INDICATION OF FAST TRIPLET FORMATION IN BIMOLECULAR QUENCHING OF EXCITED SINGLET STATES STUDIED BY CONVENTIONAL FLASH PHOTOLYSIS

The bimolecular quenching of the first excited singlet state of oxonine by allylthiourea leads to the formation of the triplet state of the dye. This has been proved by comparison with the triplet-triplet absorption spectrum of oxonine obtained by triplet-triplet energy transfer. The conventional flash experiments suggest that the dye triplet state is produced directly rather than by radical recombination.     

Charge transfer complexing in the course of triplet state quenching of carbocyanine dyes by nitroxyl radical

Quenching of triplet states of carbocyanine dyes by nitroxyl radical has been investigated by the flash photolysis method. Quenching of triplet state carbocyanine dyes with one polymethyne chain occurs via enhanced intersystem crossing on exchange interaction with the radical. Quenching of triplet state carbocyanine dyes with two polymethyne chains occurs via partial charge transfer in the collision complex with the radical. In the second case, an increase in the dielectric constant of the solvent leads to an increase of the rate of quenching. In high polarity solvents (propanol, methanol) complete electron transfer from dye triplet state to radical occurs. Kinetic and spectral characteristics of a new dye radical (Dye.⁺) are reported.     

RADICAL INTERMEDIATES IN THE FLUORESCEIN-AND EOSIN-PHOTOSENSITIZED AUTOXIDATION OF l-TYROSINE*

Abstract The Primary reactions of the cosin-and fluorescein-photosensitized autoxidation of L-tyrosine were studied in aqueous media (pH = 8.6) by the flash-photolysis technique. The dye molecules were quantitatively converted to their triplet states in a single flash. The triplet dye molecules were found to react with tyrosine or oxygen. Ground state or radical dye molecules were formed in these reactions. Some 40 per cent of the triplet-tyrosine reactions yielded radicals, in triplet dye-oxygen reactions the corresponding yield was less than 10 per cent. The ground state dye was regenerated from the semireduced dye in reactions with oxygen and from the semioxidized dye in reactions with tyrosine. In the absence of oxygen the radicals formed in the photoinduced electron-transfer between the triplet dye and tyrosine recombined to a large extent.     

Photoluminescence spectroscopy of the CN radical produced in the infrared photolysis of CH3CN

The infrared laser-induced photolysis of CH₃CN has been studied by observing luminescence from the excited CN (B²Σ⁺) radical and pulsed dye laser-induced fluorescence of ground state CN(X²Σ⁺), both produced as primary fragments. Both temporal and wavelength resolved spectroscopy have been performed on the luminescence, whereas pulsed dye laser probing has allowed time-resolution of the CN(X²Σ⁺) radical as well as measurements of the decay time of the CN(B²Σ⁺) state produced in the dye laser pumping. A reaction mechanism, characterizing the observed results, is proposed.     

PHOTOIONIZATION OF CRYSTAL VIOLET IN AQUEOUS SOLUTION

Abstract— Laser flash photolysis studies were carried out on a triphenylmethane dye, crystal violet (CV⁺), at 248 nm in aqueous solutions. The results show that CV⁺ undergoes photoionization and the resulting transients CV^-2+, hydrated electrons (e^-_aq) and CV⁺ radical formed by the reaction of e^-_aq with CV⁺ have been characterized. Studies using suitable scavengers were done to support the characterization of the transient species. Laser intensity effects show that the ionization is biphotonic. Two mechanisms are proposed to explain the observed photoionization involving higher excited singlet state and/ or another long-lived excited state of the dye.     

Strongly coupled ruthenium-polypyridyl complexes for efficient electron injection in dye-sensitized semiconductor nanoparticles

Dynamics of interfacial electron transfer (ET) in the ruthenium-polypyridyl complex [{bis(2,2'-bpy)-(4-[2-(4'-methyl-2,2'-bipyridinyl-4-yl)vinyl]benzene-1,2-diol)} ruthenium(II) hexafluorophosphate] (Ru-cat)-sensitized TiO(2) nanoparticles has been investigated using femtosecond transient absorption spectroscopy detecting in the visible and near-infrared region. It has been observed that Ru-cat is coupled strongly with the TiO(2) nanoparticles through its pendant catechol moiety. Electron injection has been confirmed by direct detection of electrons in the conduction band, cation radical of the adsorbed dye, and a bleach of the dye in real time as monitored by transient absorption spectroscopy. A single-exponential and pulse width limited (<100 fs) electron injection has been observed, and the origin of it might have been from the nonthermalized excited states of the Ru-cat molecule. The result gave a strong indication that the electron injection competes with the thermalization of the photoexcited states due to large coupling elements for the forward ET reaction. Back-ET dynamics has been determined by monitoring the decay kinetics of the cation radical and injected electron and also from recovery kinetics of the bleach of the adsorbed dye. It has been fit with a multiexponential function, where approximately 30% of the injected electrons are recombined with a time constant of <2 ps, again indicating large coupling elements for the charge recombination reaction. However, our results have shown relatively long-lived charge separation in the Ru-cat/TiO(2) system as compared to other organic dye-sensitized TiO(2) nanoparticles with similar interactions.     

