scholarly journals A kinetic study on singlet molecular oxygen (O2(1Δg)) generation and quenching by dihydroxynaphthalenes

1996 ◽  
Vol 74 (1) ◽  
pp. 49-54 ◽  
Author(s):  
Marta Luiz ◽  
Arnaldo T. Soltermann ◽  
Alicia Biasutti ◽  
Norman A. Garcia
Keyword(s):  
Kinetic Study ◽  
Solvent Polarity ◽  
Point Of View ◽  
Quantum Yields ◽  
Quenching Rate ◽  
Singlet Molecular Oxygen ◽  
Substitution Pattern ◽  
Time Resolved ◽  
Encounter Complex ◽  
Quenching Rate Constant

A kinetic study on the aerobic (O2(1Δg)-mediated) photooxidation of a series of dihydroxynaphthalenes was carried out. Members of this family of compounds include important environmental contaminants. The interaction with O2(1Δg), determined by both time-resolved phosphorescence and static methods, yields a quenching rate constant in the range of 105–109 M−1 s−1, depending on the solvent polarity, pH, and substitution pattern of the dihydroxynaphthalene. According to experimental evidence, the mechanism of the interaction seems to be mediated by an encounter complex with a considerable charge transfer component. From a mechanistic point of view this characteristic of DHN indicates a behaviour very similar to that of simple substituted phenols and dihydroxybenzenes. Quantum yields for DHN photooxidation (Φr) indicate that these substrates are excellent candidates for O2(1Δg)-mediated degradation under environment conditions. Furthermore, these compounds proved to be good self-sensitizers upon irradiation at 337 nm. Quantum yields (ΦΔ) for the production of O2(1Δg) were determined to be on the order of 0.25 in benzene. Key words: dihydroxynaphthalenes, photooxidation, quenching, sensitization.not available

Solvent effect on the reactivity of monosubstituted phenols towards singlet molecular oxygen (O2(1Δg)) in alkaline media

1993 ◽  
Vol 71 (8) ◽  
pp. 1247-1252 ◽  
Author(s):  
Marta Luiz ◽  
María I. Gutiérrez ◽  
Graciela Bocco ◽  
Norman A. García
Keyword(s):  
Molecular Oxygen ◽  
Rate Constant ◽  
Reaction Pathway ◽  
Aqueous Media ◽  
Solvent Polarity ◽  
Alkaline Media ◽  
Quantum Yields ◽  
Quenching Rate ◽  
Singlet Molecular Oxygen ◽  
Quenching Rate Constant

The influence of solvent polarity on the dye-sensitized photooxidation (singlet molecular oxygen (O2(1Δg)) mediated) of a series of para-substituted phenolates was studied. Kinetic evidence obtained shows that the overall and the pure chemical interactions, phenolate–O2(1Δg), depend on the solvent polarity in a different way. This is clearly reflected in the efficiency of O2(1Δg) photooxidation of the substrates: surprisingly, the photooxidation quantum yield increases as the overall quenching rate constant decreases. The substrate photooxidation quantum yields obtained ranged from 0.05 to 0.15, the upper limit corresponding to a moderately polar medium (a benzene–methanol mixture) and the lower to an aqueous medium. We conclude that a high solvent polarity favours only the obtainment of the encounter complex (O2(1Δg)–phenolate), whereas the reactive step is affected in much the same way as those processes where charges are neutralized along the reaction pathway. The results obtained are discussed in terms of a partly polar excited state complex between O2(1Δg) and the phenolates. The rate constant for the reactive pathway in both organic and aqueous media is correlated with the Hammet-type substituent constant R−.

Photophysics of novel 22π porphyrinoids

2012 ◽  
Vol 16 (05n06) ◽  
pp. 499-507 ◽  
Author(s):  
Daniel O. Mártire ◽  
Sigrid Russell ◽  
Hans-Jürgen Dietrich ◽  
Carlos J. Cobos ◽  
Silvia E. Braslavsky
Keyword(s):  
Triplet State ◽  
Molecular Oxygen ◽  
Photophysical Properties ◽  
Intersystem Crossing ◽  
Quenching Rate ◽  
Triplet Energy ◽  
Singlet Molecular Oxygen ◽  
Time Resolved ◽  
Quenching Rate Constant ◽  
New Compounds

