Laser photolysis of carboxymethylated chitin derivatives in aqueous solution. Part 2. Reaction of OH* and SO4*- radicals with carboxymethylated chitin derivatives

The reactions of OH* or SO4*- radicals with carboxymethyl chitin (CM-chitin) and its deacetylated product, carboxymethyl chitosan (CM-chitosan), were investigated in aqueous solutions using a laser photolysis technique. The rate constants of the reactions of OH* and SO4*- radicals with CM-chitosan are always higher than those for CM-chitin, indicating that the amino-group could increase the reactivity of carboxymethylated chitin derivatives. The rate of the reactions of CM-chitin and CM-chitosan with OH* radical was found to decrease at lower pH when polymers chains tend to the coiled conformation. In comparison, the rate constant of the reaction of SO4*- radicals with CM-chitin or CM-chitosan decreased with pH, indicating that CM-chitin or CM-chitosan has a higher reactivity with the SO4*- radical at low pH due to the protonation of the amino group.     

Antioxidant properties of melatonin: a pulse radiolysis study

Various one-electron oxidants such as OH*, tert-BuO*, CCl3OO*, Br2*- and N3*, generated pulse radiolytically in aqueous solutions at pH 7, were scavenged by melatonin to form two main absorption bands with lambda(max) = 335 nm and 500 nm. The assignment of the spectra and determination of extinction coefficients of the transients have been reported. Rate constants for the formation of these species ranged from 0.6-12.5x10(9) dm3 mol(-1) s(-1). These transients decayed by second order, as observed in the case of Br2*- and N3* radical reactions. Both the NO2* and NO* radicals react with the substrate with k = 0.37x10(7) and 3x10(7) dm3 mol(-1) s(-1), respectively. At pH approximately 2.5, the protonated form of the transient is formed due to the reaction of Br2*- radical with melatonin, pKa ( MelH* <=> Mel* + H+) = 4.7+/-0.1. Reduction potential of the couple (Mel*/MelH), determined both by cyclic voltammetric and pulse-radiolytic techniques, gave a value E(1)7 = 0.95+/-0.02 V vs. NHE. Repair of guanosine radical and regeneration of melatonin radicals by ascorbate and urate ions at pH 7 have been reported. Reactions of the reducing radicals e(aq)- and H* atoms with melatonin have been shown to occur at near diffusion rates.     

Formation of radical cations of aziridines generated by laser flash photolysis.

The radical cations of 1-butyl-trans-2,3-diphenyl aziridine (1), 1-butyl-2-phenyl aziridine (2), 1,2-diphenyl aziridine (3) and 1-(p-methoxyphenyl)-2-phenyl aziridine (4) were generated upon laser flash photolysis in aqueous and aqueous acetonitrile solutions by direct photoionisation as indicated by the broad absorption band of the solvated electron above 550 nm as well.     

Pulse radiolysis studies of beta-carotene in oxygenated DMSO solution. Formation of beta-carotene radical cation

The spectroscopic and kinetic characteristics of beta-carotene radical cation (beta-carotene(.+)) were studied by pulse radiolysis in aerated DMSO solution. The buildup of beta-carotene(.+) with k(1) = (4.8 +/- 0.2) x 10(8) dm(3) mol(-1) s(-1) [lambda(max) = 942 nm, epsilon = (1.6 +/- 0.1) x 10(4) dm(3) mol(-1) cm(-1)] results from an electron transfer from beta-carotene to DMSO(.+). The beta-carotene(.+) species decays exclusively by first-order reaction, k = (2.1 +/- 0.1) x 10(3) s(-1), probably by two processes: (1) at low substrate concentration by hydrolysis and (2) at high concentrations also by formation of dimer radical cation (beta-carotene)(2)(.+). Under the experimental conditions, a small additional beta-carotene triplet-state absorption ((3)beta-carotene) in the range of 525 to 660 nm was observed. This triplet absorption is quenched by oxygen (k = 7 x 10(4) s(-1)), resulting in singlet oxygen ((1)O(2)), whose reactions can also lead to additional formation of beta-carotene(.+).     

E.s.r. and spin-trapping studies of the reactions of hydrated electrons with dipeptides.

