粒状温敏性水凝胶的溶胀行为

研究了具有温敏性的PNIPA粒状水凝胶在不同水溶液中的溶胀过程。考察了水溶液的离子强度、pH值、温度以及凝胶组成等因素对水凝胶溶胀速率和倍率的影响。研究发现,粒状PNIPA水凝胶粒子的溶胀很快,在1到2分钟内就能达到溶胀平衡。温度和凝胶的交联度是影响溶胀速率的主要因素。由于溶质改变了网络的亲水性或离子基团的作用强度,使得凝胶的溶胀速率和倍率也相应发生变化。     

新型pH敏感性壳聚糖/明胶水凝胶的制备及其性能

用天然多糖壳聚糖和明胶制备了具有pH敏感性的壳聚糖/明胶水凝胶,研究了pH值对于该凝胶溶胀度的影响,采用红外光谱和电镜扫描对其结构进行了表征。结果表明,水凝胶在碱性和酸性环境中均具有pH敏感性,在酸性溶液中凝胶的溶胀比远大于碱性溶液中的溶胀比,其在pH值3.0时的溶胀度最大,在pH值9.0时的溶胀度最小,且其在不同pH 溶液中重复可逆溶胀收缩。同时,随着交联剂用量的增大,水凝胶的溶胀度减小。     

明胶文摘

<正>果胶一明胶原位交联水凝胶的制备与特征Bhuvanesh G, et al.Carbohydrate Polymers 2014,106:312～318.交联水凝胶是由高碘酸盐氧化果胶(OP)和明胶原位反应制得的。反应通过OP的醇基与明胶的氨基集形成希夫碱而进行。本文对不同的反应参数例如反应时间、反应温度、反应pH值以及构成成分对交联效能的影响进行了研究。通过场发射电子扫描显微镜(FESEM)观察发现在OP和明胶交联反应后,制成了均匀的单相系统。对水凝胶的溶胀性进行了研究并发现平衡溶胀随着明胶含量不同(10%～40%)在195%～324%范围内变     

HPMC水凝胶溶胀性能的影响因素研究

制备了一系列具有不同相对分子质量和取代度的羟丙基甲基纤维素(HPMC)水凝胶,并用称重的方法对凝胶的溶胀性能进行了研究,考察了温度、pH值、溶剂类型、取代度和相对分子质量对HPMC水凝胶溶胀性能的影响。结果显示,HPMC水凝胶的平衡溶胀度随温度的升高而减小;其溶胀行为受溶剂影响显著,而受溶液pH值的影响不明显;而取代度和相对分子质量都对凝胶溶胀行为有较大的影响。     

温度及pH敏感生物水凝胶的研究

运用互穿网络技术,合成了具有温敏性的聚(N 异丙基丙烯酰胺)(PNIPAm)和生物大分子明胶(gelatin)的互穿网络聚合物(PNIPAm/Gelatinsemi IPN和PNIPAm/GelatinIPN)水凝胶,该水凝胶的最低临界溶液温度(LCST)与PNIPAm水凝胶的LCST基本相同,均为33℃左右,但在LCST以下的平衡溶胀率减小、相变区域略微变宽。在此基础上,通过N 异丙基丙烯酰胺(NIPAm)与丙烯酸(AAc)交联共聚,改变了水凝胶的LCST,在pH=4 0的缓冲溶液中,各水凝胶的溶胀行为基本一致,与AAc含量无关,LCST都为28℃左右;在pH>4 0的缓冲溶液中,LCST随AAc组分含量的增加而增加,但温敏性减小。同时,AAc的加入,使水凝胶具有pH敏感性,敏感点为pH=4 5左右。还考察了该水凝胶降解的特点:戊二醛(GA)交联后的明胶网络,保留了明胶的生物降解性,但互穿网络水凝胶在实验条件下几乎未被胃蛋白酶和胰蛋白酶降解,在pH=9 6的碱性条件下,水凝胶可发生化学降解。     

