Solvent and pH Effects on the Fluorescence of 7-(Dimethylamino)-2-Fluorenesulfonate

A novel water-soluble solvatochromic molecule, 7-(dimethylamino)-2-fluorenesulfonate (2,7-DAFS), was prepared by a three-step reaction from 2-nitrofluorene in good overall yield. The pH and solvent effects on the UV-VIS absorption and fluorescence spectra of 2,7-DAFS have been studied. Protonation of the dimethylamino group switches the absorption from intramolecular charge-transfer (ICT) to π → π* transition. The ground state pKa value of 2,7-DAFS was determined as 4.51. The fluorescence spectrum of the excited basic form, *(DAFS), shows a structureless single band with a large Stokes shift, whereas that of the acidic form, *(⁺HDAFS), exhibits a structured band with a small Stokes shift. The emission intensities of the basic and acidic forms versus pH/Ho plots show stretched sigmoidal curves and indicate that (1) the rate of deprotonation of *(⁺HDAFS) is comparable to the fluorescence decay of the species, and (2) the efficient proton-induced quenching of *(DAFS) fluorescence occurs. The pKa* was estimated as −1.7 from the fluorescence titration curve. The fluorescence maximum of *(DAFS) is blue-shifted as the polarity of solvent decreases. However, no clear dependency of the emission intensity and spectral half width, and thus fluorescence quantum yield, on the solvent polarity was revealed. It appears that the fluorescence sensitivity of 2,7-DAFS is 15 ∼ 25 times greater than the sensitivity of a widely utilized fluorescent probe, 5-(dimethylamino)-1-naphthalenesulfonate. This higher sensitivity, together with the ease of derivatization, would provide the fluorene-based fluorescent molecules significant advantages for a variety of applications.     

Solvatochromic and Fluorescence Behavior of Sulfisoxazole

The Fluorescence spectroscopic and solvatochromic behavior of Sulfisoxazole, a sulfa drug with antimicrobial activities, in various pure solvents of different polarity and hydrogen bonding capability is reported. The fluorescence emission spectrum of sulfisoxazole was found to be solvent polarity dependent, where a notable red shift in emission maximum was observed with increasing solvent polarity as well as hydrogen bonding capability. The effects of the latter two solvent parameters were quantitatively investigated using the methods of Lippert–Mataga and solvatochromic comparison method (SCM) that is based on the Kamlet-Taft equation. Particularly, the Lippert–Mataga method was applied to estimate the dipole moment of the excited state (μ_e) upon plotting Stokes shift versus solvent polarizability (Δf), where a value of 11.54 Debye was obtained. On the other hand, applying the multiple regression analysis to the SCM method revealed that solvent polarizability (π*) and hydrogen-bond donor capability (α) approximately equally stabilize sulfisoxazole in the excited state with minor destabilization contribution by the hydrogen-bond acceptor capability (β). These findings revealed that the excited state of sulfisoxazole is stabilized by polar solvents, indicating that this drug molecules exhibit larger dipole moment in the excited state than in the ground state, which in turn implies that a potential intramolecular charge transfer (ICT) occurs after excitation.     

The influence of structural relaxation on the fluorescent properties of N-naphthyl-substituted pyridinium cations

N-naphthyl-substituted pyridinium cations fluoresce in liquids at 293 and 77 K and have an unusually large Stokes shift ((9−15)×10³ cm^-1). The Stokes shift is a result of the torsional relaxation of different aromatic groups. Characteristic fluorescence spectra demostrate dependence of the Stokes shift on the solvent viscosity.     

Fluorescent properties of thiochrome in solvents of different polarity

Spectral and fluorescent properties of thiochrome in solvents of different polarity were studied. It was found that the pK_a value of the transition between the cationic and neutral forms of thiochrome in aqueous solutions increased from ∼5.5 to 9.7 upon photoexcitation. It is supposed that protonation takes place in the excited state of the molecule resulting in fluorescence quenching of the thiochrome neutral form in aqueous solutions at neutral pH values. The fluorescence quantum yield of thiochrome increased by ∼2.2 times upon the transition from aqueous solutions to alcohols or polar aprotic solvents. It was found that an increase of the solvent polarity led to an increase in the Stokes shift from 3200 to 4200 cm⁻¹ for the thiochrome neutral form emission. The change in the dipole moment upon excitation into the S1-state was estimated to be less than 3D.     

