Effect of Dimer Structure and Inhomogeneous Broadening of Energy Levels on the Action of Flavomononucleotide in Rigid Polyvinyl Alcohol Films.

The results of time-resolved fluorescence measurements of flavin mononucleotide (FMN) in rigid polyvinyl alcohol films (PVA) demonstrate that fluorescence intensity decays are strongly accelerated in the presence of fluorescent dimers and nonradiative energy transfer processes. The fluorescence decay originating both from H and J dimer states of FMN was experimentally observed for the first time. The mean fluorescence lifetimes for FMN dimers were obtained: τfl = 2.66 ns (at λexc = 445 nm) and τfl = 2.02 (at λexc = 487 nm) at λobs = 600 nm and T = 253 K from H and J state of dimers, respectively. We show that inhomogeneous orientational broadening of energy levels (IOBEL) affects the shape of the fluorescence decay and leads to the dependence of the average monomer fluorescence lifetime on excitation wavelength. IOBEL affected the nonradiative energy transfer and indicated that different flavin positioning in the protein pocket could (1) change the spectroscopic properties of flavins due to the existence of "blue" and "red" fluorescence centers, and (2) diminish the effectiveness of energy transfer between FMN molecules.

On the nature of uncoupled chlorophylls in the extremophilic photosystem I-light harvesting I supercomplex.

Photosystem I core-light-harvesting antenna supercomplexes (PSI-LHCI) were isolated from the extremophilic red alga Cyanidioschyzon merolae and studied by three fluorescence techniques in order to characterize chlorophylls (Chls) energetically uncoupled from the PSI reaction center (RC). Such Chls are observed in virtually all optical experiments of any PSI core and PSI-LHCI supercomplex preparations across various species and may influence the operation of PSI-based solar cells and other biohybrid systems. However, the nature of the uncoupled Chls (uChls) has never been explored deeply before. In this work, the amount of uChls was controlled by stirring the solution of C. merolae PSI-LHCI supercomplex samples at elevated temperature (~303 K) and was found to increase from <2% in control samples up to 47% in solutions stirred for 3.5 h. The fluorescence spectrum of uChls was found to be blue-shifted by ~20 nm (to ~680 nm) relative to the fluorescence band from Chls that are well coupled to PSI RC. This effect indicates that mechanical stirring leads to disappearance of some red Chls (emitting at above ~700 nm) that are present in the intact LHCI antenna associated with the PSI core. Comparative diffusion studies of control and stirred samples by fluorescence correlation spectroscopy together with biochemical analysis by SDS-PAGE and BN-PAGE indicate that energetically uncoupled Lhcr subunits are likely to be still physically attached to the PSI core, albeit with altered three-dimensional organization due to the mechanical stress.

Remodeling of excitation energy transfer in extremophilic red algal PSI-LHCI complex during light adaptation.

Photosynthetic PSI-LHCI complexes from an extremophilic red alga C. merolae grown under varying light regimes are characterized by decreasing size of LHCI antenna with increasing illumination intensity [1]. In this study we applied time-resolved fluorescence spectroscopy to characterize the kinetics of energy transfer processes in three types of PSI-LHCI supercomplexes isolated from the low (LL), medium (ML) and extreme high light (EHL) conditions. We show that the average rate of fluorescence decay is not correlated with the size of LHCI antenna and is twice faster in complexes isolated from ML-grown cells (~25-30 ps) than from both LL- and EHL-exposed cells (~50-55 ps). The difference is mainly due to a contribution of a long ~100-ps decay component detected only for the latter two PSI samples. We propose that the lack of this phase in ML complexes is caused by perfect coupling of this antenna to PSI core and lack of low-energy chlorophylls in LHCI. On the other hand, the presence of the slow, ~100-ps, fluorescence decay component in LL and EHL complexes may be due to the weak coupling between PSI core and LHCI antenna complex, and due to the presence of particularly low-energy or red chlorophylls in LHCI. Our study has revealed the remarkable functional flexibility of light harvesting strategies that have evolved in the extremophilic red algae in response to harsh or limiting light conditions involving accumulation of low energy chlorophylls that exert two distinct functions: as energy traps or as far-red absorbing light harvesting antenna, respectively.

Understanding the Effect of Different Synthesis Conditions on the Physicochemical Properties of Mixed-Ion Perovskite Solar Cells.