P（MA—AA）／PEG水凝胶的制备与性能研究

合成了马来酸酐-丙烯酸共聚物,并与长链分子聚乙二醇交联反应制备了马来酸酐-丙烯酸共聚物／聚乙二醇水凝胶。通过红外光谱对聚合物、水凝胶结构进行了表征,测试了不同pH值下水凝胶的溶胀度以及水凝胶在酸碱条件发生变化时的溶胀速率。研究结果表明,马来酸酐-丙烯酸共聚物／聚乙二醇水凝胶具有较强的吸水溶胀能力,并且对pH值极为敏感：交联剂含量7％的凝胶在pH=10时SR=62657％、pH=2时SR=825％,酸碱条件下具有近百倍的溶胀度变化;并且在pH发生变化时P（MA-AA）／PEG凝胶具有快速的响应速率：由pH=2溶液中转移至pH=10溶液中20min即可溶胀完全,而由pH=10溶液中转移至pH=2溶液中10min即可完全收缩。     

温度及pH敏感共聚/粘土纳米复合水凝胶的合成与性能研究

以无机粘土为交联剂制备了具有温度、pH双重敏感性的聚（N-异丙基丙烯酰胺-co-甲基丙烯酸-β-羟乙酯）/粘土纳米复合水凝胶（P（NIPA-co-HEMA）/clay）,并用红外和X衍射对其结构和形态进行了表征。在弱碱性（pH=7.4）和25℃条件下,分别研究了温度和不同pH缓冲溶液对该凝胶溶胀度的影响,测定了纳米复合水凝胶的力学性能。结果表明：水凝胶的粘土已被剥离成单片层,且均匀分散在凝胶网络中,起交联作用;P（NIPA-co-HEMA）/clay具有良好的温度、pH双重敏感特性;凝胶的断裂伸长率〉1000%。     

富间规立构聚乙烯醇水凝胶的应用

用pH值为4.0、7.4和9.0的缓冲溶液（BS）在0℃制备了3种物理交联的富间规立构的聚乙烯醇（s-PVA）水凝胶。将这些凝胶浸入到温度高于0 ℃的相同BS中，这些凝胶先是溶胀后，再开始收缩12小时，分别在27℃，37℃和47℃以亮蓝从圆柱状凝胶中的释出进行了研究，该凝胶是用pH率承温度上升而加快。亮蓝释出的主要因素不在于凝胶的收缩，而在于溶胀，因为溶胀度（DS）随温度从27℃、37℃、47℃的上升而变大。从凝胶（pH=4.0)中释出的速率大于从pH为7.4的凝胶中的释出速率，这是因为早在pH为4.0时水凝胶的DS就已经增大了，在pH为7.4时从最初的60%的分级释出所求得的这些释出的表观扩散指数不大于0.45，这是因为在释出期间有了溶胀，pH为4.0时的指数为0.45，是因为即刻产生了溶胀，在不同的温度下对无规立构PVA(α-PVA)水凝胶断-续的收缩行为进行了观察。在5℃时亮蓝的释出速率低于在27℃的情况，在5℃时经过一次断-续循环后看不出有什么变化。     

PVA/明胶/淀粉水凝胶的制备及性能

采用反复冷冻一解冻法制备了不同配比的聚乙烯醇／明胶／淀粉水凝胶膜。测试了共混膜的力学性能、脱水率和溶胀度，用扫描电镜观察了共混膜的断面形貌。结果表明：除1：1配比的水凝胶膜成膜性差，其他配比的水凝胶成膜性较好，膜表面比较光滑。m（PVA）：m（明胶）为6：1时力学性能较好。脱水率和溶胀度均随PVA和明胶比例增大而减小。扫描电镜显示，水凝胶膜内部具有多孑L结构，可以用作组织工程支架材料。     

