SOLVENT EFFECTS ON THE TAUTOMERIZATION OF 5'-DEOXYPYRIDOXAL. A PHOTOPHYSICAL STUDY

Abstract— Absorption and fluorescence spectra of 5'-deoxypyridoxal (DPL) in various pure solvents and mixtures were recorded both at room temperature and over the range10–65°C. The areas under the absorption bands were analyzed to obtain the mole fraction (f_N, f_z) of two tautomers (the zwitterionic, Z, and neutral, N, forms) in the ground state. The following spectral parameters were determined from the fluorescence spectra: Stokes shift (Δ v ), fluorescence quantum yield of the neutral form (Q_N), fluorescence ratio of the neutral to the zwitterionic form (ø_N/ø_Z) and the rate constant of tautomerization ( k ₁) from Z to N in the excited state. Some of these parameters (f_N, Δ v , Q_N, k ₁) were found to depend on the proton donor character of the solvent, whereas others (ø_N/ø_Z) depended on its dipole moment. Thus, the absorption and fluorescence spectra of DPL allow one to obtain information on the polarity and the concentration of –OH groups on its environment.     

SOLVENT EFFECTS ON THE ELECTRONIC ABSORPTION AND FLUORESCENCE SPECTRA OF INDOLE-4-CARBOXYLIC ACID: PROTOTROPIC EQUILIBRIA IN AQUEOUS SOLUTIONS

Abstract— The absorption and fluorescence spectra of indole-4-carboxylic acid in various solvents have indicated that the -COOH group is more planar with respect to the indole ring in the first excited singlet state (S₁) than in the ground (S₀) state. Relatively large Stokes' shifts indicate that polarisability and dipole moment of the molecule are increased predominantly upon excitation. Prototropic reactions in the S₀ and S₁ states are the same. The -COO^- and -COOH+₂ groups are not coplanar in the S₀, but coplanar in the S₁ state. pH-dependent fluorescence spectra have revealed that both protonation and deprotonation of the -COOH group increase the basicity of the molecule upon excitation.     

QUANTIFICATION OF THE SOLVENT EFFECTS ON THE TRIPLET QUANTUM YIELD OF PSORALEN BY THE "LINEAR SOLVATION ENERGY RELATIONSHIP"

Triplet formation quantum yields (Φ_τ) of psoralen in a set of 17 pure solvents ranging from n -hexane to water and in dioxane: water mixtures were obtained by nanosecond laser flash photolysis. The triplet yield increases with solvent polarity. The extremum values are 0.009 and 0.545 in n -hexane and water, respectively. Good correlations of the experimental Φ_τ values with empirical "polarity" scales (Dimroth/Reichardt's E_T [30], Kamlet/Taft's solva-tochromic parameters β, and α, and Swains acity/basity A_S/B_S) were obtained: Ln(φ_T^-1 - 1) = 8.86 - 0.143E_T(30) Ln(φ_T^-1 - 1) = 4.40 - 2.34_τ - 1.70α Ln(φ_T^-1 - 1) = 4.65 - 3.72A_s - 1.12B_s The results are discussed in terms of the sensitivity of psoralen triplet quantum yield to solvent polarity and hydrogen-bonding abilities.     

PHOTOCHEMICAL ESTIMATION OF OXYGEN SOLUBILITY

Abstract— A photochemical technique for estimating the solubility of oxygen in a solvent has been developed and used to estimate the solubility of oxygen in chloroform. From a measurement of the change in rubrene concentration and rubrene fluorescence lifetime as a sealed rubrene solution is irradiated and from the fluorescence lifetime of rubrene in nitrogen, air and oxygen-saturated solvent the oxygen solubility constant and rate constant for oxygen quenching of rubrene fluorescence can be measured. For chloroform these values are 9.8 m M /atm and 7.9 10₉ M _-1 s_-1 respectively.     

