‑dimethylacetamide).Single‑crystal X‑ray diffraction analyses showed that both complexes 1 and 2 contain similar structures.Topological analysis indicates that complexes 1 and 2 have a{44·62}planar structure.In addition,both complexes reveal good thermal stability and fluorescence sensing performance.They exhibited good sensitivity and selectivity towards 2,4,6‑trinitrophenol(TNP)by fluorescent quenching.The limits of detection of 1 and 2 for TNP were 0.107 and 0.327μmol·L^(-1),respectively.CCDC:2475515,1;2475516,2.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
The ionothermal reaction between CuCl_(2),1,4-bis(1,2,4-triazol-1-ylmethyl)benzene(BBTZ),and(NH_(4))_(6)Mo_(7)O_(24) in 1-ethyl-3-methylimidazolium bromide((Emim)Br)led to a new octamolybdate-based coordination polyme...The ionothermal reaction between CuCl_(2),1,4-bis(1,2,4-triazol-1-ylmethyl)benzene(BBTZ),and(NH_(4))_(6)Mo_(7)O_(24) in 1-ethyl-3-methylimidazolium bromide((Emim)Br)led to a new octamolybdate-based coordination polymer(Emim)2[Cu(BBTZ)_(2)(β-Mo_(8)O_(26))](Mo_(8)-CP).Mo_(8)-CP was characterized by elemental analysis,thermogravime-try,IR,powder X-ray diffraction,and single-crystal X-ray diffraction.In Mo_(8)-CP,structural analysis reveals that Cu coordinates with BBTZ ligands to form an interlocked 1D chain.These chains are further bridged by(β-Mo_(8)O_(26))^(4-)to construct a 3D coordination polymer.Notably,(Emim)^(+)acts as a structure-directing agent,occupying the channels of the 3D coordination polymer.Based on this unique structure,the ion exchange properties of Mo_(8)-CP toward rare-earth ions were investigated.It has been found that the luminescent color of the material can be successfully regulat-ed by introducing Eu^(3+)or Tb^(3+)through ion exchange.CCDC:2475110,Mo_(8)-CP.展开更多
The morphology of active layer plays a critical role in determining the photovoltaic performance of organic solar cells(OSCs).However,binary blends often suffer from suboptimal phase separation,which limits the effici...The morphology of active layer plays a critical role in determining the photovoltaic performance of organic solar cells(OSCs).However,binary blends often suffer from suboptimal phase separation,which limits the efficiency of OSCs.Herein,two bridging polymer acceptors(PAs)—benzodithiophene-(2-ethylhexyl)oxy(BDT-C2C4)and benzodithiophene-octyloxy(BDT-C_(8))—are designed and synthesized by combining a benzodithiophene(BDT)unit as the donor moiety[poly({4,8-bis[5-(2-ethylhexyl)-4-fluorothiophen-2-yl]benzo[1,2-b:4,5-b']dithiophene-2,6-diyl}){5,8-bis[4-(2-butyloctyl)thiophen-2-yl]dithieno[3',2':3,4]},D18],and a 2,2′-((2Z,2′Z)-{[12,13-Bis(2-butyloctyl)-12,13-dihydro-3,9-dinonylthieno[2,3]thieno[3,2-b]pyrrolo[4,5-g]thieno[2,3-b]indole-2,10-diyl]bis(methanylylidene)}bis(3-oxo-2,3-dihydro-1H-indene-2,1-diylidene))dimalononitrile(Y6)derivative as the acceptor moiety.BDT-C2C4 and BDT-C_(8) are functionalized with(2-ethylhexyl)oxy and octyloxy side chains on the BDT unit,respectively.Both PAs show complementary absorption and cascaded energy levels with the donor D18 and the acceptor 2,2′-((2Z,2′Z)-{[12,13-bis(3-ethylheptyl)-3,9-diundecyl-12,13-dihydro-[1,2,5]thiadiazolo[3,4-e]thieno[2″,3″∶4′,5′]thieno[2′,3′∶4,5]pyrrolo[3,2-g]thieno[2′,3′∶4,5]thieno[3,2-b]indole-2,10-diyl]bis(meth⁃aneylylidene)}bis(5,6-difluoro-3-oxo-2,3-dihydro-1H-indene-2,1-diylidene))dimalononitrile(N3),but BDT-C_(8) exhibits better compatibility with D18 and N3 compared to BDT-C2C4.When incorporated as a third component into the D18∶N3 blend,both PAs improve the active layer morphology.In particular,the D18∶N3∶BDT-C_(8) blend shows significantly optimized morphology,featuring reduced phase separation and a fibrous network structure.As a result,the device based on D18∶N3∶BDT-C_(8) achieves a power conversion efficiency of 18.18%,significantly higher than that of the device based on D18∶N3(ca.17.37%).This work presents a compatibilizer strategy for optimizing blend morphology towards high-performance ternary OSCs.展开更多
