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At least 19 recordsLinked to original sources
PubMed1976

The study of the primary photoprocesses in photosystem I of chloroplasts. Recombination luminescence, chlorophyll triplet state and triplet-triplet annihilation.

The dependence of the delayed luminescence of Photosystem I on the state of the reaction centers has been studied. Light flash induces a charge separation in the centers: P-700-P-430 hv in equilibrium P-700+-P-430-. Dark recombination of charges is accompanied by the recombination luminescence with tau1/2 congruent to 20ms. If the centers are in the P-700-P-430- state or if P-430 is inactivated by heat, then flashing of Photosystem I generates the triplet state chlorophyll with tau1/2 congruent to 0.5 ms. The triplet state has been measured by the delayed fluorescence of chlorophyll at 20 degrees C and 77 degrees K and by the chlorophyll phosphorescence at 77 degrees K. The delayed fluorescence at 20 degrees C arises from the thermal activation of the triplet state up to the excited singlet level of chlorophyll and at 77 degrees K it is due to triplet-triplet annihilation. The quantum yield of the triplet formation, estimated by a comparison of the light saturation curves of delayed fluorescence at 20 degrees C and of P-700 photooxidation under the same experimental (optical) conditions, is approximately 0.9 of the P-700+ yield. Only one triplet of chlorophyll can be generated per P-700. Under heat inactivation of P-430 the triplet formation is not observed when P-700 is oxidized. It is assumed that the triplet-triplet annihilation at 77 degrees K is related with the strong interaction between the chlorophyll molecules in the pigment complex of Photosystem I. The possibility of a triplet participation in the primary processes of photosynthesis is discussed.

Chlorophyll↗
PubMed2003

Calculation of triplet-triplet energy transfer rates from emission and absorption spectra. The quenching of hemicarcerated triplet biacetyl by aromatic hydrocarbons.

The kinetics of triplet-triplet (T-T) energy transfer have been analysed with a view to linking theories of chemical reactions (involving the rupture and formation of bonds) with theories of processes, such as electron transfer or energy transfer, which preserve chemical bonding. As for the latter, our analysis does not support the claim that, of the two rival expressions for T-T energy transfer, both rooted in the golden rule, only one is applicable to electron transfer or T-T transfer. Though the two expressions do reflect different standpoints, the distinction is eroded by the assumption of a delta-function distribution for the vibrational spectrum. It is shown that theories of chemical reactions also furnish estimates of Franck-Condon factors; rates of chemical reactions and chemical processes are both related to the properties (strengths and lengths) of the reactive bonds, but differ in the mode of energy dissipation. The relationship between the rates of reactions and processes presents new possibilities for a unified view of chemical reactivity.

Journal Article↗
PubMed1999

Multifetal pregnancy reductions of triplets to twins: comparison with nonreduced triplets and twins.

OBJECTIVE: Multifetal pregnancy reduction has been shown to improve survival rates in high-order multifetal pregnancies (>/=4). There is, however, some controversy as to whether multifetal pregnancy reduction improves pregnancy outcomes of triplets reduced to twins. The purpose of this study was to evaluate this issue by comparing outcomes of triplet gestations undergoing reduction to twins with outcomes of nonreduced twin gestations and expectantly managed triplet gestations. STUDY DESIGN: The study included 143 triplet pregnancies that underwent reduction to twins over a 10-year period at a single center. These were compared with 12 nonreduced triplet pregnancies from the Wayne State University Perinatal Database and with 2 groups of twin pregnancies: 605 from the Wayne State University Perinatal Database and 207 from the Quest Diagnostics Database. RESULTS: The miscarriage rate for expectantly managed triplets was 25%, compared with 6.2% for triplets reduced to twins. This rate was similar to the rates for both groups of nonreduced twins: 5.8% (Quest) and 6.3% (Wayne State University). Severe prematurity occurred in 25% of nonreduced triplets compared with 4. 9% of twins after reduction. This rate was also similar to that of nonreduced twins: 7.7% (Quest) and 8.4% (Wayne State University). The mean gestational age at delivery for expectantly managed triplets (32.9 +/- 4.7 weeks) was significantly shorter than for triplets reduced to twins (35.6 +/- 3.1 weeks). By comparison, nonreduced twins had a mean gestational age at delivery of 35.8 +/- 3.9 weeks for Quest and 34.4 +/- 3.6 weeks for Wayne State University. Mean birth weights were significantly lower in expectantly managed triplets as compared with triplets undergoing reduction to twins (1636 +/- 645 g vs 2381 +/- 602 g, respectively). Nonreduced twins had a mean birth weight of 2254 +/- 653 g for Quest and 2123 +/- 634 g for Wayne State University. Pregnancy loss rates, mean length of gestation, and mean birth weight did not vary significantly between triplets who underwent reduction to twins and nonreduced twins. CONCLUSIONS: Reduction of triplets to twins significantly reduces the risk for prematurity and low birth weight and may also be associated with a reduction in overall pregnancy loss. This suggests that multifetal pregnancy reduction of triplets to twins is a medically justifiable procedure not only from an actuarial viewpoint but also from the ethical perspective of supporting patients' autonomy and respect for patients' individual circumstances.

