The Pivotal Role of Hot Carriers in Plasmonic Catalysis of C-N Bond Forming Reaction of Amines.

Here, we demonstrate the simultaneous utilization of both the hot carriers (electrons and holes) in the photocatalytic transformation of benzylamine to N-benzylidenebenzylamine and the scope of reaction has also been successfully demonstrated with catalytic oxidation of 4-methoxybenzylamine. The wavelength-dependent excitation of AuNP allows us to tune the potential energy of charge carriers relative to the redox potential of the reactants which leads to energetically favorable product formation on the nanoparticle surface. We capture the formation of reaction intermediates and products by using in situ Raman spectroscopy, complemented by NMR spectroscopy and GC-MS. Based on the experimental substantiations, a plausible reaction mechanism has been proposed.

Unearthing the factors governing site specific rates of electronic excitations in multicomponent plasmonic systems and catalysts.

We use experimental and computational studies of core-shell metal-semiconductor and metal-molecule systems to investigate the mechanism of energy flow and energetic charge carrier generation in multicomponent plasmonic systems. We demonstrate that the rates of plasmon decay through the formation of energetic charge carriers are governed by two factors: (1) the intensity of the local plasmon induced electric fields at a specific location in the multicomponent nanostructure, and (2) the availability of direct, momentum conserved electronic excitations in the material located in that specific location. We propose a unifying physical framework that describes the flow of energy in all multicomponent plasmonic systems and leads us towards molecular control of the energy flow and excited charge carrier generation in these systems.

Chemical Requirement for Extracting Energetic Charge Carriers from Plasmonic Metal Nanoparticles to Perform Electron-Transfer Reactions.

Performing electron-transfer reactions on metal nanoparticles requires separation of charge carriers at the nanoparticle and their transfer to the reacting molecules. Inducing these reactions using light is challenging due to the exceedingly short lifetimes of energetic charge carriers formed in metal nanoparticles under light illumination. The results described here show that certain conditions must be met to drive these electron-transfer reactions on plasmonic nanoparticles. One critical requirement is that the process of electronic excitation takes place at the nanoparticle/molecule interface. This is accomplished by high plasmonic electric fields at the surface of plasmonic nanoparticles. Furthermore, it is also evident from our study that the electron (or hole)-donating capacity of the hole (or electron) scavengers needs to be high enough to allow for the extraction of holes (or electrons) from the nanoparticle/molecule complex, therefore completing the catalytic cycle. We discuss these findings through a case study of the conversion of methylene blue (MB) into a reduced MB ion radical on the surface of plasmonic Ag and Ag-Pt core-shell nanoparticles. To directly monitor the reduction reaction of MB on the nanoparticle surfaces, we have used time-dependent in situ surface-enhanced Raman scattering measurement, which also informs us about the underlying mechanistic details of plasmon-driven charge transfer.

Probing single-molecule electron-hole transfer dynamics at a molecule-NiO semiconductor nanocrystalline interface.

Interfacial charge transfer dynamics in dye-sensitized NiO nanoparticles are being investigated for photocathodes in p-type dye-sensitized solar cells. In the photoreaction, after fast electron transfer from NiO to a molecule, the recombination of the hole in the nanoparticles with the electron in a reduced molecule plays an important role in the charge separation process and solar energy harvesting. Nevertheless, knowledge of the interfacial charge recombination (CR) rate and its mechanism is still limited due to the complex photoinduced electron and hole dynamics and lack of characterization of the inhomogeneity of the dynamics. Here, we report our work on probing interfacial charge recombination dynamics in Zn(ii)-5,10,15,20-tetra(3-carboxyphenyl)porphyrin (m-ZnTCPP) dye-sensitized NiO nanoparticles by correlating single-molecule fluorescence blinking dynamics with charge transfer dynamics using single-molecule photon-stamping spectroscopy. The correlated analyses of single-molecule fluorescence intensity, lifetime, and blinking reveal the intrinsic distribution and temporal fluctuation of interfacial charge transfer reactivity, which are closely related to site-specific molecular interactions and dynamics.

Simultaneous Spectroscopic and Topographic Imaging of Single-Molecule Interfacial Electron-Transfer Reactivity and Local Nanoscale Environment.