A new principle for producing fire-resistant polymer materials with increased deformation properties using a flame retardant not as a heterogeneous additive,but as a thermoplastic flame retardant in a hybrid polymer m...A new principle for producing fire-resistant polymer materials with increased deformation properties using a flame retardant not as a heterogeneous additive,but as a thermoplastic flame retardant in a hybrid polymer mixture with a polyhydrocarbon is considered.Hybrid polymer blends of low-molecular ammonium polyphosphate(APP)with an ethylene-vinyl acetate copolymer(EVA)with an APP content of 80 wt%with enhanced deformation properties were obtained by extrusion mixing at various temperatures in the range from 200°C to 250°C.A chemical scheme for the transformations of the components during the formation of the composite is proposed.X-ray diffraction analysis showed the formation of new crystalline structures of APP.The phase structure of the systems corresponding to the model of a dispersed-filled composite in which EVA plays the role of a matrix,determining the deformation of the mixture,and the filler is ammonium polyphosphate,was studied by scanning electron microscopy(SEM).The method of FTIR microscopy showed chemical interactions between EVA and APP with the formation of amide groups.The conditions for obtaining compositions characterized by heat resistance of 210°C,oxygen index of 55 and ultimate elongation at drawing of 213%were established.展开更多
Commercial-level sodium metal batteries require electrolytes with high ionic mobility and excellent thermo-mechanical and electrochemical stability.Conventional flammable liquid electrolytes,prone to dendrite growth a...Commercial-level sodium metal batteries require electrolytes with high ionic mobility and excellent thermo-mechanical and electrochemical stability.Conventional flammable liquid electrolytes,prone to dendrite growth and unstable interfacial reactions,rarely perform beyond coin-cell demonstrations.To address these shortcomings,a multifunctional composite quasi-solid polymer electrolyte(QSPE)that incorporates boron nitride(BN)as an engineered filler in a highly conductive polymer blend system has been developed.The optimized formation(15BN QSPE)delivers a room-temperature ionic conductivity of 2.15 m S cm^(-1)and a sodium-ion transference number of 0.80.Molecular dynamics simulations elucidate the coordination environment and show improved transport in the presence of BN.BN is chemically active and bifunctional:boron acts as an electron acceptor,interacting with solvents and macromolecules,while nitrogen coordinates with sodium ions,tailoring the solvation environment and transport pathways to promote efficient ion migration.The 15BN QSPE is self-extinguishing,resists oxidative thermal degradation,and enables stable cycling in symmetric sodium cells for>1400 h at0.5 m A cm^(-2).A Prussian blue full cell achieves>1500 stable cycles at 1C with -99% Coulombic efficiency in coin-cell configuration.A two-layer pouch cell with dual 15BN QSPE layers delivers 600 stable cycles at 0.125C and withstands rigorous mechanical abuse.These results position 15BN QSPE as a scalable,highperformance electrolyte offering enhanced safety and efficiency for next-generation sodium metal batteries.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
