The Preparation and Properties of Thermosensitive Hydrogels Based on Chitosan Grafted N-isopropylacrylamide via γ-Radiation

Thermosensitive hydrogels were prepared by graft polymerization of chitosan and N-isopropylacrylamide via 60 Co ?-radiation. The effects of monomer concentration and total irradiation dose on percent grafting and grafting efficiency were studied. The thermosensitivity and swelling properties of the hydrogels were investigated.

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.

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

The adsorption of linear poly(N-isopropylacrylamide) (PNIPAM) chains on surfactant-freepolystyrene (PS) nanoparticles was used as a model system to study the hydrophobic adsorption of polymeron the surface, because the hydrophobility of PNIPAM can be continuously varied by a small temperaturechange. 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 PNIPAMadsorbed on the surface. In dynamic LLS, the hydrodynamic thickness of the adsorbed PNIPAM layer wasaccurately measured. For a given particle concentration, the adsorption increases as thc PNIPAMconcentration and the incubation temperature increase. The average density of the adsorbed PNIPAM layer isreciprocally proportional to the number of the PNIPAM chains on the surface, revealing a simple scaling ofthe chain density distribution. The adsorption follows the Langmuir’s isotherm. The enthalpy changeestimated from the adsorption at 25℃and 30℃is slightly positive, indicating that the adsorption involvesthe coil-to-globule transition of the chains on the surface.

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.

Polymeric Nanohydrogels of Poly(N-Isopropylacrylamide)Combined with Others Functionalized Monomers:Synthesis and Characterization

Nanohydrogels from inverse microemulsion (w/o) polymerization, at 25°C, of N-isopropylacrylamide (NIPA) and functionalized monomers are described. The functionalized monomers were: N-(pyridine-4-ylmethyl) acrylamide (NP4MAM) and tert-butyl 2-acrylamidoethyl carbamate (2AAECM). The polymeric nanohydrogel obtained was characterized by attenuated total reflectance Fourier-transformed infrared spectroscopy (ATR-FTIR) and proton nuclear magnetic resonance spectrometry (1HNMR), while their morphology and particle size was assessed by scanning electron microscopy (SEM) and dynamic light scattering. Their thermal properties were studied by Differential Scanning Calorimetry (DSC) and Thermogravimetric Analysis (TGA). As a preliminary measure of biocompatibility, in vitro evaluations of the nanohydrogels were carried out by cellular toxicity (colon carcinoma cells, CT-26) and hemocompatibility tests. These evaluations showed that these nanohydrogels were not toxic in the examined concentration range and exhibited preliminary blood compatibility;therefore they could be used in biomedical applications.

One-pot and One-step Cu(0)-mediated Reversible-Deactivation Radical Polymerization of N-Isopropylacrylamide(NIPAM) in Water

Copper(0)-mediated reversible-deactivation radical polymerization(Cu(0)-mediated RDRP) of the water-soluble monomer Nisopropylacrylamide(NIPAM) has been challenging with the problems of high dispersity, poor control over the molecular weights(MWs) or complex or multi reaction steps, etc. In this work, we report the well-controlled polymerization of NIPAM in water via a facile one-pot and one-step Cu(0)-mediated RDRP. The results of this approach show that the key for kicking off the Cu(0)-mediated NIPAM RDRPs is to ensure sufficient Cu~I at the very beginning, and the key to achieve a well-controlled chain growth is to provide adequate deactivation strength during the polymerization process. For NIPAM, which has a high propagation rate constant, the deactivation control can be effectively enhanced by extra adding deactivator(i.e., Cu~II) to the system. Moreover, a low reaction temperature(4 ℃) is necessary in the controlled synthesis of higher MW poly(Nisopropylacrylamide)(PNIPAM) to avoid the compromise in control caused by the phase transition from its lower critical solution temperature(LCST). Through this new kinetically controlled strategy, PNIPAMs with well-defined structure, narrow molecular weight distributions(MWDs) and varied MWs were successfully achieved.