Abortion, Spontaneous↗
PubMed1995

[Antenatal complications in triplet pregnancies and birth weights of triplets compared with those of twins].

A mailed questionnaire survey was conducted on 96 mothers of triplets to study antenatal complications in triplet pregnancies and birth weights of triplets, and compared to 122 controls recruited from mothers of twins. The following results were obtained. 1) Antenatal complications occurred in approximately 80% of both triplet and twin pregnancies. In the triplet pregnancies the incidence of toxemia of pregnancy and anemia was 25.0% and 47.9%, respectively. There was no significant difference in the incidence of antenatal complications, toxemia of pregnancy and anemia between triplet and twin pregnancies. On the other hand, the incidence of preterm labor and threatened miscarriage was higher in triplets (70.8% and 34.4% respectively) than in twin pregnancies (45.9% and 12.3% respectively). 2) The mean birth weight was 1831.7 g for each individual triplet and 5495.0 g for each triplet set. In triplets, 94.7% were low in birth weight (< 2500 g). 3) The antenatal complications of preterm labor and threatened miscarriage in triplet pregnancies have increased since 1990 in Japan. The frequency of toxemia of pregnancy and anemia did not particularly change significantly during the surveyed years. However, mean birth weight for each individual triplet showed a tendency to decrease from year to year (1978-1989, 1934.5 g; 1990-1991, 1900.3 g; 1992-1993, 1741.1 g).

Adult↗
PubMed2002

Conformational energetics of stable and metastable states formed by DNA triplet repeat oligonucleotides: implications for triplet expansion diseases.

We have embedded the hexameric triplet repeats (CAG)(6) and (CTG)(6) between two (GC)(3) domains to produce two 30-mer hairpins with the sequences d[(GC)(3)(CAG)(6)(GC)(3)] and d[(GC)(3)(CTG)(6)(GC)(3)]. This construct reduces the conformational space available to these repetitive DNA sequences. We find that the (CAG)(6) and (CTG)(6) repeats form stable, ordered, single-stranded structures. These structures are stabilized at 62 degrees C by an average enthalpy per base of 1.38 kcal.mol(-1) for the CAG triplet and 2.87 kcal.mol(-1) for the CTG triplet, while being entropically destabilized by 3.50 cal.K(-1).mol(-1) for the CAG triplet and 7.6 cal.K(-1).mol(-1) for the CTG triplet. Remarkably, these values correspond, respectively, to 1/3 (for CAG) and 2/3 (for CTG) of the enthalpy and entropy per base values associated with Watson-Crick base pairs. We show that the presence of the loop structure kinetically inhibits duplex formation from the two complementary 30-mer hairpins, even though the duplex is the thermodynamically more stable state. Duplex formation, however, does occur at elevated temperatures. We propose that this thermally induced formation of a more stable duplex results from thermal disruption of the single-stranded order, thereby allowing the complementary domains to associate (perhaps via "kissing hairpins"). Our melting profiles show that, once duplex formation has occurred, the hairpin intermediate state cannot be reformed, consistent with our interpretation of kinetically trapped hairpin structures. The duplex formed by the two complementary oligonucleotides does not have any unusual optical or thermodynamic properties. By contrast, the very stable structures formed by the individual single-stranded triplet repeat sequences are thermally and thermodynamically unusual. We discuss this stable, triplet repeat, single-stranded structure and its interconversion with duplex in terms of triplet expansion diseases.

Base Sequence↗
PubMed1998

Photophysics of the cationic 5,10,15,20-tetrakis (4-N-methylpyridyl) porphyrin bound to DNA, [poly (dA-dT)]2 and [poly (dG-dC)]2: interaction with molecular oxygen studied by porphyrin triplet-triplet absorption and singlet oxygen luminescence.

