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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

Studies on LCST of poly (N-isopropylacrylamide-co-acrylic acid-co-N-diacetone acrylamide)

Linear copolymers from N-isopropylacrylamide （NIPA）, acrylic acid （AA） and diacetone acrylamide （DAA） have been prepared. The effect of composition, ionic strength and pH on their lower critical solution temperature （LCST） has been investigated.

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.

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.

In-Situ Synthesized Myoglobin Imprinted Poly(N-Isopropylacrylamide)/Silica Nanocomposite Gels by Using the Molecular Imprinting Method

Temperature sensitive imprinted poly(N-isopropylacrylamide) nanocomposite gels were syntheses via in-situ, free radical crosslinking polymerization of corresponding monomer in nano-sized silica and five different concentrations of myoglobin solution by using the molecular imprinting method. Mb adsorption from five different concentrations of Mb solutions was investigated by two types of nanocomposite gel systems prepared by non-imprinted and imprinted methods. Nanocomposite gels imprinted with Mb showed higher adsorption capacity and specificity for Mb than nanocomposite gels prepared by the usual procedure. The highest Mb adsorption was observed via the imprinted nanocomposite gels with 12.5% Mb. In addition, selectivity studies were also performed by using two reference molecules as fibrinogen and hemoglobin. The imprinted nanocomposite gels had higher adsorption capacity for Mb than the non-imprinted gels and also exhibited good selectivity for Mb and high adsorption rate depending on the number of Mb sized cavities.

Thermo-Responsive Electrospun Nanofibers from Poly( N-isopropylacrylamide )/Polyvinyl Pyrrolidone Blends

A novel nanofiber composite poly(N-isopropylacrylamide)(PNIPAAm)/polyvinyl pyrrolidone(PVP)was successfully prepared by electrospinning.Analogous medicated fibers loaded with ketoprofen(KET)as a model drug were prepared.X-ray diffraction(XRD)demonstrated that the drug was presented in the fibers with an amorphous form.Both scanning and transmission electron microscopy showed that the fibers had an even diameter and smooth surface,and no phase separation was observed.The KET loaded nanofibers did not affect the morphology of the fibers,and no drug aggregation was separated from the polymer fibers.Water contact angle measurements proved that the PNIPAAm/PVP fibers switched from hydrophilic to hydrophobic when the temperature increased the lower critical solution temperature of 32℃.In vitro drug release studies were also undertaken and the result indicated that the PNIPAAm/PVP blend nanofiber presented the properties of the two polymers,having temperature-sensitive systems with sustained release properties.In addition,MTT assay demonstrated that the nanofiber film was non-toxic and suitable for cell growth.Thus,the nanofiber can be used as thermoresponsive carriers for sustained release of poor water soluble drugs.

New Insights into Folding Kinetics of α,ω Dye-Functionalized Poly(N-isopropylacrylamide)

Two narrowly-distributed poly(N-isopropylacrylamide)(PNIPAM) samples were prepared via atom transfer radical polymerization (ATRP) with a novel dansyl functionalized initiator. The other end of the PNIPAM was functionalized by dabcyl group via click reaction. From the static fluorescence measurements, the fluorescence intensity of dansyl group and energy transfer efficiency between dansyl and dabcyl groups increased when the temperature increased from 36 °C to 45 °C, indicating that the microenvironment surrounding dansyl became hydrophobic and the distance between dansyl and dabcyl decreased. The kinetics of the conformational change of the dye-labeled PNIPAM was studied by a home-made laser-induced temperature jump device with fluorescent measurement. Our results revealed that the characteristic transition time was 3.8 and 5.8 ms for PNIPAM with degrees of polymerization of 85 and 142, respectively, indicating that the characteristic transition time was related to the chain length. Besides, characteristic transition time for the change of the energy transfer efficiency was 2.9 ms for PNIPAM with the degree of polymerization of 85, suggesting that the energy transfer efficiency change was faster than the fluorescence intensity change of dansyl group.

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.

Preparation and Chiral Recognition of Thermosensitive Poly（N-isopropylacrylamide） Microgels Containing Modified L-Phenylalanine Groups

Thermosensitive poly[N-isopropylacrylamide（NIPAM）-co-N-acryloyl-L-phenylalanine ethyl ester （NALPE）] microgels were prepared by the free radical polymerization of NIPAM and chiral monomer, NALPE. Such microgels exhibited spherical shape and favorable monodispersity. Increasing the content of NALPE units would en- hance the average diameter, but decrease the thermosensitivity and volume-phase transition temperatures of the mi- crogels. Compared with PNIPAM microgels, the microgels containing NALPE units performed chiral recognozable capacities for D-phenylalanine and D-tartaric acid, and the enantioselectivity and adsorption capacity of the microgels improved with increasing the temperature and/or the content of NALPE units.