Dependence of the properties of the dual luminescence of 3-hydroxyflavone on the excitation wavelength

The luminescence and luminescence excitation spectra of 3-hydroxyflavone in acetonitrile obtained at different excitation/recording wavelengths are studied. The dependences of the position of the normal luminescence band maximum and of the intensity ratio of the normal and proton-transfer bands, on the excitation wavelength are found and studied for the first time. It is found that the spectral contour of dual luminescence also depends on the excitation wavelength and the blue emission band is cut off at a sufficiently long-wavelength excitation in the region of 390 nm. In the luminescence excitation spectrum, an additional wide band is observed in the proton-transfer region at 200–260 nm. Excitation in the region of 380–440 nm allowed us to reveal a wide structureless band near 470 nm (with the maximum of its excitation near 420 nm) belonging to the anionic form of 3-hydroxyflavone. Addition of water at a concentration of ～2.2 M quenches this band almost completely.     

Modulation of the proton transfer rate by excitation photons

The effect of the exciting photon energy on the excited state proton transfer in a dye with dual fluorescence—FET (4′-diethylamino)-3-hydroxyflavone)—is studied. The steady-state fluorescence spectra are studied upon selective excitation by photons with different energies in the region of the main absorption band, as well as at its long-wavelength wing, in the temperature range of 2–30°C. It is found that, at all temperatures, the ratio of the integral emission of the normal and tautomeric forms, which are observed at 480 and 570 nm, respectively, depends on the excitation wavelength; namely, this ratio noticeably decreases with increasing excitation wavelength in the region of the main absorption band and its long-wavelength wing at 390–440 nm, and the rate of this decrease depends on temperature. In the same region, the long-wavelength excitation effect, which is atypical for inviscid solvents at room temperature, is observed; i.e., a short-wavelength emission band is bathochromically shifted by 6–15 nm depending on temperature. This spectral shift is directly related to the inhomogeneous broadening of the electronic spectra of the normal FET form, which is very large due to a considerable (>10 D) difference in the dye dipole moments. Most probably, the excitation creates the possibility of emission from nonrelaxed nonequilibrium orientational sublevels because their lifetime becomes shorter due to the proton transfer reaction, the rate of which in acetonitrile is comparable with the rate of intermolecular orientational relaxation. It is proposed to explain these dependences using energy diagram taking into account the dependence of the free energy on the orientational polarization of the solvent.     

Fluorescent probe based on proton transfer in 4′-(diethylamino)-3-hydroxyflavone: Spectral and luminescent characteristics upon selective excitation

The spectral characteristics of acetonitrile solutions of 4′-(diethylamino)-3-hydroxyflavone dye with dual fluorescence are studied under selective excitation. This dye is a structural analog of 3-hydroxyflavone and exhibits excited-state proton transfer, which, in contrast to 3-hydroxyflavone, has a thermodynamic rather than a kinetic character. The fluorescence spectra at different excitation photon energies and the excitation spectra of different fluorescence bands are studied. It is found that the intensity ratio of the normal and tautomeric fluorescence bands lying near 507 and 570 nm, respectively, depends on the excitation wavelength, namely, this ratio is 1.45 and almost does not change in the region of the main absorption band (370–420 nm), while, in the region of the second singlet band (near 280 nm), it decreases to 1.15. This can be explained by an increase in the probability of proton transfer with formation of a tautomeric form in the case of excitation into the second band. Another interesting feature is the existence of a latent third emission band peaked at 535 nm, which was found and reliably recorded upon excitation at wavelengths of 470–500 nm. Addition of water quenches this emission, which indicates that it belongs to the anionic form of the dye.     

Molecular probe FET: Long-wavelength fluorescence excitation effect and proton transfer reaction

