温敏水凝胶的新进展

从改变亲水／疏水单体比值、与离子单体共聚、改变水凝胶内部结构、调整凝胶溶胀剂四个方面介绍了合成具有不同临界相转变温度、温度响应速度及溶胀比的温敏水凝胶及此类凝胶在药物控释、分离萃取等方面的应用。     

含金刚烷基的N-异丙基丙烯酰胺共聚物水凝胶的制备和性能研究

合成了含金刚烷基的甲基丙烯酸金刚烷酯(AdMA)疏水单体,并通过与N-异丙基丙烯酰胺(NIPAM)共聚,制备了温敏性的(P(NIPAM-co-AdMA))共聚物水凝胶.用傅里叶变换红外光谱仪(FTIR)表征了凝胶的化学结构,用环境扫描电镜(ESEM)对凝胶断层结构的形貌进行了观察,用DSC测试了凝胶的体积相转变温度(LCST),并研究了共聚水凝胶的溶胀性能.结果表明,共聚物水凝胶的LCST能够高效地通过改变疏水单体的含量来调节,在实验所考察的范围内,LCST随AdMA含量的增加而线性降低;疏水单体的含量对凝胶的孔洞结构和溶胀性能存在一最优值,在最优的单体配比下,水凝胶具有均匀规整的大孔结构和超快的响应速率.如疏水单体含量为3%(AdMA∶NIPAM=3%)的共聚物水凝胶具有如渔网般均匀的多孔结构,当发生去溶胀时,在5min内就可以失去92%的水,不到10min的时间就可以完全达到去溶胀平衡,水保留率在4%以下.     

N-异丙基丙烯酰胺-丙烯酰胺热敏凝胶的溶胀特性

制备并表征了N-异丙基丙烯酰胺-丙烯酰胺热敏凝胶(NIPAm-Am),研究了单体配比、引发剂、交联剂用量和温度对其溶胀特性的影响。结果表明：NIPAm-Am热敏凝胶是由亲水和疏水基团组成的非晶高聚物。mAm／mNIPAm越大,凝胶的平衡溶胀率越大;增加交联剂的用量,凝胶的溶胀率减小,当引发剂的质量分数为0．008时溶胀率达最大值;温度的增加会使凝胶的溶胀率减小,在相转变温度时,溶胀率的变化最大。     

聚（N，N＇-二乙基丙烯酰胺）水凝胶的制备及其溶胀动力学

以N,N’-二乙基丙烯酰胺（DEA）为单体,偶氮二异丁腈（AIBN）为引发剂,分别采用疏水性的1,2-二乙烯苯（DVB）和水溶性的N,N’-亚甲基双丙烯酰胺（BIS）为交联剂制备了温度敏感水凝胶聚（N,N’-二乙基丙烯酰胺）（PDEA）。制得的PDEA水凝胶的低临界溶解温度（LCST）在30℃附近,初步讨论了交联剂的用量和性质对水凝胶性能的影响。并对其在不同温度下达到溶胀平衡时的溶胀比,去溶胀动力学及干凝胶的再溶胀动力学过程进行了研究。     

α,β-聚-DL-天冬酰胺衍生物水凝胶的合成及其溶胀性能研究

以ＤＬ 天冬氨酸为单体，通过缩合聚合反应合成聚 ＤＬ 丁二酰亚胺，然后用不同比例的乙醇胺和丁二胺进行开环和交联，获得α，β 聚 ＤＬ 天冬酰胺衍生物水凝胶．测定了水凝胶在几种不同溶液中的溶胀比，结果表明该水凝胶在蒸馏水中的溶胀比为１１０～４４０倍，在不同浓度的盐溶液中的溶胀比有不同程度的降低，在０１６ｍｏｌ／Ｌ的抗肿瘤药物５ 氟尿嘧啶（５ Ｆｕ）水溶液中的溶胀比可达１４０倍．研究了聚丁二酰亚胺分子量、溶剂用量及交联剂用量等因素对凝胶溶胀性能的影响．     

