Deactivation of singlet molecular oxygen by organo-selenium compounds exhibiting glutathione peroxidase activity and by sulfur-containing homologs.

The bimolecular rate constants (k) of quenching of molecular singlet oxygen 1O2 (1 delta g) by organo-selenium compounds exhibiting glutathione peroxidase activity and by sulfur analogs have been determined by time resolved phosphorescence detection of 1O2 in CD3OD and C6D6, with no solvent effect. The rate constants of quenching by the Se-containing compounds were found to be approximately one order of magnitude higher than those of the S-containing homologs. A linear correlation was observed between log k and the Hammett constant omega ortho with p = -0.89, the rate constant being higher for molecules with an electron-donating substituent and lower for those with an electron-withdrawing substituent. This observation is consistent with the involvement of a charge transfer complex in the deactivation of singlet oxygen.     

QUENCHING OF SINGLET MOLECULAR OXYGEN BY PHTHALOCYANINES AND NAPHTHALOCYANINES

Using the direct measurement of the photosensitized luminescence of singlet molecular oxygen (1O2) the rate constants (kq) have been determined for 1O2 quenching by the monomeric molecules of the following phthalocyanines and naphthalocyanines in chloroform: tetra-(4-tert-butyl) phthalocyanine (I); octa-(3,6-butoxy) phthalocyanine (II), tetra-(6-tert-butyl)-2,3 naphthalocyanine (III), aluminium tetra-(1-tert-phenyl)-2,3 naphthalocyanine (IV), tri-(n-hexyl-siloxy) derivatives of silicon- (V), tin- (VI), aluminium- (VII) and gallium- (VIII) 2,3 naphthalocyanine. The following kq values were obtained (kq x 10(-8) M-1 s-1): 2.9 (I), 59 (II), 100 (III), 20 (IV), 3.9 (V), 53 (VI), 33 (VII), 110 (VIII). As most of the quenchers have the low-lying triplet levels, a contribution of the quenching mechanism based on the energy transfer from 1O2 to these levels has been analysed. A formula is proposed describing the relation between kq values caused by this mechanism, and photophysical constants of the quencher triplet state. This formula was applied to phthalocyanines, naphthalocyanines, beta-carotene and bacterochlorophyll a. The data suggest that the energy transfer can fully explain the activity of V and strongly contributes into the activities of II, III and VI-VIII. A charge transfer interaction might be an additional mechanism involved in 1O2 quenching by compounds studied. As some phthalocyanines and naphthalocyanines are strong physical quenchers of singlet oxygen they can be used as efficient inhibitors for photodestructive processes in photochemical systems.     

THE QUENCHING OF SINGLET OXYGEN BY AMINO ACIDS AND PROTEINS

Abstract— The physical quenching of singlet molecular oxygen (¹Δ_g) by amino acids and proteins in D₂O solution has been measured by their inhibition of the rate of singlet oxygen oxidation of the bilirubin anion. Steady-state singlet oxygen concentrations are produced by irradiating the oxygenated solution with the 1–06 μm output of a Nd-YAG laser, which absorbs directly in the electronic transition ¹Δ_g+ 1 v →³Σ_g^-. The rate of quenching by most of the proteins studied is approximated by the sum of the quenching rates of their amino acids histidine, tryptophan and methionine, which implies that these amino acids in the protein structure are all about equally accessible to the singlet oxygen. The quenching constants differ from those obtained by the ruby-laser methylene-blue-photosensitized method of generating singlet oxygen, or from the results of steady-state methylene-blue-photosensitized oxidation, where singlet oxygen is assumed to be the main reactive species. The singlet oxygen quenching rates in D₂O, pD 8, are (10⁷ℒ mol^-1 s^-1): alanine 0–2, methionine 3, tryptophan 9, histidine 17, carbonic anhydrase 85, lysozyme 150, superoxide dismutase 260, aposuperoxide dismutase 250.     