Interaction between molecular oxygen and the cationic free-base 5,10,15,20-tetrakis (4-N-methylpyridyl) porphyrin (H2TMpyP4+) complexed with [poly (dA-dT)]2, [poly (dG-dC)]2 and calf thymus DNA, has been monitored in air-saturated heavy water solutions through porphyrin triplet-triplet absorption and singlet oxygen luminescence. Three different rate constants of porphyrin triplet state quenching have been found which correspond to different accessibilities of molecular oxygen to porphyrins embedded in the duplexes. The longest triplet state lifetime (30 microseconds), found for porphyrin bound to [poly (dG-dC)]2, corresponds to molecules well protected from oxygen. This supports the hypothesis of an intercalative binding mode of the porphyrin between GC base-pairs ('type A' sites). The fraction fT delta of the porphyrin triplet states quenched by molecular oxygen with singlet oxygen generation, is unity. In [poly (dA-dT)]2-porphyrin complexes, two sites ('type B' and 'C' sites of interaction) are involved, yielding very different triplet state lifetimes (5.5 microseconds and 20.5 microseconds) and efficiencies of singlet oxygen generation (fT delta = 0.50 and 0.82). The fT delta decreases can likely be explained in terms of competition between energy and electron transfer from the porphyrin excited triplet state to molecular oxygen. All three types (A, B and C) of interaction sites can be expected in porphyrin-DNA complexes.

Absorption↗
PubMed2003

p-Benzyne derivatives that have exceptionally small singlet-triplet gaps and even a triplet ground state.

In an effort to find a p-benzyne (1,4-didehydrobenzene) derivative with a triplet ground state, we have investigated tetrasubstitution by -F, -NH(2), -CH(3), and -NO(2) groups. These were predicted to reduce the singlet-triplet gap, but none led to a triplet ground state because of unexpected destabilization of one of the radical orbitals. This effect is likely the result of rehybridization of the substituted C atom, which has been observed for substituted benzene and perturbs the side sigma and sigma* orbital energies of the phenyl ring. The role of substituent rotation on the energy difference between the two nominally singly occupied orbitals (S and A) was then investigated. The energy of the A radical orbital was found to be much more sensitive to perturbations within the sigma C[bond]C framework than the S MO. Consequently, we believe that rehybridization of the ring carbons destabilizes the A radical orbital and can lead to large singlet-triplet splittings. To test this hypothesis, calculations on a p-benzyne with 2,6 substitution by oxygen were performed. Interestingly, a triplet ground state was predicted. Yet, examination of the geometry and wave function showed that 2,6-quinone p-benzyne is a very twisted molecule with a C3-C4-C5 allene linkage and a C1 triplet carbene center.

Journal Article↗
PubMed2002

Thermodynamic contributions for the incorporation of GTA triplets within canonical TAT/TAT and C+GC/C+GC base-triplet stacks of DNA triplexes.

Nucleic acid triple helices may be used in the control of gene expression. One limitation of using triplex-forming oligonucleotides as therapeutic agents is that their target sequences are limited to homopurine tracts. To increase the repertoire of sequences that can be targeted, it has been postulated that a guanine can target a thymidine forming a stable GTA mismatch triplet. In this work, we have used a combination of optical and calorimetric techniques to determine thermodynamic unfolding profiles of two triplexes containing a single GTA triplet, d(A(3)TA(3)C(5)T(3)AT(3)C(5)T(3)GT(3)) (ATA) and d(AGTGAC(5)TCACTC(5)TCGCT) (GTG), and their control triplexes, d(A(7)C(5)T(7)C(5)T(7)) (TAT7) and d(AGAGAC(5)TCTCTC(5)TCTCT) (AG5T). In general, the presence of a GTA mismatch in DNA triplexes is destabilizing; however, this destabilization is greater when placed in a C(+)GC/C(+)GC base-triplet stack than between a TAT/TAT stack. These destabilizations are accompanied by a reduced unfolding enthalpy of approximately 10 kcal/mol, suggesting a decrease in the base stacking contributions surrounding the mismatch. Relative to their corresponding control triplexes, the folding of ATA is accompanied by a lower counterion uptake and a similar proton uptake, while GTG folding is accompanied by an increase in the counterion and proton uptakes. These effects are consistent with the observed decrease in stacking interactions. The overall results indicate that the main difficulty of targeting pyrimidine interruptions is that the decrease in stacking contributions, due to the incorporation of a GTA mismatch, affects the stability of the neighboring base triplets. This suggests that nucleotide analogues that increase the strength of these base-triplet stacks will result in a more effective targeting of pyrimidine interruptions.

