几类甲基丙烯酸pH—敏感水凝胶的溶胀行为研究

本文合成了以甲基丙烯酸为基础的各类ｐＨ敏感型水凝胶,并研究它们的溶胀行为。初步探索了水凝胶的组成与其ｐＨ敏感的关系,比较了阴离子型水凝胶、阳离子型水凝胶和两性水凝胶的溶胀热力学动力学行为,得出了两性水凝胶在整个ｐＨ范围内都有一定的溶胀比,且在ｐＨ中性时,其溶胀速率要高于相应的阴离子型和阳离子型水凝胶。     

pH敏感水凝胶聚甲基丙烯酸的超声合成

在超声作用下,以甲基丙烯酸为原料,N,N’-亚甲基双丙烯酰胺为交联剂,过硫酸钾为引发剂,自由基引发聚合制备了pH敏感水凝胶聚甲基丙烯酸,采用红外光谱(FT-IR)和扫描电镜(SEM)对水凝胶分子结构与性能进行表征.在此基础上,重点研究了超声合成对于水凝胶的溶胀性能、消溶胀性能等性质的影响.实验结果表明,超声作用下合成的聚甲基丙烯酸水凝胶溶胀动力学性能以及响应灵敏性均优于常规合成方法.     

甲基丙烯酸烷基酯为疏水成分的溶剂改性pH-敏感凝胶的溶胀行为

以不同酯烷基链长的甲基丙烯酸烷基酯为疏水成分，甲基丙烯酸二乙氨基乙酯(DEA)为可离子化单体，及以二甲基丙烯酸乙二醇酯(EGDM)或二乙烯苯(DVB)为交联剂，合成了数个系列甲苯改性的不同交联度的疏水阳离子凝胶，研究了这些凝胶以pH-敏感溶胀为主的容胀行为．发现以甲基丙烯酸正丁酶(BMA)，EGDM及DEA合成的改性凝胶，与以苯乙烯(St)，DVB及DEA合成的溶剂改性凝胶具有十分相似的平衡溶胀和动力学溶胀性质．研究结果为增加疏水阳离子凝胶的载药种类，拓宽由pH改变而触发释药的控释体系的应用范围提供了新的途径．     

快速pH响应丝胶/聚甲基丙烯酸互穿网络水凝胶的合成及表征

采用同步互穿网络方法制备丝胶蛋白(SS)/聚甲基丙烯酸(PMAA)为组分的互穿网络(IPN)水凝胶. 研究了互穿网络水凝胶对介质pH的刺激响应性能. 结果表明, IPN水凝胶具有强烈的pH刺激响应性能. 在pH=9.2的缓冲溶液中, -COOH解离成 -COO^-, 渗透压与网络之间的静电排斥作用导致IPN的溶胀度增大; 当pH减小时, 溶胀度随之减小. IPN水凝胶具有快速退溶胀速率及可逆溶胀-收缩性能.     

pH敏感阳离子聚电解质凝胶的溶胀和释药性能

共聚物;pH敏感阳离子聚电解质凝胶的溶胀和释药性能     

聚甲基丙烯酸纳米水凝胶的水相合成及其磁性功能化

利用十二烷基硫酸钠/吐温20复配表面活性剂和原位生成的聚甲基丙烯酸甲酯(PMMA)种子乳胶,发展了一种可在全水相中"绿色"合成较高浓度的聚甲基丙烯酸(PMAA)纳米水凝胶的新方法.以PMAA纳米水凝胶为前驱体,采用原位氧化沉淀法制备了磁性PMAA纳米微球.利用动态光散射法、FTIR分析、TEM观察、振动样品磁强计测试(VSM)、热重分析(TG)等对纳米水凝胶和磁性微球进行了表征,并探讨了PMAA纳米水凝胶的形成机理.结果表明,吐温20与MAA和PMAA间的氢键作用,促成了交联PMAA/吐温20复合物层在PMMA种子乳胶表面的选择性生长,导致生成了具有核壳结构的PMAA纳米水凝胶.PMAA纳米水凝胶表现出良好的p H响应性,当介质的p H值由1增加至6时,其流体力学体积扩张了近50倍.磁性PMAA纳米微球具有超顺磁性,其饱和磁化强度高达50 A·m~2/kg.     

聚甲基丙烯酸基纳米水凝胶的“绿色”合成

利用原位生成的聚甲基丙烯酸甲酯种子乳胶模板以及表面活性剂与功能单体间的正负电荷作用,发展了一种可在全水相中“绿色”合成聚甲基丙烯酸(PMAA)基纳米水凝胶的新方法.利用动态光散射法、ξ-电位测定、FTIR和TEM对纳米水凝胶的尺寸及其分布、表面电荷、组成、形态、结构和pH响应行为进行了表征.结果表明,PMAA基纳米水凝胶具有聚甲基丙烯酸甲酯内核和交联聚甲基丙烯酸外壳的核壳结构.当甲基丙烯酸(MAA)的用量由2 mL增至3 mL时,PMAA基纳米水凝胶的尺寸变大.当MAA的用量增加至5 mL时,反应体系中除了生成PMAA基纳米水凝胶外,还生成了PMAA次级粒子.PMAA基纳米水凝胶表现出良好的pH响应性:当介质的pH值由2增加至7时,其流体力学体积扩张了近80倍.     