Liver is a vital organ in the human body and plays a central role in the metabolism and detoxification of endotoxins and exotoxins.Bilirubin is an endotoxin derived from hemoglobin(Hb).Removing excess bilirubin in the...Liver is a vital organ in the human body and plays a central role in the metabolism and detoxification of endotoxins and exotoxins.Bilirubin is an endotoxin derived from hemoglobin(Hb).Removing excess bilirubin in the blood is crucial for the treatment of liver diseases.Hemoperfusion,which relies on adsorbents to efficiently adsorb toxins,is a widely applied procedure for the removal of blood toxins.To broaden and improve the range and performance of hemoperfusion adsorbents,we synthesized cationic hyper crosslinked polymers(HCPs)with strong affinity for bilirubin.This material exhibited outstanding adsorption performance,with a maximum adsorption capacity of 934 mg/g and a removal efficiency of 96%.Further investigation confirmed their excellent selectivity,reusability,and biocompatibility.These findings expand the potential applications of HCPs and provide insight into strategies for constructing promising hemoperfusion adsorbent materials.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
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
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
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
基金financially supported by the Guangdong Natural Science Foundation(No.020891)
文摘Cross-linkedβ-cyclodextrin polymer/Fe3O4 composite nanoparticles with core-shell structures were prepared via cross linking reaction on the surface of carboxymethylβ-cyclodextrin（CM-β-CD） modified Fe3O4 nanoparticles inβ-cyclodextrin alkaline solution by using epichlorohydrin as crosslinking agent.The morphology,structure and magnetic properties of the prepared composite nanoparticles were investigated by transmission electron microscopy（TEM）,Fourier transform infrared（FTIR） spectrometry,X-ray diffraction（XRD） measurement,thermogravimetric analysis（TGA） and Vibrating sample magnetometry （VSM）,respectively.
基金the financial support from the National Natural Science Foundation of China(Nos.21155001 and 21375117)a project funded by the Priority Academic ProgramDevelopment of Jiangsu Higher Education Institutionsthe Foundation of the Excellence Science and Technology Invention Team in Yangzhou University
文摘Ionic liquids functionalized β-cyclodextrin polymer, a mono-6-deoxy-6-（1,2-dimethylimida- zolium）-β-cyclodextrin iodide polymer （ILs-β-CDCP）, was synthesized as a solid-phase adsorbent coupled with high-performance liquid chromatography for separating or analyzing magnolol in drug samples. The results showed that magnolol was adsorbed rapidly on ILs-D-CDCP and eluted with methanol. Under the optimum conditions, preconcentration factor of the proposed method was 12. The linear range, limit of detection （LOD）, correlation coefficient （R） and relative standard deviation （RSD） were found to be 0.02-8.00 μg/mL, 1.9 ng/mL, 0.9992 and 2.76% （n=3, c=2.00 pg/mL）, respectively. The interaction between 1Ls-]）-CDCP and magnolol was studied through the inclusion constant, FTIR and TGA analysis. This proposed method has been successfully applied to the determination of magnolol in real samples.
基金Supported by the National Natural Science Foundation of China (21036009,21176268)the Higher-level Talent Project for Guangdong Provincial Universities+1 种基金the Fundamental Research Funds for the Central UniversitiesGuangdong Province 211 Project
文摘Insoluble β-cyclodextrin polymers were prepared from β-cyclodextrin(β-CD) using epichlorohydrin(EPI) as crosslinking agent under basic conditions.The polymers were characterized by Fourier Transform Infrared(FTIR),Thermogravimetry(TG),X-ray diffraction(XRD) and TG-FTIR.The results demonstrated that the polym-erization between EPI and β-CD indeed occurred,and a number of CD rings were interconnected to form a three-dimensional network.Moreover,different factors influencing the polymerization,e.g.molar ratio of EPI to β-CD,the concentration of NaOH and reaction temperature,have been investigated.The polymer prepared under the optimal conditions(the molar ratio EPI:β-CD of 44,the NaOH concentration 50% in mass,and the temperature at 65 ℃) showed excellent thermal stability and insolubility in organic solvents or strong acid/base.In addition,the β-cyclodextrin polymers also presented high catalytic activity for aqueous oxidation of benzyl alcohol with hy-pochlorite as oxidant.
