Polystyrene fluorescence spectra. Molecular weight dependence in different solvents

The emission spectra from polystyrene samples of molecular weights ranging from 500 to 612,000 were measured in solvents of different thermodynamic character. The excimer to monomeric emission ratio depends upon the polymer molecular weight but is independent of the solvent. The molecular weight dependence is explained in terms of a distribution of the excimer traps among the macromolecules.     

Solvent effects on infrared spectra of methyl 4-hydroxybenzoate in pure organic solvents and in ethanol/CCl4 binary solvents

Infrared spectroscopy studies of methyl 4-hydroxybenzoate (MHB) in 17 different organic solvents and in ethanol/CCl4 binary solvent were undertaken to investigate the solvent-solute interactions. The frequencies of carbonyl stretching vibration nu(C=O) of MHB in single solvents were correlated with the solvent acceptor number (AN) and the linear solvation energy relationships (LSER). The assignments of the two bands of nu(C=O) of MHB in alcohols and the single one of that in non-alcoholic solvents were discussed. The shifts of nu(C=O) of MHB in ethanol/CCl4 binary solvents showed that several kinds of solute-solvent hydrogen bonding interactions coexisted in the mixture solvents, with a change in the mole fraction of ethanol in the binary solvents.     

How the environment controls absorption and fluorescence spectra of PRODAN: a quantum-mechanical study in homogeneous and heterogeneous media

The spectroscopic behavior of 6-propionyl-2-(N,N-dimethyl)aminonaphthalene (PRODAN) is investigated in different environments, ranging from homogeneous solutions of different polarities to diffuse interfaces mimicking membranes. The variety of experimental data as well as computational results present in the literature still do not clarify the nature of the emission process; in particular, it is not well-established whether fluorescence in such a molecule occurs from a planar or from a twisted intramolecular charge transfer state. The first part of the work is thus devoted to better understand how the electronic transition processes occur in homogeneous solvents. The effect of the medium polarity as well as the hydrogen bond formation are studied. In the second part of the paper, a first attempt to interpret the experimental results of PRODAN in unilamellar vesicles is carried out. The complexity of the still-open questions about the photophysics of PRODAN has prompted us to base the study on quantum-mechanical calculations performed at various levels of theory, namely, DFT, TDDFT, CIS, and SAC-CI, and to include the effects of the environment in a self-consistent way. This is achieved by using the integral equation formalism version of the polarizable continuum model (IEFPCM). IEFPCM is a quite versatile approach, being able to treat equilibrium and nonequilibrium solvation in both homogeneous and heterogeneous media.     

Electronic absorption spectra of some azo compounds with condensed ring systems in non-aqueous and mixed buffer solvents

The electronic absorption spectra of eight substituted phenylazo derivatives of α-and β-naphthol, 9-phenanthrol and 5- and 6-chrysenol were studied in different organic solvents. The assignment of the spectral bands obtained and also the effect of organic solvents on the colour of the compounds was investigated. The spectra in buffer solution over the pH range 2–14 were recorded and explained; also the pK_a values were determined.     

Quantitative study of fluorescence excitation and emission spectra of bean leaves

A quantitative and comprehensive knowledge of leaf fluorescence is required for the interpretation of fluorescence signals at the canopy level and also for the modelling of leaf and canopy fluorescence. In this work we present full range fluorescence excitation and emission spectra of intact leaves, expressed in units of apparent spectral fluorescence yield, from both the adaxial and the abaxial sides of the leaves, and for both front-side and back-side geometries. Emission spectra were measured for incident radiations in the blue and the green spectral range. The red/far-red fluorescence ratio depended on the measurement geometry and on the excitation wavelength. Excitation spectra were measured for emissions at 687 and 760 nm. When the abaxial side was illuminated, the measured spectra always had a larger intensity compared to adaxial side that is explained by the higher scattering of the spongy tissues. At 760 nm, the spectra had the same shape for front-side and back-side geometry, indicating that scattering predominated. At 687 nm, the shape of the spectra was very different for front-side and back-side geometry due to re-absorption of red fluorescence within the leaf. The comparison of excitation spectra measured from the adaxial or the abaxial side revealed differences in carotenoid absorption.     

