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PubMed2005

Theoretical study on spin alignments in ferromagnetic heterospin chains with competing exchange interactions: a generalized ferrimagnetic system containing organic biradicals in the singlet ground state.

Spin alignments in heterospin chains are examined from numerical calculations of model spin Hamiltonians. The Hamiltonians of the heterospin chains mimic an open-shell molecular assemblage composed of an organic biradical in a singlet (S = 0) ground state and a doublet (S = 1/2) monoradical, which are coupled by intermolecular ferromagnetic exchange interactions. It is found from numerical calculations of the spin Hamiltonians that the spin value S2 of the ground-state singlet biradical embedded in the exchange-coupled assemblage deviates from zero and contributes to the bulk magnetization. The alternating chain is found to have two kinds of ground spin states, a high- and a low-spin state. All the spins are parallel to each other in the high-spin state, which is characterized by the spin correlation function of (S(i).S(j)) = 0.25. On the other hand, the spin alignment in the low-spin state is found to be dependent on the topology of the intermolecular exchange interactions. The energy preference of the two states depends on the relative amplitude of the exchange interactions in the chain. The intermolecular ferromagnetic couplings are competing in the ground-state singlet biradical with the intramolecular antiferromagnetic interaction. The appearance of the two kinds of ground states is attributed to a quantum spin frustration effect inherent in the triangular motif of the competing interactions. Magnetic properties of a zigzag chain complex composed of a nitronyl nitroxide biradical with a singlet ground state and Cu(hfac)2 are examined on the basis of the theoretical calculations. The vanishing magnetic moments, or the product of susceptibility and temperature chiT, at low temperatures observed for the complex are consistent with those of the low-spin state predicted in the theoretical calculations.

Journal Article↗
PubMed2005

Theoretical study of singlet and triplet excitation energies in oligothiophenes.

We have analyzed singlet and triplet excitation energies in oligothiophenes (up to five rings) using time-dependent density-functional theory (TD-DFT) with different exchange-correlation functionals and compared them with results from the approximate coupled-cluster singles and doubles model (CC2) and experimental data. The excitation energies have been calculated in geometries obtained by TD-DFT optimization of the lowest excited singlet state and in the ground-state geometries of the neutral and anionic systems. TD-DFT methods underestimate photoluminescence energies but the energy difference between singlet and triplet states shows trends with the chain-length similar to CC2. We find that the second triplet excited state is below the first singlet excited state for long oligomers in contrast with the previous assignment of Rentsch et al. (Phys.Chem. Chem. Phys. 1999, 1, 1707). Their photodetachment photoelectron spectroscopy measurements are better described by considering higher triplet excited states.

Journal Article↗
PubMed2006

Singlet energy transfer in porphyrin-based donor-bridge-acceptor systems: interaction between bridge length and bridge energy.

Singlet excitation energy transfer is governed by two donor-acceptor interactions, the Coulombic and exchange interactions giving rise to the Förster and Dexter mechanisms, respectively, for singlet energy transfer. In transfer between colliding molecules or between a donor (D) and acceptor (A) connected in donor-bridge-acceptor (D-B-A) system by an inert spacer (B), the distinction between these two mechanisms is quite clear. However, in D-B-A systems connected by a pi-conjugated bridge, the exchange interaction between the donor and acceptor is mediated by the virtual low-lying excited states (unoccupied orbitals) of that bridge and, as a consequence, becomes much more long-range in character. Thus, the clear distinction to the Coulombic mechanism is lost. This so-called superexchange mechanism for singlet energy transfer has been shown to make a significant contribution to the energy transfer rates in several D-B-A systems, and its D-A distance as well as D-B energy gap dependencies have been studied. We here demonstrate that in a series of oligo-p-phenyleneethynylene (OPE) bridged porphyrin-based D-B-A systems with varying D-A distances the Förster and through-bond (superexchange) mechanisms both make considerable contributions to the observed singlet energy transfer rates. The donor is either a zinc porphyrin or a zinc porphyrin with a pyridine ligand, and the acceptor is a free base porphyrin. By comparison to a homologous series where only the D-B energy gaps varies, a separation between the two energy transfer mechanisms was possible and, moreover, an interplay between distance and energy gap dependencies was noted. The distance dependence was shown to be approximately exponential with an attenuation factor beta=0.20 A-1. If the effect of the varying D-B energy gaps in the OPE series was taken into account, a slightly higher beta-value was obtained. Ground-state absorption, steady-state, and time-resolved emission spectroscopy were used. The experimental study is accompanied by time-dependent density functional theory (TD-DFT) calculations of the electronic coupling, and the experimental and theoretical results are in excellent qualitative agreement (same distance dependence).

