A new family of fluorescent thiophene and thienothiophene-containing squaraine dyes is described with tunable wavelengths that cover the absorption/emission range of 600–800 nm. The deep-red and near-infrared fluorescent compounds were easily prepared by simple synthesis and purification methods. Spectral studies showed that each squaraine was rapidly encapsulated by a tetralactam macrocycle, with nanomolar affinity in water, to produce a threaded supramolecular complex with high chemical stability, increased fluorescence quantum yield, and decreased fluorescence quenching upon dye self-aggregation. Energy transfer within the supramolecular complex permitted multiplex emission. That is, two separate dyes with fluorescence emission bands that match the popular Cy5 and Cy7 channels, could be simultaneously excited with a beam of 375 nm light. A broad range of practical applications is envisioned in healthcare diagnostics, microscopy, molecular imaging, and fluorescence-guided surgery.
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Fluorescent surfactants from common dyes – Rhodamine B and Eosin Y
Abstract Eight fluorescent surfactants were synthesized by attaching aliphatic chains of 6, 10, 12, or 16 carbons to the fluorescent dyes Rhodamine B and Eosin Y. The obtained critical micelle concentrations (CMC) demonstrate an increasing CMC with decreasing aliphatic chain length, which is a typical behavior for surfactants. Additionally, fluorescence quantum yield experiments show a decrease in quantum yield with increasing aliphatic chain length, suggesting that the tails can interact with the dye, influencing its excited state. Finally, applications for the fluorescent surfactants were demonstrated; as a cellular stain in Panc-1 cells and as a dispersion and imaging tool for carbon and boron nitride nanotubes. These surfactants could provide a useful tool for a wide array of potential applications, from textile dyes to fluorescence imaging.
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- Award ID(s):
- 1807737
- NSF-PAR ID:
- 10111489
- Date Published:
- Journal Name:
- Pure and Applied Chemistry
- Volume:
- 0
- Issue:
- 0
- ISSN:
- 0033-4545
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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Abstract The ability to monitor types, concentrations, and activities of different biomolecules is essential to obtain information about the molecular processes within cells. Successful monitoring requires a sensitive and selective tool that can respond to these molecular changes. Molecular aptamer beacon (MAB) is a molecular imaging and detection tool that enables visualization of small or large molecules by combining the selectivity and sensitivity of molecular beacon and aptamer technologies. MAB design leverages structure switching and specific recognition to yield an optical on/off switch in the presence of the target. Various donor–quencher pairs such as fluorescent dyes, quantum dots, carbon‐based materials, and metallic nanoparticles have been employed in the design of MABs. In this work, the diverse biomedical applications of MAB technology are focused on. Different conjugation strategies for the energy donor–acceptor pairs are addressed, and the overall sensitivities of each detection system are discussed. The future potential of this technology in the fields of biomedical research and diagnostics is also highlighted.
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The binding of linear diamine counterions with different methylene chain lengths to the amino-acid-based surfactants undecanoic L-isoleucine (und-IL) and undecanoic L-norleucine (und-NL) was investigated with NMR spectroscopy. The counterions studied were 1,2-ethylenediamine, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, and 1,6-diaminohexane. These counterions were all linear diamines with varying spacer chain lengths between the two amine functional groups. The sodium counterion was studied as well. Results showed that when the length of the counterion methylene chain was increased, the surfactants’ critical micelle concentrations (CMC) decreased. This decrease was attributed to diamines with longer methylene chains binding to multiple surfactant monomers below the CMC and thus acting as templating agents for the formation of micelles. The entropic hydrophobic effect and differences in diamine counterion charge also contributed to the size of the micelles and the surfactants’ CMCs in the solution. NMR diffusion measurements showed that the micelles formed by both surfactants were largest when 1,4-diaminobutane counterions were present in the solution. This amine also had the largest mole fraction of micelle-bound counterions. Finally, the und-NL micelles were larger than the und-IL micelles when 1,4-diaminobutane counterions were bound to the micelle surface. A model was proposed in which this surfactant formed non-spherical aggregates with both the surfactant molecules’ hydrocarbon chains and n-butyl amino acid side chains pointing toward the micelle core. The und-IL micelles, in contrast, were smaller and likely spherically shaped.more » « less
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Abstract Ultrabright fluorescent nanoparticles (NPs) hold great promise for demanding bioimaging applications. Recently, extremely bright molecular crystals of cationic fluorophores were obtained by hierarchical coassembly with cyanostar anion‐receptor complexes. These small‐molecule ionic isolation lattices (SMILES) ensure spatial and electronic isolation to prohibit aggregation quenching of dyes. We report a simple, one‐step supramolecular approach to formulate SMILES materials into NPs. Rhodamine‐based SMILES NPs stabilized by glycol amphiphiles show high fluorescence quantum yield (30 %) and brightness per volume (5000 M−1 cm−1/nm3) with 400 dye molecules packed into 16‐nm particles, corresponding to a particle absorption coefficient of 4×107 M−1 cm−1. UV excitation of the cyanostar component leads to higher brightness (>6000 M−1 cm−1/ nm3) by energy transfer to rhodamine emitters. Coated NPs stain cells and are thus promising for bioimaging.
- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1515/pac-2019-0219
