聚N-异丙基丙烯酰胺水凝胶研究进展

简要阐述了聚N-异丙基丙烯酰胺(简称PNIPAM)水凝胶的制备方法、性能特点、应用等方面的研究进展。利用PNIPAM特有的温敏性特点,可以将PNIPAM与其他有机物复合,改善了其机械强度和温度敏感性,大大提高了PNIPAM的响应速度和溶胀率。制备的高分子材料在生物医学、免疫分析、分离提纯、蓄热等领域都有广泛的应用。     

快速响应聚(N-异丙基丙烯酰胺)水凝胶的制备及性能

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、过硫酸铵为引发剂、N,N,N,′N′-四甲基乙二胺为加速剂,在不同浓度的羧甲基纤维素的水溶液中,在低温下聚合/交联制备了一系列快速响应的温度敏感性聚(N-异丙基丙烯酰胺)水凝胶。用SEM观察了其表面形态,测定了不同温度下达到平衡时水凝胶的溶胀比,研究了水凝胶的去溶胀动力学。结果表明,与传统水凝胶相比,该水凝胶的溶胀性能有所提高,并且对温度的变化具有较快的响应速率。以质量分数为0.75%的羧甲基纤维素水溶液中制备的水凝胶为例,该水凝胶在20℃时的溶胀比为21.4,而传统水凝胶在相同温度时的溶胀比仅为12.9;该水凝胶在1 m in内失去60%的水,在4 m in内失去约80%的水,而传统水凝胶在15 m in内仅失去66%左右的水。     

聚(N-异丙基丙烯酰胺)温敏性水凝胶研究进展

具有温度敏感性的PNIPAAm水凝胶是目前凝胶研究的热点之一。文章介绍了PNIPAAm温敏性水凝胶的合成方法和提高性能的方法,总结了此类凝胶的应用,最后对PNIPAAm温敏性水凝胶的发展做了展望。     

N-异丙基丙烯酰胺类环境敏感性水凝胶的聚合及应用研究进展

N-异丙基丙烯酰胺(NIPA)类水凝胶是典型的温敏性凝胶,重点介绍了NIPA的均聚反应及其与天然高分子的复合,并对其在药物释放、物质分离及生物医用材料体系中的研究进展进行了总结。     

化学改性聚N-异丙基丙烯酰胺交联水凝胶的研究进展

综述了国内外关于温敏性聚N-异丙基丙烯酰胺(PNIPAM)交联水凝胶化学改性的研究现状。重点总结了无规共聚、接枝改性、嵌段改性等化学改性方法对PNIPAM交联水凝胶的结构、溶胀性能、温度响应性的影响,并对化学改性的方法和PNIPAM交联水凝胶的应用提出了展望。     

温敏性聚(N-异丙基丙烯酰胺)/聚丙烯酰胺互穿网络水凝胶

采用紫外引发法制备了物理交联的聚(N-异丙基丙烯酰胺)和化学交联聚丙烯酰胺为组分的互穿网络水凝胶。利用FFIR对所得的凝胶进行了结构分析;测定了该水凝胶在20℃时的溶胀率和50℃时的水保持率;利用DMA和DSC分别研究了水凝胶的储能模量随温度的变化及相转变行为。结果表明:与聚(N-异丙基丙烯酰胺)水凝胶相比,该水凝胶有较好的溶胀率;且具有超快的响应速率,如10 min内失去90%的水;其储能模量增加;虽然其相转变行为变弱,但临界溶解温度(LCST)有所提高。     

N-异丙基丙烯酰胺/N-羟甲基丙烯酰胺共聚物及其水凝胶的合成与温敏性研究

通过自由基聚合合成了N-异丙基丙烯酰胺(NIPAm)与-羟甲基丙烯酰胺(NHMPA)的共聚物及其水凝胶。研究发现,调节两单体的配比可得到不同的低临界溶液温度(LCST)值的共聚物及水凝胶。结果表明,NHMPA的加入不改变PNIPAm的温敏性,但可有效地调节其LCST值。     

含PEG组分的聚(N-异丙基丙烯酰胺)水凝胶的制备研究

首先合成了二丙烯酰基封端的聚乙二醇(PEG)大分子交联剂,然后使其与N,N-亚甲基双丙烯酰胺(BIS)和(N-异丙基丙烯酰胺)(NIPAM)单体进行交联反应,制备了PNIPAM-co-PEG-co-BIS水凝胶。与通常的PNIPAM-co-BIS凝胶比较,PNIPAM-co-PEG-co-BIS凝胶显示了明显加速的去溶胀动力学。这种加速的去溶胀性能归因于凝胶中的PEG组分为凝胶提供了亲水通道,在缩水过程中有利于凝胶的脱水。     

活性自由基聚合法制备温度敏感聚(N-异丙基丙烯酰胺-co-丙烯酰胺)水凝胶及其性能研究

以水与二甲基甲酰胺作混合溶剂,选用五甲基二乙烯基三胺作ATRP的催化剂配体,实现了ATPR法制备P(NIPAM-co-AM)温敏性智能型水凝胶。通过提高组分中AM的摩尔分率,水凝胶溶胀率增加,其LCST也随之提高,溶胀速率加快。相对于传统自由基聚合法,利用ATRP法制备的P(NIPAM-co-AM)水凝胶具有最低临界温度(LCST)低,溶胀速率快,保水量高等特点。     