Dye induced quenching of firefly luciferase-luciferin bioluminescence

The quenching of firefly bioluminescence (BL) in presence of xanthene dyes and tetratolylporphyrin was investigated. The BL intensity was quenched with an altered decay pattern in presence of xanthene dyes and tetratolylporphyrin. The electronic absorption spectra indicate that there is no significant interaction occurring between the dyes and the BL components in the ground state. The BL quenching decay rate and fluorescence quenching studies of luciferin by the dyes suggest an energy transfer through an exciplex, involving oxyluciferin, in the excited state and the dyes, in the ground state. The bimolecular quenching rate constant (K(q)) values obtained from fluorescence studies varied between 7.7 x 10(12) and 19.8 x 10(12)M(-1)s(-1). The magnitude of the bimolecular quenching rate constants confirmed the complex formation between dye and excited oxyluciferin. The exciplex subsequently undergoes a non-radiative decay to the ground state via a combination of heavy atom induced and F?rster-type energy transfer. The decay rate constants in presence and in absence of dyes vary between 7.47 x 10(-4) and 7.6 x 10(-2)s(-1). In the presence of dyes the effective decay rate constants (k(eff)) increased while the lifetime of light emitting species decreased. The kinetic studies in presence of singlet oxygen scavengers, like beta-carotene and NaN(3), prove that there is no significant quenching of the firefly BL due to the formation of singlet oxygen.     

Fatty acid profiles of sebaceous triglycerides by capillary gas chromatography with mass-selective detection

Fatty acid methyl esters prepared from the triglyceride fraction of skin surface lipids from six adult human males were chromatographed on a 50-m fused-silica column coated with the highly polar cyanopropylpolysiloxane phase. This permitted the resolution of double-bond positional and geometric isomers. By means of mass-selective detection, 33 saturated and 14 unsaturated fatty acid chain types were analysed. Interpretation of the mass spectra combined with precise calculation of equivalent chain length values permitted the identification of 22 saturated and all of the unsaturated chain types. Quantification by integration of total-ion and selected-ion chromatograms revealed marked variation in the triglyceride fatty acid composition between different subjects. The greatest variation was observed in the concentrations of even-carbon-numbered iso-branched acids, which ranged from 1.5 to 11% of the saturated and from 1.9 to 12.7% of the monounsaturated acids. The anteiso chain structures constituted 4-9% of the saturated and 3-6% of the unsaturated members. Fatty acids with 4-methyl branch showed the least variation, in the range 5.7-7.4%. Other methyl-branched acids made up 4-10% of the saturated group, but were not detected in the unsaturated acids fraction. Two 18:1 fatty acids were identified (a delta 8 and a delta 9), which possibly have different anatomical origins. Similarly, two 18:2 fatty acids (linoleic and a 2,3-dimethyl derivative) were identified. A 2-methyl C17 acid, probably of bacterial origin, was detected.     

Kinetic study of the quenching reaction of singlet oxygen by flavonoids in ethanol solution

The quenching rate of singlet oxygen (1O2) by seven kinds of flavonoids (flavone, flavonol, chrysin, apigenin, rutin, quercetin, and myricetin) with 2,3-double bonds has been measured spectrophotometrically in ethanol at 35 degrees C. The overall rate constants kQ (= kq + kr, physical quenching + chemical reaction) increased as the number of OH groups substituted to the flavone skeleton (that is, the total electron-donating capacity of flavonoids) increases. The existence of catechol or pyrogallol structure in the B-ring is essential for the 1O2 quenching of flavonoids. Log kQ was found to correlate with their peak oxidation potentials, E(P); the flavonoids that have smaller E(P) values show higher reactivities. Similarly, log kQ values of flavonoids correlate with the energy level of the highest occupied molecular orbital (E(HOMO)), calculated by the PM3 MO method, and the longest wavelength pi pi* excitation energy (E(ex)). The contribution of the chemical reaction (kr) was found to be negligible in these flavonoids. The kQ values of rutin, quercetin, and myricetin [(1.21 approximately 5.12) x 10(8) M(-1) s(-1)] were found to be larger than those of lipids [(0.9 approximately 6.4) x 10(4) M(-1) s(-1)], amino acids (<3.7 x 10(7) M(-1) s(-1)), and DNA (5.1 x 10(5) M(-1) s(-1)). The result suggests that these flavonoids may contribute to the protection of oxidative damage in foods and plants, by quenching 1O2.     

