Ultrasonic-assisted Synthesis of Fe Nanoparticles in the Presence of Poly（N-vinyl-2-pyrrolidone）

Zero-valent iron particles were prepared by wet reduction chemistry assisted with ultrasonic treatment. Such prepared particles have uniform size, exhibit crystalline structure and show strong pararnagnetic property. Their surface modification by coating poly（N-vinyl-2-pyrrolidone） （PVP） was investigated. The resulting Fe（0）-PVP particles were monodispersed and possessed enhancing magnetization saturation. Those synthesis conditions to control the particle size and distribution were exploited.

NOVEL AMPHIPHILIC FLUORESCENT GRAFT COPOLYMER: SYNTHESIS, CHARACTERIZATION AND ENCAPSULATION OF A HYDROPHOBIC AGENT

Novel amphiphilic fluorescent graft copolymer （PVP-PyAHy） was successfully synthesized by the free radical copolymerization of hydrophobic monomer N-（1-pyrenebutyryl）-N＇-acryloyl hydrazide （PyAHy） with hydrophilic precursor polymers of vinyl-functionalized poly（N-vinylpyrrolidone） （PVP） in DMF. The copolymer is amphiphilic and has intrinsic fluorescence. FT-IR, ^1H-NMR, TEM, gel permeation chromatography-multi-angle laser light scattering, UV-Vis spectroscopy and fluorescence spectroscopy were used to characterize this copolymer. The TEM observation shows that the copolymer PVP-PyAHy forms micelles in aqueous solution. Results of fluorometric measurements illustrate that the critical micelle concentration （CMC） value of PVP-PyAHy in aqueous solution is about 0.90 mg/mL. To examine the encapsulation ability of the copolymer in aqueous media, methyl yellow was employed as a model hydrophobic agent. The loading level of the polymer to methyl yellow is 8.8 mg/g. The cytotoxicity assays for Madin Darby Canine Kidney （MDCK） cells shows good biocompatibility of PVP-PyAHy in vitro. These results suggest the potential of this copolymer PVP-PyAHy as drugs delivery carrier and fluorescent tracer.

Y-shaped block copolymers of poly(ethylene glycol) and poly(N-isopropylacrylamide) synthesized by ATRP

Novel Y-shaped block copolymers of poly（ethylene glycol） and poly（N-isopropylacrylamide）, PEG-b-（PNIPAM）2, were successfully synthesized through atom transfer radical polymerization （ATRP）. A difunctional macroinitiator was prepared by esterification of 2,2-dichloroacetyl chloride with poly（ethylene glycol） monomethyl ether （PEG）. The copolymers were obtained via the ATRP ofN-isopropylacrylamide （NIPAM） at 30℃ with CuCl/Me6TREN as a catalyst system and DMF/H2O （v/v = 3：1） mixture as solvent. The resulting copolymers were characterized by gel permeation chromatography （GPC） and ^1H NMR. These block copolymers show controllable molecular weights and narrow molecular weight distributions （PDI 〈 1.15）. Their phase transition temperatures and the corresponding enthalpy changes in aqueous solution were measured by differential scanning calorimetry （DSC）. As a result, the phase transition temperature of PEG45-b-（PNIPAM55）2 is higher than that of PNIPAM, however, the corresponding enthalpy change is much lower, indicating the significant influence of the macromolecular composition and architecture on the phase transition.

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.

Reversible Aggregation Kinetics of Poly(N-isopropylacrylamide-co-N-vinylpyrrolidone) in Aqueous Solutions Revealed by Elastic Light Scattering Spectroscopy

Poly（N-isopropylacrylamide-co-N-vinylpyrrolidone） [P（NIPAM-co-NVP）] copolymers with different content of N-vinylpyrrolidone （NVP） were synthesized, and reversible aggregation kinetics of the copolymers in aqueous solutions was investigated with elastic light scattering （ELS） spectra. The results indicated that the apparent activation energy of aggregation process during heating and dissociation process during cooling increased with the NVP content increasing. The phase transition temperature also increased as the content of NVP increased, suggesting that the hydrophilic nature of NVP strongly affected the phase behavior of the copolymer solutions. The higher the content of NVP, the higher the temperature required to break the balance between the hydrophilic and hydrophobie interaction. Besides, during heating and cooling process, the phase transition hysteresis of P（NIPAM-co-NVP） chains decreased when the hydrophilic comonomer increased.

