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N2O removal in N2 or air by ArF excimer laser photolysis at atmospheric pressure.

A photochemical process is proposed as a new efficient N(2)O removal technique in N(2) or air at atmospheric pressure and room temperature without using any catalysts. N(2)O diluted in N(2) or air was decomposed into N(2), O(2), and NO by using a 193 nm ArF excimer laser. The maximum conversion of N(2)O in N(2)O/N(2) or N(2)O/N(2)/O(2) mixtures was 93% at a laser power of 136 mJ, a repetition frequency of 5 Hz, and an irradiation time of 30 min. The formation ratios of N(2):O(2):NO in N(2)O/N(2) and N(2)O/N(2)/O(2) mixtures were 64:31:5.1% and 60:27:13%, respectively. The decomposition mechanism of N(2)O under 193 nm photolysis was discussed by comparing experimental data with calculated model using known photochemical and gas kinetic data.

Air↗

Structure and potential mutagenicity of new hydantoin products from guanosine and 8-oxo-7,8-dihydroguanine oxidation by transition metals.

In vitro work in this laboratory has identified new DNA lesions resulting from further oxidation of a common biomarker of oxidative damage, 8-oxo-7,8-dihydroguanine (OG). The major product of oxidation of OG in a nucleoside, nucleotide, or single-stranded oligodeoxynucleotide using metal ions that act as one-electron oxidants is the new nucleoside derivative spiroiminodihydantoin (Sp). In duplex DNA an equilibrating mixture of two isomeric products, guanidinohydantoin (Gh) and iminoallantoin (Ia), is produced. These products are also formed by the overall four-electron oxidation of guanosine by photochemical processes involving O(2). DNA template strands containing either Sp or Gh/Ia generally acted as a block to DNA synthesis with the Klenow exo(-) fragment of pol I. However, when nucleotide insertion did occur opposite the lesions, only 2'-deoxyadenosine 5-triphosphate and 2'-deoxyguanine 5-triphosphate were used for primer extension. The Escherichia coli DNA repair enzyme Fpg was able to remove the Sp and Gh/Ia lesions from duplex DNA substrates, although the efficiency was depended on the base opposite the lesion.

Biomarkers↗

Destruction of helminth eggs by photosensitized porphyrin.

Tunisian untreated wastewater exhibits an average of 30 human helminth eggs per litre. After treatment, the concentration decreases to one egg per litre, or more in some cases. The percentage removal cited for wastewater processes provides no real indication of the destruction of the organisms, but merely of their transfer to another medium. In this study, we report the use of an environmentally friendly photoactive compound for wastewater disinfection. Photosensitization involves the generation of very toxic short-lived species on absorption of light by porphyrin. Microorganism photosensitization is potentially useful for sterilization and for the treatment of certain bacterial diseases. Gram-positive bacteria can be photoinactivated by a range of photosensitizers, but Gram-negative bacteria are not usually susceptible to photosensitized destruction. Our findings clearly demonstrate that the cationic meso-substituted porphyrin, tetra-(4-N-methylpyridyl) porphin tetra-tosylate (T4MPYP), is an efficient photosensitizer of helminth eggs on visible light illumination. The microscopic observation of helminth eggs shows that many types of ultrastructural alterations are potentially associated with exposure to T4MPYP and an adequate intensity of light: morphological changes without breakage; small alterations of eggshells; complete destruction. The degree of egg alteration increases with both increasing T4MPYP concentration and irradiation time. Moreover, the dissolved oxygen concentration, water quality and the type of eggs can influence the sensitivity of helminth eggs to photosensitization. Indeed, suspended solids (turbidity) were the most influential solution parameter on the efficiency of the photochemical process.

Animals↗

Medium effects on zwitterionic-biradicaloid intermediates from two phenyl-alpha-oxoamides. Irradiations in fluid and solid protic media, neat solid phases, and the solid, smectic and isotropic phases of a completely saturated phosphonium salt at different temperatures.