Photophysical Characterization of New 3-Amino and 3-Acetamido BODIPY Dyes with Solvent Sensitive Properties

The structural, electronic and photophysical properties of three new asymmetric, highly fluorescent difluoroborondipyrromethene (BODIPY) dyes, bearing an amino or an acetamido group at position 3 of the chromophoric core, have been studied in different apolar, polar and polar/protic solvents. The presence of the 3-amido group extents the delocalization of the π-system, leading to bathochromic shifts in the absorption and fluorescence bands, as predicted by quantum mechanic calculations. The 3-amino dye shows photophysical properties highly dependent on the solvent polarity and acidity, and is characterized by a hypsochromic shift of its absorption band, with regard to the corresponding acetylated dye, as well as a low fluorescence quantum yield in acid media with proton concentration lower than 4 × 10⁻⁴ M. In media with higher proton concentration, the BF₂ bridge group of the 3-amino dye is removed, yielding the corresponding non-fluorescent dipyrromethene precursor. These results suggest that the 3-amino dye could be used as a fluorescence probe for the study of the acidity of different environments.     

Frequency shift and relaxation of muon-spin-precession in Cd1−xMnxTe

Transverse-field muon spin roation (μSR) is studied in Cd_1−xMn_xTe, x=0.4 and 0.6 mixed crystals. A large temperature dependent frequency shift and a strong relaxation of the μSR-signal are observed. In the vicinity of the spinglass transition, the relaxation rate becomes so large that the signal disappears. The rate of Mn spin fluctuations causing the μ⁺-line narrowing at high temperatures is estimated to be of the order of 10⁹ S⁻¹.     

Recent applications of μSR-spectroscopy in solid state physics

A progress report will be presented on recent applications of μSR to problems in metallic systems, i. e. hydrogen (μ⁺) induced lattice relaxation, quantum diffusion, μ⁺-Knight shift anisotropy in bismuth, spin glasses and heavy electron systems. In addition the recent introduction of level crossing techniques into μSR-spectroscopy will be discussed.     

Chain length effect on dynamical structure of poly (vinyl pyrrolidone)-polar solvent mixtures in dilute solution of dioxane studied by microwave dielectric relaxation measurement

Dielectric relaxation study of the binary mixtures of poly(vinyl pyrrolidone) (PVP) (Mw=24000, 40000 and 360000 g mol⁻¹) with ethyl alcohol (EA) and poly(ethylene glycol)s (PEGs) (Mw=200 and 400 g mol⁻¹) in dilute solutions of dioxane were carried out at 10.1 GHz and 35°C. The relaxation time of PVP-EA mixtures was interpreted by the consideration of a wait-and-switch model in the local structure of self-associated ethyl alcohol molecules and also the PVP chain length as a geometric constraint for the reorientational motion of ethyl alcohol molecules. The formation of complexes and effect of PVP chain length on the molecular dynamics, chain flexibility and stretching of PEG molecules in PVP-PEG mixtures were explored from the comparative values of dielectric relaxation time. Further, relaxation time values in dioxane and benzene solvent confirm the viscosity independent molecular dynamics in PVP-EA mixtures but the values vary significantly with the non-polar solvent environment.     

μSR-Study of CeH2.7

Metallic CeH_2.7 shows a sizably increased electronic specific heat of γ=100 mJ/mol·K², compared to γ=0.04 mJ/mol·K² in LaH_2.7 at low tempratures, which could qualify it as another heavy electron system. μSR Knight shift and relaxation studies were started on a powderous CeH_2.7 sample in order to test this possibility further. It is found that the relaxation rate λ_T depends strongly on the applied field strength. These values indicate that the relaxation must be of electronic origin. Strong irreproducibilities at low temperature point to pronounced hysteretic features, which might be related to structural changes. The Knight shift shows a shallow peak around 150 K but no conspicious increase at low temperatures.     

Time‐differential radio‐frequency muon spin resonance (TD‐RFμSR) technique at a pulsed muon beam

Longitudinal‐field μSR methods, e.g., radio‐frequency μ⁺ spin resonance (RFμSR), are well suited to investigate dynamic processes that destroy the phase coherence of the muon spin ensemble. Additional information on relaxation processes of the muon species under investigation is obtained from time‐differential (TD) data acquisition. In this paper we describe the set‐up of a TD‐RFμSR spectrometer installed at the ISIS pulsed muon facility at the Rutherford Appleton Laboratory (RAL, Chilton, UK). As an example, results of TD‐RFμSR measurements on muons in diamagnetic environment μ^d in a boron‐doped silicon sample under illumination at 55 K are presented. This revised version was published online in August 2006 with corrections to the Cover Date.     

