Sequence‐Controlled Synthesis of Advanced Clickable Synthetic Oligonucleotides. Issue 16 (29th July 2020)

• Record Type: Journal Article
• Authors: Han, Xun; Fairbanks, Benjamin D.; Sinha, Jasmine; Bowman, Christopher N.
• Is Part Of: Macromolecular rapid communications. Volume 41:Issue 16(2020)
• Page Start: n/a
• Page End: n/a
• Publication Date: 2020-07-29
• Subjects: click‐reaction -- nucleotides -- photopolymerization -- sequence‐control -- thiol‐ene; Macromolecules -- Periodicals; Polymers -- Periodicals; Chemistry -- Periodicals; 547.705
• DOI: 10.1002/marc.202000327
• Languages: English
• ISSNs: 1022-1336

Abstract

Abstract: Through thiol‐ene photopolymerization of presynthesized oligomers, advanced clickable nucleic acids (CNA‐2G) are synthesized with sequence‐controlled repeating units. As examples, poly(thymine‐adenine) (polyTA) CNA‐2G and poly(thymine‐thymine‐cytosine) CNA‐2G are synthesized by polymerizing thiol‐ene heterofunctional dimers with pendant thymine‐adenine nucleobases and trimer with pendant thymine‐thymine‐cytosine nucleobases. Based on size exclusion chromatography (SEC) analysis, polyTA and polyTTC have number average molecular weights of 2000 and 1800, respectively, which contain 7–8 pendant nucleobases. Based on the different behavior of the CNA‐2G monomers and CNA‐2G oligomers with two or more pendant nucleobases in photopolymerization, an unusual thiol‐ene chain‐growth propagation mechanism is observed for the former and a common thiol‐ene step‐growth propagation mechanism for the latter. The uncommon thiol‐ene chain‐growth propagation is hypothesized to rely on a six‐membered ring mediated intramolecular hydrogen atom transfer process. Abstract : Sequence‐controlled and inexpensive second generation clickable nucleic acids (CNA‐2G) are simply made from direct photopolymerization of presynthesized oligomers. The different polymerization behaviors of monomers and oligomers are attributed to chain‐growth and step‐growth propagation mechanisms respectively.