Добірка наукової літератури з теми "Triplet Photosensitizers"

Photosensitizers equipped with high reactive oxygen species (ROS) generation capability and bright emission are essential for accurate tumor imaging and precise photodynamic therapy (PDT). However, traditional aggregation-caused quenching (ACQ) photosensitizers cannot simultaneously produce desirable ROS and bright fluorescence, resulting in poor image-guided therapy effect. Herein, we report an aggregation-induced emission (AIE) photosensitizer TCM-Ph with a strong donor–π–acceptor (D–π–A) structure, which greatly separates the HOMO–LUMO distribution and reduces the ΔEST, thereby increasing the number of triplet excitons and producing more ROS. The AIE photosensitizer TCM-Ph has bright near-infrared emission, as well as a higher ROS generation capacity than the commercial photosensitizers Bengal Rose (RB) and Chlorine e6 (Ce6), and can effectively eliminate cancer cells under image guidance. Therefore, the AIE photosensitizer TCM-Ph has great potential to replace the commercial photosensitizers.

An unsymmetrical (A3B) palladium porphyrin bearing a cyanoacrylic acid at one meso position has been synthesized for evaluation as a photosensitizer in dye-sensitized solar cells based on titanium dioxide ( TiO 2) as a comparison to other metalloporphyrins and as a proxy for other potential triplet-state photosensitizer compounds. The synthesis of this palladium porphyrin has provided new insight into the mechanism and product distribution of decarboxylative hydrolysis of malonic acid when attached at the porphyrin meso position. A crystal structure determination for a meso-formyl palladium porphyrin has been determined, showing saddle-distortion of the porphyrin core. The photophysical behavior of the palladium porphyrin sensitizer and its performance in photoelectrochemical cells are described and interpreted in the context of bimolecular excited state quenching pathways including oxygen sensitization, triplet–triplet annihilation and electron transfer events. Palladium porphyrins are proposed as a sensitizer class with potential for high efficiency dye-sensitized solar cells, but with the caveat that some overpotential for electron injection is necessary to compete against the multiple decay pathways that are specially available to triplet state photosensitizers.

Photocatalytic carbon dioxide reduction transforms CO2 to useful chemicals and fuels, reducing CO2 emissions and making fossil fuels more renewable. Due to a lack of earthabundant sensitizers, we want to design new earth-abundant sensitizers to go with the many known carbon dioxide reduction catalysts. Zn(II) dipyrrin complexes strongly absorb visible light, but their excited state properties have not been widely studied. To investigate their photophysical properties, two Zn dipyrrin complexes, with and without heavy atoms, were synthesized and characterized by NMR and mass spectrometry. The photophysical properties of the two complexes were measured in polar and non-polar solvents, particularly fluorescence quantum yield and extinction coefficient. Also, through transient absorption spectroscopy, the triplet state quantum yield of both complexes was measures to determine the effect of solvent polarity and heavy atoms on the triplet state formation.

About 85% of the world’s energy is derived from non-renewable sources—coal, petroleum, and natural gas. Solar photocatalysis is one way to potentially generate renewable fuels. Zinc dipyrrin complexes have the potential to be efficient sensitizers for reductive photochemistry, but their ability to form long-lived triplet excited states needs further investigation. The overall aim of this research is to compare the photophysical properties zinc and boron dipyrrin complexes and investigate the role of the charge separated state in triplet state formation. This presentation will describe the synthesis and purification of zinc and boron dipyrrin complexes and their photophysical characterization, including fluorescence quantum yields in a series of solvents and their emission at low temperatures.

About 85% of the world’s energy is derived from non-renewable sources—coal, petroleum, and natural gas. Solar photocatalysis is one way to potentially generate cheap renewable fuels by harnessing energy from the sun and converting it into chemical energy. Photosensitizers serve as materials that absorb and store sunlight in the form of chemical energy. The efficiency of a photosensitizer depends on its capacity to form a prolonged triplet excited state. Zinc dipyrrin complexes have the potential to be efficient sensitizers for reductive photochemistry, but their ability to form long-lived triplet excited states still needs extensive research. The overall aim of this research is to probe the role charge separation plays in the formation of triplet state in metal complexes of dipyrrin photosensitizers. The specific objectives are to synthesize and characterize zinc and boron dipyrrin complexes, analyze their photophysical properties—such as steady-state spectroscopy, low-temperature emission spectroscopy—and quantify their triplet states using time-resolved transient absorption spectroscopy.

