THE PHOTOPHYSICS OF 5-METHOXYINDOLE. A NON-EXCIPLEX FORMING INDOLE: ADDITIONAL EVIDENCE FOR TWO CLASSES OF EXCIPLEXES*

Abstract— 5-Methoxyindole is a non-exciplex forming indole, and its excited state behavior is qualitatively different from that of indole and its methyl substituted derivatives. This fact supports the idea that there are two limiting classes of exciplexes, charge-transfer and dipole-dipole stabilized. The fluorescence quantum yield in water is 0.29 with a lifetime of 4.0 ns at 25d?C. The activation energy for fluorescence quenching in water is 15.9 pM 0.5 kJ/mol, which is smaller than for indole and the methyl substituted indoles which have been measured. In cyclohexane at 25d?C, the fluorescence quantum yield is 0.63 with a lifetime of 6.7 ns. The fluorescence is efficiently quenched by electron scavengers, as is the case for other indoles. Some electron ejection to solvent probably occurs in both solvents.     

Intra- and intermolecular fluorescence quenching in 7-(pyridyl)indoles

Three isomeric 7-(pyridyl)indoles reveal very different, solvent-dependent photophysical properties. Due to rapid excited state depopulation involving intramolecular hydrogen bonding, 7-(2′-pyridyl)indole is practically nonfluorescent at room temperature. In nonpolar and polar aprotic solvents, 7-(3′-pyridyl)indole and 7-(4′-pyridyl)indole fluorescence strongly, but the emission is quenched in alcohols. Syn and anti rotameric forms of 7-(3′-pyridyl)indole are detected, each quenched to a different degree. This differential quenching is interpreted as evidence of enhanced S₁ → S₀ internal conversion being more efficient in cyclic solvates, with alcohol molecules forming a bridge between the proton donor and acceptor groups of an excited chromophore.     

Fluorescence quenching of carbazole and indole by ethylenetrithiocarbonate

The fluorescence of quenching of carbazoles and indoles by ethylenetrithiocarbonate has been studied. Both steady-state and transient fluorescence experiments were carried out in order to determine rate constants in the case of carbazoles. The results obtained support the charge-transfer mechanism. Ground-state complex formation is assumed to explain the higher rate constants for indole and its derivatives, which appear as positive curvatures in Stem-Volmer plots.     

THE FORMATION OF HYDRATED ELECTRONS FROM THE EXCITED STATE OF INDOLE DERIVATIVES

Abstract— –Hydrogen atoms can be observed in u.v. irradiated aqueous solutions of indole derivatives. These H' atoms are produced in a reaction between H⁺ and solvated electrons which are formed in the excited state of indole. Protons are also known to be good quenching agents for the fluorescence of indole. However the pH dependence and effect of oxygen on the yield of hydrogen atoms indicates clearly that although both fluorescence and electron ejection originate in the excited singlet state the fluorescence quenching by protons is not caused by a transfer of electronic charge from the excited ring to H⁺. The temperature dependencies of both fluorescence and electron ejection yield an abnormally large "activation energy". It is proposed that this temperature dependence is to a large extent determined by a process characteristic of water as a solvent.     

Photophysics and photocatalytic behavior of composite CdS-purine nanoparticles in the presence of certain indoles

The photophysics of purine-capped Q-CdS has been examined in the presence of certain indoles. The addition of indole does not modify electronic spectrum of purine-capped Q-CdS but it forms a fluorescing charge-transfer intermediate with illuminated CdS, which has an emissive peak at 495 nm. The intensity and the lifetime of this intermediate are enhanced initially with an increase in concentration of indole. In the presence of other indoles, the fluorescence is simply quenched in a dynamic process without forming any fluorescing intermediate. In contrast, emissive CT intermediate is not formed in the presence of indole or any of its derivatives with adenine-capped Q-CdS. In all the cases the quenching of fluorescence, monitored by steady state and time-resolved methods, follows the Stern-Volmer relationship and takes place with a bimolecular rate constant of approximately 10(10) dm(3)mol(-1)s(-1). Purine-capped Q-CdS sensitizes the reactions of the investigated indole(s)-O2 couple much more efficiently than adenine-capped Q-CdS. The differences in quenching of fluorescence and reactivity of holes between purine-capped Q-CdS and adenine-capped Q-CdS are explained by the difference in the binding of indole to the particle. In the case of purine-capped Q-CdS, specific channels for the binding of the solutes are created through the H-bond with the surface-capped purine.     

