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PubMed1993

Acceptor side mechanism of photoinduced proteolysis of the D1 protein in photosystem II reaction centers.

A 23-kDa breakdown product, containing the N terminus of the D1 protein, has been detected after photoinhibitory treatment of isolated photosystem II (PSII) reaction centers. The ability to induce charge separation in the reaction center and the presence of oxygen seem to be required for the generation of this fragment. It is suggested that, under these conditions, the initial light-induced damage to the complex occurs via singlet oxygen generated by the P680 triplet state and contrasts with the situation when an electron acceptor is present and donor-side photoinhibition gives rise to a 24-kDa C-terminal fragment of the D1 protein. The temperature sensitivity of the appearance of the 23-kDa N-terminal fragment suggests that the cleavage is not by a direct photochemical process but that it is proteolytic in nature, being triggered possibly by a conformational change induced by singlet oxygen-mediated photodestruction of the P680 chlorophylls. The existence of an intrinsic serine-type protease, within the reaction center itself, is supported by inhibition of the appearance of the 23-kDa N-terminal fragment by stoichiometric levels of soybean trypsin inhibitor. It seems likely that the 23-kDa N-terminal fragment which we have detected is the same as that identified in vivo by Greenberg et al. [Greenberg, B. M., Gaba, V., Mattoo, A. K., & Edelman, M. (1987) EMBO J. 6, 2865-2869] and originates from the acceptor-side mechanism advocated by Vass et al. [Vass, I., Styring, S., Hundal, T., Koivuniemi, A., Aro, E.-M., & Andersson, B. (1992) Proc. Natl. Acad. Sci. U.S.A. 89, 1408-1412].

Bacterial Proteins↗

PubMed1992

Photocycle of phoborhodopsin from haloalkaliphilic bacterium (Natronobacterium pharaonis) studied by low-temperature spectrophotometry.

Phoborhodopsin (pR) is the fourth retinal pigment of Halobacterium halobium and works as a photoreceptor for the negative phototactic response. A similar pigment was previously found in haloalkaliphilic bacterium (Natronbacterium pharaonis) and also works as the receptor of the negative phototactic response; this pigment is called pharaonis phoborhodopsin (ppR). In this paper, the photocycle of ppR was investigated by means of low-temperature spectrophotometry. The absorption maximum of ppR is located at 498 nm, while that of pR is at 487 nm. The absorption spectra of the two have similar vibrational structures. Irradiation of ppR below -100 degrees C produced a K-like intermediate (ppRK) which was a composite of two components. The original ppR and ppRK were perfectly photoreversible. On warming, ppRK was directly converted to an M-like intermediate without formation of the L-like intermediate. The M-like intermediate was converted to the O-like intermediate at pH 7.2, but the O-like intermediate was not detected at pH 9.0. The O-like intermediate then reverted to the original pigment. On the basis of these findings, the photocycle and the primary photochemical process of ppR are presented.

Archaeal Proteins↗

PubMed1994

Formation of cyclobutane dimers and (6-4) photoproducts upon far-UV photolysis of 5-methylcytosine-containing dinucleotide monophosphates.

The far-UV photochemistry of 5-methylcytosine, a minor DNA base, was studied in three dinucleoside monophosphates, including m5dCpT, Tpm5dC, and m5dCpdC. The model compounds were exposed to 254-nm radiation, and the resulting photoproducts were isolated by reverse-phase HPLC and characterized as cyclobutane dimers, (6-4) adducts, and the related Dewar valence isomers by UV, mass, and 1H NMR spectroscopies. The rate of formation of the different photoproducts was compared with those obtained by photolysis of TpT and the corresponding cytosine dinucleoside monophosphates, including dCpT, TpdC, and dCpdC. The formation of deaminated m5dC-containing photoproducts was observed in each of the far-UV irradiated solution of m5dCpT, Tpm5dC, and m5dCpdC. They were shown to be generated mainly through a photochemical process since methylation of the C5 atom of the cytosine ring appeared to dramatically decrease the deamination rate of the C5-C6 saturated photoproducts.

5-Methylcytosine↗

PubMed1987

Resonance Raman spectroscopy of octopus rhodopsin and its photoproducts.