Synthesis of Poly(N-vinylpyrrolidone) Nanofibers Containing Gold Nanoparticles via Electrospinning Technique

Poly（N-vinylpyrrolidone）（PVP）nanofibers containing gold nanoparticles were prepared by electrospinning method.This simple route was used to prepare composites on a large scale,and the syntheses are simple.The optical property of gold nanoparticles in PVP aqueous solution was investigated by UV-Visible absorption spectra.The morphology of the fibers and the distribution of particles were characterized by transmission electron microscopy.The structure of the composite was characterized by Fourier transform infrared spectroscopy.

Nano-hydroxyapatite formation via co-precipitation with chitosan-g-poly（N-isopropylacrylamide） in coil and globule states for tissue engineering application

With the excellent biocompatibility and osteo- conductivity, nano-hydroxyapatite （nHA） has shown significant prospect in the biomedical applications. Con- trolling the size, crystallinity and surface properties of nHA crystals is a critical challenge in the design of HA based biomaterials. With the graft copolymer of chitosan and poly（N-isopropylacrylamide） in coil and globule states as a template respectively, a novel composite from chitosan-g-poly（N-isopropylacrylamide） and nano-hydro- xyapatite （CS-g-PNIPAM/nHA） was prepared via co- precipitation. Zeta potential analysis, thermogravimetric analysis and X-ray diffraction were used to identify the formation mechanism of the CS-g-PNIPAM/nHA compo- site and its morphology was observed by transmission electron microscopy. The results suggested that the physical aggregation states of the template polymer could induce or control the size, crystallinity and morphology of HA crystals in the CS-g-PNIPAM/nHA composite. The CS-g-PNIPAM/nHA composite was then introduced to chitosan-gelatin （CS-Gel） polyelectronic complex and the cytocompatibility of the resulting CS- Gel/composite hybrid film was evaluated. This hybrid film was proved to be favorable for the proliferation of MC 3T3-E1 cells. Therefore, the CS-g-PNIPAM/nHA compo- site is a potential biomaterial in bone tissue engineering.

Synthesis and Drug Release Properties of Thermosensitive Poly(N-vinylacetamide-co-vinylacetate) Hydrogels

Thermosensitive poly[N-vinylacetamide-co-vinylacetate][P（NVA-co-VAc）] hydrogels were prepared via free radical copolymerization from hydrophilic NVA and hydrophobic VAc in the presence of butylenes-bis （N-vinylacetamide）（Bis-NVA） as crosslinker. Scanning electron microscopy（SEM） images reveal that the as-prepared hydrogels were of three-dimensional network with irregular cave structure. The prepared hydrogels with more NVA in the feed swelled faster and the swelling ratio of the hydrogels gradually decreased with temperature increasing from 10 °C to 60 °C. The dynamic swelling studies indicate that the swelling process of the hydrogels was controlled by diffusion of water molecules considered as Fickian-controlled case. The adsorption amount of model drug, sodium salicylate（SS） was higher in the hydrogels containing more NVA units, whose corresponding release could reach equilibrium in about 6 h.