Adenosine↗
PubMed1988

Frequency of triplets and triplet zygosity types among U.S. births, 1964.

The frequency of triplets in the U.S. white population may have reached an all-time low around 1964, at 78 sets per million deliveries. One-fourth of those were monozygotic as estimated by the difference method, or 18% by Bulmer's theoretical model. By 1983 the frequency of triplets had nearly doubled, the increase presumably occurring in dizygotic and trizygotic types. In Belgium most triplet pregnancies now result from artificial induction of ovulation, which is expected to occur mainly in older mothers. In the U.S., however, triplets have increased as much in young mothers as in older mothers, proportionally. This age distribution of the increase may be partly explained by a decrease in parity in older mothers since 1964.

Birth Rate↗
PubMed1988

The Northwestern University Triplet Study. II: Fourteen triplet pregnancies delivered between 1981 and 1986.

Fourteen triplet deliveries conducted between 1 January 1981 and 30 June 1986 at the principal teaching hospitals of Northwestern University Medical School are reviewed. Maternal demographic characteristics are listed, as are the obstetric outcomes, including mode of delivery, and the fetal outcome. The recent literature of triplet delivery is reviewed. The rate of triplet delivery in our study was 0.37 per 1,000 live births. About two-thirds of the pregnancies resulted from the use of fertility-inducing agents. Ultrasonic confirmation was available in all cases. The majority of women were delivered by cesarean section (85%). No consistent pattern of presentation was seen. The mean weight of all 42 infants was 1,779 g (+/- 594). Unlike-sex triplets accounted for most of the sets (77%). The mean 5-min Apgar score of all infants was 9 and had no association with the order of deliveries. The weight differences by sex regardless of birth order were clinically insignificant. Neonatal mortality was 2.3%.

Adult↗
PubMed1981

Mortality rate of Japanese twins and triplets. III. Infant deaths of triplets after birth to one year of age.

The rate of infant mortality of triplet individuals (deaths under one year of age) was computed using 34 sets of triplets born in the first half of 1974. The rates were 8.82%, 9.68%, and 10.34% for the first-, second-, and the third-born triplets, respectively. For males and females the rates were 8.33% and 10.34%, respectively, and the difference was not significant. The rate decreased with gestational age up to 32-35 weeks. For those with heavier weight at birth (less than or equal to 2,000 g) the rate was lower (0%) than for those with lighter weight (less than 2,000 g, 8.16%), but the difference is not significant (P = 0.087). Infant mortality rate of triplets decreased with increased monthly expenditure of the household.

Birth Order↗
PubMed2001

Enhanced Access to the Dark Triplet States of (7)Li(2) through New Singlet-Triplet A(1)Sigma(+)(u) approximately b(3)Pi(u) Perturbation Window Levels: Perturbation-Facilitated Optical-Optical Double Resonance Study of the 2(3)Sigma(+)(g) State.

Two new pairs of singlet-triplet A(1)Sigma(+)(u) approximately b(3)Pi(u) mixed levels of (7)Li(2) have been observed and used here as "window" levels in cw perturbation-facilitated optical-optical double-resonance (PFOODR) experiments. Previously, only one b(3)Pi(u) vibrational level, v = 19, was known to mix with the singlet A(1)Sigma(+)(u) v = 13 level, resulting in three perturbed A approximately b pairs [L. Li, T. An, T.-J. Whang, A. M. Lyyra, W. C. Stwalley, R. W. Field, and R. A. Bernheim, J. Chem. Phys. 96, 3342 (1992)]. The scarcity of window levels and the resulting difficulty in accessing the dark triplet states of Li(2) is caused by the weak spin-orbit interaction of Li(2). The two new mixed b(3)Pi(u) v = 15 and 22 levels reported here enhance access to the dark triplet state manifold through expansion of the Franck-Condon overlap factor range. Furthermore, the earlier range of accessible rotational levels, N = 5, 7, and 10, is now expanded to include N = 8 and N = 16, thereby allowing for more reliable determination of the excited triplet states rotational structure. To demonstrate the importance of the new A(1)Sigma(+)(u) approximately b(3)Pi(u) mixed levels, we have studied the 2(3)Sigma(+)(g) state by cw PFOODR fluorescence excitation spectroscopy. New molecular constants and RKR potential curve have been determined. As previously reported [L. Li, G. Lazarov, and A. M. Lyyra, J. Mol. Spectrosc. 191, 387 (1998)], the 2(3)Sigma(+)(g) state interacts with the repulsive 1(3)Pi(g) state by L-uncoupling and predissociates. We show that some 2(3)Pi(g) levels predissociate accidentally by the 1(3)Pi(g) state via the 2(3)Sigma(+)(g) state through L-uncoupling. Copyright 2001 Academic Press.

