Finikova OS, Chen P, Ou Z
… +2 more, Kadish KM, Vinogradov SA
J Photochem Photobiol A Chem
· 2008 · PMID 19030124
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Two-photon-enhanced dendritic nanoprobes are being developed for two-photon (2P) laser scanning microscopy of oxygen [1]. In these molecular constructs, phosphorescence of metalloporphyrins is coupled to two-photon absor...Two-photon-enhanced dendritic nanoprobes are being developed for two-photon (2P) laser scanning microscopy of oxygen [1]. In these molecular constructs, phosphorescence of metalloporphyrins is coupled to two-photon absorption (2PA) of electronically separate antenna dyes via intramolecular Förster-type resonance energy transfer (FRET). In the originally developed probes, competing electron transfer (ET) between the antennae and the long-lived triplet states of metalloporphyrins partially quenched the phosphorescence, reducing the probe's sensitivity and dynamic range. The rate of such ET can be reduced by tuning the redox potentials of the chromophores. In order to identify the optimal metalloporphyrin-2P antenna pairs, we performed screening of several phosphorescent Pt porphyrins (FRET acceptors) and 2P dyes (FRET donors) using dynamic quenching of phosphorescence. Phosphorescence lifetimes of Pt porphyrins were measured as a function of the dye concentration in organic solutions. The obtained Stern-Volmer quenching constants were correlated with the corresponding ET driving forces (DeltaG(ET)), calculated using the Rehm-Weller equation. FRET-pairs with minimal quenching rates were identified. The developed approach allows convenient screening of candidate-compounds for covalent assembly of 2P-enhanced triplet nanodevices. Systematic electrochemical measurements in a series of Pt porphyrins with varying peripheral substitution and conjugation pathways are presented.
J Photochem Photobiol A Chem
· 2008 Sep · PMID 20339480
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The photodegradation of adsorbed perylene is strongly influenced by the environment in which it is found as demonstrated by the nature of the photoproducts characterized on the adsorbed state in comparison to its photoch...The photodegradation of adsorbed perylene is strongly influenced by the environment in which it is found as demonstrated by the nature of the photoproducts characterized on the adsorbed state in comparison to its photochemical behavior in solution. The separation, characterization, and identification of the products were carried out using HPLC equipped with UV-Vis diode array and MS detection. Two of the products were identified as 1,12-perylenedione and 3,10-perylenedione. Three additional products were characterized as a perylenedione and two perylenediols based on their m/z ratio. Based on this information, two possible mechanisms of formation were proposed for the identified diones. The experimental data showed that both the radical cation and singlet oxygen participate in the route of photodegradation of perylene which occurs through a mixed Type I and Type II pathway. These results assist in the understanding of complex processes undergone by perylene and other PAHs in the environment.
J Photochem Photobiol A Chem
· 2007 Apr · PMID 23772136
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Photodegradation of a mixture of three polycyclic aromatic hydrocarbons fluorene (FLU), dibenzofuran (DBF), and dibenzothiophene (DBT) using UV and UV/HO processes was studied. Treating a mixture of the PAHs stimulated a...Photodegradation of a mixture of three polycyclic aromatic hydrocarbons fluorene (FLU), dibenzofuran (DBF), and dibenzothiophene (DBT) using UV and UV/HO processes was studied. Treating a mixture of the PAHs stimulated a more realistic contamination composition present in polluted water. Effects of pH, PAH concentration, and water matrix composition on removal rates and efficiencies of these compounds are discussed. Batch experiments were conducted using both monochromatic low pressure (LP, 253.7 nm) and polychromatic medium pressure (MP, 200-400 nm) UV sources, in a quasi-collimated beam setup. A synergistic effect was observed during direct photolysis and LP-UV/HO of the mixture as compared to photodegradation as a single component in an aqueous solution. Similar results were obtained for FLU using MP-UV/HO whereas, degradation of DBF and DBT was inhibited in a mixture. Natural water enhanced the direct photolysis compared to laboratory buffered water, whereas, degradation of the PAHs in the natural water was inhibited using UV/HO process. Toxicity testing using a luminescent inhibition bioassay was correlated to intermediates generated during UV-based oxidation reactions.
Gryczynski I, Piszczek G, Lakowicz JR
… +1 more, Lagarias JC
J Photochem Photobiol A Chem
· 2002 Jul · PMID 31824128
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Phytofluors are highly fluorescent proteins in which the chromophore in a phytochrome is replaced with phycoerythrobilin (PEB), the pigment precursor of the cyanobacterial light harvesting protein phycoerythrin. We exami...Phytofluors are highly fluorescent proteins in which the chromophore in a phytochrome is replaced with phycoerythrobilin (PEB), the pigment precursor of the cyanobacterial light harvesting protein phycoerythrin. We examined the fluorescence spectra of the N-terminal region of the cyanobacterial phytochrome 1 from cyanobacterium sp. Pcc 6803 bound to PEB. This protein, Cph1(N514)-PEB, displayed a good two-photon cross-section of 20-30 GM for excitation at 792 nm. This phytofluor also exhibits a high fundamental anisotropy at most practical two-photon excitation (2PE) wavelengths from 700 to 900 nm. Identical lifetimes and correlation times with one and 2PE indicates that the phytofluor is not adversely affected by the intensities needed for 2PE. The one-photon absorption extends well beyond the absorption spectrum and even beyond the emission spectrum to 700 nm. The phytofluor thus appears to be a suitable probe for 2PE and/or cellular imaging.
J Photochem Photobiol A Chem
· 2001 Oct · PMID 32025171
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The spectroscopic and photophysical properties of two donor-acceptor derivatives of 1,4-diphenylbuta-1,3-diene and 1,6-diphenylhexa-1,3,5-diene are described. Both compound posses a dimethylamino and a boronic acid group...The spectroscopic and photophysical properties of two donor-acceptor derivatives of 1,4-diphenylbuta-1,3-diene and 1,6-diphenylhexa-1,3,5-diene are described. Both compound posses a dimethylamino and a boronic acid groups as electron-donor and electron-withdrawing groups, respectively. Solvent polarity effects on the steady-state and fluorescence intensity decay are presented and show the formation of an excited-state charge-transfer (CT) state for both compounds. The formation of the anionic form of the boronic acid group at high pH induces a blue shift and an increase of the intensity in the emission spectra for both compounds. These spectral changes are interpreted as the lost of the electron-withdrawing property of the anionic form of the boronic acid group. The observed p of both compounds is around 8.8 and decrease to ~6 and ~7 in presence of fructose and glucose, respectively. Both compounds display a decrease of the mean lifetime at higher pH. Effects of the sugars on the fluorescence spectra and fluorescence lifetimes are also presented. For both compounds, a blue shift and an increase of the intensity are observed. These spectral changes lead to a wavelength-ratiometric method for the sugar recognition and analysis. Titration curves against fructose, galactose and glucose and dissociation constants are presented. Both compounds show a higher affinity for fructose. The affinity decreases for galactose and for glucose, respectively. Sugar effects on the fluorescence intensity decay are also presented. Both compounds display a decrease of the mean lifetime after addition of sugar.