Mannich aminomethylation reactions of a series of bis(α-amino acidato)metal(II) complexes with formaldehyde and diethylmalonate: Crystal structure of (5,5-dicarboxyethyl-3,7-diazanonanedioato)copper(II) monohydrate

Mannich aminomethylation reactions involving M(aa)₂, where M = Cu, Ni and aa = glycine(gly), dl-alanine(dl-ala), l-alanine(l-ala), with formaldehyde and diethylmalonate have been carried out, resulting in carboxylate appended systems in high yield. All the compounds have been characterized by UV-Vis spectroscopy, infrared spectroscopy and elemental analysis. One of the synthesized complexes, (5,5-dicarboxyethyl-3,7-diazanonanedioato)copper(II) monohydrate, has been characterized by single crystal XRD and has been used as catalyst in the hydrogen peroxide-induced degradation of pyrocatechol violet (PCV) dye. The variations in the rate of degradation of the dye with respect to change in concentration of hydrogen peroxide, dye, catalyst and pH have been studied. Effect of addition of NaCl has been studied and a suitable mechanism based on the formation of free radical species during the degradation process has been proposed.     

Free radical oxidation reaction for selectively solvatochromic sensors with dynamic sensing ability

A novel BODIPY (boradiazaindacene) dye denoted as BODIPY-DT containing terpyridine unit has been designed and characterized. The dye is found to be selective and visual solvatochromic sensor toward DMF among test organic solvents. The sensing process displays time-controllable, dynamic signal outputs in the emission colors including red, purple, yellow and even white emission colors. It is presented that selective free radical oxidation reaction happens during the recognition process.     

PHOTOPHYSICAL and PHOTOCHEMICAL PROPERTIES OF COUMARIN DYES IN AMPHIPHILIC MEDIA

Abstract— Photophysical properties of coumarin dyes solubilized in aqueous detergent solutions have been investigated including measurement of absorption and fluorescence emission maxima, and fluorescence quantum yields. Use of coumarin 4 as a fluorescence probe of sodium dodecyl sulfate (SDS) and cetyltrimethylammonium bromide (CTAB) solutions led to the conclusion that the sites for dye incorporation in micelles are significantly hydrogen-bonded (hydrated). The inhibition of photochemical decomposition for detergent-solubilizcd dyes has also been observed. Electron transfer from micelle-bound dye to a water soluble acceptor, methyl viologen, has been investigated by flash photolysis.     

REACTIVITY OF ACRIDINE DYE TRIPLET STATES IN ELECTRON TRANSFER REACTIONS

Abstract—Rate constants, k _q , for the reaction of cationic and neutral acridine orange and 10-methylacridine orange triplet states (³AOH ⁺, ³AO, ³MAO⁺) with a series of electron donors have been measured. Two different protolytic forms of the semireduced dye radical are produced by acridine orange triplet quenching at various pH^M values in methanolic solution.
It is found that k ₄ decreases with increasing oxidation potential of the reducing agent for all triplet states in a manner which is expected for electron transfer reactions. The different reactivities of the cationic and neutral triplet forms can, therefore, be attributed to the difference in reduction potentials of these species. The difference in reduction potentials is related to the p K ^M values of triplet state, p K _T^M , and semireduced dye radical, p K ^M_S , by thermodynamic consideration. p K _T^M (³AOH⁺/³AO) is determined to be 11.2. From thisp K _S^M (AOH./AO;) is estimated to be 17–18. This is in striking contrast to the protolytic equilibrium of the semireduced dye radicals found to be pK^F= 4.1. We conclude that the last value represents the second protonation equilibrium (AOH⁺₂./AOH). This conclusion is confirmed by spectroscopic data.     

