Kalyanasis Sahu

Temperature dependence of solvation dynamics and anisotropy decay in a protein: ANS in bovine serum albumin

Temperature dependence of solvation dynamics and fluorescence anisotropy decay of 8-anilino-1-naphthalenesulfonate (ANS) bound to a protein, bovine serum albumin (BSA), are studied. Solvation dynamics of ANS bound to BSA displays a component (300 ps) which is independent of temperature in the range of 278-318 K and a long component which decreases from 5800 ps at 278 K to 3600 ps at 318 K. The temperature independent part is ascribed to a dynamic exchange of bound to free water with a low barrier. The temperature variation of the long component of solvation dynamics corresponds to an activation energy of 2.1 kcal mol(-1). The activation energy is ascribed to local segmental motion of the protein along with the associated water molecules and polar residues. The time scale of solvation dynamics is found to be very different from the time scale of anisotropy decay. The anisotropy decays are analyzed in terms of the wobbling motion of the probe (ANS) and the overall tumbling of the protein.

Fluorescence Quenching of Hydrogen-Bonded Coumarin 102-Phenol Complex: Effect of Excited-State Hydrogen Bonding Strength

The fate of intermolecular hydrogen bond (H-bond) upon electronic excitation of a H-bonded complex has been debated in literature. For a model H-bonded complex, coumarin 102 (C102)-phenol in a noninteracting solvent ethylene tetrachloride, time-resolved infrared spectroscopy experiment of Nibbering and coworkers suggests that the H-bond between the C102 and phenol ruptures upon electronic excitation (C. Chudoba et al. J. Phys. Chem. A1999, 103, 5625-5628). On the contrary, Zhao and Han have demonstrated for the first time that the intermolecular hydrogen bond is significantly strengthened, while not disrupted, in the electronically excited states of the hydrogen-bonded complexes upon electronic excitation using the time-dependent density functional theory method (G. J. Zhao and K. L. Han J. Phys. Chem. A2007, 111, 2469-2474). The two excited-state hydrogen bonding dynamics mechanisms have widely different predictions of the emission or electronic relaxation of the excited H-bonded complex. The excited-state hydrogen-bond strengthening mechanism proposed by Zhao and Han anticipates a stronger intermolecular interaction, while the H-bond breaking mechanism speculates no interaction between C102 and phenol. The speculation has been tested here on the same system (H-bonded C102-phenol complex) in another noninteracting solvent cyclohexane. We found a strong quenching of the C102 emission in the H-bonded complex. Selectively excited (λex = 405 nm) H-bonded complex relaxes on a fast time scale of 400-600 ps and may be attributed to the conversion of the locally excited (LE) state to a nonfluorescent charge transfer (CT) state assisted by the strong excited-state H-bond formation. A minor component (∼10%) of 2.5 to 1.8 ns is ascribed to the LE complex without a H-bond. The findings are in accordance with the new fluorescence quenching mechanism that the excited-state intermolecular hydrogen bond strengthening facilitates CT from phenol to coumarin in the excited state (G. J. Zhao et al. J. Phys. Chem. B2007, 111, 8940-8945). Fluorescence quenching was absent for anisole, where H-bond formation is not possible and was more pronounced for p-Cl-phenol, where even stronger H-bonding is expected.

A femtosecond study of excitation wavelength dependence of solvation dynamics in a PEO-PPO-PEO triblock copolymer micelle

