Molecular chain properties of poly (N-isopropyl acrylamide)

A series of poly( N-isopropyl acrylamide) (PNIPAM) samples with molecular weight ranging from 2.23×10~4 to 130×10~4 and molecular weight distribution M_w/M_n≤1.28 were obtained by free radical polymerization and repeat precipitation fractionation. The molecular weight M_w, second virial coefficient A_2 as well as the mean-square-root radius of gyration 〈S~2〉 for PNIPAM samples in tetrahydrofuran (THF) were determined by light scattering, and the relations were estimated at A_2 ∞ M_w~0.25) and 〈S~2〉~(1/2)=1.56×10~(-9) M_w~(0.56). The intrinsic viscosity for THF solution and methanol solution of PNIPAM samples was measured and the Mark-Houwink equations were obtained as [η]=6.90×10~(-5) M~(0/73) (THF solution) and [η]=1.07×10~(-4) M~(0.71) (methanol solution). The above results indicate that both THF and methanol are good solvents for PNIPAM. The limit characteristic ratio C_∞ for PNIPAM in the two solutions was determined to be 10.6 by using Kurata-Stockmayer equation, indicating that the f     

Polyglycol-templated synthesis of poly(N-isopropyl acrylamide) microgels with improved biocompatibility

We report on the synthesis and characterization of thermally responsive poly(N-isopropyl acrylamide) (PNIPAM) nanoparticle hydrogels (i.e., microgels). Microgels with narrow size distributions were synthesized after optimizing the concentrations of monomer, surfactant, and initiator. Polyglycol block copolymers (trade name Pluronic) and sodium dodecylsulfate (SDS) surfactants were compared. In all cases, the particles' size decreased with increasing surfactant concentration, and comparable sizes could be produced with any of the surfactants. The choice of surfactant, however, had a significant influence on the biocompatibility of the PNIPAM microgels. The copolymer-stabilized microgels were less cytotoxic than those stabilized by SDS, as measured using 3(4,5-dimethylthiazol-2-yl)-5-(3-carboxymethoxyphenyl)-2-(4-sulfophenyl)-2H-tetrazolium, inner salt assays. Even after dialysis (for 3 days) to remove most surfactant, the SDS-based microgels remained more cytotoxic than particles prepared with Pluronics. After exposing cells to polyglycol surfactant solutions, it was found that the polyglycol with highest fraction of polyethylene oxide (Pluronic F127) showed the lowest level of cytotoxicity over the studied range of concentrations. Similarly, PNIPAM microgels synthesized with this surfactant had the lowest level of cytotoxicity. Finally, drug loading and release studies were performed using doxorubicin as a model drug.     

Thermoresponsive poly(N-isopropylacrylamide) nanogels/poly(acrylamide) nanostructured hydrogels

Here we report the preparation and characterization of nanostructured thermo-responsive poly(acrylamide) (PAM)-based hydrogels. The addition of slightly crosslinked poly(N-isopropylacrylamide) (PNIPA) nanogels to AM reactive aqueous solution produces nanostructured hydrogels that exhibit a volume phase transition temperature (T_VPT). Their swelling kinetics, T_VPT's and mechanical properties at the equilibrium-swollen state (H_eq) are investigated as a function of the concentration of PNIPA nanogels in the nanostructured hydrogels. Nanostructured hydrogels with PNIPA nanogels/AM mass ratios of 20/80 and above exhibit higher H_eq and longer time to reach the equilibrium swelling than those of the conventional PAM hydrogels. However, the PNIPA nanogels possess thermo-responsive character missing in conventional PAM hydrogels. The T_VPT of nanostructured hydrogels depends on PNIPA nanogel content but their elastic and Young moduli are larger than those of conventional hydrogels at similar swelling ratios. Swelling kinetics, T_VPT, and mechanical properties are explained in terms of the controlled in-homogeneities introduced by the PNIPA nanogels during the polymerization.     

