利用高分子/表面活性剂聚集体为探针研究有机小分子与表面活性剂之间相互作用
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摘要
高分子-表面活性剂相互作用及其复配体系广泛的工业应用赋予其基础研究重要的实际意义和丰富的研究内容。本论文对高分子-表面活性剂相互作用及利用高分子／表面活性剂复合物研究有机小分子-表面活性剂相互作用相关的几个问题进行了较为深入和细致地探讨，取得了如下研究结果：
通过粘度、电导、表面张力及荧光光谱研究了聚乙烯基吡咯烷酮(PVP)与十二烷基硫酸钠(SDS)的相互作用,当cac(临界聚集浓度) 利用PVP/SDS聚集体作为探针,根据PVP/SDS复合物溶液在添加β-CD时溶液粘度对β-CD浓度的依赖性可反映β-CD与SDS主客体包合比为1：1的包合作用,并且通过PVP/SDS/β-CD复配溶液ηr～Cβ-CD图中粘度最小值位置可以计算β-CD与SDS包合作用的主客体包合比。β-CD的疏水空腔与SDS的疏水链的包合作用屏蔽了SDS分子与PVP链或其它SDS分子的疏水相互作用,使得已经缔合于PVP链上的SDS分子脱落。β-CD对缔合于PVP链上的SDS分子和未缔合于PVP链上的SDS分子的包合并不具有选择性。根据PVP/SDS复合物溶液在添加β-CD时溶液电导率对β-CD浓度的依赖性可反映β-CD与SDS的包合作用,并且通过PVP/SDS/β-CD复配溶液κ～Cβ-CD图中实验曲线转折浓度可以计算β-CD与SDS先后进行主客体包合比为1：1和2：1的包合过程。
利用PVP/SDS聚集体为探针,根据PVP/SDS复合物溶液在添加苯甲醇时溶液粘度对苯甲醇浓度的依赖性可反映苯甲醇对SDS胶束化行为的影响。苯甲醇浓度较小时,其对SDS胶束化行为的影响表现为共表面活性剂效应,苯甲醇与溶液中的自由SDS分子通过疏水相互作用形成混合聚集体并缔合于高分子链,使得缔合于PVP链上的SDS分子数量增加,静电排斥作用增强,溶液粘度增大,同时溶液电导率减小；苯甲醇浓度较大时,其对SDS胶束化行为的影响表现为共溶剂效应,随苯甲醇浓度增大,溶液更加疏水,表面活性剂疏水链与高分子链间的疏水相互作用减弱,使与PVP链缔合的SDS胶束从PVP链脱落,静电排斥作用减弱,溶液粘度减小,同时溶液电导率增大。SDS在PVP上饱和缔合量当苯甲醇存在时减小,至苯甲醇浓度较大时基本不变,与PVP缔合的SDS胶束的电离度当苯甲醇存在时比没有苯甲醇存在时增大约30%,至苯甲醇浓度较大时基本不变,二者导致的高分子-缔合表面活性剂之间的静电相互作用的变化可以相互补偿。
利用PVP/SDS聚集体为探针,根据PVP/SDS复合物溶液在添加正丁酸、正丁胺、正丁醇时溶液粘度对添加物浓度的依赖性可反映正丁酸、正丁胺、正丁醇对SDS的胶束化行为的影响。PVP/SDS复合物溶液性质对添加极性头基电荷性质不同的正丁酸、正丁胺、正丁醇的响应有显著差别。
正丁酸极性头基与SDS离子头基均带负电荷,添加正丁酸使PVP侧基羰基上带部分负电的氧原子更易质子化,氮原子带部分正电,因而PVP链所带正电荷数增加,PVP链以更加卷曲的构象与SDS聚集体缔合,高分子链收缩。随正丁酸浓度增大,正丁酸与SDS混合胶束化并缔合于PVP链,使缔合于PVP链上的SDS分子数量增加,静电排斥作用增强,PVP链更加伸展。继续添加正丁酸,正丁酸对静电相互作用的屏蔽使得缔合于PVP链的SDS离子间的静电排斥作用减弱,高分子链收缩。
正丁胺在水溶液中其极性头基带正电。通过疏水链间的疏水相互作用及极性头基间的静电吸引作用正丁胺与缔合于PVP链的SDS分子形成混合聚集体,其极性头基的正电性一方面对SDS头基的负电性起到中和作用,另一方面与PVP正电性侧基发生静电排斥,二者均使得PVP-SDS相互作用减弱,导致已缔合于PVP链的SDS胶束脱落,高分子链收缩,直至缔合于PVP链的SDS胶束全部脱落。
正丁醇浓度较小时,表现为共表面活性剂效应,正丁醇与溶液中自由SDS分子通过疏水相互作用形成混合聚集体并缔合于PVP链,使得缔合于PVP链上的SDS分子数量增加,静电排斥作用增强,PVP链更加伸展。正丁醇浓度较大时,表现出共溶剂效应,溶液更加疏水,表面活性剂疏水链与高分子链间的疏水相互作用减弱,缔合于PVP链的SDS胶束从PVP链脱落,静电排斥作用减弱,高分子链收缩。
疏水基团大小不同使得PVP/SDS复合物溶液对添加正丁醇与苯甲醇的响应有显著差别。正丁醇的疏水基团体积较小,插入与PVP缔合的SDS胶束后,使SDS排列更加紧密,在SDS胶束中的增溶量较多,使胶束表面电荷密度降低更为显著,与PVP缔合的SDS胶束的电离度随正丁醇浓度增大而显著增大,而苯甲醇的疏水基团体积较大,插入与PVP缔合的SDS胶束后,对SDS分子的相互靠近起空间位阻作用,不利于SDS紧密排列,在SDS胶束中的增溶量较少,与PVP缔合的SDS胶束的电离度在苯甲醇浓度较大时基本不随苯甲醇浓度而改变。
