Preferential solvation of 6-propionyl(N,N-dimethylamino)naphthalene in binary, polar solvent mixtures

Zurawsky, Walter; Scarlata, Suzanne

doi:10.1021/j100193a067

Cited by 41 publications

(34 citation statements)

References 3 publications

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“…Scarlata and Zurawsky have documented this behavior with PRODAN in binary mixtures of methanol with acetone, acetonitrile and pyridine and with isooctane/acetone. 26 They found that methanol preferentially interacts with PRODAN via H-bonding, but that dielectric enrichment is not important in isooctane/acetone. In contrast to these studies both water and isopropanol can form H-bonds, but water is a stronger H-bond donor than isopropanol.…”

Section: Resultsmentioning

confidence: 99%

Carbonyl-Twisted 6-Acyl-2-dialkylaminonaphthalenes as Solvent Acidity Sensors

et al. 2012

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Derivatives of 2-propionyl-6-dimethylaminonaphthalene (PRODAN) with twisted carbonyl groups were investigated as highly responsive sensors of H-bond donating ability. The PRODAN derivative bearing a pivaloyl group (4) was prepared. The torsion angle between the carbonyl and naphthalene is 26° in the crystal. It shows solvatochromism that is similar to five other PRODAN derivatives (1-3, 5-6). Twisted-carbonyl derivatives 3, 4 and 6 show strong fluorescence quenching in protic solvents. The order of magnitude of the quenching is linearly related to the H-bond donating ability of the solvent (SA), but not to other solvent properties. Binary mixtures of protic solvents show specific interaction effects with respect to quenching and solvatochromism. Aggregation in water is an issue with the pivaloyl derivatives.

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Section: Resultsmentioning

confidence: 99%

Carbonyl-Twisted 6-Acyl-2-dialkylaminonaphthalenes as Solvent Acidity Sensors

et al. 2012

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“…Fluorescent probes such as prodan (6-propionyl-2-dimethylaminonaphthalene) and laurdan (6-dodecanoyl-2-dimethylaminonaphthalene) are widely used in biological and biophysical research [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15]. The fluorescence properties of prodan and laurdan have been described in the literature as simultaneously existing local-excited (LE) and twisted internal charge-transfer (TICT) states.…”

Section: 37mentioning

confidence: 99%

Effect of proton-donor solvent and structural flexibility of prodan and laurdan molecules on their spectral-luminescent properties

et al. 2009

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535.37The influence of structural flexibility on dipole moments, energy-level locations, and charge distributions in prodan and laurdan molecules was studied. A quantum-chemical calculation of isolated prodan and laurdan molecules in the fluorescent state geometry was conducted. Rate constants for radiative and non-radiative processes and fluorescence quantum yields for these probe molecules were calculated. Interaction centers of prodan and laurdan with a proton-donor solvent were estimated quantitatively. The possibility of using fluorescent probes for estimating the polarity of proton-donor and proton-acceptor solvents was shown.Keywords: fluorescent probe, prodan, laurdan, structural flexibility, proton-donor properties, fluorescence quantum yield.Introduction. Fluorescent probes such as prodan (6-propionyl-2-dimethylaminonaphthalene) and laurdan (6-dodecanoyl-2-dimethylaminonaphthalene) are widely used in biological and biophysical research [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15]. The fluorescence properties of prodan and laurdan have been described in the literature as simultaneously existing local-excited (LE) and twisted internal charge-transfer (TICT) states. However, the latter term should be used very arbitrarily because the state has been observed only at very low temperatures [2]. These states are strongly delocalized at temperatures near ambient and above [2]. It has been shown [5] that the positions of fluorescence maxima in phospholipids bilayers depend on the phase state of the phospholipids, i.e., 435 and 440 nm for the short-wavelength band in the gel phase; 515 and 490 nm, for prodan and laurdan in the liquid-crystalline phase. Two fluorescence bands (430 and 500 nm) were observed for laurdan in glycerin with λ ex = 380 nm at room temperature. The short-wavelength band at 430 nm disappeared as the temperature was raised to 370 K.The large shifts of prodan and laurdan fluorescence bands in solvents of different polarity have been explained by the significant change of dipole moment in the excited state as compared with the ground state. According to formulas for calculating common effects of solvents [16,17], changing the prodan dipole moment from 5.5 to 10.2 D causes a shift of the S 0 → S 1 -transition [18,19] in its fluorescence spectra of 770 cm -1 and 800 cm -1 on going to isopropanol and water, respectively, from a non-polar solvent [19,20]. The experimental shifts in fluorescence spectra of prodan were 3790 and 5520 cm -1 in isopropanol and water, i.e., the size of the dipole moment and its change from