The photochemical processes of two N,N-dialkyl phenyl-alpha-oxoamides, N,N-diisopropyl phenyl-alpha-oxoamide (1) and N,N-dibenzyl phenyl-alpha-oxoamide (2), are investigated at different temperatures in methanol and ethylene glycol (to probe the influences of H-bonding and viscosity), in the solid phase of D-sorbitol at room temperature (to compare with the results in the liquid alcohols and to assess the influence of a poorly organized "stiff" environment), in the neat solid phase (to probe the influence of well-ordered, "stiff" matrices), and in the solid, smectic A2 and isotropic phases of methyl-tris-tetradecylphosphonium tetrafluoroborate (1P14BF4) (to assess the ability of the intermediates to respond to subtle changes in the order and polarity of their local environments). From differences between the activation parameters for product pathways from irradiations in methanol and in 1P14BF4, we conclude that the zwitterionic pre-product intermediate from 1 is much more sensitive to the polarity, viscosity and order of its local environment than is the isomeric pre-product biradicaloid intermediate or either of the pre-product intermediates from 2. A very sensitive balance among the medium parameters, as well as internal steric and electronic factors of 1 and 2, controls the reactive pathways of the photochemically generated intermediates.

Journal Article↗

Biotransformation of benzo[a]pyrene and other polycyclic aromatic hydrocarbons and heterocyclic analogs by several green algae and other algal species under gold and white light.

This laboratory has shown that the metabolism of benzo[a]pyrene (BaP), a carcinogenic polycyclic aromatic hydrocarbon (PAH), by a freshwater green alga, Selenastrum capricornutum, under gold light proceeds through a dioxygenase pathway with subsequent conjugation and excretion. This study was undertaken to determine: (1) the effects of different light sources on the enzymatic or photochemical processes involved in the biotransformation of BaP over a dose range of 5-1200 mg/l; (2) the phototoxicity of carcinogenic PAHs and mutagenic quinones to a green alga; (3) the ability of other algal systems to metabolize BaP. Cultures were exposed to different doses of BaP for 2 days at 23 degrees C under gold, white or UV-A fluorescent light on a diurnal cycle of 16 h light, 8 h dark. Under gold light, metabolites of BaP produced by Selenastrum capricornutum were the dihydrodiols of which the 11,12-dihydrodiol was the major metabolite. Under white light, at low doses, the major metabolite was the 9,10-dihydrodiol. With increasing dose, the ratio of dihydrodiols to quinones decreased to less than two. With increasing light energy output, from gold to white to UV-A in the PAH absorbing region, BaP quinone production increased. Of other carcinogenic PAHs studied, only 7H-dibenz[c,g]carbazole was as phototoxic as BaP while 7,12-dimethylbenz[a]anthracene, dibenz[a,j]acridine and non-carcinogenic PAHs, anthracene and pyrene, were not phototoxic. The 3,6-quinone of BaP was found to be highly phototoxic while quinones that included menadione, danthron, phenanthrene-quinone and hydroquinone were not. The data suggest that the phototoxicity of BaP is due to photochemical production of quinones; the 3,6-quinone of BaP is phototoxic and is probably the result of the production of short lived cyclic reactive intermediates by the interaction of light with the quinone. Lastly, only the green algae, Selenastrum capricornutum, Scenedesmus acutus and Ankistrodesmus braunii almost completely metabolized BaP to dihydrodiols. The green alga Chlamydomonas reinhardtii, the yellow alga Ochromonas malhamensis, the blue green algae Anabaena flosaquae and euglenoid Euglena gracilis did not metabolize BaP to any extent. The data indicate that algae are important in their ability to degrade PAHs but the degradation is dependent on the dose of light energy emitted and absorbed, the dose of PAHs to which the algae are exposed, the phototoxicity of PAHs and their metabolite(s) and the species and strain of algae involved. All of these factors will be important in assessing the degradation and detoxification pathways of recalcitrant PAHs by algae.

Anabaena↗

Photooxidation of A2-PE, a photoreceptor outer segment fluorophore, and protection by lutein and zeaxanthin.