Perovskite solar cells, composed of a mixture of methylammonium (MA) and formamidinium (FA) cations [in the benchmark proportions of (FAPbI3 )0.85 (MAPbBr3 )0.15 ] and titania as an electron-accepting material, are prepared under different conditions, with the objective of finding correlations between the solar cell performance and several important stationary and dynamical parameters of the material. The effects of humidity, oxygen, the use of anti-solvent, and the presence and quality of a mesoporous titania layer are investigated. It is found that an increase in the photocurrent corresponds to a higher content of the desired cubic perovskite phase and to increased long-wavelength absorption of the sample. On the contrary, for poorer-quality cells, additional short-wavelength bands in both absorption and emission spectra are present. Furthermore, a higher photocurrent of the cells is correlated with faster interfacial charge-transfer dynamics. For the highest photocurrent of >20 mA cm-2 , the characteristic times of about 1 µs are observed by electrochemical impedance spectroscopy, and emission half-lifetimes of about 6 ns by time-resolved fluorescence spectroscopy (upon excitation with 420 nm pulses of ≈0.5 mW power). Both first- and second-order rate constants, extracted from the emission measurements, are greater for the cells showing higher photocurrents, probably owing to a more rapid charge injection.

Comparison of charge transfer dynamics in polypyridyl ruthenium sensitizers for solar cells and water splitting systems.

Standard ruthenium components of dye-sensitized solar cells (sensitizer N719) and dye-sensitized photoelectrochemical cells (sensitizer RuP and water oxidation catalyst RuOEC) are investigated in the same solar cell configuration to compare their photodynamics and charge separation efficiency. The samples are studied on time scales from femtoseconds to seconds by means of transient absorption, time-resolved emission and electrochemical impedance measurements. RuP shows significantly slower electron injection into a mesoporous titania electrode and enhanced fast (sub-ns) electron recombination with respect to those of N719. Moreover, RuOEC is found to be responsible for partial light absorption and electron injection with low efficiency. The obtained results reveal new insights into the reasons for the lower charge separation efficiency in water splitting systems with respect to that in solar cells. The important role of the initial processes occurring at the dye-titania interface within the first nanoseconds in this efficiency is emphasized.

Differences in photoinduced optical transients in perovskite absorbers for solar cells.

Methylammonium lead iodide films and powdered crystals were studied by time-resolved absorption and emission spectroscopy on the time scales from femtoseconds to nanoseconds. Strikingly different transient absorption signals were observed, changing from strong long-wavelength band-edge bleach to weak signatures of band-shift, which depended on the absorber form (films or polycrystals) and preparation method (stoichiometric or non-stoichiometric). The observed differences were correlated with the variation in absorption and emission spectra, changes in photo-induced carrier lifetimes and solar cell efficiency. These differences also pointed out that similar perovskite absorbers can provide significantly different transient responses and emphasize that special care must be taken when interpolating the obtained findings to the processes occurring in the most efficient devices.

Electron transfer in silicon-bridged adjacent chromophores: the source for blue-green emission.

Si-Bridged chromophores have been proposed as sources for blue-green emission in several technological applications. The origin of this dual emission is to be found in an internal charge transfer reaction. The current work is an attempt to describe the details of these processes in these kinds of substances, and to design a molecular architecture to improve their performance. Nuclear motions essential for intramolecular charge transfer (ICT) can involve processes from twisted internal moieties to dielectric relaxation of the solvent. To address these issues, we studied ICT between adjacent chromophores in a molecular compound containing N-isopropylcarbazole (CBL) and 1,4-divinylbenzene (DVB) linked by a dimethylsilylene bridge. In nonpolar solvents emission arises from the local excited state (LE) of carbazole whereas in solvents of higher polarity dual emission was detected (LE + ICT). The CT character of the additional emission band was concluded from the linear dependence of the fluorescence maxima on solvent polarity. Electron transfer from CBL to DVB resulted in a large excited-state dipole moment (37.3 D) as determined from a solvatochromic plot and DFT calculations. Steady-state and picosecond time-resolved fluorescence experiments in butyronitrile (293-173 K) showed that the ICT excited state arises from the LE state of carbazole. These results were analyzed and found to be in accordance with an adiabatic version of Marcus theory including solvent relaxation.

Determination of Interfacial Charge-Transfer Rate Constants in Perovskite Solar Cells.