基金supported by the National Natural Science Foundation of China (Nos. 21675047, 21375034, 21190040)the Foundation for Innovative Research Groups of National Natural Science Foundation of China (No. 21521063)
文摘Apurinic/apyrimidinic endonuclease 1（APE1） plays an important role in protecting the fidelity of genetic material and is also a promising biomarker of cancers. Herein, a simple and sensitive fluorescent method for APE1 activity detection was designed based on host-vip interaction between β-cyclodextrin polymer（β-CDP） and pyrene. In this method, pyrene-labelled DNA probes（AP-S1 S2） and β-CDP functioned as fluorescent signal producer and enhancer, respectively. When APE1 was absent, pyrene on the AP-S1 S2 could not enter the cavity of β-CDP because of steric hindrance, leading to a weak fluorescence intensity/anisotropy. When APE1 was present, it would recognize and cleave AP site in APS1 S2, thus producing a dissociated pyrene-labelled oligonucleotide segment. Pyrene labelled at the 50 end of oligonucleotide segment could be easily trapped into the cavity of β-CDP via host-vip interaction, leading to a significant enhancement of fluorescence intensity/anisotropy. This assay offered a dynamic range of 0.05 U/m L–5 U/m L and an estimated detection limit of 0.05 U/m L. Furthermore,assessment of APE1 activity in He La cell extracts was successfully implemented, which hold the potential for APE1-related cancer diagnosis and biological researches.
基金supported by National Natural Science Foundation of China(21868002 and 21961160741)the Natural Science Foundation of Guangxi Province(2018GXNSFAA281206,2020GXNSFGA297001,2020GXNSFAA297044)+2 种基金Dean Project of Guangxi Key Laboratory of Petrochemical Resource Processing and Process Intensification Technology(2021Z010)Specific research project of Guangxi for research bases and talents(AD18126005)special funding for‘Guangxi Bagui Scholars’,Guangxi scholarship fund for the middle-aged backbone teachers。
文摘Adsorptive recovery of valuable components from industrial wastewater is highly desirable for avoiding resource wastage but remains a challenge.Herein,we develop an efficient continuous adsorption process for recovering aromatic compounds in wastewater from styrene monomer and propylene oxide coproduction(SMPO)plant.Based on our insight into the potential of bio-based porous materials for adsorption application,starch-graft-polystyrene(SPS)and aryl-modifiedβ-cyclodextrin(ACD)were prepared,and novel hypercrosslinked porous polymers combined SPS with ACD(HSPS-ACDs)were synthesized through external crosslinking approach.In a binary-component system,the best-performing one HSPS-ACD(H)with high ACD content and large specific surface area possessed superior capacities for the representative aromatic compounds,acetophenone(AP,2.81 mmol·g^(-1))and 1-phenylethanol(1-PE,1.35 mmol·g^(-1))compared with the previously reported materials.Further,the adsorption properties of aromatic compounds on HSPS-ACD(H)were investigated in batch mode.For practical application,continuous adsorption experiments were conducted in a HSPS-ACD(H)-packed fixed bed,where the target aromatic components in wastewater were effectively retained and further released by elution.Besides showing the reversible adsorption and efficient enrichment effect,the HSPS-ACD(H)-packed fixed bed also maintained great stability in multiple cycles.Moreover,quantum chemical calculations were performed to elucidate the potential mechanism of adsorption of AP and 1-PE onto HSPS-ACD(H).
