Preparation of Hollow Silica Microspheres via Poly（N-isopropylacrylamide）

Core-shell structured SiO2/poly（N-isopropylacrylamide） （SiO2/PNIPAM） microspheres were successfully fabricated through hydrolysis and condensation reaction of tertraethyl orthosilicate （TEOS） on the surface of PNIPAM template at 50 ~C. The PNIPAM template can be easily removed by water at room temperature so that SiO2 hollow microspheres were finally obtained. The transmission electron microscope and scanning electron microscope observations indicated that SiO2 hollow microspheres with an average diameter of 150 nm can be formed only if there are enough concentration of PNIPAM and TEOS, and the hy- drolysis time of TEOS. FTIR analysis showed that part of PNIPAM remained on the wall of SiO2 because of the strong interaction between PNIPAM and silica. This work provides a clean and efficient way to prepare hollow microspheres.

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.

Rheological behavior of ZnO suspension with thermosensitive poly(N-isopropylacrylamide) for colloidal processing of ceramics

Novel colloidal processing using thermosensitive poly（N-isopropylacrylamide） （PNIPAM） as a coagulating agent has beendeveloped to prepare complex-shaped ceramic components. In this work, the properties of PNIPAM aqueous solutions and therheological behavior of ZnO suspensions with PNIPAM were investigated. The results show that the PNIPAM solutions exhibitobvious thermosensitivity and its transition temperature is around 32℃. When the temperature is above 40℃ （Tc, the criticaltransition temperature of thermosensitive suspension）, the 50% ZnO （volume fraction） suspension with 8 mg/mL PNIPAM has asharp increase in viscosity and reaches up to 11.49 Pa·s at 50℃, displaying strong elasticity. The main reasons are the increase ofeffective volume fraction attributed to precipitation of PNIPAM segments and the flocculation between ZnO powder particles. Inaddition, the maximum solid loading （volume fraction） at 20 ℃ is higher than that at 40℃, which proves that the phase transition ofPNIPAM can induce the flocculation of suspension.

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.

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.

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.

POLY(N-ISOPROPYL ACRYLAMIDE) MICROGEL DOPED WITH LUMINESCENT PBS QUANTUM DOTS

Thiol-stabilized PbS quantum dots （QDs） with dimensions 3-5 nm capped with a mixture of 1-thioglycerol/dithioglycerol （TGL/DTG） were coUoidally prepared at room temperature. Room temperature photoluminescence quantum efficiency of freshly prepared PbS QDs （7%-11%） remained higher than 5% upon aging for three weeks when the nanocrystals （NCs） were stored in an ice-bath in the dark, and higher than 5%for at least five weeks when extra DTG ligands were introduced into the nanocrystal solution followed by stirring every two weeks. Poly（N-isopropyl acrylamide） （PNIPAM） microgels were produced via precipitation polymerization with dimensions of ca. 230 nm and polydispersity of 3-5%. Incorporation of PbS QDs into PNIPAM microgels indicated that PbS can be incorporated into the interior of microgel particles and not at the microgel interface. The combination of reasonable room temperature quantum efficiency and strong, efficient luminescence covering the 1.3-1.55 μm telecommunication window makes these nanoparticles promising materials in optical devices and telecommunications.

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.

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.

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.

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.

A Temperature-sensitive Hydrogel Refolding System: Preparation of Poly(N-isopropyl acrylamide) and Its Application in Lysozyme Refolding

Temperature-sensitive hydrogel—poly(N-isopropyl acrylamide) (PNIPA) was prepared and applied to protein refolding. PNIPA gel disks and gel particles were synthesized by the solution polymerization and inverse suspension polymerization respectively. The swelling kinetics of the gels was also studied. With these prepared PNIPA gels, the model protein lysozyme was renatured. Within 24h, PNIPA gel disks improved the yield of lysozyme activity by 49.3% from 3375.2U·mg^-1 to 5038.8U·mg^-1. With the addition of faster response PNIPA gel beads, the total lysozyme activity recovery was about 68.98% in 3h, as compared with 42.03% by simple batch dilution. The novel refolding system with PNIPA enables efficient refolding especially at high protein concentrations. Discussion about the mechanism revealed that when PNIPA gels were added into the refolding buffer, the hydrophobic interactions between denatured proteins and polymer gels could prevent the aggregation of refolding intermediates, thus enhanced the protein renaturation.