Journal Article↗
PubMed2005

Local aromaticity of the lowest-lying singlet States of [N]acenes (N = 6-9).

The local aromaticities of the six-membered rings in the two lowest-lying singlet states of [n]acenes (n = 6-9) have been assessed by means of three probes of local aromaticity based on structural, magnetic, and electron delocalization properties. Important differences between the local aromaticities of the closed-shell and diradical singlet electronic states are found. Thus, while the inner rings have the largest aromatic character in the closed-shell singlet states, the outer rings become the most aromatic for the diradical singlet states.

Letter↗
PubMed2005

Theory of long-lived nuclear spin states in solution nuclear magnetic resonance. I. Singlet states in low magnetic field.

We have recently demonstrated the existence of exceptionally long-lived nuclear spin states in solution-state nuclear magnetic resonance. The lifetime of nuclear spin singlet states in systems containing coupled pairs of spins-12 may exceed the conventional relaxation time constant T1 by more than an order of magnitude. These long lifetimes may be observed if the long-lived singlet states are prevented from mixing with rapidly relaxing triplet states. In this paper we provide the detailed theory of an experiment which uses magnetic field cycling to observe slow singlet relaxation. An approximate expression is given for the magnetic field dependence of the singlet relaxation rate constant, using a model of intramolecular dipole-dipole couplings and fluctuating external random fields.

Journal Article↗
PubMed2006

Characterization of singlet ground and low-lying electronic excited states of phosphaethyne and isophosphaethyne.

The singlet ground ((approximate)X(1)Sigma1+) and excited (1Sigma-,1Delta) states of HCP and HPC have been systematically investigated using ab initio molecular electronic structure theory. For the ground state, geometries of the two linear stationary points have been optimized and physical properties have been predicted utilizing restricted self-consistent field theory, coupled cluster theory with single and double excitations (CCSD), CCSD with perturbative triple corrections [CCSD(T)], and CCSD with partial iterative triple excitations (CCSDT-3 and CC3). Physical properties computed for the global minimum ((approximate)X(1)Sigma+HCP) include harmonic vibrational frequencies with the cc-pV5Z CCSD(T) method of omega1=3344 cm(-1), omega2=689 cm(-1), and omega3=1298 cm(-1). Linear HPC, a stationary point of Hessian index 2, is predicted to lie 75.2 kcal mol(-1) above the global minimum HCP. The dissociation energy D0[HCP((approximate)X(1)Sigma+)-->H(2S)+CP(X2Sigma+)] of HCP is predicted to be 119.0 kcal mol(-1), which is very close to the experimental lower limit of 119.1 kcal mol(-1). Eight singlet excited states were examined and their physical properties were determined employing three equation-of-motion coupled cluster methods (EOM-CCSD, EOM-CCSDT-3, and EOM-CC3). Four stationary points were located on the lowest-lying excited state potential energy surface, 1Sigma- -->1A", with excitation energies Te of 101.4 kcal mol(-1) (1A"HCP), 104.6 kcal mol(-1)(1Sigma-HCP), 122.3 kcal mol(-1)(1A" HPC), and 171.6 kcal mol(-1)(1Sigma-HPC) at the cc-pVQZ EOM-CCSDT-3 level of theory. The physical properties of the 1A" state with a predicted bond angle of 129.5 degrees compare well with the experimentally reported first singlet state ((approximate)A1A"). The excitation energy predicted for this excitation is T0=99.4 kcal mol(-1) (34 800 cm(-1),4.31 eV), in essentially perfect agreement with the experimental value of T0=99.3 kcal mol(-1)(34 746 cm(-1),4.308 eV). For the second lowest-lying excited singlet surface, 1Delta-->1A', four stationary points were found with Te values of 111.2 kcal mol(-1) (2(1)A' HCP), 112.4 kcal mol(-1) (1Delta HPC), 125.6 kcal mol(-1)(2(1)A' HCP), and 177.8 kcal mol(-1)(1Delta HPC). The predicted CP bond length and frequencies of the 2(1)A' state with a bond angle of 89.8 degrees (1.707 A, 666 and 979 cm(-1)) compare reasonably well with those for the experimentally reported (approximate)C(1)A' state (1.69 A, 615 and 969 cm(-1)). However, the excitation energy and bond angle do not agree well: theoretical values of 108.7 kcal mol(-1) and 89.8 degrees versus experimental values of 115.1 kcal mol(-1) and 113 degrees. of 115.1 kcal mol(-1) and 113 degrees.