The photophysical properties of toluene solutions of two new 22π expanded porphycene compounds were measured using a combination of various steady-state and time-resolved techniques. The determined triplet energy (E T = 109 ± 3) kJ.mol-1, coincident with the calculated E T = (96.0 ± 10) kJ.mol-1, of both red absorbing compounds is higher than the energy required to excite ground state molecular oxygen to singlet molecular oxygen. However, the intersystem crossing yield is very low (ca. 10-2), which makes these compounds poor photosensitizers. The triplet state yield of the two expanded 22π porphyrinoid compounds is much lower than that of the parent porphycene, whereas their fluorescence is as high (ca. 30%) as the value for porphycene. The slower than diffusional quenching rate constant of a porphycene triplet state by the two new compounds reflects a steric hindering factor of the exothermic energy transfer.

Lifetime of Singlet Oxygen and Quenching by NaN3 in Mixed Solvents

1982 ◽  
Vol 37 (5) ◽  
pp. 649-652 ◽  
Author(s):  
N. Miyoshi ◽  
M. Ueda ◽  
K. Fuke ◽  
Y. Tanimoto ◽  
M. Itoh ◽  
...  
Keyword(s):  
Activation Energy ◽  
Charge Transfer ◽  
Singlet Oxygen ◽  
Mixed Solvents ◽  
Solvent Polarity ◽  
Thermal Lensing ◽  
Partial Charge ◽  
Partial Charge Transfer ◽  
Quenching Rate ◽  
Quenching Rate Constant

Singlet oxygen was generated by the photosensitization of erythrosine. The lifetime of singlet oxygen and the quenching rate constant for singlet oxygen by NaN3 were measured by a thermal lensing method in MeOH-H2O mixed solvents. The reciprocal of the lifetime increased linearly with the increase of the H2O mole fraction. Semi-log plot of the quenching constant against the reciprocal of the solvent polarity exhibited a linear relation. The quenching of the singlet oxygen by NaN3 may proceed through a partial charge-transfer intermediate. The activation energy for the quenching reaction of N3- + 1O2 →[N3·1O2-] increased with the increase of the solvent polarity. The lifetime was also measured in MeOH-ethyleneglycol mixed solvents, and its relation with viscosity was obtained

scholarly journals Effect of the Substitution Position on the Electronic and Solvatochromic Properties of Isocyanoaminonaphthalene (ICAN) Fluorophores

Molecules ◽  
2019 ◽  
Vol 24 (13) ◽  
pp. 2434 ◽  
Author(s):  
Sándor Lajos Kovács ◽  
Miklós Nagy ◽  
Péter Pál Fehér ◽  
Miklós Zsuga ◽  
Sándor Kéki
Keyword(s):  
Radiative Decay ◽  
Fluorescence Emission ◽  
Solvent Polarity ◽  
Decay Rates ◽  
Quantum Yields ◽  
Time Resolved Fluorescence ◽  
Solvatochromic Shift ◽  
Fluorescence Emission Spectra ◽  
Time Resolved ◽  
Donor And Acceptor

The properties of 1,4-isocyanoaminonaphthalene (1,4-ICAN) and 2,6-isocyanoaminonaphthalene (2,6-ICAN) isomers are discussed in comparison with those of 1,5-isocyanoaminonaphthalene (1,5-ICAN), which exhibits a large positive solvatochromic shift similar to that of Prodan. In these isocyanoaminonaphthalene derivatives, the isocyano and the amine group serve as the donor and acceptor moieties, respectively. It was found that the positions of the donor and the acceptor groups in these naphthalene derivatives greatly influence the Stokes and solvatochromic shifts, which decrease in the following order: 1,5-ICAN > 2,6-ICAN > 1,4-ICAN. According to high-level quantum chemical calculations, this order is well correlated with the charge transfer character of these compounds upon excitation. Furthermore, unlike 1,5-ICAN, the 1,4-ICAN and 2,6-ICAN isomers showed relatively high quantum yields in water, that were determined to be 0.62 and 0.21, respectively. In addition, time-resolved fluorescence experiments revealed that both the radiative and non-radiative decay rates for these three ICAN isomers varied unusually with the solvent polarity parameter ET(30). The explanations of the influence of the solvent polarity on the resulting steady-state and time-resolved fluorescence emission spectra are also discussed.