The fundamental information related to the energy flow between molecules and substrate surfaces as a function of surface site geometry and molecular structure is critical for understanding interfacial electron-transfer (ET) dynamics. The inhomogeneous nanoscale molecule-surface and molecule-molecule interactions are presumably the origins of the complexity in interfacial ET dynamics; thus, identifying the environment of molecules at nanoscale is crucial. We have developed atomic force microscopy (AFM) correlated single-molecule fluorescence intensity/lifetime imaging microscopy (AFM-SMFLIM) capable of identifying and characterizing individual molecules distributed across the heterogeneous surface at the nanometer length scale. Using the novel AFM-SMFLIM imaging, we are able to obtain nanoscale morphology and interfacial ET dynamics at a single-molecule level. Moreover, the observed blinking behavior and lifetime of each molecule in combination with the topography of the environment at nanoscale provide the location of each molecule on the surface (TiO2 vs cover glass) at nanoscale and the coupling strength of each molecule with TiO2 nanoparticles.

Probing Electric Field Effect on Covalent Interactions at a Molecule-Semiconductor Interface.

Fundamental understanding of the energetic coupling properties of a molecule-semiconductor interface is of great importance. The changes in molecular conformations and vibrational modes can have significant impact on the interfacial charge transfer reactions. Here, we have probed the change in the interface properties of alizarin-TiO2 system as a result of the externally applied electric field using single-hot spot microscopic surface-enhanced Raman spectroscopy (SMSERS) and provided a theoretical understanding of our experimental results by density functional theory (DFT) calculations. The perturbation, caused by the external potential, has been observed as a shift and splitting of the 648 cm(-1) peak, typical indicator of the strong coupling between alizarin and TiO2, at SMSERS. On the basis of our experimental results and DFT calculations, we suggest that electric field has significant effects on vibrational coupling at the molecule-TiO2 interface. The presence of perturbed alizarin-TiO2 coupling under interfacial electric potential may lead to changes in the interfacial electron transfer dynamics. Additionally, heterogeneously distributed dye molecules at the interface on nanometer length scale and different chromophore-semiconductor binding interactions under charge accumulation associated interfacial electric field changes create intrinsically inhomogeneous interfacial ET dynamics associated with both static and dynamic disorders.

Probing Driving Force and Electron Accepting State Density Dependent Interfacial Electron Transfer Dynamics: Suppressed Fluorescence Blinking of Single Molecules on Indium Tin Oxide Semiconductor.

Photoinduced, interfacial electron transfer (ET) dynamics between m-ZnTCPP and Sn-doped In2O3 (ITO) film has been studied using single-molecule photon-stamping spectroscopy. The observed ET dynamics of single m-ZnTCPP adsorbed on ITO was compared with that of m-ZnTCPP adsorbed on TiO2 NPs with and without applied electric potential. Compared to m-ZnTCPP on the TiO2 NP surface, m-ZnTCPP on the ITO surface shows a reduced lifetime as well as suppressed blinking and a quasi-continuous distribution of fluorescence intensities, presumably due to higher electron density in ITO. The higher electron density leads to the occupancy of CB acceptor states/trap states, which supports a higher backward electron transfer (BET) rate that results in a quasi-continuous distribution of fluorescence intensities. The dependence of BET rate on electron density and charge trapping is consistent with our previous observations of quasi-continuous distribution of fluorescence intensities of m-ZnTCPP on TiO2 NPs with applied negative potential across the dye-TiO2 interface. The quasi-continuous distribution of fluorescence intensities in both cases of m-ZnTCPP on the ITO surface and m-ZnTCPP on TiO2 NPs with applied negative potential indicates that the electron density in the semiconductor plays a dominant role in dictating the changes in rates of charge transfer, rather than the relative energetics between electrons in the semiconductor and the oxidized sensitizer.

Single-molecule interfacial electron transfer dynamics of porphyrin on TiO2 nanoparticles: dissecting the interfacial electric field and electron accepting state density dependent dynamics.

Single-molecule photon-stamping spectroscopy correlated with electrochemical techniques was used to dissect complex interfacial electron transfer (ET) dynamics by probing an m-ZnTCPP molecule anchored to a TiO2 NP surface while electrochemically controlling the energetically-accessible surface states of TiO2 NPs. Application of negative potential increases the electron density in TiO2 NPs, resulting in hindered forward ET and enhanced backward ET due to the changes in the interfacial electric field and the occupancy of acceptor states.