亲水/疏水半互穿网络凝胶对温度的响应

研究了一种亲水/疏水型半互穿网水凝胶（PAAc/QPVPD gels）对温度的刺激响应.在弱酸性或弱碱性（pH=7.5）溶液中,该凝胶的溶胀比在低温区（< 28 ℃）随温度的升高微微增大,约在28 ℃出现最大值,然后随温度升高而迅速减小,温度约为32.5 ℃时溶胀比趋于最低值.这主要是由于聚丙烯酸网络(PAAc)中氢键的解离与疏水改性聚电解质N-正十二烷基聚（4-乙烯吡啶）溴化盐(QPVPD)的疏水相互作用共同引起的.     

pH敏感性两亲聚合物网络PAA—l—PTHF的研究

以具有良好柔性和生物相容性的聚四氢呋喃（ＰＴＨＦ）为疏水链段,具有ｐＨ敏感性的聚丙烯酸（ＰＡＡ）为亲水链段,通过ＰＴＨＦ双端基大分子单体与丙烯酸自由基共聚,首次合成了聚丙烯酸－ｌ－聚四氢呋喃（ＰＡＡ－ｌ－ＰＴＨＦ）两亲聚合物网络,并对网络的结构、组成以及交联点密度进行了表征。两亲聚合物网络溶胀行为研究表明,ＰＡＡ－ｌ－ＰＴＨＦ既能在水中溶胀又能在有机溶剂中溶胀,在水中的溶胀度随网络亲水链段ＰＡＡ含     

P（DMAA-co—AM）水凝胶制备及其固定a-淀粉酶研究

采用氧化还原引发体系,水溶液聚合法制备P（DMAA-co-AM）水凝胶,并以其作为载体固定a-淀粉酶。采用单一变量法研究交联剂（N,N＇-亚甲基双丙烯酰胺）用量、引发剂（过硫酸铵）用量、单体浓度和单体配比对凝胶性能的影响。以水凝胶的最大平衡溶胀度为指标,得出制备P（DMAA-co-AM）水凝胶的优化条件：交联剂用量为0．3％,引发剂用量为0．6％,单体浓度为20％,N,N’-二甲基丙烯酰胺与丙烯酰胺的摩尔比为2：1。在优化条件下,采用原位聚合法固定a-淀粉酶,测定不同单体配比的P（DMAA-co-AM）水凝胶固定化a-淀粉酶的活性。     

高机械性能的聚(丙烯酸-co-甲基丙烯酸十八酯)疏水缔合凝胶的溶胀行为研究

以丙烯酸(AA)、甲基丙烯酸十八酯(OMA)、十二烷基硫酸钠(SDS)为原料,采用胶束共聚的方法合成了疏水缔合(HA)凝胶.在HA凝胶内部,表面活性剂SDS与疏水单体OMA组成的增溶胶束起到物理交联作用,将亲水的聚合物链交联起来.通过单向拉伸试验证实了该凝胶具有较高的机械性能.此外,也测试了HA凝胶在不同pH值溶液中的溶胀行为.结果显示,HA凝胶具有特殊的溶胀行为,其溶胀过程可以分为凝胶溶蚀、溶胀平衡和凝胶瓦解3个阶段.在强酸性条件下,凝胶的溶胀被抑制,没有出现凝胶瓦解阶段.在强碱性条件下,凝胶的溶胀被促进,溶胀平衡阶段被越过.盐的存在也会抑制HA凝胶的溶胀,但在SDS溶液中,溶液中的SDS会促使凝胶中的疏水改性聚合物溶解到溶液中去,组成新的缔合结构,而使溶液增稠。     

侧链含不同功能性羟基的温敏性N-异丙基丙烯酰胺共聚物微凝胶的制备及性能比较

选择含有活性羟基的亲水单体多缩乙二醇单甲基丙烯酸酯(PEGMA)、甲基丙烯酸羟乙酯(HEMA),分别和N-异丙基丙烯酰胺(NIPAM)交联共聚,制备了侧链含有功能性羟基、链长不同的温敏性微凝胶.研究发现,亲水单体HEMA和PEGMA的引入对微凝胶的去溶胀性能有不同的影响,PEGMA的引入使得微凝胶的体积相转变温度升高,微凝胶的去溶胀比随着PEGMA投料比的增加而降低.而HEMA的引入使得微凝胶的体积相转变温度降低;微凝胶的去溶胀比随着HEMA投料比的增加先是增加然后降低,当HEMA的投料比为8mol%时,去溶胀比达到最大.     