基金financially supported by the National Natural Science Foundation of China (Nos. 21305002 and 21705002)the Scientific Research Foundation of Anhui Agricultural University (No. yj2017-19)
文摘Adenosine triphosphate plays a crucial role in regulation of many biological pathways and has been used as an indicator for many diseases.In this pape r,based on the fact that β-cyclodextrin polymer(polyβ-CD)could significantly enhance pyrene fluorescence through supramolecular assembly(host-gest interaction),a sensitive and facile method for adenosine triphosphate detection has been developed.A 3’-pyrene-labelled ATP-binding aptamer was employed as the fluorescence probe,which could be digested by exonuclease I to obtain mononucleotides,with pyrene attached on.The pyrene attached on mononucleotides could easily enter the hydrophobic cavity of polyβ-CD,accompanied with prominent fluo rescence enhancement.While ATP was introduced,ATP and its aptamer could combine together and the obtained hairpin complex could not be cleaved by exonuclease Ⅰ,The pyrene labelled on the probe could not enter the cavity of polyβ-CD belong to the complex’steric hindrance,accompanied with the weak pyrene’fluorescence.So we could quantify the concentration of adenosine triphosphate facilely by measuring the fluorescence intensity of the system.The detection limit of this method for adenosine triphosphate was 11 μmol/L(S/N=3),The developed method showed sufficient selectivity and could successfully assay adenosine triphosphate in biological samples.The developed method provides a potential platform for biological micromoles assay.
文摘Enantiomer of n-pyrrolidinyl phenylpropanol was studied by capillary electrophoresis using b-cyclodextrin polymer as chiral selector. We determined the enantiomeric excess value of n-pyrrolidinyl phenylpropanol with RSD 0.48%.
基金supported by the National Natural Science Foundation of China(Nos.21703200 and 21773203)the Chey Institute for Advanced Studies International Scholar Exchange Fellowship for the Academic Year of 2021-2022China Scholarship Council Program(No.201908320084)。
文摘As a member of the curcuminoid compound family,curcumin(Cur)has many interesting therapeutic properties.However,its low aqueous solubility and stability have resulted in poor bioavailability and restricted clinical efficacy.Based on size matching,β-cyclodextrin polymer(β-CDP),with its hydrophilic polymer chains and hydrophobic cavities,can form an inclusion complex with Cur.To improve the water solubility and stability of Cur,a simple and eco-friendly grinding method was designed to formβ-CDP inclusion complexes.According to the Boltzmann-Hamel's method and Job's method,the molar ratio of theβ-CD unit inβ-CDP to Cur was determined to be 1:1.The diffusion coefficient and diffusion activation energy of Cur-β-CDP were calculated in an electrochemical study.This supramolecular complex worked well in vitro to inhibit the proliferation of hepatoma carcinoma cells HepG2.Remarkably,this method visibly reduced the undesirable side effects on normal cells,without weakening the anti-cancer activity of the drugs.We expect that the obtained host-vip complex will provide a new approach for delivering natural drug molecules,having low water solubility.
文摘Under solvothermal conditions,1,4‑naphthalenedicarboxylic acid(H_(2)ndc)and 9,9′‑dihexyl‑2,7‑di(pyridin‑4‑yl)fluorene(hfdp)reacted with Co^(2+)ions and Cd^(2+)ions to form two coordination polymers,[Co(hfdp)(ndc)(H2O)]·DMA}n(1)and{[Cd(hfdp)(ndc)(H_(2)O)]·DMA}_(n)(2),respectively(DMA=N,N‑dimethylacetamide).Single‑crystal X‑ray diffraction analyses showed that both complexes 1 and 2 contain similar structures.Topological analysis indicates that complexes 1 and 2 have a{44·62}planar structure.In addition,both complexes reveal good thermal stability and fluorescence sensing performance.They exhibited good sensitivity and selectivity towards 2,4,6‑trinitrophenol(TNP)by fluorescent quenching.The limits of detection of 1 and 2 for TNP were 0.107 and 0.327μmol·L^(-1),respectively.CCDC:2475515,1;2475516,2.