We studied the steady-state fluorescence spectra of solutions of FET (4′-(diethylamino)-3-hydroxyflavone) in acetonitrile that were excited at different temperatures by quanta with different energies located in the range of the main absorption band and in its long-wavelength wing. We found that, at room temperature, the emission intensity ratio of the bands of the normal and tautomeric forms, which are located at 505 and 570 nm, respectively, depends on the excitation wavelength. In the range of the main absorption band 300–360 nm, this ratio remains nearly the same, i.e., 1.45, while, upon excitation in the range of the long-wavelength wing 360–380 nm of the main band, it decreases to 1.33 at a wavelength of 460 nm. In this same range, a long-wavelength excitation effect that is unusual for liquid inviscid solvents at room temperature, i.e., a bathochromic shift of the entire short-wavelength emission band by 11 nm, manifests itself. We propose to explain these dependences using energy diagrams, which take into account the dependence of free energy on the orientational polarization of the polar solvent. The observed effect of the long-wavelength shift of the fluorescence spectrum with increasing excitation wavelength is explained in terms of the inhomogeneous broadening of electronic spectra of polar solutions, and it should be described using the scheme of energy states that takes into account sublevels of orientational broadening due to orientational dipole-dipole interactions of the fluorophore with nearest molecules of the polar solvent, as well as the relation between the fluorophore lifetime in the excited state and the dielectric relaxation time of solvent molecules in the field of the fluorophore dipole.     

Effects of long-wavelength fluorescence excitation in liquid solutions of N-pyrrolobenzonitrile

The absorption, dual fluorescence, and fluorescence excitation spectra of N-pyrrolobenzonitrile (P5C) in a set of solvents with different polarities are studied upon irradiation of solutions by light with different photon energies. The dual fluorescence from the locally excited Frank-Condon and charge-transfer states are recorded in all cases. The change in the excitation photon energy does not affect the fluorescence band positions, but noticeably changes the intensity ratio between the bands in favor of the long-wavelength band belonging to the charge-transfer state. The effects observed are explained using the data of quantum-mechanical calculations, which demonstrate that the solutions of these systems can very likely contain rotational isomers with different pyrrole orientations with respect to the benzene ring. In the excited state, these isomers have different charge-transfer reaction rates, which leads to different intensity ratios of the recorded fluorescence bands.     

Excimer Emission of Acridine Orange Adsorbed on Gadolinium-Yttrium Orthovanadate Nanoparticles

Studying the complexes of inorganic nanoparticles – organic dye molecules is of great importance for their theranostics application. In this paper, we report gadolinium-yttrium orthovanadate nanoparticles (VNPs) – Acridine Orange (AO) complex formation in water solutions. To study the interactions between VNPs and AO, the methods of steady-state and time-resolved spectroscopy were used. It was shown that in aqueous solutions containing VNPs, AO aggregation takes place with a sandwich-like stacking of AO molecules in the near-surface layer of VNPs. The VNPs–AO complex formation causes significant changes in the AO fluorescence spectrum, namely, the appearance of a new broad, structureless band in the long-wavelength spectral edge, which was not observed in AO spectrum in a pure water solution. By analyzing of the absorption, fluorescence excitation spectra and fluorescence decay, the static excimer origin of the long-wavelength fluorescence band has been established.     

Spectral properties of molecular charge-transfer probe QMOM

The spectral characteristics of solutions of a dye with dual fluorescence, 1-methyl-2-(4-methoxy)phenyl-3-hydroxy-4(1H)-quinolone, in acetonitrile are studied upon selective excitation. This dye is a structural analogue of 3-hydroxyflavone and also exhibits excited-state proton transfer, which, as well as in the case of 3-hydroxyflavone, has a kinetic nature. The fluorescence spectra are studied upon excitation by photons of various energies, and the excitation spectra are recorded at wavelengths of different fluorescence bands. It is found that the intensity ratio of the emission of the normal and tautomeric forms (at wavelength of 415 and 518 nm, respectively) is almost the same (0.23–0.25) for excitation in the regions of the main and the second absorption bands. At the same time, in the case of excitation between these bands, this ratio decreases to 0.19. The second interesting feature is the existence of a third latent emission band peaked at about 480 nm, which is reliably detected upon excitation at wavelengths in the region of 400–450 nm. This study shows that this emission belongs to the anionic form of the dye. This form is also responsible for a decrease in the intensity ratio of the emission of the two main forms in the case of excitation between the first and second absorption bands.     