Synthesis and characterization of thermoresponsive poly(<Emphasis Type="Italic">N</Emphasis>-isopropylacrylamide-co-<Emphasis Type="Italic">N</Emphasis>-hydroxymethylacrylamide-co-2-hydroxyethyl methacrylate) hydrogels

Thermoresponsive hydrogels based on N-isopropylacrylamide, N-hydroxymethylacrylamide, and 2-hydroxyethyl methacrylate, poly(NIPAM–co-NHMAAm–co-HEMA), have been synthesized and their swelling—deswelling behavior studied as a function of NIPAM concentration, NIPAM/NHMAAm and NIPAM/HEMA mole ratio, and total monomer concentration. Copolymers varying in composition have been obtained by redox copolymerization of these three monomers. Temperature has been changed in the ranges from 4 to 70 °C at fixed pH and total ionic strength. Equilibrium swelling ratio, dynamic swelling ratio, and dynamic deswelling ratio were evaluated for all hydrogel systems. The equilibrium swelling ratios of the copolymeric gels decrease with increasing NHMAAm and HEMA content. The formation of the intermolecular hydrogen bonding between hydroxyl and amido groups decreases the hydrophilic group numbers of the gel and the affinity of the gel towards water decreases. The copolymer gels also showed rapid volume transitions with time. The time required for equilibrium shrinking increased with increasing NHMAAm and HEMA content in the gel.     

THERMAL-SENSITIVE BETA-CYCLODEXTRIN-CONTAINED POLY(N-ISOPROPYLACRYLAMIDE) HYDROGELS CROSS-LINKED BY Si―O―Si BONDS

A series of novel p（N-isopropylacrylamide） （PNIPAM） hydrogels were synthesized by radical copolymerization of N-isopropylacrylamide （NIPAM） and 3-methacryloxypropyltrimethoxysilane （MPTMS）. The copolymers were then crosslinked through hydrolysis of the siloxane in acetic acid/water mixed solvent. Beta-cyclodextrin （Beta-CD） was introduced into the polymeric networks by condensation of 3-glycidoxypropyltrimethoxysilane derived beta-cyclodextrin （KH560-beta-CD） with MPTMS under acidic condition. These gels were heterogeneous, porous and exhibited fast deswelling kinetics when the temperature was elevated to above lower critical solution temperature （LCST）. The swelling ratios of the gels containing beta-CD at room temperature were higher than that of the normal PNIPAM hydrogel, which was caused by the lower crosslinking density in beta-CD contained gels. In comparison to that of the normal PNIPAM gel, the amount of loaded-drug in the hydrogel containing beta-CD was higher, and the release time of 5-fluorouracil （5-Fu） was prolonged, which was attributed to the formation of inclusion compounds between 5-Fu and beta-CD in gel network.     

THERMAL-SENSITIVE BETA-CYCLODEXTRIN-CONTAINING POLY(N-ISOPROPYLACRYLAMIDE) HYDROGELS CROSSLINKED BY Si-O-Si BONDS -SYNTHESIS, CHARACTERIZATION AND PROLONGING IN VITRO RELEASE OF 5-FLUOROURACIL

