Department of Chemical and Biological Engineering/Physical Chemistry, Chalmers University of Technology, S-41296 Gothenburg, Sweden.
ACS Nano. 2010 Sep 28;4(9):5037-46. doi: 10.1021/nn100667b.
We have synthesized and studied a supramolecular system comprising a 39-mer DNA with porphyrin-modified thymidine nucleosides anchored to the surface of large unilamellar vesicles (liposomes). Liposome porphyrin binding characteristics, such as orientation, strength, homogeneity, and binding site size, was determined, suggesting that the porphyrin is well suited as a photophysical and redox-active lipid anchor, in comparison to the inert cholesterol anchor commonly used today. Furthermore, the binding characteristics and hybridization capabilities were studied as a function of anchor size and number of anchoring points, properties that are of importance for our future plans to use the addressability of these redox-active nodes in larger DNA-based nanoconstructs. Electron transfer from photoexcited porphyrin to a lipophilic benzoquinone residing in the lipid membrane was characterized by steady-state and time-resolved fluorescence and verified by femtosecond transient absorption.
我们合成并研究了一个超分子系统，该系统由一个带有卟啉修饰的胸腺嘧啶核苷的 39 个碱基的 DNA 与大单层囊泡（脂质体）的表面相连。研究了脂质体卟啉的结合特性，如取向、强度、均一性和结合位点大小，表明与目前常用的惰性胆固醇锚相比，卟啉非常适合作为光物理和氧化还原活性脂质锚。此外，还研究了结合特性和杂交能力作为锚定尺寸和锚定点数量的函数，这些特性对于我们未来计划在更大的基于 DNA 的纳米结构中使用这些氧化还原活性节点的可寻址性非常重要。通过稳态和时间分辨荧光研究了光激发卟啉到位于脂质膜中的亲脂性苯醌的电子转移，并通过飞秒瞬态吸收进行了验证。
