Dynamics of 4-Benzylamino-7-nitrobenzofurazan in the 1-Propanol/Water Binary Solvent System. Evidence for Composition-Dependent Solvent Organization

Stevenson, Sarah A.; Blanchard, G. J.

doi:10.1021/jp057039g

Cited by 6 publications

(7 citation statements)

References 57 publications

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“…Despite this limitation, we assert on physical grounds that the most plausible change is occurring with the effective hydrodynamic volume of the reorienting species. Deviations from the modified DSE equation have been reported previously in binary systems, where specific solute–solvent interactions and consequent changes in the hydrodynamic volume have been cited as reasons for nonconformity to model behavior. − Stevenson et al reported a compositional dependence in the reorientation times of 4-benzylamino-7-nitrobenzylfurazan (BBD) in 1-propanol/water binary systems, where the hydrodynamic volume of the reorienting entity was found to change on the basis of the inclusion of interacting solvent molecule(s) …”

Section: Resultsmentioning

confidence: 90%

“…35−38 Stevenson et al reported a compositional dependence in the reorientation times of 4-benzylamino-7-nitrobenzylfurazan (BBD) in 1-propanol/water binary systems, where the hydrodynamic volume of the reorienting entity was found to change on the basis of the inclusion of interacting solvent molecule(s). 38 In the case of the wet NOP system, the change in hydrodynamic volume of the reorienting entity can be accounted for in the context of the chromophore residing in a primarily aqueous environment that is surrounded by NOP molecules, and the reorienting entity is (LRSC•nH 2 O), with n being the depth-dependent quantity. In this model, the reorienting entity would be a nominally spherical chromophore−water complex (S = 1).…”

Section: ■ Results and Discussionmentioning

confidence: 99%

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Detection and Characterization of Liquid|Solid and Liquid|Liquid|Solid Interfacial Gradients of Water Nanodroplets in Wet N-Octyl-2-Pyrrolidone

2014

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We report on the rotational diffusion dynamics and fluorescence lifetime of lissamine rhodamine B sulfonyl chloride (LRSC) in two thin-film experimental configurations. These are liquid|solid interfaces, where N-octyl-2-pyrrolidone (NOP) containing water and ethylene glycol (EG) thin films are each supported on glass, and a liquid|liquid|solid interface where thin films of water and NOP, both supported on glass, are in contact with one another, forming an NOP|water interface. The reorientation dynamics and fluorescence lifetime of LRSC are measured as a function of distance from the NOP|glass and EG|glass interfaces and from the NOP|water and NOP|glass interfaces in the liquid|liquid|solid experimental configuration. Fluorescence anisotropy decay data from the liquid|solid systems reveal a liquid film depth-dependent gradient spanning tens of micrometers from the NOP|glass interface into the wet NOP phase, while this gradient is absent in EG. We interpret these findings in the context of a compositional gradient in the NOP phase. The spatially resolved fluorescence lifetime and anisotropy decay data for an NOP|water|glass interfacial structure exhibits the absence of a gradient in the anisotropy decay profile normal to the NOP|water interface and the presence of a fluorescence lifetime gradient as a function of distance from the NOP|water interface. The compositional heterogeneity for both interfacial systems is in the form of water nanodroplets in the NOP phase. We understand this compositional gradient in the context of the relative surface energies of the water, NOP, and glass components.

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Section: Resultsmentioning

confidence: 90%

Section: ■ Results and Discussionmentioning

confidence: 99%

Detection and Characterization of Liquid|Solid and Liquid|Liquid|Solid Interfacial Gradients of Water Nanodroplets in Wet N-Octyl-2-Pyrrolidone

2014

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“…4,34,35 Such a solvent-attachment approach to understanding experimental reorientation data has been useful for solvents capable of hydrogen bonding. 36 For solvents that are not capable of forming H-bonds, such an explanation is not appropriate.…”