A simple protocol to study the dynamics of charge transfer to selective contacts in perovskite solar cells, based on time-resolved laser spectroscopy studies, in which the effect of bimolecular electron-hole recombination has been eliminated, is proposed. Through the proposed procedure, the interfacial charge-transfer rate constants from methylammonium lead iodide perovskite to different contact materials can be determined. Hole transfer is faster for CuSCN (rate constant 0.20 ns(-1) ) than that for 2,2',7,7'-tetrakis-(N,N-di-4-methoxyphenylamino)-9,9'-spirobifluorene (spiro-OMeTAD; 0.06 ns(-1) ), and electron transfer is faster for mesoporous (0.11 ns(-1) ) than that for compact (0.02 ns(-1) ) TiO2 layers. Despite more rapid charge separation, the photovoltaic performance of CuSCN cells is worse than that of spiro-OMeTAD cells; this is explained by faster charge recombination in CuSCN cells, as revealed by impedance spectroscopy. The proposed direction of studies should be one of the key strategies to explore efficient hole-selective contacts as an alternative to spiro-OMeTAD.

Weak temperature dependence of P (+) H A (-) recombination in mutant Rhodobacter sphaeroides reaction centers.

In contrast with findings on the wild-type Rhodobacter sphaeroides reaction center, biexponential P (+) H A (-)  â†’ PH A charge recombination is shown to be weakly dependent on temperature between 78 and 298 K in three variants with single amino acids exchanged in the vicinity of primary electron acceptors. These mutated reaction centers have diverse overall kinetics of charge recombination, spanning an average lifetime from ~2 to ~20 ns. Despite these differences a protein relaxation model applied previously to wild-type reaction centers was successfully used to relate the observed kinetics to the temporal evolution of the free energy level of the state P (+) H A (-) relative to P (+) B A (-) . We conclude that the observed variety in the kinetics of charge recombination, together with their weak temperature dependence, is caused by a combination of factors that are each affected to a different extent by the point mutations in a particular mutant complex. These are as follows: (1) the initial free energy gap between the states P (+) B A (-) and P (+) H A (-) , (2) the intrinsic rate of P (+) B A (-)  â†’ PB A charge recombination, and (3) the rate of protein relaxation in response to the appearance of the charge separated states. In the case of a mutant which displays rapid P (+) H A (-) recombination (ELL), most of this recombination occurs in an unrelaxed protein in which P (+) B A (-) and P (+) H A (-) are almost isoenergetic. In contrast, in a mutant in which P (+) H A (-) recombination is relatively slow (GML), most of the recombination occurs in a relaxed protein in which P (+) H A (-) is much lower in energy than P (+) H A (-) . The weak temperature dependence in the ELL reaction center and a YLH mutant was modeled in two ways: (1) by assuming that the initial P (+) B A (-) and P (+) H A (-) states in an unrelaxed protein are isoenergetic, whereas the final free energy gap between these states following the protein relaxation is large (~250 meV or more), independent of temperature and (2) by assuming that the initial and final free energy gaps between P (+) B A (-) and P (+) H A (-) are moderate and temperature dependent. In the case of the GML mutant, it was concluded that the free energy gap between P (+) B A (-) and P (+) H A (-) is large at all times.

Study of photophysical properties of 5-deazaalloxazine and 1,3-dimethyl-5-deazaalloxazine in dependence of pH using different spectral techniques.

The photophysical properties of 5-deazaalloxazine and 1,3-dimethyl-5-deazalloxazine at different pH values were characterized using absorption spectra, fluorescence emission spectra, fluorescence excitation spectra, synchronous fluorescence spectra and total fluorescence spectra. Their ionised and/or neutral forms were discussed in comparison with those obtained for other derivatives of 5-deazaalloxazine and/or 5-deazaisoalloxazine. Steady-state and time-resolved techniques were used to study the protonation/deprotonation equilibria between cationic and neutral forms of both compounds and between neutral and monoanionic forms of 5-deazalloxazine, as well as between monoanionic forms of this compound and its dianion. We estimated pKa values for these equilibria both in the ground and excited states. Our steady-state and time-resolved measurements indicate that the cation of 5-deazaalloxazine in its isoalloxazinic form exhibits fluorescence that is quenched by protons in a dynamic process. Contrary to that, the cation of 1,3-dimethyl-5-deazaalloxazine has almost no fluorescence. Additionally, we found that the neutral forms of 5-deazalloxazine and 1,3-methyl-5-deazalloxazine are also quenched in acidic conditions by protons. In basic conditions, 5-deazaalloxazine forms two structurally different anions, namely the alloxazinic monoanion and the isoalloxazinic monoanion; both simultaneously dissociate into the isoalloxazinic dianion at even higher pH values. The synchronous fluorescence spectra and total fluorescence spectra demonstrated their suitability to characterize and differentiate different fluorescent forms of 5-deazalloxazine, namely: the cation, the neutral form, two monoanions, and the dianion, in a wide pH range.