Preparation of poly（N-isopropylacrylamide） brush grafted silica particles via surface-initiated atom transfer radical polymerization used for aqueous chromatography

Thermoresponsive poly（N-isopropylacrylamide） （PNIPAAm） brushes were densely grafted onto silica surface via surface-initiated atom transfer radical polymeriza- tion （SI-ATRP）. The grafting reaction started from the surfaces of 2-bromoisobutyrate- functionalized silica particles in 2-propanol aqueous solution at ambient temperature using CuCIICuCI21N, N,N＇,N＇,N”.pentamethyldiethylenetriamine （PMDETA） as the catalytic system. Based on thermogravimetric analysis （TGA） results, the grafting amount and grafting density of PNIPAM chains on the surface of silica were calculated to be 1.29 mg/ m^2 and 0.0215 chains/nm^2, respectively. The gel permeation chromatography （GPC） result showed the relatively narrow molecular weight distribution （MwlMn= 1.21） of the grafted PNIPAAm. The modified silica particles were applied as high-performance liquid chromatography （HPLC） packing materials to successfully separate three aromatic compounds using water as mobile phase by changing column temperature. Temperature- dependent hydrophilic/hydrophobic property alteration of PNIPAAm brushes grafted on silica particles was determined with chromatographic interaction between stationary phase and analytes. Retention time was prolonged and resolution was improved with increasing temperature. Baseline separation with high resolution at relatively low temperatures was observed, demonstrating dense PNIPAAm brushes were grafted on silica surfaces.

Microwave-assisted Preparation of Temperature Sensitive Poly(N-isopropylacrylamide) Hydrogel with Improved Responsive Properties

Poly（N-isopropylacrylamide）-based hydrogel was prepared under microwave irradiation The hydrogel thus prepared, comparing with that prepared by thermal heating method, exhibits faster swelling and shrinking kinetics. The improved responsive properties are due to the more heterogeneous and porous networks formed under microwave irradiation.

Poly(N-isopropylacrylamide)-based Vertically Sandwich-typed Hydrogel with Fast Temperature-response Speed and Its Controlled-release Characteristics

A novel poly（N-isopropylacrylamide）-based sandwich-typed hydrogel, which was featured with both ends of linear poly（N-isopropylaerylamide） （PNIPAM） chains being grafted onto cross-linked PNIPAM chains, was successfully prepared in a three-step process by a method of sequential synthesis. The proposed hydrogel displays faster and hydration/dehydration dynamic response to temperature cycling owing to linear PNIPAM chains to form big-pore structure. This work may lead to high attraction for targeting drug delivery systems, polymeric pump, sensors and so on.

Temperature-pH Sensitive IPN Hydrogels Composed of Silk Sericin and Poly(N-isopropylacrylamide)

Interpenetrating polymer network （IPN） composed of silk sericin （SS） and poly（N-isopropylacrylamide） （PNIPAAm） was prepared. The morphology of the IPNs, in which the SS phase was stained with ammonium cuprate, was examined with TEM and a relative homogeneous distribution of the two polymers was exhibited. The swelling behavior of the IPN hydrogels showed both temperature and pH dependences.

THERMAL-SENSITIVE BETA-CYCLODEXTRIN-CONTAINING POLY(NISOPROPYLACRYLAMIDE)HYDROGELS CROSSLINKED BY Si—O—Si BONDS—SYNTHESIS,CHARACTERIZATION AND PROLONGING IN VITRO RELEASE OF 5-FLUOROURACIL

A series of novel p（N-isopropylacrylamide） （PNIPAM） hydrogels were synthesized by radical copolymerization of N-isopropylacrylamide （NIPAM） and 3-methacryloxypropyltrimethoxysilane （MPTMS）. The copolymers were then crosslinked through hydrolysis of the siloxane in acetic acid/water mixed solvent. Beta-cyclodextrin （Beta-CD） was introduced into the polymeric networks by condensation of 3-glycidoxypropyltrimethoxysilane derived beta-cyclodextrin （KH560-beta-CD） with MPTMS under acidic condition. These gels were heterogeneous, porous and exhibited fast deswelling kinetics when the temperature was elevated to above lower critical solution temperature （LCST）. The swelling ratios of the gels containing beta-CD at room temperature were higher than that of the normal PNIPAM hydrogel, which was caused by the lower crosslinking density in beta-CD contained gels. In comparison to that of the normal PNIPAM gel, the amount of loaded-drug in the hydrogel containing beta-CD was higher, and the release time of 5-fluorouracil （5-Fu） was prolonged, which was attributed to the formation of inclusion compounds between 5-Fu and beta-CD in gel network.

