基于阴离子环糊精衍生物/阳离子双子表面活性剂构筑液液凝聚相及其对染料的富集性能

doi:10.6023/A25070251

摘要/Abstract

本工作采用浊度滴定、冷冻透射电镜(Cryo-TEM)、核磁共振氢谱(¹H NMR)以及ζ-电位分析等方法, 系统研究了阴离子环糊精衍生物磺丁基-β-环糊精钠盐(SBE-β-CD)与阳离子双子表面活性剂十二烷基-s-十二烷基二甲基溴化铵(12-s-12, s为联接基中亚甲基的数目)混合体系的分子间相互作用及其聚集行为. 结果表明, 在固定浓度的SBE-β-CD中逐渐加入12-s-12后, 二者通过静电吸引与主客体作用形成复合物, 并聚集成为小粒径球形聚集体. 随着12-s-12浓度增大, 这些球形聚集体之间通过复合物疏水尾链间的桥联作用相互缔合, 形成尺寸更大的锁链状聚集体. 随着体系中净电荷逐渐减少, 锁链状聚集体之间进一步相互缠绕形成液液凝聚相. 当体系中12-s-12过量之后, 聚集体之间的静电排斥逐渐增强, 液液凝聚相重新转变为锁链状聚集体, 并最终转变为小尺寸球形聚集体. 通过比较不同12-s-12结构形成液液凝聚相区域发现, 随着表面活性剂联接基团中亚甲基由3增加至6, 其与SBE-β-CD形成液液凝聚相的能力增加, 形成区间更宽. 而由SBE-β-CD/12-6-12形成的凝聚相可实现对水中刚果红和甲基橙的完全富集提取, 表现出优异的染料富集性能. 相比之下, 该体系对酸性蓝和亚甲基蓝的富集提取率较低, 这种选择性吸附分离特性使其可应用于染料分离纯化等领域.

关键词: 液液凝聚相, 染料富集, 阴离子环糊精衍生物, 阳离子双子表面活性剂, 聚集行为

Owing to their unique enrichment and phase-separation properties, coacervates not only enable the efficient capture and removal of pollutants but also differ fundamentally from conventional oil-water separation systems by operating in an aqueous environment, thereby offering significant advantages in pollutant remediation. Surfactant-based coacervates, in particular, exhibit superior solubilization capacity for pollutants while maintaining simple molecular structures and high degradability. Consequently, the development of surfactant-based coacervates holds considerable promise as an emerging technology for wastewater treatment. This study investigated the intermolecular interactions and aggregation behaviors of the mixed system comprising anionic cyclodextrin derivative sulfobutyl-β-cyclodextrin sodium salt (SBE-β-CD) and cationic gemini surfactant alkanediyl-α,ω-bis(dimethyldodecylammonium) bromide (12-s-12) through turbidity titration, cryo-transmission electron microscopy (Cryo-TEM), proton nuclear magnetic resonance (¹H NMR), and zeta potential analysis. The results reveal that upon gradually adding 12-s-12 to a fixed concentration of SBE-β-CD, the two components form complexes through electrostatic attraction and host-guest interactions, which further assemble into small-sized spherical aggregates. As the concentration of 12-s-12 increases, these spherical aggregates associate into larger chain-like aggregates via hydrophobic bridging between the tails of the complexes. With the gradual reduction of net charge in the system, the chain-like aggregates become increasingly entangled, ultimately leading to the formation of coacervates. When 12-s-12 is excessive in the system, the electrostatic repulsion between aggregates increase, causing the coacervates to revert to chain-like aggregates and eventually to small spherical aggregates. Comparison of coacervate formation regions for different 12-s-12 structures shows that as the methylene units in the spacer group of the gemini surfactants increase from 3 to 6, their ability to form coacervates with SBE-β-CD strengthens, resulting in a broader formation range. Besides, the coacervates formed by SBE-β-CD/12-6-12 can achieve complete enrichment and extraction of congo red and methyl orange from aqueous solutions, demonstrating excellent dye enrichment performance. In contrast, the system exhibits relatively low extraction efficiency for acid blue and methylene blue. This selective enrichment behavior suggests its application in the separation of dyes and wastewater treatment.

Key words: coacervate, dye enrichment, anionic cyclodextrin derivative, cationic gemini surfactant, aggregation behavior

引用此文

乔富林, 张超, 秦冰, 江建林, 周丽丽. 基于阴离子环糊精衍生物/阳离子双子表面活性剂构筑液液凝聚相及其对染料的富集性能[J]. 化学学报, 2025, 83(12): 1514-1522.

Fulin Qiao, Chao Zhang, Bing Qin, Jianlin Jiang, Lili Zhou. Construction of Coacervates Based on Anionic Cyclodextrin Derivative/Cationic Gemini Surfactants and their Dye Enrichment Performance[J]. Acta Chimica Sinica, 2025, 83(12): 1514-1522.