The reactions of hydrated electrons (eaq-) with 55 dipeptides and 25 acetyl and formyl amino acids have been studied by e.s.r. and spin-trapping techniques. Gamma-radiolysis of deaerated aqueous solutions was used to generate eaq-, and sodium formate or t-BuOH was added to scavenge the OH radicals. t-Nitrosobutane was employed as the spin-trapping reagent. The radical,--CO---NH--, which is the initial product of the reactions of eaq- with dipeptides, was observed only for val-gly, val-ala, val-leu and ile-ala. For most of the dipeptides this radical converts to the primary deamination radical, CHR'-CONH-CHR-COO-, where R and R' are the side-chains of the common amino acids. In many cases a radical of the type CHR-COO-, formed by secondary deamination, was also observed. Only secondary deamination reactions were observed for dipeptides containing beta-alanine as the amino terminal residue and for acetyl and formyl amino acids. The secondary deamination reactions of eaq- with dipeptides, acetyl and formyl amino acids in aqueous solutions have not been observed previously. This type of reaction is of interest since it brings about main-chain scission in polypeptides and proteins.     

Reaction of peroxynitrite with carbon dioxide: intermediates and determination of the yield of CO3 •– and NO2 •

CO2 catalyses the isomerization of the biological toxin ONOO- to NO3- via an intermediate, presumably ONOOCO2-, which has an absorption maximum near 650 nm. The reflection spectrum of solid NMe4+ ONOO- exposed to CO2 shows a similar band near 650 nm; this absorption decays over minutes. Stopped-flow experiments in which CO2 solutions were mixed with alkaline ONOO- solutions indicate the formation of at least one intermediate. The initial absorption at 302 nm is less than that of ONOO-, which indicates that reactions take place within the mixing time, and this absorption is dependent (but not linearly) on the ONOO- and CO2 concentrations. We found that reaction of peroxynitrite with carbon dioxide forms some trioxocarbonate(*1-) (CO3*-) and nitrogen dioxide (NO2*) radicals via homolysis of the O-O bond in ONOOCO2-. We determined the extent of radical formation by mixing peroxynitrite, carbon dioxide and nitrogen monoxide. The later reacts with CO3*- and NO2* radicals to form, effectively, three NO2- per homolysis; ONOOCO2- that does not undergo homolysis yields NO3- and CO2. Based on the NO3- and NO2- analyses, the extent of conversion to NO3- is 96 +/- 1% and that of homolysis is 3 +/- 1%, respectively, significantly less than that reported in the literature.     

E.s.r. of spin-trapped radicals in aqueous solutions of amino acids. Reactions of the hydrated electron.

The reactions of hydrated electrons (eaq-) with amino acids were investigated by the spin-trapping method and by electron spin resonance. Tertiary nitrosobutane was used as a spin-trap to stabilize the short-lived radicals. Hydrated electrons were produced by gamma-radiolysis of de-aerated aqueous solutions of amino acids in the presence of sodium formate or tertiary butanol to scavenge OH. Radicals produced by reductive deamination of 19 amino acids were identified. Radicals formed by scission of the CH3-S- and -S-CH2- bonds of methionine as well as by deamination were observed. In the case of phenylalanine the radical formed by electron addition followed by proton transfer was identified. The reaction of proline and of hydroxyproline with eaq- resulted in the opening of the cyclic structure.     

Photochemistry of 6-chloro and 6-bromopicolinic acids in water. Heterolytic vs. homolytic photodehalogenation.

The photochemistry of 6-chloro and 6-bromopicolinate ions ( and , respectively) was investigated by product studies and ns laser flash photolysis (LFP). In deoxygenated pH 5.4 water, yields 6-hydroxypicolinic acid (70%) and a substituted pyrrole. In 2-propanol-water (1 : 1) mixture, the reaction yields, very unselectively, 6-hydroxypicolinic acid, 2-carboxypyridine, pyridine and bipyridines. Photolysis of aqueous leads to 6-hydroxypicolinic acid (78%) and hydroxybipyridines. Oxygen suppresses the photolysis of but does not affect that of . By LFP, we detected a short-lived transient at the pulse end from (lambda(max)= 305 nm, k=(2.8 +/- 0.2)x 10(5) s(-1), epsilonphi= 2200 +/- 200 dm3 mol(-1) cm(-1)). This is quenched either by oxygen or methyl acrylate and thus assigned to the triplet excited state. The triplet excited state of is detected at pH 1 only (lambda(max)= 320 nm, k > 3 x 10(7) s(-1)). The radical ion Cl2- could be successfully detected by photolysing in 2-propanol-water (1 : 1) in the presence of Cl-. Similarly, Br2- could be detected by irradiating aqueous in the presence of Br-. These results show that the photodehalogenation of is heterolytic in water and mainly homolytic in 2-propanol-water mixtures while that of is both heterolytic and homolytic in water. A mechanism in which the triplet excited state undergoes homolysis of the C-X bond and subsequent electron transfer from the carboxypyridyl radical to the halogen atom to form an ion pair may account for these observations.     