聚(异丙基丙烯酰胺-羟甲基丙烯酰胺)/壳聚糖水凝胶的制备及其释药性能

以异丙基丙烯酰胺(NIPAAm)和羟甲基丙烯酰胺(NHMAm)为共聚单体与壳聚糖(CS)制备形成了温度敏感和pH敏感的互穿网络(IPN)水凝胶Poly(NIPAAm-co-NHMAm)/CS;用红外光谱表征了其结构特征,研究了不同条件下水凝胶的溶胀性能,并初步研究了水凝胶对药物双氯芬酸钠(DS)的缓释效果。结果表明,该水凝胶具有明显的温度和pH敏感性,温度越高,溶胀度越小,释药越慢;pH越小,溶胀度越大;CS含量为0.6%时溶胀度最大。在NHMAm单体质量配比为8.7%时,水凝胶的低临界溶液温度(LCST)达到38℃,且此时对DS持续释药时间可达到24 h。水凝胶的释药动力学曲线符合修正的一级动力学模型。该水凝胶体系可通过改变NHMAm单体配比来调节温敏特性,是一种潜在的温度和pH双重敏感的药物缓释载体。     

Poly(N-isopropylacrylamide) Hydrogels Crosslinked by Small-Molecular Crosslinkers Through Click Chemistry

A well-defined azido-poly(N-isopropylacrylamide) (PNIPA) was prepared by reversible addition-fragmentation chain transfer polymerization of NIPA and glycidyl methacrylate followed by the azidization of pendant epoxyl groups. Then the polymer was crosslinked via Click chemistry by bis- or tetra-alkynyl terminated compounds, which were synthesized through esterification of 1,3-propanediol and pentaerythritol with propiolic acid and 6-heptynoic acid, to fabricate PNIPA hydrogels. And the swelling properties of obtained hydrogels were studied as functions of crosslinker dosage and species. The results showed that the decrease of crosslinker dosage or increase of chain length thereof could enhance swelling capacities of hydrogels due to bigger free volumes within networks; the functionality of crosslinkers almost had no influence on swelling properties of hydrogels. In addition, no obvious distinction was found for lower critical solution temperature and swelling response to a temperature jump during reswelling and deswelling course, no matter what and how much crosslinker was used.     

N-异丙基丙烯酰胺凝胶在乙醇水溶液中的溶胀平衡

N-isopropylacrylamide (NIPAAm) was used to synthesize NIPAAm homopolymer (nonionized) and NIPAAm-sodium methacrylate copolymer (ionized). The swelling equilibria for both gels were obtained in aqueous solution of ethanol with concentration ranging from 0 to 100%(by mass) at 25℃. The swollen gel in water shrank first with the addition of a small amount of ethanol and then reswelled with further addition of ethanol showing not only a discontinuous volume phase transition but also a typical reentrant phenomenon. A thermodynamic model based on the UNIQUAC with the “free-volume“ contribution was applied to correlate and predict the swelling behavior of the poly(NIPAAM)-gels in ethanol-water mixture.     

Thermosensitive Poly(N-isopropylacrylamide-co-acrylonitrile) Hydrogels with Rapid Response

Acrylonitrile （AN） was copolymerized with N-isopropylacrylamide （NIPA） to synthesize thermosensitive hydrogels, and the on-off switch behavior of poly（NIPA-co-AN） hydrogels with different fraction of hydrophobic component （AN） was investigated. It is found that the lower critical solution temperature （LCST）, the swelling ratio at certain temperature and the reswelling rate of poly（NIPA-co-AN） hydrogels decreased as AN unit fraction in copolymers increased. In order to improve the responsive rate of poly（NIPA-co-AN） hydrogels, they were further treated by surface crosslinking using N, N′-methylene bisacrylamide （BIS） as a crosslinking agent. The swelling and deswelling behaviors of these copolymers were compared with those of the untreated hydrogels. The results indicated that the responsive rate of poly（NIPA-co-AN） hydrogel was improved by surface crosslinking. The resulting hydrogels bearing cyano groups with fast response have potential applications in the field of drug-controlled release and immobilization of biomolecules.     

