Multiblock poly(ether-b-amide)copolymers comprised of PA1212 and PPO-PEO-PPO with specific moisture-responsive and antistatic properties

Functional multiblock poly(ether-b-amide)(PEBA)copolymers,comprised of PA1212(polyamide 1212)as hard segments and Jeffamine ED-2003 as soft segments,were successfully prepared via two-step melt polycondensation without any amidation catalyst.Here,using diamino-terminated poly(propylene oxide)-poly(ethylene oxide)-poly(propylene oxide)(PPO-PEO-PPO),Jeffamine ED-2003,enhances the compatibility between polyamide oligomer and polyether,which is better than the traditional route using hydroxyl-terminated polyether.The chemical structure of multiblock PEBAs,as well as the microphase separated structure with crystalline phase of polyamide and polyether,were confirmed by heteronuclear multiple-bond correlation spectrum,heteronuclear multiple quantum correlation spectrum,Fourier transform infrared spectroscopy(FT-IR),differential scanning calorimetry and dynamic mechanical analysis.The hydrophilic PEBA copolymers showed water adsorption ranging from 87.3%to 17.1%depending on the polyether content,and specially showed moisture responsive behavior within seconds when exposed to moisture.The corresponding mechanism was studied using time-resolved attenuated total reflectance FT-IR spectroscopy in the molecular level and the water diffusion coefficient was estimated to be 1.07×10^(–8)cm^(2)∙s^(-1).Two-dimensional correlation FT-IR spectra analysis was performed to confirm that the interaction between water and polyether phase was in preference to that between water and polyamide matrix,and water molecule only forms hydrogen bond with the polyether segment.Due to the incorporation of PEO segments,the PEBAs have the surface resistivity varying from 5.6×10^(9)to 6.5×10^(10)Ω,which makes PEBA potential candidate as permanent antistatic agent.

Kinetic hydrate inhibitor performance of new copolymer poly(N-vinyl-2-pyrrolidone-co-2-vinyl pyridine)s with TBAB

In oil and gas field, the application of kinetic hydrate inhibitors （KHIs） independently has remained problematic in high subcooling and high water-cut situation. One feasible method to resolve this problem is the combined use of KHIs and some synergists, which would enhance KHIs’ inhibitory effect on both hydrate nucleation and hydrate crystal growth. In this study, a novel kind of KHI copolymer poly（N-vinyl-2-pyrrolidone-co-2-vinyl pyridine）s （HGs） is used in conjunction with TBAB to show its high performance on hydrate inhibition. The performance of HGs with different monomer ratios in structure II tetrahydrofuran （THF） hydrate is investigated using kinetic hydrate inhibitor evaluation apparatus by step-cooling method and isothermal cooling method. With the combined gas hydrate inhibitor at the concentration of 1.0 wt%, the induction time of 19 wt% THF solution could be prolonged to 8.5 h at a high subcooling of 6℃. Finally, the mechanism of HGs inhibiting the formation of gas hydrate is proposed.

Mesoporous poly(ionic liquid)s with dual active sites for highly efficient CO_(2)conversion

Atmospheric CO_(2)concentrations are soaring due to the continued use of fossil fuels in energy production,an anthropogenic activity that is playing a leading role in global warming.Thus,research aimed at the capture and conversion of CO_(2)into value-added products,such as cyclic carbonates,is booming.While CO_(2)is an abundant,cheap,non-toxic,and readily accessible Cl feedstock,its thermodynamic stability necessitates the development of highly efficient catalysts that are able to promote chemical reactions under mild conditions.In this work,a novel mesoporous poly(ionic liquid)with dual active sites was synthesized through a facile method that involves co-polymerization,post-synthetic metalation,and supercritical CO_(2)drying.Due to a high density of nucleophilic and electrophilic sites,the as-prepared poly(ionic liquid),denoted as P2D-4BrBQA-Zn,offers excellent performance in a CO_(2)cycloaddition reaction using epichlorohydrin as the substrate(98.9%conversion and 96.9%selectivity).Moreover the reaction is carried out under mild,solvent-free,and additive-free conditions.Notably,P2D-4BrBQA-Zn also efficiently promotes the conversion of various other epoxide substrates into cyclic carbonates.Overall,the catalyst is found to have excellent substrate compatibility,stability,and recyclability.