A step toward the development of high-temperature stable ionic liquid-in-oil microemulsions containing double-chain anionic surface active ionic liquid.

Owing to their fascinating properties and wide range of potential applications, interest in nonaqueous microemulsions has escalated in the past decade. In the recent past, nonaqueous microemulsions containing ionic liquids (ILs) have been utilized in performing chemical reactions, preparation of nanomaterials, synthesis of nanostructured polymers, and drug delivery systems. The most promising fact about IL-in-oil microemulsions is their high thermal stability compared to that of aqueous microemulsions. Recently, surfactant-like properties of surface active ionic liquids (SAILs) have been used for preparation of microemulsions with high-temperature stability and temperature insensitivity. However, previously described methods present a limited possibility of developing IL-in-oil microemulsions with a wide range of thermal stability. With our previous work, we introduced a novel method of creating a huge number of IL-in-oil microemulsions (Rao, V. G.; Ghosh, S.; Ghatak, C.; Mandal, S.; Brahmachari, U.; Sarkar, N. J. Phys. Chem. B2012, 116, 2850-2855), composed of a SAIL as a surfactant, room-temperature ionic liquids as a polar phase, and benzene as a nonpolar phase. The use of benzene as a nonpolar solvent limits the application of the microemulsions to temperatures below 353 K. To overcome this limitation, we have synthesized N,N-dimethylethanolammonium 1,4-bis(2-ethylhexyl) sulfosuccinate (DAAOT), which was used as a surfactant. DAAOT in combination with isopropyl myristate (IPM, as an oil phase) and ILs (as a polar phase) produces a huge number of high-temperature stable IL-in-oil microemulsions. By far, this is the first report of a huge number of high-temperature stable IL-in-oil microemulsions. In particular, we demonstrate the wide range of thermal stability of [C6mim][TF2N]/DAAOT/IPM microemulsions by performing a phase behavior study, dynamic light scattering measurements, and (1)H NMR measurements and by using coumarin-480 (C-480) as a fluorescent probe molecule.

Effect of alkyl chain of room temperature ionic liquid (RTILs) on the phase behavior of [C2mim][C(n)SO4]/TX-100/cyclohexane microemulsions: solvent and rotational relaxation study.

In this investigation, we present microemulsions comprising a nonionic surfactant, Triton X-100 (TX-100), cyclohexane as nonpolar phase, and room temperature ionic liquids (RTILs) as a polar medium. To investigate the effect of alkyl chain length of ionic liquid on the physicochemical properties of microemulsions, we have used 1-ethyl-3-methylimidazolium n-butyl sulfate [C2mim][C4SO4], 1-ethyl-3-methylimidazolium n-hexyl sulfate [C2mim][C6SO4], and 1-ethyl-3-methylimidazolium n-octyl sulfate [C2mim][C8SO4] as polar media. The phase behavior of these ternary systems is investigated by direct observation of transition from clear transparent solution to turbid solution by using UV-vis spectrophotometer at 298 K. The single-phase region is found to increase with increase in chain length of RTIL anion. Dynamic light scattering (DLS) measurements revealed the formation of highly stable nano-sized RTIL-containing microemulsions. The size of the microemulsions increases with the addition of ionic liquid. The maximum increase in size is observed with the addition of [C2mim][C4SO4]. It is proposed that the long octyl chain of octyl sulfate allows the anion to align itself along the TX-100 molecules which increases the rigidity of microemulsions, whereas in case of [C2mim][C4SO4], the short butyl chain is apparently unable to do the same. The dynamics of solvent and rotational relaxation of coumarin 480 (C-480) has also been investigated in these ionic liquid containing microemulsions ([C2mim][C4SO4]/TX-100/cyclohexane, [C2mim][C6SO4]/TX-100/cyclohexane, and [C2mim][C8SO4]/TX-100/cyclohexane) using picosecond time-resolved fluorescence spectroscopy. In RTIL microemulsions, solvent relaxation becomes retarded compared to neat RTIL. We have also shown that with increasing R value, the solvation dynamics becomes faster and the decrease in average solvation time is more pronounced in [C2mim][C4SO4]/TX-100/cyclohexane compared to [C2mim][C6SO4]/TX-100/cyclohexane and [C2mim][C8SO4]/TX-100/cyclohexane microemulsions.