粘度、电导和荧光光谱实验结果证实明胶与gemini表面活性剂亚乙基-α,ω-双(N,N,N-二甲基(顺-13-二十二烯基))(22-2-22)溴化铵的相互作用可以分为三个阶段。第一阶段,22-2-22通过与明胶分子疏水性氨基酸残基的疏水相互作用插入明胶分子的疏水微区,以单体形式与明胶分子缔合。第二阶段,与明胶分子链缔合的22-2-22形成类胶束聚集体,导致明胶分子的链间交联。第三阶段,与明胶分子链缔合的22-2-22形成类胶束聚集体增多,明胶分子的链间交联解开,继而发生链内交联。利用明胶内源(酪氨酸残基)荧光光谱最大发射强度对表面活性剂浓度作图中峰值位置可以确定明胶-22-2-22相互作用历程中与明胶分子链缔合的22-2-22开始形成类胶束聚集体的临界聚集浓度cac。
Interactions between polymer and surfactant in aqueous solutions have attracted significant interest for their widespread applications and relatively complex behaviors. Several aspects are discussed in this thesis about the utility of polymer/surfactant complex to study the interaction between small organic molecules with surfactants. The main findings are as follows:
1. Data presented in viscosity, conductivity, surface tension and fluorescence studies on the interaction between Poly(vinyl pyrrolidone)(PVP) and Sodium Dodecyl Sulfate(SDS) in aqueous solution indicates that the interaction between PVP and SDS can be separated into two stages. In the first stage the anionic headgroups of SDS individually bind to the cationic side groups of PVP chain due to electrostatic attraction. In the second stage when the surfactant concentration reaches the second critical aggregation concentration cac2, the micellization of polymer-bound surfactant occurs.
2. Using PVP/SDS complex as a probe the inclusion complexation betweenβ-cyclodextrin(β-CD) and SDS has been studied. Viscosity measurements show that the inclusion complexation betweenβ-CD and SDS may cause the SDS molecules being stripped off the PVP chains, resulting in the decrease of the solution viscosity due to the decaease of electrostatic repulsion between polymer-bound SDS molecules. The viscosity minimum at Cβ-CD/CSDS=1 indicate the molecular ratio of host molecule to guest molecule is 1:1 in theβ-CD/SDS inclusion complex. Data from conductivity measurements indicate that there is the 2:1 inclusion complexation betweenβ-CD and SDS after the 1:1 inclusion complexation being finished.