Glycoconjugated hypocrellin: photosensitized generation of free radicals (O2*-, *OH, and GHB*-) and singlet oxygen (1O2).

To improve water solubility and specific affinity for malignant tumors, glycoconjugated hypocrellin B (GHB) has been synthesized. Illumination of deoxygenated DMSO solution containing GHB generates a strong electron paramagnetic resonance (EPR) signal. The EPR signal is assigned to the semiquinone anion radical of GHB (GHB*-) based on a series of experimental results. Spectrophotometric measurements show that the absorption bands at 645 nm and 502 nm (pH 8.0) or 505 nm (pH 11.0) arise from the semiquinone anion radical (GHB*-) and hydroquinone (GHBH2) of GHB, respectively. GHBH2 is readily formed via the decay of GHB*- in water-contained solution. The increase of pH value of the reaction media promotes this process. When oxygen is present, superoxide anion radical (O2*-) is formed, via the electron transfer from GHB*-, the precursor, to ground state molecular oxygen. Hydroxyl radical can be readily detected by DMPO spin trapping when aerobic aqueous solution containing GHB is irradiated. As compared with the parent compound, hypocrellin B (HB), the efficiency of O2* and *OH generation by GHB photosensitization is enhanced significantly. Singlet oxygen (1O2) can be produced via the energy transfer from triplet GHB to ground state oxygen molecules, with a decreased quantum yield, i.e., 0.19. These findings suggest that the new GHB possesses an enhanced type I process and a decreased type II process as compared with hypocrellin B.     

Laser flash photolysis study of the triplet reactivity of beta-lapachones

The photochemical reactivity of beta-lapachone (1), nor-beta-lapachone (2) and beta-lapachone 3-sulfonic acid (3) has been examined by laser flash photolysis. Excitation (lambda = 266 nm) of degassed solutions of , in acetonitrile or dichloromethane, resulted in the formation of detectable transients with absorption maxima at 300, 380 and 650 nm. These transients, with lifetimes of 5.0 micros, were quenched by beta-carotene at a diffusion-controlled rate constant and assigned to the triplet excited states of 1-3. Addition of hydrogen donors, such as 2-propanol, 1,4-cyclohexadiene, 4-methoxyphenol or indole led to the formation of new transients, which were assigned to the corresponding ketyl radicals obtained from the hydrogen abstraction reaction by the triplets 1-3 . In the presence of triethylamine it was observed the formation of the long-lived anion radical derived from , which shows absorption maxima at 300 and 380 nm. The low values observed for the hydrogen abstraction rate constants for the beta-lapachones 1-3 using 2-propanol and 1,4-cyclohexadiene as quenchers led us to conclude that their triplet excited states show pi pi* character.     

Single crystals of alpha-chitin.

Single crystals of alpha-chitin were grown by the addition of precipitants to dilute solutions of low molecular weight chitin fractions dissolved in aqueous LiSCN. At temperatures around 200 degrees C, bundles of thin needle-shaped crystals were obtained. Each of these needles was an alpha-chitin single crystal, characterized by a spot electron diffraction pattern which could be indexed along the hk0 reciprocal net corresponding to the Minke and Blackwell unit cell [a = 0.474 nm, b = 1.88 nm, c (fibre axis) = 1.032 nm, space group P2(1)2(1)2(1)]. In a crystal, the a* parameter was along the crystal axis and the b* perpendicular to it.     

