查看更多>>摘要：Open-shell oligomers and polymers have exhibited intriguing electronic and magnetic properties,making them highly desirable for a wide range of applications,including ambipolar organic field-effect transistors(OFETs),photodetectors,organic thermoelectrics,and spintronics.Although open-shell ground states have been observed in certain small molecules and doped organic semiconductors,the exploration of open-shell ground-state conjugated polymers is still limited,and the strategies for designing these polymers remain obscure.This review aims to briefly introduce the theory and characterization methods of open-shell conjugated polymers,along with an overview of recent progress and applica-tions.The objective is to stimulate further advancements and investigations in this promising area by shedding light on the potential of open-shell conjugated polymers and the challenges that lie ahead.
查看更多>>摘要：By the reaction of poly(acryloyl chloride)with N-(3-aminopropyl)imidazole,poly(N-(3-(1H-imidazol-1-yl)propyl)acrylamide)was syn-thesized.The new polymer contains an imidazole ring removed from the main chain by a spacer of five bonds.The structure and purity,molecu-lar weight,hydrodynamic and thermosensitive properties of the obtained sample were studied by1H-and 13C-NMR,FTIR spectroscopy,acid-base titration,light scattering,turbidimetry and viscometry.The observed ability of the imidazole-containing polymer to form and destroy associates in water-salt solutions at pH 6.6-7.4 and temperatures of 29-48 ℃ indicates that these are promising candidates for designing complex biomedi-cal systems.The new polymer is able to form complexes with oligo-DNA more actively than poly(1-vinylimidazole),which is of interest for gene delivery applications.The polymer cross-linked with epichlorohydrin gives micro-relief coatings on the plastic surface,and the modified surface is able to attach negatively charged objects.This thermo-and pH-sensitive polymer modification can be applied to create finely controlled surfaces for cell culturing.
查看更多>>摘要：There is an urgent imperative to discover practical and efficacious artificial catalysts for the expeditious decontamination of toxic organophosphates.Herein,we propose a novel molecularly imprinted approach utilizing electrospun fiber scaffolds.Specifically,an amidoxime-based functional polymer(PMAOX)has been synthesized,which contains amidoxime groups that can act as nucleophiles and ligands for the for-mation of catalytic active sites.This polymer was blended with polyacrylonitrile(PAN),a well-processable material,to prepare a nanofiber mat using electrospinning techniques.Then,the amidoxime side groups on fiber surface were further cross-linked after the molecular coordination of templates to complete the molecularly imprinting process.This approach can not only enhance the content of functional molecularly imprinted polymers without affecting structural stability,but also combines surface Ml technology to fully expose and leverage the advantages of active sites.The as prepared molecularly imprinted electrospun nanofibers MIF-Zn-PMAOX/PAN-6/4 catalyzes the degradation of paraoxon with a half-life of 32 min,and MIF-Ag-PMAOX/PAN catalyzes the degradation of parathion with a half-life of 18 min.The maximum catalytic rate evidence rate enhancements nearly 3700-fold of the self-hydrolysis.Thus,the mono-amidoxime based molecularly imprinted fibers demonstrate the ver-satility and superiority as self-detoxifying for organophosphates.
查看更多>>摘要：Natural rubber(NR)is widely used in various fields including aerospace,military industry and transportation due to its superior elastici-ty and comprehensive mechanical properties.Nonetheless,the commercial NR prepared by different methods usually exhibits different mechani-cal properties,primarily due to variations in processing conditions during the conversion from latex to bulk rubber material.Consequently,this poses challenges in scientific research and industrial production of NR.In order to assess the properties of various commercially available NR and identify key structural and compositional components,this study systematically compares and analyzes four representative NR raw materials:air dried sheet(ADS),ribbed smoked sheets(RSS),constant viscidity NR(CV),and whole field latex rubber(WF).The investigation focuses on evaluat-ing their static mechanical behavior,SIC behavior,wear resistance,and fatigue resistance.The findings indicate that protein and gel content ex-hibit a crucial influence on the NR properties.These constituents contribute to the formation of a high-crosslinking density region,generating a heterogeneous network structure within the rubber.This structure amplifies strains during deformation,leading to earlier and stronger strain-induced crystallization(SIQ.Among the four commercial NR brands,RSS demonstrates superior overall mechanical and dynamic properties ow-ing to its high protein and gel content.This study serves as a valuable reference for comprehending the differences in properties among various commercial NR,thereby offering guidance for the actual processing and selection of NR.
