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Self‐Assembly of Perylenediimide–Single‐Strand‐DNA Conjugates: Employing Hydrophobic Interactions and DNA Base‐Pairing To Create a Diverse Structural Space
Author(s) -
Mishra Ashutosh Kumar,
Weissman Haim,
Krieg Elisha,
Votaw Kevin A.,
McCullagh Martin,
Rybtchinski Boris,
Lewis Frederick D.
Publication year - 2017
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.201700752
Subject(s) - oligonucleotide , conjugate , base pair , pairing , crystallography , dna , sticky and blunt ends , transmission electron microscopy , chemistry , biophysics , materials science , nanotechnology , physics , biochemistry , biology , mathematical analysis , superconductivity , mathematics , quantum mechanics
The self‐assembly behavior of DNA conjugates possessing a perylenediimide (PDI) head group and an N‐oligonucleotide tail has been investigated using a combination of optical spectroscopy and cryogenic transmission electron microscopy (cryo‐TEM) imaging. To obtain insight into the interplay between PDI hydrophobic interactions and DNA base‐pairing we employed systematic variation in the length and composition of the oligo tails. Conjugates with short (TA) n or (CG) n oligo tails ( n ≤3) form helical or nonhelical fibers constructed from π‐stacked PDI head groups with pendent oligo tails in aqueous solution. Conjugates with longer (TA) n oligo tails also form stacks of PDI head groups, which are further aggregated by base‐pairing between their oligo tails, leading to fiber bundling and formation of bilayers. The longer (CG) n conjugates form PDI end‐capped duplexes, which further assemble into PDI‐stacked arrays of duplexes leading to large scale ordered assemblies. Cryo‐TEM imaging reveals that (CG) 3 gives rise to both fibers and large assemblies, whereas (CG) 5 assembles preferentially into large ordered structures.