Fine-structure spectra of metal complexes of porphin in tetrahydrofuran at low temperatures: Manifestation of nonplanarity effects

The fine-structure fluorescence spectra of Mg and Zn porphins in solid tetrahydrofuran matrices at the liquid helium temperature are recorded for the first time. The fluorescence spectra of Mg porphin molecules deposited from the gas phase on a sapphire substrate simultaneously with tetrahydrofuran molecules are measured. Based on the data obtained from the fluorescence and fluorescence excitation spectra, it is ascertained that there are two noninteracting spectrally different long-and short-wavelength forms of metal complexes of porphins in the ground state. In the case of Mg porphin, the spectral gap for these two forms at 4.2 K amounts to 330 cm^?1. The short-wavelength form is attributed to the nonplanar saddle conformation of a porphin molecule, while the long-wavelength form is associated with the nonplanar domed conformation, in which the central metal ion is displaced out of the plane of the porphyrin ligand. The fine-structure fluorescence spectra of both forms of Mg and Zn porphins are measured in tetrahydrofuran at 4.2 K upon selective laser excitation. The frequencies of the normal vibrations in the ground electronic state are determined and the reasons for the differences in the vibrational frequencies of the forms are discussed.     

Application of the method of selective fluorescence excitation to investigation of complexation and solvation processes of polar organic dye molecules in binary solvents

It is proposed to use the method of selective fluorescence excitation to find absorption spectra (fluorescence excitation spectra) of 1 : 1 primary solvated complexes between polar molecules of an organic dye and the active component of a binary solvent, whose neutral component is a nonpolar or low-polarity liquid. The technique was tested with diluted solutions of 4-dimethylaminochalcone (4-DMC) in mixtures of ethylbenzene with dimethyl formamide at extremely low contents of the latter. It is shown that the experimental absolute shift of the long-wavelength vibronic absorption band of three-component DMC solutions is in a good quantitative agreement with the analogous shift obtained independently based on the semi-empirical theory describing the joint effect of nonlinear (complexation) and linear (solvation) dipole-dipole interactions on the shift of spectral bands.     

Temporal characteristics of the fluorescence of the anionic form of 3-hydroxyflavone

The spectral and temporal characteristics of the fluorescence of the anionic form of 3-hydroxyflavone in acetonitrile are studied. This form can be selected upon excitation in the region from 380 to 440 nm with the maximum near 420 nm. The fluorescence spectrum of this form has the shape of a wide structureless band peaked at about 470 nm. The lifetimes of the fluorescence of the anionic form in the region from 460 to 530 nm are measured; the average lifetimes do not depend on the recording wavelength in the entire region and are equal to 3.7 ± 0.2 ns. Addition of water to the solution leads to a gradual quenching of the fluorescence and its complete vanishing at a concentration of 10 M. This is a static quenching or quenching of the first kind according to Vavilov’s classification; i.e., it occurs in the ground state.     

Spectral Properties of Thioflavin T and Its Complexes with Amyloid Fibrils

Comparative analysis of the absorption and fluorescence spectra and fluorescence excitation spectra of thioflavin T (ThT) in various solvents and in the composition of amyloid fibrils has shown that ThT, when excited in the region of the long-wavelength absorption band, fluoresces in the spectral region with a maximum at 478–484 nm. The appearance in aqueous and alcohol solutions of a fluorescence band with a maximum near 440 nm has been attributed to the presence in the composition of the ThT preparations of an impurity with an absorption band in the 340–350-nm range. The literature data showing that in glycerol ThT has a wide fluorescence spectrum with two maxima are due to the artifact connected with the use of a high concentration of the dye. It has been suggested that the cause of the low quantum yield of ThT aqueous and alcohol solutions is the breakage of the system of conjugated bonds due to the reorientation of the benzothiozole and benzaminic rings of ThT in the excited state with respect to one another. The main factor determining the high quantum yield of fluorescence of ThT incorporated in fibrils is the steric restriction of the rotation of the rings about one another under these conditions. The suggestions made have been verified by the quantum-chemical calculation of the ThT molecule geometry in the ground and excited states.     

Investigations of spectral and luminescent properties of neutral and ionic phenol and <Emphasis Type="Italic">PARA</Emphasis>-chlorophenol forms in aqueous micellar solutions

Special features of the absorption and fluorescence spectra of phenols (phenol and para-chlorophenol) in alkalized and acidified aqueous-micellar solutions are studied. It is established that the absorption band of the anionic phenol form is formed in aqueous-alkali media in the presence of ionogenic surfactants. The fluorescence intensity of the anionic phenol form solubilized in micelles is higher than that in water.__________Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 11, pp. 76–80, November, 2004.     

