Tuhin Pradhan

Intramolecular charge transfer reaction, polarity, and dielectric relaxation in AOT/water/heptane reverse micelles: pool size dependence.

Intramolecular charge transfer (ICT) reaction in a newly synthesized molecule, of 4-(1-morpholenyl) benzonitrile (M6C), in AOT/water/heptane reverse micelles at different pool sizes has been studied by using steady-state and time-resolved fluorescence emission spectroscopy. The pool size dependences of the reaction equilibrium constant and reaction rate have been explained in terms of the average polarity of the confined solvent pools estimated from the fluorescence emission Stokes shift of a nonreactive probe, coumarin 153, dissolved in these microemulsions. The complex permittivity measurements in the frequency range 0.01<or=nu/GHz<or=2 for these microemulsions at different pool sizes (0<or=w0<or=40) and AOT concentrations (0.1<or=c/M<or=0.5) at 298.15 K have also been performed. At sufficient water content, a large dispersion with a relaxation time of approximately 600 ps has been observed at approximately 300 MHz and attributed to the average reorientation of water molecules residing in the close vicinity of the polar interface of the AOT headgroup and n-heptane. The reorientation of these interfacial water molecules is probably responsible for the nanosecond component observed in numerous polar solvation dynamics experiments in these reverse micelles. Subsequently, the estimated polarity and the measured reorientational time scale have been used to explain the dramatic slowing down of the ICT reaction rate and its dependence on pool size in these confined environments.

Excited State Intramolecular Charge Transfer Reaction in Binary Mixtures of Water and Tertiary Butanol (TBA) : Alcohol Mole Fraction Dependence

The excited state intramolecular charge transfer reaction of 4-(1-azetidinyl)benzonitrile (P4C) has been studied in water-tertiary butanol (TBA) mixtures at different alcohol mole fractions by using steady state and time-resolved fluorescence spectroscopy. The ratio between the areas under the locally excited (LE) and charge transferred (CT) emission bands is found to exhibit a sharp rise at alcohol mole fraction approximately 0.04, a value at which several thermodynamic properties of this mixture is known to show anomalous change due to the enhancement of H-bonding network. The radiative rate associated with the LE emission also shows a maximum at this TBA mole fraction. Although the structural transition from the water-like tetrahedral network to the alcohol-like chain is reflected in the red shift of the absorption spectrum up to TBA mole fraction approximately 0.10, the emission bands (both LE and CT) show the typical nonideal alcohol mole fraction dependence at all TBA mole fractions. Quantum yield, CT radiative rate as well as transition moments also exhibit a nonideal alcohol mole fraction dependence. The time-resolved emission decay of P4C has been found to be biexponential at all TBA mole fractions, regardless of emission collection around either the LE or the CT bands. The time constant associated with the slow component (tau(slow)) shows a minimum at TBA mole fraction approximately 0.04, whereas such a minimum for the fast time constant, tau(fast) (representing the rate of LE --> CT conversion reaction) is not observed. The nonobservation of the minimum in tau(fast) might be due to the limited time resolution employed in our experiments.

Spectroscopic Studies of Catanionic Reverse Microemulsion: Correlation with the Superactivity of Horseradish Peroxidase Enzyme in a Restricted Environment

Catanionic microemulsions formed by dodecyltrimethylammonium bromide (DTAB), sodium dodecyl sulfate (SDS), n-hexanol, dodecane, and citrate buffer have been characterized by using dynamic light scattering (DLS) and spectroscopic studies. While the DLS measurements provide information about the hydrodynamic diameters of the microemulsion droplets formed upon variation of the constituents, steady-state and time-resolved fluorescence emission experiments probe the polarity and the dynamics of the trapped solvent pool inside of the microemulsion droplets of nanometer dimension. In addition, time-resolved fluorescence anisotropy shows the rigidity of the confined solvent pool as well as the coupling between the motion of a solute and those of the solvent molecules. The results obtained from the DLS and those from the steady-state and time-resolved fluorescence emission studies have been found to correlate well with the superactivity of horseradish peroxidase enzyme in the catanionic microemulsions. Subsequently, the time-zero estimate for the dynamic Stokes shift in these microemulsions reveals that approximately 50% of the total solvent dynamical response is missed due to the limited time resolution employed in our experiments. The amplitude of the missing portion is similar to what has been observed recently for nanoscopic water by Fayer and co-workers (Piletic, I. R.; Tan, H.-S.; Fayer, M. D. J. Phys. Chem. B 2005, 109, 21273).