Oxygen sensing based on lifetime of photoexcited triplet state of platinum porphyrin-polystyrene film using time-resolved spectroscopy

2000 ◽  
Vol 04 (03) ◽  
pp. 292-299 ◽  
Author(s):  
YUTAKA AMAO ◽  
KEISUKE ASAI ◽  
ICHIRO OKURA
Keyword(s):  
Triplet State ◽  
Flash Photolysis ◽  
Laser Flash Photolysis ◽  
Oxygen Sensing ◽  
Laser Flash ◽  
Quenching Rate ◽  
Time Resolved ◽  
Quenching Rate Constant ◽  
Volmer Plot ◽  
Platinum Porphyrin

Optical oxygen-sensing systems based on the quenching of the photoexcited triplet state of platinum porphyrins—platinum octaethylporphyrin (PtOEP) and platinum tetrakis(pentafluorophenyl)porphyrin (PtTFPP)—in polystyrene (PS) using two different time-resolved spectroscopies (luminescence lifetime measurement and diffuse reflectance laser flash photolysis) have been developed. Using both spectroscopies, the same values of Stern-Volmer constant KSV and quenching rate constant kq (KSV = kqτ0) are obtained. The decays of the luminescence and triplet-triplet reflectance of the platinum porphyrins in PS consisted of two components (faster and slower lifetimes) in the absence and presence of oxygen. For both faster and slower components the lifetime decreases with increasing oxygen concentration. For both components a Stern-Volmer plot of the platinum porphyrin-PS films exhibits linearity. However, kq of the faster component is larger than that of the slower component (for PtOEP, three times larger; for PtTFPP, 40 times larger), indicating that two different oxygen-accessible sites exist in the platinum porphyrin-PS films. The faster and slower components are related to oxygen-accessible sites on the surface and in the bulk of the platinum porphyrin films respectively. Concerning the fractional contributions of each lifetime component, the contribution of the faster component is greater than that of the slower component, indicating that the sensing site on the surface is important for optical sensing. The contribution of different oxygen-accessible sites in platinum porphyrin-PS films for oxygen sensing is clarified by these techniques.

scholarly journals Characteristics of the excited triplet states of thiolated guanosine derivatives and singlet oxygen generation

2018 ◽  
Vol 17 (10) ◽  
pp. 1469-1476 ◽  
Author(s):  
Shoma Miyata ◽  
Shunsuke Tanabe ◽  
Tasuku Isozaki ◽  
Yao-Zhong Xu ◽  
Tadashi Suzuki
Keyword(s):  
Singlet Oxygen ◽  
Triplet States ◽  
Quenching Rate ◽  
Singlet Molecular Oxygen ◽  
Excited Triplet ◽  
Oxygen Generation ◽  
Singlet Oxygen Generation ◽  
Oxygen Conditions ◽  
Quenching Rate Constant ◽  
Excited Triplet States

The long intrinsic lifetime and low self-quenching rate constant of the triplet 6,8-dithioguanosine lead to efficient singlet molecular oxygen generation under carcinomatous oxygen conditions.

A Spectroscopic Approach with Theoretical Studies to Study the Interaction of 9-aminoacridine with Certain Phenols

2017 ◽  
Vol 231 (5) ◽  
Author(s):  
Chandrakumar Manivannan ◽  
Rajadurai Vijay Solomon ◽  
Ponnambalam Venuvanalingam ◽  
Rajalingam Renganathan
Keyword(s):  
Steady State ◽  
Bathochromic Shift ◽  
Acetonitrile Solution ◽  
Theoretical Studies ◽  
Time Resolved Fluorescence ◽  
Quenching Rate ◽  
Time Resolved ◽  
Fluorescence Measurements ◽  
Quenching Rate Constant ◽  
Bimolecular Quenching

AbstractThe influence of phenols upon the fluorescence quenching of 9-aminoacridine (9-AA) was examined in acetonitrile solution by employing steady state and time-resolved fluorescence measurements. On increasing the concentration of quencher molecules the absorption spectra of 9-AA change with significant bathochromic shift. The fluorescence intensity of 9-AA change in presence of quencher molecules were measured at various temperatures as a function of the quencher concentrations. The observed bimolecular quenching rate constant (k

scholarly journals A Time-Resolved Study on the Reactivity of Alcoholic Drinks with the Hydroxyl Radical

Molecules ◽  
2019 ◽  
Vol 24 (2) ◽  
pp. 234 ◽  
Author(s):  
Gemma Rodriguez-Muñiz ◽  
Miguel Miranda ◽  
M. Marin
Keyword(s):  
Hydroxyl Radical ◽  
Flash Photolysis ◽  
Laser Flash Photolysis ◽  
Laser Flash ◽  
White Wine ◽  
Alcoholic Beverages ◽  
Quenching Rate ◽  
Time Resolved ◽  
Quenching Rate Constant ◽  
Different Origins