About 85% of the world’s energy is derived from non-renewable sources—coal, petroleum, and natural gas. Solar photocatalysis is one way to potentially generate cheap renewable fuels by harnessing energy from the sun using a photosensitizer and converting it into chemical energy. The efficiency of a photosensitizer depends on its capacity to form a prolonged triplet excited state. Zinc dipyrrin complexes have the potential to be efficient sensitizers for reductive photochemistry, but their ability to form long-lived triplet excited states still needs extensive research. The overall aim of this research is to probe the role charge separation plays in the formation of triplet state in metal complexes of dipyrrin photosensitizers. The specific objectives are to synthesize and characterize zinc and boron dipyrrin complexes, analyze their photophysical properties—such as steady state spectroscopy, low temperature emission spectroscopy—and quantify their triplet states using time-resolved transient absorption spectroscopy.

Photosensitizing effects of xenobiotics are of increasing concern in public health since modern lifestyle often associates sunlight exposure with the presence of chemical substances in the skin. An important number of chemicals like perfumes, sunscreen components, or therapeutic agents have been reported as photosensitizers. In this context, a considerable effort has been made to design a model system for photosafety assessment. Indeed, screening for phototoxicity is necessary at the early phase of drug discovery process, even before introducing drugs and chemicals into clinical therapy, to prevent undesired photoreactions in humans. In the case of new pharmaceuticals, their phototoxic potential has to be tested when they absorb in the regions corresponding to the solar spectrum, that is, for wavelengths >290 nm. So, there is an obvious need for a screening strategy based on in vitro experiments. The goal of the present thesis was the photochemical study of different photoactive drugs to investigate the key molecular aspects responsible for their photosensitivity side effects. In a first stage, rosuvastatin was considered in chapter 3 as representative compound of the statin family. This lipid-lowering drug, also known as “superstatin”, contains a 2-vinylbiphenyl-like moiety and has been previously described to decompose under solar irradiation, yielding stable dihydrophenanthrene analogues. During photophysical characterization of rosuvastatin, only a long-lived transient at ca. 550 nm was observed and assigned to the primary photocyclization intermediate. Thus, the absence of detectable triplet-triplet absorption and the low yield of fluorescence ruled out the role of the parent drug as an efficient sensitizer. In this context, the attention was placed on the rosuvastatin main photoproduct (ppRSV). Indeed, the photobehavior of this dihydrophenanthrene-like compound presented the essential components needed for an efficient biomolecule photosensitizer i.e. (i) a high intersystem crossing quantum yield (ΦISC =0.8), (ii) a triplet excited state energy of ca. 67 kcal mol−1 , and (iii) a quantum yield of singlet oxygen formation (Φ∆) of 0.3. Furthermore, laser flash photolysis studies revealed a triplet-triplet energy transfer from the triplet excited state of ppRSV to thymidine, leading to the formation of cyclobutane thymidine dimers, an important type of DNA lesion. Finally, tryptophan was used as a probe to investigate the Type I and/or Type II character of ppRSV-mediated oxidation. In this way, both an electron transfer process giving rise to the tryptophanyl radical and a singlet oxygen mediated oxidation were observed. On the basis of the obtained results, rosuvastatin, through its major photoproduct ppRSV, should be considered as a potential sensitizer. Then, itraconazole (ITZ), a broad-spectrum antifungal agent, was chosen as main character of chapter 4. Its photochemical properties were investigated in connection with its reported skin photosensitivity disorders. Steady state photolysis, fluorescence and phosphorescence experiments were performed to understand ITZ photoreactivity in biological media. The drug is unstable under UVB irradiation, suffering a primary dehalogenation of the 2,4-dichlorophenyl moiety that occurs mainly at the ortho-position. In poorly H-donating solvents, as acetonitrile, the major photoproduct arises from intramolecular attack of the initially generated aryl radical to the triazole ring. In addition, reduced compounds resulting from homolytic cleavage of the C-Cl bond in ortho or para positions and subsequent Habstraction from the medium are obtained to a lesser extent. In good H-donating solvents, such as ethanol, the main photoproducts are formed by reductive dehalogenation. Furthermore, irradiation of a model dyad containing a tryptophan unit and the reactive 2,4-dichlorophenyl moiety of itraconazole leads to formation of a new covalent link between these two substructures revealing that homolysis of the C-Cl bond of ITZ can result in alkylation of reactive amino acid residues of proteins, leading to formation of covalent photoadducts. Therefore, it has been established that the key process in the photosensitization by itraconazole is cleavage of the carbon-halogen bond, which leads to aryl radicals and chlorine atoms. These highly reactive species might be responsible for extensive free radical-mediated biological damage, including lipid peroxidation or photobinding to proteins. In chapter 5, photobehavior of imatinib (IMT) was addressed. This is a promising tyrosine kinase inhibitor used in the treatment of some types of human cancer, which constitutes a successful example of rational drug design based on the optimization of the chemical structure to reach an improved pharmacological activity. Cutaneous reactions, such as increased photosensitivity or pseudoporphyria, are among the most common nonhematological IMT side effects; however, the molecular bases of these clinical observations have not been unveiled yet. Thus, to gain insight into the IMT photosensitizing properties, its photobehavior was studied together with that of its potentially photoactive anilino-pyrimidine and pyridyl-pyrimidine fragments. In this context, steady-state and time resolved fluorescence, as well as laser flash photolysis experiments were run, and the DNA photosensitization potential was investigated by means of single strand breaks detection using agarose gel electrophoresis. The obtained results revealed that the drug itself and its anilino-pyrimidine fragment are not DNA-photosensitizers. By contrast, the pyridyl-pyrimidine substructure displayed a marked photogenotoxic potential, which was associated with the generation of a long-lived triplet excited state. Interestingly, this reactive species was efficiently quenched by benzanilide, another molecular fragment of IMT. Clearly, integration of the photoactive pyridyl-pyrimidine moiety in a more complex structure strongly modifies its photobehavior, which in this case is fortunate as it leads to an improved toxicological profile. Thus, on the bases of the experimental results, direct in vivo photosensitization by IMT seems unlikely. Instead, the reported photosensitivity disorders could be related to indirect processes, such as the previously suggested impairment of melanogenesis or the accumulation of endogenous porphyrins. Finally, a possible source of errors in the TEMPO/EPR method for singlet oxygen detection was analyzed. For many biological and biomedical studies, it is essential to detect the production of 1O2 and to quantify its production yield. Among the available methods, detection of the characteristic 1270 nm phosphorescence of singlet oxygen by time-resolved near infrared (TRNIR) emission constitutes the most direct and unambiguous approach. An alternative indirect method is electron paramagnetic resonance (EPR) in combination with trapping. This is based on the detection of the TEMPO free radical formed after oxidation of TEMP (2,2,6,6- tetramethylpiperidine) by singlet oxygen. Although the TEMPO/EPR method has been largely employed, it can produce misleading data. This was demonstrated by the present study, where the quantum yields of singlet oxygen formation obtained by TRNIR emission and by the TEMPO/EPR method were compared for a set of well-known photosensitizers. The results revealed that the TEMPO/EPR method leads to significant overestimation of singlet oxygen yield when the singlet or triplet excited state of the photosensitizers were efficiently quenched by TEMP, acting as electron donor. In such case, generation of the TEMP+• radical cation, followed by deprotonation and reaction with molecular oxygen gives rise to a EPR detectable TEMPO signal that is not associated with singlet oxygen production. This knowledge is essential for an appropriate and error-free application of the TEMPO/EPR method in chemical, biological and medical studies.
Nardi, G. (2014). MECHANISTIC STUDIES ON THE PHOTOTOXICITY OF ROSUVASTATIN, ITRACONAZOLE AND IMATINIB [Tesis doctoral no publicada]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/48535
TESIS