The effect of fluctuations on emission spectra: practical distinctions between raman and fluorescence spectra

By the use of stochastic theory it is clearly shown that two types of emission should to fluctuations such as would occur during interactions with their environment are resonantly driven by light. In our approach the electromagnetic field is treated in a classical manner and decay is introduced by a Wigner-Weisskopfansatz. The two types of emission should occur for a three-level system and relaxation to other levels is not involved in the mechanism. Also included is a discussion of operational definitions of fluorescence (and other spontaneous emissions) and of the relationship between absorption and scattering in terms of dephasing or T₂ processes, especially as this relates to conventional emission phenomena.     

Photokinetic analysis of PRODAN and LAURDAN in large unilamellar vesicles from multivariate frequency-domain fluorescence

This paper describes a multivariate photokinetic analysis of the membrane phase dependence of PRODAN and LAURDAN photokinetics in DMPC vesicles. Decay data, arranged in the form of Fourier transformed emission-decay matrices (FT-EDMs), were collected as a function of temperature around the gel phase transition temperature. Each matrix was partitioned into the emission spectra and decay profiles of the underlying emission components using methods based on principal components analysis. The analysis revealed that both probes typically emit at least three spectral components, which vary in intensity as the membrane undergoes gel to liquid-crystalline phase transitions: a locally excited species (lambda max approximately 415 nm), a charge-transfer species (lambda max approximately 435 nm), and a solvent relaxed species (lambda max approximately 490 nm). In contrast to previous reports, the most red-shifted species is not photoexcited, but evolves from the locally excited species and does not exhibit the dynamic Stokes' shifts associated with conventional solvent relaxation. The primary difference in the emission of the two probes is the prominence of the charge-transfer species in the LAURDAN emission.     

Solvatochromic behavior on the absorption and fluorescence spectra of Rose Bengal dye in various solvents

The absorption and fluorescence spectra of Rose Bengal dye were studied in various solvents. It was found that solvent effects on the absorption wavelength are consistent with the solvatochromic model of Kamlet, Abboud and Taft. The solvent polarizability value pi* was found to have a linear relationship with the absorption wavelength of the dye in various solvents. Additionally, the normalized transition energy value (E(T)(N)) showed some scattering when plotted versus Deltanu(af). Density functional calculations were used to assign the absorption in the region 540-570 nm to a pi-pi* transition between the HOMO and LUMO of the anion. Experimental ground state and excited state dipole moments were calculated by using the solvatochromatic shifts of absorption and fluorescence spectra as a function of the dielectric constant (epsilon) and refractive index (n). The dipole moment for Rose Bengal was found to be 1.72 Debye in the ground state, whereas this value was 2.33 Debye in the excited state.     

The self-association of ethanol in non-polar solvents

The self-association of ethanol in solutions of n-hexane, cyclopentane, cyclohexane, carbon tetrachloride and benzene is studied on the basis of heat of dilution data published in the literature. The tetramer formation model fits the experimental data better than other self-association models. The corresponding self-association constants, K_1,4, and heats of reaction, ΔH_1,4, are calculated. The solvent effect is studied using the solvent polarity factor, E_T, and the existence of a linear dependance of log K_1,4 on E_T values is shown.     

Dual fluorescence of diphenyl carbazide and benzanilide: effect of solvents and pH on electronic spectra

The absorption and fluorescence spectra of benzanilide (BA) and diphenyl carbazide (DPC) in solvents of different polarities and pH have been analysed. The spectral characteristics of DPC and BA are compared with diphenyl amine molecule. In water and methanol, a dual fluorescence is observed for both DPC and BA molecules. The normal stokes shifted emission originates from a locally excited pi* electronic state and the large stokes shifted band is due to emission from a twisted intramolecular charge transfer (TICT) state. pH studies show that both monocations and monoanions are non-fluorescent. The excited state acidity constants determined by fluorimetric titration and F?rster cycle methods, have been reported and discussed.     