A2-PE is a pigment that forms as a byproduct of the visual cycle, its synthesis from all-trans-retinal and phosphatidylethanolamine occurring in photoreceptor outer segments. A2-PE is deposited in retinal pigment epithelial (RPE) cells secondary to phagocytosis of shed outer segment membrane and it undergoes hydrolysis to generate the RPE lipofuscin fluorophores, A2E, iso-A2E and other minor cis-isomers of A2E. We have demonstrated that A2-PE can initiate photochemical processes that involve the oxidation of A2-PE and that, by analogy with A2E are likely to include the formation of reactive moieties. We also show that potential sources of protection against the photooxidation of A2-PE are the lipid-soluble carotenoids zeaxanthin and lutein (xanthophylls), that constitute the yellow pigment of the macula. Irradiation of A2-PE in the presence of lutein or zeaxanthin suppressed A2-PE photooxidation and in experiments in which we compared the antioxidant capability of zeaxanthin and lutein to alpha-tocopherol, the carotenoids were more potent. Additionally, the effect with zeaxanthin was consistently more robust than with lutein and when alpha-tocopherol was combined with either carotenoid, the outcome was additive. Lutein, zeaxanthin and alpha-tocopherol were all efficient quenchers of singlet oxygen. We have also shown that lutein and zeaxanthin can protect against A2-PE/A2E photooxidation without appreciable consumption of the carotenoid by chemical reaction. This observation contrasts with the pronounced susceptibility of A2E and A2-PE to photooxidation and is of interest since lutein, zeaxanthin, A2E and A2-PE all have conjugated systems of carbon-carbon double bonds terminating in cyclohexenyl end-groups. The structural features responsible for the differences in quenching mechanisms are discussed. It has long been suspected that macular pigment protects the retina both by filtering high-energy blue light and by serving an antioxidant function. Evidence presented here suggests that the photochemical reactions against which lutein and zeaxanthin protect, may include those initiated by the A2-PE. Quantitative HPLC analysis revealed that in eyecups of C57BL/6J and BALB/cByJ mice, levels of A2-PE were several fold greater than the cleavage product, A2E. Taken together, these results may have implications with respect to the involvement of A2-PE formation in mechanisms underlying blue light-induced photoreceptor cell damage and may be significant to retinal degenerative disorders, such as those associated with ABCA4 mutations, wherein there is a propensity for increased A2-PE synthesis.

Animals↗

Evaluation of processing characteristics of photochemically treated pooled platelets: target requirements for the INTERCEPT Blood System comply with routine use after process optimization.

To ensure good performance of pathogen inactivation with the INTERCEPT blood system, specific target requirements must be met for platelet dose, volume, plasma content and residual red blood cells (RBCs) prior to photochemical treatment (PCT). A two-arm in vitro study was conducted to compare quality parameters of pooled platelet concentrates (PCs), either treated (test units) or nontreated (control units). PCs meeting European requirements were evaluated with reference to their compliance with INTERCEPT guard bands. Of 50 PCs (25 tests and 25 controls) meeting European quality requirements, 24% (three test and three controls units) did not reach INTERCEPT requirements, particularly in terms of sufficient volumes and RBC contamination. The buffy-coat optimization procedure assessed prior to this study ensured plasma contents well within target limits of 30 to 45%. Due to PCT-related in-process loss of 11% in volume (34.38 +/- 3.94) and in platelet dose (0.41 +/- 0.14), the mean platelet dose was significantly (P < 0.001) lower in test units: 3.1 +/- 0.3 versus 3.6 +/- 0.4 x 10(11). After treatment, six of the overall 25 test units (25%) would not have met the European guideline for platelet dose (3.0 x 10(11)). Before implementation of techniques for pathogen reduction, each centre should optimize processing steps during a validation procedure to ensure PC complying with INTERCEPT targets before and European targets after treatment. Besides buffy-coat optimization for sufficient plasma reduction, centrifugation profiles need to be optimized as well to prevent PC with low volumes and, in particular, with higher than acceptable RBC contamination.

Blood Banking↗

Electron paramagnetic resonance spectroscopy of free radicals in corneal tissue following excimer laser irradiation.

BACKGROUND AND OBJECTIVES: Free radicals, detected previously in corneal tissue following 193 nm laser irradiation, may be important agents in the laser/tissue interaction. Electron paramagnetic resonance spectroscopy (EPR) has been used to examine such radical formation in detail. STUDY DESIGN/MATERIALS AND METHODS: Bovine corneal strips were frozen in liquid nitrogen, irradiated with excimer laser pulses, and assayed by EPR. Exposure conditions were varied to study radical formation dependence on laser intensity and repetition. Results were measured against a quantifiable standard to calculate radical quantum yield. RESULTS: Either weak or intense laser fluences produced comparable tissue EPR signals. Radicals accumulated in frozen tissue for at least 10 initial ablation pulses. Radical quantum yield in cornea was 0.15%. CONCLUSION: Corneal radical formation is largely a photochemical process driven by the 193 nm laser radiation. Reactive radical species are produced in substantial numbers and likely have a significant clinical role.