We report here the resonance Raman spectra of octopus rhodopsin and its photoproducts, bathorhodopsin and acid metarhodopsin. These studies were undertaken in order to make comparisons with the well-studied bovine pigments, so as to understand the similarities and the differences in pigment structure and photochemical processes between vertebrates and invertebrates. The flow method was used to obtain the Raman spectrum of rhodopsin at 13 degrees C. The bathorhodopsin spectrum was obtained by computer subtraction of the spectra containing different photostationary mixtures of rhodopsin, isorhodopsin, hypsorhodopsin, and bathorhodopsin, obtained at 12 K using the pump-probe technique and from measurements at 80 K. Like their bovine counterparts, the Schiff base vibrational mode appears at approximately 1660 cm-1 in octopus rhodopsin and the photoproducts, bathorhodopsin and acid metarhodopsin, suggesting a protonated Schiff base linkage between the chromophore and the protein. Differences between the Raman spectra of octopus rhodopsin and bathorhodopsin indicate that the formation of bathorhodopsin is associated with chromophore isomerization. This inference is substantiated by the chromophore chemical extraction data which show that, like the bovine system, octopus rhodopsin is an 11-cis pigment, while the photoproducts contain an all-trans pigment, in agreement with previous work. The octopus rhodopsin and bathorhodopsin spectra show marked differences from their bovine counterparts in other respects, however. The differences are most dramatic in the structure-sensitive fingerprint and the HOOP regions. Thus, it appears that although the two species differ in the specific nature of the chromophore-protein interactions, the general process of visual transduction is the same.

Animals↗

PubMed1989

A comparative study of the infrared difference spectra for octopus and bovine rhodopsins and their bathorhodopsin photointermediates.

Fourier-transform infrared difference spectroscopy has been used to detect the vibrational modes in the chromophore and protein that change in position and intensity between octopus rhodopsin and its photoproducts formed at low temperature (85 K), bathorhodopsin and isorhodopsin. The infrared difference spectra between octopus rhodopsin and octopus bathorhodopsin, octopus bathorhodopsin and octopus isorhodopsin, and octopus isorhodopsin and octopus rhodopsin are compared to analogous difference spectra for the well-studied bovine pigments, in order to understand the similarities in pigment structure and photochemical processes between the vertebrate and invertebrate systems. The structure-sensitive fingerprint region of the infrared spectra for octopus bathorhodopsin shows strong similarities to spectra of both all-trans-retinal and bovine bathorhodopsin, thus confirming chemical extraction data that suggest that octopus bathorhodopsin contains an all-trans-retinal chromophore. In contrast, we find dramatic differences in the hydrogen out-of-plane modes of the two bathorhodopsins, and in the fingerprint lines of the rhodopsins and isorhodopsins for the two pigments. These observations suggest that while the primary effect of light in the octopus rhodopsin system, as in the bovine rhodopsin system, is 11-cis/11-trans isomerization, the protein-chromophore interactions for the two systems are quite different. Finally, striking similarities and differences in infrared lines attributable to changes in amino acid residues in the opsin are found between the two pigment systems. They suggest that no carboxylic acid or tyrosine residues are affected in the initial changes of light-energy transduction in octopus rhodopsin. Comparing the amino acid sequences for octopus and bovine pigments also allows us to suggest that the carboxylic acid residues altered in the bovine transitions are Glu-122 and/or Glu-134.

Amino Acids↗

PubMed2005

Photochemical production of ionic and particulate aluminum and iron in lakes.

Photochemical liberation of allochthonous organically bound aluminum (Al) and iron (Fe) and in-lake hydroxide precipitation are important sources of these metals to lake sediments. Mass budgets of ionic Al and Fe (Ali, Fei), organically bound Al and Fe (Alo, Feo), and particulate Al and Fe (Alp, Fep) were measured for two western Czech Republic forest lakes (Plesne and Certovo) in the 2000-2003 hydrological years. The lakes were net sinks of Ali, Alo, and Feo and net sources of Alp and Fep. The average Alo and Feo inputs from terrestrial sources (66-110 and 12-17 mmol m(-2) yr(-1), respectively, on a lake area basis) were reduced 45% and 25% in the lakes. Mass budgets of dissolved organic carbon, particulate organic C, and Al species indicated that only a minor part of the observed in-lake retention of Alo could be explained by coagulation and sedimentation of organic matter, or from Ali hydrolysis and formation of Alp. Laboratory experiments with a short-time irradiation (approximately 300 nm, approximately 800 W m(-2)) of water from inlets to Plesne Lake showed the importance of photochemical processes in the liberation of Al and Fe from Alo and Feo. After 12 h of irradiation, Alo and Feo concentrations decreased 54 +/- 6% and 70 +/- 16%, respectively, compared to those of the dark controls. The photoliberated Alo and Feo increased the Ali and Fei concentrations reciprocally, on a 1:1 mass basis. The subsequent hydrolysis of Ali and Fe1 in lakes forms insoluble hydroxides, increasing the sediment concentrations of Al and Fe.