Dual-Fluorescence Probe of Environment Basicity (Hydrogen Bond Accepting Ability) Displaying no Sensitivity to Polarity

3-Hydroxyquinolones (3HQs) are a new class of water soluble dual fluorescence probes that can monitor both polarity and basicity (H-bond accepting ability) parameters. Both parameters play an important role in proteins and lipid membranes. Nevertheless, no method exists actually to measure the basicity parameter separately from the polarity. To achieve this aim, we synthesized 2-benzofuryl-3-hydroxy-4(1H)-quinolone (3HQ-Bf) and characterized its photophysical properties by UV, steady-state and time-resolved fluorescence spectroscopy. Due to its extended conjugation and totally planar conformation, 3HQ-Bf is characterized by a high fluorescence quantum yield. In solution, this dye shows an excited state intramolecular proton transfer (ESIPT) reaction resulting in two tautomer bands in the emission spectra. The ESIPT reaction can be considered as irreversible and is governed by rate constants from 0.6 to 8 × 10⁹ s⁻¹, depending on the solvent. The analysis of the spectral properties of 3HQ-Bf in a series of organic solvents revealed a marginal sensitivity to the solvent polarity, but an exquisite sensitivity to solvent basicity, as shown by the linear dependence of the logarithm of the emission bands intensity ratio, log(I_N*/I_T*), as well as the absorption or emission maxima wavenumbers as a function of the solvent basicity parameter. This probe may find useful applications through coupling to a protein ligand, for characterizing the H-bond acceptor ability at the ligand binding site as well as for studying the basicity changes of lipid membranes during their chemo- and thermotropic conversions.     

Solvent Relaxation in Phospholipid Bilayers: Principles and Recent Applications

Although there exist a number of methods, such as NMR, X-ray, e.g., which explore the hydration of phospholipid bilayers, the solvent relaxation (SR) method has the advantage of simple instrumentation, easy data treatment and possibility of measuring fully hydrated samples. The main information gained from SR by the analysis of recorded “time-resolved emission spectra” (TRES) is micro-viscosity and micro-polarity of the dye microenvironment. Based on these parameters, one can draw conclusions about water structure in the bilayer. In this review, we focus on physical background of this method, on all the procedures that are needed in order to obtain relevant parameters, and on the requirements on the fluorescence dyes. Furthermore, a few recent applications (the effect of curvature, binding of antibacterial peptides and phase transition) illustrating the versatility of this method are mentioned. Moreover, limitations and potential problems are discussed.     

Laurdan and Prodan as Polarity-Sensitive Fluorescent Membrane Probes

The steady-state and dynamic fluorescence spectral properties of 2-dimethylamino-6-lauroylnaphthalene (LAURDAN) and several other naphthalene derivatives are summarized to illustrate their sensitivity to the polarity of the environment. Results obtained both in solvents of different polarity and in phospholipid vesicles in two phase states are presented. The emission red shift observed in polar solvents and in the phospholipid liquid–crystalline phase is explained on the basis of dipolar relaxation of solvent molecules surrounding the fluorescent naphthalene moiety of these probes. In phospholipid environments, experimental evidence is shown that excludes the intramolecular relative reorientation of the dimethylamino and carbonyl groups in the naphthalene and the reorientation of the entire fluorescent moiety. The solvent dipolar relaxation observed for LAURDAN and PRODAN in phospholipid bilayers has been attributed to a small number of water molecules present at the membrane interface. A comparison between LAURDAN emission in phospholipid vesicles prepared in D₂O and in H₂O is also presented. The definition and the derivation of the generalized polarization function are also discussed.     