Dual-responsive poly(styrene-alt-maleic acid)-graft-poly(N-isopropyl acrylamide) micelles as switchable emulsifiers

Self-assembled polymeric micelles can be used as efficient particulate emulsifiers. To explore the relationship between micellar structure and emulsification performance, pH- and temperature-responsive self-assembled micelles were prepared and used as emulsifiers, based on a novel grafted polymer poly(styrene-alt-maleic acid)-graft-poly(N-isopropyl acrylamide) (PSMA-g-PNIPAm). Structure of PSMA-g-PNIPAm micelles varies in response to pH and temperature changes and can be classified into four typical states, including shrunken, moderately swollen, extremely swollen, and inverted states, confirmed by a combination of electrophoresis, dynamic light scattering (DLS), transmission electron microscopy (TEM), and (1)H NMR. This structural variation plays a key role in the emulsification performance of PSMA-g-PNIPAm micelles, according to the emulsifying characteristics of the four typical PSMA-g-PNIPAm micelles as well as the micellar morphologies on the surface of oil droplets as observed by SEM. Emulsions stabilised by micelles with moderately swollen structure are especially stable compared with either the shrunken micelles or the extremely swollen micelles, because the moderately swollen micelles combine the advantages of solid particulate emulsifiers and polymeric surfactants.     

The sol-gel approach towards thermo-responsive poly(N-isopropyl acrylamide) hydrogels with improved mechanical properties

A new type of thermo-responsive hydrogels based on the polymer poly(N-isopropyl acrylamide) (PNIPAA) has been synthesized with the sol-gel technology. For the preparation of this type of nano-structured hydrogels, the inorganic silica phase was synthesized by the sol-gel process in the presence of an aqueous solution of high molecular weight PNIPAA. This combination of the organic and inorganic phases forms hybrid hydrogels with a semi-IPN morphology. The unique structure of these hydrogels improves the mechanical stability to a great extent as compared to conventional PNIPAA-hydrogels. This was shown by stress-strain experiments and the capability to absorb and desorb large amounts of water. The silica only slightly influences the transition temperature of the hydrogels but allows us to vary the thermo-responsive properties of the materials to a great extent.     

Temperature responsive flocculation and solid-liquid separations with charged random copolymers of poly(N-isopropyl acrylamide)

Temperature-responsive random copolymers based on poly(N-isopropyl acrylamide) (PNIPAM) with 15 mol% of either acrylic acid or dimethylaminoethyl acrylate quaternary chloride were prepared. The effect of the charge and its sign were investigated in the solid-liquid separation of silica and alumina mineral suspensions. The results were compared to PNIPAM homopolymer of similar molecular weight. PNIPAM copolymers of the same charge as the particles (co-ionic PNIPAM) act as dispersants at both 25°C and 50°C. Flocculation occurs when counter-ionic PNIPAM facilitates selective aggregation and rapid sedimentation of minerals at both 25°C and 50°C. Adsorption and desorption studies showed that, unlike non-ionic PNIPAM, little desorption of the counter-ionic copolymers from the oxides occurred after cooling a suspension from 50°C to below the lower critical solution temperature. Thus, incorporation of counter-ionic charge into the temperature sensitive polymer PNIPAM was found to reduce the sediment bed consolidation upon cooling when compared to PNIPAM homopolymers. The lack of secondary consolidation upon cooling is attributed to attractive inter-particle forces, such as conventional polyelectrolyte flocculation mechanisms (bridging, charge neutralization or charge patch) which persist at both 25°C and 50°C when counter-ionic PNIPAM is used. On the other hand, it was possible to obtain rapid sedimentation with the counter-ionic PNIAPMs even when they were added to the suspension already at 50°C, a process which has not been possible with neutral PNIPAM homopolymers.     

