A Facile Construction of Supramolecular Complex from Polyaniline and Cellulose in Aqueous System
A Facile Construction of Supramolecular Complex from Polyaniline and Cellulose in Aqueous System
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水体系中聚苯胺和纤维素超分子复合物的简便构建
DOI：
10.1021/ma2009904
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发表时间：
2011-06
期刊：
影响因子：
5.5
通讯作者：
Xianhong Wang
中科院分区：
文献类型：
--
作者：
Xingwei Shi;Lina Zhang;Jie Cai;Gongzhen Cheng;Hongming Zhang;Ji Li;Xianhong Wang
近年来，聚苯胺（PANI）因其合成简单、易操作、环境稳定性好、可控性好而备受关注，在导电薄膜、纳米棒、手性材料、纳米纤维、螺旋纳米纤维、中空纤维、中空纳米管、金属聚合物、有机/无机杂化物等方面的新发现，使得1,2和PANI材料具有诱人的前景。3,4导电聚合物提供了实现新一代材料的希望，这些材料表现出良好的电学和光学性能，并保留了有吸引力的机械性能和加工优势。为了提高聚苯胺的可加工性和机械性能，已经报道了许多与传统聚合物共混的尝试，使用原位化学聚合技术将聚苯胺沉积在微孔醋酸纤维素膜上，以及进行聚苯胺接枝共聚物。值得注意的是，Jean-Marie Lehn引入了“超分子化学”这一术语，它涉及到由两种或两种以上的化学物质通过分子间作用力结合在一起而产生的更高复杂性的有组织实体。通过非共价相互作用构建的超分子复合物因其迷人的性能而引起了越来越多的关注，并且通过氢键、双响应超分子聚合物凝胶和非共价连接胶束制备超分子共聚物对的新途径已经开辟。纤维素是替代油基原料的主要候选，但只有通过使用破坏氢键的特定溶剂才能溶解纤维素。在我们的实验室里，用7wt %的NaOH和12wt %的尿素水溶液冷却来快速溶解纤维素。低温下纤维素在水体系中的良好溶解是由于溶剂（氢氧化钠、尿素和水）与纤维素大分子之间的自组装过程，导致通过氢键形成包裹物（IC），包裹物被尿素包围。此外，从纤维素浆料，各种再生纤维素纤维，薄膜，微球，和水凝胶已成功地通过使用一个简单的和“绿色”的过程。我们注意到，水介质中的非共价相互作用对于更好地理解和控制超分子化学非常重要。此外，由亲水段较短的磷酸酯掺杂的聚苯胺在水中表现出一定的分散性。利用聚苯胺和纤维素之间的氢键相互作用来诱导聚苯胺的溶解，然后构建与这两种成分相结合的先进材料，是一项值得努力的工作。本文首次在NaOH/尿素水溶液中通过氢键重排，构建了亲水性纤维素和疏水性聚苯胺的低温超分子复合物。将纤维素溶解在7 wt% NaOH/12 wt%尿素预冷至À12 C的水溶液中制备纤维素溶液，然后将掺杂酸性磷酸酯的聚苯胺立即分散到纤维素溶液中，在5分钟内得到蓝色聚苯胺/纤维素配合物溶液（图S1）。有趣的是，聚苯胺在没有纤维素的NaOH/尿素水溶液中不能溶解，这表明纤维素和聚苯胺在溶解过程中形成了超分子复合物。在我们的研究中，纤维素对聚苯胺的溶解起着重要的作用。聚苯胺/纤维素溶液在NaOH/尿素水溶液体系中稳定1个月，而原来的…
Recently, polyaniline (PANI) has attracted much attention due to its simple and facile synthesis, good environment stability, and controllability, 1, 2 and PANI materials offer enticing prospects on the basis of new findings such as conductive thin films, nanorods, chiral materials, nanofibers, helical nanofibers, hollow fibers, hollow nanotubes, metallic polymers, and organic/inorganic hybrids. 3, 4 Conducting polymers offer the promise of achieving a new generation of materials which exhibit the good electrical and optical properties and which retain the attractive mechanical properties and processing advantages. 5 To improve the processability and mechanical properties of PANI, numerous attempts in blending with conventional polymers, depositing PANI on microporous cellulose acetate membranes using in situ chemical polymerization techniques, and conducting PANI graft copolymer have been reported. 6 It is worth noting that Jean-Marie Lehn has introduced the term “supramolecular chemistry”, which bearing on the organized entities of higher complexity that result from the association of two or more chemical species held together by intermolecular forces. 7 The supramolecular complex constructed through the noncovalent interaction has attracted increasing interest because of their fascinating properties, and new routes to fabricate supramolecular copolymer pairs by hydrogen bonding, dual-responsive supramolecular polymer gel and noncovalently connected micelles have been opened up. 8 Cellulose is a prime candidate for replacing oil-based feedstocks, but only through the use of specific solvents which disrupt hydrogen bonds cellulose can be dissolved. 9 In our laboratory, 7 wt% NaOH and 12 wt% urea aqueous solution with cooling have been used to rapidly dissolve cellulose. The good dissolution of cellulose in the aqueous system at low temperatures arises as a result of a self-assembly process among solvent (NaOH, urea, and water) and the cellulose macromolecules, leading to the formation of an inclusion complex (IC) surrounded by urea through hydrogen bonds. 10 Furthermore, from the cellulose dope, various regenerated cellulose fibers, films, microspheres, and hydrogels have been fabricated successfully by using a simple and “green” process. 11 It is noted that noncovalent interactions in aqueous media are important for obtaining a better understanding and control of supramolecular chemistry. 12 Moreover, PANI doped by phosphate ester having short hydrophilic segment exhibits the certain dispersion in water. 13 A worthwhile endeavor would be to utilize hydrogen-bonding interactions between PANI and cellulose to induce dissolution of PANI and then to construct advanced materials associated with the two components. In the present work, supramolecular complex from hydrophilic cellulose and hydrophobic PANI in the NaOH/urea aqueous solution at low temperature through rearrangement of hydrogen bonds were constructed for the first time. The cellulose solution was prepared by dissolving cellulose in 7 wt% NaOH/12 wt% urea aqueous solutions precooled to À12 C, and then PANI doped with acidic phosphate ester was immediately dispersed to the cellulose solution to obtain a blue PANI/cellulose complexes solution within 5 min (Figure S1). Interestingly, PANI could not be dissolved in NaOH/urea aqueous solution without cellulose, suggesting that supramolecular complex formed from cellulose and PANI during the dissolution. In our findings, cellulose played an important role on the dissolution of PANI. The PANI/cellulose solution in the NaOH/urea aqueous system was stable for 1 month, whereas the original …
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影响因子：
64.8
作者：
Lee, K;Cho, S;Lee, SH
通讯作者：
Lee, SH
DOI：
10.1021/jp109455m
发表时间：
2011-02
期刊：
The journal of physical chemistry. B
影响因子：
--
作者：
A. Qaiser;M. Hyland;D. Patterson
通讯作者：
A. Qaiser;M. Hyland;D. Patterson
影响因子：
29.4
作者：
Chiou, NR;Epstein, AJ
通讯作者：
Epstein, AJ
影响因子：
4.9
作者：
Domingues, Sergio H.;Salvatierra, Rodrigo V.;Zarbin, Aldo J. G.
通讯作者：
Zarbin, Aldo J. G.
影响因子：
5.5
作者：
Sahoo, SK;Nagarajan, R;Cholli, AL
通讯作者：
Cholli, AL