Molecular characterization of the human platelet integrin GPIIb/IIIa and its constituent glycoproteins

Human platelet plasma membrane glycoproteins IIb (GPIIb) and IIIa (GPIIIa) form a Ca(2+)-dependent heterodimer, the integrin GPIIb/IIIa, which serves as the receptor for fibrinogen and other adhesive proteins at the surface of activated platelets. Below the critical micellar concentration of Triton X100 (TtX), the three glycoproteins do not bind appreciably to TtX and form association products of large size. The size-exclusion chromatographic patterns of GPIIb, GPIIIa and GPIIb/IIIa have been obtained at 0.2% TtX, and the molecular properties of the association products and monomer fractions have been determined by analysis of the detergent bound to the glycoproteins, laser-light scattering, sedimentation velocity, and electron microscopy (TEM). The monomer of the GPIIb-TtX complex was identified by the molecular mass (M) of the glycoprotein moiety (125 +/- 15 kDa), the molecular size (9.5 +/- 1.5 nm x 11 +/- 1.5 nm) and globular shape observed by TEM. It has a molecular mass (M*) of 197 +/- 20 kDa, a sedimentation coefficient s degrees 20* of 5.8 +/- 0.1 S, a Stokes radius R s* of 6.8 +/- 0.4 nm, and a frictional ratio f*/fmin* of 1.7 +/- 0.14. The (GPIIb)n-TtX complexes are disulphide-bonded size-heterogeneous association products of GPIIb, tetramers being the smallest species found. GPIIIa has a greater propensity to self-associate than GPIIb, this tendency being lower below 1 mg GPIIIa/ml, 0.1 mM Ca2+, pH 9.0. The (GPIIIa)n-TtX complexes are noncovalent size-heterogeneous association products of GPIIIa, tetramers being the smallest form observed. The monomer of the GPIIIa-TtX complex was identified by the 103 +/- 15 kDa M determined for the glycoprotein moiety, and the 9 +/- 1.5 nm x 10 +/- 1.5 nm size and globular shape observed by TEM. It has a M* of 136 +/- 15 kDa, a s degrees 20* of 3.9 +/- 0.3 S, a Rs* of 6.4 +/- 0.5 nm, a f*/fmin* of 1.9 +/- 0.3, and, when stored at pH 7.4, has a certain tendency to form filamentous association products (20-70 nm x 2-5 nm), as observed by TEM. The GPIIb/IIIa-TtX complex in 0.2% TtX/0.1 mM Ca2+ elutes as a single monomeric fraction, as deduced from the 210 +/- 15 kDa M determined for its glycoprotein moiety and the 12 +/- 1.5 nm x 14 +/- 1.5 nm size of the globular forms observed by TEM.(ABSTRACT TRUNCATED AT 400 WORDS)     

ESR and UV-Vis studies of semiquinone radical anion and hydroquinone generated by irradiation of 15-deacetyl-13-glycine substituted hypocrellin B

15-Deacetyl-13-glycine substituted hypocrellin B (GDHB) is a new type of hypocrellin derivative with enhanced red absorption longer than 600 nm and water solubility. When an anaerobic DMSO or DMSO-buffer (pH 7.4) solution of GDHB was illuminated with >470 nm light, a strong electron spin resonance (ESR) signal was formed. The ESR signal was assigned to the semiquinone anion radical of GDHB (GDHB*-) based on a series of experiments. GDHB*- was predominantly photoproducted via the self-electron transfer between the excited- and ground-state species. Decay of this species, both in the presence and absence of electron donor, was consistent with second-order kinetics. In aqueous solution, the TEMPO counter-spin experiment indicated the formation of GDHB*- that could not be detected by ESR method directly. The formation of GDHB*- and hydroquinone of GDHB (GDHBH*-) was also confirmed by spectrometric method. These findings suggested that GDHB was at least a favorable type I phototherapeutic agent.     

Detection of a tryptophan radical in the reaction of ascorbate peroxidase with hydrogen peroxide.