Section: Resultsmentioning

confidence: 99%

“…To compound matters, the estimation of V and S can give rise to significant uncertainty because of the intrinsic dynamics and variability in the range of structural conformations that these chromophores can take on over time. Also, depending on the solvent system used, strong and persistent solvent−solute interactions can give rise to a rotating entity that is larger, on average, than the bare chromophore. ,, Such a solvent-attachment approach to understanding experimental reorientation data has been useful for solvents capable of hydrogen bonding . For solvents that are not capable of forming H-bonds, such an explanation is not appropriate.…”

Section: Resultsmentioning

confidence: 99%

Evaluating the Role of Chromophore Side Group Identity in Mediating Solution-Phase Rotational Motion

Greenough

Blanchard

2006

J. Phys. Chem. A

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We report on the rotational diffusion dynamics of the chromophore 7-nitrobenz-2-oxa-1,3-diazole (NBD) in a series of protic and polar aprotic solvents, as a function of the identity of the side group appended to the chromophore amine functionality. The central issue we address is whether or not the side groups play a role in mediating the anisotropic reorientation dynamics of the chromophore. To understand the motional properties of the chromophores in detail, we use both one-photon and two-photon excited fluorescence anisotropy decay measurements, and from these complementary excitation methods, we extract two of the Cartesian components of the rotational diffusion constant, D. The experimental data indicate that, regardless of the functionality of the pendant side group, the reorienting moieties exhibit ratios of Dz/Dx in the range 1.8-2.0. There is a small but discernible difference between the substituted chromophores. For all of the substituted NBD chromophores, dielectric friction plays a discernible role in determining their reorientation dynamics.

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“…Studying binary solvent systems has proven to be a somewhat greater challenge than neat liquids with the fundamental issue of import being the homogeneity of the solution phase at the molecular scale. − There are many instances where local organization and/or heterogeneity in liquid phase systems has given rise to dynamic behavior at odds with that expected for a homogeneous medium. Studies using steady-state and time-resolved spectroscopic methods, theoretical treatments, and molecular dynamics simulations have been performed to understand solute molecular motion in binary solvent systems. − We have reported recently on a binary solvent system that is anomalous by virtue of its constituents .…”

Section: Introductionmentioning

confidence: 99%

Evidence for Preferential Solvation in the Cyclohexane/n-Butanol Binary Solvent System

Qiu

Blanchard

2015

J. Phys. Chem. B

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We report on the rotational diffusion and vibrational population relaxation dynamics of the polycyclic aromatic hydrocarbon (PAH) perylene in a series of cyclohexane/n-butanol binary solvent systems. The molecular scale heterogeneity of this binary system is seen in both types of data. The rotational diffusion results show that in neat n-butanol and neat cyclohexane perylene reorients as an oblate rotor, but for all binary solvent systems examined this chromophore reorients as a prolate rotor. The perylene ring breathing mode is nearly degenerate with the n-butanol terminal methyl group rocking mode and vibrational population relaxation data for the perylene ring breathing mode reveal a substantial decrease in the relaxation time constant with the addition of small amounts of n-butanol to cyclohexane. This finding, in concert with the rotational diffusion data, indicates that perylene is solvated preferentially by n-butanol in cyclohexane/n-butanol binary solvent systems. The implication of this finding is that the cyclohexane/n-butanol binary solvent mixture is not homogeneous on nanometer length scales.

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Dynamics of 4-Benzylamino-7-nitrobenzofurazan in the 1-Propanol/Water Binary Solvent System. Evidence for Composition-Dependent Solvent Organization

Cited by 6 publications

References 57 publications

Detection and Characterization of Liquid|Solid and Liquid|Liquid|Solid Interfacial Gradients of Water Nanodroplets in Wet N-Octyl-2-Pyrrolidone

Detection and Characterization of Liquid|Solid and Liquid|Liquid|Solid Interfacial Gradients of Water Nanodroplets in Wet N-Octyl-2-Pyrrolidone

Evaluating the Role of Chromophore Side Group Identity in Mediating Solution-Phase Rotational Motion

Evidence for Preferential Solvation in the Cyclohexane/n-Butanol Binary Solvent System

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