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。     

溶剂改性疏水pH-敏感凝胶的溶胀行为

在甲苯存在下，以甲基丙烯酸二乙氨基乙酯、苯乙烯和二乙烯苯为单体，通过悬浮聚合方法合成了不同交联度的疏水阳离子凝胶，研究了这些凝胶的pH－敏感溶胀行为。发现以良溶剂甲苯改性的凝胶不仅溶胀度增加，而且溶胀性质对交联度改变出现特异的依赖关系。当凝胶的交联度高于20％时，平衡溶胀度和溶胀速度随交联度的提高不是降低，而是提高。同时发现，随交联度提高，改性凝胶的溶胀逐渐具有零级动力学特性。这对设计由溶胀控制的，具有零级动力学释药特性的控释体系是十分有意义的。     

葡萄糖敏感微凝胶的溶胀动力学研究

通过沉淀聚合法合成了P(NIPAM-co-AA)微凝胶,然后在EDC催化下用3-氨基苯硼酸对微凝胶进行改性,制备了P(NIPAMI-co-AAPBA)微凝胶.红外光谱检测证明改性完全.改性后的微凝胶仍具有很好的温敏性,但由于引入疏水的苯硼酸基团,微凝胶的体积相转变温度大大降低.P(NIPAM-co-AAPBA)微凝胶具...     

离子键交联的聚两性电解质凝胶在不同pH和不同电解质溶液中溶胀行为研究

以丙烯酸(AA)和甲基丙烯酸二乙氨基乙酯(DEAM)形成的离子复合物与丙烯酰胺(AAm)共聚,合成了一种新型的离子键交联的聚两性电解质凝胶(PADA).由于分子之间的氢键作用,PADA凝胶并不是在A/C(负正离子单体摩尔比)为1,而是在A/C为1.55处有最大消溶胀.与共价键交联的聚两性电解质凝胶相比,PADA凝胶的溶胀行为具有更强的pH敏感性.PADA凝胶在不同pH缓冲溶液中的溶胀行为表明,在pH 3~4之间消溶胀程度最大.在偏离该pH区域时凝胶均发生溶胀.但凝胶的溶胀程度在pH<3的酸性溶液中随A/C的增加而降低;而在pH>4的偏碱性溶液中随其增加而增加.在不同价数的离子溶液中,离子浓度对于PADA凝胶的平衡溶胀有着不同的影响.对于一价的NaCl溶液,PADA凝胶有典型的反聚电解质效应.但对于高价的CaCl2和柠檬酸三钠溶液,只在较低的浓度下,才表现出反聚电解质效应.而在较高盐浓度时,随盐浓度的增加其溶胀比反而降低.这可能与高价离子形成的离子键交联有关.与pH对PADA凝胶溶胀程度的影响相似,在CaCl2溶液中,PADA凝胶的溶胀程度随A/C的增加而降低;而在柠檬酸三钠溶液中则刚好相反.这种独特的溶胀行为似乎与高价离子电荷的正负性有关.     

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。     

pH敏感性P(AM-AA-co-C8PhEO10Ac)水凝胶溶胀动力学及其对茶碱的控释

以丙烯酰胺(AM)、丙烯酸(AA)和丙烯酸辛基酚聚氧乙烯醚酯(C8PhEO10Ac)为单体,采用自由基交联共聚法合成了具有pH敏感性的P(AM-AA-co-C8PhEO10Ac)水凝胶.研究了pH、单体配比对凝胶溶胀性能、溶胀动力学和退溶胀动力学的影响.初步探讨了模拟胃液(pH=1.4)、肠液(pH=7.4)中水凝胶对茶碱的控释情况.结果表明:凝胶具有高溶胀、退溶胀速率和良好的pH敏感性等特征;水凝胶的扩散行为在pH=7.4的缓冲溶液中为非Fickian扩散模式;载药凝胶在模拟肠液中对药物的累积释放率明显大于胃液中的累积释放率,其中n(C8PhEO10Ac)∶n(AM)∶n(AA)为1∶20∶30的载药水凝胶对茶碱的累积释放率最大.     

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     

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．     

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.     

两性表面活性剂与阴离子聚丙烯酰胺复配体系的抗盐性

通过单因素实验分析两性表面活性剂浓度、无机盐浓度及pH值对聚丙烯酰胺复配体系黏度的影响规律,应用SPSS软件对均匀实验结果进行非线性回归,得到复配体系黏度与聚合物浓度、两性表面活性剂浓度及无机盐浓度的定量关系式,进而理论分析了各因素对复配体系抗盐性的影响规律.结果表明,当两性表面活性剂的浓度低于临界缔合浓度(CAC)时,复配体系的黏度变化不大;当其浓度高于CAC后,随着浓度的增加,体系黏度急剧增大;当其浓度达到聚合物饱和浓度(PSP),复配体系黏度达到最大值;当再进一步加入表面活性剂时,聚集体间的网状结构将被破坏,从而使体系黏度逐渐降低;无机盐对复配体系的作用具有双重性,低浓度盐将促使体系黏度升高,中高浓度盐则会导致体系黏度降低;不同pH值条件下,复配体系的抗盐能力顺序为碱性(pH=11.4)＞酸性(pH=2.8)＞中性(pH=7).     