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The ionothermal reaction between CuCl_(2),1,4-bis(1,2,4-triazol-1-ylmethyl)benzene(BBTZ),and(NH_(4))_(6)Mo_(7)O_(24) in 1-ethyl-3-methylimidazolium bromide((Emim)Br)led to a new octamolybdate-based coordination polymer(Emim)2[Cu(BBTZ)_(2)(β-Mo_(8)O_(26))](Mo_(8)-CP).Mo_(8)-CP was characterized by elemental analysis,thermogravime-try,IR,powder X-ray diffraction,and single-crystal X-ray diffraction.In Mo_(8)-CP,structural analysis reveals that Cu coordinates with BBTZ ligands to form an interlocked 1D chain.These chains are further bridged by(β-Mo_(8)O_(26))^(4-)to construct a 3D coordination polymer.Notably,(Emim)^(+)acts as a structure-directing agent,occupying the channels of the 3D coordination polymer.Based on this unique structure,the ion exchange properties of Mo_(8)-CP toward rare-earth ions were investigated.It has been found that the luminescent color of the material can be successfully regulat-ed by introducing Eu^(3+)or Tb^(3+)through ion exchange.CCDC:2475110,Mo_(8)-CP.
文摘The morphology of active layer plays a critical role in determining the photovoltaic performance of organic solar cells(OSCs).However,binary blends often suffer from suboptimal phase separation,which limits the efficiency of OSCs.Herein,two bridging polymer acceptors(PAs)—benzodithiophene-(2-ethylhexyl)oxy(BDT-C2C4)and benzodithiophene-octyloxy(BDT-C_(8))—are designed and synthesized by combining a benzodithiophene(BDT)unit as the donor moiety[poly({4,8-bis[5-(2-ethylhexyl)-4-fluorothiophen-2-yl]benzo[1,2-b:4,5-b']dithiophene-2,6-diyl}){5,8-bis[4-(2-butyloctyl)thiophen-2-yl]dithieno[3',2':3,4]},D18],and a 2,2′-((2Z,2′Z)-{[12,13-Bis(2-butyloctyl)-12,13-dihydro-3,9-dinonylthieno[2,3]thieno[3,2-b]pyrrolo[4,5-g]thieno[2,3-b]indole-2,10-diyl]bis(methanylylidene)}bis(3-oxo-2,3-dihydro-1H-indene-2,1-diylidene))dimalononitrile(Y6)derivative as the acceptor moiety.BDT-C2C4 and BDT-C_(8) are functionalized with(2-ethylhexyl)oxy and octyloxy side chains on the BDT unit,respectively.Both PAs show complementary absorption and cascaded energy levels with the donor D18 and the acceptor 2,2′-((2Z,2′Z)-{[12,13-bis(3-ethylheptyl)-3,9-diundecyl-12,13-dihydro-[1,2,5]thiadiazolo[3,4-e]thieno[2″,3″∶4′,5′]thieno[2′,3′∶4,5]pyrrolo[3,2-g]thieno[2′,3′∶4,5]thieno[3,2-b]indole-2,10-diyl]bis(meth⁃aneylylidene)}bis(5,6-difluoro-3-oxo-2,3-dihydro-1H-indene-2,1-diylidene))dimalononitrile(N3),but BDT-C_(8) exhibits better compatibility with D18 and N3 compared to BDT-C2C4.When incorporated as a third component into the D18∶N3 blend,both PAs improve the active layer morphology.In particular,the D18∶N3∶BDT-C_(8) blend shows significantly optimized morphology,featuring reduced phase separation and a fibrous network structure.As a result,the device based on D18∶N3∶BDT-C_(8) achieves a power conversion efficiency of 18.18%,significantly higher than that of the device based on D18∶N3(ca.17.37%).This work presents a compatibilizer strategy for optimizing blend morphology towards high-performance ternary OSCs.
基金financially supported by Ministry of Science and Higher Education of the Russian Federation.