Permeability properties of isometrically temperature-responsive poly(acrylic acid)-graft- oligo(N-isopropylacrylamide) gel membranes

A series of temperature-responsive hydrogels were prepared by grafting oligo(N-isopropylacrylamide) (ONIPAAm) chains onto a crosslinked poly(acrylic acid) (PAAc) network, intending an application to drug delivery systems (DDS). Cloud points and swelling ratios of the obtained PAAc-graft-ONIPAAm gels were measured as a function of temperature under various pH conditions. At pH > 4.5, the clear cloud points were observed at 31–33°C, which were almost the same values as that of poly(N-isopropylacrylamide) (PNIPAAm), whereas swelling/shrinkage phenomenon was not observed in the temperature range 25–45°C. It seemed that grafted ONIPAAm chains underwent the coil-to-globule transition, while the crosslinked PAAc network remained unchanged, due to the anionic charges on the main chains. In the presence of NaCl in the buffer solution, the phase transition temperature was slightly lowered. To assess the applicability of these temperature-responsive PAAc-graft-ONIPAAm gels to DDS, permeability of theophylline through the gel membranes was measured as a function of temperature. At a temperature below the cloud point, the permeability of theophylline was low, whereas it was high at an elevated temperature above the cloud point. © 1998 John Wiley & Sons, Inc. J. Appl. Polym. Sci. 70: 1027–1034, 1998     

Polymeric Hydrogels for In Vitro 3D Ovarian Cancer Modeling

Ovarian cancer (OC) grows and interacts constantly with a complex microenvironment, in which immune cells, fibroblasts, blood vessels, signal molecules and the extracellular matrix (ECM) coexist. This heterogeneous environment provides structural and biochemical support to the surrounding cells and undergoes constant and dynamic remodeling that actively promotes tumor initiation, progression, and metastasis. Despite the fact that traditional 2D cell culture systems have led to relevant medical advances in cancer research, 3D cell culture models could open new possibilities for the development of an in vitro tumor microenvironment more closely reproducing that observed in vivo. The implementation of materials science and technology into cancer research has enabled significant progress in the study of cancer progression and drug screening, through the development of polymeric scaffold-based 3D models closely recapitulating the physiopathological features of native tumor tissue. This article provides an overview of state-of-the-art in vitro tumor models with a particular focus on 3D OC cell culture in pre-clinical studies. The most representative OC models described in the literature are presented with a focus on hydrogel-based scaffolds, which guarantee soft tissue-like physical properties as well as a suitable 3D microenvironment for cell growth. Hydrogel-forming polymers of either natural or synthetic origin investigated in this context are described by highlighting their source of extraction, physical-chemical properties, and application for 3D ovarian cancer cell culture.     

Photopolymerization synthesis of poly(N-isopropylacrylamide) hydrogels

Poly(N-isopropylacrylamide) (NIPAAm) gels were formed by photopolymerization of NIPAAm in the absence of a crosslinker using a water solvent at 25°C. Factors affecting formation were the wavelength region of irradiated light, the type of photoinitiators, and the concentrations of the photoinitiator and monomer. A high-pressure mercury lamp (400 W) was used as a light source. An NIPAAm concentration of 10 wt % and irradiation time of 15 h was used for the photopolymerization. The gel (68% yield) was formed when the quartz glass system was used, but no gelation was observed for the Pyrex glass system that transmits light with π > 290 nm. The gel (100% yield) was easily formed, even in the latter system, when 30 mmol/L of hydrogen peroxide and potassium persulfate were used as the photoinitiator. Water soluble photoinitiators such as ferric chloride and sodium anthraquinone-2,7-disulfonate were not effective for the gel formation. Yield of the gel increased with increasing the potassium persulfate concentration (1–30 mmol/L), but it decreased when a high concentration of hydrogen peroxide (60 mmol/L) was used. The gel yield increased with the NIPAAm concentration (5–20 wt %). The degree of swelling of the resultant poly(NIPAAm) gels, which was measured by immersing the gels in water at various temperatures (0–50°C) for 24 h, steeply decreased at about 30°C with increasing temperature, exhibiting a temperature-responsive character. The gels swelled and shrank in water below and above the temperature, respectively. The extent of the character depended on the concentrations of hydrogen peroxide and monomer. The formation mechanism of the gel in the photopolymerization of NIPAAm using hydrogen peroxide photoinitiator was discussed. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 65:1313–1318, 1997     

Studies on preparation and swelling properties of the N-isopropylacrylamide/chitosan semi-IPN and IPN hydrogels

Semi-interpenetrating network (semi-IPN) polymer gels and interpenetrating network (IPN) polymer gels with thermosensitivity were prepared by introducing a biodegradable polymer, chitosan, into the N-isopropyacrylamide (PNIPAAm) gel system. The swelling behavior, temperature sensitivity, pH sensitivity, gel strength, and drug-release behavior of PNIPAAm/chitosan semi-IPN and IPN hydrogels were investigated. The results indicated that the NIPAAm/chitosan semi-IPN and IPN hydrogels exhibited pH and temperature-sensitivity behavior and could slow drug release and diffusion from the gels. From the stress–strain curves of the hydrogels, the compression moduli of IPN gels containing crosslinked chitosan were higher than those of semi-IPN gels. This is because IPN gels have a more compact structure. The morphology of PNIPAAm/chitosan hydrogels was also investigated. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 2487–2496, 2001     

涂料用高分子表面活性剂的研究

介绍了高分子表面活性剂的合成方法包括缩聚法、共聚法、高分子化学反应法和高分子表面活性剂的性质如表面张力、乳化性能、分散性能、絮凝性能、增溶性能等,并且阐述了高分子表面活性剂在石油工业、造纸工业、材料改性、日用化工、有机合成等方面的应用.