INTERACTIONS AMONG PHOTOSYNTHETIC ANTENNA EXCITED STATES

Abstract. The data of Kung and DeVault (1978) showing high-order fluorescence from chromatophores of photosynthetic bacteria are analyzed in relation to other data on first-order fluorescence of photosynthetic systems, particularly that of Monger and Parson (1977). The wavelengths of emission observed (down to 445 nm) require energy equivalent to two lowest singlet-excited states. The dependence on excitation intensity is best explained by any of the following third-order processes: (a) 3 S ₁→3 S ₀; (b) 2 S ₁+ T , → 2 S ₀+ T ₁; (c) S ₁+ 2 T ₁→ 3 S ₀. However, (c) is ruled out because it predicts heavy T ₁-destruction which is not observed. Contribution from the second order process: 2 S ₁→ S ₀ is probable, but even the data of Monger and Parson show that it is insufficient by itself. Two-photon absorption: S ₀+ hv ₁→ S ₁; S ₁+ hv ₁→ S _n; S _n S ₀+ hv ₂ could also account for the high-order fluorescence and its dependence on excitation intensity. [ S ₀, S ₁ S _n are ground, first excited and a higher excited singlet states, respectively, of antenna bacteriochlorophyll, T _t is the lowest triplet state, c/v , is the exciting wavelength (694 or 868 nm) and c/v ₂ the wavelength of the high-order fluorescence (445, 535. or 600 nm), where c = velocity of light.] Maximum values are estimated for some of the rate constants.     

COMPUTER SIMULATION OF EXCITON JUMPING STATISTICS AND ENERGY FLOW IN C-PHYCOCYANIN OF ALGAE Agmenellum quadruplicatum IN THE PRESENCE OF TRAPS

Abstract—Energy migration has been studied in C-phycocyanin (C-PC) rods with traps located in the terminal trimer disc, using the Monte Carlo method and the system of differential equations. It has been found that jump time statistics can be described by the function F = C(t/0>)exp(-t/ < t_o>), where C is the constant, t and < t₀ > are, respectively, the exciton jump time and its averaged value for chromophores of the corresponding spectral types (α 84 , β84 or β155). The values < t₀ > were calculated for the cases of C-PC monomers, trimers and higher associates.
The C-PC model, which consists of three hexamers with traps located in the β84 chromophores of the peripheral trimer, was examined. It was found that the total efficiency of excitation capturing, ø_tr, exceeds 90%, provided "local" quantum yield of energy trapping ø₀ > 10%. The ø₀ value influences both the excitation lifetime (τ) and the mean number of excitation jumps (N_iump) before its conversion. For the ø₀ = 100% and 10%, the corresponding lifetimes and numbers of jumps were calculated to be τ= 75 and 155 ps and N_jump= 105 and 222 jumps, respectively.
The dynamics of excitation redistribution along the C-PC rods and the fluorescence kinetics for various ø₀ values were calculated for C-PC chromophores excited by a +, and the correlation between these processes and ø ₀ , was disclosed. The transient processes of excitation redistribution were shown to proceed within a time period t < 30 ps.     

A METHOD FOR THE CORRECTION OF QUANTUM YIELDS OF FLUORESCENCE IN SOLUTIONS

Abstract— The correction factors due to the overlap of absorption and emission spectra have been calculated for various concentrations of fluorescein dye at pH 12 by using the experimentally obtained value of apparent molar absorptivity, ε₂, for the fluorescence radiation. The observed fluorescence intensities for the same-surface detection for a given geometry have been corrected for the secondary emission effect thus calculated, and also for refraction and dilution effects, to give corrected relative quantum yields for the solutions. These have been converted to the absolute values by comparison of the integrated fluorescence quantum spectrum of a dilute solution of fluorescein with that for quinine sulphate in 0.1 N H₂SO₄. The corrected quantum yields compare well with values given in the literature.     

ESR STUDY OF ORIENTED TRIPLET MOLECULES GENERATED BY EXCITATION WITH POLARIZED LIGHT

Abstract— The lowest-lying triplet states of a variety of aromatic molecules and complexes have been generated by the irradiation of these compounds in solvent glasses with plane-polarized light. Measurements of the allowed (Δ M=± 1) ESR transitions clearly demonstrate that the triplets so formed are oriented with respect to the external magnetic field. By this method the triplet zero-field splitting parameters, D and E , can be evaluated simply and reliably. Intramolecular energy transfer is postulated to explain the triplet spectra of Zn( o -phen)₂(NO₃)₂ and Zn( o -phen)₃(NO₃)₂. It was observed that in triplet-triplet energy transfer from benzophenone to naphthalene there is no apparent orientation requirement between the donor and acceptor molecules. Further areas of significance and application of this technique are suggested.     