Journal Article↗
PubMed1994

Singlet molecular oxygen evolution upon simple acidification of aqueous hypochlorite: application to studies on the deleterious health effects of chlorinated drinking water.

A study of the pH profile of the decomposition of aqueous hypochlorite has revealed the evolution (onset at pH 8) of single (1 delta g) molecular oxygen (singlet spin state dioxygen) detected spectroscopically (1268 nm), prior to the appearance of chlorine (onset at pH 5.5). The possible mechanism of the singlet state dioxygen evolution is presented, and the origin of its chloride ion dependence is discussed, especially in reference to chloride ion dependence of singlet molecular oxygen evolution in biological systems. Recent epidemiological analyses of the correlation of human cancer with chlorinated water supplies focus attention on the singlet oxygen mechanisms of DNA lesion formation.

Chlorine↗
PubMed1996

Mutagenicity of the fullerene C60-generated singlet oxygen dependent formation of lipid peroxides.

Fullerene C60 dissolved in polyvinylpyrrolidone was mutagenic for Salmonella strains TA102, TA104 and YG3003 in the presence of rat liver microsomes when it was irradiated by visible light. The mutagenicity was elevated in strain YG3003, a repair enzyme-deficient mutant of TA102. The mutation was reduced in the presence of beta-carotene and parabromophenacyl bromide, a scavenger and an inhibitor, respectively, of phospholipase. The results suggest that singlet oxygen was generated by irradiating the C60 by visible light and that the mutagenicity was due to oxidized phospholipids in rat liver microsomes. Of the phospholipids in rat liver microsomes, the linoleate fraction isolated by high performance liquid chromatography was a major component, and played an important role in mutagenicity. Methyl linoleate, which was prepared for gas chromatographic analysis, was readily oxidized to hydroperoxymethyl linoleate, and associated with both 10- and 12-hydroxyl derivatives with a double bond in chemical structure by singlet oxygen: radicals to the hydroxyl function were probably generated. Because of the instability of the hydroxymethyl linoleate radicals, guanine residues generated radicals. The results of ESR spectrum analysis suggested generation of radicals at the guanine base but not thymine, cytosine and adenine bases as estimated with the g value of 2.0150. On the other hand, the singlet oxygen-generating C60 formed 8-hydroxydeoxyguanosine (8-OH-dG) upon treatment with 2' deoxyguanosine and microsomes or linoleate. The formation of 8-OH-dG was highly elevated in the presence of microsomes and linoleate. The level of 8-OH-dG formed with and without the microsome fraction was 47 and 9.6 units, respectively, per 10(4) deoxyguanosine. It was considered that the mechanism is indirect action of singlet oxygen due to lipid peroxidation of linoleate that causes oxidative DNA damage.

8-Hydroxy-2'-Deoxyguanosine↗
PubMed1995

Melatonin protects neurons from singlet oxygen-induced apoptosis.

Singlet oxygen (O2[1 delta g]) is a very reactive molecule that can be produced by living cells and may contribute to cytotoxicity. The pineal hormone melatonin has been reported to possess potent antioxidant activity, and to be capable of scavenging O2(1 delta g). We investigated whether melatonin might reduce the neurotoxic action of O2(1 delta g). The cytotoxic effect of singlet oxygen was studied in primary cultures of cerebellar granule neurons pretreated with a photosensitive dye, rose bengal, and exposed to light--a procedure that generates O2(1 delta g). We found that this procedure triggers neuronal death, which is preceded by mitochondrial impairment (assayed by the rate of the reduction of MTT, 3-[4,5-dimethylthiazol-2-yl]-2,5-diphenyl tetrazolium bromide, into formazan), and by DNA fragmentation--a marker of apoptosis. DNA fragmentation was determined in situ by terminal deoxynucleotidyl transferase assay; cell death was assayed with 0.4% trypan blue solution--viable cells with an intact membrane are not permeable to trypan blue; dead cells are, and thus, they are stained blue. Neuroprotection was obtained with the pineal hormone melatonin. In a cell-free system, melatonin also protected the enzyme creatine kinase (EC 2.7.3.2) from the rose bengal-induced injury. The results suggest that melatonin might counteract the cytotoxic action of singlet oxygen. Further studies are needed to clarify the exact role singlet oxygen and melatonin might play in neurodegenerative diseases.

