A Novel Initiator Containing Alkyne Group for the Polymerization of 2-Ethyl-2-oxazoline

A novel trifunctional initiator with one alkyne and two trifluoromethanesulfonate moieties was synthesized from a protected alcohol 5-hydroxyl-2-phenyl-1, 3-dioxane. The alkyne func- tionalized intermediate with two protected alcohol groups was synthesized by reacting with propargyl bromide. The alcohol groups were cleaved using a mixture of tetrahydrofuran and hydrochloric acid aqueous solution. In the last step the initiator was synthesized us- ing triflic anhydride in carbon tetrachloride. The initiator was characterized by 1H NMR and used for the polymerization of 2-ethyl-2-oxazoline which gives polymers with narrow distribution. For comparison a similar initiator with two tosylates was prepared and used for the polymerization of the monomer 2-ethyl-2-oxazoline, the resulting product has a wide molecular weight distribution and most of the initiator remains unreacted after 24 h which may be due to the steric hindrance between the two tosylate groups. To further explore the steric hindrance phenomenon, a linear tosylate initiator was synthesized, but still some of the initiator remains unreacted, illustrating that both steric hindrance and electrophilic balance affect the efficiency of the cationic ring-opening polymerization. All of the polymers were characterized in detail by using IH NMR, matrix-assisted laser desorption/ionization time-of-flight mass spectroscopy, and size exclusion chromatography to confirm the purity and distribution of the polymers.

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.

Delivery of docetaxel using pH-sensitive liposomes based on D-α-tocopheryl poly(2-ethyl-2-oxazoline) succinate:Comparison with PEGylated liposomes

This study aimed to investigate the ability of the novel materials D-α-tocopheryl poly(2-ethyl-2-oxazoline) succinate(TPOS) to construct pH-sensitive liposomes. TPOS was initially synthesized and characterized by TLC, FTIR, and ~1H-NMR. The buffering capacity of polyethylene glycol-distearoyl phosphatidylethanolamine(PEG-DSPE) and TPOS was determined by acid-base titration, and TPOS displayed a slower downtrend and gentler slope of titration curve than PEG-DSPE within pH 7.4–5.0. Studies on the in vitro drug release demonstrated that TPOS modified docetaxel(DOC) liposomes(TPOS-DOC-L) had a slower drugrelease rate at pH 7.4 similar to PEGylated-DOC liposomes(PEG-DOC-L), whereas the release rate reached approximately 86.92% ± 1.69% at pH 6.4. In vitro cellular uptake assays by microplate reader, and flow cytometry revealed that TPOS modified coumarin 6 liposomes(TPOS-C6-L) had stronger cellular uptake at pH 6.4 than that at pH 7.4( P < 0.01). Conversely, for PEGylated C6 liposomes(PEG-C6-L) and conventional C6 liposomes(C6-L), very similar cellular uptakes were exhibited at different pH values. Confocal laser scanning microscopy images showed that PEG-C6-L and C6-L were mainly located in lysosomes. By contrast, TPOS-C6-L showed broader cytoplasmic release and distribution at 4 h. MTT assay showed that the cytotoxicity of TPOS-DOC-L was similar to that of PEG-DOC-L and conventional DOC liposomes(DOC-L) at the same DOC concentration and at pH 7.4, but was much lower than those at pH 6.4 after 48 h of incubation. The apoptosis of PEG-DOC-L and DOC-L had no remarkable improvement with decreased pH from 7.4 to 6.4. Meanwhile, TPOS-DOC-Lsignificantly induced the apoptosis of HeLa cells with decreased pH. Therefore, TPOS can be a biomaterial for the construction of a pH-sensitive drug delivery system.

MECHANISM-TRANSFORMATION SYNTHESIS AND CHARACTERIZATION OF POLY(STYRENE-b-2-ETHYL-2-OXAZOLINE) DIBLOCK COPOLYMER

By mechanism-transformation (anionic --> cationic) poly(styrene-6-2-ethyl-2-oxazoline) diblock copolymer, PS-b-PEOx, was synthesized in two steps. The first step is the polymerization of styrene block capped with ethylene oxide and its tosylation; the second step is the cationic ring-opening polymerization of 2-ethyl-2-oxazoline. The products were thoroughly characterized by various methods, such as H-1-NMR, IR, DMA, TEM and SAXS. The results show that the copolymer obtained possesses high molecular weight and narrow molecular weight distribution.