Dual fluorescence of the isoquinolinium cation in methanol: time-resolved emission spectra and semiempirical calculations

The fluorescence behavior of the N-ethyl isoquinolinium (iso-NEQ) cation in viscous methanol is reported and discussed on the basis of time-resolved fluorescence spectra, polarization measurements and semiempirical calculations. Dual fluorescence results from two nearby excited states (S₁ and S₂) above 300 nm only at low temperature. The detection of an isoemissive point verifies this two-state model of the emission. We use the numerical self-consistent reaction field (SCRF) to include solute–solvent interactions for the calculations of the absorption transitions of iso-NEQ in methanol. We also involved the so-called supermolecular approach with three methanol molecules to reproduce the absorption transitions. The latter results are in good agreement with our experimental data.     

Resolved fluorescence of the two tryptophan residues in horse apomyoglobin

The composite fluorescence emission from the two tryptophans (W7 and W14) of horse heart apomyoglobin was explored by fluorescence quenching experiments. The fluorescence of the W7 residue is the only one involved in the quenching by iodide or trichloroethanol (TCE) titration. The fluorescence contribution of W7 is 49% of the total apomyoglobin emission, and its spectrum is red-shifted compared to the W14 emission. The fluorescence decay of Trp residues gives an average fluorescence lifetime of 2.06 ns for W14 and 2.84 ns for W7. The static fluorescence quenching by TCE was used to monitor the individual motions of the two tryptophans in apomyoglobin. The short correlation time of W7 (rho = 3 ns) explains why this residue can experience various environments without having to assume the existence of several protein conformations occurring during its lifetime emission.     

Simulations of time-dependent fluorescence in nano-confined solvents

The time-dependent fluorescence of a model diatomic molecule with a charge-transfer electronic transition in confined solvents has been simulated. The effect of confining the solvent is examined by comparing results for solutions contained within hydrophobic spherical cavities of varying size (radii of 10-20 angstroms). In previous work [J. Chem. Phys. 118, 6618 (2002)] it was found that the solute position in the cavity critically affects the absorption and fluorescence spectra and their dependence on cavity size. Here we examine the effect of cavity size on the time-dependent fluorescence, a common experimental probe of solvent dynamics. The present results confirm a prediction that motion of the solute in the cavity after excitation can be important in the time-dependent fluorescence. The effects of solvent density are also considered. The results are discussed in the context of interpreting time-dependent fluorescence measurements of confined solvent systems.     

NMR spectra of 1,2-difluoroethane in nematic solvents

In 1,2-difluoroethane, the gauche conformation predominates strongly. This circumstance allows the determination of its relative geometry by NMR in liquid crystals, though certain assumptions have still to be made, e.g. neglect of intermediate conformations. The principal result of the structure determination is the value of 69–70° for the dihedral angle ∠FCCF, which is quite insensitive to variations of the other internal coordinates. The value is, within the limits of error, equal to that obtained by microwave spectroscopy, but deviates from results of electron diffraction measurements.It is impossible to describe the average orientation of 1,2-difluoroethane using less than three orientation parameters. This indicates that the interconversion of the two gauche rotamers is slow compared with the reorientational motion.In an attempt to explain the lower energy of the gauche conformation relative to the trans conformation, and the high value of the dihedral angle, ∠FCCF, some explorative empirical calculations were carried out. These could not, however, reproduce the experimental data.     

Excitation wavelength and solvent dependent emission spectra in weakly polar aprotic solvents at room temperature and 77 K

Excitation wavelength-dependent emission spectra of 4-methyl-2,6-diformylphenol (MFOH) and o-hydroxybenzaldehyde (OHBA) have been examined both in pure weakly polar aprotic solvents and in the presence of a base at room temperature and 77 K. It is shown that fluorescence quantum yield shape, position of the spectra, and number of conformers are dependent upon the excitation energy and also on the proton-accepting ability of the solvents. Fluorescence spectra cannot be correlated with the solvent dielectric properties. At 77 K, deactivation occurs via phosphorescence only at a particular experimental condition in all the solvents studied here. The decay rates are relatively slower in an environment where the probability of hydrogen bonding interaction is stronger.     