Study of Phase Separation of Poly（N-isopropylacrylamide-co-styrene） Aqueous Solutions with Rayleigh Scattering Technique

A thermally sensitive copolymer, poly（N-isopropylacrylamide-co-styrene） [P（NIPAM-co-St）] （Mn=9.5× 10^5 g/mol and Mw/Mn= 1.51） was synthesized by soap-free emulsion polymerization. The phase separation of the copolymer in water was investigated by Rayleigh scattering （RS） technique. The RS spectra revealed the transition of molecular conformation and the aggregation of molecular chains in the course of phase separation. The coil-to-globule and globule-to-coil transitions of P（NIPAM-co-St） chains were found in one heating-and-cooling cycle. By means of Avrami formula, apparent activation energy of phase separation of P（NIPAM-co-St） aqueous solutions was estimated. Moreover, a model was proposed to describe the phase separation process.

Laterally Sandwich-typed Hydrogel Columns with Liner Poly(N-isopropylacrylamide) Layer:Preparation, Swelling/deswelling Kinetics and Drug Delivery Characteristics

A novel thermo-responsive hydrogel column, featured with both ends of linear poly（N- isopropylacrylarnide） （PNIPAM） chains being grafted onto cross-linked PNIPAM chains, was reported. The laterally sandwich-typed hydrogel columns were fabricated by radical polymerization in a three-step process using a method of ice-melting synthesis. The initiating path, morphology and thermoresponsive characteristics of the prepared hydrogel columns were experimentally studied. The results show that the hydrogel column obtained by the initiator inside part has more quick swelling and deswelling rates responsing to temperature cycling than other hydrogels owing to linear PNIPAM chains to form supermacroporous structure. The proposed hydrogel structure provide a new mode of the phase transition behavior for thermo-sensitive ＂smart＂ or ＂intelligent＂ monodisperse micro-actuators, which is highly attractive for targeting drug delivery systems, chemical separations, and sensors and so on.

Photorefractive Effect in an Azobenzene Chromophore Side Groups Polymer

We have analyzed the photorefractive（PR） effect of a polymer composite was reported which combines a novel bi-functional poly（N-vinyl）-3-[p-nitrophenylazo]carbazolyl（PVNPAK） and 2,4,7-trinitro-9-fluorenone（TNF）. PVNPAK was synthesized by a post-azo-coupling reaction, with an azo derivative as the electrooptic chromophore and carbazolyl as photoconductive moiety. The asymmetric two-beam coupling gain of 13.9 cm-1 and diffraction efficiency of 1.2% for poled polymer film fabricated using a corona poling are obtained at the wavelength of 647.1 nm, confirming photorefractivity. We interpreted this result as the orientational enhancement, in which the spatial charge field may enhance the modulated orientation of the azobenzen chromophore. It is unexpected that the photorefractive gain of 9.5 cm-1 for the unpoled polymer film also was observed without external field in two-beam coupling（TBC） experiment. This phenomenon is attributed to a light-induced orientational grating when the azobenzene groups are illuminated by polarized light.

N⁃苯基马来酰亚胺共聚物的合成及对PVC树脂耐热改性效果研究

通过种子乳液聚合结合半连续加料方式,成功聚合出分子结构一致且与聚氯乙烯(PVC)树脂具有良好相容性的聚(N‐苯基马来酰亚胺‐苯乙烯‐丙烯腈)(PNSA)共聚物胶乳,将其与PVC树脂直接复合制备PNSA/PVC复合材料,并对PNAS耐热改性的效果进行评价。结果表明,PNSA纳米胶乳颗粒粒径在155.3~251.5 nm之间,粒径分布均一;PNSA共聚物分子组成呈无规结构,分子结构一致,差示扫描量热曲线呈现单一的玻璃化转变温度(T_(g)),且与PVC树脂具有极佳的相容性;PNSA含量由0升高至50%(质量比,下同)时,复合材料的T_(g)由84.8℃提高到107.2℃,提高了22.4℃,维卡软化温度由71.2℃提高到91.9℃,提高了20.7℃;除耐热性改善以外,复合材料的力学性能也有一定程度的提高,本文的研究有利于PVC应用领域的进一步拓展。