Aluminum↗

PubMed2005

Triplet-sensitized photodegradation of sulfa drugs containing six-membered heterocyclic groups: identification of an SO2 extrusion photoproduct.

The aquatic photochemical behavior of a class of sulfa drugs containing six-membered heterocyclic substituents (sulfamethazine, sulfamerazine, sulfadiazine, sulfachloropyridazine, and sulfadimethoxine) was investigated. Photodegradation of the sulfa drugs in a natural water sample was significantly enhanced relative to the degradation in deionized water, with the exception of sulfadimethoxine. This indicated an indirect photochemical process that was identified through the use of quenchers to be attributable to interaction with triplet excited-state dissolved organic matter (3DOM). The direct photolysis rate constant and quantum yield for both the neutral and anionic species of each sulfa drug were calculated using matrix deconvolution methods. The quantum yield values range from 0.01 x 10(-3) for the neutral form of sulfadimethoxine to 5 x 10(-3) for the anionic form of sulfamethazine and are significantly lower than those observed in a previous study for sulfa drugs containing five-membered heterocyclic substituents, although the rate constants are of similar magnitude. The primary product formed in both direct and indirect photodegradation for all five compounds was identified as a sulfur dioxide extrusion product. The predicted environmental half-lives solely attributable to direct photolysis range from 8.6 h in midsummer at 30 degrees latitude in pH 7 surface water for sulfachloropyridazine to 420 h in midwinter at 45 degrees in pH 7 surface water for sulfadimethoxine. These half-lives, except for sulfadimethoxine, will be decreased by interaction with 3DOM.

Acetophenones↗

PubMed2006

Semicontinuous measurements of organic carbon and acidity during the Pittsburgh Air Quality Study: implications for acid-catalyzed organic aerosol formation.

Laboratory evidence suggests that inorganic acid seed particles may increase secondary organic aerosol yields secondary organic aerosol (SOA) through heterogeneous chemistry. Additional laboratory studies, however, report that organic acidity generated in the same photochemical process by which SOA is formed may be sufficient to catalyze these heterogeneous reactions. Understanding the interaction between inorganic acidity and SOA mass is important when evaluating emission controls to meet PM2.5 regulations. We examine semicontinuous measurements of organic carbon (OC), elemental carbon (EC), and inorganic species from the Pittsburgh Air Quality Study to determine if we can detect coupling in the variations of inorganic acidity and OC. We were not able to detect significant enhancements of SOA production due to inorganic acidity in Western Pennsylvania most of the time, but its signal might have been lost in the noise. If we assume a causal relationship between inorganic acidity and OC, reductions in OC for Western Pennsylvania that might result from drastic reductions in inorganic acidity were estimated to be 2 +/- 4% by a regression technique, and an upper bound for this geographic area was estimated to be 5 +/- 8% based on calculations from laboratory measurements.

Acids↗

PubMed2006

Aquatic photochemistry of nitrofuran antibiotics.

The aquatic photochemical degradation of a class of pharmaceuticals known as the nitrofuran antibiotics (furaltadone, furazolidone, and nitrofurantoin) was investigated. Direct photolysis is the dominant photodegradation pathway for these compounds with the formation of a photostationary state between the syn and the anti isomers occurring during the first minutes of photolysis. The direct photolysis rate constant and quantum yield were calculated for each of the three nitrofurans. Reaction rate constants with reactive oxygen species (ROS), 102 and *OH, were also measured, and half-lives were calculated using environmentally relevant ROS concentrations. Half-lives calculated for reaction with 1O2 and *OH are in the ranges of 120-1900 and 74-82 h, respectively. When compared to the direct photolysis half-lives, 0.080-0.44 h in mid-summer at 45 degrees N latitude, it is clear that indirect photochemical processes cannot compete with direct photolysis. The major photodegradation product of the nitrofurans was found to be nitrofuraldehyde, which is also photolabile. Upon photolysis, nitrofuraldehyde produces NO, which is easily oxidized to nitrous acid. The acid produced further catalyzes the photodegradation of the parent nitrofuran antibiotics, leading to autocatalytic behavior. Natural waters were found to buffer the acid formation.