A series of novel p(N-isopropylacrylamide) (PNIPAM) hydrogels were synthesized by radical copolymerization of N-isopropylacrylamide (NIPAM) and 3-methacryloxypropyltrimethoxysilane (MPTMS). The copolymers were then crosslinked through hydrolysis of the siloxane in acetic acid/water mixed solvent. Beta-cyclodextrin (Beta-CD) was introduced into the polymeric networks by condensation of 3-glycidoxypropyltrimethoxysilane derived beta-cyclodextrin (KH560-beta-CD) with MPTMS under acidic condition. These gels were heterogeneous, porous and exhibited fast deswelling kinetics when the temperature was elevated to above lower critical solution temperature (LCST). The swelling ratios of the gels containing beta-CD at room temperature were higher than that of the normal PNIPAM hydrogel, which was caused by the lower crosslinking density in beta-CD contained gels. In comparison to that of the normal PNIPAM gel, the amount of loaded-drug in the hydrogel containing beta-CD was higher, and the release time of 5-fluorouracil (5-Fu) was prolonged, which was attributed to the formation of inclusion compounds between 5-Fu and beta-CD in gel network.     

PAMPS/SiO_2杂化水凝胶的合成及电场敏感性研究

以2-丙烯酰胺-2-甲基丙磺酸(AMPS)为有机原料,正硅酸乙酯(TEOS)为无机原料,过硫酸钾为引发剂,N,N'-亚甲基双丙烯酰胺为交联剂,通过原位-凝胶水溶液聚合法合成了一系列不同二氧化硅含量和不同聚离子浓度的聚(2-丙烯酰胺-2-甲基丙磺酸)/二氧化硅杂化电场敏感性水凝胶.通过扫描电子显微镜(SEM)表征凝胶的结构,研究水凝胶在去离子水以及氯化钠溶液中的溶胀和消溶胀行为.结果表明,系列凝胶的平衡溶胀度介于224.9至325.6之间,复合凝胶的溶胀速率随TEOS用量的增加而降低;除理想杂化凝胶外,随着聚离子浓度的升高,凝胶在氯化钠溶液中的消溶胀速率逐渐减小.对凝胶的电场敏感性研究表明,当聚离子浓度大于氯化钠溶液浓度时,凝胶进一步溶胀,反之则消溶胀,其中杂化凝胶的再溶胀性能减弱,而消溶胀行为变得更为明显.同时制得的理想杂化凝胶,较纯有机凝胶具有更为理想的力学性能,最大抗压缩强度可达23.4 MPa.     

Synthesis and characterization of thermally reversible macroporous poly(N-isopropylacrylamide) hydrogels

Macroporous hydrogels are characterized by large pore sizes, high pore volumes, and high specific surface area. Besides these characteristics, macroporous hydrogels based on thermally reversible polymers respond to temperature changes much faster than hydrogels prepared by a conventional method. Crosslinked poly(N-isopropylacrylamide) (polyNIPAAm) forms a thermally reversible hydrogel which shows a lower critical solution temperature (LCST) ca. 33°C in aqueous solutions. We have synthesized thermally reversible polyNIPAAm hydrogels having macroporous structures by a new method. These macroporous hydrogels have large pore volumes, large average pore sizes, and faster macromolecule permeation rates in comparison to conventional polyNIPAAm hydrogels synthesized by a conventional method. Compared with conventional polyNIPAAm hydrogels, the macroporous polyNIPAAm hydrogels have higher swelling ratios at temperatures below the LCST and exhibit faster deswelling and reswelling rates. The deswelling rates are especially rapid. These thermally reversible macroporous hydrogels may be very useful in controlled active agent delivery and toxin removal, as well as dewatering of solutions. Peptides or proteins may behave as if they were in bulk solution within the large aqueous pores, and this may reduce their inactivation when such gels are used for their storage and later release. The gels may also be useful in microrobotic devices due to their fast response to temperature. © 1992 John Wiley & Sons, Inc.     