Animals↗

Metabolic effects of photodynamically induced apoptosis in an erythroleukemic cell line. A (31)P NMR spectroscopic study of Victoria-Blue-BO-sensitized TF-1 cells.

Victoria Blue BO (VB BO) is a new and promising photosensitizer currently being evaluated for photodynamic therapy (PDT). Its photochemical processes are mediated by oxygen radicals, but do not involve singlet oxygen. We used (31)P NMR spectroscopy of VB-BO sensitized TF-1 leukemic cells to gain further insight into the biochemical mechanisms underlying PDT-induced cell death. Sham-treatment experiments were performed to evaluate the effects of this photosensitizer in the absence of light irradiation. Significant metabolic differences were detected for TF-1 cells incubated with VB BO but not exposed to light, as compared with native cells (controls). These changes include reductions in phosphocreatine, UDP-hexose and phosphodiester levels (as percentage of total phosphate) and slightly reduced intracellular pH. Complete phosphocreatine depletion, significant acidification and concomitant inorganic-phosphate accumulation were observed for TF-1 cells irradiated after incubation with VB BO. Moreover, significant changes in phospholipid metabolites, i.e., accumulation of cytidine 5'-diphosphate choline and a decrease in phosphodiester levels, were observed for PDT-treated vs. sham-treated cells. Perturbations of phospholipid metabolism may be involved in programmed cell death, and the detection of a characteristic DNA ladder pattern by gel electrophoresis confirmed the existence of apoptosis in PDT-treated TF-1 cells.

Apoptosis↗

Buckminsterfullerene and photodynamic inactivation of viruses.

The development of new virus inactivation procedures has become an area of growing interest mainly due to increased demands concerning the safety of biological products. Photochemical processes represent the most promising methods for the future to inactivate viruses. In these methods, dyes are the most widely used photosensitising reagents. The current article covers a new interesting alternative, namely the use of buckminsterfullerene (C60). The unique properties of this molecule make it a valid candidate for future applications in the inactivation of viruses in biological fluids. Copyright 1998 John Wiley & Sons, Ltd.

Journal Article↗

Modified windmill porphyrin arrays: coupled light-harvesting and charge separattion, conformational relaxation in the S1 state, and S2-S2 energy transfer.

The architecture of windmill hexameric zinc(II) -porphyrin array 1 is attractive as a light-harvesting functional unit in view of its three-dimensionally extended geometry that is favorable for a large cross-section of incident light as well as for a suitable energy gradient from the peripheral porphyrins to the meso-meso-linked diporphyrin core. Three core-modified windmill porphyrin arrays 2-4 were prepared for the purpose of enhancing the intramolecular energy-transfer rate and coupling these arrays with a charge-separation functional unit. Bisphenylethynylation at the meso and meso' positions of the diporphyrin core indeed resulted in a remarkable enhancement in the intramolecular S1-S1 energy transfer in 2 with tau=2 approximately 3 ps, as revealed by femtosecond time-resolved transient absorption spectroscopy. The fluorescence lifetime of the S2 state of the peripheral porphyrin energy donor determined by the fluorescence up-conversion method was 68 fs, and thus considerably shorter than that of the reference monomer (150 fs), suggesting the presence of the intramolecular energy-transfer channel in the S2 state manifold. Such a rapid energy transfer can be understood in terms of large Coulombic interactions associated with the strong Soret transitions of the donor and acceptor. Picosecond time-resolved fluorescence spectra and transient absorption spectra revealed conformational relaxation of the S1 state of the diporphyrin core with tau = 25 ps. Upon photoexcitation of models 3 and 4, which bear a naphthalenetetracarboxylic diimide or a meso-nitrated free-base porphyrin attached to the modified diporphyrin core as an electron acceptor, a series of photochemical processes proceeded, such as the collection of the excitation energy at the diporphyrin core, the electron transfer from the S1 state of the diporphyrin to the electron acceptor, and the electron transfer from the peripheral porphyrins to the diporphyrin cation radical, which are coupled to provide a fully charge-separated state such as that in the natural photosynthetic reaction center. The overall quantum yield for the full charge separation is better in 4 than in 3 owing to the slower charge recombination associated with smaller reorganization energy of the porphyrin acceptor.

Journal Article↗

One- and two-photon photochemistry and photophysics of poly(arylenevinylene)s containing a biphenyl moiety.