查看更多>>摘要：Polyelectrolyte complexes(PECs)of hyperbranched(HB)and linear polysaccharides are promising as more effective encapsulation agents compared to PECs formed by linear polysaccharides.We investigated the PECs between the HB anionic polysaccharide fucoidan(FUC)and the cationic linear polysaccharide chitosan(CS).The FUC had a molecular weight(MW)of 30×106.The PECs were prepared in three solvents(wa-ter,0.01 and 0.1 mol/L acetic acid)with CS of MW of 15,110 and 170 kDa,and deacetylation degrees(DDA)of 70％and 97％.The structures of the PECs and the initial FUC were investigated by multi-angle static and dynamic light scattering.As the FUC contained 18 wt％of-OSO3 groups and 5 wt％of uronic acid units,it was a"strong-weak"copolyanion,so the HB macromolecules of the FUC formed nanogel particles in 0.1 mol/L AcOH and open branched structures in water,as confirmed by the Kratky plots.After mixing the solutions of original components,the PEC struc-tures underwent an equilibration period,the duration of which increased with the MW of CS.As the charge stoichiometry was approached,the PECs shrank;the fractal dimension approached unity,indicating the side-by-side packing of adjacent FUC branches with the help of CS.Sec-ondary aggregation in the vicinity of the charge compensation was hardly observed,as it occurred in a very narrow region.The PEC content at theζ-potential inversion depended on solvents'pH and the DDA of CS.In the extreme case of core-shell PECs in 0.1 mol/L AcOH,obtained by mixing FUC nanogels with the solutions of high MW CS of 97％DDA,the protruding tails of CS formed a positively charged shell in the whole range of FUC content(10 wt％＜WFUC＜90 wt％).Scanning electron microscopy and atomic force microscopy images of dried samples were discussed in relation to the light scattering results.
查看更多>>摘要：With the global ban on plastics intensifying,the substitution of plastic with paper has garnered increasing attention.However,the in-adequate water and oil repellency of pulp molding hinders its practical applications.Currently,the common method to enhance the oil and wa-ter repellency of pulp molding is by adding fluorinated water and oil repellents.Nevertheless,fluorinated compounds are environmentally and physiologically harmful.Therefore,the development of fluorine-free,water and oil repellent alternatives is crucial.In this study,chitosan and stearic acid were utilized as the first and second layers of the oil and water repellent coatings,respectively.The coated samples exhibited favor-able water repellency,with a water contact angle of 116.4°,and excellent oil repellency,achieving a 12/12 rating on the kit scale.Importantly,the samples did not exhibit any leakage after being soaked in hot water and hot oil at 95±5 ℃ for 30 min,demonstrating remarkable performance as a barrier against hot water and oil.Moreover,the coated samples displayed outstanding mechanical properties,thermal stability,biodegradabili-ty,and recyclability.The approach presented in this study is simple,cost-effective,environmentally friendly,and represents a promising tech-nique for producing fluoride-free,oil-and water-resistant pulp molding products.
Laura A.RishinaYury V.KissinSvetlana S.LalayanArtem A.Antonov...