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“…[13][14][15][16] This model provides a theoretically sound method for interpreting spectrochemical shifts in solvent mixtures and offers a methodology for separating dielectric enrichment, dielectric nonideality and specific interaction (i.e., hydrogen bonding) effects from one another. 11,15,[17][18][19][20][21][22][23][24] When a dipole is immersed in a binary solvent system with a polar and a nonpolar component, the solvent composition of its solvation sphere (the local composition) differs from the average solvent composition, even in the absence of specific solvent-solute interactions. The local composition is enriched in the polar solvent component because solvent dipole-solute dipole interactions are strongest between the solute and the polar component.…”

Section: Introductionmentioning

confidence: 99%

Separation of Dielectric Nonideality from Preferential Solvation in Binary Solvent Systems: An Experimental Examination of the Relationship between Solvatochromism and Local Solvent Composition around a Dipolar Solute

et al. 2001

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Dielectric nonideality of a binary solvent system refers to the deviation of the Onsager reaction field function from linearity in the polar mole fraction of the solvent mixture. A dipolar fluorophore dissolved in an ideal dielectric mixture exhibits a solvatochromic shift that is linear in the solvent polar mole fraction in it's solvation sphere. As a result, the "local composition" can be easily determined from the peak shift. Here we identify the conditions under which this linear approximation is appropriate for estimating local compositions around dipolar solutes. In a previous study (Khajehpour, M. H.; Kauffman, J. F. J. Phys. Chem. A 2000, 104, 7151-7159), we have demonstrated the influence of dielectric nonideality on the observed emission peak shifts of the charge-transfer excited state of ADMA [1-(9-anthryl)-3-(4-N,N-dimethylaniline)propane] in hexanesethanol mixtures. The linear approximation fails for this binary solvent, and a more elaborate method of analysis such as Suppan's nonlinearity ratio method must be used to determine the local composition from solvatochromic shifts. In this work, we examine mixture nonideality and dielectric enrichment in hexanetetrahydrofuran and hexane-dichloromethane mixtures. Our analysis demonstrates that the contribution of nonideality to the observed solvatochromic shifts cannot be neglected in these binary solvents. Using Suppan's theory of dielectric enrichment, we have calculated the local composition of ADMA's solvation sphere and find that it is enriched in the polar component by ∼30% over the bulk composition. This calculated value agrees with experimental measures of the local composition based on analysis of solvatochromic shifts using Suppan's nonlinearity ratio method which accounts for dielectric nonideality. The linear approximation overpredicts this composition by as much as 50%, even though these binary solvents are more nearly ideal than the hexane-ethanol system. Following this observation, we have identified conditions under which the linear approximation is justified, and find that for most cases of practical importance the linear approximation will not provide accurate estimates of the local solvent composition from solvatochromic studies. Similarly, solvatochromic shifts can only be accurately predicted from theoretical local compositions if dielectric nonideality is taken into account. These results along with our previous studies indicate that the chargetransfer excited state of ADMA behaves as an ideal dipolar solute.

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Preferential solvation of 6-propionyl(N,N-dimethylamino)naphthalene in binary, polar solvent mixtures

Cited by 41 publications

References 3 publications

Carbonyl-Twisted 6-Acyl-2-dialkylaminonaphthalenes as Solvent Acidity Sensors

Carbonyl-Twisted 6-Acyl-2-dialkylaminonaphthalenes as Solvent Acidity Sensors

Effect of proton-donor solvent and structural flexibility of prodan and laurdan molecules on their spectral-luminescent properties

Separation of Dielectric Nonideality from Preferential Solvation in Binary Solvent Systems: An Experimental Examination of the Relationship between Solvatochromism and Local Solvent Composition around a Dipolar Solute

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