ABSORPTION AND EMISSION STUDIES OF ELECTRONIC STATES OF N-ARYLBENZAMIDES

Abstract— Absorption and emission spectra of several N-arylbenzamides have been measured. The quantum yields for their fluorescence were found to be dependent on matrix viscosity and temperature. Singlet-triplet splittings for these compounds were determined from their emission spectra and found to be abnormally small for π. π* states (˜ 1500 cm^-1). Indeed, the phosphorescence maxima of N-arylbenzamides occur slightly to the blue relative to their fluorescence maxima. Intersystem crossing efficiencies were determined for several of these compounds and are consistent with S₁→ S ₀ radiationless decay.     

SOME PHOTOPHYSICAL PROPERTIES OF 3-CARBETHOXYPSORALEN, 8-METHOXYPSORALEN and 5-METHOXYPSORALEN TRIPLET STATES

Abstract Triplet absorption spectra, extinction coefficients (ɛ_T), decay rates ( K ₁), oxygen quenching rates (k_q) and intersystem crossing yields (φ_T) for 3-carbethoxypsoralen (3-CPs). 8-methoxypsoralcn (8-MOP) and 5-methoxypsoralen (5-MOP) in methanol are reported. For 8-MOP and 3-CPs corresponding values are also reported with water as the solvent. Some photophysical data are also reported for 5-MOP in water, but ɛ_T and φ_T were not obtained.
The phosphorescence spectra for these furocoumarin derivatives in ethanol at 77 K are reported together with the corresponding lowest triplet energy and lifetime. The values of the various photophysical properties obtained are compared with values reported by previous workers.     

RECONSTITUTION OF ALLOPHYCOCYANIN FROM Mastigocladus laminosus WITH ISOLATED LINKER POLYPEPTIDE

The core linker polypeptide L_c^8.9 was isolated from Mastigocladus laminosus and purified on a preparative scale. A method for the reconstitution of allophycocyanin (AP)—linker complexes from isolated polypeptides was developed. The complex (α^AP(β^AP)₃ L_c^8.9 was reconstituted and compared to (α^APβ^AP) and (α^APβ^AP)₃ by sucrose density gradient ultracentrifugation, absorption, fluorescence emission and circular dichroism spectroscopy. Differences in the spectra of reconstituted and of directly isolated AP complexes are discussed.     

A PULSE RADIOLYSIS STUDY OF THE ONE-ELECTRON OXIDATION AND REDUCTION OF 5, 10-METHENYLTETRAHYDROFOLATE

Abstract— The one-electron reduction and oxidation of 5,10-methenyltetrahydrofolate has been studied in aqueous solution in the acidity range H₀= -1 to pH = 7 using the reducing species CO^-₂ and (CH₃)₂-COH and oxidising species Br^-₂, and H₂SeO+₃. The spectral and other properties of the radicals so formed were found to be indcpendent of the reductant/oxidant used. Two protolytic forms of both the oxidised and reduced radicals were observed with approximate p K , values of 0.5 ± 0.3 being determined. Both the bridged form (5.10-methenyltetrahydrofolate) and the unbridged form (5- formyltetrahydrofolate) were found to be easily oxidised, whereas only the former could be reduced.     

ACTINOMETRY IN MONOCHROMATIC FLASH PHOTOLYSIS: THE EXTINCTION COEFFICIENT OF TRIPLET BENZOPHENONE AND QUANTUM YIELD OF TRIPLET ZINC TETRAPHENYL PORPHYRIN