OPTICAL ABSORPTION AND EMISSION STUDIES ON LASER DYE INCORPORATED IN NAFION MEMBRANE

Abstract— Incorporation of the laser dye 7-amino-4-methyl coumarin (C-120) in a perfluoro sulfonate cation exchange membrane (Nafion) from aqueous solution has been studied by following its light absorption and emission (fluorescence) characteristics. It is shown that in the H⁺ form of the membrane the dye exists in its monoprotonated cationic form, whereas in different cation exchanged forms of the membrane it is incorporated as the unprotonated neutral molecules. By repeated equilibration with the aqueous solution, high concentrations of the dye could be loaded into the membrane. As compared to an aqueous solution, the polymer matrix was found to confer very good photostability to the dye.     

CHRONIC ULTRAVIOLET RADIATION-INDUCED INCREASE IN SKIN IRON and THE PHOTOPROTECTIVE EFFECT OF TOPICALLY APPLIED IRON CHELATORS 1,*

In the skin of albino hairless mice (Skh:HR-1) there is a basal level of non-heme iron. Chronic exposure of mice to sub-erythemal doses of ultraviolet (UV) B radiation results in an increased skin level of non-heme iron. The iron increase may be the result of a UVB radiation-induced increase in vascular permeability, which we measured in vivo with the dye marker Evans Blue. We also observed greater non-heme iron in sun-exposed vs non-exposed body sites of human skin, suggesting that similar events occur in man. Iron may have a role in skin photodamage by participating in formation of reactive oxygen species. These species have been implicated in skin photodamage. It is known that iron can contribute to oxygen radical production by acting catalytically in the formation of species such as hydroxyl radical. While the basal level of skin iron may be available for catalysis, the elevated iron content of UV-exposed skin increases the potential for iron-catalyzed radical production. Topical application of certain iron chelators to Skh albino hairless mice dramatically delayed the onset of UVB radiation-induced skin photodamage. Non-chelating analogs provided no significant protection.     

TRANSIENT SPECIES IN THE PHOTOCHEMISTRY OF EOSIN*

Abstract— Photochemical reactions of eosin in aqueous solution were studied using the flash photolysis technique. In deaerated solution the dye was converted quantitatively to the triplet state during flashing. The triplet dye decayed by first and second order reactions which partly regenerated the dye in the ground state and partly produced semioxidized and semireduced eosin. These radical species were formed in an electron dismutation reaction between two triplet molecules and also in a reaction between one triplet and one unexcited molecule. The radicals recombine rapidly to give the dye in the ground state.
An efficient reversible photooxidation reaction was observed in eosin solutions containing potassium ferricyanide. Semioxidized eosin was formed in high yield by reaction between the triplet dye and the oxidant. The dye was regenerated rapidly in a reverse reaction between the products of the oxidation reaction.
An analogous type of reaction was found to occur in eosin solutions containing p -pheny-lene diamine. This reagent reduced the triplet dye to semireduced eosin; the dye was regenerated in the ground state in a very efficient reverse reaction. The protolytic behaviour of semireduced eosin was studied by varying the pH.
Absorption spectra of the transient products were determined and rate constants for the observed reactions were measured. The results are compared with results from previous studies of fluorescein.     

A mechanistic investigation of a three‐component radical photoinitiator system comprising methylene blue,N‐methyldiethanolamine,and diphenyliodonium chloride

Three‐component systems, which contain a light‐absorbing species (typically a dye), an electron donor (typically an amine), and a third component (usually an iodonium salt), have emerged as efficient, visible‐light‐sensitive photoinitiators. Although three‐component systems have been consistently found to be faster and more efficient than their two‐component counterparts, these systems are not well understood and a number of distinct mechanisms have been reported in the literature. In this contribution, photodifferential scanning calorimetry and in situ, time‐resolved, laser‐induced, steady‐state fluorescence spectroscopy were used to study the initiation mechanism of the three‐component system methylene blue, N‐methyldiethanolamine and diphenyliodonium chloride. Kinetic studies based upon photodifferential scanning calorimetry reveal a significant increase in polymerization rate with increasing concentration of either the amine or the iodonium salt. However, the laser‐induced fluorescence experiments show that while increasing the amine concentration dramatically increases the rate of dye fluorescence decay, increasing the DPI concentration actually slows consumption of the dye. We concluded that the primary photochemical reaction involves electron transfer from the amine to the dye. We suggest that the iodonium salt reacts with the resulting dye‐based radical (which is active only for termination) to regenerate the original dye and simultaneously produce a phenyl radical (active in initiation) derived from the diphenyliodonium salt. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 2057–2066, 2000     

Proton‐Coupled Electron Transfer Induced by Near‐Infrared Light

A proton‐coupled electron transfer reaction induced by near‐infrared light (>710 nm) has been achieved using a dye that shows intense NIR absorption property and electron/proton‐accepting abilities. The developed system generated long‐lived radical species and showed high reversibility and robustness. Mechanistic investigations suggested that the rate‐determining step of the reaction involves the proton transfer process.     

