Preparation and Characterization of Interpenetrating Polymer Hydrogels Based on Poly(acrylic acid) and Poly(vinyl alcohol)

Interpenetrating polymer hydrogels (IPHs) of Poly (vinyl alcohol) (PVA) and Poly (acrylic acid) (PAAc) have been prepared by a sequential method: crosslinked PAAc chains were formed in aqueous solution by crosslinking copolymerization of acrylic acid and N, N′-methylenebisacrylamide in the presence of PVA. The application of freezing-thawing cycles (F-T cycles) leads to the formation of a PVA hydrogel within the synthesized PAAc hydrogel. The swelling and the viscoelastic properties of the prepared IPHs were evaluated on the basis of the structural features obtained from solid state ¹³C-NMR spectroscopy.     

温敏性聚(N-异丙基丙烯酰胺)水凝胶的合成与表征

以不同粒径的硅胶颗粒为致孔剂制备了多孔的聚(N-异丙基丙烯酰胺)(PNIPAAm)水凝胶,用DSC对其相转变温度进行了表征,并测定了不同温度下达到溶胀平衡时水凝胶的溶胀率,研究了水凝胶的退胀机理及收缩凝胶的再溶胀机理。实验证明,多孔凝胶相对于无孔凝胶其溶胀性能有较大提高,孔结构的存在大幅度提高了水凝胶的响应速率,尤其是退胀速率。     

UV-Cured Antibacterial Hydrogels Based on PEG and Monodisperse Heterofunctional Bis-MPA Dendrimers

Bacterial infections are one of the major threats to human health due to the raising crisis of antibiotic resistance. Herein, second generation antibacterial heterofunctional dendrimers based on 2,2-bis(methylol)propionic acid were synthesized. The dendrimers possessed six alkenes and 12 ammonium end-groups per molecule and were used to fabricate antibacterial hydrogels together with dithiol-functional polyethylene glycol (mol wt of 2, 6 and 10 kDa) as crosslinkers via thiol-ene chemistry. The network formation can be completed within 10 s upon UV-irradiation as determined by the stabilization of the storage modulus in a rheometer. The hydrogels swelled in aqueous media and could be functionalized with the N-hydroxysuccinimide ester of the dye disperse red 13, which allowed for visually studying the degradation of the hydrogels through the hydrolysis of the ester bonds of the dendritic component. The maximum swelling ratio of the gels was recorded within 4–8 h and the swelling ratios increased with higher molecular weight of the polyethylene glycol crosslinker. The gel formed with 10 kDa polyethylene glycol crosslinker showed the highest swelling ratio of 40 and good mechanical properties, with a storage modulus of 8 kPa. In addition, the hydrogels exhibited good biocompatibility towards both human fibroblasts and mouse monocytes, while showing strong antibacterial activity against both gram-positive and gram-negative bacteria.     

Swelling kinetics of poly(aspartic acid)/poly(acrylic acid) semi‐interpenetrating polymer network hydrogels in urea solutions

Semi‐interpenetrating network (semi‐IPN) hydrogels, composed of poly(aspartic acid) (PAsp) and poly(acrylic acid) (PAAc) with various ratios of PAsp to AAc, were prepared. In this work, swelling kinetics was investigated through calculating some parameters. The swelling ratios were measured at room temperature, using urea solutions as liquids to be absorbed. Compared to in deionized water, the hydrogels showed larger swelling ratios in urea solutions, which might be attributed to the chemical composition of urea. The equilibrium swelling ratio could achieve 600 g/g, and the equilibrium urea/water contents were more than 0.99. The diffusion exponents were between 0.5 and 0.7, suggesting that the solvent transport into the hydrogel was dominated by both diffusion and relaxation controlled systems. Therefore, the PAsp/PAAc semi‐IPN hydrogels were appropriate to carry substances in a urea/water environment for pharmaceutical, agricultural, environmental, and biomedical applications. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 666–671, 2010     

Polymer-Based Superhydrophobic Coating Fabricated from Polyelectrolyte Multilayers of Poly(allylamine hydrochloride) and Poly(acrylic acid)