The reactivity of recombinant pea cytosolic ascorbate peroxidase (rAPX) towards H2O2, the nature of the intermediates and the products of the reaction have been examined using UV/visible and EPR spectroscopies together with HPLC. Compound I of rAPX, generated by reaction of rAPX with 1 molar equivalent of H2O2, contains a porphyrin pi-cation radical. This species is unstable and, in the absence of reducing substrate, decays within 60 s to a second species, compound I*, that has a UV/visible spectrum [lambda(max) (nm) = 414, 527, 558 and 350 (sh)] similar, but not identical, to those of both horseradish peroxidase compound II and cytochrome c peroxidase compound I. Small but systematic differences were observed in the UV/visible spectra of compound I* and authentic rAPX compound II, generated by reaction of rAPX with 1 molar equivalent H2O2 in the presence of 1 molar equivalent of ascorbate [lambda(max) (nm) = 416, 527, 554, 350 (sh) and 628 (sh)]. Compound I* decays to give a 'ferric-like' species (lambda(max) = 406 nm) that is not spectroscopically identical to ferric rAPX (lambda(max) = 403 nm) with a first order rate constant, k(decay)' = (2.7 +/- 0.3) x 10(-4) s(-1). Authentic samples of compound II evolve to ferric rAPX [k(decay) = (1.1 +/- 0.2) x 10(-3) s(-1)]. Low temperature (10 K) EPR spectra are consistent with the formation of a protein-based radical, with g values for compound I* (g parallel = 2.038, g perpendicular = 2.008) close to those previously reported for the Trp191 radical in cytochrome c peroxidase (g parallel = 2.037, g perpendicular = 2.005). The EPR spectrum of rAPX compound II was essentially silent in the g = 2 region. Tryptic digestion of the 'ferric-like' rAPX followed by RP-HPLC revealed a fragment with a new absorption peak near 330 nm, consistent with the formation of a hydroxylated tryptophan residue. The results show, for the first time, that rAPX can, under certain conditions, form a protein-based radical analogous to that found in cytochrome c peroxidase. The implications of these data are discussed in the wider context of both APX catalysis and radical formation and stability in haem peroxidases.     

Spectroscopic properties and reactivity of free radical forms of A2E

A pyridinium bisretinoid (A2E) is the only identified blue-absorbing chromophore of retinal lipofuscin that has been linked to its aerobic photoreactivity and phototoxicity. Pulse radiolysis has been used to study both the one-electron oxidation and the one-electron reduction of A2E in aqueous micellar solutions. The reduction to the semireduced A2E (lambda(max) broad and between 500 and 540 nm) was achieved with formate radicals and the subsequent decay of A2E* was slow (over hundreds of milliseconds) via complex kinetics. The long lifetime of the A2E* should facilitate its reactions with other biomolecules. For example, with oxygen, the A2E* produced the superoxide radical anion with a rate constant of 3 x 10(8) M(-1) s(-1). The A2E was also reduced by the NAD radical, the corresponding rate constant being 2.3 x 10(8) M(-1) s(-1). Other experiments showed that the one-electron reduction potential of A2E lies in the range -640 to -940 mV. The semioxidized form of A2E (lambda(max) 590 nm) was formed via oxidation with the Br2*- radical and had a much shorter lifetime than the semireduced form. With strongly oxidizing peroxyl radicals (CCl3O2*) our kinetic data suggest the formation of a radical adduct followed by dissociation to the semioxidized A2E. With milder oxidizing peroxyl radicals such as that from methanol, our results were inconclusive. In benzene we observed an efficient oxidation of zeaxanthin to its radical cation by the A2E radical cation; this may be relevant to a detrimental effect of A2E in vision.     

Hydrated electron-initiated main-chain scission in peptides: an e.s.r. and spin-trapping study.

The reactions of hydrated electrons (eaq-) with 19 tripeptides were investigated. Hydrated electrons were produced by gamma-radiolysis of aqueous peptide solutions containing sufficient sodium formate to remove hydroxyl radicals and hydrogen atoms. t-Butanol was also used to scavenge hydroxyl radicals. The short-lived radicals formed by the reactions of eaq- with the peptides were spin-trapped with t-nitrosobutane to form stable nitroxide radicals and identified by e.s.r. spectroscopy. The tripeptides studied contained two glycine residues. Following the addition of eaq- to tripeptides, C-N bond scission was observed at three sites. Cleavage occurred between the nitrogen of the ammonium group and the alpha-carbon and between the nitrogen of the peptide linkage and the adjoining alpha-carbons. The radicals corresponding to each of these three types of scission were identified. From a comparison of the radical yields of the reaction of eaq- with ala, (ala)2, and poly-DL-ananine with an average degree of polymerization of 1800, it was shown that eaq-, can react with many carbonyl groups of poly-DL-alanine, leading to main-chain scission. Analogous reactions of eaq- with proteins and enzymes may be expected to lead to loss of biological activity.     