Effect of Graft Yield on the Thermo-Responsive Permeability Through Porous Membranes with Plasma-Grafted Poly(N-isopropylacrylamide)Gates

The effect of graft yield on both the thermo-responsive hydraulicpermeability and the therrno-responsive diffusional permeability through porous membranes withplasma-grafted poly(N-isopropylacrylamide) (PNIPAM) gates was investigated. Both thermo-responsiveflat membranes and core-shell microcapsule membranes with a wide range of graft yield of PNIPAM wereprepared using a plasma-graft pore-filling polymerization method. The grafted PNIPAM was formedhomogeneously throughout the entire thickness of both the flat polyethylene membranes and themicrocapsule polyamide membranes. Both the hydraulic permeability and the diffusional permeabilitywere heavily dependent on the PNIPAM graft yield. With increasing the graft yield, the hydraulicpermeability (water flux) decreases rapidly at 25℃ because of the decrease of the pore size;however, the water flux at 40℃ increases firstly to a peak because of the increase ofhydrophobicity of the pore surface, and then decreases and finally tends to zero because of the poresize becoming smaller and smaller. For the diffusional permeability, the temperature showsdifferent effects on the diffusional permeability coefficients of solutes across the membranes. Whenthe graft yield was low, the diffusional coefficient of solute across the membrane was higher attemperature above the lower critical solution temperature (LCST) than that below the LCST; however,when the graft yield was high, the diffusional coefficient was lower at temperature above the LCSTthan that below the LCST. It is very important to choose or design a proper graft yield of PNIPAMfor obtaining a desired thermo-responsive 'on/off' hydraulic or diffusional permeability.

Phototactic Poly(N-isopropyl acrylamide)Microgels with Photoresponsive Property

Smart functional microgels hold great potential in a variety of applications,especially in drug transportation.However,current drug carriers based on physiological internal stimuli cannot efficiently orientate to designated locations.Therefore,it is necessary to introduce the self-propelled particles to the drug release of the microgels.In order to study self-propulsion of microgels induced by light,it is also a challenge to prepare micronsized microgels so that they can be observed directly under optical microscopes.In this work,phototactic microgels with photoresponsive properties are prepared.The microgel particles can be observed by confocal laser scanning microscopy.The photoresponsive properties of microgels are fully investigated by various instruments.Light can also regulate the state of the microgel solution,making it switch between turbidity and clarity.The phototaxis of particles irradiated by UV light was studied,which may be used for microgels enrichment and drug transportation and release.

Synthesis and Properties of Poly (N-isopropylacrylamide) and Poly (N-isopropylacrylamide-co-acrylamide) Hydrogels

The thermosensitive poly （ N-isopropylacrylamide ） （PNIPAAm） and poly （N-isopropylacrylamide-co-acrylamide） [ poly （NIPAAm-co-AAm） ] hydrogels with different acrylamide molar percentage are prepared by radiation polymerization using Co^60 γ-ray. Their swelling equilibrium data in the media of deionized water, NaCl aqueous solutions and different pH buffer solutions are determined. It appears that lower critical solution temperature （LCST） of the hydrogels will drop with the increase of ionic strength and increase with the rising of acrylamide content, A semi-empirical formula is set up with the experimental results. Moreover, it also indicates that this copolymer is pH-sensitive, which is similar to the homopolymer of PNIPAAm.

4天香烟烟雾暴露联合poly(I:C)刺激对小鼠肺部免疫应答及干扰素表达的影响

目的:探讨短期香烟烟雾暴露联合poly(I:C)刺激对小鼠肺部免疫应答及干扰素表达的影响。方法:BALB/c小鼠随机分为4组:对照组、熏烟组、poly(I:C)组和熏烟联合poly(I:C)组。检测支气管肺泡灌洗液(BALF)中总细胞数及细胞分类计数;普通光镜下观察各组细胞形态;荧光定量PCR检测肺组织细胞因子、趋化因子和干扰素及干扰素刺激基因表达。结果:与对照组相比,熏烟联合poly(I:C)组总细胞数计数、巨噬细胞与中性粒细胞计数明显升高(P<0.05),且熏烟联合poly(I:C)组巨噬细胞计数高于poly(I:C)组;与poly(I:C)组比较,熏烟联合poly(I:C)组小鼠气道灌洗液巨噬细胞体积较大,呈圆形或不规则形,细胞质较多空泡;与对照组相比,熏烟联合poly(I:C)组小鼠肺组织中性粒细胞趋化因子CXCL1(P<0.05)、CXCL2(P<0.01)和淋巴细胞趋化因子CCL2(P<0.01)mRNA表达升高,肺组织IL-1β、IL-6、TNF-αmRNA表达明显升高(P<0.01),肺组织IFN-β(P<0.01)、IFN-γ(P<0.05)、MX2(P<0.01)和IP-10(P<0.01)表达显著升高,且与poly(I:C)组小鼠相比,熏烟联合poly(I:C)组小鼠肺组织CXCL2(P<0.05)、TNF-α(P<0.01)和IFN-β(P<0.05)mRNA表达明显升高。结论:熏烟联合poly(I:C)诱导了小鼠肺部炎症反应和干扰素及干扰素刺激基因表达。同时,香烟暴露加剧了poly(I:C)诱导的小鼠肺部急性炎症反应和Ⅰ型干扰素表达。