Superhydrophobic films mainly based on poly(allylamine hydrochloride) (PAH) and poly(acrylic acid) (PAA) polyelectrolyte multilayer have been deposited onto cleaned glass substrate by a layer-by-layer dip coating method. 3 bilayers of the PAH and PAA was directly coated onto the substrate as an underlying layer for subsequent coating. Desired surface roughness on the polyelectrolyte bilayers was created by etching the bilayers in hydrochloric acid solution so as to create the open pore having suitable size at the surface. Then, nanoparticles such as SiO₂ and TiO₂ of various sizes were deposited onto the etched polyelectrolyte bilayers. Finally, the surfaces were further modified with semifluorinated silane followed by cross-linking at 180 °C for 2 h to obtain desirable surface morphological features. The effect of etching time and addition of nanoparticles on surface morphology was investigated using an atomic force microscope (AFM). Wetting ability of the prepared film was determined by measuring water droplet contact angle using a goniometer. Adhesion between the superhydrophobic films and the substrate was evaluated by using a standard tape test method (D3359). The adhesion was improved by reducing the organic content in the films.     

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。     

聚N,N-二乙基丙烯酰胺温敏水凝胶的药物释放研究

在合成聚Ｎ,Ｎ－二乙基丙烯酰胺温敏水凝胶的基础上研究了该水凝胶在ＬＣＳＴ附近对药物的释放（以氟哌酸为主）。温度与交联度的变化对药物的释放皆有明显的影响。通过对释放曲线进行计算机模拟得到释放液浓度的经验公式,并从理论上初步解释了公式中各参数的物理意义。作出了理论近似计算得到的表观扩散系数的变化曲线,其在ＬＣＳＴ附近各温度的变化趋势符合预测     

The Influence of Silkworm Species on Cellular Interactions with Novel PVA/Silk Sericin Hydrogels

Sericin peptides and PVA are chemically modified with methacrylate groups to produce a covalent PVA/sericin hydrogel. Preservation of the sericin bioactivity following methacrylation is confirmed, and PVA/sericin hydrogels are fabricated for both B. mori and A. mylitta sericin. Cell adhesion studies confirm the preservation of sericin bioactivity post incorporation in PVA gels. PVA/A. mylitta gels are observed to facilitate cell adhesion to a significantly greater degree than PVA/B. mori gels. Overall, the incorporation of sericin does not alter the physical properties of the PVA hydrogels but does result in significantly improved cellular interaction, particularly from A. mylitta gels.

     

Physical Hydrogels of Poly(vinyl alcohol) with Different Syndiotacticity Prepared in the Presence of Lactosilated Chitosan Derivatives

Poly(vinyl alcohol) (PVA) physical hydrogels were prepared by repeated freeze–thawing cycles using aqueous solutions of two PVA samples having different degrees of syndiotacticity, a‐PVA and s‐PVA with 55% and 61% of syndiotactic diads, respectively. The hydrogels were prepared in the presence of different amounts of lactosilated chitosan derivatives (LC) of different molecular weight. The PVA stereoregularity was found to have a dramatic effect on the amount of PVA incorporated into the hydrogels, leading to remarkable differences in the swelling degree and porosity of a‐PVA and s‐PVA hydrogels. A significant amount of LC was retained in the hydrogels after equilibrium swelling. The swelling of the a‐PVA hydrogels was found to increase significantly by increasing the amount of LC while it was only slightly increased in the case of s‐PVA hydrogels. The amount of LC released after equilibrium swelling was lower when chitosan derivatives with higher molecular weights were used. Increased initial concentrations of LC resulted in much higher porosity of the hydrogels. TGA and DSC studies showed that LC is stabilized by the incorporation in the PVA hydrogels. The melting temperature of the crystalline regions of PVA was not significantly influenced by LC. Conversely, the extension of the crystalline domains increased in the presence of LC. The retention of a chitosan derivative bearing β‐D ‐galactose side chain residues makes these hydrogels potentially useful as scaffolds for hepatocytes culture.

Scanning electron micrographs of PVA‐LC hydrogels: (a) a‐PVA; (b) a‐PVA/LC₁₅₀ 80:20; (c) a‐PVA/LC₁₅₀ 50:50.     