盐-水体系溶解平衡计算的自由能最小化及溶度积方法

根据电解质溶液的基本物理化学原理和近代电解质溶液理论的Pitzer离子相互作用模型,通过计算浓电解质溶液的活度系数和水的活度,研究了盐-水体系溶解平衡的计算方法.结果表明,体系Gibbs自由能最小化方法是计算盐-水体系溶解平衡的一种有效方法,其计算结果与溶度积法一致.     

Swelling of compressed cellulose fiber webs in organic liquids

Maximum liquid-holding capacities of various compressed fibers in water and in a series of various organic liquids have been investigated. The maximum liquid-holding capacity versus bulk density relationships gave polynomial curves, generally with a peak. Good relative correlations for cellulose, compressed fiber pellets and wood were found for the series of liquids tested. In general, liquids that swelled wood to a low to medium range (up to 6%) did not swell appreciably -cellulose and sulfite pulp, while good to excellent wood-swelling agents swelled all the fibers very significantly. It was also found that the hydrogen-bonding parameter of the swelling liquid was the most important factor. The swelling rate of various compressed fiber systems in organic liquids was dramatically increased by raising the temperature. Activation energies and molar volume of the swelling liquid were linearly correlated.     

A pH-Sensitive Hydrogel with Hydrophobic Association for Controlled Release of Poorly Water-Soluble Drugs

A novel pH-sensitive hydrogel has been developed by UV induced radical polymerization of acrylic acid (AA) and amphiphilic macromonomer polyethylene glycol monolaurylether monoacrylate (PEGLA) with crosslinker ethylene glycol dimethacrylate for controlled release of acyclovir, a poor water-soluble model drug. The swelling behavior was investigated in the buffer of different pH at I = 0.1 M, as well as in the ethanol/water mixture. The hydrophobic association formed by the hydrocarbon chains in PEGLA was found to dominate the swelling properties of the hydrogels with subordinate pH sensitivity due to the ionization of the AA segments. Therefore, the drug loading of acyclovir has been improved and the release rate of acyclovir was slowed down with increasing the PEGLA content in the hydrogels. By fitting the release data with Weibull equation, the acyclovir release kinetics was changed from the Fickian diffusion to an anomalous diffusion when the PEGLA content in the hydrogels was beyond 20 mol%.     

复杂阴极保护体系三维有限元建模研究

滨海电厂常以天然海水作冷却水,其碳钢水室和钛管凝汽器在实施阴极保护过程中,要求钢电位应低于-0.85V(vs.SCE),电位过正则碳钢保护不足,而钛的电位则须高于-0.75V(vs.SCE),电位过负则易使钛管发生氢脆损伤.研究牺牲阳极阴极保护,需先得出两种金属在阴极保护过程中的电位分布.本文在设计室建立碳钢水室钛管模型,根据该实验体系阴极保护过程的(稳态极化和恒电流极化)测定获得两种金属有效的边界条件,用有限元(FEM)计算在一个牺牲阳极阴极保护状态得到三维电位分布.计算结果和测量结果基本一致,为优化阴极保护设计提供了理论依据.     

ABg型超支化反应体系的平衡统计特征

应用统计力学原理, 从两种不同角度对ABg型超支化反应体系中的平衡特征进行研究, 得到该体系平衡自由能以及反应程度与热力学量之间关系的解析表达式. 进一步指出获得超支化高分子数量分布函数的两种新方法, 并结合改进的高分子格子流体理论探讨了聚合反应对体系状态方程的影响.     

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.     

COMSOL有限元分析方法在循环伏安法教学中的应用

以循环伏安法为例，介绍了如何通过COMSOL Multiphysics有限元软件建立电化学反应模型及其数值求解。通过改变电极尺寸、电子转移速率常数、均相化学反应速率常数等参数，实现了循环伏安图与扩散层内反应物浓度分布的关联和动态演示，帮助初学者形象深刻地理解循环伏安法的基本原理。     

A new formulation of the PCM solvation method: PCM-QINTn

A new formulation of the PCM electrostatic solution problem is proposed. Through a new derivation of the PCM-CLSn expression we propose an interpolation formula that improved the convergence: PCM-QINTn. All the available formulations are applied to the evaluation of the electrostatic component of the free energy of solvation for some molecular systems. In addition, PCM-QINT derivatives of G _el with respect to atomic coordinates are evaluated. The computational costs are compared with those of PCM-direct formulation. Received: 21 October 1996 / Accepted: 7 January 1997