3. The effect of benzyl alcohol on the micellization of SDS has been studied using PVP/SDS complex as a probe. When the concentration of benzyl alcohol is low benzyl alcohol behave as a cosurfactant. Through hydrophobic interaction the mixed micellization between benzyl alcohol and SDS occurs. As a result the number of polymer-bound SDS increasing. Thus the relative viscosity of PVP/SDS/benzyl alcohol solutions increases due to the stronger electrostatic repulsion and the conductivity decreases because polymer-bound SDS has lower mobility than free SDS molecule. At high concentrations benzyl alcohol behave as a cosolvent. The properties and structure of the aqueous solvent mixture are modified in such a manner that the solubility of an ionic surfactant increases, that is, the solution is more hydrophobic and the hydrophobic interaction between the SDS molecules or between PVP and SDS decrease. These factors cause the SDS molecules being stripped off the PVP chains, resulting in the increase of the conductivity and the decrease of the solution viscosity due to the decrease of electrostatic repulsion within PVP chains. In the presence of benzyl alcohol the amount of surfactant bound to the polymer viz. Cbound at saturation decreases. At different benzyl alcohol concentrations the ionization degree of PVP-bound SDS micelles does not change much, which is about 30% larger than that in the absence of benzyl alcohol. The decrease of electrostatic repulsion within PVP chains resulting from the decrease of the amount of SDS bound to PVP chains can be compensated by the increase of the ionization degree of PVP-bound SDS micelles.
4. The effect of n-butyric acid, n-butylamine and n-butanol on the micellization of SDS has been studied using PVP/SDS complex as a probe. Viscosity data indicates that the electrostatic character of the headgroups has strong effect on the response of PVP/SDS complex upon the addition of different additives. The headgroup of n-butyric acid has a negative charge, same as SDS molecule, but it has a lower ionization degree. The initiation of adding n-butyric acid cause PVP chains have more positive charge, resulting in the decrease of dimension of PVP chain which is bound to the SDS micelle. As the n-butyric acid concentration increases the mixed micellization of n-butyric acid and SDS make more SDS micelles associate with PVP chains. Thus the relative viscosity of PVP/SDS/n-butyric acid solutions increases due to the stronger electrostatic repulsion. Adding more n-butyric acid the screening effect upon the electrostatic interaction make the PVP chains shrink again. The headgroup of n-butylamine has a positive charge which is oppositely to SDS molecules. Mixed micellization is promoted by the hydrophobic interaction between the hydrocarbon chains and the electrostatic attraction between the oppositely charged headgroups. The negative charge of SDS is neutralized and there is the repulsion force between positively charged n-butylamine and PVP. As a result the interaction between PVP and SDS/n-butylamine mixed micelles decreases sharply, resulting in PVP-bound SDS being stripped off the PVP chains. At low concentrations n-butanol behaves as a cosurfactant. Through hydrophobic interaction the mixed micellization between n-butanol and polymer-bound SDS occurs. As a result the number of polymer-bound SDS micelles increasing. Thus the relative viscosity of PVP/SDS/n-butanol solutions increases due to the stronger electrostatic repulsion and the conductivity decreases because polymer-bound SDS has lower mobility than free SDS molecule. At high concentrations n-butanol behaves as a cosolvent. The solution is more hydrophobic and the hydrophobic interaction between the SDS molecules or between PVP and SDS decrease. These factors make the PVP-bound SDS micelles being stripped off the PVP chains, resulting in the increase of the conductivity and the decrease of the solution viscosity due to the decrease of electrostatic repulsion within PVP chains. In the presence of n-butanol the amount of surfactant bound to the polymer viz. Cbound at saturation decreases. As n-butanol concentration increases the ionization degree of PVP-bound SDS micelles increases distinctively. The character of the hydrophobic group has strong effect on the response of PVP/SDS complex upon the addition of different additives. The volume of hydrophobic group of n-butanol is smaller than benzyl alcohol. As a result SDS molecules are more closing in SDS/n-butanol mixed micelles than that in SDS/benzyl alcohol mixed micelles. And the solubilization amount of n-butanol is more than benzyl alcohol. Thereby the ionization degree of PVP-bound SDS micelle increases with the n-butanol concentration. The hydrophobic group of benzyl alcohol is larger. As a result the partitioning of benzyl alcohol in the PVP-bound SDS micelles blocks the closing between SDS molecules. The solubilization amount of benzyl alcohol is relatively small. Thereby the ionization degree of PVP-bound SDS micelle does not change much with the benzyl alcohol concentration.