聚丙烯酸凝胶溶胀行为的研究

本文合成了一系列不同交联度的聚丙烯酸凝胶,测定了这些凝胶在不同ｐＨ值及温度下的综合溶胀行为,包括用经典的间断称重方法测定溶胀动力学曲线,用溶胀性能自动测定仪测定溶胀应力变化的动力学曲线及平衡溶胀度等。这这类环境敏感材料的应用提供了科学数据。     

疏水改性pH敏感水凝胶P(HEMA-NaAA-DiAC_(16))的制备及其溶胀性能

以二烯丙基胺和1-溴代十六烷为原料合成了疏水单体N,N-二烯丙基正十六烷胺(DiAC16),用FTIR、1H NMR和元素分析对其进行了表征。以2-羟基甲基丙烯酸乙酯(HEMA)、丙烯酸(AA)和N,N-二烯丙基正十六烷胺为共聚单体,N,N'-亚甲基双丙烯酰胺(BIS)为交联剂,十二烷基硫酸钠(SDS)为表面活性剂,过硫酸铵-四甲基乙二胺(TMEDA)为引发体系,制得的疏水改性智能水凝胶P(HEMA-NaAA-DiAC16)具有pH敏感特性。研究了DiAC16、NaAA、BIS用量及pH值和离子强度等因素对水凝胶P(HEMA-NaAA-DiAC16)溶胀性能的影响。结果表明,凝胶在水中的平衡溶胀率(为78.9~163.91),随DiAC16、BIS用量的增加和NaAA用量的减少而减少,n值(一般在0.5~1.0之间)随DiAC16、NaAA和BIS用量的增加而增加,为非Fickian扩散。水凝胶的吸水溶胀是放热过程,ΔH m在-2.09~-3.64 kJ/mol,ΔH m的绝对值随DiAC16用量的减少、NaAA用量和BIS用量的增加而增大,聚合物与水的亲和力逐渐增强。随离子强度的增强,平衡溶胀率下降。     

两性pH敏感凝胶溶胀理论的有限元方法

两性pH敏感凝胶同时拥有可电离的酸性基团和碱性基团,与普通凝胶相比,它具有更好的溶胀特性和生物相容性,从而被广泛应用在生物医学、药物输送系统、微流体控制等领域。因其独特的pH敏感特性和非线性溶胀行为,目前还缺乏用于描述两性pH敏感凝胶的有限元方法。据此本文采用修正过的两性pH敏感凝胶平衡溶胀理论,发展了能够描述凝胶溶胀力学行为的有限元计算方法,计算两性pH敏感凝胶在均匀溶胀和非均匀溶胀下的力学行为。结论显示,该有限元方法可以很好地与凝胶溶胀理论的(半)解析解拟合,既可以为生物体中某些关键指标提供重要参数和力学上的理论参考,也可为以聚合物凝胶为材料的微流体控制阀的设计提供重要参考。     

HPAN/SPI水凝胶纤维的PH刺激响应性能

探索了聚丙烯腈(PAN)和大豆分离蛋白(SPI)在NaOH水溶液中进行PAN碱解,然后挤到凝固浴中凝固、交联,制备水解聚丙烯腈(HPAN)／SPI水凝胶纤维的方法。通过测定凝胶纤维的平衡溶胀伸长率和溶胀伸长率,观察到HPAN／SPI水凝胶纤维的滞后和可逆的伸长／收缩行为,同时在不同组成的凝胶纤维中,随着PAN含量的逐渐增大,水凝胶纤维的响应速率呈现由小到大然后减小的变化规律,当mPAN／mspt=6／4时有最好的响应性能。     

pH快速响应PNIPAAm-co-PAAc水凝胶的制备及溶胀动力学

pH快速响应PNIPAAm-co-PAAc水凝胶的制备及溶胀动力学;N-异丙基丙烯酰胺;pH敏感性;溶胀历史     

New pH-Sensitive Hydrogels for Oral Delivery of Hydrophobic Drugs

A series of acrylic copolymers containing silyl pendant groups was prepared by free radical cross-linking copolymerization. Me₃Si, Et₃Si, and Ph₃Si together with cubane-1,4-dicarboxylic acid (CDA) were covalently linked with 2-hydroxyethyl methacrylate (HEMA). CDA linked to two HEMA group is the cross-linking agent (CA). Free radical cross-linking copolymerization of the methacrylic acid (MAA) and organosilyl monomers with two different molar ratios of CA was carried out at 60–70°C. The compositions of the cross-linked three-dimensional polymers were determined by FT-IR spectroscopy. The glass transition temperature of the network polymers was determined calorimetrically. Equilibrium swelling studies were carried out in enzyme-free simulated gastric and intestinal fluids (SGF and SIF, respectively). A model hydrophobic drug, the steroid hormone estradiol, was entrapped in these gels, and the in vitro release profiles were established separately in both SGF (pH 1) and SIF (pH 7.4). Incorporation of silyl groups in a new macromolecule system modified network polymers for drug delivery.

Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements to view the free supplemental file.     

壳聚糖-聚丙烯酸复合水凝胶的药物控制释放行为

以壳聚糖(Cs)和丙烯酸(AA)为原料,利用自由基聚合法制备了具有孔洞结构的复合水凝胶Cs-PAA,并研究了AA的量、交联剂的量、聚合温度和AA的中和度对水凝胶溶胀度的影响以及复合水凝胶对烟酸的控制释放。 结果表明,Cs-PAA复合水凝胶具有良好的pH值、离子强度敏感性,且溶胀度最高达1228 g/g,其在pH=686的缓冲溶液中的烟酸累积释放率明显大于其在pH=1.80的缓冲溶液,因此Cs-PAA水凝胶可作为肠口服药物的载体。     

Synthesis of Carboxymethyl Cellulose Based Drug Carrier Hydrogel Using Ionizing Radiation for Possible Use as Site Specific Delivery System

A unique natural polymer based colon specific drug carrier was prepared from carboxymethyl cellulose (CMC) and acrylic acid (AAc) in aqueous solution employing γ‐radiation induced copolymerization and crosslinking. The effect of preparation conditions such as the natural polymer content and irradiation dose on gelation process was investigated. The swelling behavior of the prepared hydrogels was characterized by investigating the time and pH dependent swelling of the (CMC/AAc) hydrogels of different CMC content. The effects of the hydrogel composition and pH of the swelling medium on the swelling indices were estimated. The results show that the increment in the CMC content in the feed solution enhances the gelation process. The results also show the dependence of the swelling indices on both hydrogel composition and pH value of the swelling medium. To evaluate the ability of the prepared hydrogel to be used as a colon‐specific drug carrier, the release profile of theophylline was studied as a function of time at pH 1 and pH 7.     

Radiation Synthesis of Superabsorbent Hydrogels Based on Chitosan and Acrylic Acid for Controlled Drug Release

Superabsorbent hydrogels based on the natural polymer chitosan and acrylic acid (CS/AAc) was prepared using ⁶⁰Co gamma radiation as a source of initiation and crosslinking. The factors, which affect the preparation of CS/AAc hydrogels such as irradiation dose, CS/AAc ratios, and acrylic acid monomer concentrations, to get the best optimum conditions, were investigated. The kinetic studies of the swelling of CS/AAc hydrogel showed that it follows a Fickian type of water diffusion. The Fickian constant value ‘n’ was more than 0.5 with a high swelling capacity of 300 g/g as superabsorbent hydrogel. In addition, the suitability of CS/AAc hydrogel as carrier material for the drug Chlortetracycline-HCl has been investigated by adsorption isotherm studies. The performance of drug release from hydrogel systems, influenced by acrylic acid ratio and the effect of pH of the medium was studied.     

新型羧甲基壳聚糖水凝胶流变性能,药物释放及细胞相容性研究

羧甲基壳聚糖含有丰富的羧基和氨基, 通过1-乙基-(3-二甲基氨基丙基)碳二亚胺盐酸盐(EDC)和N-羟基琥珀酰亚胺(NHS)共催化交联羧甲基壳聚糖形成新型水凝胶. 调节EDC/NHS用量, 制备不同交联度的羧甲基壳聚糖水凝胶(CMCS hydrogels). 研究水凝胶的流变行为, 结果表明, 高交联度的水凝胶具有较好的弹性形变能力, 较高的储存模量, 这是因为随着交联度的升高, 羧甲基壳聚糖水凝胶化学交联网络结构趋于完善. 以胸腺五肽(TP-5)为模型药物, 初步评价CMCS水凝胶药物释放行为, 结果表明水凝胶交联度越高, 胸腺五肽释放速度越慢. MTT法初步评价了水凝胶细胞毒性, 细胞形态和细胞相对增值速率, 结果表明水凝胶毒性很低. 由此可见, 水凝胶具有良好的生物相容性, 在药物缓释和组织工程领域具有广阔的应用前景.     

Acrylamide Hydrogels Preparation via Free Radical Crosslinking Copolymerization: Kinetic Study and Morphological Investigation

The simultaneous gravimetric and dilatometric techniques have been used to study the kinetics of aqueous free radical crosslinking copolymerization of acrylamide (AAm) and N,N^'-methylenebisacrylamide (MBA) at different crosslinker ratios, and reaction temperatures. In this study, the gel properties were investigated using swelling measurements and microscopic techniques. Based on the data, it was proposed that the deviation point of the results of dilatometric technique from those of the gravimetric one can be a new criterion for gel point. The monomer conversion and the equilibrium swelling ratio of the hydrogels were measured as a function of the reaction time. Experimental data showed an inverse dependence of the critical gel point on crosslinker concentration. As the MBA/AAm ratio was decreased to 0.1?wt%, the product appearance changed. In addition, the effects of temperature on the reaction rate and critical gel point were studied. At higher temperatures, the equilibrium swelling ratio reached to its minimum value earlier. Besides, the hydrogel surface became smoother.