Excitation wavelength (lambdaex) dependence of solvation dynamics of coumarin 480 (C480) in the micellar core of a water soluble triblock copolymer, PEO20-PPO70-PEO20 (Pluronic P123), is studied by femtosecond and picosecond time resolved emission spectroscopies. In the P123 micelle, the width of the emission spectrum of C480 is found to be much larger than that in bulk water. This suggests that the P123 micelle is more heterogeneous than bulk water. The steady state emission maximum of C480 in P123 micelle shows a significant red edge excitation shift by 25 nm from 453 nm at lambdaex=345 nm to 478 nm at lambdaex=435 nm. The solvation dynamics in the interior of the triblock copolymer micelle is found to depend strongly on the excitation wavelength. The excitation wavelength dependence is ascribed to a wide distribution of locations of C480 molecules in the P123 micelle with two extreme environments-a bulklike peripheral region with very fast solvent response and a very slow core region. With increase in lambdaex, contribution of the bulklike region having an ultrafast component (< or =2 ps) increases from 7% at lambdaex=375 nm to 78% at lambda(ex)=425 nm while the contribution of the ultraslow component (4500 ps) decreases from 79% to 17%.

Heterogeneity of the Electron-Trapping Kinetics in CdSe Nanoparticles

The kinetics of electron trapping in CdSe nanoparticles are examined from 0.5 ps to 1.8 ns. The ensemble kinetics fit a slow power law, but two-dimensional measurements show that the decay of each nanoparticle is exponential. A model is proposed in which defect sites provide a gateway for surface trapping and are randomly distributed on the surface. The electric field from the particles dipole moment creates the observed heterogeneity in rates.

A facile synthesis of high optical quality silver nanoparticles by ascorbic acid reduction in reverse micelles at room temperature

We report a convenient synthesis of silver nanoparticles (AgNPs) using ascorbic acid (AA) as a reducing agent in sodium dioctylsulfosuccinate (AOT) reverse micelles at w0 (=[water]/[AOT]) values of 2, 6 and 10. Simple injection of silver nitrate and AA solutions into AOT/n-heptane mixtures leads to formation of nanoparticles at room temperature in the absence of inert atmosphere or prolonged stirring. The optical quality of the surface plasmon resonance (SPR) band of the synthesized AgNPs was found to be superior (stronger peak and narrower bandwidth) than for AgNPs obtained by common reducing agents like sodium borohydride or hydrazine under similar conditions. Transmission electron microscopy (TEM) and dynamic light scattering (DLS) measurements revealed that the nanoparticles are spherical, and are slightly larger than the pure reverse micelles. Also, the size and the polydispersity increase with increase in the w0 value.

A femtosecond study of photoinduced electron transfer from dimethylaniline to coumarin dyes in a cetyltrimethylammonium bromide micelle.

Ultrafast photoinduced electron transfer (PET) from N,N-dimethylaniline to coumarin dyes in cetyltrimethylammonium bromide (CTAB) micelle is studied using femtosecond upconversion spectroscopy. The rate of PET in a CTAB micelle is found to be highly nonexponential with components much faster (approximately 10 ps) than the slow components of solvation dynamics. The ultrafast components of electron transfer exhibits a bell-shaped dependence on the free energy change which is similar to the Marcus inversion.

Ultrafast fluorescence resonance energy transfer in a micelle

Ultrafast fluorescence resonance energy transfer (FRET) from coumarin 153 (C153) to rhodamine 6G (R6G) is studied in a neutral PEO(20)-PPO(70)-PEO(20) triblock copolymer (P123) micelle and an anionic micelle (sodium dodecyl sulfate, SDS) using a femtosecond up-conversion setup. Time constants of FRET were determined from the rise time of the acceptor emission. It is shown that a micelle increases efficiency of FRET by holding the donor and the acceptor at a close distance (intramicellar FRET) and also by tuning the donor and acceptor energies. It is demonstrated that in the P123 micelle, intramicellar FRET (i.e., donor and acceptor in same micelle) occurs in 1.2 and 24 ps. In SDS micelle, there are two ultrafast components (0.7 and 13 ps) corresponding to intramicellar FRET. The role of diffusion is found to be minor in the ultrafast components of FRET. We also detected a much longer component (1000 ps) for intramicellar FRET in the larger P123 micelle.