Singlet molecular oxygen quenching ability of carotenoids in a reverse-micelle membrane mimetic system

The influence of the medium heterogeneity upon the bimolecular rate constants for the physical quenching, kq, and chemical quenching, kr, of singlet molecular oxygen O2(1deltag) by seven natural and three synthetic carotenoids (CAR) with different substituent patterns was studied in a reverse micelle system of sodium bis(2-ethylhexyl)sulfosuccinate, hexane and water. Because O2(1deltag) was generated inside the water pools of the reverse micelles by photosensitization of the water-soluble dye rose bengal and the CAR are mainly located in the external hexane pseudophase, the quenching process was interpreted using a pseudophase model for the partition of 02(1deltag) between the water pools and the organic pseudophases. The kq values were mainly dependent on the extent of the double-bond conjugation of the CAR, as demonstrated by a good empirical relationship between log(k(q)) and the energy E(S) of the longest wavelength transition pi-->pi* of the CAR. In contrast, the kr values were almost independent of the extent of the double-bond-conjugated system and about four orders of magnitude lower than kq. However, in all cases, CAR photobleaching was observed with the formation of various oxidation products, depending on the photosensitization time. Chromatographic and spectroscopic product analysis for the reaction products of beta-carotene with O2(1deltag) indicated the formation of the beta-carotene-5,8-endoperoxide as the primary oxidation product.     

Separation of Nile Blue-labelled fatty acids by CE with absorbance detection using a red light-emitting diode

The separation of fatty acids derivatised with Nile Blue (NB) by CE with detection using a red light-emitting diode (LED) was examined. NB was selected as the derivatisation agent due to its high molar absorption coefficient of 76,000 M(-1) cm(-1) at 633 nm, making it well suited for sensitive absorbance detection using a red 635 nm LED. NB-labelled fatty acids were separated by both MEKC using SDS micelles, i-PrOH and n-BuOH and by NACE in a number of solvents including MeOH, EtOH and ACN. The sensitivity of NACE was superior to MEKC, with detection limits of 5x10(-7)-7x10(-7) M obtained for each acid, approximately 20 times lower than the MEKC method. The NACE detection limits are approximately 100 times lower than previous reports on the separation of fatty acids by CE using indirect absorbance detection, ten times lower than using indirect fluorescence detection and are inferior only to those obtained using precapillary derivatisation and direct fluorescence detection. The efficiency of the NACE method was also superior to MEKC and allowed the separation of unsaturated fatty acids to be examined, although it was not possible to baseline-resolve linoleic (C18:2) and linolenic (C18:3) acids in a reasonable time. The method was used to analyse the fatty acid profile of two edible oils, namely sunflower and sesame oils, after alkali hydrolysis, where it was possible to identify both the saturated and unsaturated fatty acids in each sample.     

Mechanism of quenching by oxygen of the excited states of ruthenium(II) complexes in aqueous media. Solvent isotope effect and photosensitized generation of singlet oxygen, O2(1Deltag), by [Ru(diimine)(CN)4]2- complex ions

In this study we report on the photophysical properties of some [RuL(CN)4](2-) complex ions where L = 2,2'-bipyridine (bpy), 5,5'-dimethyl-2,2'-bipyridine (dmb), 1,10-phenanthroline (phen), 1-ethyl-2-(2-pyridyl)benzimidazole (pbe), 2,2':6',2'-terpyridine (tpy) and [RuL3](2+) where L = bpy or phen. Measurements were carried out in H2O and D2O. The effect of the deuterium isotope effect on the lifetime of these complexes is discussed. It has also been found that the presence of cyano groups has a pronounced effect on the lifetime of the excited metal-to-ligand charge transfer ((3)MLCT) of these complexes. Quenching of the (3)MLCT states by oxygen is reported in H2O and D2O. The rate constants, k(q), for quenching of the (3)MLCT states of these ruthenium complex ions by molecular oxygen are in the range (2.55 to 7.01) x 10(9) M(-1) s(-1) in H2O and (3.38 to 5.69) x 10(9) M(-1) s(-1) in D2O. The efficiency of singlet oxygen, O2((1)Delta(g)), production as a result of the (3)MLCT quenching by oxygen, f(Delta)(T), is reported in D2O and found to be in the range 0.29-0.52. The rate constants, k(q)(Delta), for quenching of singlet oxygen by ground state sensitizers in D2O is also reported and found to be in the range (0.15 to 3.46) x 10(7) M(-1) s(-1). The rate constants and the efficiency of singlet oxygen formation are quantitatively reproduced by a model that assumes the competition of a non-charge transfer (nCT) and a CT deactivation channel. nCT deactivation occurs from a fully established spin-statistical equilibrium of (1)(T1(3)Sigma) and (3)(T1(3)Sigma) encounter complexes by internal conversion (IC) to lower excited complexes that dissociate to yield O2((1)Delta(g)), and O2((3)Sigmag-). The balance between CT and nCT deactivation channels which is described by the relative contribution p(CT) of CT induced deactivation is discussed. The kinetic model proposed for the quenching of pi-pi* triplet states by oxygen can also be applied to the quenching of (3)MLCT states by oxygen.     

