表面活性剂对疏水缔合水凝胶性能的影响

通过丙烯酰胺(AM)和丙烯酰胺基十八羧酸钠(NaAAS)共聚合,在没有任何外加化学交联剂的情况下,分别在水溶液和十二烷基硫酸钠(SDS)溶液中通过自由基聚合制备了疏水缔合水凝胶,命名为HA凝胶和SHA凝胶.系统研究HA凝胶和SHA凝胶的机械拉伸性能发现,调节AM和NaAAS的含量,可以使SHA凝胶具有相较不含SDS的HA凝胶更好的力学拉伸性能.HA凝胶在水中不溶解且在纯化和溶胀过程中几乎没有损失,而SHA凝胶体系中的SDS可以扩散出凝胶网络溶解到水中,使得SHA凝胶表现出更加明显的溶胀-去溶胀-平衡溶胀行为;在盐水中由于疏水缔合得到加强,HA凝胶和SHA凝胶都表现出化学凝胶的溶胀特点.在常温下HA凝胶不能实现自愈合,而SHA凝胶具有较好的自愈合能力,并且自愈合效果可以通过SHA凝胶中SDS和聚合物固含量调节.     

微嵌段疏水缔合聚合物/十二烷基硫酸钠溶液体系的流变特性

研究了疏水微嵌段长度和阴离子表面活性剂十二烷基硫酸钠(SDS)对聚/表体系的流变性的影响。研究表明,微嵌段长度对疏水缔合聚合物溶液的粘性有较大影响,嵌段越长聚合物越容易发生分子间缔合其溶液粘度越大。随着SDS的加入,各聚/表体系粘度短期内出现一个极值,然后降至一个稳定值,嵌段长度越长,其极值点越大。聚合物与SDS体系表现出的剪切增稠和粘弹性特征也随嵌段长度增加而增大。通过研究不同体系平台区模量(G0)和特征松弛时间(TR)的变化规律,发现嵌段长度和SDS含量对聚/表体系物理交联缔合点的密度有较大影响,对缔合点强度影响较小。本文有助于更好地解释微嵌段疏水缔合聚合物与表面活性剂相互作用的内在因素。     

新型疏水缔合聚合物P(AM/POEA)与表面活性剂的相互作用

采用粘度法、荧光探针和透射电镜研究了新型疏水缔合聚合物P(AM/POEA)和表面活性剂SDS和CTAB在水溶液中的相互作用. 聚合物P(AM/POEA)结构中, 疏水体(2-苯氧乙基丙烯酸酯)呈嵌段状无序地分布在聚丙烯酰胺主链上. 这类聚合物很容易和表面活性剂相互作用, 通过疏水缔合, 形成混合胶束状聚集体, 导致溶液粘度剧增. 随聚合物溶液中SDS的加入, 溶液粘度发生大幅度起伏变化, 出现最大值. 粘度最大值对应的表面活性剂浓度c_S,max位于表面活性剂CMC附近, 并发现它的位置不随聚合物微结构而变化. 然而它们缔合作用的增粘程度却与聚合物疏水体含量X_H及疏水嵌段尺寸N_H有关. 在实验浓度范围内, X_H和N_H愈大, 溶液的粘度越高. 此外用透射电镜直接观察到聚合物/表面活性剂体系中聚集体的交联结构形貌.     

含有4,4′-双(甲基丙烯酰胺基)偶氮苯水凝胶的合成及其在结肠位药物释放的动物实验

合成了不同链长的甲基丙烯酸酯、甲基丙烯酰胺及丙烯酸与4,4′-双(甲基丙烯酰胺基)偶氮苯交联共聚的功能凝胶.三维网络结构通过压缩弹性模量、有效交联密度及聚合物与溶剂间的相互作用参数进行了表征.主要研究了这类凝胶在pH2.2和pH7.4的缓冲溶液的平衡溶胀特性及其偶氮交联基团在体内的降解行为,并讨论了其降解机制.凝胶在胃部的性能稳定,既不发生溶胀,亦不发生降解;但在盲肠内偶氮交联基因可发生降解.其降解率与凝胶的平衡溶胀程度有一个很好的关联:交联程度、疏水基侧链的长度及含量对凝胶溶胀行为的影响结果与这些因素对偶氮交联基团体内降解的影响结果完全一致.通过调节这些因素不仅可以控制凝胶的溶胀程度,而且可以控制偶氮交联基团在体内的降解行为.     