Photochemical and photophysical properties were investigated for poly(arylenevinylene)s containing a flexible biphenyl "hinge" unit by applying one-photon (OP) and two-photon (TP) excitation to explore excited-state properties. The poly(arylenevinylene)s were poly[(2,5-dihexyloxy-p-phenylenevinylene)-alt-(4,4'-dihexyloxy-3,3'-biphenylenevinylene)] (1), poly[(2,5-dihexyloxy-p-phenylenevinylene)-alt-(2,2'-dihexyloxy-3,3'-biphenylenevinylene)] (2), and poly[(2,5-dihexyloxy-p-phenylenevinylene)-alt-(2,2'-biphenylenevinylene)] (3). Effective emission quantum yields and related photonic properties were evaluated on a realistic per-chromophore basis using effective conjugation lengths based on the Strickler-Berg relationship. Intramolecular photocyclization was deduced to occur in the one case where the biphenyl molecular connectivity permitted the reaction, based on matrix-assisted laser desorption/ionization time-of-flight (MALDI-TOF), heteronuclear multiple-quantum coherence (HMQC)-NMR, and gel-permeation chromatography (GPC) results. The various photoprocesses could be induced by either OP or TP excitation, though the first excited singlet state is the photoactive state. The higher excitation energy of the TP excited state favors indirect population of the S, state by electronic coupling between the TP and OP excited states [lambda(max)TPE (nm): 726; delta (GM): 1=229, 2=215, 3= 109). Photochemical processes occurring from the lowest OP excited state (S1) could therefore also be indirectly induced by TP excitation.

Journal Article↗

A quantitative model of ultraviolet matrix-assisted laser desorption/ionization.

A quantitative model of primary ionization in ultraviolet matrix-assisted laser desorption/ionization (UV-MALDI) is presented. It includes not only photochemical processes such as exciton pooling, but also the effects of the desorption event. The interplay of these two is found to be a crucial aspect of the MALDI process. The desorbing plume is modeled as an adiabatic expansion with entrained clusters. The parameters in the model are defined as much as possible via experiment or by analogy with known effects. The model was applied to the matrix 2,5-dihydroxybenzoic acid and found to reproduce the fluence dependence of the fluorescence yield and key features of the picosecond two-pulse ion generation efficiency curves. In addition, the model correctly predicts a fluence rather than irradiance threshold, the magnitude of the threshold, the magnitude of the ion yield, laser wavelength effects, plume temperatures, plume expansion velocities and the spot size effect.

Journal Article↗

Photolytic degradation of benorylate: effects of the photoproducts on cultured hepatocytes.

The photodegradation of benorylate [4'-(acetamido)phenyl-2-acetoxybenzoate], a drug frequently used in rheumatoid arthritis therapy, has been examined under different sets of experimental conditions. Several photoproducts have been isolated and identified on the basis of their IR, NMR, and MS spectra. The most significant photochemical process is the photo-Fries rearrangement of benorylate, leading to 5-acetamido-2'-acetoxy-2-hydroxybenzophenone (1). This compound undergoes a rapid transacylation to the isomeric 5'-acetamido-2'-acetoxy-2-hydroxybenzophenone (2). A primary culture of rat hepatocytes has been used to evaluate the possible toxicity of these two benzophenones, keeping in mind the following criteria: leakage of cytosolic enzymes, attachment index to culture plates, gluconeogenesis from lactate and fructose, glycogen balance, and albumin synthesis. At the concentrations assayed, neither of the two major photoproducts of benorylate (benzophenones 1 and 2) had significant toxic effects on liver cells in culture.

Albumins↗

A coupled soil-atmosphere model of H2O2 on Mars.