Phase boundaries, structural characteristics, and NMR spectra of ionic liquid-in-oil microemulsions containing double chain surface active ionic liquid: a comparative study.

A method developed for the first time, to create a huge number of ionic liquid (IL)-in-oil microemulsions has been discussed in our earlier publication (Rao, V. G.; Ghosh, S.; Ghatak, C.; Mandal, S.; Brahmachari, U.; Sarkar, N. J. Phys. Chem. B 2012, 116, 2850-2855). Here, we present facile methods to adjust the structural parameters of microemulsions using different ionic liquids (ILs) as additives (polar phase). We have characterized ILs/[C(4)mim][AOT]/benzene ternary system by performing a phase behavior study, dynamic light scattering (DLS) measurements, and (1)H NMR measurements. The IL loading capacity of microemulsions (area of single phase region) (i) increases with increase in alkyl chain length of cation of ILs and follows the trend [C(6)mim][TF(2)N] > [C(4)mim][TF(2)N] > [C(2)mim][TF(2)N], (ii) increases with decrease in cation anion interaction strength of added ILs and follows the trend [C(4)mim][TF(2)N] > [C(4)mim][PF(6)] > [C(4)mim][BF(4)]. So depending on the IL used, the amount of IL within the core of microemulsions can be easily manipulated to directly affect the size of aggregates in microemulsions. The size increase with increasing R value (R value is defined as the molar ratio of RTILs to [C(4)mim][AOT]) was found to be maximum in the case of [C(2)mim][TF(2)N]/[C(4)mim][AOT]/benzene microemulsions and follows the trend [C(2)mim][TF(2)N] > [C(4)mim][TF(2)N] > [C(6)mim][TF(2)N]. However, the size increase was almost the same with increase in R value in the case of ILs with different anions. The most promising fact about IL-in-oil microemulsions is their high thermal stability compared to that of aqueous microemulsions, so we investigated the effect of temperature on size of aggregates in microemulsions at R = 1.0. It is evident from dynamic light scattering measurements that the aggregates in microemulsions remain monodisperse in nature with increasing temperature, and in all the cases, the size of aggregates in microemulsions decreases with increasing temperature. The effect of water addition on IL-in-oil (IL/O) microemulsions was also studied in detail. By far, this is the first report where the effect of water addition on microemulsions containing hydrophobic ILs is being reported and compared with microemulsions containing hydrophilic ILs. We observed that the added water has a prominent effect on the microstructure of the microemulsions. In all the cases, (1)H NMR spectra provide more detailed information about intra/intermolecular interactions thus affording a clear picture of locations of (i) the RTILs in RTILs/[C(4)mim][AOT]/benzene microemulsions and (ii) the added water molecules in microemulsions.

Modulation of the photophysical properties of 2,2'-bipyridine-3,3'-diol inside bile salt aggregates: a fluorescence-based study for the molecular recognition of bile salts.

2,2'-Bipyridine-3,3'-diol (BP(OH)(2)) has been used as a sensitive excited-state intramolecular proton transfer fluorophore to assess different bile salt aggregates as one of the potential biologically relevant host systems useful for carrying many sparingly water-soluble drug molecules. The formation of inclusion complexes, complex-induced fluorescence behavior, and their binding ability have been investigated from the modulated photophysics of BP(OH)(2) by means of photophysical techniques. The constrained hydrophobic environment provided by the aggregates significantly reduces the water-assisted nonradiative decay channels and lengthens the fluorescence lifetime of the proton-transferred DK tautomer. Both the absorption and fluorescence properties of BP(OH)(2) are found to be sensitive to the change in the structure, size, and hydrophobicity of the aggregates. Fluorescence quenching experiments were performed to gain insight into the differential distribution of the probe molecules between bulk aqueous phase and nanocavities of various aggregates. The observation of longer fluorescence lifetime and rotational relaxation time in NaDC aggregates compared to that in NaCh and NaTC aggregates indicates that the binding structures of NaDC aggregates are more rigid due to its greater hydrophobicity and larger size and therefore provide better protection to the bound guest. It is noteworthy to mention that the hydrophobic microenvironments provided by bile salt aggregates are much stronger than that provided by micelles and cyclodextrins. The accessibility of water to the aggregate-bound guest can significantly be enhanced with the addition of organic cosolvents. However, the efficiency decreases in the order of dimethylformamide, acetonitrile, and methanol.

