Measurements of the Solute Dependence of Solvation Dynamics in 1-Propanol: The Role of Specific Hydrogen-Bonding Interactions

Chapman, Curtis F.; Fee, R. S.; Maroncelli, Mark

doi:10.1021/j100013a060

Cited by 169 publications

(191 citation statements)

References 11 publications

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“…27 Protic solvents form a solvation shell in the vicinity of solutes by hydrogen-bonding. [38][39][40] This solvation shell can affect the interactions between solute and the nanochannels. Anion-exchange efficiency depends on solvation strongly, as described above.…”

Section: Chromatographic Measurementmentioning

confidence: 99%

Permeation Flux of Organic Molecules through Silica-surfactant Nanochannels in a Porous Alumina Membrane

et al. 2006

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Separation membranes are used in many fields ranging from medical science to industry, and much effort has been devoted to the development of new membranes with high qualities. [1][2][3] Recently, inorganic membranes have attracted much attention because of their superior mechanical strength, thermal stability and resistance to organic solvents. A variety of preparation and application methods of inorganic membranes have been reported. [4][5][6][7][8][9][10][11][12][13][14][15] Zeolites 4-8 and ceramics 9-14 are frequently used as sources of inorganic membranes. Zeolites are porous crystalline materials, which have a high surface area to volume ratio. Membranes made of zeolites are used for catalysts, 5 pervaporation 6,7 and high temperature separation of hydrocarbon isomer vapors. 8 Ceramics such as alumina are hard and heat-resistant materials made with nonmetallic minerals, and ceramic membranes for gas separation 13 and catalysts 14 have been synthesized.Mesoporous silica has also been adopted as a source material in the synthesis of inorganic membranes. 9,15 Mesoporous silica is an ordered material that has three different mesophases: lamellar, cubic and hexagonal. 16,17 In particular, the hexagonal mesophase possesses highly regular arrays of uniform-sized channels whose diameters are in the approximate range of 1 to over 10 nm depending on the surfactants and reaction parameters. Because of its porosity, high surface area, ordered pore arrangement and pore size uniformity, mesoporous silica has been the subject of many theoretical and applied studies. 18 For practical applications, the morphology of mesoporous silica is very important. The film is an ideal morphology for separation membranes, sensor 19,20 and optics. 21,22 Usually, mesoporous silica films are prepared on a flat substrate by dipor spin-coating methods. [23][24][25] However, in the case of hexagonal mesoporous silica, the channels are aligned parallel to the substrate surface, and transport of molecules across the film is not possible. In order to achieve separation, straight channels should be oriented perpendicular to the surface to transport molecules across the film. To solve this problem, instead of hexagonal mesoporous silica, some researchers have used cubic mesoporous silica to synthesize the inorganic membrane. 15,19 Recently, a porous anodic alumina membrane with a perpendicularly oriented silica-surfactant nanochannel assembly membrane (NAM) was synthesized. 26 The porous anodic alumina membrane has a packed array of columnar pores ranging from tens to hundreds of nanometers in diameter, and the channel direction of the columnar pores is perpendicular to the membrane.When a precursor solution containing cetyltrimethylammonium bromide (CTAB) surfactant and tetraethyl orthosilicate (TEOS) as a silica source is introduced into the alumina pores, highly ordered hexagonally arranged silica-surfactant nanochannels with pores of 3.4 nm diameter are assembled inside the alumina pores. The channel direction of mesoporous silica is predomi...

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Section: Chromatographic Measurementmentioning

confidence: 99%

Permeation Flux of Organic Molecules through Silica-surfactant Nanochannels in a Porous Alumina Membrane

et al. 2006

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“…The main contribution to the interaction of polar solutes with small-molecule polar solvents is due to long range dipoledipole and charge-dipole interactions, together with hydrogen bonding in the case of protic solvents. [77][78][79] Frequently, the solute-solvent interaction in polar solvents has been described in terms of continuum models using an exponential or multiexponential dielectric response. 5,48,80 It has been argued by some researchers that due to inherent molecular nature of the solvation process, the continuum models ultimately fail to explain some important features of solvation, in particular its initial, ultrafast stage.…”

Section: C͑0 ͒ϳ2/␤ ͑44͒mentioning

confidence: 99%

Dynamic Stokes shift in solution: Effect of finite pump pulse duration

Georgievskii

Hsu

Marcus

1998

The Journal of Chemical Physics

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The time-evolution of the fluorescence spectrum of a dissolved chromophore excited by an ultrafast pump pulse is considered. The average value of the energy difference of the solute in its excited and ground states is used to describe the relaxation of the maximum of the transient fluorescence spectrum to its equilibrium value ͑dynamic Stokes shift, DSS͒. A simple formula for the normalized DSS is obtained which generalizes an earlier standard classical expression and includes the effect of a pump pulse of finite duration. As an example, dielectric dispersion data are used for a dipolar solute in water to estimate the quantum correction to the standard DSS expression. The correction is negligible when the frequency of the pump pulse is close to the maximum in the absorption spectrum, but a deviation from the standard formula can be expected for the pump pulse tuned to a far wing of the absorption band of the chromophore. An expression is given for this deviation.

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“…Solvation dynamics has been studied intensively both experimentally [1][2][3][4][5][6][7][8][9][10][11] and theoretically because it plays an important role in the kinetics of chemical reactions in solution. Observation of the dynamic Stokes shift, which is suitable for detecting ultrafast solvation dynamics, is a powerful tool in studying solvation dynamics.…”

Section: Introductionmentioning

confidence: 99%

Solvent Effect on the Fluorescence Spectra of Coumarin 120 in Water: A Combined Quantum Mechanical and Molecular Mechanical Study

et al. 2012

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The solvent effect on the steady-state and time-resolved fluorescence spectra of coumarin 120 in water was studied utilizing a molecular dynamics simulation with combined quantum mechanical/molecular mechanical method. The constructed steady-state fluorescence spectra reproduced the Stokes shift of the experimental data. The solvent effects on the spectra were examined by constructing three different spectra: spectra using the entire system, spectra including water molecules only in the first solvent shell, and spectra excluding all water molecules. We found that the variation in C-C bond length makes the largest contribution to the solvent shift in the fluorescence spectrum, which indicates the importance of the electronic structure variation.

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Measurements of the Solute Dependence of Solvation Dynamics in 1-Propanol: The Role of Specific Hydrogen-Bonding Interactions

Cited by 169 publications

References 11 publications

Permeation Flux of Organic Molecules through Silica-surfactant Nanochannels in a Porous Alumina Membrane

Permeation Flux of Organic Molecules through Silica-surfactant Nanochannels in a Porous Alumina Membrane

Dynamic Stokes shift in solution: Effect of finite pump pulse duration

Solvent Effect on the Fluorescence Spectra of Coumarin 120 in Water: A Combined Quantum Mechanical and Molecular Mechanical Study

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