Journal Article↗
PubMed1998

The rat androgen-binding protein (ABP/SHBG) gene contains triplet repeats similar to unstable triplets: evidence that the ABP/SHBG and the fragile X-related 2 genes overlap.

The rat androgen-binding protein/sex hormone-binding globulin (ABP/SHBG) gene is regulated by promoters P1 and PA. P1 regulates the mRNA encoding secreted ABP/SHBG, whereas PA regulates an alternate mRNA which encodes a modified protein that is targeted to the nucleus. Promoter PA is GC rich, consisting of 70-80% GC residues. During routine BLAST sequence analysis it was discovered that this GC-rich region is highly related to the human fragile X-related protein 2 (FXR-2) 5'-untranslated RNA sequence. Furthermore, the nucleotide coding sequence of the initial 14 FXR-2 amino acid residues was identical in the ABP/SHBG gene. The 5'-untranslated FXR-2 sequence contains triplet (CGG) repeats, which are also present in the rat ABP/SHBG gene. The meiotic instability of CGG repeats in the human fragile X (FMR1) gene causes the fragile X mental retardation syndrome. The data presented here suggest that the ABP/SHBG and FXR-2 genes overlap with each gene transcribed in the opposite direction. In support of this structure, the human ABP/SHBG and the FXR-2 genes map to the same site on chromosome 17. Thus, the ABP/SHBG gene contains triplet repeats in the alternate promoter PA. It will be of particular interest to determine if triplet instability affects ABP/SHBG gene expression. A triplet instability in the X-linked androgen receptor gene causes spinal and bulbar muscular atrophy.

Androgen-Binding Protein↗
PubMed1993

FT-IR studies on the triplet state of P680 in the photosystem II reaction center: triplet equilibrium within a chlorophyll dimer.

The structure and molecular interactions of the primary donor (P680) in the reaction center (D1-D2-cytochrome b-559 complex) of photosystem II (PS II) have been investigated by detecting light-induced FT-IR difference spectra upon the formation of its triplet state (3P680). The 3P680/P680 spectrum obtained was analyzed by comparing it with difference spectra between the ground and lowest triplet states of purified chlorophyll a (Chl) in organic solvents. The negative peaks at 1669 and 1707 cm-1 accompanied by the positive peaks at 1627 and 1659 cm-1 in the 3P680/P680 spectrum were assigned to the keto C = O stretching mode, and the appearance of these two pairs of bands indicated that P680 has a dimeric structure analogous to that of the bacterial primary donor. From the band positions of the keto and carbomethoxy C = O stretches, the hydrogen-bonding properties of these two Chl molecules were found to be asymmetrical; in one Chl molecule both the keto and carbomethoxy C = O groups form hydrogen bonds, while in the other Chl molecule the keto C = O is not hydrogen-bonded whereas the carbomethoxy C = O probably is hydrogen-bonded. The temperature dependence of the intensity ratios of the keto C = O bands revealed that the triplet state is equilibrated between the two Chl molecules with an energy gap of 8.4 +/- 0.7 meV. Most of the triplet population was found to be localized on one Chl molecule (86% at 80 K), in which both of the two C = O groups are hydrogen-bonded, that is probably attached to the D1 subunit. Considering the structure of the bacterial reaction center determined by X-ray crystallography and the sequence homology between the D1 and D2 subunits of PS II and the L and M subunits of bacteria, a model of the P680 structure and its interactions with apoproteins has been proposed.

Chlorophyll↗
PubMed1998

NGG-triplet repeats form similar intrastrand structures: implications for the triplet expansion diseases.