含有4,4′-双(甲基丙烯酰胺基)偶氮苯水凝胶的合成及其在结肠位药物释放的动物实验

合成了不同链长的甲基丙烯酸酯、甲基丙烯酰胺及丙烯酸与 4 ,4′ 双 (甲基丙烯酰胺基 )偶氮苯交联共聚的功能凝胶 .三维网络结构通过压缩弹性模量、有效交联密度及聚合物与溶剂间的相互作用参数进行了表征 .主要研究了这类凝胶在pH2 2和pH7 4的缓冲溶液的平衡溶胀特性及其偶氮交联基团在体内的降解行为 ,并讨论了其降解机制 .凝胶在胃部的性能稳定 ,既不发生溶胀 ,亦不发生降解 ;但在盲肠内偶氮交联基因可发生降解 .其降解率与凝胶的平衡溶胀程度有一个很好的关联 :交联程度、疏水基侧链的长度及含量对凝胶溶胀行为的影响结果与这些因素对偶氮交联基团体内降解的影响结果完全一致 .通过调节这些因素不仅可以控制凝胶的溶胀程度 ,而且可以控制偶氮交联基团在体内的降解行为 .     

结肠位点药物传载凝胶的溶胀动力学研究

合成了带不同疏水侧基的甲基丙烯酸酯、甲基丙烯酰胺及丙烯酸与 4,4′ 二 (甲基丙烯酰胺基 )偶氮苯交联共聚的凝胶 .主要研究了这类凝胶在pH =2 .2至pH =7.4的缓冲溶液的溶胀特性 .其溶胀过程遵循二级溶胀动力学 ,影响这类凝胶溶胀行为的因素包括交联程度、疏水基链的长度、pH值等 .通过调节这些因素是完全可以控制凝胶在小肠内的溶胀程度 ,进而避免凝胶内部的药物被提前释放     

新型疏水缔合丙烯酰胺/2-苯氧乙基丙烯酸酯共聚物的合成与性质

采用胶束共聚方法合成了一种新型的疏水缔合共聚物 ,它由丙烯酰胺 (AM)和少量的 2 苯氧乙基丙烯酸酯 (POEA) (<1 0mol% )组成 ,具有良好的水溶性 .当溶液浓度超过一定值c 后 ,由于分子间的疏水缔合 ,产生很大的增粘作用 .研究了不同聚合条件下包括单体浓度、投料比和SMR值对聚合物的结构和性能的影响 .实验结果表明 ,聚合物的粘度性质和缔合行为取决于其分子量的大小、疏水单体含量及其嵌段的长度和分布 .     

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.     

表面活性剂胶束实现疏水分子在聚合物微凝胶层层组装膜中的高效负载

基于层层组装技术制备了聚烯丙基胺-葡聚糖微凝胶(记作PAH-D)/透明质酸钠(HA)膜, 将包覆有芘分子的十二烷基硫酸钠(SDS)表面活性剂胶束基于静电作用力负载到PAH-D/HA微凝胶膜中, 实现了疏水分子芘在微凝胶膜中的高效负载. 紫外-可见吸收光谱和荧光光谱证实了SDS胶束包覆的芘分子被稳定地负载在PAH-D微凝胶膜中. 透过光谱表明负载有芘分子的(PAH-D/HA)*10微凝胶膜在可见光区仍保持良好光学透过性. 芘在膜中的负载量可以通过改变PAH-D/HA微凝胶膜的沉积周期数和SDS胶束中包覆芘分子的浓度而实现调控. 具有光致变色性质的螺吡喃分子同样可以借助SDS胶束负载到PAH-D/HA微凝胶膜中, 制备具有光致变色性质的层层组装膜. 本工作为疏水有机分子在层层组装聚合物膜中的高效负载提供了一种简便、易行的方法.     