Sous l'influence conjuguee de la lumiere et de l'oxygene, une solution de polymere et de bleu de methylene subit plusieurs transformations. La photooxygenation conduit uniquement a des hydroperoxydes allergiques: interaction entre l'etat triplet du bleu de methylene et les groupes hydroperoxydes portes par les chaines macromoleculaires. Cinetique et mecanisme

In this work, we used transient absorption spectroscopy to study three different light sensitive systems: Triplet Photosensitizers, Luminescent Solar Concentrators and Molecular Photoswitches. In all these systems, unwanted transient states can drastically reduce the rate of the following exploitable photophysical transformation. Our attention was devoted to understand the reaction mechanisms of the photoinduced processes, in order to gather information about the possible ways to improve their yield.

The photosensitized processes significantly enhance photolysis of various chemicals in the aqueous system with dissolved organic matter (DOM) as sensitizer. The excitation of chromophores on the DOM molecule further generates reactive species as triplet states DOM, singlet oxygen, hydroxyl radical, carbonate radical etc. We investigated the photosensitization properties of Beaufort Fulvic Acid, Suwannee River Fulvic Acid, South Platte River Fulvic Acid, and Jeddah wastewater treatment plant effluent organic matter with a sunlight simulator. DOM photochemical properties were characterized by observing their performances in 3DOM*, singlet oxygen, hydroxyl radical production with indirect probing protocols. Sensitized degradation of 0.1 μM and 0.02 μM 2, 4, 6- Trimethylphenol exhibited higher pseudo-first-order rate constant than that of 10 μM. Pre-irradiated DOMs were found to be depressed in photochemical properties. Photolysis of 5 different contaminants: ibuprofen, bisphenol A, acetaminophen, cimetidine, and caffeine were found to be enhanced in the presence of sensitizers. The possible reaction pathways were revealed. Long time irradiance induced change in contaminants degradation kinetics in some DOM solutions, which was proposed to be due to the irradiation initiated indirect transformation of DOMs. Key Words: Photolysis Dissolved Organic Matter, Triplet State DOM, Singlet Oxygen, Hydroxyl Radical, Contaminants Degradation.