492-500页
查看更多>>摘要：The article describes ethylene polymerization reactions with transition metal catalysts based on complexes of CoCl2 and FeCl2with an N,N,N-tridentate ligand 2,6-bis[1-(2,6-dimethylphenylimino)ethyl]pyridine.The complexes are converted into polymerization catalysts by reac-ting them either with polymethylalumoxane(MAO)or with a combination of Al(C2H5)2Cl and Mg(C4H9)2 at an[Al]:[Mg]ratio of～3.Both MAO-activated complexes readily polymerize ethylene at 35 ℃ with the formation of linear,low molecular weight polymers with a narrow molecular weight distribution.The same complexes,when activated with the Al(C2H5)2Cl-Mg(C4H9)2 combination,form multi-center catalysts and generate polyethylenes with a broad molecular weight distribution.
Giovanni RicciAnna SommazziFrancesco MasiAlessandra Forni...
501-510页
查看更多>>摘要：Several novel cobalt dichloride complexes with amino-phosphine bidentate ligands were synthesized and characterized.For some of them single crystals were obtained and their molecular structure was determined by X-ray diffraction method.All the complexes were then used in combination with MAO for the polymerization of 1,3-butadiene,obtaining polymers with different structures(i.e.,predominantly 1,2 or cis-1,4)mainly depending on the type of ligand and on the MAO/Co molar ratio.The behavior of these novel catalysts was compared with that exhibited,in the polymerization of the same monomer,by the systems CoCl2(PR3)2-MAO and CoCl2(PRPh2)2-MAO(R=alkyl or cycloalkyl group),and by the systems based on cobalt dichloride complexes with various bi-and tridentate ligands(e.g.,diphosphines,bis-imines,pyridyl-imines,bis-iminopy-ridines).The comparison between the different systems allowed us to make some clarity about the actual and effective role played by the various types of ligands in the polymerization of conjugated dienes with catalytic systems CoCl2(L)-MAO,in which L=mono-,bi-,or tri-dentate ligand.
查看更多>>摘要：Polymer/conductive filler composites have been widely used for the preparation of self-limiting heating cables with the positive tem-perature coefficient(PTC)effect.The control of conductive filler distribution and network in polymer matrix is the most critical for performance of PTC materials.In order to compensate for the destruction of the filler network structure caused by strong shearing during processing,an exces-sive conductive filler content is usually added into the polymer matrix,which in turn sacrifices its processability and mechanical properties.In this work,a facile post-treatment of the as-extruded cable,including thermal and electrical treatment to produce high-density polyethylene(HDPE)/carbon black(CB)cable with excellent PTC effect,is developed.It is found for the as-extruded sample,the strong shearing makes the CB particles disperse uniformly in HDPE matrix,and 25 wt％CB is needed for the formation of conductive paths.For the thermal-treated sample,a gradually aggregated CB filler structure is observed,which leads to the improvement of PTC effect and the notable reduction of CB content to 20 wt％.It is very interesting to see that for the sample with combined thermal and electrical treatment,CB particles are agglomerated and oriented along the electric field direction to create substantial conductive paths,which leads to a further decrease of CB content down to 15 wt％.In this way,self-limiting heating cables with excellent processability,mechanical properties and PTC effect have simultaneously been achieved.
查看更多>>摘要：Metallic copper is widely used as current collector(CC)for graphite anode of lithium-ion batteries(LIBs)due to its high electrical con-ductivity and electrochemical stability.However,the large volume density of commercial copper foil(～8.9 g·cm-3)limits the increase of energy density of battery.Here,copper-coated porous polyimide(Cu@PPI)was prepared by vacuum evaporation as collector for the graphite anode.The sandwich structure connects the copper metal on both sides of the collector with excellent electrical conductivity.Compared to commercial Cu foil,Cu@PPI has lighter mass(≤3.9 mg for disc of 12 mm diameter versus 9.9 mg of～10 μm Cu foil)and lower volume density(≤3.3 g·cm-3).In ad-dition,the porous structure allows of better adhesion of reactive substances and electrochemical properties than pure Cu foils.It is estimated that the energy density of Cu@PPI should be much higher than that of Cu foil.This strategy should be applicable for other current collectors.
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