Excited state intramolecular charge transfer reaction in nonaqueous electrolyte solutions: Temperature dependence

Temperature dependence of the excited state intramolecular charge transfer reaction of 4-(1-azetidinyl)benzonitrile (P4C) in ethyl acetate (EA), acetonitrile (ACN), and ethanol at several concentrations of lithium perchlorate (LiClO(4)) has been investigated by using the steady state and time resolved fluorescence spectroscopic techniques. The temperature range considered is 267-343 K. The temperature dependent spectral peak shifts and reaction driving force (-DeltaG(r)) in electrolyte solutions of these solvents can be explained qualitatively in terms of interaction between the reactant molecule and ion-atmosphere. Time resolved studies indicate that the decay kinetics of P4C is biexponential, regardless of solvents, LiClO(4) concentrations, and temperatures considered. Except at higher electrolyte concentrations in EA, reaction rates in solutions follow the Arrhenius-type temperature dependence where the estimated activation energy exhibits substantial electrolyte concentration dependence. The average of the experimentally measured activation energies in these three neat solvents is found to be in very good agreement with the predicted value based on data in room temperature solvents. While the rate constant in EA shows a electrolyte concentration induced parabolic dependence on reaction driving force (-DeltaG(r)), the former in ethanol and ACN increases only linearly with the increase in driving force (-DeltaG(r)). The data presented here also indicate that the step-wise increase in solvent reorganization energy via sequential addition of electrolyte induces the ICT reaction in weakly polar solvents to crossover from the Marcus inverted region to the normal region.

Limiting ionic conductivity and solvation dynamics in formamide

A self-consistent microscopic theory has been used to calculate the limiting ionic conductivity of unipositive rigid ions in formamide at different temperatures. The calculated results are found to be in good agreement with the experimental data. The above theory can also predict successfully the experimentally observed temperature dependence of total ionic conductivity of a given uniunivalent electrolyte in formamide. The effects of dynamic polar solvent response on ionic conductivity have been investigated by studying the time dependent progress of solvation of a polarity probe dissolved in formamide. The intermolecular vibration (libration) band that is often detected in the range of 100-200 cm(-1) in formamide is found to play an important role in determining both the conductivity and the ultrafast polar solvent response in formamide. The time dependent decay of polar solvation energy in formamide has been studied at three different temperatures, namely, at 283.15, 298.15, and 328.15 K. While the predicted decay at 298.15 K is in good agreement with the available experimental data, the calculated results at the other two temperatures should be tested against experiments.

Excited state intramolecular charge transfer reaction in non-aqueous reverse micelles: Effects of solvent confinement and electrolyte concentration#

Steady state and time resolved fluorescence emission spectroscopy have been employed to investigate the effects of solvent confinement and electrolyte concentration on excited state intramolecular charge transfer (ICT) reaction in 4-(1-pyrrolidinyl) benzonitrile (P5C), 4-(1-piperidinyl) benzonitrile (P6C), and 4-(1-morpholenyl) benzonitrile (M6C) in AOT/n-heptane/acetonitrile and AOT/n-heptane/methanol reverse micelles. Dramatic confinement effects have been revealed via a huge reduction (factor ranging between 100 and 20) over bulk values of both equilibrium and reaction rate constants. A strong dependence on the size of the confinement (Ws) of these quantities has also been observed. Ws dependent average static dielectric constant, viscosity and solvation time-scale have been determined. Estimated dielectric constants for confined methanol and acetonitrile show a decrease from the respective bulk values by a factor of 3–5 and viscosities increased by a factor of 2 at the highest Ws considered. Addition of electrolyte at Wsu2009=u20095 for acetonitrile is found to produce a linear increase of confined solvent viscosity but leads to a non-monotonic electrolyte concentration dependence of average solvation time. Reaction rate constant is found to decrease linearly with electrolyte concentration for P5C and P6C but non-monotonically for M6C, the highest decrease for all the molecules being ∼ 20% over the value in the absence of added electrolyte in the solvent pool. The observed huge reduction in reaction rate constant is attributed to the effects of decreased solution polarity, enhanced viscosity and slowed-down solvent reorganization of the solvent under confinement in these non-aqueous reverse micelles.

Effects of acid concentration on intramolecular charge transfer reaction of 4-(azetidinyl) benzonitrile in solution

AbstractEffects of acid concentration on excited state intramolecular charge transfer reaction of 4-(azetidinyl) benzonitrile (P4C) in aprotic (acetonitrile and ethyl acetate) and protic (ethanol) solvents have been studied by means of steady state absorption and fluorescence, and time resolved fluorescence spectroscopic techniques. While absorption and fluorescence bands of P4C have been found to be shifted towards higher energy with increasing acid concentration in acetonitrile and ethyl acetate, no significant dependence has been observed in ethanolic solutions. Reaction rate becomes increasingly slower with acid concentration in acetonitrile and ethyl acetate. In contrast, acid in ethanolic solutions does not produce such an effect on reaction rate. Time-dependent density functional theory calculations have been performed to understand the observed spectroscopic results.n Acid concentration dependence of intramolecular charge transfer reaction in a substituted benzonitryl derivative in solvents of differing polarity and association character has been investigated by using steady state and time-resolved fluorescence spectroscopic techniques where explanations have been aided by carrying out quantum chemical calculations.