The influence of cold treatment on properties of temperature-sensitive poly(N-isopropylacrylamide) hydrogels

Poly(N-isopropylacrylamide) (PNIPAAm) hydrogel exhibits a response to external temperature variation and shrinks in volume abruptly as the temperature is increased above its lower critical solution temperature. It has great potential applications in biomedical fields. A rapid response rate is essential, especially when this material is designed as an on-off switch for targeted drug delivery. However, due to the appearance of a thick, dense skin layer on the hydrogel surface during the shrinking process, the deswelling rate of conventional PNIPAAm gels is low. In this article, a novel method is proposed to modify the surface morphology of PNIPAAm gel, in which the swollen gels are frozen at low temperature (-20 degrees C). The scanning electron micrographs revealed that a fishnet-like skin layer appeared on the surfaces of the cold-treated gels. Dramatically rapid deswelling was achieved with the cold-treated gels since the fishnet-like structure with numerous small pores prevented the formation of a dense, thick skin layer during the deswelling process, which commonly occurs in normal PNIPAAm hydrogels. Prolonging the cold treatment from 1 day to 10 days resulted in a slightly higher deswelling rate. Rearrangement of the hydrogel matrix structure during the freezing process might contribute to the formation of the fishnet-like skin layer. The water uptake of the hydrogels increased nearly in proportion to the square root of time, indicating that the reswelling rate of hydrogels was controlled predominantly by water diffusion into the network. However, there were no significant differences in the equilibrated swelling ratio and reswelling kinetics at room temperature (22 degrees C) between normal gels and cold-treated gels, which implied that cold treatment did not change bulk porosity and gel tortuosity much.     

Chemically Crosslinked pH- and Temperature-Sensitive (N-isopropylacrylamide-co-1-vinyl-2-pyrrolidone) Based on New Crosslinker: I. Swelling Behavior

Novel pH- and temperature-sensitive polymer matrices based on N-isopropylacrylamide have been developed. The hydrogels were prepared by bulk radical polymerization of N-isopropylacrylamide and 1-vinyl-2-pyrrolidinone in appropriate amounts of distilled water using different mol% of traditional N,N-methylene bisacrylamide (MBA) and the new synthesized N,N,N-tris acryloyl melamine (MAAm) crosslinkers. Lower critical solution transition temperatures (LCST) were measured by differential scanning calorimetry. The synthesized hydrogels have LCST lower than 40°C. The influence of environmental conditions such as temperature and pH on the swelling behavior of these polymeric gels was investigated. The swelling behaviors of the resulting gels show pH sensitivity. The crosslinked NIPAAm/VP with MAAm hydrogels exhibited more rapid deswelling rate than NIPAAm/VP hydrogels crosslinked with MBA in pure water in response to abrupt temperature changes from 20°C to 50°C.     

NIPAM共聚物多孔水凝胶的光引发RAFT合成及其溶胀性能

采用光引发可逆加成-断裂链转移(RAFT)方法,在室温下先合成了链端含有三硫代碳酸酯基的大分子链转移剂聚(N,N'-二甲基丙烯酰胺)(PDMAM),然后与N-异丙基丙烯酰胺(NIPAM)、N,N'-二甲基双丙烯酰胺(BIS)交联共聚合,并通过聚乙二醇的制孔作用制得PNIPAM-g-PDMAM梳型/多孔水凝胶.采用FTI...     

Poly(N-isopropylacrylamide) nanocrosslinked by polyhedral oligomeric silsesquioxane: temperature-responsive behavior of hydrogels

Octa(propylglycidyl ether) polyhedral oligomeric silsesquioxane (OpePOSS) was used as a nanocrosslinking agent to prepare the crosslinked poly(N-isopropylacrylamide) (PNIPAM) networks with POSS content up to 50 wt%. The inter-component crosslinking was achieved via the reaction between NH moieties in amide group of PNIPAM and epoxide groups of OpePOSS. When the organic-inorganic nanocomposites were swollen in water the POSS-crosslinked PNIPAM exhibited the characteristics of hydrogels. With the moderate contents of POSS, the POSS-containing hybrid hydrogels displayed much faster response rates in swelling, deswelling and reswelling experiments than the PNIPAM hydrogels prepared via the free radical copolymerization of N-isopropylacrylamide (NIPAM) and N,N(')-methylenebisacrylamide (viz. the conventional crosslinker). The improved hydrogel properties have been interpreted on the basis of the formation of the nanosized hydrophobic microdomains around the POSS moieties (i.e., the nanocrosslinking sites).