ACRYLAMIDE QUENCHING OF TRYPTOPHAN PHOTOCHEMISTRY AND PHOTOPHYSICS

Studies of acrylamide quenching of tryptophan (Trp) fluorescence, photochemistry, and photoionization have been conducted. Quenching of Trp fluorescence in aqueous solution by addition of acrylamide in the concentration range 0.0-0.5 M was measured and resulted in a Stern-Volmer quenching constant of KSV = 21 +/- 3 M-1. Photolysis experiments were performed in which Trp was photolyzed at 295 nm in the presence of varying concentrations of acrylamide. The loss of Trp was monitored using reverse-phase high performance liquid chromatography (RP-HPLC) and was observed to follow first order kinetics. Production of N-formylkynurenine (NFK) was observed by RP-HPLC in irradiated Trp samples both in the presence and absence of added acrylamide. In addition, no new photochemical product was detected. This was taken as evidence that acrylamide did not alter the photochemical pathway but just reduced the reaction rate as expected for a physical quenching mechanism. Plotting the reciprocal of photolysis rate constant versus acrylamide concentration produced a Stern-Volmer constant for quenching of Trp photochemistry of KSV = 6 +/- 2 M-1. The KSV values for both fluorescence quenching and photolysis quenching were thus large, implying efficient quenching of both processes by acrylamide. Assuming an excited singlet state lifetime of 2.8 ns, the calculated second-order quenching rate constants for fluorescence and photolysis were kq = 7.5 x 10(9) and 2.1 x 10(9) M-1 s-1 respectively. The possible involvement of photoionization in the photolysis mechanism was investigated by studies of acrylamide quenching of voltage transients produced by xenon flash lamp excitation of Trp at aqueous/teflon or aqueous/mica interfaces.(ABSTRACT TRUNCATED AT 250 WORDS)     

Electron-transfer oxidation properties of unsaturated fatty acids and mechanistic insight into lipoxygenases

Rate constants of photoinduced electron-transfer oxidation of unsaturated fatty acids with a series of singlet excited states of oxidants in acetonitrile at 298 K were examined and the resulting electron-transfer rate constants (k(et)) were evaluated in light of the free energy relationship of electron transfer to determine the one-electron oxidation potentials (E(ox)) of unsaturated fatty acids and the intrinsic barrier of electron transfer. The k(et) values of linoleic acid with a series of oxidants are the same as the corresponding k(et) values of methyl linoleate, linolenic acid, and arachidonic acid, leading to the same E(ox) value of linoleic acid, methyl linoleate, linolenic acid, and arachidonic acid (1.76 V vs SCE), which is significantly lower than that of oleic acid (2.03 V vs SCE) as indicated by the smaller k(et) values of oleic acid than those of other unsaturated fatty acids. The radical cation of linoleic acid produced in photoinduced electron transfer from linoleic acid to the singlet excited state of 10-methylacridinium ion as well as that of 9,10-dicyanoanthracene was detected by laser flash photolysis experiments. The apparent rate constant of deprotonation of the radical cation of linoleic acid was determined as 8.1 x 10(3) s(-1). In the presence of oxygen, the addition of oxygen to the deprotonated radical produces the peroxyl radical, which has successfully been detected by ESR. No thermal electron transfer or proton-coupled electron transfer has occurred from linoleic acid to a strong one-electron oxidant, Ru(bpy)3(3+) (bpy = 2,2'-bipyridine) or Fe(bpy)3(3+). The present results on the electron-transfer and proton-transfer properties of unsaturated fatty acids provide valuable mechanistic insight into lipoxygenases to clarify the proton-coupled electron-transfer process in the catalytic function.     

