寡肽调控光敏分子自组装——在光能捕获和光动力治疗方面的机遇与挑战
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摘要
蛋白的组装是自然界普遍存在的现象。在天然的捕光天线复合物中,蛋白和光敏分子的共组装使光敏分子呈三维有序排列,能够高效地捕获和传递太阳能。仅含有数个氨基酸的寡肽也具备复杂的自组装行为[1,2]。我们利用寡肽对光敏分子的自组装进行调控,获得了一系列多层次、多尺度的组装体[3-5]。这些组装体一方面可作为仿生的光捕获复合物,另一方面可作为光动力治疗用纳米制剂。调控光敏分子的分级有序排列是构筑光捕获复合物的一大挑战,以苯丙氨酸二肽和赖氨酸二肽通过弱相互作用力调控四(4-磺酸基苯基)卟啉自组装,在分级组装体中成功实现了光敏分子的长程有序排列。该组装体能够选择性摄取外源性物质、光催化合成无机纳米颗粒和有机功能分子,有望在仿生光合成中实现更多功能。将光敏分子高效递送至肿瘤是光动力药物递送中的主要挑战,苯丙氨酸二肽调控二氢卟吩e6(Ce6)自组装得到高负载Ce6分子的组装体,增强了Ce6分子在肿瘤部位的富集和对肿瘤的治疗效果。寡肽调控光敏分子自组装具备分子基元结构明确、组装可控的优点,进一步研究中可整合仿生的光敏电荷分离基团或肿瘤靶向寡肽,以提高其光功能应用效果。
Self-assembly is ubiquitous at various length scales throughout biology and is a key process of life.Inspired largely by biological systems,self-assembly has been developed as a dominant technique towards creation of complex synthetic systems[1,2].However,how to achieve controlled self-assembly of functional structures towards biomimetic fabrication and biomedical application by key small biomolecules such as peptides and porphyrins remains a remarkable challenge.In this presentation,we will first report how multifunctional architectures with order at different length scales are created by hierarchical co-assembly of simple dipeptides and porphyrins[3-5].Depending on hydrophobic/hydrophilic property of dipeptides used,the resulting assemblies can be well controlled by tuning intermolecular interactions between dipeptides and porphyrins.Light-harvesting can be achieved within the assemblies including porous microspheres and fiber bundles.Following this,we will show how simple dipeptides and even amino acids can be used to tune self-assembly of photosensitive drugs for formation of well-defined nanoparticles as a future nanomedicine towards antitumor photodynamic therapy(PDT).Due to advantages of easy availability,structural simplicity,functional flexibility and effective cost of amino acids and dipeptides,such delivery systems based on co-assembly with drugs on themselves will provide a new alternative pathway for enhanced PDT against cancers.
引文
[1]Chen,C.J.;Liu,K.;Li,J.B.;Yan,X.H.Adv.Colloid Interface Sci.2015,225:177.
    [2]Zou,Q.L.;Liu,K.;Abbas,M.;Yan,X.H.Adv.Mater.2016,28:1031.
    [3]Zou,Q.L.;Zhang,L.;Yan,X.H.;Wang,A.H.;Ma,G.H.;Li,J.B.;Mohwald,H.;Mann,S.Angew.Chem.Int.Edit.2014,53:2366.
    [4]Liu,K.;Xing,R.R.;Chen,C.J.;Shen,G.Z.;Yan,L.Y.;Zou,Q.L.;Ma,G.H.;Mohwald,H.;Yan,X.H.Angew.Chem.Int.Edit.2015,54:500.
    [5]Liu,K.;Xing,R.R.;Zou,Q.L.;Ma,G.H.;Mohwald,H.;Yan,X.H.Angew.Chem.Int.Ed.2016,55:3036.

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