He Xiaoyun, Kevlishvili Ilia, Murcek Katherina, Liu Peng, Star Alexander
Department of Chemistry, ‡Department of Chemical and Petroleum Engineering, and §Department of Bioengineering, University of Pittsburgh, Pittsburgh, Pennsylvania 15260, United States.
ACS Nano. 2021 Mar 23;15(3):4833-4844. doi: 10.1021/acsnano.0c09583. Epub 2021 Mar 9.
Single-walled carbon nanotubes (SWCNTs) have been widely applied in biomedical fields such as drug delivery, biosensing, bioimaging, and tissue engineering. Understanding their reactivity with biomolecules is important for these applications. We describe here a photoinduced cycloaddition reaction between enones and SWCNTs. By creating covalent and tunable sp defects in the sp carbon lattice of SWCNTs through [2π + 2π] photocycloaddition, a bright red-shifted photoluminescence was gradually generated. The photocycloaddition functionalization was demonstrated with various organic molecules bearing an enone functional group, including biologically important oxygenated lipid metabolites. The mechanism of this reaction was studied empirically and using computational methods. Density functional theory calculations were employed to elucidate the identity of the reaction product and understand the origin of different substrate reactivities. The results of this study can enable engineering of the optical and electronic properties of semiconducting SWCNTs and provide understanding into their interactions with the lipid biocorona.
单壁碳纳米管（SWCNTs）已广泛应用于生物医学领域，如药物递送、生物传感、生物成像和组织工程。了解它们与生物分子的反应性对于这些应用很重要。我们在此描述了烯酮与单壁碳纳米管之间的光诱导环加成反应。通过[2π + 2π]光环加成在单壁碳纳米管的sp碳晶格中创建共价且可调节的sp缺陷，逐渐产生了红移明显的明亮光致发光。用各种带有烯酮官能团的有机分子（包括具有生物学重要性的氧化脂质代谢物）证明了光环加成功能化。通过实验和计算方法研究了该反应的机理。采用密度泛函理论计算来阐明反应产物的特性，并了解不同底物反应性的起源。这项研究的结果能够实现对半导体单壁碳纳米管光学和电子性质的工程设计，并有助于理解它们与脂质生物冠层的相互作用。
