Open AccessBright G-Quadruplex Nanostructures Functionalized with Porphyrin Lanterns
Author(s) -
Pravin Pathak,
Wei Yao,
Katherine Delaney Hook,
Ryan Vik,
Fernaldo Richtia Winnerdy,
J. Quincy Brown,
Bruce C. Gibb,
Zachary F. Pursell,
Anh Tuân Phan,
Janarthanan Jayawickramarajah
Publication year - 2019
Publication title -
journal of the american chemical society
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 7.115
H-Index - 612
eISSN - 1520-5126
pISSN - 0002-7863
DOI - 10.1021/jacs.9b03250
Subject(s) - porphyrin , chromophore , chemistry , synthon , supramolecular chemistry , nanotechnology , nanomaterials , self assembly , fluorescence , g quadruplex , molecule , combinatorial chemistry , photochemistry , dna , stereochemistry , materials science , organic chemistry , biochemistry , physics , quantum mechanics
The intricate arrangement of numerous and closely placed chromophores on nanoscale scaffolds can lead to key photonic applications ranging from optical waveguides and antennas to signal-enhanced fluorescent sensors. In this regard, the self-assembly of dye-appended DNA sequences into programmed photonic architectures is promising. However, the dense packing of dyes can result in not only compromised DNA assembly (leading to ill-defined structures and precipitates) but also to essentially nonfluorescent systems (due to π-π aggregation). Here, we introduce a two-step "tether and mask" strategy wherein large porphyrin dyes are first attached to short G-quadruplex-forming sequences and then reacted with per-O-methylated β-cyclodextrin (PMβCD) caps, to form supramolecular synthons featuring the porphyrin fluor fixed into a masked porphyrin lantern (PL) state, due to intramolecular host-guest interactions in water. The PL-DNA sequences can then be self-assembled into cyclic architectures or unprecedented G-wires tethered with hundreds of porphyrin dyes. Importantly, despite the closely arrayed PL units (∼2 nm), the dyes behave as bright chromophores (up to 180-fold brighter than the analogues lacking the PMβCD masks). Since other self-assembling scaffolds, dyes, and host molecules can be used in this modular approach, this work lays out a general strategy for the bottom-up aqueous self-assembly of bright nanomaterials containing densely packed dyes.