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图/表 7

图1. SBE-β-CD和12-6-12的分子结构式

Figure 1. Molecular structures of SBE-β-CD and 12-6-12

图2. SBE-β-CD/12-6-12体系浊度随12-6-12浓度的变化曲线. SBE-β-CD浓度分别固定为0.05 mmol•L−1和0.25 mmol•L−1 (a), 1.00 mmol•L−1 (b)以及2.50 mmol•L−1 (c). (d)复合体系形成的白色乳状液显微镜照片

Figure 2. Turbidity curves of SBE-β-CD/12-6-12 systems as a function of 12-6-12 concentration. The concentration of SBE-β-CD is fixed at 0.05 mmol•L−1 and 0.25 mmol•L−1 (a), 1.00 mmol•L−1 (b), and 2.50 mmol•L−1 (c), respectively. (d) A microscopic photograph of the white solution formed by the complex system

图3. 固定SBE-β-CD浓度值, SBE-β-CD/12-6-12 (a)以及SBE-β-CD/ 12-3-12 (b)复合体系浊度随阳离子双子表面活性剂浓度的变化曲线. (c) SBE-β-CD/阳离子双子表面活性剂混合体系形成液液凝聚相的浓度区间

Figure 3. Turbidity curves of SBE-β-CD/12-6-12 (a) and SBE-β-CD/ 12-3-12 (b) systems as a function of gemini surfactant concentrations, with fixed SBE-β-CD concentrations. (c) Concentration range for coacervate formation in SBE-β-CD/gemini surfactant mixed systems

图4. 固定SBE-β-CD浓度为1.00 mmol•L−1, SBE-β-CD/12-6-12体系的浊度(a)以及聚集体ζ-电位(b)随12-6-12浓度的变化曲线. 1.00 mmol•L−1 SBE-β-CD分别与以下浓度12-6-12混合后聚集体的Cryo-TEM照片: 0.25 mmol•L−1 (c); 0.70 mmol•L−1 (d); 5.00 mmol•L−1 (e); 7.50 mmol•L−1 (f)

Figure 4. Turbidity (a) and ζ-potential (b) variation curves of the SBE-β-CD/12-6-12 system as a function of 12-6-12 concentration, with the SBE-β-CD concentration fixed at 1.00 mmol•L−1. Cryo-TEM images of the aggregates formed by mixing 1.00 mmol•L−1 SBE-β-CD with 12-6-12 at concentrations of 0.25 mmol•L−1 (c), 0.70 mmol•L−1 (d), 5.00 mmol•L−1 (e) and 7.50 mmol•L−1 (f)

图5. (a) SBE-β-CD和12-6-12分子结构及质子归属; (b) SBE-β-CD浓度固定为1.00 mmol•L−1时, 混合体系在不同12-6-12浓度条件下的核磁谱图, 以及浓度均为1.00 mmol•L−1的纯SBE-β-CD和纯12-6-12的核磁谱图

Figure 5. (a) Molecular structures and proton assignments of SBE-β-CD and 12-6-12; (b) NMR spectra of the mixed system at different 12-6-12 concentrations with the SBE-β-CD concentration fixed at 1.00 mmol•L−1, along with the NMR spectra of SBE-β-CD and 12-6-12 at a concentration of 1.00 mmol•L−1

图6. (a)当12-6-12浓度低于C1时, 其与SBE-β-CD形成的复合物示意图; (b)当12-6-12浓度高于C1时, 其与SBE-β-CD形成的复合物示意图; (c) SBE-β-CD/12-6-12混合体系聚集体转变过程示意图

Figure 6. (a) Schematic illustration of the complexes formed between 12-6-12 and SBE-β-CD when the 12-6-12 concentration is below C1; (b) Schematic illustration of the complexes formed when the 12-6-12 concentration is above C1; (c) Schematic representation of the aggregation transition process in the SBE-β-CD/12-6-12 mixed system

图7. 四种不同染料的分子结构及液液相分离体系对不同浓度特定染料的富集提取效果照片: (a)刚果红; (b)甲基橙; (c)酸性蓝; (d)亚甲基蓝. (e)随染料浓度变化, 液液相分离体系对染料的富集提取效率. (f)液液相分离体系对刚果红和亚甲基蓝混合溶液的选择性分离效果照片

Figure 7. Molecular structures of different dyes and photographs showing the enrichment and extraction performance of the coacervate for the dyes: (a) Congo red, (b) Methyl orange, (c) Acid blue, (d) Methylene blue. (e) Enrichment and extraction efficiency of the coacervate for four dyes at different concentrations. (f) Photograph of the selective separation performance of the coacervate for a mixed solution of congo red and methylene blue

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