Monte Carlo simulations of excitation and electron transfer in grana membranes.

Time-resolved fluorescence measurements on grana membranes with instrumental response function of 3 ps reveal faster excitation dynamics (120 ps) than those reported previously. A possible reason for the faster decay may be a relatively low amount of "extra" LHCII trimers per reaction center of Photosystem II. Monte Carlo modeling of excitation dynamics in C2S2M2 form of PSII-LHCII supercomplexes has been performed using a coarse grained model of this complex, constituting a large majority of proteins in grana membranes. The main factor responsible for the fast fluorescence decay reported in this work was the deep trap constituted by the primary charge separated state in the reaction center (950-1090 cm(-1)). This value is critical for a good fit, whereas typical hopping times between antenna polypeptides (from ~4.5 to ~10.5 ps) and reversible primary charge separation times (from ~4 to ~1.5 ps, respectively) are less critical. Consequently, respective mean migration times of excitation from anywhere in the PSII-LHCII supercomplexes to reaction center range from ~30 to ~80 ps. Thus 1/4-2/3 of the ~120-ps average excitation lifetime is necessary for the diffusion of excitation to reaction center, whereas the remaining time is due to the bottle-neck effect of the trap. Removal of 27% of the Lhcb6 apoprotein pool by mutagenesis of DEG5 gene caused the acceleration of the excitation decay from ~120 to ~100 ps. This effect may be due to the detachment of LHCII-M trimers from PSII-LHCII supercomplexes, accompanied by deepening of the reaction center trap.

Comparison of TiO2 and ZnO solar cells sensitized with an indoline dye: time-resolved laser spectroscopy studies of partial charge separation processes.

Time-resolved laser spectroscopy techniques in the time range from femtoseconds to seconds were applied to investigate the charge separation processes in complete dye-sensitized solar cells (DSC) made with iodide/iodine liquid electrolyte and indoline dye D149 interacting with TiO2 or ZnO nanoparticles. The aim of the studies was to explain the differences in the photocurrents of the cells (3-4 times higher for TiO2 than for ZnO ones). Electrochemical impedance spectroscopy and nanosecond flash photolysis studies revealed that the better performance of TiO2 samples is not due to the charge collection and dye regeneration processes. Femtosecond transient absorption results indicated that after first 100 ps the number of photoinduced electrons in the semiconductor is 3 times higher for TiO2 than for ZnO solar cells. Picosecond emission studies showed that the lifetime of the D149 excited state is about 3 times longer for ZnO than for TiO2 samples. Therefore, the results indicate that lower performance of ZnO solar cells is likely due to slower electron injection. The studies show how to correlate the laser spectroscopy methodology with global parameters of the solar cells and should help in better understanding of the behavior of alternative materials for porous electrodes for DSC and related devices.

Photochromic cycle of 2'-hydroxyacetophenone azine studied by absorption and emission spectroscopy in different solvents.

This paper reports on the investigations of the synthesized di-(o-hydroxyaryl ketoimine) compound by the steady state absorption and emission techniques as well as picosecond time resolved emission and femtosecond transient absorption methods in different solvents. The results of the experimental observation have been supported by the theoretical DFT and TD-DFT calculations. The theoretical data have revealed the completed influence of the environmental polarity on particular conformers of studied compound. Dependencies between the activation rate constant and polarizability function as well as Kamlet-Abbond-Taft hydrogen-bonding parameter have been obtained in different solvent. The mechanism of photodynamic changes of di-(o-hydroxyaryl ketoimine) is presented.

Analysis of the temperature-dependence of P(+)HA(-) charge recombination in the Rhodobacter sphaeroides reaction center suggests nanosecond temperature-independent protein relaxation.