A New Candidate Laser Dye Based 1,4-Bis[β-(2-Naphthothiazolyle)Vinyl]Benzene. Spectroscopic Behavior,Laser Parameters and Excitation Energy Transfer

A new candidate laser dye based 1,4-bis[β-(2-naphthothisolyl) vinyl] benzene (BNTVB) were prepared, and characterized in various organic solvents. The center polarity is less sensitive than electronic absorption. A red shift was noticed in the fluorescence spectra (ca. 40 nm) with increment in the solvent’s polarity, this means that BNTVB’s polarity appreciates upon excitation. The dipole moment of ground state (μ_g) and the excited singlet state dipole moment (μ_e) are determined from Kawski – Chamma and Bakshiev–Viallet equations using the disparity of Stokes shift with solvent polarity function of ε (dielectric constant) and n (refractive index) of the solvent. The result was found to be 0.019D and 5.13D for ground and exited state, in succession. DFT/TD-DFT manners were used to understand the electronic structures and geometric of BNTVB in other solvents. The experimental and theoretical results showed a good agreement. The photochemical quantum yield (Ф_c) of BNTVB was calculated in variable organic reagents such as Dioxane, CHCl₃, EtOH and MeOH at room temperature. The values of φ_c were calculated as 2.3?×?10^?4, 3.3?×?10^?3, 9.7?×?10^?5 and 6.2?×?10^?5 in Dioxane, CHCl₃, EtOH and MeOH, respectively. The dye solutions (2?×?10^?4 M) in DMF, MeOH and EtOH give laser emission in the blue-green region. The green zone is excited by nitrogen pulse 337.1 nm. The tuning range, gain coefficient (α) and cross – section emission (σ_e) of laser were also estimated. Excitation energy transfer from BNTVB to rhodamine-6G (R6G) and N,N-bis(2,6-dimethyphenyl)-3,4:9,10-perylenebis-(dicarboximide) (BDP) was also studied in EtOH to increase the laser emission output from R6G and BDP when excited by nitrogen laser. The dye-transfer power laser system (ETDL) obeys the Foster Power Transmission (FERT) mechanism with a critical transmission distance, R_o of 40 and 32 ? and k_ET equals 2.6?×?10¹³ and 1.06?×?10¹³ M^?1 s^?1 for BNTVB / R6G and BNTVB / BDP pair, respectively.     

Temperature-dependent Time-resolved Fluorescence Study of Cinchonine Alkaloid Dication

Photo induced excited state dynamical processes of cinchonine alkaloid dication (C⁺⁺) have been studied over a wide range of temperature using steady state and nanosecond time-resolved fluorescence spectroscopic techniques. The temperature-dependent fluorescence studies of C⁺⁺ clearly indicate the existence of two distinct emitting species having their own characteristic decay rates. The shorter-lived species shows a usual temperature dependence with increasing non-radiative deactivation at higher temperatures, while the longer-lived species show features resembling to the excited state solvent relaxation process with a large solvent relaxation time (τ _r ∼ 6 ns). The species emitting in the lower energy side, having longer decay time is found to be more sensitive towards chloride ion quenching and has a charge transfer character. Further, concentration quenching with decrease in τ _r of long lived species shows the possibility of energy migration along with solvent relaxation in C⁺⁺.     

Influence of the polarity of a medium on the photonics of a merocyanine dye with a high quadratic polarizability

The influence of the polarity of a medium on the spectral and luminescent properties of 2-[(2E,4E)-6-(1,3,3-trimethyl-2,3-dihydro-1H-2-indolyliden)-2,4-hexadienyliden]malononitrile (THDM) in solutions and polymer matrices is studied at room temperature under conditions of steady-state and pulsed laser excitation. A large bathochromic shift of the absorption spectra observed upon an increase in the polarity of a solvent is caused by a strong increase in the molecular dipole moment μ due to a transition of molecules from the ground state (μ_g = 7.6 D) to an excited Franck-Condon state (μ^FC = 33.5 D). Based on the solvatochromic data, the quadratic polarizability was calculated to be β = (3.2 ± 0.6) × 10^?28 esu, which is close to the experimentally determined value β_ex = (3.9 ± 0.2) × 10^?28 esu. A strong narrowing of the fluorescence spectra in comparison with the absorption spectra is observed upon an increase in the solvent polarity. This narrowing is explained by a decrease in the bond length alternation parameter and by weakening of vibronic interactions in the singlet excited state. The dynamic solvatofluorochromism of THDM in the picosecond range is caused by reorientations of molecules of the polar environment occurring during a time period consistent with the dielectric relaxation time of these molecules.     