Abstract— The extinction coefficient ε_T, of triplet benzophenone in benzene has been directly determined by absolute measurements of absorbed energy and triplet absorbance, Δ D ⁰_T, under demonstrably linear conditions where incident excitation energy, E ₀, and ground state absorbance, A ₀, are both extrapolated to zero. The result, 7220 ± 320 M ^-1 cm^-1 at 530 nm, validates and slightly corrects many measurements relative to benzophenone of triplet extinction coefficients made by the energy transfer technique, and of triplet yields obtained by the comparative method.
As E ₀ and A ₀ both decrease, Δ D ⁰_T becomes proportional to their product. In this situation, the ratio R = (1/ A ₀)(dΔ D ⁰_T/d E ₀) = (ε_T - ε_G)φ_T. Measurements of R , referred to benzophenone, give (ε_T - ε_G)φ_T for any substance, without necessity for absolute energy calibration.
Both absolute and relative laser flash measurements on zinc tetraphenyl porphyrin (ε_T - ε_G at 470 nm = 7.3 × 10⁴ M ^-1 cm^-1) give φ_T= 0.83 ± 0.04.     

PHOTOVOLTAIC PROPERTIES OF MESO-TETRAARYLPORPHYRINS

Abstract— The photovoltaic properties of meso -tetraphenylporphyrin and its derivatives with various para -substituents, meso-tetrakis(2,4-dimethoxyphenyl)porphyrin and meso -tetrakis (2-fluorenyl)porphyrin have been investigated. The forward dark current-voltage characteristics of Al/porphyrin/Ag cells are attributed to the MIS Schottky barriers consisting of Al/Al₂O₃/porphyrin. The barrier parameters such as the apparent diffusion potential V ₀ the barrier width w₀ and the density of ionized impurity N are estimated by using the capacitor discharge method. The action spectra of photocurrents closely follow the optical absorption spectra of the porphyrin films. The photocurrents vary as i _pα I ^γ, where I is the incident light intensity, and the Sight exponents y range between 0.83 and 1.0. The sublinear difference from unity could be related to the exponential distribution of hole traps in films of the porphyrins. No obvious correlation between the photocurrent and the fluorescence quantum yields of the sublimed porphyrin films is found. The electron donating substituents such as OCH₃ and CH₃ strikingly increase the photocurrents. The photocurrent quantum yields correlate exponentially with the first ring oxidation potentials of the porphyrins and also with the substituent constants for the Hammett linear free-energy relationship. The current quantum yields estimated for the porphyrins studied, range in the order of 10^-4–10^-2 with power conversion efficiencies 10^-7–10^-3.     

PHOTOCHEMISTRY OF trans-[Rh(BIS(DIPHENYLPHOSPHINO)ETHANE)2X2][PF6]: TRANSIENT ABSORBANCE KINETIC STUDIES OF METAL-HALOGEN BOND HOMOLYSIS

Abstract— Laser flash photolysis of trans -[Rh(dppe)₂X₂][PF₆] (X=Br and I; dppe=bis(diphenylphosphino)ethane) in CH₂Cl₂ or CH₃CN produces the d⁷ Rh(II) radicals, [Rh(dppe)₂X]⁺, and halogen atoms. The kinetics of the disappearance of [Rh(dppe)₂X]⁺ radicals in CH₂Cl₂ or CH₃CN were mixed order: H-atom abstraction from solvent to produce the rhodium hydrides, [RhH(dppe)₂X][PF₆], and Rh/X recombination. In the poor H-atom donor solvent, benzonitrile, Rh/Br recombination was observed to be uncomplicated by competing H-atom abstraction. The hydride complexes [RhH(dppe)²X][PF₆], formed by H-atom abstraction were completely characterized by ³¹P{¹H}-NMR, ¹H-NMR, and mass specrometry. Cyclohexene was used as an effective trap for photogenerated Br atoms and yielded bromocyclohexane and 3-bromocyclohexene in a relative yield, 1:9. The photochemical mechanism is discussed in light of the transient absorbance and trapping studies.     

Energetics of Photoinduced Electron Transfer in the Indole-O2 Cluster in Gas Phase: Possible Consequences for Photoexcited Tryptophan in Solution

Abstract— A direct process for an activationless electron transfer from photoexcited tryptophan to molecular oxygen is proposed. By photodetachment of mass-selected indole-O_2- clusters in gas phase a neutral indole₊ O_2- charge-separated exciplex state is found at 2.25 0.2 eV above the neutral ground state. By theory also, the existence of an excited charge separated state at 3.05 0.2 eV is postulated. In gas phase both charge-separated cluster states are energetically below the first singlet states ₁L_b and ₁L_a and the lower even below the first triplet state T₁ of indole. In gas-phase clusters these energetics imply a very efficient quenching of photoexcited indole by fast electron transfer to oxygen. We discuss a similar mechanism for tryptophan-O₂ in aqueous environment and find it without activation barrier and presumably extremely fast. In the collisional tryptophan_*-O₂ complex the efficiency and the time scale of the charge transfer process should be mostly solvent independent. In polar solvent a complete charge separation and free superoxide formation are expected. We correlate this model with previous fluorescence and phosphorescence quenching data of excited tryptophan by O₂ and propose electron transfer to be the relevant process.     