Cyclometalated iridium and platinum complexes as singlet oxygen photosensitizers: quantum yields, quenching rates and correlation with electronic structures

Photophysical properties are reported for a series of cyclometalated platinum and iridium complexes that can serve as photosensitizers for singlet oxygen. The complexes have the formula (C;N)(2)Ir(O;O) or (C;N)Pt(O;O) where C;N is a monoanionic cyclometalating ligand such as 2-(phenyl)pyridyl and 2-(phenyl)quinolyl, and O;O is the ancillary ligand acetylacetonate (acac) or dipivaloylmethane (dpm). Also examined were a series of (N;N)PtMe(2) complexes where N;N is a diimine such as 2,2'-bipyridyl. In general, the cyclometalated complexes are excellent photosensitizers for the production of singlet oxygen, while the (N;N)PtMe(2) complexes were ineffective at this reaction. Quantum yields of singlet oxygen production range from 0.9-1.0 for the cyclometalated Pt complexes and 0.5-0.9 for Ir complexes. Luminescence quenching and singlet oxygen formation of the Ir complexes occurs from a combination of electron and energy transfer processes, whereas the Pt complexes only react by energy transfer. For Ir complexes with low emission energy, physical deactivation of the triplet excited state becomes competitive with energy transfer to ground state dioxygen. The rates of singlet oxygen quenching for the complexes presented here are in the range 6 x 10(6)-2 x 10(7) M(-1) s(-1) for Pt complexes and 2 x 10(5)-2 x 10(7) M(-1) s(-1) for Ir complexes, respectively. Differences in the efficiency of both forming and quenching singlet oxygen between the Ir and Pt cyclometalates are believed to come about from the more exposed coordination geometry in the latter species.     

Quenching of singlet molecular oxygen (1O2) by azide anion in solvent mixtures.

The azide ion is a strong physical quencher of singlet molecular oxygen (1O2) and is frequently employed to show involvement of 1O2 in oxidation processes. Rate constants (k(q)) for the quenching of 1O2 by azide are routinely used as standards to calculate k(q) values for quenching by other substrates. We have measured k(q) for azide in solvent mixtures containing deuterium oxide (D2O), acetonitrile (MeCN), 1,4-dioxane, ethanol (EtOH), propylene carbonate (PC), or ethylene carbonate (EC), mixtures commonly used for many experimental studies. The rate constants were calculated directly from 1O2 phosphorescence lifetimes observed after laser pulse excitation of rose bengal (RB), used to generate 1O2. In aqueous mixtures with MeCN and carbonates, the rate constant increased nonlinearly with increasing volume of organic solvent in the mixtures. k(q) was 4.78 x 10(8) M(-1) s(-1) in D2O and increased to 26.7 x 10(8) and 27.7 x 10(8) M(-1) s(-1) in 96% MeCN and 97.7% EC/PC, respectively. However, in EtOH/D2O mixtures, k(q) decreased with increasing alcohol concentration. This shows that a higher solvent polarity increases the quenching efficiency, which is unexpectedly decreased by the proticity of aqueous and alcohol solvent mixtures. The rate constant values increased with increasing temperature, yielding a quenching activation energy of 11.3 kJ mol(-1) in D2O. Our results show that rate constants in most solvent mixtures cannot be derived reliably from k(q) values measured in pure solvents by using a simple additivity rule. We have measured the rate constants with high accuracy, and they may serve as a reliable reference to calculate unknown k(q) values.     

Photochemical studies on xanthurenic acid

The tryptophan metabolite xanthurenic acid (Xan) has been isolated from aged human cataractous lenses. The photophysical properties of Xan were examined to determine if it is a potential chromophore for age-related cataractogenesis. We found that Xan produces singlet oxygen (psi delta = 0.17 in CD3OD) with the same efficiency as the lenticular chromophore N-formyl kynurenine and quenches singlet oxygen at a rate similar (2.1 x 10(7); CD3OD) to other tryptophan metabolites found in the eye. As the mechanisms of induction of cataracts may also involve redox reactions, the interactions of hydrated electrons (e(aq)-), the azide radical (N3*) and hydroxyl radical (OH*) with Xan were studied using the technique of pulse radiolysis. The reaction rate constants of e(aq)-, N3* and OH* with Xan were found to be of the same order of magnitude as other tryptophan metabolites. The rate constant for reaction of Xan with e(aq)- solvated electrons was found to be diffusion controlled (k = 1.43 x 10(10) M(-1) s(-1); the reaction with N3* was very fast (k = 4.0 x 10(9) M(-1) s(-1)); and with OH* was also near diffusion controlled (k = 1.0 x 10(10) M(-1) s(-1)). Superoxide O2*- production by irradiated Xan in methanol was detected by electron paramagnetic resonance and substantiated by determining that the enhanced rate of oxygen consumption of Xan irradiated in the presence of furfuryl alcohol was lowered by superoxide dismutase.     