New Approach to Determine the Phase Transition Temperature,Cloud Point,of Thermoresponsive Polymers

In this study, a novel method to determine the cloud point temperature variation in aqueous solutions of thermoresponsive homo- and copolymers was developed. Poly(N-vinylcaprolactam) (PVCL) and triblock copolymers of poly(t-butyl acrylate-co-acrylic acid)-b-poly(N-vinylcaprolactam)-b-(t-butyl acrylate-co-acrylic acid) (P[(tBA-co-AA)-b-PVCL-b-P(tBA-co-AA)] were synthesized by reversible addition-fragmentation chain transfer (RAFT) polymerization and used as models. The incorporation of AA units (hydrophilic segments) into the polymeric chain of PVCL influenced the phase transition, increasing the cloud point temperature of the final copolymer. The cloud point temperatures of the PVCL and the triblock copolymer P(tBA-co-AA)-b-PVCL-b-P(tBA-co-AA) were determined by measuring the transmittance of aqueous solutions of the polymers in a Turbiscan Lab instrument in the range of 29 to 40 C. This is the first study in which Turbiscan Lab is used to determine the cloud point temperature.     

Collapse of Poly(methacrylic acid) Hydrogels in Response to Simultaneous Stimulation by an Electric Field and Complex Formation

Complex formation of poly(methacrylic acid) hydrogels with linear poly(ethylene glycol) has been studied at different pH values and in the presence of an electric field. The fastest contraction of the gel samples was observed under simultaneous action of electric field and complex formation.

Dependence of the volume ratio V/V₀ of PMAA sample on time: Sample in the absence of an electric field immersed in 0.1 M PEG solution at (1) pH 8.2, (2) at pH 5.1, and in the presence of an electric field (3) in water and (4) 0.1 M PEG solution at pH 5.1.     

Synthesis and Properties of IPN Hydrogels Based on Konjac Glucomannan and Poly（acrylic acid）

As a random copolymer of β-(1,4) linked D-mannose and D-glucose, konjac gluco- mannan (KGM) is a naturally occurring water-soluble polysaccharide, and has been paid attention in the field of drug controlled release carriers potentially used in colon1,2. …     

In situ ATR-FTIR and SFM Studies on the Influence of Adsorption time on Deposition and Nanostructure of Poly(ethyleneimine)/Poly(acrylic acid) Multilayers

Summary: The deposition and the nanostructure of polyelectrolyte multilayers (PEM) of branched poly(ethyleneimine)/poly(acrylic acid) (PEI/PAC) was studied in dependence of the adsorption time (t_ADS) of the individual steps. PEM were reproducibly deposited applying up to z = 20 adsorption steps at the fixed pH combination of 10/4 and polyelectrolyte concentration c_PEL = 0.005 M in a flow cell using an automated valve system. in situ ATR-FTIR spectroscopy and SFM were used for quantitative determination of deposited amount and thickness, respectively. A linear relation between PEL band integrals and thickness of thin PEM films was found. Varying t_ADS from 0.5 to 5 min in each of the adsorption steps resulted in a steep rise of the deposited PEM amount. For t_ADS > 5 min the deposition did only marginally increase. Evidence for the release of outermost located PEI upon PAC immersion (even step) and of outermost PAC upon PEI immersion (odd step) was obtained. SFM images on consecutively deposited PEM-6 showed a slight increase in structure size and roughness for increasing t_ADS. These studies help to prepare polyelectrolyte based films with controlled thickness for the interaction with biofluids in the biomedical and food field.     

瓜胶/聚丙烯酸互穿聚合物网络水凝胶对模型药物的负载与控制释放

考察了以牛乳清蛋白(BSA)为模型药物,通过相平衡分配法制备载药瓜胶(GG)/聚丙烯酸(PAA)互穿聚合物网络(IPN)水凝胶的工艺条件.借助紫外可见光谱仪研究了载药水凝胶在结肠酶存在下的控制释放行为.结果表明:载药容量(CM)随瓜胶、丙烯酸用量的增加而下降,半IPN水凝胶的Cm较全IPN的略大;结肠酶能明显提高半IPN与全IPN中的BSA释放速率,且提高幅度随GG含量的增加而加快,GG/PAA IPN水凝胶具有结肠定位降解的特性,有望成为靶向结肠给药的理想载体材料.     