The temperature dependence of charge recombination of the pair P(+)HA(-) in isolated reaction centers from the purple bacterium Rhodobacter sphaeroides with prereduced quinone QA was studied by sub-nanosecond to microsecond time-scale transient absorption. Overall, the kinetics slowed down substantially upon cooling from room temperature to ∼200 K, and then remained virtually unchanged down to 77 K, indicating the coexistence of two competitive pathways of charge recombination, a thermally-activated pathway appearing only above ~200 K and a temperature-independent pathway. In our modelling, the thermally activated pathway includes an uphill electron transfer from HA(-) to BA(-) leading to transient formation of the state P(+)BA(-), whereas the temperature-independent pathway is due to direct downhill electron transfer from HA(-) to P(+). At all temperatures studied, the kinetics could be approximated by a four-component decay. Detailed analysis of the lifetimes and amplitudes of particular phases over the range of temperatures suggests that the kinetically resolved phases reveal the consecutive appearance of three conformational states characterized by an increasing free energy gap between the states P(+)BA(-) and P(+)HA(-). The initial gap between these states was estimated to be only ~8 meV, the intermediate gap being ~92 meV, and the final gap ~135 meV, with no dependence on temperature. It was also calculated through a very straightforward approach that the relaxation process from the initial to the intermediate state occurs within 0.6 ± 0.1 ns, whereas the second step of relaxation from the intermediate to the final state takes 11 ± 2 ns. Both phases of the protein relaxation process are essentially temperature-independent. Possible alternative models to describe the experimental data that cannot be definitely excluded are also discussed.

Dynamics of local Stark effect observed for a complete D149 dye-sensitized solar cell.

A complete, functioning dye-sensitized solar cell made of popular indoline D149 sensitizer is studied by means of transient absorption in visible light in the time scale of nanoseconds to seconds. Photocurrent and photovoltage decays are also measured under the same experimental conditions. A local electric field causing a Stark shift of the D149 absorption band is found to strongly influence the transient spectra and kinetics. The presence of electrons in titania has a major contribution to the Stark shift and the effect disappears over many time scales with an average rate of 5 × 10(3) s(-1). This is much slower than the decay of the oxidized dye (2 × 10(6) s(-1)) but, on the other hand, significantly faster than the decay of electrons in titania nanoparticles (3 × 10(2) s(-1) at standard AM1.5 irradiation and open circuit conditions). Possible explanations of this phenomenon are discussed. Electron recombination from the titania conduction band to the oxidized dyes proceeds at an average rate of 2-16 × 10(4) s(-1), depending on the excitation energy density, and does not influence the efficiency of dye regeneration.

The influence of temperature on C153 steady-state absorption and fluorescence kinetics in hydrogen bonding solvents.

In a recent paper (J Fluoresc (2011) 21:1547-1557) a temperature induced modulation of Coumarin 153 (C153) fluorescence lifetime and quantum yield for the probe dissolved in the polar, nonspecifically interacting 1-chloropropane was reported. This modulation was also observed in temperature dependencies of the radiative and nonradiative rates. Here, we show that the modulation is also observed in another 1-chloroalkane-1-chlorohexane, as well as in hydrogen bonding propionitrile, ethanol and trifluoroethanol. Change in the equilibrium distance between S (0) an S (1) potential energies surfaces was identified as the source of this modulation. This change is driven by temperature changes. It leads to a modulation of the fluorescence transition dipole moment and it is the primary source of the experimental effects observed. Additionally, we have found that proticity of the solvent induces a rise in the fluorescence transition dipole moment, which leads to a shortening of the fluorescence lifetime. Hydrogen bonds are formed by C153 also with hydrogen accepting solvents like propionitrile. We show that while such bonds do not affect the transition probability, they do change the S(0) an S(1) energy gap which in turn implies a change in non-radiative transition rate in a similar way as in protic solvents, as well as in the fluorescence spectrum position. Finally, the influence of temperature on the energies of hydrogen bonds formed by C153 when acting as hydrogen donor or acceptor is reported.

Influence of pH on photophysical properties of (E)-1-(4-chlorobenzyl)-4-(4-hydroxystyryl)pyridinium chloride.

