Lu Hao, Cai Jiansong, Fang Yang, Ren Mengqi, Tan Xuyu, Jia Fei, Wang Dali, Zhang Ke
Departments of Chemistry and Chemical Biology, Bioengineering, and Chemical Engineering, Northeastern University, Boston, Massachusetts 02115, United States.
Department of Chemistry, Massachusetts Institute of Technology, 77 Massachusetts Avenue, Cambridge, Massachusetts 02139, United States.
Macromolecules. 2022 Mar 22;55(6):2235-2242. doi: 10.1021/acs.macromol.1c02624. Epub 2022 Mar 1.
Herein, we demonstrate that macromonomers consisting of organics-soluble, chemically protected oligonucleotides (protDNA) and poly(ethylene glycol) (PEG) chains can be converted into bottlebrush polymers of distinct architectures via ring-opening metathesis polymerization (ROMP). Using a custom norbornene-containing phosphoramidite, two types of macromonomers were obtained: a linear norbornene-protDNA-PEG structure and a Y-shaped structure where the polymerizable norbornene group is situated at the junction where protDNA and PEG meet. With this strategy, the PEG chains can be placed either near the backbone of the bottlebrush or on its periphery, and in principle anywhere between these two extremes by adjusting the norbornene location, which makes this strategy attractive for constructing architecturally sophisticated oligonucleotide-containing copolymers.
在此,我们证明了由有机可溶性、化学保护的寡核苷酸(保护型DNA)和聚乙二醇(PEG)链组成的大分子单体可以通过开环易位聚合(ROMP)转化为具有不同结构的刷状聚合物。使用定制的含降冰片烯的亚磷酰胺,获得了两种类型的大分子单体:线性降冰片烯-保护型DNA-PEG结构和Y形结构,其中可聚合的降冰片烯基团位于保护型DNA和PEG相遇的交界处。通过这种策略,PEG链可以放置在刷状聚合物主链附近或其外围,并且原则上通过调整降冰片烯的位置可以处于这两个极端之间的任何位置,这使得该策略对于构建结构复杂的含寡核苷酸共聚物具有吸引力。