Ultrafast fluorescence resonance energy transfer in a reverse micelle: excitation wavelength dependence

Fluorescence resonance energy transfer (FRET) from coumarin 480 (C480) to fluorescein 548 (F548) in a sodium dioctyl sulfosuccinate (AOT) reverse micelle is studied by picosecond and femtosecond emission spectroscopy. In bulk water, at the low concentration of the donor (C480) and the acceptor (F548), no FRET is observed. However, when the donor (C480) and the acceptor (F548) are confined in a AOT reverse micelle very fast FRET is observed. The time constants of FRET were obtained from the rise time of the emission of the acceptor (F548). In a AOT microemulsion, FRET is found to occur in multiple time scales--3, 200, and 2700 ps. The 3 ps component is assigned to FRET in the water pool of the reverse micelle with a donor-acceptor distance, 16 A. The 200 ps component corresponds to a donor-acceptor distance of 30 A and is ascribed to the negatively charged acceptor inside the water pool and the neutral donor inside the alkyl chains of AOT. The very long 2700 ps component may arise due to FRET from a donor outside the micelle to an acceptor inside the water pool and also from diffusion of the donor from bulk heptane to the reverse micelle. With increase in the excitation wavelength from 375 to 405 nm the relative contribution of the FRET due to C480 in the AOT reverse micelle (the 3 and 200 ps components) increases.

Ultrafast photoinduced electron transfer from dimethylaniline to coumarin dyes in sodium dodecyl sulfate and triton X-100 micelles

The primary steps of photoinduced electron transfer (PET) from N,N-dimethylaniline (DMA) to five coumarin dyes are studied in an anionic micelle [sodium dodecyl sulfate (SDS)] and a neutral micelle [triton X-100 (TX-100)] using femtosecond upconversion. The rate of PET in micelle is found to be highly nonexponential. In both the micelles, PET displays components much faster (approximately 10 ps) than the slow components (180-2900 ps) of solvation dynamics. The ultrafast components of electron transfer exhibit a bell-shaped dependence on the free energy change. This is similar to Marcus inversion. The rates of PET in TX-100 and SDS micelle are, in general, faster than those in cetyltrimethylammonium bromide (CTAB) micelle. In the SDS and TX-100 micelle, the Marcus inversion occurs at -DeltaG0 approximately 0.7 eV which is lower than that (approximately 1.2 eV) in CTAB micelle. Possible causes of variation of PET in different micelles are discussed.

Heterogeneous Reaction Rates in an Ionic Liquid: Quantitative Results from Two-Dimensional Multiple Population-Period Transient Spectroscopy

The hypotheses that ionic liquids are structurally heterogeneous at the molecular level and, even further, that this heterogeneity can transfer to the rates of reactions run in ionic liquids is being actively debated. Here, this hypothesis is tested using multiple population-period transient spectroscopy (MUPPETS), an emerging type of multidimensional measurement that resolves the kinetics of subensembles within a heterogeneous sample. A previous MUPPETS study of the excited-state twisting and electronic relaxation of auramine indicated that an ionic-liquid solvent induces rate dispersion due to a combination of heterogeneous and homogeneous processes, but those data could not quantitatively separate these contributions [Khurmi, C.; Berg, M. A. J. Phys. Chem. Lett.2010, 1, 161]. New MUPPETS data that include phase resolution and subtraction of thermal gratings are presented here and are successfully modeled. The total range of reaction rates (10--90%) is a factor of 70. If the solvent effect is viewed as a set of local viscosities, the viscosity distribution is broad and highly asymmetric. However, if the solvent is viewed as changing a reaction barrier, the data correspond to a Gaussian distribution of barrier heights. The relaxation of each subensemble is nonexponential with an initial induction period, but the shape of the decay is invariant across the rate distribution. A small (2%), long-lived component is identified as a part of the homogeneous kinetic scheme and thus as a secondary channel for excited-state relaxation, not as an impurity or alternative ground-state form of auramine. On the basis of these results, we suggest that the primary cause of rate heterogeneity is a long-lived local electric field acting on the charge redistribution during the reaction.