5. Interaction between gelatin and cationic gemini surfactant 1,2-ethane bis(N, N, N-dimethyl (Z-13-docosenyl) quaternary ammonium bromide) (22-2-22) has been studied by conductivity, viscosity and fluorescence spectroscopy. In the initial binding of surfactant to gelatin molecule the hydrophobic interaction between the surfactant and the hydrophobic segments of gelatin causes the breaking of the hydrophobic microdomain on polymer chains, resulting in the extension of polymer chains, that is, the partially denaturing of gelatin. With the further addition of 22-2-22 at low surfactant concentrations inter-polymer association mediated by the surfactant aggregates dominates. One surfactant aggregates may bind more than one polymer strands. While at high surfactant concentrations the intra-polymer association dominates. Then with the increase of C22-2-22 one polymer strand may accommodate several surfactant micelles forming a pearl-necklace complex. By using fluorescence method a critical concentration of 22-2-22 can be defined, viz. cac, beyond which the micellization of gelatin-bound 22-2-22 occurs.
通过粘度、电导、表面张力及荧光光谱研究了聚乙烯基吡咯烷酮(PVP)与十二烷基硫酸钠(SDS)的相互作用,当cac(临界聚集浓度)
利用PVP/SDS聚集体为探针,根据PVP/SDS复合物溶液在添加苯甲醇时溶液粘度对苯甲醇浓度的依赖性可反映苯甲醇对SDS胶束化行为的影响。苯甲醇浓度较小时,其对SDS胶束化行为的影响表现为共表面活性剂效应,苯甲醇与溶液中的自由SDS分子通过疏水相互作用形成混合聚集体并缔合于高分子链,使得缔合于PVP链上的SDS分子数量增加,静电排斥作用增强,溶液粘度增大,同时溶液电导率减小；苯甲醇浓度较大时,其对SDS胶束化行为的影响表现为共溶剂效应,随苯甲醇浓度增大,溶液更加疏水,表面活性剂疏水链与高分子链间的疏水相互作用减弱,使与PVP链缔合的SDS胶束从PVP链脱落,静电排斥作用减弱,溶液粘度减小,同时溶液电导率增大。SDS在PVP上饱和缔合量当苯甲醇存在时减小,至苯甲醇浓度较大时基本不变,与PVP缔合的SDS胶束的电离度当苯甲醇存在时比没有苯甲醇存在时增大约30%,至苯甲醇浓度较大时基本不变,二者导致的高分子-缔合表面活性剂之间的静电相互作用的变化可以相互补偿。
利用PVP/SDS聚集体为探针,根据PVP/SDS复合物溶液在添加正丁酸、正丁胺、正丁醇时溶液粘度对添加物浓度的依赖性可反映正丁酸、正丁胺、正丁醇对SDS的胶束化行为的影响。PVP/SDS复合物溶液性质对添加极性头基电荷性质不同的正丁酸、正丁胺、正丁醇的响应有显著差别。
正丁酸极性头基与SDS离子头基均带负电荷,添加正丁酸使PVP侧基羰基上带部分负电的氧原子更易质子化,氮原子带部分正电,因而PVP链所带正电荷数增加,PVP链以更加卷曲的构象与SDS聚集体缔合,高分子链收缩。随正丁酸浓度增大,正丁酸与SDS混合胶束化并缔合于PVP链,使缔合于PVP链上的SDS分子数量增加,静电排斥作用增强,PVP链更加伸展。继续添加正丁酸,正丁酸对静电相互作用的屏蔽使得缔合于PVP链的SDS离子间的静电排斥作用减弱,高分子链收缩。
正丁胺在水溶液中其极性头基带正电。通过疏水链间的疏水相互作用及极性头基间的静电吸引作用正丁胺与缔合于PVP链的SDS分子形成混合聚集体,其极性头基的正电性一方面对SDS头基的负电性起到中和作用,另一方面与PVP正电性侧基发生静电排斥,二者均使得PVP-SDS相互作用减弱,导致已缔合于PVP链的SDS胶束脱落,高分子链收缩,直至缔合于PVP链的SDS胶束全部脱落。
正丁醇浓度较小时,表现为共表面活性剂效应,正丁醇与溶液中自由SDS分子通过疏水相互作用形成混合聚集体并缔合于PVP链,使得缔合于PVP链上的SDS分子数量增加,静电排斥作用增强,PVP链更加伸展。正丁醇浓度较大时,表现出共溶剂效应,溶液更加疏水,表面活性剂疏水链与高分子链间的疏水相互作用减弱,缔合于PVP链的SDS胶束从PVP链脱落,静电排斥作用减弱,高分子链收缩。
疏水基团大小不同使得PVP/SDS复合物溶液对添加正丁醇与苯甲醇的响应有显著差别。正丁醇的疏水基团体积较小,插入与PVP缔合的SDS胶束后,使SDS排列更加紧密,在SDS胶束中的增溶量较多,使胶束表面电荷密度降低更为显著,与PVP缔合的SDS胶束的电离度随正丁醇浓度增大而显著增大,而苯甲醇的疏水基团体积较大,插入与PVP缔合的SDS胶束后,对SDS分子的相互靠近起空间位阻作用,不利于SDS紧密排列,在SDS胶束中的增溶量较少,与PVP缔合的SDS胶束的电离度在苯甲醇浓度较大时基本不随苯甲醇浓度而改变。
粘度、电导和荧光光谱实验结果证实明胶与gemini表面活性剂亚乙基-α,ω-双(N,N,N-二甲基(顺-13-二十二烯基))(22-2-22)溴化铵的相互作用可以分为三个阶段。第一阶段,22-2-22通过与明胶分子疏水性氨基酸残基的疏水相互作用插入明胶分子的疏水微区,以单体形式与明胶分子缔合。第二阶段,与明胶分子链缔合的22-2-22形成类胶束聚集体,导致明胶分子的链间交联。第三阶段,与明胶分子链缔合的22-2-22形成类胶束聚集体增多,明胶分子的链间交联解开,继而发生链内交联。利用明胶内源(酪氨酸残基)荧光光谱最大发射强度对表面活性剂浓度作图中峰值位置可以确定明胶-22-2-22相互作用历程中与明胶分子链缔合的22-2-22开始形成类胶束聚集体的临界聚集浓度cac。
Interactions between polymer and surfactant in aqueous solutions have attracted significant interest for their widespread applications and relatively complex behaviors. Several aspects are discussed in this thesis about the utility of polymer/surfactant complex to study the interaction between small organic molecules with surfactants. The main findings are as follows:
1. Data presented in viscosity, conductivity, surface tension and fluorescence studies on the interaction between Poly(vinyl pyrrolidone)(PVP) and Sodium Dodecyl Sulfate(SDS) in aqueous solution indicates that the interaction between PVP and SDS can be separated into two stages. In the first stage the anionic headgroups of SDS individually bind to the cationic side groups of PVP chain due to electrostatic attraction. In the second stage when the surfactant concentration reaches the second critical aggregation concentration cac2, the micellization of polymer-bound surfactant occurs.
2. Using PVP/SDS complex as a probe the inclusion complexation betweenβ-cyclodextrin(β-CD) and SDS has been studied. Viscosity measurements show that the inclusion complexation betweenβ-CD and SDS may cause the SDS molecules being stripped off the PVP chains, resulting in the decrease of the solution viscosity due to the decaease of electrostatic repulsion between polymer-bound SDS molecules. The viscosity minimum at Cβ-CD/CSDS=1 indicate the molecular ratio of host molecule to guest molecule is 1:1 in theβ-CD/SDS inclusion complex. Data from conductivity measurements indicate that there is the 2:1 inclusion complexation betweenβ-CD and SDS after the 1:1 inclusion complexation being finished.
3. The effect of benzyl alcohol on the micellization of SDS has been studied using PVP/SDS complex as a probe. When the concentration of benzyl alcohol is low benzyl alcohol behave as a cosurfactant. Through hydrophobic interaction the mixed micellization between benzyl alcohol and SDS occurs. As a result the number of polymer-bound SDS increasing. Thus the relative viscosity of PVP/SDS/benzyl alcohol solutions increases due to the stronger electrostatic repulsion and the conductivity decreases because polymer-bound SDS has lower mobility than free SDS molecule. At high concentrations benzyl alcohol behave as a cosolvent. The properties and structure of the aqueous solvent mixture are modified in such a manner that the solubility of an ionic surfactant increases, that is, the solution is more hydrophobic and the hydrophobic interaction between the SDS molecules or between PVP and SDS decrease. These factors cause the SDS molecules being stripped off the PVP chains, resulting in the increase of the conductivity and the decrease of the solution viscosity due to the decrease of electrostatic repulsion within PVP chains. In the presence of benzyl alcohol the amount of surfactant bound to the polymer viz. Cbound at saturation decreases. At different benzyl alcohol concentrations the ionization degree of PVP-bound SDS micelles does not change much, which is about 30% larger than that in the absence of benzyl alcohol. The decrease of electrostatic repulsion within PVP chains resulting from the decrease of the amount of SDS bound to PVP chains can be compensated by the increase of the ionization degree of PVP-bound SDS micelles.