疏水改性智能水凝胶P(NIPA-co-DiAB)的合成及其温敏行为

以N-异丙基丙烯酰胺(NIPA)和N,N-双烯丙基苄胺(DiAB)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(APS)-四甲基乙二胺(TMEDA)为氧化还原引发体系,采用自由胶束交联共聚法合成了疏水基团为芳香基的疏水改性温敏性智能水凝胶P(NIPA-co-DiAB)。研究了DiAB摩尔分数(x(DiAB))对水凝胶溶胀性能的影响。 在初始溶胀阶段,随着x(DiAB)由0增大至3%,P(NIPA-co-DiAB)水凝胶的溶胀行为由Fickian扩散转变为non-Fickian扩散。x(DiAB)分别为0、1%、2%和3%时,P(NIPA-co-DiAB)水凝胶的平衡溶胀率SR0在蒸馏水中分别为63.6、93.5、141.6和167.4,在0.01 mol/L SDS溶液中分别为63.1、71.0、59.0和77.5,在CTAB溶液中分别为37.6、42.2、44.1和60.0,在Triton X-100溶液中分别为30.9、49.4、68.5和88.3。 结果表明,P(NIPA-co-DiAB)水凝胶的(SR0)大于PNIPA水凝胶,且在蒸馏中比在0.01 mol/L表面活性剂溶液中要大。 加入0.01 mol/L Triton X-100、CTAB或SDS后,PNIPA水凝胶的体积相变温度或较低临界溶解温度(LCST)由32.5 ℃分别增加至35.4、45.6和80 ℃。P(NIPA-co-DiAB)水凝胶的LCST由32.0～32.5 ℃分别增加至34.7～35.6 ℃、45.8~46.2 ℃和80 ℃。 加入表面活性剂能增加P(NIPA-co-DiAB)水凝胶的体积相变温度,高的体积相变温度与DiAB含量无关。     

Intelligent Hydrogels Via Gamma-Ray Induced Polymerization of Micellar Monomer Solutions and Microemulsions

Summary: Intelligent hydrogels were prepared upon polymerization of micellar aqueous comonomer solutions and microemulsions containing the cationic surfactant monomer 11-acryloyloxyundecyltrimethylammonium bromide (AUTMAB) and N-isopropylacrylamide (NIPAM). A chemically and physically cross-linked network structure is formed consisting of blocks of P-NIPAM and P-AUTMAB. The P-AUTMAB blocks act as physical cross-linking units improving the mechanical stability of the gel. While pure P-NIPAM hydrogels are disrupted under low compression, gels polymerized from micellar solution or microemulsion can be reversibly compressed. The presence of AUTMAB in the gel increases the swelling up to a factor of 30 compared with the pure P-NIPAM gel. Rapid and reversible swelling is observed for hydrogels with an AUTMAB content up to 2.5 wt.-%.     

Interactions between covalently crosslinked ethyl(hydroxyethyl)cellulose and SDS

The equilibrium swelling of chemically crosslinked gels based on ethyl(hydroxyethyl)cellulose (EHEC) in aqueous solutions of sodium dodecyl sulphate (SDS) was studied as a function of the SDS concentration at various temperatures and salt concentrations. Comparisons were made with gels based on poly-N-isopropylacrylamide (p-NIPA). Both polymers are known to form complexes with SDS above a critical association concentration (cac) of the surfactant, and both display a lower critical solution temperature (LCST) in water. For both types of gels, an increase in the equilibrium gel volume was seen with increasing SDS concentration above the cac, up to a maximum value when the SDS concentration in the external solution reached the critical micelle concentration (cmc). Above the cmc, the equilibrium gel volume decreased slowly with increasing SDS concentration. A volume collapse of the EHEC gels was observed in a temperature interval around the LCST of EHEC in solution. Above the cac, the collapse transition moved monotonically towards higher temperatures with added SDS. At lower SDS concentrations, however, the opposite trend was found. The swelling of the gel was less in the presence of salt and SDS, and a pronounced minimum in swelling appeared with added SDS when the salt concentration was sufficiently high (ca. 10 mmoles/l). Under these salt conditions, the LCST of the linear EHEC also passes through a deep minimum (below room temperature) on addition of SDS.     

Swelling of poly(ethylene oxide) gel in aqueous solutions of sodium dodecyl sulfate with added sodium chloride

The swelling behavior of poly(ethylene oxide) (PEO) gels in aqueous solutions of sodium dodecyl sulfate (SDS) with and without NaCl was investigated. In the absence of NaCl, PEO gels with different degrees of cross-linking began to swell from a concentration lower than the critical micelle concentration (cmc) of SDS, then showed sigmoidal enhancements of swelling in a higher SDS concentration region until the degrees of swelling reached maximum values. The SDS concentration at which the swelling began to appear was in reasonable agreement with the critical aggregation concentration (cac) value reported for the aqueous PEO system. For the cases where NaCl was present, the swelling behavior of PEO gel was different from that when NaCl was absent in the following way. The concentrations where the swelling begins to appear, and hence those where the degree of swelling rises steeply, decreased with an increase in NaCl concentration. The ultimate degrees of swelling at higher concentration regions also decreased with an increase in the NaCl concentration. The lowering of the SDS concentrations at which the PEO gel began to swell is in line with the decreases in the cmc of SDS solutions containing NaCl and also with the decreases in the cac of PEO solution. Electronic Publication     

