Molecular-Level Helical Stack of a Nucleotide-Appended Oligo(p-phenylenevinylene) Directed by Supramolecular Self-Assembly with a Complementary Oligonucleotide as a Template

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• 作者：Rika Iwaura ; Freek J. M. Hoeben ; Mitsutoshi Masuda ; Albertus P. H. J. Schenning ; E. W. Meijer ; Toshimi Shimizu
• 刊名：Journal of the American Chemical Society
• 出版年：2006
• 出版时间：October 11, 2006
• 年：2006
• 卷：128
• 期：40
• 页码：13298 - 13304
• 全文大小：446K
• 年卷期：v.128,no.40(October 11, 2006)
• ISSN：1520-5126

文摘

The nucleotide-appended oligo(p-phenylenevinylene), {bis[2,5-bis(2-methoxyethoxy)-1,4-phenylene]bis(2,1-ethenediyl-1,4-phenylenemethylene)}bis(2'-deoxy-3'-thymidylic acid) (8), has been synthesized, and self-assembly of the single-component 8 and binary self-assembly of 8 with a complementarysingle-stranded 20-meric oligodeoxyadenylic acid (9) have been examined in aqueous solutions. Atomicforce microscopy (AFM), UV-visible (UV-vis), and circular dichroism (CD) measurements revealed thatright-handed helical stacks with 6.4- and 5.1-nm diameters self-assemble from the binary components of8 and 9 as a template depending on the residual stoichiometry of the two components (thymine (T):adenine(A) = 1:1 and T:A = 2:1, respectively). The concentration of 9 was found to strongly influence the CDspectra of 8 in aqueous solutions. Consequently, we concluded that the one side of the thymine moietiesin the stacked assemblies of 8 complexes with a single chain of 9. Complementary T-A base pairs thusformed and induced helical stack of the oligo(p-phenylenevinylene)s in the binary self-assembly. In contrast,self-assembly of the single-component 8 and binary self-assembly of 8 with the noncomplementary 20-meric oligothymidylic acid (10) produced no remarkable formation of fibrous structures like helical stacks.