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Towards DNA‐Encoded Micellar Chemistry: DNA‐Micelle Association and Environment Sensitivity of Catalysis
Author(s) -
Klika Škopić Mateja,
Gramse Christian,
Oliva Rosario,
Pospich Sabrina,
Neukirch Laura,
Manisegaran Magiliny,
Raunser Stefan,
Winter Roland,
Weberskirch Ralf,
Brunschweiger Andreas
Publication year - 2021
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.202100980
Subject(s) - micelle , chemistry , copolymer , polymerization , catalysis , polymer , chain transfer , molar mass , polymer chemistry , quenching (fluorescence) , dna , reversible addition−fragmentation chain transfer polymerization , organic chemistry , combinatorial chemistry , fluorescence , radical polymerization , aqueous solution , biochemistry , physics , quantum mechanics
The development of DNA‐compatible reaction methodologies is a central theme to advance DNA‐encoded screening library technology. Recently, we were able to show that sulfonic acid‐functionalized block copolymer micelles facilitated Brønsted acid‐promoted reactions such as the Povarov reaction on DNA‐coupled starting materials with minimal DNA degradation. Here, the impact of polymer composition on micelle shape, and reaction conversion was investigated. A dozen sulfonic acid‐functionalized block copolymers of different molar mass and composition were prepared by RAFT polymerization and were tested in the Povarov reaction, removal of the Boc protective group, and the Biginelli reaction. The results showed trends in the polymer structure‐micellar catalytic activity relationship. For instance, micelles composed of block copolymers with shorter acrylate ester chains formed smaller particles and tended to provide faster reaction kinetics. Moreover, fluorescence quenching experiments as well as circular dichroism spectroscopy showed that DNA‐oligomer‐conjugates, although highly water‐soluble, accumulated very effectively in the micellar compartments, which is a prerequisite for carrying out a DNA‐encoded reaction in the presence of polymer micelles.