Mechanism of TiO2-assisted photocatalytic degradation of dyes under visible irradiation: photoelectrocatalytic study by TiO2-film electrodes

Photoelectrocatalytic degradation of various dyes under visible light irradiation with a TiO(2) nanoparticles electrode has been investigated to reveal the mechanism for TiO(2)-assisted photocatalytic degradation of dyes. The degradation of both cationic and anionic dyes at different biases, including the change in the degradation rate of the dyes and the photocurrent change with the bias potential, the degraded intermediates, the voltage-induced adsorption of dyes, the accumulation of electrons in the TiO(2) electrode, the effect of various additives such as benzoquinone (BQ) and N,N-dimethyl aniline (DMA), and the formation of active oxygen species such as O(2)(*-) and H(2)O(2) were examined by UV-visible spectroscopy, HPLC, TOC, and spin-trap ESR spectrometry. It was found that the dyes could controllably interact with the TiO(2) surface by external bias changes and charging of dyes. The cationic dyes such as RhB and MG underwent efficient mineralization at negative bias, but the N-dealkylation process predominated at positive bias under visible light irradiation. The discolorations of the anionic dyes SRB and AR could not be accelerated significantly at either negative or positive bias. At a negative bias of -0.6 V vs SCE, O(2)(*-) and dye(*+) were formed simultaneously at the electrode/electrolyte interface during degradation of cationic RhB. In the case of anionic dyes, however, it is impossible for the O(2)(*-) and dye cationic radical to coexist at the electrode/electrolyte surface. Experimental results imply both the superoxide anionic radical and the dye cationic radical are essential to the mineralization of the dyes under visible light-induced photocatalytic conditions.     

Metal‐Free,Room‐Temperature,Radical Alkoxycarbonylation of Aryldiazonium Salts through Visible‐Light Photoredox Catalysis

The first radical alkoxycarboxylation of aryldiazonium salts using CO gas through visible‐light‐induced photoredox catalysis (16 W blue LEDs) has been developed. This reaction is entirely metal‐free, is carried out at room temperature with a low loading of an organic dye as a photocatalyst (0.5 mol %), and provides a wide range of arylcarboxylic acid esters in high yields. Importantly, this photocatalytic system can be successfully extended to other carboxylation reactions.     

Metal‐Free,Room‐Temperature,Radical Alkoxycarbonylation of Aryldiazonium Salts through Visible‐Light Photoredox Catalysis

The first radical alkoxycarboxylation of aryldiazonium salts using CO gas through visible‐light‐induced photoredox catalysis (16 W blue LEDs) has been developed. This reaction is entirely metal‐free, is carried out at room temperature with a low loading of an organic dye as a photocatalyst (0.5 mol %), and provides a wide range of arylcarboxylic acid esters in high yields. Importantly, this photocatalytic system can be successfully extended to other carboxylation reactions.     

PHOTO-CIDNP OF THE AMINO ACIDS

A photochemically induced dynamic nuclear polarisation (photo-CIDNP) study is presented of the amino acids that are polarisable with a flavin dye. These include derivatives of tryptophan, tyrosine, histidine, methylated lysines and methionine. The influence of pH, concentration and chemical modification on the magnitude of the CIDNP effect has been studied to obtain mechanistic information about the radical pair formation. The pH and concentration dependence of tyrosine and tryptophan polarisation could be accounted for quantitatively. The CIDNP evidence indicates that hydrogen-atom abstraction is important in generating radical pairs in the case of histidine and tyrosine, while electron transfer prevails in the case of tryptophan, the methylated lysines and methionine.     

Mechanism of heminal recombination of ketyl and aminyl radicals in solid poly(methyl methacrylate)

The mechanism of formation and recombination of radical pairs upon photoreduction of benzophenone by diphenylamine in solid poly(methyl methacrylate) has been studied. By analyzing the concentration dependences of the yield of recombination products (triarylmethane dye or triarylcarbinol), it has been found that the reaction occurs only in relatively large local sites with an effective radius of ～1.4 nm. In contrast, the quenching of ketone phosphorescence by amine, resulting in the generation of primary radical pairs, is carried out in nearly every molecular site with an approximate radius of 1.0 nm containing the initial reagents. In films prepared from chlorinated solvents, the degradation of poly(methyl methacrylate) accompanied by the formation of end macroradicals and dehydrochlorination are important side processes. These processes are mainly responsible for significant long-term photochemical posteffect. The absence of marked magnetic effects indicates that the molecular dynamics of reacting particles and their local environment, rather than spin dynamics, controls the evolution of radical pairs.