EFFECTS OF SOLVENT ON THE FLUORESCENCE PROPERTIES OF BACTERIOCHLOROPHYLL a

Fluorescence lifetimes (τ_f) of bacteriochlorophyll a (BChl a ) have been measured by the method of time-correlated single-photon counting on dilute (1 μ M ) solutions of the pigment in 15 solvents. There is a pronounced dependence of τ_f on the nature of the solvent. Specifically, τ_f, is longer when the central magnesium is hexacoordinated than when pentacoordinated and shorter when the macrocycle is hydrogen-bonded than when it is not, but the latter effect is more pronounced. Both trends were confirmed by parallel studies on bacteriopheophytin a (BPheo a ). Because of the short lifetimes (˜ 2.2–3.6 ns), quenching of fluorescence by molecular oxygen is not a significant factor in aerated solutions of the bacterial pigments. However, reabsorption artifacts are non-negligible, which necessitates studies on dilute solutions. Fluorescence quantum yields (ø_f) have been estimated for BChl a in 13 solvents by comparing the observed fluorescence lifetimes with the radiative lifetimes calculated from the integrated absorption spectra.     

A DETAILED RESONANCE RAMAN STUDY OF THE M412 INTERMEDIATE IN THE BACTERIORHODOPSIN PHOTOCYCLE

Abstract— Resonance Raman spectra of various M₄₁₂ species associated with the bacteriorhodopsin photocycle have been obtained. These correspond to the two forms observed during the formation of M₄1₂ and the two forms that are observed during its decay in absorption experimeents. We do not see any significant difference between the Raman spectra of any of these forms. We therefore conclude that the differences in these species are due to the differences in the protein structure and not in the chromophore.     

LIGHT-INDUCED QUENCHING OF PHOTOSYSTEM II FLUORESCENCE AT 77 K

Abstract— Light-induced quenching of the low temperature fluorescence emission from photosystem II (PS II) at 695 nm ( F ₆₉₅) has been observed in chloroplasts and whole leaves of spinach. Photosystem I (PS I) fluorescence emission at 735 nm ( F ₇₃₅) is quenched to a lesser degree but this quenching is thought to originate from PS II and is manifest in a reduced amount of excitation energy available for spillover to PS I. Differential quenching of these two fluorescence emissions leads to an increase in the F ₇₃₅/ F ₆₈₅ ratio on exposure to light at 77 K. Rewarming the sample from -196°C discharges the thermoluminescence Z-band and much of the original unquenched fluorescence is recovered. The relationship between the thermoluminescence Z-band and the quenching of the low temperature fluorescence emission ( F ₆₉₅) is discussed with respect to the formation of reduced pheophytin in the PS II reaction center at 77 K.     

CHEMILUMINESCENCE AND FLUORESCENCE OF THE EUROPIUM IONS-ADENINE NUCLEOTIDES SYSTEM AND ITS POSSIBLE BIOLOGICAL SIGNIFICANCE

Abstract— Chemiluminescence of the Eu(II)/Eu(III)-adenine nucleotide-H₂O₂ system and fluorescence of the Eu(III)-adenosine triphosphate system have been investigated. The spectral distribution of the chemiluminescence emission has shown an occurrence of three main bands (Λ=470–480,590–620 and ca. 700 nm). The energy transfer process from the adenosine triphosphate molecules to the Eu(III) ions has been observed in the fluorescence spectrum. The examined chemiluminescence and fluorescence spectra show that these both kinds of emission originate from the ⁵ D _***τ⁷F_*** ( n =1–4) transitions in the Eu(III) ions.