Tandem repeats of certain trinucleotides show extensive intergenerational instability in humans that is associated with a class of genetic disorders known as the Triplet Expansion Diseases. This instability is thought to be a consequence of the formation of intrastrand structures, including hairpins, triplexes and tetraplexes, by the tandem repeats. I show here that CGG-repeats which are associated with this group of diseases, and AGG- and TGG-repeats which are not currently known to be, form several intrastrand structures including tetraplexes. In all cases the tetraplexes have the same overall conformation in which all the G residues are involved in G4-tetrads. CGG-repeats also form stable hairpins, but AGG- and TGG-repeats do not form hairpins of comparable stability. However, since tetraplexes can be thought of as folded hairpins, many of the properties ascribed to disease-associated triplets that form hairpins, may apply to these sequences as well. The fact that AGG- and TGG-repeats are not currently associated with any triplet expansion disease suggests either that the ability to adopt an intrastrand folded structure is not sufficient for expansion, or that other diseases associated with such triplets might remain to be identified.

Base Sequence↗
PubMed1988

Triplet state properties and triplet-state-oxygen interactions of some linear and angular furocoumarins.

Linear and angular furocoumarins with conjugated external carbonyl substituents show higher triplet and singlet oxygen yields than the corresponding unsubstituted molecules. The efficiency of the oxygen quenching process to yield singlet oxygen is also higher for these substituted molecules. These changes are interpreted in terms of the "proximity effect" associated with two nearly degenerate n pi* and pi pi* excited states, and variations in the excess energy following furocoumarin triplet quenching by ground state triplet oxygen to yield singlet oxygen.

Benzene↗
PubMed1993

Transient electron paramagnetic resonance of the triplet state of P700 in photosystem I: evidence for triplet delocalization at room temperature.

Spin-polarized EPR spectra of the triplet state of P700, the primary electron donor in photosystem I (PS I), have been measured for the first time at room temperature. The measurements were performed on intact PS I from Synechococcus sp. after prereduction of all iron-sulfur centers and on vitamin K1 depleted PS I from Synechocystis 6803. The two preparations give similar spectra with a polarization pattern which indicates that the triplet state is formed via recombination of a radical pair. The axial and nonaxial zero-field splitting (zfs) parameters are found to be magnitude of D = (284 +/- 15) x 10(-4) cm-1 and magnitude of E = (22 +/- 3) x 10(-4) cm-1, respectively. The E-value is 42% smaller than in monomeric chlorophyll a, while the D-value is nearly the same. Measurements of the Synechocystis 6803 sample at 4.5 K yielded zfs parameters which are identical with those of the chlorophyll monomer, in agreement with previous results. In order to explain this behavior, it is proposed that the triplet excitation is delocalized over the two halves of a chlorophyll dimer at room temperature but appears localized on one half at low temperature. The observed zfs parameters are obtained if (1) the magnetic z-axes of the two chlorophylls are collinear, (2) the magnetic y-axes (and x-axes) of the two chlorophylls make an angle of approximately 55 degrees with each other, and (3) the admixture of charge-transfer states to 3P700 is negligible.(ABSTRACT TRUNCATED AT 250 WORDS)

Chlorophyll↗
PubMed2001

Analysis of fluoroquinolone-mediated photosensitization of 2'-deoxyguanosine, calf thymus and cellular DNA: determination of type-I, type-II and triplet-triplet energy transfer mechanism contribution.

Fluoroquinolone (FQ) antibacterials are known to exhibit photosensitization properties leading to the formation of oxidative damage to DNA. In addition, photoexcited lomefloxacin (Lome) was recently shown to induce the formation of cyclobutane pyrimidine dimers via triplet-triplet energy transfer. The present study is aimed at gaining further insights into the photosensitization mechanisms of several FQ including enoxacin (Enox), Lome, norfloxacin (Norflo) and ofloxacin (Oflo). This was achieved by monitoring the formation of DNA base degradation products upon UVA-mediated photosensitization of 2'-deoxyguanosine, isolated and cellular DNA. Oflo and Norflo act mainly via a Type-II mechanism whereas Lome and, to a lesser extent, Enox behave more like Type-I photosensitizers. However, the extent of oxidative damage was found to be relatively low. In contrast, it was found that cyclobutane thymine dimers represent the major class of damage induced by Enox, Lome and Norflo within isolated and cellular DNA upon UVA irradiation. This striking observation confirms that FQ are able to promote efficient triplet energy transfer to DNA. The levels of photosensitized formation of strand breaks, alkali-labile sites and oxidative damage to cellular DNA, as measured by the comet assay, were confirmed to be rather low. Therefore, we propose that the phototoxic effects of FQ are mostly accounted for energy transfer mechanism rather than by Type-I or -II photosensitization processes.

Animals↗