Animals↗
PubMed1989

Singlet oxygen generation of porphyrins, chlorins, and phthalocyanines.

The production of singlet oxygen was measured indirectly for three classes of photosensitizers: porphyrins (Photofrin II, TPPS4), chlorins (MACE, DACE), and a phthalocyanine (CASPc). Buffered solutions of sensitizers and singlet oxygen acceptors were irradiated with a CW dye laser and the oxygen depletion was monitored electrochemically with a Clark-type microelectrode. A comparison of oxygen-depletion rate constants and quantum efficiencies yields the order of efficiency of the sensitizers: TPPS4 greater than MACE greater than PII greater than DACE greater than CASPc. For singlet oxygen acceptors the order was: furfuryl alcohol greater than imidazole greater than tryptophan. CHO cell suspensions were also used as acceptors. Here the order of efficiency (per absorbed photon) was PII greater than MACE approximately CASPc. Expressed in terms of oxygen depletion per cell the order was CASPc approximately PII greater than MACE. When performing cell clonogenicity studies the order of efficiencies, expressed as percentage cell kill per unit weight of sensitizer, was CASPc greater than PII greater than MACE approximately DACE. The discrepancy between the efficiencies of sensitizers to generate singlet oxygen and their cytotoxicity was explained in terms of photodegradation (for the chlorins), intracellular localization (for PII), and contributions from a Type I mechanism (for CASPc).

Animals↗
PubMed1991

Singlet oxygen interaction with Ca(2+)-ATPase of cardiac sarcoplasmic reticulum.

We investigated the role of singlet oxygen (generated from photoactivation of rose bengal) on the calcium transport and Ca(2+)-ATPase activity of cardiac sarcoplasmic reticulum (SR). Isolated cardiac SR exposed to rose bengal (10 nM) irradiated at 560 nm resulted in significant inhibition of Ca2+ uptake (from 2.27 +/- 0.05 to 0.62 +/- 0.05 mumol Ca2+/mg.min [mean +/- SEM], p less than 0.01) and Ca(2+)-ATPase activity (from 2.08 +/- 0.05 to 0.28 +/- 0.04 mumol Pi/min.mg [mean +/- SEM], p less than 0.01). The inhibition of calcium uptake and Ca(2+)-ATPase activity by rose bengal-derived activated oxygen (singlet oxygen) was dependent on the duration of exposure and intensity of light. Singlet oxygen scavengers ascorbic acid and histidine significantly protected SR Ca(2+)-ATPase against rose bengal-derived activated oxygen species, but superoxide dismutase and catalase did not attenuate the inhibition. Sodium dodecyl sulfate-polyacrylamide gel electrophoresis of SR exposed to photoactivated rose bengal for up to 14 minutes demonstrated complete loss of the Ca(2+)-ATPase monomer band, which was significantly protected by histidine. The addition of dithiothreitol (5 mM) had a slight protective effect, showing that new disulfide bond formation was not a major cause of aggregation. The results were also confirmed by high-performance liquid chromatography of the SR exposed to irradiated rose bengal. Irradiation of rose bengal also caused an 18% loss of total sulfhydryl groups of SR. On the other hand, superoxide radical (generated from xanthine oxidase action on xanthine) and hydroxyl radical (in the presence of Fe(3+)-EDTA or 0.5 mM H2O2 plus Fe(2+)-EDTA) as well as H2O2 (0.25-12 mM) were without any effect on the 97,000-d Ca(2+)-ATPase band of SR. Generation of radical species (superoxide and hydroxyl radical) from rose bengal was studied by electron paramagnetic resonance spectroscopy using the spin trap 5,5-dimethyl-1-pyrroline-N-oxide (DMPO). The results showed that irradiation of rose bengal formed a 1:2:2:1 quartet, characteristic of the DMPO-OH adduct, which was scavenged by ethanol but not by superoxide dismutase, catalase, or histidine. No radical species could be detected from irradiated rose bengal or irradiated DMPO under the assay conditions used. Peroxy adducts of DMPO might be produced but would be observed only at very low temperatures. Similarly, we could not detect any measurable.O2- anion from irradiation of rose bengal as indicated by either cytochrome c reduction at 550 nm or nitro blue tetrazolium reduction at 560 nm. These results show that SR is damaged most likely by singlet oxygen derived from rose bengal.(ABSTRACT TRUNCATED AT 400 WORDS)

Animals↗
PubMed1994

Toxicity of singlet oxygen generated thermolytically in Escherichia coli.

