NanoFN10: A High-Contrast Turn-On Fluorescence Nanoprobe for Multiphoton Singlet Oxygen Imaging.

An “off-on” fluorescent nanoprobe for near-infrared multiphoton imaging of singlet oxygen has been developed. The nanoprobe comprises a naphthoxazole fluorescent unit and a singlet-oxygen-sensitive furan derivative attached to the surface of mesoporous silica nanoparticles. In solution, the fluorescence of the nanoprobe increases upon reaction with singlet oxygen both under one- and multiphoton excitation, with fluorescence enhancements up to 180-fold. The nanoprobe can be readily internalized by macrophage cells and is capable of imaging intracellular singlet oxygen under multiphoton excitation.Partial funding for open access charge: Universidad de Málag

Experimental and theoretical studies of the photophysics of 7-amino-3-phenyl-2H-benzo[b] [1,4]oxazin-2-one in homogeneous solvents and b-cyclodextrin aqueous solutions

The photophysical behavior of 7-amino-3-phenyl-2Hbenzo[b][1,4]oxazin-2-one was studied in organic solvents and in aqueous solutions of b-cyclodextrin using steady-state fluorescence and computational chemistry methods. In homogeneous media, fluorescence spectra show a noteworthy solvatochromic effect leading to large Stokes shifts. Linear solvation energy relationship and Lippert-Mataga equation analysis of the Stokes shifts indicate an increase of the dipolar moment in the singlet excited state and the participation of a partial chargetransfer state in the deactivation process. Incorporation of 7-amino-3-phenyl-2H-benzo[b][1,4]oxazin-2-one into the b-cyclodextrin inner cavity was monitored by observing the increase of fluorescence as a function of the cyclodextrin concentration. Analysis of fluorescence data in terms of Job plots and the Benesi-Hildebrand equation are indicate the formation of a 1:1 complex. The binding constantobtained from Benesi-Hildebrand plots was 597 M-1 at 298K. Also, the values of thermodynamics parameters determinedfrom the dependence of the binding constant on thetemperature show that inclusion is an enthalpy-driven process.Docking studies suggest that the complex stability is due to favorable van der Waals interactions within the cavity and a hydrogen bond interaction between the amino substituent and hydroxyl groups located in the narrow rim of the cavity. The same conclusion was achieved employing the Molecular Mechanics Poisson-Boltzmann Surface Area methodology to determine the energy contributions to the total free energy for the inclusion process

Sucrose Monoester Micelles Size Determined by Fluorescence Correlation Spectroscopy (FCS)

One of the several uses of sucrose detergents, as well as other micelle forming detergents, is the solubilization of different membrane proteins. Accurate knowledge of the micelle properties, including size and shape, are needed to optimize the surfactant conditions for protein purification and membrane characterization. We synthesized sucrose esters having different numbers of methylene subunits on the substituent to correlate the number of methylene groups with the size of the corresponding micelles. We used Fluorescence Correlation Spectroscopy (FCS) and two photon excitation to determine the translational D of the micelles and calculate their corresponding hydrodynamic radius, Rh. As a fluorescent probe we used LAURDAN (6-dodecanoyl-2-dimethylaminonaphthalene), a dye highly fluorescent when integrated in the micelle and non-fluorescent in aqueous media. We found a linear correlation between the size of the tail and the hydrodynamic radius of the micelle for the series of detergents measured

Structure-activity study of furyl aryloxazole fluorescent probes for the detection of singlet oxygen

In this study, we report the synthesis and the photochemical behavior of a series of new "click-on" fluorescent probes designed to detect singlet oxygen. They include a highly fluorescent chemical structure, an aryloxazole ring, linked to a furan moiety operating as singlet oxygen trap. Their activity depends on both the structure of the aryloxazole fluorophore and the electron-donating and electron-accepting properties of the substituents attached to the C-5 of the furan ring. All probes are selectively oxidized by singlet oxygen to give a single fluorescent product in methanol and produce negligible amounts of singlet oxygen themselves by self-sensitization. The most promising dyad, (E)-2-(2-(5-methylfuran-2-yl)vinyl)naphtho[1,2-d]oxazole, FN-6, shows outstanding reactivity and sensitivity: it traps singlet oxygen with a rate constant (5,8 ± 0.1) x 1(07) M-1 s-1 and its fluorescence increases by a factor of 500 upon reaction. Analysis of the dyads reactivity in terms of linear free energy relationships using the modified Swain and Lupton parameter F and the Fukui condensed function for the electrophilic attack, suggests that cycloaddition of singlet oxygen to the furan ring is partially concerted and possibly involves an exciplex with a "more open" structure than could be expected for a concerted cycloaddition.status: publishe

Singlet oxygen reactions with flavonoids. a theoretical - experimental study

Detection of singlet oxygen emission, λmax = 1270 nm, following laser excitation and steady-state methods were employed to measure the total reaction rate constant, kT, and the reactive reaction rate constant, kr, for the reaction between singlet oxygen and several flavonoids. Values of kT determined in deuterated water, ranging from 2.4×107 M-1s-1 to 13.4×107 M-1s-1, for rutin and morin, respectively, and the values measured for kr, ranging from 2.8×105 M-1s-1 to 65.7×105 M-1s-1 for kaempferol and morin, respectively, being epicatechin and catechin chemically unreactive. These results indicate that all the studied flavonoids are good quenchers of singlet oxygen and could be valuable antioxidants in systems under oxidative stress, in particular if a flavonoid-rich diet was previously consumed. Analysis of the dependence of rate constant values with molecular structure in terms of global descriptors and condensed Fukui functions, resulting from electronic structure calculations, suppor

Structure-activity study of furyl aryloxazole fluorescent probes for the detection of singlet oxygen

<div><p>In this study, we report the synthesis and the photochemical behavior of a series of new "click-on" fluorescent probes designed to detect singlet oxygen. They include a highly fluorescent chemical structure, an aryloxazole ring, linked to a furan moiety operating as singlet oxygen trap. Their activity depends on both the structure of the aryloxazole fluorophore and the electron-donating and electron-accepting properties of the substituents attached to the C-5 of the furan ring. All probes are selectively oxidized by singlet oxygen to give a single fluorescent product in methanol and produce negligible amounts of singlet oxygen themselves by self-sensitization. The most promising dyad, (E)-2-(2-(5-methylfuran-2-yl)vinyl)naphtho[1,2-d]oxazole, <b>FN-6</b>, shows outstanding reactivity and sensitivity: it traps singlet oxygen with a rate constant (5,8 ± 0.1) x 10⁷ M^-1 s^-1 and its fluorescence increases by a factor of 500 upon reaction. Analysis of the dyads reactivity in terms of linear free energy relationships using the modified Swain and Lupton parameter F and the Fukui condensed function for the electrophilic attack, suggests that cycloaddition of singlet oxygen to the furan ring is partially concerted and possibly involves an exciplex with a "more open" structure than could be expected for a concerted cycloaddition.</p></div