PHOTOPHYSICAL STUDIES OF INDOLE ALKANOIC ACIDS and TRYPTAMINE IN REVERSE MICELLES OF SODIUM DIOCTYL SULFOSUCCINATE

Abstract— The fluorescence spectra and emission lifetimes of several 3-alkanoic indoles of different chain length and tryptamine (TA) were studied in sodium dioctyl sulfosuccinate (AOT)/heptane reverse micelles over a wide range of water/AOT ratio (R - 5 to 44). Fluorescence quenching experiments were done using carbon tetrachloride and acrylamide as quenchers. Experiments with TA were carried out using water at pH 3 in order to assure its protonation. Under these conditions, the results indicate that the indole moiety of TA remains at the micellar interface over all the range considered. Furthermore, the results can be interpreted assuming for the TA population a single microenvironment whose properties remain almost invariant when R increases from 11 to 44. The studies employing the 3-alkanoic indoles were carried out at pH 10. Under these conditions, the anions are progressively displaced to the water pool when the R value increases. This displacement is determined by the length of the side alkyl chain of the 3-indole derivatives. For these compounds, the quenching experiments indicate that, even at low R values, the excited indole moieties are distributed among different microenvironments.     

FLASH PHOTOLYSIS OF TRYPTOPHAN AND N-ACETYL-L-TRYPTOPHANAMIDE; THE EFFECT OF BROMIDE ON TRANSIENT YIELDS

Abstract— Electronic spectra of indoles are very sensitive to solvents. These solvent effects are particularly pronounced in the case of the fluorescence spectra of indoles. In order to elucidate the solvent band shifts during the relaxation of the excited states, particularly in polar solvents, the dipole moments of the excited singlet states have been estimated from the data of solvent-dependent Stokes shifts. In addition to indole, indole-5-carboxylic acid, indole-3-carboxylic acid, indole-2-carboxylic acid, 5-cyano- and 5-bromo-indoles have been investigated. All indoles showed a substantial increase in dipole moment upon excitation to the emitting state. These results are generally consistent with the Pariser-Parr-Pople SCF MO calculations.     

Hydrogen-Bonding Interactions between Harmane and Pyridine in the Ground and Lowest Excited Singlet States

Abstract— A spectroscopic (UV-visible, Fourier transform IR, steady-state and time-resolved fluorescence) study of hydrogen-bonding interactions between harmane (1-meth-yl-9H-pyrido/3,4- b /indole) and pyridine in the ground and lowest excited singlet state is reported. In low polar and weakly or nonhydrogen-bonding solvents, such as cy-clohexane, chloroform, carbon tetrachloride, toluene and benzene, the analysis of the spectroscopic data indicates that harmane and pyridine form 1:1 stoichiometric hydrogen-bonded complexes in both the ground and singlet excited states. The formation constants of the complexes are greater in the excited than in the ground state. Hydrogen-bonding interaction in the excited state is essential for the quenching of the fluorescence of harmane by pyridine. The stabilities of the hydrogen-bonded complexes between harmane and pyridine diminish as the polarity and hydrogen-bonding ability of the solvent increase.     