Thermo-responsive stick-slip behavior of advancing water contact angle on the surfaces of poly(N-isopropylacrylamide)-grafted polypropylene membranes

Wettability of a solid surface is highly important to its practical application,especially for the surface that shows thermoresponsive properties.In this paper,we describe a thermo-responsive stick-slip behavior of water droplets on the surfaces of poly(N-isopropylacrylamide)(PNIPAM)-grafted polypropylene membranes.Field emission scanning electron microscope(FESEM) images elucidate that the morphology of PNIPAM-grafted membrane surface is thermo-responsive,i.e.,the surface becomes rougher above the lower critical solution temperature(LCST) of PNIPAM.On the surface of nascent polypropylene membranes,the water droplet shows a smooth motion resulting in advancing and receding water contact angles of 111° and ～65°,respectively.On the PNIPAM-grafted membrane surfaces,the water droplet shows a stick-slip pattern above the LCST,whereas it advances smoothly below the LCST.This phenomenon is reproducible and can be ascribed to the energy barriers enhanced by the shrink of PNIPAM chains above the LCST.We also find that the slip contact angle decreases from 102° to 92° after several stick-slip cycles.This decrease is attributed to the water adsorption on the grafted PNIPAM layer,which is confirmed by the continuous decrease of the receding water contact angle.

Synthesis of thermoresponsive polystyrene-based comb-type grafted poly(N-isopropylacrylamide)

Narrowly distributed polystyrene-g-p(N-isopropylacrylamide) (PSt-g-PNIPAM) was prepared by atom transfer radical polymerization (ATRP) of N-isopropylacrylamide using the brominated polystyrene as macroinitiator and CuCl combined with hexamethyltriethylenetetramine as catalyst. Fourier transform infrared (FT-IR) spectroscopy and nuclear magnetic resonance (NMR) spectroscopy confirmed the structure of PSt-g-PNIPAM. The gel permeation chromatography (GPC) showed that the graft copoly- mer had a single distribution peak with molecular weight, Mn (g/mol) of 19815 g/mol (using polystyrene as the standard). Differential scanning calorimetry (DSC) revealed that due to both effects of hydro- phobic isopropyl groups and hydrogen bonds in the amide group, the glass transition temperature (Tg) of PSt-g-PNIPAM enhanced 16.0 ℃ compared to the Tg of the polystyrene.

Graft copolymerization of N-isopropylacrylamide with 3-(methacryloxy)propyl trimethoxysilane on ultrafine silica and its application in chromatography separation

Thermosensitive core-shell particles were synthesized through graft copolymerization of N-isopropylacrylamide with[3-(methacryloxy)propyl]trimethoxysilane(MPT)coupled on the surface of ultrafine silica beads.The copolymerization was carried out using polyvinyl alcohol as a surfactant,water and cyclohexanol as mixed solvent,and 2,29-azobis(isobutyronitrile)as an initiator.The effect of surfactant concentration and the composition of the mixed solvent on the graft rate were investigated.The structure of modified silica was confirmed by infrared spectra.Differential scanning calorimetry(DSC)has revealed the thermosensitivity of the particles.The thermosensitive particles were used as packing materials of high performance liquid chromatography(HPLC)columns for separating naphthalene derivatives.Satisfactory separation was obtained by controlling the temperature of the column.In contrast,the packing material of silica-MPT has no such separation efficiency due to the lack of thermosensitivity.The effect of the composition of the mobile phase on the separating efficiency was also investigated.The temperature-controlled separation was effective only when the water content was higher than 90%(v/v)in the water-methanol mobile phase.The mechanism for the temperature-controlled separation is attributed to a polarity change of poly(N-isopropylacrylamide)which undergoes volume phase transition on the silica surface as the temperature increases.

Fluorocarbon- containing hydrophobically modified poly(N-isopropylacrylamide)

A fluorocarbon-modified poly(N-isopropylacrylamide) has been synthesized by copolymerization of N-isopropyl acrylamide with a small amount of acrylate or methacrylate containing a perfluoroalkyl group. It was found that the hydrophilicity of macromolecular backbone is an important factor to the solution properties of the copolymers and that hydrophobic association between fluorocarbon groups is stronger than that between the corresponding hydrocarbon analogies. The viscosity of some of the copolymer solutions was very sensitive to temperature. It was dilatant at higher fluorocarbon comonomer content ( 】 0.20-1.0 mol%) and was Newtonian at very low fluorocarbon comonomer content (0.03-0.2 mol% ) . Evidence for hydrophobic association of the fluorocarbon groups was obtained from the effects of adding Nad and surfactants on the solution viscosity. The LC-ST properties of these copolymers were studied by DSC method and this was also found to be consistent with hydrophobic association between the