CONDUCTING BLENDS OF POLY (2-VINYL PYRIDINE) AND POLYETHYLENE OXIDE WITH HIGH MOLECULAR WEIGHT

Ionic, electronic and mixed (ionic-electronic) conductivities of blends of poly(2-vinyl pyridine) (P2VP) and poly(ethylene oxide) (PEO) with high molecular weight after doped with LiClO4, TCNQ or LiClO4 and TCNQ were investigated. Effects of LiClO4 and TCNQ concentrations on the conductivity of PEO/P2VP/LiClO4 or TCNQ blend were studied. The ionic conductivity of PEO/P2VP/LiClO4 blend increases with increasing PEO content. At a Li/ethylene bride molar ratio of 0.10 and a TCNQ/2-vinyl pyridine molar ratio of 0.5, the mixed conductivity of PEO/P2VP/LiClO4/TCNQ is higher than the total of ionic conductivity of PEO/P2VP/LiClO4 and electronic conductivity of PEO/P2VP/TCNQ when the weight ratio of PEO and P2VP is 6/4 or 5/5. Scanning electron microscopy (SEM) on the broken cross-section of the PEO/P2VP/LiClO4 blend and differential scanning calorimetry (DSC) results show that LiClO4 could act as a compatibilizer in the blend.

Dye-sensitized TiO2 Solid Solar Cell Using Poly (4-vinylphenyloxy-methyltriphenylamine) as Hole Transport Material

A dye-sensitized TiO2 solid solar cell, which contains poly(4-vinylphenyloxy-methyltriphenylamine) in hole transport layer (HTL) doped with LiSCN and methyl-hexyl-imidazolium iodide (MHIml), was prepared. The solar cell shows that the conversion efficiency is 0.59%, Jsc is 3.03mA/cm2, and V^ is 0.53V at 1 sun light intensity.

Novel sandwich structured glass fiber Cloth/Poly(ethylene oxide)-MXene composite electrolyte

Recently,poly(ethylene oxide)(PEO)-based solid polymer electrolytes have been attracting great attention,and efforts are currently underway to develop PEO-based composite electrolytes for next generation high performance all-solid-state lithium metal batteries.In this article,a novel sandwich structured solid-state PEO composite electrolyte is developed for high performance all-solid-state lithium metal batteries.The PEO-based composite electrolyte is fabricated by hot-pressing PEO,LiTFSI and Ti_(3)C_(2)T_(x) MXene nanosheets into glass fiber cloth(GFC).The as-prepared GFC@PEO-MXene electrolyte shows high mechanical properties,good electrochemical stability,and high lithium-ion migration number,which indicates an obvious synergistic effect from the microscale GFC and the nanoscale MXene.Such as,the GFC@PEO-1 wt%MXene electrolyte shows a high tensile strength of 43.43 MPa and an impressive Young's modulus of 496 MPa,which are increased by 1205%and 6048%over those of PEO.Meanwhile,the ionic conductivity of GFC@PEO-1 wt%MXene at 60℃ reaches 5.01×10^(-2) S m^(-1),which is increased by around 200%compared with that of GFC@PEO electrolyte.In addition,the Li/Li symmetric battery based on GFC@PEO-1 wt%MXene electrolyte shows an excellent cycling stability over 800 h(0.3 mA cm^(-2),0.3 mAh cm^(-2)),which is obviously longer than that based on PEO and GFC@PEO electrolytes due to the better compatibility of GFC@PEO-1 wt%MXene electrolyte with Li anode.Furthermore,the solid-state Li/LiFePO_(4) battery with GFC@PEO-1 wt%MXene as electrolyte demonstrates a high capacity of 110.2–166.1 mAh g^(-1) in a wide temperature range of 25–60C,and an excellent capacity retention rate.The developed sandwich structured GFC@PEO-1 wt%MXene electrolyte with the excellent overall performance is promising for next generation high performance all-solid-state lithium metal batteries.

CARBONYLATION OF ALLYL HALIDES CATALYZED BY POLY(N-VINYL-2-PYRROLIDONE) ANCHORED PALLADIUM CATALYST UNDER ATMOSPHERIC PRESSURE

Carbonylation of allyl halides catalyzed by poly(N-vinyl-2-pyrro- lidone) anchored palladium catalyst affords β,r-butonic acid under atmo- spheric pressure and at room temperature.The activity and efficiency of the catalyst are much higher than those of the reported catalysts for this reaction.

Preparation of Zn²⁺-Chelated Carboxymethyl Poly(1-Vinylimidazole) for Intracellular Zn²⁺Delivery

Zinc ions (Zn2+), known to be a novel intracellular second messenger related to various biological functions, have been delivered inside cells. For the intracellular Zn2+ delivery, Zn2+ has been chelated to carboxymethyl poly(1-vinylimidazole) (CM-PVIm) by mixing zinc chloride (ZnCl2) or zinc acetate (Zn(OAc)2) with CM-PVIm. The resulting Zn2+-chelated CM-PVIm, that is, Zn2+/CM-PVIm complex by mixing ZnCl2 exhibited smaller particle size below 10 nm and possessed larger amount of Zn2+ ions, as compared to the Zn2+/CM-PVIm by mixing Zn(OAc)2. The both Zn2+/CM-PVIm complexes exhibited no significant cytotoxicity, leading to intracellular Zn2+ delivery. The Zn2+/CM-PVIm by mixing ZnCl2 delivered larger amount of intracellular Zn2+ ions than that by mixing Zn(OAc)2. These results suggest that the optimal Zn2+/CM-PVIm complex is a useful tool for intracellular Zn2+ delivery to control various biological functions.