咔唑及其衍生物对 9-氰基蒽的荧光猝灭机理的研究

本文研究咔唑及其衍生物对9-氰基蒽(9CNA)的荧光猝灭机理。结果表明, 猝灭过程有以下三种方式:(1)一系列N-烷基咔唑及1,4-二咔唑丁烷、反式1,2-二咔唑环丁烷、N-苄基咔唑等对9CNA的荧光猝灭是通过形成激基复合物。(2)咔唑对9CNA的荧光猝灭是通过形成氢键。(3)1,3-二咔唑丙烷及N-痖烯基咔唑对9CNA的荧光猝灭是属于一般碰撞猝灭过程。以上所有猝灭过程主要都是来自电荷转移相互作用。另外, 还讨论了空间位阻对形成激基复合物的影响。并由稳态和动态荧光实验结果,应用Ware关于激基复合物的形成和解离的动力学公式计算出一系列光物理速率常数。     

EXCIPLEX STUDIES–V. ELECTRON EJECTION FROM INDOLE AND METHYL-INDOLE DERIVATIVES*

Abstract— Electron-scavenging experiments with N₂O as scavenger demonstrate at least two electron-producing reactions of the excited singlet states of the exciplex species formed by indole or 1 -methyl-indole with water. Most electrons reacting with N₂O result from collision of the scavenger with a metastable state formed from the initial exciplex state but finite electron yields from indole and 1-methyl-indole at limiting scavenger concentrations suggest that the intermediate states also eject electrons directly into the solvent. The formation of the first metastable state from the fluorescent exciplex state has an activation energy, E_M, estimated to be about 13 kcal/mole for both indole and 1 -methyl-indole water exciplexes. The E_M values for 1-methyl-indole from fluorescence and electron yields are the same, Indicating that at neutral and alkaline pH fluorescence quenching and electron extraction are both being controlled by the formation of the first metastable intermediate. Observed electron yields from indole-water and indole-methanol exciplexes are less than predicted using fluorescence data, although E_M values of 1 kcal/mole are obtained for the indole-methanol exciplex by both methods. At pH 12·0 and 28°C the total electron yields for indole-water and 1 -methyl-indole-water exciplexes are 0·30 and 0·25, respectively. The residual yields attributed to outright formation of hydrated electrons from the initial exciplex excited stateare 0·11 and 0·05, respectively. Electron yields from the indole-water exciplex are strongly pH dependent only near pH 1 where the fluorescence yields as well as the electron yields decrease rapidly with increasing acidity. The 1-methyl-indole-water exciplex shows an additional pH dependence which is first-order in hydrogen-ion activity and has an effective pK_a of about 11·5. Comparable yields for indole and 1-methyl-indole are found only above pH 12. High electron yields are found with indole in the exciplex-forming solvent dioxane and in the non-exciplex forming solvent cyclohexane. For the latter system electrons are probably derived only from the lowest excited state of indole on collision with N₂O.     

ELECTRONIC STATES OF THE INDOLE-ACRYLAMIDE MOLECULAR PAIR

A model is suggested for tryptophan fluorescence quenching by acrylamide based on the prediction that acrylamide can absorb a photon from the excited indole moiety and then dissipate the optical energy into a sink of fast exchanging conformations. Semiempirical electronic structure calculations of the indole-acrylamide pair indicate little actual intermolecular orbital mixing at van der Waals contact distances. However, the two lowest singlet transitions of the molecular pair, assigned to the acrylamide (pi *)----n(O) line and to the indole 1Lb----1A1 line, respectively, vary significantly in energies and in transition and excited state moments with the geometry of interaction between the two entities. The distribution of optimal quenching coordinations depends separately on the benzene and pyrrole portions and has a distinctly non-spherical shape at these distances.     

On the nature of the fluorescent state of methylated indole derivatives

A quantitative study has been made of the solvent effects on the fluorescence properties of 1- and 3-methyl indole, with the aim of further understanding the origin of the unusually large Stokes shift in polar solvents. For the derivatives considered here the fluorescence transition probability is decreased in solvents of moderate and high polarities, and the spectrum shifts to the red. The data (in two-component, solute and solvent, systems) can be interpreted on the basis of the stabilisation, by solvent-solute relaxation, of a state with an increased charge-transfer character, relative to the initially excited state. Å consideration of the decay data for other indole derivatives suggests that this state has its origin in the ¹L₄ state (S₂ in non-polar media). Thus we conclude that the appropriate label of the fluorescent state of many substituted indoles in polar solvents is ¹L_a/CT. This is consistent with the observed solvent, temperature, time and substituent dependence of the decay kinetics of these derivatives.     