Particular features of fluorescence of jet-cooled vapor of 2,3-diazabicyclooctene

The fluorescence and fluorescence excitation spectra of azocompound, 2,3-diazabicyclo[2.2.2]oct-2-ene, have been studied using jet cooling. The violation of the mirror symmetry between the fluorescence and fluorescence excitation spectra due to an intense long-wavelength emission that manifests itself in solutions and in the gas phase cannot be eliminated even by jet cooling. It has been revealed that the bands of pure electronic and vibronic transitions are split by 0.55 cm^?1, which is caused by tunneling with accompanying emission from an intermediate short-lived state and which may be the reason for the violation of the mirror symmetry of the spectra upon tunnel inversion.     

Effects of long-wavelength fluorescence excitation in N, N′-dimethylaminobenzonitrile liquid solutions

We have studied the properties of the emission, absorption, and excitation of dual fluorescence of N,N??-dimethylaminobenzonitrile in a set of solvents of different polarity under selective irradiation of solutions by light with different energies of quanta in the range of the long-wavelength absorption band. In all cases, dual fluorescence is observed, which is caused by emission from locally excited Franck-Condon and charge-transfer states. A change in the energy of excitation quanta has no effect on the position of the fluorescence bands; however, the intensity ratio between the bands noticeably changes in favor of the intensity of the long-wavelength band, which belongs to the charge-transfer state. To explain the observed effects, we involve data of quantum-mechanical calculations, which show that there is a considerable probability of occurrence in solutions of these systems of rotational isomers that differ in the orientation of the dimethylamino group with respect to benzonitrile. In the excited state, these rotamers have different charge-transfer reaction rates, which leads to a change in the intensity ratio of the observed fluorescence bands upon using the selective excitation.     

Modulation of charge transfer rate in (N,N′-dimethylamino)benzonitrile liquid solutions

We studied the properties of the emission, absorption and excitation of dual fluorescence of (N,N′?dimethylamino)benzonitrile in a polar aprotic solvent acetonitrile under selective irradiation of solutions by light with different energies of quanta to elucidate mechanisms of dual fluorescence arising in this solvent at different temperatures in the range 274–313 K. In all cases, dual fluorescence of the solute in acetonitrile was observed, which is caused by emission from locally excited Franck-Condon and charge-transfer states. A change in the energy of excitation quanta has a weak effect on the position of the fluorescence bands; however, the intensity ratio between the bands noticeably changes in favour of the intensity of the long-wavelength band at excitation in the range of the long-wavelength absorption band. An interesting and unusual fact is that solution heating is accompanied by essential growth of quantum yield of dual fluorescence at all wavelengths of the excitation. To explain the observed effects, the same dependences were measured and analysed for DMABN in neutral solvent n-hexane in the same conditions. We involve also the data of quantum-mechanical calculations, which show that there is a considerable probability of occurrence in solutions of DMABN rotational isomers with differing orientation of the dimethylamino group with respect to the benzonitrile. In the excited state, these have different charge-transfer rates, resulting in a modulation in the intensity ratio of the observed fluorescence bands with change excitation energy quanta on the red wing of the absorption band, doi: 10.1134/S0030400X12050219.     

Electronic spectra of cationic forms of meso-tetrapropylporphin in a nanoporous silicate gel matrix

We have studied the fluorescence and fluorescence excitation spectra at 300 K, 77 K, and 4.2 K for silicate gel matrices colored with meso-tetrapropylporphin by impregnation of the matrix with a solution of the pigment. Comparison of the data obtained with the absorption spectra in acidified solutions and analysis of the low-temperature fine-structure vibronic spectra, and also taking into account data obtained earlier for octaethylporphin in a xerogel showed formation of two cationic forms of meso-tetrapropylporphin in the gel matrix: the short-wavelength form has a dicationic structure, while the long-wavelength form has a monocationic structure. We have traced out the correlations of the vibrational structure in the spectra of the dicationic form with data for the porphin dication, and we have drawn a number of conclusions concerning the normal vibrational modes that are active in the vibronic fluorescence and absorption spectra of the studied cationic forms. Using the AM1 semiempirical quantum chemical method, we optimized the geometry of the mesotetrapropylporphin dication: the most stable of the possible conformers is the dication structure with saddleshaped macrocycle nonplanarity. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 73, No. 4, pp. 453–461, July–August, 2006.     