面向凝聚态核磁共振的新型NaKV_(4)O_(9)·2H_(2)O材料与多铁性材料的物性研究

近年来凝聚态物理领域中,学者逐渐利用更加先进的技术,如核磁共振技术对不同材料进行更加详细的研究。因此研究利用凝聚态核磁共振技术对新型NaKV_(4)O_(9)·2H_(2)O材料与多铁性材料CuBr_(2)的物理性质进行测量与分析。结果表明,NaKV_(4)O_(9)·2H_(2)O曲线的峰部位置随着温度的不断增长,且在温度到120K附近的时候偏移量达到最大。CuBr_(2)的相变温度从72K升高到117.5K。综上所述,通过凝聚态核磁共振技术能更准确地察觉不同材料的物性变化规律。

Poly I:C刺激对杜洛克×二花脸F2猪血液参数的影响

为研究聚肌胞苷酸(polyinosinic:polycytidylic acid,简称Poly I:C)刺激对杜洛克×二花脸F2猪群血液参数的影响,选用杜洛克×二花脸F2猪393头,在33d时前腔静脉采血(对照组),在35d时用Poly(I:C)刺激,4h后采血(处理组),对刺激前后血液参数进行相关性和主成分等分析。研究结果表明,处理组与对照组相比,白细胞中的嗜中性粒细胞百分比(NE%)、淋巴细胞数(LY)和淋巴细胞百分比(LY%)这3项血液参数差异显著相关,红细胞中的红细胞压积(HCT%)和红细胞数(RBC)差异相关性显著,而血小板第一主成分中决定性指标血小板数(PLT)和血小板压积(PCT)在刺激前后不存在显著差异。

Anticorrosion Coatings from Poly(Aniline-co-2-Ethylaniline) Micro/Nanostructures

PANI copolymer micro/nanostructures with different surface wettability were obtained from the chemical oxidation copolymerization of aniline(Ani)with 2-ethyl aniline(EA)at diverse[EA]/[Ani+EA]molar ratios,by employing ammonium persulfate as an oxidant.The results revealed that the poly(aniline-co-2-ethyl aniline)(PANI-EA)copolymer micro/nanostructures exhibited satisfactory anticorrosion performance for carbon steel,and the corrosion protection efficiency increased with the increase of water repellent property.Poly(2-ethyl aniline)(PEA)showed the largest contact angle(CA=145°)and show the best corrosion protection for the carbon steel(h=87.29%).It is found that the superior anticorrosion property of PEA is attributed to its high hydrophobicity,low conductivity and low porosity.

Synthesis of Comblike Poly(methyl methacrylate) by Atom Transfer Radical Polymerization with Poly(ethyl 2-bromoacrylate) as Macroinitiator

Comblike poly(methyl methacrylate) was synthesized by atom transfer radical polymerization of methyl methacrylate with poly(ethyl 2-bromoacrylate) as a macroinitiator, which was prepared by conventional free radical polymerization of ethyl 2-bromoacrylate. The obtained comblike polymers were characterized by GPC and 1H NMR.

Preparation and phase change performance of Na_2HPO_4·12H_2O@poly(lactic acid) capsules for thermal energy storage

Micro-encapsulated phase-change materials(micro PCMs) with Na_2 HPO_4·12 H_2 O encapsulated in poly(lactic acid)(PLA) shell were prepared by a solvent evaporation–precipitation method that involves the use of a coaxial needle. The effects of PLA concentration, stirring speed, injection rate of core and shell solutions, and polyvinyl alcohol(PVA) concentration on phase change properties were investigated. The thermal properties of microP CMs were characterized by differential scanning calorimetry(DSC). The capsules prepared under the optimal conditions are about 2 mm in diameter and show a latent heat of up to 122.2 J·g^(-1).

SYNTHESIS AND CHARACTERIZATION OF POLY{4-[2-(tert-BUTYLDIMETHYLSILOXY)ETHYL]STYRENE}AND ITS HYDROLYSIS DERIVATIVE

The living cationic polymerization of 4-[2-(tert-butyldimethylsiloxy)ethyl]styrene (TBDMES) was studied in methylcyclohexane (MeChx)/methylchloride (MeCl) (50/50 V/V) solvent mixture at -80 degrees C. The initiator 1,1-diphenylethylene (DPE) capped 2-chloro-2,4,4-trimethylpentane (TMPCl) was formed in situ in conjunction with titanium tetrachloride (TiCl(4)). The Lewis acidity of TiCl(4) was decreased by the addition of titanium(IV) isopropoxide (Ti(OiPr)(4)) to accomplish living polymerization of TBDMES. Hydrolysis of poly(TBDMES) in the presence of tetra-butylammonium fluoride yielded poly[4-(2-hydroxyethyl)styrene] (poly(HOES)). FT-IR, NMR and DSC demonstrated the hydrolysis was complete.