AM与HEMA共聚制备水凝胶接触镜材料及其溶胀性能

采用丙烯酰胺(AM)与甲基丙烯酸β-羟乙酯(HEMA)进行本体共聚制备水凝胶接触镜材料,研究了水凝胶的溶胀性能及其温度和pH值敏感性。结果表明,引发剂过氧化苯甲酰(BPO)用量为反应单体总质量的0.3%、反应温度80℃,产物溶胀之后为无色透明的玻璃状水凝胶;共聚物水凝胶具有较好的pH值敏感性,水凝胶在酸性溶液中溶胀,在碱性溶液中收缩:含有AM的水凝胶,其pH值敏感性较大:随AM的含量增大,共聚物水凝胶的溶胀速度和饱和含水量增大,随温度升高,水凝胶的饱和含水量下降,共聚物水凝胶中AM的含量对其温度敏感性无显著影响:SEM照片显示,AM与HEMA共聚物存在均匀的纤维状结构,并且共聚物中AM的含量越大,这种纤维状结构越大、越明显。     

Synthesis and characterization of pH- and/or temperature-sensitive hydrogels

A series of pH-sensitive hydrogels that exhibit volume phase transition phenomena have been synthesized in aqueous solution and characterized with respect to their dynamic swelling behaviors. Positively charged hydrogels were prepared by copolymerizing varying ratios of N-isopropylacrylamide and NN′-dimethylaminopropylmethacrylamide. The hydrogels based on a temperature-sensitive hydrogel demonstrate a large change of equilibrium swelling in response to small variations of pH and/or temperature. These hydrogels exhibit different lower critical solution temperature (LCST) ranges depending on the environmental pH values. Below their LCST, they exhibit small and broad pH sensitivities normally observed in most hydrophilic polyelectrolyte gels, but above their LCST, they exhibit sharp pH dependent phase transition behaviors. The pH-dependent phase transition is strongly affected by temperature, while the temperature-dependent transition is, in turn, largely influenced by the pH. As the temperature is raised, the transitional degree of gel swelling change becomes sharper and larger, and the phase transition pH value shifts to a lower pH. It was also found that swelling is faster than deswelling for these cationic hydrogels, which suggests the existence of a water diffusion barrier during the deswelling. The swelling kinetics of initially dry and glassy gels were strongly dependent on both the pH value and temperature.     

Biodegradable stimuli‐responsive hydrogels based on amphiphilic polyaspartamides with tertiary amine pendent groups

Novel thermo‐ and pH‐responsive hydrogels based on amphiphilic polyaspartamides possessing a lower critical solution temperature (LCST) and a volume‐phase transition were prepared and characterized. The polyaspartamide derivatives were synthesized from polysuccinimide, which is the polycondensate of L ‐aspartic acid monomer, through successive ring‐opening reactions using hydrophobic 2‐diisopropylaminoethylamine and hydrophilic ethanolamine. The amphiphilic copolymer was then crosslinked with hexamethylene diisocyanate to afford the corresponding gel. The LCST of the copolymer in an aqueous solution was varied by changing both the graft composition and pH of the medium. The crosslinked gels showed stimuli‐responsive behavior, with their degree of swelling and porous structure morphology changing with temperature and pH. In addition, hydrolytic degradation depending on the crosslinking density of the hydrogel was examined. Copyright © 2009 Society of Chemical Industry     

交联三维网络结构PINPAm的制备及其性能研究

聚N-异丙基丙烯酰胺(PINPAm)水凝胶是一种亲水但不溶于水,具有交联三维网络结构的高分子聚合物,具有一定条件下的溶胀/退溶胀行为,同时具有输送和渗透性、能量转换、吸附分离、生物相容性等功能。本文研究了用不同量的引发剂过硫酸铵(APS)对水凝胶形成的影响;反应温度分别为低温(低于5℃、20℃、30℃、40℃对水凝胶形成的影响。所制备的PNIPAm水凝胶分别测定了相转变温度(LCST)和凝胶溶胀率(SR)。结果表明引发剂量用量增多时水凝胶形成反应时间变短;反应温度升高水凝胶外观出现由无色透明凝胶→乳白半透明凝胶→乳白色凝胶→乳白色且无固定形态凝胶的变化。低温生成的水凝胶相转变温度(LCST)在33~34℃之间,水凝胶体积发生不连续收缩现象;交联剂N,N-亚甲基双丙烯酞胺(BIS)使用量越多溶胀率越小。     