Synthesis of Poly (3-acetylpyrrolyl methine) with Azobenzene Side Groups and Study on Its Third-order Nonlinear Optical Property

A novel soluble π-conjugated polymer, poly [（3-acetylpyrrole-2, 5-diyl） p-（N, N-dimethylamino） azobenzylidene] （PAPDMAABE）, was synthesized by condensation of 3-acetylpyrrole with 4-aldehyde-4＇-dimethylaminoazobenzene （ADMAA）. The chemical structure of PAPDMAABE was characterized by Fourier transform infrared spectroscopy （FTIR）, ^1H-NMR, and UV-Vis-NIR spectra. Transmission electron microscope （TEM） analysis for PAPDMAABE indicates that part of PAPDMAABE is in crystal state, due to the short-range order of the polymer. Thermogravimetric analysis （TGA） curve shows that the polymer has good thermal stability and its decomposition temperature is 248℃. The optical band gap of PAPDMAABE obtained from the optical absorption spectrum is about 1.73 eV. The resonant third-order nonlinear optical property of PAPDMAABE at 532 nm was studied using degenerate four-wave mixing （DFWM） technique. The resonant third-order nonlinear optical susceptibility of the polymer is about 7.48×10^-8 esu.

Fast electron transfer and enhanced visible light photocatalytic activity by using poly-o-phenylenediamine modified AgCl/g-C_3N_4 nanosheets

Exfoliation of bulk graphitic carbon nitride(g‐C3N4)into two‐dimensional(2D)nanosheets is one of the effective strategies to improve its photocatalytic properties so that the 2D g‐C3N4 nanosheets(CN)have larger specific surface areas and more reaction sites.In addition,poly‐o‐phenylenediamine(PoPD)can improve the electrical conductivity and photocatalytic activity of semiconductor materials.Here,the novel efficient composite PoPD/AgCl/g‐C3N4 nanosheets was first synthesized by a precipitation reaction and the photoinitiated polymerization approach.The obtained photocatalysts have larger specific surface areas and could achieve better visible‐light response.However,silver chloride(AgCl)is susceptible to agglomeration and photocorrosion.The PoPD/AgCl/CN composite exhibits an extremely high photocurrent density,which is three times that of CN.Obviously enhanced photocatalytic activities of PoPD/AgCl/g‐C3N4 are revealed through the photodegradation of tetracycline.The stability of PoPD/AgCl/CN is demonstrated based on four cycles of experiments that reveal that the degradation rate only decreases slightly.Furthermore,.O2^-and h+are the main active species,which are confirmed through a trapping experiment and ESR spin‐trap technique.Therefore,the prepared PoPD/AgCl/CN can be considered as a stable photocatalyst,in which PoPD is added as a charge carrier and acts a photosensitive protective layer on the surface of the AgCl particles.This provides a new technology for preparing highly stable composite photocatalysts that can effectively deal with environmental issues.

Conformational Transition of Poly （Acrylic Acid） Detected by Microcantilever Sensing

Poly （acrylic acid） （PAA） chains are grafted on one side of a microcantilever by the self-assembled method and the deflections of the microcantilever are detected as a function of medium pH from 3 to 11. It is found that when the pH varies, the microcantilever deflects because of the changing surface stress. By analysing the electrostatic repulsive effect, the surface stress change is related to the conformation transition of PAA from a collapse state to a swelling state. This method offers the interaction information among the polymer chains during the conformational transition and affords an alternative way to study conformational change of polymers.