Tags

Type your tag names separated by a space and hit enter

Bright G-Quadruplex Nanostructures Functionalized with Porphyrin Lanterns.
J Am Chem Soc 2019; 141(32):12582-12591JA

Abstract

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.

Authors+Show Affiliations

Department of Chemistry , Tulane University , 2015 Percival Stern Hall , New Orleans , Louisiana 70118 , United States.Department of Chemistry , Tulane University , 2015 Percival Stern Hall , New Orleans , Louisiana 70118 , United States.Department of Biochemistry and Molecular Biology , Tulane University , New Orleans , Louisiana 70112 , United States.Department of Chemistry , Tulane University , 2015 Percival Stern Hall , New Orleans , Louisiana 70118 , United States.School of Physical and Mathematical Sciences , Nanyang Technological University , Singapore 637371 , Singapore.Department of Biomedical Engineering , Tulane University , New Orleans , Louisiana 70118 , United States.Department of Chemistry , Tulane University , 2015 Percival Stern Hall , New Orleans , Louisiana 70118 , United States.Department of Biochemistry and Molecular Biology , Tulane University , New Orleans , Louisiana 70112 , United States.School of Physical and Mathematical Sciences , Nanyang Technological University , Singapore 637371 , Singapore.Department of Chemistry , Tulane University , 2015 Percival Stern Hall , New Orleans , Louisiana 70118 , United States.

Pub Type(s)

Journal Article

Language

eng

PubMed ID

31322869

Citation

Pathak, Pravin, et al. "Bright G-Quadruplex Nanostructures Functionalized With Porphyrin Lanterns." Journal of the American Chemical Society, vol. 141, no. 32, 2019, pp. 12582-12591.
Pathak P, Yao W, Hook KD, et al. Bright G-Quadruplex Nanostructures Functionalized with Porphyrin Lanterns. J Am Chem Soc. 2019;141(32):12582-12591.
Pathak, P., Yao, W., Hook, K. D., Vik, R., Winnerdy, F. R., Brown, J. Q., ... Jayawickramarajah, J. (2019). Bright G-Quadruplex Nanostructures Functionalized with Porphyrin Lanterns. Journal of the American Chemical Society, 141(32), pp. 12582-12591. doi:10.1021/jacs.9b03250.
Pathak P, et al. Bright G-Quadruplex Nanostructures Functionalized With Porphyrin Lanterns. J Am Chem Soc. 2019 Aug 14;141(32):12582-12591. PubMed PMID: 31322869.
* Article titles in AMA citation format should be in sentence-case
TY - JOUR T1 - Bright G-Quadruplex Nanostructures Functionalized with Porphyrin Lanterns. AU - Pathak,Pravin, AU - Yao,Wei, AU - Hook,Katherine Delaney, AU - Vik,Ryan, AU - Winnerdy,Fernaldo Richtia, AU - Brown,Jonathon Quincy, AU - Gibb,Bruce C, AU - Pursell,Zachary F, AU - Phan,Anh Tuân, AU - Jayawickramarajah,Janarthanan, Y1 - 2019/08/01/ PY - 2019/7/20/pubmed PY - 2019/7/20/medline PY - 2019/7/20/entrez SP - 12582 EP - 12591 JF - Journal of the American Chemical Society JO - J. Am. Chem. Soc. VL - 141 IS - 32 N2 - 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. SN - 1520-5126 UR - https://www.unboundmedicine.com/medline/citation/31322869/Bright_G-Quadruplex_Nanostructures_Functionalized_with_Porphyrin_Lanterns L2 - https://dx.doi.org/10.1021/jacs.9b03250 DB - PRIME DP - Unbound Medicine ER -