Anti-Bacterial Agents↗

PubMed2002

Structural, spectroscopic, and reactivity comparison of xanthene- and dibenzofuran-bridged cofacial bisporphyrins.

A comparison of the structure, spectroscopy, and oxygen atom-transfer reactivity of cofacial bisporphyrins anchored by xanthene (DPX) and dibenzofuran (DPD) pillars is presented. The synthesis and characterization of dicopper(II) and dinickel(II) complexes of DPD completes a homologous series of homobimetallic zinc(II), copper(II), and nickel(II) complexes for both cofacial platforms. X-ray crystallographic analysis of the parent free-base porphyrins H(4)DPX (1) and H(4)DPD (5) confirms the face-to-face arrangement of the two porphyrin macrocycles with a large available range of vertical pocket sizes: 1 (C(80)H(92)Cl(2)N(8)O), triclinic, space group P1 macro, a = 13.5167(12) A, b = 21.7008(18) A, c = 23.808(2) A, alpha = 80.116(2) degrees, beta = 76.832(2) degrees, gamma = 80.4070(10) degrees, Z = 4; 5 (C(80)H(83)N(8)O(2)), monoclinic, space group C2/c, a = 22.666(2) A, b = 13.6749(14) A, c = 42.084(4) A, beta = 94.554(2) degrees, Z = 8. EPR spectroscopy of dicopper(II) derivatives Cu(2)DPX (3) and Cu(2)DPD (7) complements the crystallographic studies by probing intramolecular metal-metal arrangements in frozen solution. Exciton interactions between the porphyrin subunits in fluid solution are revealed by steady-state and time-resolved electronic absorption and emission spectroscopy. The resulting compilation of structural and spectroscopic data provides a benchmark for the use of these and related platforms for the activation of small-molecule substrates. A structure-function relation is developed for the photoinduced oxygen atom-transfer reactions of bisiron(III) mu-oxo derivatives of DPX and DPD. The efficiency of the photochemical process is markedly dependent (approximately 10(4)-fold) on the vertical flexibility of cofacial architecture provided by the spacer.

Benzofurans↗

PubMed2003

Zeolite-mediated photochemical charge separation using a surface-entrapped ruthenium-polypyridyl complex.

Employing the strategy of quaternization of the 2,2' N atoms of the conjugated bipyridine ligand 1,4-bis[2-(4'-methyl-2,2'-bipyrid-4-yl)ethenyl]benzene (L), a polypyridyl complex of ruthenium(II) was tethered on the surface of zeolite Y. Electrochemical and spectroscopic properties of the complex suggest that, upon visible photoexcitation of the MLCT band, the electron is localized on the conjugated ligand rather than the bipyridines. Electron transfer from the surface complex to bipyridinium ions (methyl viologen) within the zeolite was observed. Visible light photolysis of the ruthenium-zeolite solid ion-exchanged with diquat and suspended in a propyl viologen sulfonate solution led to permanent formation of the blue propyl viologen sulfonate radical ion in solution. The model that is proposed involves intrazeolitic charge transfer to ion-exchanged diquat followed by interfacial (zeolite to solution) electron transfer to propyl viologen sulfonate in solution. Because of the slow intramolecular back-electron-transfer reaction and the forward electron propagation via the ion-exchanged diquat, Ru(III) is formed. This Ru(III) complex formed on the zeolite is proposed to react rapidly with water in the presence of light, followed by reaction with the propyl viologen sulfonate, to form pyridones and regeneration of Ru(II), which then continues the photochemical process.

Journal Article↗

PubMed2005

Tunable DNA photocleavage by an acridine-imidazole conjugate.