Preparation and chromatographic evaluation of thermoresponsive N-isopropylacrylamide copolymers stationary phases containing amino groups

Two cationic thermoresponsive stationary phases were designed and prepared containing poly [ N-isopropylacrylamide-co-（ 2-dimethylamino ） ethylmethacrylate ] and poly [ N-isopropylacryl- amide-co-（2-diethylamino） ethylmethacrylate] via a simple method, the direct copolymerization of monomers with double bonds on silica surfaces. The two copolymers were synthesized by radical polymerization and then characterized using Fourier transform infrared and gel permeation chroma- tography. The thermoresponsive property and amounts of copolymers grafted on silica were deter- mined through transmittance measurements and thermogravimetric analysis, respectively. The copol- ymers grafted silica particles were then applied as high-performance liquid phase （HPLC） stationary phases for chromatographic separation. Chromatographic properties of mobile phases at different pH values were evaluated by changing temperatures and using benzene and hydrocortisone as the test an- alytes. Retention time of the analytes was prolonged with increasing temperature on both thermore- sponsive columns due to enhanced hydrophobic interaction between analytes and stationary phases. The resolution increased with increasing pH of mobile phase. The optimal separation was obtained at phosphate buffer solution （ 10 raM, pH 8. 0） and at 50 ℃. The pH of mobile phase had a crucial effect on separation efficiency. The results illustrated that poly（ N-isopropylacrylamide-co-（2-diethyl- amino） ethylmethacrylate ] copolymer modified silica was more advantageous for the temperature-re- sponsive chromatographic separation because its lower critical solution temperature was relatively lower compared to the poly [ N-isopropylacrylamide-co-（2-dimethylamino） ethylmethacrylate ] sta- tionary phase.

THE ADSORPTION OF LINEAR POLY(N-ISOPROPYLACRYLAMIDE)CHAINS ON SURFACTANT-FREE POLYSTYRENE NANOPARTICLES

The adsorption of linear poly(N-isopropylacrylamide) (PNIPAM) chains on surfactant-free polystyrene (PS) nanoparticles was used as a model system to study the hydrophobic adsorption of polymer on the surface, because the hydrophobility of PNIPAM can be continuously varied by a small temperature change. The adsorption was investigated by a combination of static and dynamic laser light scattering (LLS) measurements. In static LLS, the absolute excess scattered light intensity led to the amount of PNIPAM adsorbed on the surface. In dynamic LLS, the hydrodynamic thickness of the adsorbed PNIPAM layer was accurately measured. For a given particle concentration, the adsorption increases as the PNIPAM concentration and the incubation temperature increase. The average density of the adsorbed PNIPAM layer is reciprocally proportional to the number of the PNIPAM chains on the surface, revealing a simple scaling of the chain density distribution. The adsorption follows the Langmuir's isotherm. The enthalpy change estimated from the adsorption at 25 degrees C and 30 degrees C is slightly positive, indicating that the adsorption involves the coil-to-globule transition of the chains on the surface.

APPLICATION OF SURFACE GRAFTED POLY N-ISOPROPYL ACRYLAMIDE BY RADIATION TECHNOLOGY FOR PROTEIN SOLUTION CONCENTRATION

Poly N-isopropyl acrylamide (abbreviated as PNIPA) as a kind of thermally sensitive hydrogel is utilized to concentrate Bovin Serum Albumin (BSA) solution. In order to decrease its surface adsorption to BSA in aqueous solution, surface layer grafting of the gels by radiation technology was carried out. The results showed that hydroxyl propyl methacrylate (HPMA) grained gel exhibited a low level of BSA adsorption and still kept the original thermally sensitive properties of PNIPA hydrogels.