含环糊精的聚乙烯亚胺-g-聚(N-异丙基丙烯酰胺)的合成与表征

以支化聚乙烯亚胺(BPEI)为骨架,将β-环糊精(β-CD)和聚(N-异丙基丙烯酰胺)(PNIPAm)引入到BPEI上,合成出了接枝共聚物(BPEI-CD)-g-PNIPAm。用FTIR、SEC/MALLS和1H NMR进行了表征。结果表明,聚合物具有温度敏感性和超分子包合性能。

Self-Oscillating Structural Polymer Gels

self-oscillating polymer gel has become a distinguished class of smart soft materials. Here we fabricated and demonstrated a self-oscillating structural gel network with the incorporation of the Belousov-Zhabotinsky (BZ) reaction. The structural polymer gel oscillates at a macroscopic level with remarkably faster kinetics compared to a normal gel of similar chemical compositions. The structural polymer gel also displays larger oscillating amplitude compared to the normal gel because of the increased diffusion of fluids surrounding the gel particles. This type of structural polymer gels can be harnessed to provide novel and feasible applications in a wide variety of fields, such as drug delivery, nanopatterning, chemical and biosensing, and photonic crystals.

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.

Gold-Loaded Polymeric Micelles with TemperatureModulated Catalytic Activity

Four-armed amphiphilic block copolymers, polystyrene-b-poly(N-isopropylacrylamide)(PS-bPNIPAM)4, were synthesized by atom transfer radical polymerization(ATRP).(PS-b-PNIPAM)4 self-assembled into micelles with PS block as core and thermoresponsive PNIPAM block as corona. The gold nanoparticles(Au NPs) with average diameter about 5.8 nm were immobilized on the surfaces of the micelles by the reduction of the corresponding ions. The micelle-supported gold nanoparticles(Au-micelles) were applied to catalyze the reduction of p-nitrophenol. Moreover, the activity of the Au-micelle catalyst could be modulated by the temperature and the Au-micelles could be easily recovered by changing the temperature and recycled four times with high catalytic activity.

THE ■-STATE OF A SINGLE HOMOPOLYMER CHAIN IN SOLUTION

It has been an established practice to estimate the Θ-temperature of a polymer solution from thedisappearance of the interchain interactions （A2 = 0） Recently, in studies of the temperature dependence ofthe chain conformation in solution, we found that the change of the chain conformation clearly underwentthree different stages which could be viewed as the "gas". "liquid" and "solid" states in terms of the freedomof the "blobs" on the chain. The transition temperature between the first and second stages corresponds nicelyto the Θ-temperature determined by the conventional method. It reveals, for the first time, that the Θ-temperature can be deduced from the conformation change of a single polymer chain in solution, which isimportant not only in conception, but also in practice.

4D printing of core-shell hydrogel capsules for smart controlled drug release

Personalized drugs,as well as disease-specific and condition-dependent drug release,have been highly desired in drug delivery systems for effective and safe therapies.Four-dimensional(4 D)printing,as a newly emerging technique to develop drug capsules,displays unique advantages that can autonomously control drug release according to the actual physiological circumstances.Herein,core-shell structured hydrogel capsules were developed using a multimaterial extrusion-based 4 D printing method,which consists of a model drug as the core and UV cross-linked poly(N-isopropylacrylamide)(PNIPAM)hydrogel as the shell.Owing to the lower critical solution temperature(LCST)-induced shrinking/swelling properties,the prepared PNIPAM hydrogel capsules showed temperature-responsive drug release along with the topography changes in the cross-linked PNIPAM network.The in vitro drug release test confirmed that the PNIPAM hydrogel capsules can autonomously control their drug release behaviors according to changes in ambient temperature.Moreover,the increased shell thickness of these capsules causes an obvious reduction in drug release rate,distinctly indicating that the drug release behavior can be well adjusted by setting the shell thickness of the capsules.The proposed 4 D printing strategy pioneers the paradigm of smart drug release by showing great potential in the smart controlled release of drugs and macromolecular active agents.