We report the synthesis and characterization of photonucleases N,N'-bis[2-[bis(1H-imidazol-4-ylmethyl)amino]ethyl]-3,6-acridinediamine (7) and N-[2-[bis(1H-imidazol-4-ylmethyl)amino]ethyl]-3,6-acridinediamine (10), consisting of a central 3,6-acridinediamine chromophore attached to 4 and 2 metal-coordinating imidazole rings, respectively. In DNA reactions employing 16 metal salts, photocleavage of pUC19 plasmid is markedly enhanced when compound 7 is irradiated in the presence of either Hg(II), Fe(III), Cd(II), Zn(II), V(V), or Pb(II) (low-intensity visible light, pH 7.0, 22 degrees C, 8-50 microM 7). We also show that DNA photocleavage by 7 can be modulated by modifying buffer type and pH. Evidence of metal complex formation is provided by EDTA experiments and by NMR and electrospray ionization mass spectral data. Sodium azide, sodium benzoate, superoxide dismutase, and catalase indicate the involvement of type I and II photochemical processes in the metal-assisted DNA photocleavage reactions. Thermal melting studies show that compound 7 increases the Tm of calf thymus DNA by 10 +/- 1 degrees C at pH 7.0 and that the Tm is further increased upon the addition of either Hg(II), Cd(II), Zn(II), or Pb(II). In the case of Fe(III) and V(V), a colorimetric assay demonstrates that compound 7 sensitizes one electron photoreduction of these metals to Fe(II) and V(IV), likely accelerating the production of type I reactive oxygen species. Our data collectively indicate that buffer, pH, Hg(II), Fe(III), Cd(II), Zn(II), V(V), Pb(II), and light can be used to "tune" DNA cleavage by compound 7 under physiologically relevant conditions. The 3,6-acridinediamine acridine orange has demonstrated great promise for use as a photosensitizer in photodynamic therapy. In view of the distribution of iron in living cells, compound 7 and other metal-binding acridine-based photonucleases should be expected to demonstrate excellent photodynamic action in vivo.

Aminoacridines↗

PubMed2003

Observation of quantum coherence for recurrence motion of exciton in anthracene dimers in solution.

The quantum beat signal associated with recurrence motion of exciton was observed for two types of anthracene dimers connected through a phenyl ring, on femtosecond fluorescence anisotropy decay. The time periods of oscillation were 0.3-0.9 ps, which correspond to exciton interactions of 30-50 cm-1, and the damping time constants (dephasing time) were 0.7-1.0 ps. The results show that the coherent aspect in photochemical processes is observable even in solution at room temperature, if one employs dimers of rigid structures.

Journal Article↗

PubMed2004

Core electron transitions as a probe for molecular chirality: natural circular dichroism at the carbon K-edge of methyloxirane.

We have measured for the first time the X-ray natural circular dichroism (XNCD) of a chiral molecule in an isotropic medium. In this condition the only surviving term contributing to CD is the cross product between the electric dipole and the magnetic dipole transition moments. The non-zero value of the magnetic dipole transition moment in a 1s-to-valence electron transition is attributed to contribution of valence states to core molecular orbitals. These results open the way to a "local" chiral molecular analysis and to the study of stereochemically selected photochemical processes.

Journal Article↗

PubMed2004

Mechanism of stereo- and regioselectivity in the Paternò-Büchi reaction of furan derivatives with aromatic carbonyl compounds: importance of the conformational distribution in the intermediary triplet 1,4-diradicals.

Temperature and substituent effects on the stereo- and regioselectivity have been investigated in the photochemical [2 + 2] cycloaddition reaction, the so-called Paternò-Büchi (PB) reaction, of unsymmetrically substituted furans 2a,b (2-methyl- and 3-methylfuran) with aromatic carbonyl compounds 1a,b (benzaldehyde and benzophenone). The regio-random but stereoselective (exo/endo > 97/3) formation of lower substituted oxetane 3a and higher substituted oxetane 4a is found in the reaction with benzaldehyde (1a). The exclusive stereoselectivity is not dependent on the position of methyl substituent on the furan ring and the reaction temperature. The double-bond selection (3a versus 4a) is slightly dependent on the reaction temperature (3a/4a = 55/45 to 40/60). The Eyring plots of the regioselectivity are linear. Contrastively, in the reaction with benzophenone (1b), the double-bond selection (3b versus 4b) largely depends on the reaction temperature. The Eyring plots are not linear, but the inflection points are observed. The transient absorption spectroscopic analyses (picosecond time scale) clarify the intervention of triplet 2-oxabutane-1,4-diyls in the photochemical processes. Computational studies reveal the equilibrium structures of the triplet diradicals, energy barriers between the conformers, and the equilibrium constants. A rational mechanism is herein proposed by the support of both experimental and computational investigations to account for not only the exclusive formation of the exo-configured oxetanes 3a and 4a but also the nonlinear Eyring plots observed in the reaction with 1b.