Quenching of tryptophan (1)(pi,pi*) fluorescence induced by intramolecular hydrogen abstraction via an aborted decarboxylation mechanism

CASSCF computations show that the hydrogen-transfer-induced fluorescence quenching of the (1)(pi,pi*) excited state of zwitterionic tryptophan occurs in three steps: (1) formation of an intramolecular excited-state complex, (2) hydrogen transfer from the amino acid side chain to the indole chromophore, and (3) radiationless decay through a conical intersection, where the reaction path bifurcates to a photodecarboxylation and a phototautomerization route. We present a general model for fluorescence quenching by hydrogen donors, where the radiationless decay occurs at a conical intersection (real state crossing). At the intersection, the reaction responsible for the quenching is aborted, because the reaction path bifurcates and can proceed forward to the products or backward to the reactants. The position of the intersection along the quenching coordinate depends on the nature of the states and, in turn, affects the formation of photoproducts during the quenching. For a (1)(n,pi*) model system reported earlier (Sinicropi, A.; Pogni, R.; Basosi, R.; Robb, M. A.; Gramlich, G.; Nau, W. M.; Olivucci, M. Angew. Chem., Int. Ed. 2001, 40, 4185-4189), the ground and the excited state of the chromophore are hydrogen acceptors, and the excited-state hydrogen transfer is nonadiabatic and leads directly to the intersection point. There, the hydrogen transfer is aborted, and the reaction can return to the reactant pair or proceed further to the hydrogen-transfer products. In the tryptophan case, the ground state is not a hydrogen acceptor, and the excited-state hydrogen transfer is an adiabatic, sequential proton and electron transfer. The decay to the ground state occurs along a second reaction coordinate associated with decarboxylation of the amino acid side chain and the corresponding aborted conical intersection. The results show that, for (1)(pi,pi*) states, the hydrogen transfer alone is not sufficient to induce the quenching, and explain why fluorescence quenching induced by hydrogen donors is less general for (1)(pi,pi*) than for (1)(n,pi*) states.     

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.     

Dye induced quenching of firefly luciferase-luciferin bioluminescence

The quenching of firefly bioluminescence (BL) in presence of xanthene dyes and tetratolylporphyrin was investigated. The BL intensity was quenched with an altered decay pattern in presence of xanthene dyes and tetratolylporphyrin. The electronic absorption spectra indicate that there is no significant interaction occurring between the dyes and the BL components in the ground state. The BL quenching decay rate and fluorescence quenching studies of luciferin by the dyes suggest an energy transfer through an exciplex, involving oxyluciferin, in the excited state and the dyes, in the ground state. The bimolecular quenching rate constant (K(q)) values obtained from fluorescence studies varied between 7.7 x 10(12) and 19.8 x 10(12)M(-1)s(-1). The magnitude of the bimolecular quenching rate constants confirmed the complex formation between dye and excited oxyluciferin. The exciplex subsequently undergoes a non-radiative decay to the ground state via a combination of heavy atom induced and F?rster-type energy transfer. The decay rate constants in presence and in absence of dyes vary between 7.47 x 10(-4) and 7.6 x 10(-2)s(-1). In the presence of dyes the effective decay rate constants (k(eff)) increased while the lifetime of light emitting species decreased. The kinetic studies in presence of singlet oxygen scavengers, like beta-carotene and NaN(3), prove that there is no significant quenching of the firefly BL due to the formation of singlet oxygen.     