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。

Preparation and shape memory properties of TiO_2/PLCL biodegradable polymer nanocomposites

The preparation of TiO2/poly（L-lactide-co-ε-caprolactone）（PLCL） nanocomposites and their properties were reported.TiO2nanoparticles were surface modified by ring-opening polymerization of ε-caprolactone（ε-CL）.The resulting poly（ε-caprolactone）-grafted TiO2（g-TiO2） was characterized by Fourier transform infrared spectroscopy（FTIR）,thermogravimetric analysis（TGA） and transmission electron microscopy（TEM）.The g-TiO2can be uniformly dispersed in chloroform and the g-TiO2/PLCL nanocomposites were successfully fabricated through solvent-casting method.The effects of the content of g-TiO2nanoparticles on tensile properties and shape memory properties were investigated.A significant improvement in the tensile properties of the 5% g-TiO2/PLCL mass fraction nanocomposite is obtained：an increase of 113% in the tensile strength and an increase of 11% in the elongation at break over pure PLCL polymer.The g-TiO2/PLCL nanocomposites with a certain amount of g-TiO2content have better shape memory properties than pure PLCL polymer.The g-TiO2nanoparticles play an additional physical crosslinks which are contributed to improvement of the shape memory properties.

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.

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.

One-pot Synthesis of 2,5-Disubstituted Oxazoles Using Poly[styrene(iodosodiacetate)]

Disubstituted oxazoles were prepared conveniently by treatment of aromatic -methyl ketones and nitriles with poly[styrene(iodosodiacetate)] in one-pot process.

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.

Photochemical reactions of poly(3-butoxythiophene-2,5-diyl) with chloroform

Photochemical reactions of poly(3-butoxythiophene-2,5-diyl) with chloroform under irradiation with light were studied. The reactions were separately carried out under air, oxygen, and nitrogen. The obtained results showed that this reaction belongs to the pseudo-first-order reaction with a rate constant kobs of 1.4×10?5 s?1 at room temperature. The presence or absence of air, oxygen, and nitrogen did not have obvious effects on the reaction rate under irradiation with light.

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.

Low-Temperature Plasma Induced Grafting of 2-Methacryloyloxyethyl Phosphorylcholine onto Poly(tetrafluoroethylene) Films

Modification of poly(tetrafluoroethylene)(PTFE) films with 2-methacryloyloxyethyl phosphorylcholine(MPC) was performed by low-temperature plasma treatment and grafting polymerization.Surface properties of PTFE were characterized by attenuated total reflectance Fourier transform infrared(ATR-FTIR) spectra,X-ray photoelectron spectroscopy(XPS) ,and static contact angle.The results show that MPC has been grafted onto PTFE film surface successfully.Contact angle for the modified PTFE films in the water decreased from 108°to 58.25°,while surface energy increased from 17.52 mN/m to 45.47 mN/m.The effects of plasma treatment time,monomer concentration and grafting time on degree of grafting were determined.In the meanwhile,blood compatibility of the PTFE films was studied by checking thrombogenic time of blood plasma.

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.

Cu^（2＋）对三螺旋poly（A：2I）解旋的结构分析

通过圆二色谱（ＣＤ）和吸收光谱研究了Ｃｕ（２＋）对三螺旋ｐｏｌｙ（Ａ：２Ｉ）的解旋行为，并从结构的角度分析了其解旋机理。结果表明：Ｃｕ（２＋）通过与ｐｏｌｙ（Ａ：２Ｉ）中的碱基的结合，破坏了Ｈｏｏｇｓｔｅｅｎ碱基对和Ｗａｔｓｏｎ－Ｃｒｉｃｋ碱基对中的氢键，从而导致了三螺旋ｐｏｌｙ（Ａ：２Ｉ）不可复性的解旋。

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.