Novel naphthalimide derivatives with near-infrared emission: synthesis via photochemical cycloaromatization, fluorescence in solvents and living cell

In this Letter, a pair of novel naphthalimide derivatives with long-wavelength emission (>600 nm) and larger Stokes shift (>140 nm) have been developed through the photochemical cycloaromatization, in which intramolecular radical-induced 1,3-aromatic hydrogen transfer might be occurred. Cell uptake experiments showed that dye 2 could be used as a potential NIR fluorescence imaging agent.     

Ground-state complexes between polar solvents and 1-methylindole: the origin of the stokes'' shift in their fluorescence spectra

In iso-octane solutions containing small concentrations of the polar solvents butanol or ethyl acetate, a ground-state complex between the solute 1-methylindole and the polar solvent is formed. Previous workers aseribed the fluorescence intensity and spectral shifts of 1-methylindole in polar solvents to exciplex formation. However we show that these fluorescence properties are entirely explained in terms of ground-state complexes.     

Synthesis and emission spectra of anionic para-substituted polyacrylophenones

Polyacrylophenone (aPAP), poly-4′-ethylacrylophenone (aP4EAP), poly-4′-methoxyacrylophenone (aP4MAP) and poly-4′-phenylacrylophenone (aP4PAP) were prepared by anionic polymerization initiated by lithium tert-butoxide. ¹H NMR analysis revealed higher content of isotactic dyads for aPAP (86%) and aP4MAP (88%) compared with polymers rPAP (60%) and rP4MAP (60%) prepared by radical polymerization. ¹H NMR spectra of a aP4EAP and a P4PAP were too complicated for analysis and ¹³C NMR spectra were not sensitive to stereostructure. The molecular weights of anionic polyacrylophenones were about 5000. In emission spectra, a bathochromic shift was observed in going from model compound to anionic and radical polymer doped in poly(methyl methacrylate) film at 77°K. The emission decay of rP4PAP and aP4PAP is non-exponential in comparison with model 4′-phenyl-3-chloropropiophenone. The bathochromic shift in the emission spectra and the non-exponential emission decay of polymers depends on molecular weight suggesting that the number of structural perturbations (triplet excimers) increases with molecular weight.     

Characterization of spilled oils by measuring fluorescence emission spectra of fractions separated by high-speed gel-permeation chromatography

Summary Fluorescence emission spectra of oil fractions separated by high-speed gel-permeation chromatography (GPC) were measured to characterize the oils spilled into the environment. Crude oils, weathered crude oils, and tar balls were analysed. In GPC, polystyrene gel and tetrahydrofuran were used as a stationary phase and a mobile phase, respectively; the eluate was separated into five equi-volume fractions. Fluorescence emission spectra of the fractions were obtained at an excitation wavelength of 340 nm. Maximum emission wavelength, relative emission intensity at 386 nm, and emission intensity ratio (440 nm/386 nm) on the spectra of fractions were studied as identification parameters. The change of the identification parameters with weathering the crude oil (Murban) was small. The proposed method was applied to the characterization of tar balls sampled in the sea near Japan.

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Charakterisierung von Ölverschmutzungen durch Auswertung der Fluorescenz-Emissionsspektren von Fraktionen, die durch Hochgeschwindigkeits-Gelpermeations-Chromatographie getrennt wurden

Zusammenfassung Rohöle, verwitterte Rohöle sowie Teerballen wurden untersucht. Bei der Chromatographie wurde Polystyrolgel als stationäre und Tetrahydrofuran als mobile Phase verwendet. Das Eluat wurde in fünf Fraktionen gleichen Volumens getrennt. Für die Fluorescenzmessung wurde eine Anregungswellenlänge von 340 nm benutzt. Als Identifizierungsparameter dienten die maximale Emissionswellenlänge, die relative Emissionsintensität bei 386 nm sowie das Verhältnis der Emissionsintensitäten bei 440/386 nm. Die Veränderung der Parameter bei der Verwitterung (Murban-Öl) war nur gering. Die Methode wurde zur Charakterisierung von Teerballen angewendet, die aus dem Meer in der Nähe Japans entnommen worden waren.