Reactive oxygen species (ROS) can provoke damage to cells, where their concentrations are regulated by antioxidants. As the hydroxyl radical (•OH) is the most oxidizing ROS, we have focused our attention on the use of a mechanistically based time-resolved methodology, such as laser flash photolysis, to determine the relative reactivity of alcoholic beverages towards •OH as an indicator of their antioxidant potential. The selected drinks were of two different origins: (i) those derived from grapes such as red wine, white wine, white vermouth, marc and brandy and (ii) spirits not derived from grapes: triple sec, gin, whisky, and rum. Initially, we determined the quenching rate constant of ethanol with •OH and then we explored the reactivity of the different beverages, which was higher than expected based on their alcoholic content. This can be attributed to the presence of antioxidants and was especially remarkable for the grape-derived drinks.

PDT-related photophysical properties of conformationally distorted palladium(II) porphyrins

2001 ◽  
Vol 05 (12) ◽  
pp. 853-860 ◽  
Author(s):  
A. WIEHE ◽  
H. STOLLBERG ◽  
S. RUNGE ◽  
A. PAUL ◽  
M. O. SENGE ◽  
...  
Keyword(s):  
Quantum Yield ◽  
Molecular Oxygen ◽  
Photophysical Properties ◽  
Bathochromic Shift ◽  
Luminescence Spectroscopy ◽  
Quantum Yields ◽  
Triplet States ◽  
Singlet Molecular Oxygen ◽  
Time Resolved ◽  
Phosphorescence Quantum Yield

The photodynamic therapy (PDT) related photophysical properties of five palladium(II) porphyrins with increasing steric demand of the meso-substituents were investigated by steady state and time-resolved absorption and luminescence spectroscopy. The steric strain of the meso-substituents is reflected in a bathochromic shift of the B-band in the absorption spectra. In contrast to free-base porphyrins, the palladium(II) complexes exhibit only a very weak fluorescence with Φ Fl ~ 10-4. Instead, the corresponding triplet states of the porphyrins are formed via inter system crossing (ISC) with a quantum yield ΦISC of nearly unity. A phosphorescence quantum yield ΦISC of 10-4 was determined assuming dynamic quenching. The triplet state of all compounds is efficiently quenched by molecular oxygen, generating singlet molecular oxygen with a quantum yield of ΦΔ ~ 0.85. The various substitution patterns exerted no significant influence on the ISC rates or singlet oxygen quantum yields. Significant differences, on the other hand, were observed with respect to the triplet lifetimes, with a tendency of longer lifetimes for the porphyrins with sterically more demanding substituents (in air-saturated solution). All porphyrins were successfully incorporated into liposomes. The phototoxic activity of three compounds was investigated in cell suspensions. The use of the new porphyrinato-palladium(II) in PDT applications is discussed.

scholarly journals Photophysical Properties of Protoporphyrin IX, Pyropheophorbide-a, and Photofrin® in Different Conditions

2021 ◽  
Vol 14 (2) ◽  
pp. 138
Author(s):  
Bauyrzhan Myrzakhmetov ◽  
Philippe Arnoux ◽  
Serge Mordon ◽  
Samir Acherar ◽  
Irina Tsoy ◽  
...  
Keyword(s):  
Singlet Oxygen ◽  
Photophysical Properties ◽  
Protoporphyrin Ix ◽  
Fluorescence Emission ◽  
Solvent Polarity ◽  
Visible Absorption ◽  
Light Dosimetry ◽  
Time Resolved ◽  
Pyropheophorbide A ◽  
Influence Of Solvent

Photodynamic therapy (PDT) is an innovative treatment of malignant or diseased tissues. The effectiveness of PDT depends on light dosimetry, oxygen availability, and properties of the photosensitizer (PS). Depending on the medium, photophysical properties of the PS can change leading to increase or decrease in fluorescence emission and formation of reactive oxygen species (ROS) especially singlet oxygen (1O2). In this study, the influence of solvent polarity, viscosity, concentration, temperature, and pH medium on the photophysical properties of protoporphyrin IX, pyropheophorbide-a, and Photofrin® were investigated by UV-visible absorption, fluorescence emission, singlet oxygen emission, and time-resolved fluorescence spectroscopies.

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