Solvent and rotational relaxation of coumarin-153 and coumarin-480 in ionic liquid (1-butyl-3-methylimidazolium tetrafluoroborate) modified sodium 1,4-bis(2-ethylhexyl) sulfosuccinate (NaAOT) micelle.

Understanding ion transport dynamics, structure of surfactant aggregates in ionic liquids or ionic liquid/water solutions are quite interesting and potentially important due to widespread applications of surfactant-based systems. In this manuscript we have investigated the effect of 1-butyl-3-methylimidazolium tetrafluoroborate (bmimBF(4)) addition on solvent and rotational relaxation of coumarin-153 (C-153) and coumarin-480 (C-480) in aqueous solution of sodium 1,4-bis(2-ethylhexyl) sulfosuccinate (NaAOT) using steady state and picosecond time resolved fluorescence spectroscopy. The strong adsorption of the bmim(+) at the interface and the role of the ionic liquid particularly the cation bmim(+) in the modification of the interfacial geometry were probed by the analysis of decay parameters and the rotational relaxation parameters. Since the addition of the NaAOT in water-bmimBF(4) mixture above critical micellar concentration (48 mM, obtained from observing pyrene fluorescence) causes strong adsorption of the ionic liquid particularly the cation bmim(+), the average solvation time, particularly the slow component increases significantly. More importantly we have found the probe dependent solvation dynamics due to the different location of the probe molecules, C-153 and C-480. C-153 being hydrophobic in nature resides in the stern layer and the adsorption of the bmim(+) at the interface modifies stern layer more effectively. So we have observed more pronounced change in solvation dynamics in case of C-153 compared to that in case of C-480. The fluorescence anisotropy decays of the probe molecules were found to be biexponential in nature. The anisotropy decay was interpreted by using a model which consists of the wobbling (rotational) and translational diffusion of the dye coupled with the rotational motion of the micelle as a whole.

Aggregation behavior of Triton X-100 with a mixture of two room-temperature ionic liquids: can we identify the mutual penetration of ionic liquids in ionic liquid containing micellar aggregates?

In this manuscript, we have characterized two different micellar aggregates containing all nonvolatile components. We have shown (i) the effect of ethylammonium nitrate (EAN) addition on the properties of micellar solution of Triton X-100 in 1-butyl-3-methylimidazolium hexafluorophosphate (bmimPF(6)) and (ii) the effect of bmimPF(6) addition on the properties of micellar solution of Triton X-100 in EAN. To investigate the effect, we have used (1)H NMR, pulsed-field gradient spin-echo NMR (PFGSE NMR), and methyl orange (MO) and coumarin 153 (C-153) as absorption and emission probes, respectively. The penetration of added EAN inside the Triton X-100/bmimPF(6) micellar aggregates is indicated by (i) red shift in both the absorption spectra of MO and emission spectra of C-153 and (ii) downfield shift of proton signals of ethylene oxide units in Triton X-100. On the other hand, (1)H NMR and PFGSE NMR indicates the penetration of added bmimPF(6) inside the Triton X-100/EAN micellar aggregates. However, the constancy of both the absorption spectra of MO and emission spectra of C-153 indicates that the microenvironment around the probe molecules remains unaffected. We have also investigated the effect of micelle formation and the effect of penetration of ionic liquids (ILs) in micellar aggregates, on the solvation dynamics of C-153. The solvent relaxation around C-153 gets retarded on going from neat ILs to the micellar solution of Triton X-100 in ILs. In addition to this, we have also observed that with the addition of EAN in Triton X-100/bmimPF(6) micellar aggregates the solvation dynamics becomes faster, whereas with the addition of bmimPF(6) in Triton X-100/EAN micellar aggregates we did not observe any notable change in solvation dynamics. This observation further supports the conclusions drawn from UV-visible and NMR studies.

Study of fluorescence resonance energy transfer in zwitterionic micelle: ionic-liquid-induced changes in FRET parameters.