Swelling and mechanical behavior of poly(N-isopropylacrylamide)/Na-montmorillonite layered silicates composite gels

Clay-polymer hydrogel composites have been synthesized based on poly(N-isopropylacrylamide) (PNIPAM) gels containing 0.25-4 wt% of the expandable smectic clay Na-montmorillonite layered silicates (Na-MLS). The morphology of the composite gels has been studied using a polarized optical microscope. The size of Na-MLS aggregates increases with Na-MLS concentration. The swelling ratio of the Na-MLS/PNIPAM composite in water is increased at the low Na-MLS concentration but decreases as the concentration increases. Correspondingly, the shear modulus of the gel is found to exhibit a distinct minimum against clay concentration. For Na-MLS concentrations ranging from 2.0 to 3.2 wt%, the composite gels have larger swelling ratio and stronger mechanical strength than those for a pure PNIPAM. The presence of Na-MLS does not affect the value of the lower critical solution temperature (LCST) of the PNIPAM. However, the gel volume change at the LCST is first increased and then decreased upon the increase of the Na-MLS. No pH induced phase transition is observed for the Na-MLS/PNIPAM composites. The experimental results can be explained by considering that Na-MLS is physically entrapped inside rather than chemically bonded into the gel.     

温敏性萃取水凝胶对生物大分子的分离

合成了均聚的聚N 异丙基丙烯酰胺(PNIPAM)水凝胶以及N 异丙基丙烯酰胺与丙烯酰胺共聚的〔P(NIPAM-AM)〕水凝胶,并研究了它们的溶胀性能及其对生物大分子的萃取分离性能。结果表明,两种温敏凝胶具有很好的溶胀性能,其低临界共溶温度(LCST)分别为30 4和31 0℃,它们对蛋白质和酶的分离效率在LCST附近发生突跃,如PNIPAM水凝胶对白蛋白的分离效率在LCST前后从96 2%降至59 8%。当交联剂N,N 次甲基双丙烯酰胺(Bis)的质量分数w(Bis)>4%时,分离效率大于90%(LCST以下)。     

Independent control of lower critical solution temperature and swelling behavior with pH for poly(N‐isopropylacrylamide‐co‐maleic acid)

Polymer solutions that gel in response to changes in temperature and pH are of interest for various forms of drug delivery, and it is desirable to increase swelling for diffusion‐controlled release without bringing the lower critical solution temperature (LCST) above 37°C. N‐isopropylacrylamide (NIP) was polymerized with maleic acid (MAc), a diprotic acid, and acrylic acid (AAc), a monoprotic acid, to compare swelling and temperature response with changes in pH. For samples with equal acid contents and almost identical LCST responses to pH, poly(N‐isopropylacrylamide‐co‐maleic acid) (pNIP MAc) demonstrated greater swelling than poly(N‐isopropylacrylamide‐co‐acrylic acid) (pNIP AAc). The LCST increase for MAc occurred at a pH corresponding to the deprotonation of almost all of the first acid groups. Further increases in pH led to the deprotonation of the second ? COOH and only served to increase the charge concentration at a given location. These results provide strong support for the theory that LCST results largely from uninterrupted chain lengths of NIP and that swelling results from the actual charge density of acid groups along the chain. Because the use of a diprotic acid copolymer allows swelling to be decoupled from LCST, pNIP MAc may be an appropriate candidate for pH‐sensitive drug‐delivery applications. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 2110–2116, 2004     

Swelling behavior of pH‐ and temperature‐sensitive copolymers containing 2‐hydroxy‐ethyl methacrylate and N‐vinyl‐2‐pyrrolidone crosslinked with new crosslinkers