4. The effect of n-butyric acid, n-butylamine and n-butanol on the micellization of SDS has been studied using PVP/SDS complex as a probe. Viscosity data indicates that the electrostatic character of the headgroups has strong effect on the response of PVP/SDS complex upon the addition of different additives. The headgroup of n-butyric acid has a negative charge, same as SDS molecule, but it has a lower ionization degree. The initiation of adding n-butyric acid cause PVP chains have more positive charge, resulting in the decrease of dimension of PVP chain which is bound to the SDS micelle. As the n-butyric acid concentration increases the mixed micellization of n-butyric acid and SDS make more SDS micelles associate with PVP chains. Thus the relative viscosity of PVP/SDS/n-butyric acid solutions increases due to the stronger electrostatic repulsion. Adding more n-butyric acid the screening effect upon the electrostatic interaction make the PVP chains shrink again. The headgroup of n-butylamine has a positive charge which is oppositely to SDS molecules. Mixed micellization is promoted by the hydrophobic interaction between the hydrocarbon chains and the electrostatic attraction between the oppositely charged headgroups. The negative charge of SDS is neutralized and there is the repulsion force between positively charged n-butylamine and PVP. As a result the interaction between PVP and SDS/n-butylamine mixed micelles decreases sharply, resulting in PVP-bound SDS being stripped off the PVP chains. At low concentrations n-butanol behaves as a cosurfactant. Through hydrophobic interaction the mixed micellization between n-butanol and polymer-bound SDS occurs. As a result the number of polymer-bound SDS micelles increasing. Thus the relative viscosity of PVP/SDS/n-butanol solutions increases due to the stronger electrostatic repulsion and the conductivity decreases because polymer-bound SDS has lower mobility than free SDS molecule. At high concentrations n-butanol behaves as a cosolvent. The solution is more hydrophobic and the hydrophobic interaction between the SDS molecules or between PVP and SDS decrease. These factors make the PVP-bound SDS micelles being stripped off the PVP chains, resulting in the increase of the conductivity and the decrease of the solution viscosity due to the decrease of electrostatic repulsion within PVP chains. In the presence of n-butanol the amount of surfactant bound to the polymer viz. Cbound at saturation decreases. As n-butanol concentration increases the ionization degree of PVP-bound SDS micelles increases distinctively. The character of the hydrophobic group has strong effect on the response of PVP/SDS complex upon the addition of different additives. The volume of hydrophobic group of n-butanol is smaller than benzyl alcohol. As a result SDS molecules are more closing in SDS/n-butanol mixed micelles than that in SDS/benzyl alcohol mixed micelles. And the solubilization amount of n-butanol is more than benzyl alcohol. Thereby the ionization degree of PVP-bound SDS micelle increases with the n-butanol concentration. The hydrophobic group of benzyl alcohol is larger. As a result the partitioning of benzyl alcohol in the PVP-bound SDS micelles blocks the closing between SDS molecules. The solubilization amount of benzyl alcohol is relatively small. Thereby the ionization degree of PVP-bound SDS micelle does not change much with the benzyl alcohol concentration.
5. Interaction between gelatin and cationic gemini surfactant 1,2-ethane bis(N, N, N-dimethyl (Z-13-docosenyl) quaternary ammonium bromide) (22-2-22) has been studied by conductivity, viscosity and fluorescence spectroscopy. In the initial binding of surfactant to gelatin molecule the hydrophobic interaction between the surfactant and the hydrophobic segments of gelatin causes the breaking of the hydrophobic microdomain on polymer chains, resulting in the extension of polymer chains, that is, the partially denaturing of gelatin. With the further addition of 22-2-22 at low surfactant concentrations inter-polymer association mediated by the surfactant aggregates dominates. One surfactant aggregates may bind more than one polymer strands. While at high surfactant concentrations the intra-polymer association dominates. Then with the increase of C22-2-22 one polymer strand may accommodate several surfactant micelles forming a pearl-necklace complex. By using fluorescence method a critical concentration of 22-2-22 can be defined, viz. cac, beyond which the micellization of gelatin-bound 22-2-22 occurs.
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