文摘A new principle for producing fire-resistant polymer materials with increased deformation properties using a flame retardant not as a heterogeneous additive,but as a thermoplastic flame retardant in a hybrid polymer mixture with a polyhydrocarbon is considered.Hybrid polymer blends of low-molecular ammonium polyphosphate(APP)with an ethylene-vinyl acetate copolymer(EVA)with an APP content of 80 wt%with enhanced deformation properties were obtained by extrusion mixing at various temperatures in the range from 200°C to 250°C.A chemical scheme for the transformations of the components during the formation of the composite is proposed.X-ray diffraction analysis showed the formation of new crystalline structures of APP.The phase structure of the systems corresponding to the model of a dispersed-filled composite in which EVA plays the role of a matrix,determining the deformation of the mixture,and the filler is ammonium polyphosphate,was studied by scanning electron microscopy(SEM).The method of FTIR microscopy showed chemical interactions between EVA and APP with the formation of amide groups.The conditions for obtaining compositions characterized by heat resistance of 210°C,oxygen index of 55 and ultimate elongation at drawing of 213%were established.
基金a seed grant from IIT Delhi(SGNF148)supported by the JST-ERATO Yamauchi Materials SpaceTectonics Project(JPMJER2003)+2 种基金the ARC Australian Laureate Fellowship(FL230100095)the UQ-Yonsei International Joint Research Projectthe support from JSPS Postdoctoral Fellowships for Research in Japan。
文摘Commercial-level sodium metal batteries require electrolytes with high ionic mobility and excellent thermo-mechanical and electrochemical stability.Conventional flammable liquid electrolytes,prone to dendrite growth and unstable interfacial reactions,rarely perform beyond coin-cell demonstrations.To address these shortcomings,a multifunctional composite quasi-solid polymer electrolyte(QSPE)that incorporates boron nitride(BN)as an engineered filler in a highly conductive polymer blend system has been developed.The optimized formation(15BN QSPE)delivers a room-temperature ionic conductivity of 2.15 m S cm^(-1)and a sodium-ion transference number of 0.80.Molecular dynamics simulations elucidate the coordination environment and show improved transport in the presence of BN.BN is chemically active and bifunctional:boron acts as an electron acceptor,interacting with solvents and macromolecules,while nitrogen coordinates with sodium ions,tailoring the solvation environment and transport pathways to promote efficient ion migration.The 15BN QSPE is self-extinguishing,resists oxidative thermal degradation,and enables stable cycling in symmetric sodium cells for>1400 h at0.5 m A cm^(-2).A Prussian blue full cell achieves>1500 stable cycles at 1C with -99% Coulombic efficiency in coin-cell configuration.A two-layer pouch cell with dual 15BN QSPE layers delivers 600 stable cycles at 0.125C and withstands rigorous mechanical abuse.These results position 15BN QSPE as a scalable,highperformance electrolyte offering enhanced safety and efficiency for next-generation sodium metal batteries.
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financially supported by the International Cooperation Program of the Ministry of Science and Technology of Hubei Province(No.2023EHA069)Shenzhen Science and Technology Program(No.JCYJ20230807143702005)the National Foreign Experts Program(No.G2022027015L)。
文摘Liver is a vital organ in the human body and plays a central role in the metabolism and detoxification of endotoxins and exotoxins.Bilirubin is an endotoxin derived from hemoglobin(Hb).Removing excess bilirubin in the blood is crucial for the treatment of liver diseases.Hemoperfusion,which relies on adsorbents to efficiently adsorb toxins,is a widely applied procedure for the removal of blood toxins.To broaden and improve the range and performance of hemoperfusion adsorbents,we synthesized cationic hyper crosslinked polymers(HCPs)with strong affinity for bilirubin.This material exhibited outstanding adsorption performance,with a maximum adsorption capacity of 934 mg/g and a removal efficiency of 96%.Further investigation confirmed their excellent selectivity,reusability,and biocompatibility.These findings expand the potential applications of HCPs and provide insight into strategies for constructing promising hemoperfusion adsorbent materials.
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(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.
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.