Copolymers of 2‐hydroxyethyl methacrylate (HEMA) and N‐vinyl‐2‐pyrrolidone (VP) and homopolymers of HEMA and VP were crosslinked in the presence of different mol% of melamine trimethacrylamide (MMAm) and melamine triacrylamide (MAAm) as crosslinkers by bulk radical polymerization. The resultant xerogels were characterized by extracting the soluble fractions and measuring the equilibrium water content. Lower critical solution transition temperatures (LCST) were measured by DSC. The properties of crosslinked HEMA and VP copolymers, VP and HEMA series were evaluated in terms of compositional drift of polymerization, heterogeneous crosslinking, and chemical structure of the relevant components. Soluble fractions of the crosslinked networks were reduced by varying the MAAm and MMAm concentrations. 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. This behavior is explained on the basis that amide groups of VP or crosslinkers could be hydrolyzed to form negatively charged carboxylate ion groups in the produced networks in response to an external pH variation. Copyright © 2004 Society of Chemical Industry     

Uses of electron‐beam irradiation to prepare pH‐ and temperature‐sensitive hydrogels from reactive poly(vinyl alcohol) grafts

Thermosensitive poly(vinyl alcohol)‐graft‐(maleic anhydride), PVA‐MA, and poly(vinyl alcohol)‐graft‐(N‐isopropylacrylamide maleic anhydride) (PVA‐MA‐NIPAAm) copolymers containing carboxyl groups were prepared using electron beam irradiation at dose 80 kGy. The swelling ratios of the cross‐linked gels were measured at various temperatures. The LCST values were measured using DSC technique. The temperature dependence of the swelling ratios of the cross‐linked copolymers and terpolymers were measured at different temperatures. The swelling ratios of copolymers increased with increasing temperature up to 25–38°C, then decreased. The swelling behavior of both copolymers and terpolymers was referred to formation of hydrogen bonds between amide group of NIPAAm moieties and carboxyl group in MA moieties and to hydrophobic interaction due to methyl groups of NIPAAm. The swelling behaviors of these gels were analyzed in buffer solution at various pH. Swelling ratios of all gels were relatively high and they showed reasonable sensitive to pH. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

具有pH及温度敏感性的共聚物Poly(NIPAm-co-IA)水凝胶的合成及其性能研究

用自由基聚合合成了具有两水亲性的异丙基丙烯酰胺与衣康酸共聚物 ,对它们水溶液及其水凝胶的 p H及温敏性进行了研究。结果表明 ,在一定的范围内 ,随衣康酸含量增加、水溶液浓度减少和 p H值增大 ,共聚物水溶液的低临界溶解温度随之升高。共聚物水凝胶的溶胀率随温度升高呈下降趋势 ,并且 p H值低时的溶胀率随温度的升高而下降的趋势比 p H高时的要快 ,而且表现出明显的溶胀 -退胀可逆过程。     

Preparation and characterization of thermo‐sensitive poly(vinyl alcohol)‐based hydrogel as drug carrier

Poly(vinyl alcohol)s (PVA) with high and low molecular weights were chemically modified by introducing acetaldehyde onto the polymer backbone to induce thermal‐responsive properties. The influence of both molecular weight ( ) and acetalization degree on the lower critical solution temperature (LCST) of thermo‐sensitive polymer was investigated. Moreover, a temperature responsive hydrogel was prepared by controlled cross‐linking of acetalized poly(vinyl alcohol) (APVA) and glutaraldehyde. As a model drug, ciprofloxacin was introduced into the prepared thermal sensitive hydrogel to reveal the drug loading and release behaviors. The structure, thermo‐sensitivity, swelling/deswelling kinetics, morphology, and drug loading/release behaviors were also investigated. The results indicated that the APVA polymer solution exhibited temperature responsivity, and APVA with high acetalization degree showed low LCST, whereas those with high PVAs showed high LCST. Meanwhile, morphology study was identical with the swelling/de‐swelling behavior. The loading and release of ciprofloxacin were controllable. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39720.