Three water-soluble derivatives of naphthalene endoperoxide were prepared to examine the toxicity of singlet oxygen towards Escherichia coli. On incubation without irradiation, these endoperoxides produce singlet oxygen thermolytically in a dose-dependent manner. The amount of singlet oxygen produced per unit time can be controlled by varying both the incubation temperature and the number of methyl substituents of the naphthalene endoperoxide derivatives. 3-(1,4-Dihydro-1,4-epidioxy-4-methyl-1-naphthyl)propionic acid (EP-1), one of the derivatives, inhibited E. coli growth dose- and incubation temperature-dependently and caused E. coli lethality. Furthermore, EP-1 did not induce superoxide dismutase or catalase in E. coli even when the cells were incubated in nutritionally rich medium containing trypticase/soy/yeast extract. Singlet oxygen, one of the reactive oxygen species, did not act as a signal for induction of superoxide dismutase and catalase, in contrast to the actions of superoxide and hydrogen peroxide.

Escherichia coli↗
PubMed1990

[Inhibitory effects of naturally occurring furan fatty acids on hemolysis of erythrocytes induced by singlet oxygen].

As a continuation of the study on the biological roles of furan fatty acids (F acids) which are still vague, their inhibitory effects on the hemolysis of erythrocytes induced by singlet oxygen were examined. Hemolysis proceeded smoothly in the absence of F acids, but was suppressed significantly and dose dependently in their presence. No significant differences in inhibitory effects on the hemolysis induced by singlet oxygen between tetra-alkylsubstituted F acid (F3) and di-alkylsubstituted F acid (NMF) could be detected. The acids underwent oxidation to give the corresponding diketo-enes, indicating a reaction with singlet oxygen to suppress hemolysis. The inhibitory effects of F acids on hemolysis were compared with those of known singlet oxygen quenchers such as dimethylfuran, alpha-tocopherol, ascorbic acid and uric acid and F acids were found to be the most effective quenchers.

Animals↗
PubMed2000

Photophysical properties of the lowest excited singlet and triplet states of thio- and seleno-psoralens

The decay processes of the lowest excited singlet and triplet states of five heteropsoralens (HPS) were investigated by steady-state and shift-phase fluorometry and by laser-flash photolysis in different solvents. The emission spectra of HPS are detectable only in trifluoroethanol (TFE), where fluorescence lifetimes (tau F) and quantum yields (phi F) were measured. The triplet lifetimes (tau T), triplet (phi T) and singlet-oxygen production (phi delta) quantum yields were determined in benzene, ethanol and TFE by laser-flash photolysis. Semiempirical (INDO/1-CI) calculations allowed the nature of the lowest excited singlet and triplet states and transition probabilities to be obtained. Theoretical and experimental results indicate that the two lowest excited singlet states S1 and S2 of HPS are close-lying and different in nature (pi,pi* and n,pi*). The "proximity effect" between these two states controls the photophysical properties of HPS as it does for the other furocoumarins. However, HPS have a peculiar behavior with respect to the related compounds because they are fluorescent and have, in three cases, detectable intersystem crossing only in TFE. This behavior can be tentatively explained by a different energy gap and/or order between the S1 and S2 states.

Journal Article↗
PubMed2000

Singlet oxygen, but not oxidizing radicals, induces apoptosis in HL-60 cells.

Oxidizing species (OS), produced by photosensitization or derived from cytotoxic agents, activate apoptotic pathways. We investigated whether two different OS, formed at the same subcellular sites, have equivalent ability to initiate apoptosis in HL-60 cells. Our previous work showed that absorption of visible light by rose bengal (RB) produces singlet oxygen exclusively, whereas absorption of ultraviolet A produces RB-derived radicals in addition to singlet oxygen. Singlet oxygen, but not the RB-derived radicals, induced nuclear condensation and DNA fragmentation into nucleosome-size fragments in a dose dependent manner. In contrast, the RB-derived radicals caused greater lipid oxidation than singlet oxygen. These results indicate that different OS, produced at the same subcellular sites, do not have the same ability to induce apoptosis and that the ability of an OS to initiate lipid oxidation does not necessarily correlate with its ability to induce apoptosis.

Apoptosis↗
PubMed1987

New singlet oxygen source and trapping reagent for peroxide intermediates.