单重态氧化学VII. 迷迭香中主要抗氧化成分对单重态氧的猝灭作用

本文研究了迷迭香酚和鼠尾草酚对单重态氧的猝灭作用。实验证明迷迭香酚和鼠尾草酚在甲醇中猝灭单重态氧的总速率常数K~A分别为2.51×10^7和7.19×10^6mol^1.dm^-3.s^-1, 其中化学猝灭的速率常数k~r分别为1.27×10^7和9.82×10^5mol.dm^-3.s^-1, 相应的半猝灭浓度β值为4.6×10^-3和1.6×10^-2mol.dm^-3。这是一类有实用价值的高效抗氧化剂。     

Effect of borate buffer on the photolysis of riboflavin in aqueous solution

The photolysis of riboflavin (RF) in the presence of borate buffer (0.1-0.5M) at pH 8.0-10.5 has been studied using a specific multicomponent spectrophotometric method for the determination of RF and photoproducts, formylmethylflavin (FMF), lumichrome (LC) and lumiflavin (LF). The overall first-order rate constants for the photolysis of RF (1.55-4.36 x 10(-2)min(-1)) and the rate constants for the formation of FMF (1.16-3.52 x 10(-2)min(-1)) and LC (0.24-0.84 x 10(-2)min(-1)) have been determined. The values of all these rate constants decrease with an increase in buffer concentration suggesting the inhibition of photolysis reaction by borate species. The kinetic data support the formation of a RF-borate complex involving the ribityl side chain to cause the inhibition of photolysis. The second-order rate constants for the borate inhibited reaction range from 1.17-3.94 x 10(-2)M(-1)min(-1). The log k-pH profiles for the reaction at various buffer concentrations indicate a gradual increase in rate, with pH, up to 10 followed by a decrease in rate at pH 10.5 probably due to ionization of RF and quenching of fluorescence by borate species. A graph of second-order rate constants against pH is a sigmoid curve showing that the rate of photolysis increases with an increase in pH. The results suggest the involvement of excited singlet state, in addition to excited triplet state, in the formation of LC.     

Quenching of singlet oxygen (1deltag) by cobalt complexes with four nitrogen atoms in the equatorial plane

The quenching of singlet oxygen (1deltag) by cobalt(III)-bis-1,2-benzosemiquinone-diiminato complexes (general structure LCo(111)(BQDI)2ClO4) has been studied in different solvents by measuring the singlet oxygen phosphorescence decay in time-resolved experiments. The axial ligand (Ph3As, Ph3Sb, N-methyl-imidazole, pyrrolidine) has practically no influence on the quenching; however, the chlorinated benzosemiquinone-diiminato complex has a markedly lower quenching rate constant. The solvent effects can be fully explained by the difference in viscosity, which supports the assumption that the quenching is diffusion controlled. The reactive radius of the encounter pair has been estimated to be 0.3 nm, shorter than the radius of the complex itself, which points to the fact that singlet oxygen must approach the central cobalt atom at the (partially) open axial position. The significance of these results regarding the quenching of singlet oxygen by vitamin B12 derivatives is discussed.     

Photoinduced intramolecular electron-transfer reactions of reconstituted met- and zinc-myoglobins appending acridine and methylacridinium ion as DNA-binders