The protonation/deprotonation equilibrium was investigated for N-p-chlorobenzyl-substituted (E)-4'-hydroxy stilbazolium halide, namely (E)-1-(4-chlorobenzyl)-4-(4-hydroxystyryl)pyridinium chloride (EPC). Absorption, emission and synchronous scanning spectra were used to explain the observed phenomena. The excited state lifetimes of the protonated and deprotonated forms of EPC were measured and discussed. Absorption spectra were used to determine its pK(a) value in the ground state. We conclude that the protonation/deprotonation equilibrium is not attained in the first excited state of EPC, for kinetic reasons. The quinoid and benzenoid structures of EPC in the ground and excited state are discussed in acidic and basic range of pH. Aqueous solutions of EPC were yellow at pH < 7 and red at pH > 7, and addition of alcohols (methanol or 2-propanol) enhanced this change. Therefore, quaternary stilbazolium salts were investigated for application as acid-base indicators.

Acid-base equilibriums of lumichrome and its 1-methyl, 3-methyl, and 1,3-dimethyl derivatives.

Lumichrome photophysical properties at different pH were characterized by UV-vis spectroscopy and steady-state and time-resolved fluorescence techniques, in four forms of protonation/deprotonation: neutral form, two monoanions, and dianion. The excited-state lifetimes of these forms of lumichrome were measured and discussed. The results were compared to those obtained for similar forms of alloxazine and/or isoalloxazine, and also to those of 1-methyl- and 3-methyllumichrome and 1,3-dimethyllumichrome. The absorption, emission, and synchronous spectra of lumichrome, 1-methyl- and 3-methyllumichrome, and 1,3-dimethyllumichrome at different pH were measured and used in discussion of fluorescence of neutral and deprotonated forms of lumichrome. The analysis of steady-state and time-resolved spectra and the DFT calculations both predict that the N(1) monoanion and the N(1,3) dianion of lumichrome have predominantly isoalloxazinic structures. Additionally, we confirmed that neutral lumichrome exists in its alloxazinic form only, in both the ground and the excited state. We also confirmed the existence and the alloxazinic structure of a second N(3) monoanion. The estimated values of pK(a) = 8.2 are for the equilibrium between neutral lumichrome and alloxazinic and isoalloxazinic monoanions, with proton dissociation from N(1)-H and N(3)-H groups proceeding at the almost the same pH, while the second value pK(a) = 11.4 refers to the formation of the isoalloxazinic dianion in the ground state.

Temperature influence on 4-aminophthalimide emission in 1-chloroalkanes plus water mixtures.

Thermochromic emission shifts of 4-aminophthalimide (4-AP) dissolved in three 1-chloroalkanes, namely, 1-chloropropane, 1-chlorobutane, and 1-chlorohexane, together with fluorescence decays measured at different wavelengths, all solvents containing different small amounts of water (10(-4)-10(-2) M), are reported in a broad temperature range covering the bulk water melting point. Our studies have shown that 4-AP is an effective indicator of water presence even at concentrations given by solvent suppliers for so-called "dry" solvents. Additionally, indications of water ice-clusters formation in 1-chloroalkanes, starting at different temperatures depending on water concentration, have been found. Finally, 4-AP in 1-chloroalkane + water mixture is shown to present at different temperatures three basic types of sources of time-resolved emission spectra (TRES) time/spectral evolution: emission of two kinetically coupled species, solvent relaxation, and simultaneous emission of two independent species.

Influence of water on photophysical properties of N-bromobenzyl- or nitrobenzyl derivatives of substituted 4-hydroxystilbazolium hemicyanines.

Absorption, steady-state and timed-resolved fluorescence spectra of nine N-p-bromobenzyl substituted (E)-4'-hydroxy-4-stilbazolium bromides and N-p-bromo- (or nitro-) benzyl substituted (E)-4'-hydroxy-3'methoxy-4-stilbazolium bromides, belonging to the hemicyanine class of compounds, were studied in dry and water-containing polar solvents and in water. All of the studied compounds displayed negative solvatochromism. In solvents with small amounts of water the solutions of each of the compounds change color to red, blue-green or blue, while in extra dry solvents they are all yellow. The new band causing the change in color is interpreted as belonging to the deprotonated form of the respective compound. The absorption and emission spectra of protonated and deprotonated forms of hemicyanines in solvents are presented in comparison with those of selected, isolated deprotonated forms (merocyanines) of the same compounds. The discrimination between the quinoid and zwitterionic deprotonated forms was achieved based on the absorption band location. Time-resolved fluorescence measurements in selected dry and water-containing solvents were also performed.