智能型水凝胶结构及响应机理的研究进展

综述了智能型水凝胶研究的新进展,简要介绍了几类新型的刺激响应性水凝胶,分析了影响水凝胶敏感性的结构因素,介绍了水凝胶的有关理论,动力学研究和敏感性机理。     

光化学合成P(DMAA-co-MMA)/Nano-SiO2复合水凝胶及其性能研究

以N,N-二甲基丙烯酰胺(DMAA)及甲基丙烯酸甲酯(MMA)为单体,Irgacure 2959为光引发剂,N,N′-二甲基双丙烯酰胺(Bis)为交联剂,利用紫外光引发自由基聚合制备了聚N,N′-二甲基丙烯酰胺(PDMAA)及P(DMAA-co-MMA)水凝胶,并通过加入少量表面改性后的纳米SiO₂对该水凝胶进行改性,制得了P(DMAA-co-MMA)/纳米SiO₂复合水凝胶,用FT-IR和SEM对产物进行了表征,同时研究该复合凝胶的溶胀动力学、消溶胀动力学、pH值响应性、离子强度等.该方法简便、快捷,大大缩短了聚合时间,合成过程仅需2-3 min.     

Application of Ultrasonic Attenuation Measurements in the Studies on Macromolecular Conformational Behaviors

——Phase Behavior of the Aqueous Solution of Poly(vinyl methyl ether) Sensitive to Temperature and the Modification of the Behavior by Using Poly(acrylic acid) The phase behavior of the aqueous solution of poly(vinyl methyl ether) (PVME) sensitive to temperature and the modification of the behavior by using poly(acrylic acid) (PAA) have been studied by ultrasonic attenuation measurements and fluorescence probe techniques. It has been observed that PVME solution is transparent at room temperature and becomes turbid upon heating. The solution turns clear again as soon as the temperature is decreased to room temperature. The heating and cooling process can be repeated for many times. The phase behavior of the solution sensitive to temperature is attributed to the conformational changes of the polymer. PVME may adopt an open coil conformation at room temperature. With this conformation, the polymer is well miscible with the solvent, water, and thereby the system is a real solution. The polymer may adopt a compact coil conformation when the temperature is higher than a specific value, which is called the LCST (the lower critical solution temperature) of PVME. In this case, the polymer tangles to each other and forms various aggregates, which can scatter incident light and ultrasonic waves greatly, resulting in the phase separation. Introduction of PAA decreases the temperature sensitivity of the phase behavior of the polymer. The nature of the inhibition is attributed to the complexation of PAA with PVME and the strong hydrophilicity of PAA. Results from fluorescence probe studies are in accordance with those from ultrasonic attenuation measurements, indicating again that the ultrasonic attenuation method can be successfully used for the qualitative studies of polymer conformations and complexation between polymers.     

Polyelectrolyte complexes of linear copolymers and hydrogels based on 2‐[(methacryloyloxy)ethyl]trimethylammonium chloride and N‐isopropylacrylamide

The formation of polyelectrolyte complexes of linear copolymers and hydrogels based on copolymers of 2‐[(methacryloyloxy)ethyl]trimethylammonium chloride with N‐isopropylacrylamide (MADQUAT–NIPAAM) and poly(acrylic acid) (PAA) has been studied. The composition of the copolymer has been found to affect the composition of the polyelectrolyte complexes significantly, and the molecular weight of PAA influences their aggregation stability. Hydrogels of MADQUAT–NIPAAM immersed in solutions of PAA undergo contraction because of the formation of gel–polymer complexes. The rate of contraction and the final swelling degree of the gel–polymer complexes depend on the concentration of PAA in solution and its molecular weight. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 1506–1513, 2004     

Mechanism of carbon nanotube dispersion and precipitation during treatment with poly(acrylic acid)

Carbon nanotubes have been shown to be easily dispersed within an acidic aqueous solution of poly(acrylic acid) but precipitate when the pH is increased. Transmission electron microscopy showed that the nanotubes were more exfoliated under the acidic condition but highly aggregated under the basic condition. Carbon K‐edge NEXAFS spectroscopy showed that the carbon nanotubes did not chemically react with poly(acrylic acid) during the dispersion or precipitation and that the dispersion mainly involved physical adsorption of poly(acrylic acid) onto the nanotubes. Together with the carbon K‐edge NEXAFS spectra, the cobalt L_{3, 2}‐edge NEXAFS spectra suggested that under the basic condition, the cobalt impurity within the nanotubes strongly reacted with poly(acrylic acid) resulting in complex formation. Cobalt reduces the adsorption of poly(acrylic acid) onto the nanotubes, which then reduced the nanotube dispersion and resulted in the precipitation. Copyright © 2008 John Wiley & Sons, Ltd.