Thermoresponsive poly(N-isopropylacrylamide) copolymers: contact angles and surface energies of polymer films

Surface properties of poly(N-isopropylacrylamide) (PNIPAM) copolymer films were studied by contact angle measurements and optical and atomic force microscopy. We prepared a series of copolymers of N-isopropylacrylamide with N-tert-butylacrylamide (NtBA) in order of increasing hydrophobicity. The measurements of the advancing contact angle of water at 37 degrees C were hampered by the observation of a distinct stick/slip pattern on all polymers in the series with the exception of poly(NtBA) (PNtBA). We attributed this behavior to the film deformation by the vertical component of liquid surface tension leading to the pinning of the moving contact line. This was confirmed by the observation of a ridge formed at the pinned contact line by optical microscopy. However, meaningful contact (without the stick/slip pattern and with a time-independent advancing contact angle) angles for this thermoresponsive polymer series could be obtained with carefully selected organic liquids. We used the Li and Neumann equation of state to calculate the surface energy and contact angles of water for all polymers in the series of copolymers and van Oss, Chaudhury, and Good (vOCG) acid-base theory for PNtBA. The surface energies of the thermoresponsive polymers were in the range of 38.9 mJ/m2 (PNIPAM) to 31 mJ/m2 (PNtBA) from the equation of state approach. The surface energy of PNtBA calculated using vOCG theory was 29.0 mJ/m2. The calculated contact angle for PNIPAM (74.5 +/- 0.2 degrees ) is compared with previously reported contact angles obtained for PNIPAM-modified surfaces.     

超声波合成温敏型聚合物——聚(N-异丙基丙烯酰胺)

以N-异丙基丙烯酰胺为单体,N,N′-亚甲基双丙烯酰胺为交联剂,THF为溶剂,采用超声辐照聚合法合成了一种温敏型聚合物——聚(N-异丙基丙烯酰胺)(1),其结构经FT-IR表征.用UV-Vis研究了1的热相转变性能.结果表明,1具有温度敏感性,其最低临界共溶温度为34℃.     

Functional graft poly(N-isopropyl acrylamide)s using reversible addition-fragmentation chain transfer (RAFT) polymerisation

A series of NIPAM/4-vinyl benzyl chloride copolymers were substituted with 4(5)-imidazole dithioic acid or N-pyrrole dithioic acid to form multi-functional linear dithioate-functional polymers, which can be used as macromolecular transfer agents in a controlled radical polymerisation (RAFT) process. The presence of imidazole dithioate or N-pyrrole dithioate units along the NIPAM copolymer was determined by (1)H NMR, which showed broad CH-imidazole or CH-N-pyrrole resonances. Subsequent reaction of these multi-branch point polymers to produce graft polymers was achieved by reaction with NIPAM in the presence of AIBN. The graft polymers are produced as mixtures containing the desired product and linear polymer. The linear polymer is produced following transfer to the pendant dithioate group. Some of the branched polymers formed from the imidazole dithioate polymers were insoluble in water whilst others were found to be water soluble only in the presence of copper(II) ions. The use of N-pyrrole dithioate groups was found to substantially increase the solubility of the branched polymers in conventional solvents.     

Cationic temperature-responsive poly(N-isopropyl acrylamide) graft copolymers: from triggered association to gelation

In this work temperature-triggered association and gel formation within aqueous solutions of a new family of cationic poly( N-isopropyl acrylamide) (PNIPAm) graft copolymers have been investigated. Five copolymers were synthesized using aqueous atom transfer radical polymerization (ATRP) involving a macroinitiator based on quaternarized N, N-dimethylaminoethyl methacrylate units (DMA+). The PDMA+) x - g-(PNIPAmn)y copolymers have x and y values that originate from the macroinitiator; values for n correspond to the PNIPAm arm length. The copolymer solutions exhibited temperature-triggered formation of nanometer-sized aggregates at the cloud point temperature, which was 33-34 degrees C. The aggregates were investigated using variable-temperature turbidity, hydrodynamic diameter, and electrophoretic mobility measurements. The aggregates were clearly evident using SEM and flowerlike or spherical morphologies were observed. Variable-temperature electrophoretic mobility measurements revealed that the zeta potentials of the aggregates increased with DMA+ content. A study of the effect of added NaNO3 showed that electrostatic interactions controlled the size of the aggregates. The concentrated graft copolymer solutions showed temperature-triggered gelation when the copolymer concentrations exceeded 5 wt %, Fluid-to-gel phase diagrams were constructed. It was found that electrostatic interactions also controlled the gelation temperature. A correlation was found between aggregate size and the minimum copolymer concentration needed to form a gel. A mechanism for the temperature-triggered structural changes leading to the formation of aggregates (in dilute solution) or gels (in concentrated solutions) is proposed.     