Luminescence of fluctuation tails of disordered solid solutions

The form of the stationary luminescence spectra of excitons, localized by composition fluctuations, in disordered solid solutions under weak excitation is calculated. The tail states for which there are no nonradiative transition channels are distinguished by means of continuum percolation theory. Such states are responsible for the “zero-phonon” luminescence band. The shape of the short-wavelength luminescence band edge is determined mainly by the number of isolated localizing clusters and their smallest complexes, which decreases rapidly near the mobility threshold. The real luminescence spectrum is due to the simultaneous emission of phonons. The phonon emission determines the form of the long-wavelength wing of the emission band. The computed shape of the emission spectrum is compared with the experimental luminescence spectra of the solid solution CdS_(1−c)Se_c. Pis’ma Zh. éksp. Teor. Fiz. 65, No. 3, 274–279 (10 February 1997)     

Direct observation of proton transfer from the excited <Emphasis Type="Italic">S</Emphasis><Subscript>2</Subscript> state in the 3-hydroxyflavone molecule

The spectra of dual fluorescence of 3-hydroxyflavone molecules excited by 44-ps pulses in the region of the S ₁ and S ₂ absorption bands are measured with a picosecond resolution. The dynamics of the spectra directly demonstrates the time development of the proton transfer from the carboxyl to the carbonyl group of the molecule. Upon excitation into the main absorption band, the transfer process occurs for about 210 ps. The excitation into the region of the S ₂ band results in a faster (～170 ps) process, and the relative contribution made to the total spectrum by the long-wavelength band, which belongs to the proton-transfer state, is higher in this case for all the time ranges of luminescence recording. The data obtained directly point to an additional channel of proton transfer via the S ₂ state. The probability of this process is estimated to be 0.84 × 10¹² s^?1.     

LASER FLUORESCENCE SPECTROSCOPY AS A METHOD FOR STUDYING HUMIC SUBSTANCE

This paper summarizes the results obtained by fluorescence spectroscopic techniques with conventional and laser light sources for the characterization of the spectral luminescent properties of aquatic humic substances (AHS). The band profiles of corrected absorption, fluorescence emission, and fluorescence excitation spectra are compared in graphical form with unique functions used for the axes. In order to calculate the quantum efficiency of fluorescence, we used the Raman signal from water molecules as an internal reference. The temperature dependence of the fluorescence spectra of humic matter has been recorded in solid (?160°C to 0°C) and in liquid (0°C to +300°C) aqueous solutions. The behavior of the fluorescence band shape is discussed. A new method of nonlinear fluorimetry is proposed to enhance the capabilities of fluorescence spectroscopy. This method is based on the fluorescence saturation effect manifesting itself under powerful laser pumping (excitation) conditions. The use of the technique allows one to determine certain photophysical properties of molecules, as a complement to the normal spectral data. Using three different samples of aquatic humic substances with very similar fluorescence band shapes, it is demonstrated that these compounds have distinct molecular luminescent parameters and therefore, can be identified. The similarity of the fluorescence band shapes of humic substances in natural water of different types; the absence of any noticeable effect of temperature across a wide range and the fluorescence saturation on the fluorescence band contour can be explained. This assumes that in all of the samples of aquatic humic substances studied, with different molecular weight fractions, that there is a single dominant fluorescent functionality present.     

Separation of a weak fluorescence signal of 3-hydroxyflavone using dynamic quenching

The spectral and time characteristics of the dual fluorescence of a 3-hydroxyflavone probe in a solution with a fluorescence quencher are studied in the temperature range of 20–80°C. At room temperature, the fluorescence consists of two bands that belong to the normal and tautomeric forms of the luminophore, while heating of the solution results in the appearance of an additional fluorescence band belonging to the anionic form of the luminophore. The additional band is strongly overlapped with the band of the normal form, and its intensity rapidly increases with temperature to exceed the intensity of the normal band. The introduction of the TEMPO spin quencher of excited states into the solution completely quenches the fluorescence of the anionic form, which allows one to record the pure dual fluorescence of 3-hydroxyflavone in the entire temperature range studied. The detection of probe signals in the pure form is important for applications of proton transfer molecular probes using the intensity ratio of the fluorescence bands as the main sensitive parameter.