Absorption and Fluorescence Characteristics of Some 2-Aryl-and 2-Heteroaryl-benzothiazoles in Different Solvents and at Various pH Values

The parameters characterizing the absorption and fluorescence of seven 2-substituted benzothiazoles in different solvents and at various acid/base concentrations were studied. It was found that both the kind of substituent and the solvent polarity influenced the changes of the spectral properties of the examined molecules. 2-Aryl substituted benzothiazoles exhibit larger Stokes shifts than 2-heteroaryl derivatives. The linear relationship between solvent polarity and pH values against Stokes shift and fluorescence sensitivity, respectively, was observed. The mostly fluorescent compound was 2-(2-benzofuryl)benzothiazole.     

Photophysical characteristics of three novel benzanthrone derivatives: Experimental and theoretical estimation of dipole moments

The effect of solvents on absorption and fluorescence spectra and dipole moments of novel benzanthrone derivatives such as 3-N-(N′,N′-Dimethylformamidino) benzanthrone (1), 3-N-(N′,N′-Diethylacetamidino) benzanthrone (2) and 3-morpholinobenzanthrone (3) have been studied in various solvents. The fluorescence lifetime of the dyes (1-3) in chloroform were also recorded. Bathochromic shift observed in the absorption and fluorescence spectra of these molecules with increasing solvent polarity indicates that the transitions involved are π→π^?. Using the theory of solvatochromism, the difference in the excited-state (μ_e) and the ground-state (μ_e) dipole moments was estimated from Lippert-Mataga, Bakhshiev, Kawski-Chamma-Viallet, and McRae equations by using the variation of Stokes shift with the solvent’s relative permittivity and refractive index. AM1 and PM6 semiempirical molecular calculations using MOPAC and ab-initio calculations at B3LYP/6-31 G^? level of theory using Gaussian 03 software were carried out to estimate the ground-state dipole moments and some other physicochemical properties. Further, the change in dipole moment value (Δμ) was also calculated by using the variation of Stokes shift with the molecular-microscopic empirical solvent polarity parameter (E_T^N). The excited-state dipole moments observed are larger than their ground-state counterparts, indicating a substantial redistribution of the π-electron densities in a more polar excited state for all the systems investigated.     

On the Photophysics of 3,5,6-Trichlorosalicylic Acid: Spectroscopic Study Combined with Hartree-Fock and Density Functional Theory Calculations

The present contribution reports a detailed photophysical study of a simple salicylic acid derivative viz., 3,5,6-Trichlorosalicylic acid (TCSA) based on steady state absorption, emission and time-resolved emission spectroscopy. Anomalous “dual” emission coupled with a large Stokes shift and negligible solvent polarity dependence marks the spectroscopic signature for Excited State Intramolecular Proton Transfer (ESIPT) reaction. Variation of medium polarity and pH of the medium have been implemented as fruitful tools to decipher the photophysics of TCSA. Quantum chemical calculation by ab initio Hartree-Fock and Density Functional Theory methods yields consistent results to follow experimental findings with distinct illustration of the inoperativeness of GSIPT reaction as well as occurrence of ESIPT process. A rigorous comparison of our experimental and theoretical measurements of TCSA with the parent compound salicylic acid, 5-chlorosalicylic acid and 3,5-dichlorosalicylic acid reveals the impact of chlorine substitution on the photophysics of the studied molecular systems with simultaneous exploration of the complexities induced in TCSA with respect to salicylic acid.     

Two-photon—induced fluorescence and electronic structure of substituted dicyanomethylene pyrans in solutions under femtosecond excitation

The method of two-quantum etalon is used to determine the two-photon absorption cross sections of eight dicyanomethylene (DCM) pyran dyes (DCM derivatives). Measurements of two-photon absorption of femtosecond Ti: sapphire-laser (λ = 800 nm, τ = 100 fs, and f = 89 MHz) radiation have been carried out. The nature of nonlinear excitation has been confirmed by the dependence of the fluorescence intensity on the excitation radiation intensity, which is close to a square-law one. Based on the measured two-photon absorption cross sections, the sizes of delocalized π-electronic clouds of DCM dye molecules with different substitutes are estimated in solvents with different polarity parameters. It is demonstrated that an increase in the polarity parameter of the solvent causes the two-photon absorption cross sections and sizes of delocalized π-electronic clouds of DCM, DCM-doa, DCM-17, DCM-5M, and DCM-11 dyes to increase. It is demonstrated that the size of the delocalized π-electronic cloud and the quantum fluorescence yield of the DCM-ul dye decrease with increasing polarity of the solvent despite the growth of the two-photon absorption cross section. __________ Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 11, pp. 69–73, November, 2005.