The collapse transition of poly(styrene-b-(N-isopropyl acrylamide)) diblock copolymers in aqueous solution and in thin films

The thermal behavior of a poly(styrene-b-N-isopropyl acrylamide) diblock copolymer was studied in aqueous solution as well as in thick and in thin films. The polymer was synthesized using reversible addition–fragmentation chain transfer. The critical micelle concentration in aqueous solution was determined using fluorescence correlation spectroscopy. The lower critical solution temperature (LCST) of micellar solutions was detected using microcalorimetry and turbidimetry at 31 °C. Using dynamic light scattering, the collapse of the micelles at the LCST as well as their clustering above was observed. These findings were corroborated with small-angle X-ray scattering. In thick films immersed in water, similar findings were made. In a thin film, however, the LCST is depressed and is found at 26–27 °C.     

Thermo-sensitive colloidal crystals of silica spheres in the presence of large spheres with poly (N-isopropyl acrylamide) shells

Thermo-sensitive colloidal crystals are prepared simply by mixing colloidal silica spheres and large thermo-sensitive gel spheres. The thermo-reversible change in the lattice spacing of colloidal crystals of monodisperse silica spheres (CS82, 103 nm in diameter) depends on the size of the admixed temperature-sensitive gel spheres. For spheres with sizes less and greater than that of the silica spheres, the lattice spacing upon temperature increase above the lower critical solution temperature of poly(N-isopropyl acrylamide) decreases (cf. Okubo et al. Langmuir 18:6783, 2002) and increases, respectively. A mechanism, which is able to explain these experimental findings, is proposed. Moreover, crystal growth rates and the rigidities of the thermo-sensitive colloidal crystals are studied.     

Drying dissipative structures of the thermosensitive gels of poly(N-isopropyl acrylamide) on a cover glass

Drying dissipative structural patterns of the thermosensitive gels of poly(N-isopropyl acrylamide) were studied on a cover glass. As the temperature of suspension and room rose from 25 to 50 °C, the small size of drying pattern area extended to the beautiful flickering spoke-like ones transitionally at the critical temperature ca. 35 °C. The principal patterns at 25 °C were the single or multiple broad rings of the hill accumulated with the gels. At 50 °C, on the other hand, the flickering spoke-like patterns were observed at the inner area of the broad ring especially at the gel concentrations higher than 1 × 10⁻³ g/ml. These observations support that the extended gels at low temperatures apt to associate weakly to each other, whereas the gels at high temperatures shrink and move rather freely with the convectional flow of water, though the very weak intergel attractions still remain. In the presence of sodium chloride at high temperatures, the cooperative patterns formed between the gel spheres and the salt. The gravitational and Marangoni convectional flow of the gels and the very weak interactions between the gels and substrate (cover glass) are important for the flickering spoke-like pattern formation.     

Thermal reversible gelation during phase separation of poly(N-isopropyl acrylamide)/water solution

By dynamic viscoelastic measurement for PNIPAM/water solution it has been found that below the phase separation temperature (about 32 ℃), the system is homogeneous fluid; while upon being heated to about 32 ℃, the solution undergoes phase separation and the storage modulus G' increases sharply and exceeds the loss modulus G", indicating the physical network formation during the phase separation. Based on the percolation model, the gel points Tgel, were obtained by applying the dynamic scaling theory (DST) and winter's criterion. The critical exponent n was also obtained to be 0.79 through DST, which is different from 0.67, the critical point of chemically crosslinked network predicted through DST. The obtained n value reflects the special property of physical network being different from chemical network.     