Polymer-Decorated 2D MoS2 Synaptic Transistors for Biological Bipolar Metaplasticities Emulation

Biological bipolar metaplasticities were successfully mimicked in two-dimensional(2D)MoS2 transistors via the implementation of two different MoS2 surface decorations,poly(vinyl alcohol)(PVA)and chitosan bio-polymers.Interestingly,the depressing metaplasticity was successfully mimicked when the PVA bio-polymer was used as the surface decoration layer,whereas the metaplasticity of long-term potentiation was realized when the chitosan bio-polymer was taken as the surface decoration layer.Furthermore,the electronic band structures of the 2D MoS2 devices with different surface decorations were further investigated using first-principles calculations for understanding the underlying mechanisms of such bipolar metaplasticities.These results will deepen our understanding of metaplasticity,and have great potential in neuromorphic computing applications.

MICROPOROUS PVDF-HFP-BASED POLYMER MEMBRANES FORMED FROM SUPERCRITICAL CO_2 INDUCED PHASE SEPARATION

Microporous poly(vinylidene fluoride-co-hexafluoropropylene)(PVDF-HFP)membranes following supercritical CO_2 induced phase separation process were prepared using four solvents.The solid electrolytes of PVDF-HFP were formed by microporous PVDF-HFP membranes filled and swollen by a liquid electrolyte.The effect of the solvents on the morphology and structure,electrolyte absorptions and lithium ionic conductivity of the activated membranes were investigated.It was approved that all the membrane had the similar...

Effect of Hyperbranched Poly(amine-ester) Grafted Nano-SiO_2 on Reinforcement and Toughness of PVC

Nano-SiO2 was modified using silane coupling agent （KH-550） and hyperbranched poly（amine-ester） respectively, and Poly（vinyl chloride） （PVC）/modified nano-SiO2 composites were made by melt-blending. The composites＇ structures andmechanical properties were characterized by transmission electron microscopy（TEM）, sanning electronic microscopy（SEM） and electronic universal testing machine. The results. show that nano-SiO2 grafted by hyperbranched poly （amine-ester） increases obviously in dispersion in PVC matrix, and mechanical properties of PVC are effectively improved. Moreover, it was found that mechanical properties of PVC/nano-SiO2 composites reach the best when weight percent of nano-SiO2 in PVC matrix is 1%. Compared with crude PVC, the tensile strength of hyperbranched poly （amine-ester） grafted nano-SiO2/ PVC composite increases by 24.68 % and its break elongation, flexural strength and impact strength increase by 15.73%, 4.07% and 1 841.84%, respectively. Moreover, the processing of the composites is improved.

Nucleobase-crosslinked poly(2-oxazoline) nanoparticles as paclitaxel carriers with enhanced stability and ultra-high drug loading capacity for breast cancer therapy

Poly(2-oxazoline)(POx)has been regarded as a potential candidate for drug delivery carrier to meet the challenges of nanomedicine clinical translation,due to its excellent biocompatibility and self-assembly properties.The drug loading capacity and stability of amphiphilic POxs as drug nanocarriers,however,tend to be insufficient.Herein,we report a strategy to prepare nucleobase-crosslinked POx nanoparticles(NPs)with enhanced stability and ultra-high paclitaxel(PTX)loading capacity for breast cancer therapy.An amphiphilic amine-functionalized POx(PMBEOx-NH_(2))was firstly prepared through a click reaction between cysteamines and vinyl groups in poly(2-methyl-2-oxazoline)-block-poly(2–butyl–2-oxazoline-co-2-butenyl-2-oxazoline)(PMBEOx).Complementary nucleobase-pairs adenine(A)and uracil(U)were subsequently conjugated to PMBEOx-NH2 to give functional POxs(POxA and POxU),respectively.Due to the nucleobase interactions formed between A and U,NPs formed by POxA and POxU at a molar ratio of 1:1 displayed ultrahigh PTX loading capacity(38.2%,PTX/POxA@U),excellent stability,and reduced particle size compared to the uncross-linked PTX-loaded NPs(PTX/PMBEOx).Besides the prolonged blood circulation and enhanced tumor accumulation,the smaller PTX/POxA@U NPs also have better tumor penetration ability compared with PTX/PMBEOx,thus leading to a higher tumor suppression rate in two murine breast cancer models(E0711 and 4T1).These results proved that the therapeutic effect of chemotherapeutic drugs could be improved remarkably through a reasonable optimization of nanocarriers.