Thermosensitive poly(N-isopropylacrylamide-co-acrylamide) hydrogels: Synthesis, swelling and interaction with ionic surfactants

Thermosensitive hydrogels were prepared by free-radical polymerization in aqueous solution from N-isopropylacrylamide (NIPA) and acrylamide (AAm) monomers. N,N-Methylenebis(acrylamide) (MBAAm) was used as a crosslinker. A kinetic study of the absorption determined the transport mechanism. The diffusion coefficients of these hydrogels were calculated for the Fickian mechanism. It was shown that the swelling behavior of the P(NIPA-co-AAm) hydrogels can be controlled by changing the amount of MBAAm. The swelling equilibrium of the P(NIPA-co-AAm) hydrogels was also investigated as a function of temperature in aqueous solutions of the anionic surfactant sodium dodecyl sulfate (SDS) and the cationic surfactant dodecyltrimethylammonium bromide (DTAB). In SDS and DTAB solutions, the equilibrium swelling ratio of the hydrogels increased, this is ascribed to the conversion of non-ionic P(NIPA-co-AAm) hydrogel into polyelectrolyte hydrogels due to binding of surfactant molecules through the hydrophobic interaction. Additionally, the amount of free SDS and DTAB ions was measured at different temperatures by a conductometric method, it was found that the electric conductivity of the P(NIPA-co-AAm)—surfactant systems depended strongly on both the type and concentration of surfactant solutions.     

IPAAm凝胶在丙酮水溶液中溶胀行为的关联与预报

基于Maurer和Prausnitz的凝胶相平衡条件，建立了凝胶的溶胀模型.模型假设凝胶是以凝胶组分及凝胶吸收的溶液为核心，以弹性半渗透膜为壳的复合体.并采用UNIQUAC方程计算凝胶相及与之共存液相的Gibbs过剩自由能，采用“phantomnetwork”理论计算凝胶的弹性自由能，采用“自由体积”计算分子的尺度效应.同时以N-异丙基丙烯酰胺（IPAAm）为单体合成了IPAAm凝胶.研究了25 ℃时IPAAm凝胶在丙酮水溶液中的溶胀行为，并测定了丙酮在胶体相和与之共存液相中的分配，以检验模型的关联与预报能力.结果表明,模型预报的单体总量和交联剂浓度对凝胶溶胀的影响与实验符合得很好.而且凝胶溶胀时，能很好地预测丙酮在两相中的分配,表明模型具有很好的关联和预报能力.     

Studies on preparation and properties of NIPAAm/hydrophobic monomer copolymeric hydrogels

A series of thermoreversible copolymeric hydrogels with various molar ratios of N-isopropylacrylamide (NIPAAm) and hydrophobic monomers such as 2,2,3,3,4,4,5,5-octafluoropentyl methacrylate (OFPMA) and n-butyl methacrylate (BMA) were prepared by emulsion polymerization. The effect of hydrophobic monomer on the swelling behavior and mechanical properties of the present copolymeric hydrogels was investigated. Results showed that the equilibrium swelling ratio and critical gel transition temperature (CGTT) decreased with an increase of the content of hydrophobic monomer, but the gel strength of the gel increased with an increase of the content of hydrophobic monomer. Due to stronger hydrophobicity of OFPMA, the NIPAAm/OFPMA copolymeric hydrogels had lower swelling ratios and higher gel strengths than NIPAAm/BMA copolymeric gels.     