纤维素纳米纤维接枝聚(N-异丙基丙烯酰胺)水凝胶的制备与表征

将具有温度响应的聚N-异丙基丙烯酰胺(PNIPAm)接枝到电纺纤维素纳米纤维膜上,制备温度响应型纤维素接枝聚N-异丙基丙烯酰胺(PNIPAm-g-Cell)纳米纤维水凝胶。 研究接枝单体(N)与纤维素(c)的质量比、反应温度、反应时间和引发剂浓度对产物接枝率、溶胀性和形貌的影响。 结果表明,最佳聚合反应条件为m(N):m(c)=15:1、反应温度40 ℃、反应时间3 h、引发剂浓度为10 mmol/L,得到PNIPAm-g-Cell接枝率和溶胀率分别为35%和31%。 与PNIPAm相比,PNIPAm-g-Cell水凝胶的低临界相转变温度(LCST)显著升高,说明亲水性纤维素的引入改变了体系的亲疏水平衡。 去溶胀动力学测试表明,0.5 min内接枝率为25%和35%的水凝胶保水率分别降低至93%和61%。 说明接枝率越高PNIPAm-g-Cell水凝胶对温度的响应速度越快,对温度越敏感。     

Fluorescence and viscometry study of complexation of poly(acrylic acid) with poly(acrylamide) and hydrolysed poly(acrylamide)

Interpolymer complexation of poly(acrylic acid) with poly(acrylamide) and hydrolysed poly(acrylamide) was studied by fluorescence spectroscopy and viscometry in dilute aqueous solutions. Changes in chain conformation and flexibility due to the interpolymer association are reflected in the intramolecular excimer fluorescence of pyrene groups covalently attached to the polymer chain. Both poly(acrylamide) and hydrolysed poly(acrylamide) form stable complexes with poly(acrylic acid) at low pH. The molecular weight of poly(acrylic acid) and solution properties such as pH and ionic strength were found to influence the stability and the structure of the complexes. In addition, the polymer solutions mixing time showed an effect on the mean stoichiometry of the complex. The intrinsic viscosity of the solutions of mixed polymers at low pH suggested a compact polymer structure for the complex.     

Highly branched stimuli responsive poly[(N-isopropyl acrylamide)-co-(1,2-propandiol-3-methacrylate)]s with protein binding functionality

Highly branched poly(NIPAM) have been prepared using the technique of reversible addition-fragmentation chain transfer (RAFT) polymerisation using a chain transfer agent that allows the incorporation of imidazole functionality in the polymer chain-ends. The lower critical solution temperature (LCST) of the polymers can be controlled by the amount of hydrophobe and GMA incorporated during copolymerisation procedures. These thermally responsive "smart" polymers were used to purify a His-tagged BRCA-1 protein fragment by affinity precipitation. [Diagram: see text]     

Temperature-responsive solid-liquid separations with charged block-copolymers of poly(N-isopropyl acryamide)

Temperature responsive charged block-copolymers of poly(N-isopropylacrylamide) (PNIPAM) have been used in the solid-liquid separation of alumina mineral particles from aqueous solution. The effects of temperature, polymer charge-sign and fraction of charged segment have been investigated. Batch settling and adsorption studies showed that rapid sedimentation results for suspensions with polymers of opposite charge-sign to the particle surface-charge (counterionic) at 50 °C. Cooling the suspensions after flocculation at 50 °C was found to increase the final solids volume fraction of the sediment beds formed through a mechanism related to partial desorption of polymer and the reduction of the hydrophobic attraction. Suspension stability results after dosing with polymers of similar charge-sign to the particle surface-charge (co-ionic) at both 25 and 50 °C. Increasing the amount of polymer charge increased the influence of polymer charge-sign on the adsorption and solid-liquid separation behavior. The performance of the charged block copolymers are compared to that of the random charged copolymer and neutral homopolymer PNIPAM structures.