Application of newly-developed water-soluble singlet oxygen sources in the oxidation of biologically important compounds and the electron-transfer process involving singlet oxygen has been reviewed. Particularly, oxidation products of tryptophan by chemically generated singlet oxygen were compared to those obtained in dye-sensitized photooxygenation. The usefulness of trimethylsilyl cyanide as a trapping reagent for dipolar peroxide intermediates has been demonstrated in the photooxygenation of N-methylindoles, 2-(methoxymethylene)adamantane and adamantylideneadamantane in aprotic solvents. Based on these trapping reactions mechanism of singlet oxygen reaction of electron-rich enol ethers and enamines is discussed in light of theoretical calculation.

Cyanides↗
PubMed1992

Intracellular singlet oxygen generation by phagocytosing neutrophils in response to particles coated with a chemical trap.

To determine if singlet oxygen (O2(1 delta g)) is produced by neutrophils (PMNs) during the process of phagocytosis, glass beads were coated with a specific chemical trap for O2(1 delta g), 9,10-diphenylanthracene (DPA). Singlet oxygen, but not other reactive oxygen species, reacts rapidly with DPA at a rate of kr = 1.3 x 10(6) M-1 s-1 to form a stable product, DPA-endoperoxide (Corey, E. J., and Taylor, W. C. (1964) J. Am. Chem. Soc. 86, 3881-3882; Wasserman, H. H., Scheffer, J. R., and Cooper, J. L. (1972) J. Am. Chem. Soc. 94, 4991-4996; Turro, N. J., Chow, M.-F., and Rigaudy, J. (1981) J. Am. Chem. Soc. 103, 7218-7224). The production of DPA-endoperoxide was determined by ultraviolet spectroscopy as a decrease in DPA absorbance at 355 nm. The absorbance of DPA was normalized to the absorbance of perylene, which was included in the coating on the beads as a nonreactive, internal standard. In the present study, DPA- and perylene-coated beads were initially allowed to adhere to fibronectin-coated coverslips. PMNs were then added to the bead-coated coverslips and allowed to adhere and phagocytose the beads for 1 h at 37 degrees C. In some experiments, 4B-phorbol-12-myristate-13-acetate (PMA) (1 ng/2.5 x 10(7) cells/ml), a known activator of the PMN NADPH-oxidase, was added as a co-stimulant. The amount of O2(1 delta g) produced by phagocytically stimulated PMNs was calculated to be 11.3 +/- 4.9 nmol of O2(1 delta g)/1.25 x 10(6) cells. Low dose PMA co-stimulation increased the production of O2(1 delta g) to 14.1 +/- 4.1 nmol/1.25 x 10(6) cells. Averaged together these amounts represent approximately 19 +/- 5.0% of the total oxygen consumed by PMNs in response to DPA- and perylene-coated beads. The specificity of the DPA reaction with O2(1 delta g) was confirmed by warming to 120 degrees C, which releases O2(1 delta g) from the DPA-endoperoxide, regenerating the parent DPA compound (Wasserman et al., 1972; Turro et al., 1981) and the absorbance at 355 nm. In addition, beta-carotene, an avid quencher of O2(1 delta g), was included in the coating of some bead preparations; assays in which these beads were used showed no change in the absorbance at 355 nm. Singlet oxygen production by myeloperoxidase was also measured using the coated bead assay and the results suggest that this is a major pathway by which singlet oxygen is generated in phagocytically stimulated PMNs.(ABSTRACT TRUNCATED AT 400 WORDS)

Animals↗
PubMed1975

Superoxide, hydrogen peroxide, and singlet oxygen in lipid peroxidation by a xanthine oxidase system.

1. Xanthine oxidase acting aerobically upon acetaldehyde was found to cause the peroxidation of linolenate. This was demonstrated by increased absorbance at 233 nm due to diene conjugation and by the detection of a lipid peroxide spot on the thin layer chromatograms. 2. Superoxide dismutase inhibited this lipid peroxidation, as did catalase, thus indicating that both O2- and H2O2 were essential intermediates. Scavengers of singlet oxygen also inhibited the peroxidation of linolenate, whereas scavengers of hydroxyl radical did not. These effects, which were observed in the absence of iron salts, led to the proposal that O2- and H2O2 can directly give rise to a singlet oxygen, as follows: O2- + H2O2 leads to OH- + OH. + O2. 3. This proposal was further supported through the use of 2,5-dimethylfuran, as an indicating scavenger of singlet oxygen. Thus, when this compound was exposed to a known source of singlet oxygen, it gave a product which was detectable by thin layer chromatography. This product was also observed when 2,5-dimethylfuran was exposed to the xanthine oxidase system, in which case its accumulation was prevented by superoxide dismutase or by catalase, but not by scavengers of hydroxyl radical.

Acetaldehyde↗