Synthesis of P(NIPAM-co-Am)/Mesoporous Silica Composites and Their Temperature- Responsive Anion Exchange

The purpose of this study is to examine the structure and the temperature-responsive anion exchange property of amino-functionalized mesoporous silica coated with temperature-responsive copolymer, poly(N-isopropylacrylamide-co-acrylamide) (P(NIPAM-co-Am)). For this purpose, the composites which contained 0, 10, or 20 wt% of Am were synthesized. From the TG results, it was found that the amounts of copolymer immobilized on the mesoporous silica were 1.6 - 2.6 wt%. XRD patterns revealed that the structures of composites were hexagonal and almost the same as that of original mesoporous silica without polymer. At low temperature the methyl orange (MO) anions adsorbed and desorbed reversibly with changing pH of the solution, while at high temperature the MO anions did not. This temperature, at which the amount of adsorbed MO anions changed considerably, shifted to the higher temperature side with increasing the amount of added Am.

Fabrication of a superhydrophilic/underwater superoleophobic stainless steel mesh for oil/water separation with ultrahigh flux

Because of the increasing amount of oily wastewater produced each day,it is important to develop superhydrophilic/underwater superoleophobic oil/water separation membranes with ultrahigh flux and high separation efficiency.In this paper,a superhydrophilic/underwater superoleophobic N-isopropylacrylamide-coated stainless steel mesh was prepared through a simple and convenient graft polymerization approach.The obtained mesh was able to separate oil/water mixtures only by gravity.In addition,the mesh showed high-efficiency separation ability(99.2%)and ultrahigh flux(235239 L·m^(−2)·h^(−1)).Importantly,due to the complex cross-linked bilayer structure,the prepared mesh exhibited good recycling performance and chemical stability in highly saline,alkaline and acidic environments.

Fabrication of core-shell PLGA/PLA-pNIPAM nanocomposites for improved entrapment and release kinetics of antihypertensive drugs

Polylactic acid (PLA)and poly(lactic-co-glycolic)acid (PLGA)are two commonly applied biodegrad- able polymers for the preparation of nanocomposites used in drug-delivery systems.However,these polymers lack desirable attributes such as resistance to aggregation during long-term storage due to lyophilisation.To improve their efficacy,in this work,PLA and PLGA were encapsulated within a shell of poly(N-isopropylacrylamide)(pNIPAM)using a single emulsion technique followed by an aqueous free radical precipitation polymerisation process,yielding core-shell PLA/PLGA-pNIPAM nanocomposites. The nanocomposites were cbaracterised using zeta potential,dynamic light scattering,and transmission electron microscopy analyses and were further applied as a delivery system for ramipril,an antihypertensive drug.The drug-loaded PLGA-pNIPAM core-shell nanoparticles exhibited a higher drug content (91%)and entrapment efficiency (78%)than their PLA counterparts.An in vitro release study of the formulations at pH 7.3in phosphate-buffered saline indicated that PLGA was more efficient than PLA with a sustained release of 86% of ramipril from the polymer matrix within 24h.Furthermore,to determine the release kinetics,the data were fitted to Korsmeyer-Peppas and Higuchi models;the release of ramipril from the polymer matrix followed zero-order rate kinetics and an anomalous (non-Fickian)diffusion mechanism.

Construction of PS/PNIPAM core-shell particles and hollow spheres by using hydrophobic interaction and thermosensitive phase separation

This paper reports an easy and effective way to fabricate polystyrene/poly(N-isopropylacrylamide)(PS/PNIPAM)core-shell particles and PNIPAM hollow spheres.The main point of the method is to take advantage of the hydrophobic interaction between initiator and PS particles.The hydrophobic azodiisobutyronitriles automatically concentrate around the PS particles and initiate polymerization of N-isopropylacrylamide(NIPAM)and the crosslinkermethylene bisacrylamide(MBA),which dissolve in the aqueous phase,at the surface of the PS nanoparticles.Then,PNIPAM adheres to the PS particles to form a coreshell structure as a result of their hydrophobic interaction.This interaction is due to the unique property of PNIPAM,namely,its ability to transition from hydrophilic to hydrophobic when the temperature rises to 32℃.Furthermore,the hollow PNIPAM spheres were obtained by etching the PS core with chloroform.