Search results for "Singlet"
showing 10 items of 352 documents
Interligand Electron Transfer Determines Triplet Excited State Electron Injection in RuN3−Sensitized TiO2 Films
2004
Electron injection from the transition metal complex Ru(dcbpy)(2)(NCS)(2) (dcbpy = 2,2'-bipyridine-4,4'-dicarboxylate) into a titanium dioxide nanoparticle film occurs along two pathways. The dominating part of the electron injection proceeds from the initially excited singlet state of the sensitizer into the conduction band of the semiconductor on the sub-hundred-femtosecond time scale. The slower part of the injection occurs from the thermalized triplet excited state on the picosecond time scale in a nonexponential fashion, as was shown in a previous study (Benko, G.; et al. J. Am. Chem. Soc. 2002, 124, 489). Here we show that the slower channel of injection is the result of the excited s…
Effect of phosphatydylcholine on spectral properties and photostability of 3,3′-diethyloxadicarbocyanine iodide (DODCI) — a potent anti-tumor photose…
1998
Abstract The potential anti-tumor photosensitizer 3,3′-diethyloxadicarbocyanine iodide (DODCI) has been immobilized in dimyristoyl phosphatidylcholine (DMPC) vesicles. Binding of the dicarbocyanine to the lipid vesicles induces several changes in the electronic absorption, emission and excitation spectra of the dye. The monomeric dye molecules exist in at least two forms when immobilized in the DMPC liposomes and the non-luminescing H-aggregates of the dye show efficient excitation energy transfer to the DODCI monomers. Entrapment of the dye in the liposomes generally decreases the photostability of DODCI. While emission from singlet oxygen (1O2) has not been recorded, indirect results sugg…
Excitons and nonlinear optical spectra in conjugated polymers.
1992
Excitons in conjugated polymers are studied theoretically in the Su-Schrieffer-Heeger model supplemented by long-range Coulomb interactions. The relationship between exciton energies and basic interaction parameters is clarified. Linear and third-order nonlinear optical susceptibilities (two-photon absorption, electroabsorption, and third-harmonic generation) have been calculated, elucidating the significance of singlet and triplet excitons and unbound electron-hole pairs. Using only moderate interaction strength, various experiments in polydiacetylene can be interpreted in a consistent way
Revisiting the photochemical synthesis of [FeFe]-hydrogenase mimics: reaction optimization, mechanistic study and electrochemical behaviour
2020
The photoreaction of [(μ-S)2Fe2(CO)6] and alkenes or alkynes has been optimized to readily obtain functionalized [FeFe]-hydrogenase mimics. Irradiation under low CO pressure in THF produces the corresponding photo-adducts in good/acceptable (alkenes/alkynes) yields, with retention of the starting olefin stereochemistry. DFT-calculations provide plausible reaction pathways in both, singlet and triplet states. The DFT-calculation based in the singlet state is energetically more favorable. The electrochemical behavior of the synthesized compounds is also presented, including studies in acidic media. The electrochemical properties of the products vary in the presence of a double bond (cycloaddi…
Water-soluble hyperbranched polyglycerol photosensitizer for enhanced photodynamic therapy
2020
Porphyrin and its derivatives as promising photosensitizers have been widely utilized in photodynamic therapy (PDT). However, the water-solubility and biocompatibility of porphyrins are the typical bottlenecks in clinical PDT processes. Herein, we successfully fabricated a new type of water-soluble, hyperbranched polyglycerol photosensitizer through one-step esterification between water-soluble hyperbranched polyglycerol (hbPG) and fluorophenylporphyrin (FP). Compared with the linear control polymer, i.e., FP covalently connected with linear polyethylene glycol (LPEG), the hyperbranched structures bearing multiple porphyrin units generated more singlet oxygen and exhibited higher cytotoxici…
Photooxidations of Alkenes in Fluorinated Constrained Media: Fluoro-organically Modified NaY as Improved Reactors for Singlet Oxygen “Ene” Reactions
2007
Creating a stationary fluorinated environment inside the zeolite cavity can increase the reactivity observed for intrazeolite photooxidation of alkenes. Exchanging the zeolite with fluorinated organic cations is a much more effective strategy than simply using a fluorinated solvent for slurry irradiations. Use of cations containing C-F bonds is also more efficient than use of deuterated cations for creation of a singlet oxygen friendly environment where the quenching processes are slowed down. Doping the zeolite with fluoro-organic cation 4 resulted in an increase in the singlet oxygen lifetime to 12 micros.
Photosensitization of DNA by β-carbolines: Kinetic analysis and photoproduct characterization
2012
β-Carbolines (βCs) are a group of alkaloids present in many plants and animals. It has been suggested that these alkaloids participate in a variety of significant photosensitized processes. Despite their well-established natural occurrence, the main biological role of these alkaloids and the mechanisms involved are, to date, poorly understood. In the present work, we examined the capability of three important βCs (norharmane, harmane and harmine) and two of its derivatives (N-methyl-norharmane and N-methyl-harmane) to induce DNA damage upon UV-A excitation, correlating the type and extent of the damage with the photophysical characteristics and DNA binding properties of the compounds. The r…
Watching the photo-oxidation of a single aromatic hydrocarbon molecule
2001
International audience; The photooxidation of single dye molecules (see scheme) can be followed by confocal fluorescence microscopy. The self-sensitized reaction with singlet oxygen leads to a suite of products, which may be differentiated spectrally. Tentative structures for certain photoproducts have been obtained from quantum-chemical calculations.
A new experimental protocol for intrazeolite photooxidations. The first product-based estimate of an upper limit for the intrazeolite singlet oxygen …
2002
The intrazeolite photooxidations of several alkenes have been examined in hexane and in perfluorohexane slurries. The ability of perfluorohexane to increase the affinity of alkenes for the interior of the zeolite was documented. The nearly identical reaction rates in the two slurry solvents are attributed to a leveling of the singlet oxygen lifetime by the zeolite framework. A consideration of the rates of the various intrazeolite processes was used to estimate an upper limit for the intrazeolite lifetime of singlet oxygen.
Copper(II) complexes with sulfonamides derived from 2-picolylamine and their use as chemical nucleases
2006
Reaction between 2-picolylamine (2-aminomethylpyridine) with 2-mesitylenesulfonyl and 4- tert -butylbenzene sulfonyl chlorides leads to the formation of 2,4,6-trimethyl- N -[pyridin-2-ilmethyl]benzenesulfonamide (Hpmesa) and 4-ter-butyl- N -[pyridin-2-ilmethyl]benzenesulfonamide (Hptbsa). These compounds react with Cu(II) salts to yield coordination compounds with CuL 2 stoichiometry. The immediate environment of the metal ion is a highly distorted tetrahedron, the sulfonamide ligands acting in a bidentate fashion. Compound Hpmesa crystallizes in monoclinic space group P 2 1 /c (number 14), with Z = 4; complex [Cu(pmesa) 2 ] crystallizes in monoclinic space group P 1 ¯ (number 2), with Z …