Mechanical Properties and Network Structure of Hydrophobic Association Hydrogels Prepared from Octylphenol Polyoxyethylene(7) Acrylate and Sodium Dodecyl Sulfate

Hydrophobic association hydrogels(HA-gels) with high mechanical strength were prepared by free radical micellar copolymerization in aqueous solutions of acrylamide(AM), anion surfactant sodium dodecyl sulfate(SDS) and a small amount of hydrophobic monomer octylphenol polyoxyethylene(7) acrylate(OP-7-AC). We found that the molar ratio of SDS to OP-7-AC has a great effect on the tensile strength and other mechanical property parameters. The best ratio point R' was determined. On the basis of Mooney theory and statistical theory, the critical tensile ratios and critical tensile strengths of the hydrogels were obtained, elastic parameters C₁ and C₂ were calculated via uniaxial tensile equation and structural parameters, such as the effective network chain density and the averaged molecular weight of the chain between cross-linking points of all the hydrogels were evaluated. The results indicate that the variation of mechanical property parameters depends on the number of effective cross-linking points and the match degree of long and short chains.     

Swelling-shrinking behavior of chemically cross-linked polypeptide gels from poly(α-L-lysine), poly(α-DL-lysine), poly(ɛ-L-lysine) and thermally prepared poly(lysine): effects of pH, temperature and additives in the solution

We synthesized the glutaraldehyde cross-linked hydrogels using four kinds of poly(lysine)s (PLs) and measured the equilibrium swelling ratio (Q) as a function of pH. Also measured was the temperature change of Q at a fixed pH (11.6) in the absence and presence of additives (LiBr, methanol and urea) that affect the secondary structure of PLs. The swelling data were examined using a force balance approach in which the repulsive and attractive interactions among the cross-linked PL chains were considered based on the conformational properties of PLs in aqueous solutions. It was found that the formation of the helical segments in the cross-linked chain has little effect in the gel collapse, but their association acts as the attractive interaction causing the gel to shrink. The formation of the beta-sheet structure within the network also acts as the attractive interaction. These attractive interactions are mainly due to the hydrogen bonding, but hydrophobic interactions between the lysine side chains should be considered. In addition, in the swelling behavior of all the PL gels the polyampholyte nature appears due to electrostatic interactions of the basic groups with the C-terminal carboxyl group.     

Superswelling of Hydrogels Based on the Copolymer of Acrylamide and Methacrylic Acid

Weakly crosslinked hydrogels of copolymers of acrylamide and methacrylic acid are synthesized by radical polymerization in aqueous solution in a wide range of comonomer ratios. It is found that gels containing 20–40 mol % methacrylic acid are characterized by superswelling that exceeds the degree of swelling of homopolymer hydrogels by tens of times. The observed degree of swelling reaches 830, corresponding to an almost completely stretched conformation of subchains between network junctions. For dried hydrogel samples, the equilibrium degree of swelling is also maximal in the mentioned composition range; however, its maximum value is lower than the equilibrium degree of swelling for the initial samples. The possible reason behind the superswelling of hydrogels containing 20–40% units of methacrylic acid is an increase in ionization of network subchains. This hypothesis is proved by an increased sensibility of hydrogels of this composition to a change in the pH of a medium and the lowest values of the effective acidity constant determined by potentiometric titration for methacrylic acid units. The values of partial heat capacity of a gel polymer network are determined by calorimetry. These values are significantly higher than the heat capacities typical of vinyl polymers. This is evidence that the hydrophobic type of hydration predominates in the copolymers of acrylamide and methacrylic acid. The partial heat capacity reaches its maximum within the copolymer composition range corresponding to superswelling.     

Hydrophobically modified hydrogels containing azoaromatic cross-links: swelling properties, degradation in vivo and application in drug delivery

Hydrogels based on n-alkyl methacrylate esters (n-AMA) of various chain lengths, acrylic acid, and acrylamide cross-linked with 4,4-di(methacryloylamino)azobenzene were synthesized. The equilibrium swelling degree of the hydrogels in buffered solutions at pH 7.4 was shown to be very low in the pH range of the stomach. The entire swelling processes of the gels in the gastrointestinal tract were mainly dependent on those in the small intestine. In the buffered solution of pH 7.4 the diffusion of water into the gel slabs was discussed on the stress relaxation model of polymer chains. The results obtained are in good agreement with Schott's second-order diffusion kinetics. The biodegradability in vivo of their azobenzene cross-linking groups as well as the mechanism of degradation by cecal bacteria was studied. The gels are stable in the stomach but degradable by ananerobes present in the colon. The extent of degradation was considerably related to the equilibrium degree of swelling. The factors influencing the swelling degree were shown to influence the in vivo degradation of the gels. By changing these factors such as the degree of cross-linking, the length and content of the n-AMA side chains, it is possible to control both the degree of swelling and the degradation of the hydrogels.