Journal Article↗

PubMed2004

Structures and reactivity of Zr(IV) chlorobenzene complexes.

The synthesis, structures, and unusual reactivity of (C5R5)2ZrR'(ClPh)+ chlorobenzene complexes are described. The reaction of (C5R5)2ZrR'2 with [Ph3C][B(C6F5)4] in C6D5Cl affords [(C5R5)2ZrR'(ClC6D5)][B(C6F5)4] chlorobenzene complexes (1-d5, R' = CH2Ph and (C5R5)2 = (C5H5)2; 2a-d-d5, R' = Me and (C5R5)2 = rac-(1,2-ethylene(bis)indenyl) (2a), (C5H5)2 (2b), (C5H4Me)2 (2c), (C5Me5)2 (2d, C5Me5 = Cp*)). Complexes 1 and 2b,c are thermally robust but are converted to [{(C5R5)2Zr(mu-Cl)}2][B(C6F5)4]2 (4b,c) by a photochemical process in ClPh solution. In contrast, 2d undergoes facile thermal ortho-C-H activation to yield [Cp*2Zr(eta2-C,Cl-2-Cl-C6H4)][B(C6F5)4] (5), which slowly rearranges to [(eta4,eta1-C5Me5C6H4)Cp*ZrCl][B(C6F5)4] (6) via beta-Cl elimination and benzyne insertion into a Zr-CCp* bond. The higher thermal reactivity of 2d versus that of 1 and 2b,c is attributed to steric crowding associated with the Cp* ligands of 2d, which forces a ClPh ortho-hydrogen close to the Zr-Me group.

Journal Article↗

PubMed2004

Counterion controlled photoisomerization of retinal chromophore models: a computational investigation.

CASPT2//CASSCF photoisomerization path computations have been used to unveil the effects of an acetate counterion on the photochemistry of two retinal protonated Schiff base (PSB) models: the 2-cis-penta-2,4-dieniminium and the all-trans-epta-2,4,6-trieniminium cations. Different positions/orientations of the counterion have been investigated and related to (i) the spectral tuning and relative stability of the S0, S1, and S2 singlet states; (ii) the selection of the photochemically relevant excited state; (iii) the control of the radiationless decay and photoisomerization rates; and, finally, (iv) the control of the photoisomerization stereospecificity. A rationale for the results is given on the basis of a simple (electrostatic) qualitative model. We show that the model readily explains the computational results providing a qualitative explanation for different aspects of the experimentally observed "environment" dependent PSB photochemistry. Electrostatic effects likely involved in controlling retinal photoisomerization stereoselectivity in the protein are also discussed under the light of these results, and clues for a stereocontrolled electrostatically driven photochemical process are presented. These computations provide a rational basis for the formulation of a mechanistic model for photoisomerization electrostatic catalysis.

Biomimetic Materials↗

PubMed2005

Theoretical study on the photolysis mechanism of 2,3-diazabicyclo[2.2.2]oct-2-ene.

A CASPT2/CASSCF study has been carried out to investigate the mechanism of the photolysis of 2,3-diazabicyclo[2.2.2]oct-2-ene (DBO) under direct and triplet-sensitized irradiation. By exploring the detailed potential energy surfaces including intermediates, transition states, conical intersections, and singlet/triplet crossing points, for the first excited singlet (S(1)) and the low-lying triplet states (T(1), T(2), and T(3)), we provide satisfactory explanations of many experimental findings associated with the photophysical and photochemical processes of DBO. A key finding of this work is the existence of a significantly twisted S(1) minimum, which can satisfactorily explain the envelope of the broad emission band of DBO. It is demonstrated that the S(1) (n-pi*) intermediate can decay to the T(1) (n-pi*) state by undergoing intersystem crossing (rather inefficient) to the T(2) (pi-pi*) state followed by internal conversion to the T(1) state. The high fluorescence yield and the extraordinarily long lifetime of the singlet excited DBO are due to the presence of relatively high barriers, both for intersystem crossing and for C-N cleavage. The short lifetime of the triplet DBO is caused by fast radiationless decay to the ground state.

Bridged Bicyclo Compounds, Heterocyclic↗