Reduction in free-radical-induced DNA strand breaks and base damage through fast chemical repair by flavonoids

This paper provides evidence that dietary flavonoids can repair a range of oxidative radical damages on DNA, and thus give protection against radical-induced strand breaks and base alterations. We have irradiated dilute aqueous solutions of plasmid DNA in the absence and presence of flavonoids (F) in a "constant *OH radical scavenging environment", k of 1.5 x 10(7) s(-1) by decreasing the concentration of TRIS buffer in relation to the concentration of added flavonoids. We have shown that the flavonoids can reduce the incidence of single-strand breaks in double-stranded DNA as well as residual base damage (assayed as additional single-strand breaks upon post-irradiation incubation with endonucleases) with dose modification factors of up to 2.0+/-0.2 at [F] < 100 microM by a mechanism other than through direct scavenging of *OH radicals. Pulse radiolysis measurements support the mechanism of electron transfer or H* atom transfer from the flavonoids to free radical sites on DNA which result in the fast chemical repair of some of the oxidative damage on DNA resulting from *OH radical attack. These in vitro assays point to a possible additional role for antioxidants in reducing DNA damage.     

Effect of structural modifications on photosensitizing activities of hypocrellin dyes: EPR and spectrophotometric studies.

Mono-substituted hypocrellin B (MHB) and di-substituted hypocrellin B (DHB) by mercaptoacetic acid are new photosensitizers synthesized to improve the red absorption and water solubility of the parent hypocrellin B (HB). The photochemistries (Type I and/or Type II) of MHB and DHB have been studied in homogeneous solutions using electron paramagnetic resonance (EPR) and spectrophotometric methods. In anaerobic homogeneous DMSO solution, DHB*- (or MHB*-) was predominantly photoproduced via self-electron transfer between the excited- and ground-state species. The presence of an electron donor significantly promotes the formation of the reduced form of DHB (or MHB). As compared with hypocrellin B, the efficiencies of DHB*- and MHB*- generation was enhanced obviously. When oxygen-saturated solutions of DHB (or MHB) were illuminated with 532 nm light, singlet oxygen (1O2), superoxide anion radical (O2*-), hydroxyl radical (*OH) and hydrogen peroxide (H2O2) were formed. DHB and MHB generate 1O2 with quantum yields of 0.18 and 0.22, respectively, which are much lower than that of HB (0.76) in chloroform. The superoxide anion radical was significantly enhanced by the presence of electron donors. The rate of O2*- production was also dependent on the concentration of DHB or MHB. Moreover, O2*- upon disproportionation can generate H2O2 and ultimately the highly reactive *OH via the Fenton reaction and other pathway with the involvement of DHB*- (or MHB*-). As in the case of DHB*- (or MHB*-), the efficiencies of O2*- and *OH generation by DHB and MHB were also enhanced obviously, consistent with the fact that DHB*- (or MHB*-) acts as the precursor of O2* and thus *OH. These findings suggest that the photodynamic actions of DHB and MHB may proceed via enhanced Type I mechanism and reduced Type II mechanism as compared with that of HB.     

Nuclear wavepacket motion producing a reversible charge separation in bacterial reaction centers

The excitation of bacterial reaction centers (RCs) at 870 nm by 30 fs pulses induces the nuclear wavepacket motions on the potential energy surface of the primary electron donor excited state P*, which lead to the fs oscillations in stimulated emission from P* [M.H. Vos, M.R. Jones, C.N. Hunter, J. Breton, J.-C. Lambry and J.-L. Martin (1994) Biochemistry 33, 6750-6757] and in Qy absorption band of the primary electron acceptor, bacteriochlorophyll monomer B(A) [A.M. Streltsov, S.I.E. Vulto, A.Y. Shkuropatov, A.J. Hoff, T.J. Aartsma and V.A. Shuvalov (1998) J. Phys. Chem. B 102, 7293-7298] with a set of fundamental frequencies in the range of 10-300 cm(-1). We have found that in pheophytin-modified RCs, the fs oscillations with frequency around 130 cm(-1) observed in the P*-stimulated emission as well as in the B(A) absorption band at 800 nm are accompanied by remarkable and reversible formation of the 1020 nm absorption band which is characteristic of the radical anion band of bacteriochlorophyll monomer B(A)-. These results are discussed in terms of a reversible electron transfer between P* and B(A) induced by a motion of the wavepacket near the intersection of potential energy surfaces of P* and P+B(A)-, when a maximal value of the Franck-Condon factor is created.