Three types of reconstituted met- and zinc-myoglobin (metMb and ZnMb) dyads, ZnMbAc(4)Me+, ZnMbAc(6)Me+, and metMbAc(6) have been prepared by incorporating chemically modified metalloporphyrin cofactor appending an acridine (Ac) or a methylacridinium ion ([AcMe]+) into apo-Mb. In the bimolecular system between ZnMb and [AcMe]+, the photoexcited triplet state of ZnMb, 3(ZnMb)*, was successfully quenched by [AcMe]+ to form the radical pair of ZnMb cation (ZnMb*+) and reduced methylacridine ([AcMe]*), followed by a thermal back ET reaction. The rate constants for the intermolecular quenching ET (kq) and the back ET reaction (kb) at 25 degrees C were successfully obtained as kq = (8.8 +/- 0.4) x 10(7) M(-1) s(-1) and kb = (1.2 +/- 0.1) x 10(8) M(-1) s(-1), respectively. On the other hand, in case of the intramolecular photoinduced ET reactions of ZnMbAc(4)Me+ and ZnMbAc(6)Me+ dyads, the first-order quenching rate constants (kET) of 3(ZnMb)* by [AcMe]+ moiety were determined to be kET = 2.6 x 10(3) and 2.5 x 10(3) s(-1), respectively. When such ET occurs along the alkyl spacer via through-bond mechanism at the surface of Mb, the obtained kET is reasonable to provide decay constant of beta (1.0-1.3 A(-1)). Upon photoirradiation of [AcMe]+ moiety, kinetic studies also presented the intramolecular quenching reactions from the excited singlet state, 1([AcMe]+)*, whose likely process is the photoinduced energy-transfer reaction. For metMbAc(6) dyad, steady-state fluorescence was almost quenched, while the signal around 440 nm gradually appeared in the presence of various concentrations of DNA. Our study implies that synthetic manipulation at the Mb surface, by using an artificial DNA-binder coupled with photoinduced reaction, may provide valuable information to construct new Mb-DNA complex and sensitive fluorescent for DNA.     

Photosensitized generation of singlet oxygen from rhenium(I) and iridium(III) complexes

Photophysical properties in dilute acetonitrile solution are reported for a number of iridium(III) and rhenium(I) complexes. The nature of the lowest excited state of the complexes under investigation is either metal-to-ligand charge transfer ((3)MLCT) or a ligand centred ((3)LC) state. Rate constants, k(q), for quenching of the lowest excited states by molecular oxygen are in the range 1.5 x 10(8) to 1.4 x 10(10) M(-1) s(-1). Efficiency of singlet oxygen production, f(Delta)(T), following oxygen quenching of the lowest excited states of these complexes, are in the range of 0.27-1.00. The rate constants and the efficiency of singlet oxygen formation are quantitatively reproduced by a model that assumes the competition between a non-charge transfer (nCT) and a CT deactivation channel. The balance between CT and nCT deactivation channels, which is described by the relative contribution p(CT) of CT induced deactivation, is discussed. The kinetic model is found to be successfully applied in the case of quenching of the excited triplet states of coordination compounds by oxygen in acetonitrile, as was proposed for the quenching of pi-pi* triplet states by oxygen.     

SYNTHETIC CAROTENOIDS, NOVEL POLYENE POLYKETONES AND NEW CAPSORUBIN ISOMERS AS EFFICIENT QUENCHERS OF SINGLET MOLECULAR OXYGEN

Novel synthetic polyene polyketones and new synthetic capsorubin isomers were examined for their ability to quench singlet molecular oxygen (1O2) generated by the thermodissociation of the endoperoxide of 3,3'-(1,4-naphthylene) dipropionate (NDPO2). C28-polyene-tetrone (1) exhibits the highest physical quenching rate constant with 1O2 (kq = 16 x 10(9) M-1 s-1). For comparison, the rate constant for the most efficient biological carotenoid, lycopene (3) is kq = 9 x 10(9) M-1 s-1 and that of beta-carotene (5) kq = 5 x 10(9) M-1 s-1. The presence of two oxalyl chromophores at the ends of the polyene chain seems to enhance the 1O2 quenching ability in the C28-polyene-tetrone (1). C28-polyene-tetrone-diacetal (2) (kq = 9 x 10(9) M-1 s-1) and C40-epiisocapsorubin (4) (kq = 8 x 10(9) M-1 s-1) also have high 1O2 quenching abilities. Two carotenoids from plants, phytoene and phytofluene, were much less efficient, kq values being below 10(7) M-1 s-1. Due to the very high singlet oxygen quenching abilities, C28-polyene-tetrone (1), C28-polyene-tetrone-diacetal (2) and C40-epiisocapsorubin (4) may have potential use in preventing 1O2-induced damage in biological and non-biological systems.