Bioconjugatable synthetic chlorins rendered water-soluble with three PEG-12 groups via click chemistry

2020 ◽  
Vol 24 (01n03) ◽  
pp. 362-378 ◽  
Author(s):  
Nobuyuki Matsumoto ◽  
Masahiko Taniguchi ◽  
Jonathan S. Lindsey
Keyword(s):  
Aqueous Solution ◽  
Quantum Yield ◽  
Click Chemistry ◽  
Fluorescence Quantum Yield ◽  
Molecular Design ◽  
Water Soluble ◽  
Propanoic Acid ◽  
Free Base ◽  
Yield Formula ◽  
Water Solubilization

Chlorins provide many ideal features for use as red-region fluorophores but require molecular tailoring for solubilization in aqueous solution. A chlorin building-block bearing 18,18-dimethyl, 15-bromo and 10-[2,4,6-tris(propargyloxy)phenyl] substituents has been transformed via click chemistry with CH3(OCH2CH[Formula: see text]-N3 followed by Suzuki coupling with 3-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)propanoic acid, thereby installing a water-solubilization motif and a bioconjugatable handle, respectively. In toluene, [Formula: see text]-dimethylformamide (DMF) or water, the resulting facially encumbered free base chlorin exhibits characteristic chlorin absorption ([Formula: see text] [Formula: see text]412, 643 nm) and fluorescence ([Formula: see text] [Formula: see text]645 nm) spectra with only modest variation in fluorescence quantum yield ([Formula: see text] values (0.24, 0.25 and 0.19, respectively). The zinc chlorin derived therefrom exhibits similar spectral constancy ([Formula: see text] [Formula: see text]414 and 613 nm, [Formula: see text] [Formula: see text]616 nm) and [Formula: see text] 0.094, 0.10 and 0.086 in the three solvents. The results together indicate the viability of the molecular design and synthetic methodology to create red-region fluorophores for use in diverse applications.

scholarly journals Fluorescence quantum yield rationalized by the magnitude of the charge transfer in π-conjugated terpyridine derivatives

2016 ◽  
Vol 18 (42) ◽  
pp. 29387-29394 ◽  
Author(s):  
Marie Humbert-Droz ◽  
Claude Piguet ◽  
Tomasz A. Wesolowski
Keyword(s):  
Dipole Moment ◽  
Charge Transfer ◽  
Quantum Yield ◽  
Excited States ◽  
Charge Separation ◽  
Fluorescence Quantum Yield ◽  
Molecular Design ◽  
Electron Hole ◽  
Two Measures

Two measures of charge separation in ground and excited states (length of the change in dipole moment and the electron–hole distance) provide a remarkable tool for the molecular design of a fluorescent polyaromatic antenna.

Interaction of cationic water-soluble meso-tetrakis(4-N-methylpyridiniumyl)porphyrin (TMPyP) with ionic and nonionic micelles: aggregation and binding

2008 ◽  
Vol 12 (08) ◽  
pp. 942-952 ◽  
Author(s):  
Patrícia S. Santiago ◽  
Shirley C.M. Gandini ◽  
Leonardo M. Moreira ◽  
Marcel Tabak
Keyword(s):  
Aqueous Solution ◽  
Sodium Dodecyl ◽  
Water Soluble ◽  
Ionic Surfactant ◽  
Spectroscopic Techniques ◽  
Free Base ◽  
Saxs Data ◽  
Cationic Porphyrin ◽  
Electrostatic Contribution ◽  
Triton X

The equilibrium of meso-tetrakis(4-N-methylpyridiniumyl)porphyrin (TMPyP) in aqueous solution in the presence of surfactants was studied by optical spectroscopic techniques and SAXS (small angle X-ray scattering). Anionic SDS (sodium dodecyl sulfate), zwitterionic HPS (N-hexadecyl-N,N-dimethyl-3-ammonio-1-propanesulfonate) and nonionic TRITON X-100 (t-octylphenoxypolyethoxyethanol), surfactants were used. TMPyP is characterized by a protonation equilibrium with a pKa around 1.0, associated with the diacid-free base transition, and a second pKa around 12.0 related with the transition between the free base and the monoanion form. Three independent species were observed for TMPyP at pH 6.0 as a function of SDS concentration: free TMPyP, TMPyP-SDS aggregates and porphyrin monomer bound to micelles. For HPS and TRITON X-100, the equilibrium of TMPyP as a function of pH is quite similar to that obtained in pure aqueous solution: no aggregation was observed, suggesting that electrostatic contribution is the major factor in the interaction between TMPyP and surfactants. SAXS data analysis demonstrated a prolate ellipsoidal shape for SDS micelles; no significant changes in shape and size were observed for SDS-TMPyP co-micelles. Moreover, the ionization coefficient, α, decreases with the increase of the porphyrin concentration, suggesting the "screening" of the anionic charge of SDS by the cationic porphyrin. These results are consistent with optical absorption, fluorescence and RLS (resonance light scattering) spectroscopies data, allowing to conclude that neutral surfactants present a smaller interaction with the cationic porphyrin as compared with an ionic surfactant. Therefore, the interaction of TMPyP with the ionic and nonionic surfactants is predominantly due to the electrostatic contribution.

scholarly journals A red fluorescent BODIPY probe for iridium (III) ion and its application in living cells

2019 ◽  
Vol 6 (1) ◽  
pp. 181090 ◽  
Author(s):  
Xingyu Qu ◽  
Yongjun Bian ◽  
Jianqing Li ◽  
Yufeng Pan ◽  
Yang Bai
Keyword(s):  
Aqueous Solution ◽  
Quantum Yield ◽  
Fluorescent Probe ◽  
Fluorescence Quantum Yield ◽  
High Selectivity ◽  
Stokes Shift ◽  
Living Cells ◽  
Optical Performance ◽  
High Fluorescence ◽  
High Fluorescence Quantum Yield

A new red fluorescent probe 1 based on BODIPY skeleton has been successfully synthesized through introduction of 2-(thiophen-2-yl) quinoline moiety at meso - and 3-position, which exhibits excellent optical performance, including high fluorescence quantum yield, large pseudo Stokes' shift as well as high selectivity and sensitivity towards iridium (III) ion in aqueous solution and in living cells.

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