Explaining Level Inversion of the La and Lb States of Indole and Indole Derivatives in Polar Solvents

Quantum chemical methods are used to study the solvent effects on the spectra of indole and a series of methyl‐substituted indoles. We focus on the low‐lying L_a and L_b states and study their interplay. We find that the solvent mainly affects emission from the L_a state, by stabilizing its energy in its excited‐state geometry. The stabilization of the L_a state increases with increasing solvent polarity, which accounts for the large fluorescence shift observed in indoles and leads to an inversion in the nature of the lowest emitting state, from L_b in vacuum to L_a in water. To the best of our knowledge, this is the first theoretical evidence for level inversion done for a series of indoles. The underlying mechanism of level inversion is analyzed in detail. The usual interpretation of level inversion in terms of their static dipole moment is criticized and an improved predictive measurement is suggested.     

FLUORESCENCE QUENCHING OF INDOLIC COMPOUNDS BY ALIPHATIC AMINO ACIDS. EVIDENCE FOR EXCITED STATE COMPLEXES

Abstract The fluorescence quenching of indole, tryptophan, tryptamine and indole-3-acetic by aliphatic amino acids was studied. The bimolecular rate constant ( k _q) for the deactivation of the excited state was determined. The k _q values were in the range 0.6 × 10⁸–1.6 × 10⁹ M ^–1 S^–1 and they increased in the order tryptophan < tryptamine < indole ≈ indole-3-acetic acid. When the rate constant was corrected for diffusion al effects a good linear correlation was found between the log ( k '_q) and the ionization equilibrium constant of the carboxylic group of the amino acid (p ^k _a1). This was interpreted as arising from a charge transfer mechanism in which the indole moiety acts as an electron donor and the carbonyl group of the amino acid as the acceptor.
The activation parameter for the quenching processes were also determined. The ΔH^≠ values were in the range —4.0 to +4.0 kcal/mol and the ΔH^≠ in the range –7 to –37 e.u. For the systems with lower values of k _q negative values for ΔH^≠ were observed. A good enthalpy-entropy compensation was found with an isokinetic temperature of 229 K. These results suggest that a common mechanism is operating for all the systems and that it involves the formation of an excited state complex between the indolic compound and the amino acid.     

PHOTOPHYSICAL PROPERTY OF SANGUINARINE IN THE EXCITED SINGLET STATE

The photophysical property of the alkanolamine form of sanguinarine has been studied in aqueous and organic medium under various environmental conditions from the measurement of absorption, fluorescence and NMR spectroscopy. Alkanolamine fluorescence shows an excitation time dependent fluorescence quenching and the rate of quenching increases significantly with increasing pH and concentration of the species, while it decreases with increasing temperature. This phenomenon is explained by excited state intramolecular proton transfer from a 6-OH group to the lone pair of nitrogen through the formation of zwitterion.     

竹红菌甲素和吲哚类化合物的相互作用

本文利用吸收光谱,荧光光谱研究了竹红菌甲素(以下简称HA)和吲哚类化合物的相互作用。发现HA和吲哚类化合物在一定条件下可形成复合物。这种复合物带有电荷转移性质。吲哚环上带有给电子取代基,位阻小,溶剂的极性大和溶液呈中性有利于该复合物的形成。     

Proton-transfer mediated quenching of pyrene/indole charge-transfer states in isooctane solutions

The fluorescence quenching of pyrene (Py) by a series of N-methyl and N-H substituted indoles was studied in isooctane at 298 K. The fluorescence quenching rate constants were evaluated by mean of steady-state and time-resolved measurements. In all cases, the quenching process involves a charge-transfer (CT) mechanism. The I(o)/I and tau(o)/tau Stern-Volmer plots obtained for the N-H indoles show a very unusual upward deviation with increasing concentration of the quenchers. This behavior is attributed to the self-quenching of the CT intermediates by the free indoles in solution. The efficiency of quenching of the polyaromatic by the N-H indoles increases abruptly in the presence of small amount of added pyridine (or propanol). A detailed analysis of the experimental data obtained in the presence of pyridine provides unambiguous evidence that the self-quenching process involves proton transfer from the CT states to indoles.