Liang Yifei, Sun Hao, Cao Wei, Thompson Matthew P, Gianneschi Nathan C
Department of Chemistry, International Institute for Nanotechnology, Simpson-Querrey Institute, Chemistry of Life Processes Institute, Lurie Cancer Center, Northwestern University, 2145 Sheridan Road, Evanston, Illinois 60208, United States.
Departments of Biomedical Engineering, Materials Science and Engineering, and Pharmacology, Northwestern University, 2145 Sheridan Road, Evanston, Illinois 60208, United States.
ACS Macro Lett. 2020 Oct 20;9(10):1417-1422. doi: 10.1021/acsmacrolett.0c00401. Epub 2020 Sep 15.
We report the synthesis of a degradable polyphosphoramidate via ring-opening metathesis polymerization (ROMP) with the Grubbs initiator (IMesH)(CHN)(Cl)Ru═CHPh. Controlled ROMP of a low ring strain diazaphosphepine-based cyclic olefin was achieved at low temperatures to afford well-defined polymers that readily undergo degradation in acidic conditions via the cleavage of the acid-labile phosphoramidate linkages. The diazaphosphepine monomer was compatible in random and block copolymerizations with phenyl and oligo(ethylene glycol) bearing norbornenes. This approach introduced partial or complete degradability into the polymer backbones. With this chemistry, we accessed amphiphilic poly(diazaphosphepine-norbornene) copolymers that could be used to prepare micellar nanoparticles.
我们报道了通过开环易位聚合(ROMP)与Grubbs引发剂(IMesH)(CHN)(Cl)Ru═CHPh合成可降解聚磷酰胺。在低温下实现了基于二氮杂磷杂环庚烷的低环张力环烯烃的可控ROMP,得到了结构明确的聚合物,该聚合物在酸性条件下通过酸不稳定的磷酰胺键的断裂容易发生降解。二氮杂磷杂环庚烷单体在与带有降冰片烯的苯基和聚(乙二醇)的无规和嵌段共聚中具有相容性。这种方法将部分或完全可降解性引入到聚合物主链中。利用这种化学方法,我们获得了可用于制备胶束纳米颗粒的两亲性聚(二氮杂磷杂环庚烷-降冰片烯)共聚物。