The Viking Gas Chromatograph Mass Spectrometer failed to detect organic compounds on Mars, and both the Viking Labeled Release and the Viking Gas Exchange experiments indicated a reactive soil surface. These results have led to the widespread belief that there are oxidants in the martian soil. Since H2O2 is produced by photochemical processes in the atmosphere of Mars, and has been shown in the laboratory to reproduce closely the Viking LR results, it is a likely candidate for a martian soil oxidant. Here, we report on the results of a coupled soil/atmosphere transport model for H2O2 on Mars. Upon diffusing into the soil, its concentration is determined by the extent to which it is adsorbed and by the rate at which it is catalytically destroyed. An analytical model for calculating the distribution of H2O2 in the martian atmosphere and soil is developed. The concentration of H2O2 in the soil is shown to go to zero at a finite depth, a consequence of the nonlinear soil diffusion equation. The model is parameterized in terms of an unknown quantity, the lifetime of H2O2 against heterogeneous catalytic destruction in the soil. Calculated concentrations are compared with a H2O2 concentration of 30 nmoles/cm3, inferred from the Viking Labeled Release experiment. A significant result of this model is that for a wide range of H2O2 lifetimes (up to 10(5) years), the extinction depth was found to be less than 3 m. The maximum possible concentration in the top 4 cm is calculated to be approximately 240 nmoles/cm3, achieved with lifetimes of greater than 1000 years. Concentrations higher than 30 nmoles/cm3 require lifetimes of greater than 4.3 terrestrial years. For a wide range of H2O2 lifetimes, it was found that the atmospheric concentration is only weakly coupled with soil loss processes. Losses to the soil become significant only when lifetimes are less than a few hours. If there are depths below which H2O2 is not transported, it is plausible that organic compounds, protected from an oxidizing environment, may still exist. They would have been deposited by meteors, or be the organic remains of past life.

Atmosphere↗

Observations of CH4, C2H6, and C2H2 in the stratosphere of Jupiter.

We have performed high-resolution spectral observations at mid-infrared wavelengths of CH4 (8.14 micrometers), C2H6 (12.16 micrometers), and C2H2 (13.45 micrometers) on Jupiter. These emission features probe the stratosphere of the planet and provide information on the carbon-based photochemical processes taking place in that region of the atmosphere. The observations were performed using our cryogenic echelle spectrometer CELESTE, in conjunction with the McMath-Pierce 1.5-m solar telescope between November 1994 and February 1995. We used the methane observations to derive the temperature profile of the jovian atmosphere in the 1-10 mbar region of the stratosphere. This profile was then used in conjunction with height-dependent mixing ratios of each hydrocarbon to determine global abundances for ethane and acetylene. The resulting mixing ratios are 3.9(+1.9)(-1.3) x 10(-6) for C2H6 (5 mbar pressure level), and 2.3 +/- 0.5 x 10(-8) for C2H2 (8 mbar pressure level), where the quoted uncertainties are derived from model variations in the temperature profile which match the methane observation uncertainties.

Acetylene↗

Photochemical synthesis of simple organic free radicals on simulated planteary surfaces-an ESR study.

Electron spin resonance spectroscopy provided evidence for formation of hydroxyl radicals during ultraviolet photolysis (254 nm) at -170C of H2O adsorbed on silica gel or of silica gel alone. The carboxyl radical was observed when CO or CO2 or a mixture of CO and CO2 absorbed on silica gel at -170C was irradiated. The ESR signals of these radicals slowly disappeared when the irradiated samples were warmed to room temperature. However, re-irradiation of CO or CO2, or the mixture CO and CO2 on silica gel at room temperature then produced a new species, the carbon dioxide anion radical, which slowly decayed and which was identical with that produced by direct photolysis of formic acid adsorbed on silica gel. The primary photochemical process may involve formation of hydrogen and hydroxyl radicals by means of (1) photodissociation of H2O physically adsorbed on the silica gel, or (2) absorption of the excitation energy by the silica gel surface with subsequent cleavage of the silanol bonds, or (3) dissociation of H2O molecules throug photosensitization by the surfaces or a combination of (1) to (3). Subsequent reactions of these radicals with adsorbed CO or CO2 or both yield carboxyl radicals, CO2H, the precsursors of formic acid. Our results confirm the formation of formic acid under simulated Martian conditions and provide a mechanistic basis for gauging the potential importance of gas-solid photochemistry for chemical evolution on other extraterrestrial bodies, on the primitive earth and on dust grains in the interstellar medium.

Adsorption↗

Photobiochemistry without light.

Efficient excited state formation - much higher than that hitherto expected - may occur in organelles and in intact cells. Excited triplet states can be enzymatically generated in high yields by different routes. An example is the oxidation of isobutanal to acetone and formic acid, catalyzed by horseradish peroxidase. Other enzymatic systems that generate triplet carbonyls are linear aliphatic aldehydes when oxidized by peroxidase/O2, or the indole-3-acetic acid/peroxidase/O2-reaction. The latter is widespread in plants. This new field - photobiochemistry without light - has led to a growing awareness of the idea that cells may utilize excited states to trigger photochemical processes even in the dark. Such phenomena are of considerable importance, also for the understanding of weak photon emission from biological systems.

Acetone↗