The fluorescence resonance energy transfer (FRET) using Coumarin-153 (C-153) as the donor and Rhodamine 6G (R6G) as the acceptor is studied in an aqueous solution of N-hexadecyl-N,N-dimethylammonio-1-propanesulfonate (SB-16) micelles by steady-state and picosecond time-resolved fluorescence spectroscopy. We have determined the rate of FRET (k(FRET)) from the rise of the acceptor (R6G) emission. In the absence of donor (C-153), the acceptor (R6G) displays a single-exponential decay with average lifetime of 4.77 ns, whereas in presence of donor (C-153), the acceptor (R6G) exhibits a biexponential fluorescence transient having a distinct rise component of 0.94 ns and decay component of 5.16 ns. We have carried out a comparative study of changes in FRET parameters upon addition of three different ionic liquids (ILs), 1-ethyl-3-methylimidazolium ethylsulfate [C(2)mim][C(2)SO(4)], 1-ethyl-3-methylimidazolium n-butylsulfate [C(2)mim][C(4)SO(4)], and 1-ethyl-3-methylimidazolium n-hexylsulfate [C(2)mim][C(6)SO(4)], where each ionic liquid bears the same cationic part and the anionic parts differ in the alkyl chain length only. It has been observed that with gradual addition of the ILs [C(2)mim][C(2)SO(4)], [C(2)mim][C(4)SO(4)], and [C(2)mim][C(6)SO(4)], the rise component gradually decreases and the rate of FRET (k(FRET)) gradually increases. The k(FRET) was found to be 1.06 × 10(9) s(-1) in 28 mM aqueous SB-16 micelles. With the addition of 100 mM [C(2)mim][C(2)SO(4)], the k(FRET) increases by a factor of 1.33 (1.41 × 10(9) s(-1)), whereas with the addition of 100 mM [C(2)mim][C(6)SO(4)] it increases by a factor of 3.25 (3.45 × 10(9) s(-1)). This rapid increase in k(FRET) in the case of [C(2)mim][C(6)SO(4)] can be explained by our earlier observation ( Rao, V. G.; Ghatak, C.; Ghosh, S.; Mandal, S.; Sarkar, N. J. Phys. Chem. B2012, 116, 3690-3698 ), where we have shown that with the addition of [C(2)mim][C(6)SO(4)], C-153 moves toward the outer surface of the micelle. This movement of C-153 causes reduction in donor-acceptor distance and enhancement in FRET rate (k(FRET)). This is well-supported by the reduced donor-acceptor distance (R(DA)) observed with the addition of [C(2)mim][C(6)SO(4)]. The R(DA) was found to be 29.1 Å in 28 mM aqueous SB-16 micelles. With the addition of 100 mM [C(2)mim][C(6)SO(4)], the R(DA) decreases to 24.8 Å. With further increase in the concentration of [C(2)mim][C(6)SO(4)], the R(DA) decreases, but the time constant for the rise of acceptor emission decreases to such an extent that we are unable to observe it by our instrumental setup.

Tuning the probe location on zwitterionic micellar system with variation of pH and addition of surfactants with different alkyl chains: solvent and rotational relaxation studies.

In this manuscript, we have modulated the location of an anionic probe, Coumarin-343 (C-343) in a zwitterionic (N-hexadecyl-N,N-dimethylammonio-1-propanesulfonate (SB-16)) micellar system by three different approaches. The effect of addition of the surfactant sodium dodecyl sulfate (SDS) and the room temperature ionic liquid (RTIL), 1-ethyl-3-methylimidazolium octylsulfate (EmimOs) and N,N-dimethylethanol hexanoate (DAH), to the micellar solution has been studied. The effect of pH variation has been studied as well using solvent and rotational measurements. Migration of the anionic probe, C-343, from the palisade layer of SB-16 micelle to the bulk water has been observed to varying extents with the addition of SDS and EmimOs. The effect is much more pronounced in the presence of SDS and can be ascribed to the presence of the long alkyl (dodecyl) chain on SDS which can easily orient itself and fuse inside the SB-16 micelle and facilitate the observed migration of the probe molecule. This phenomenon is confirmed by faster solvation and rotational relaxation of the investigated probe molecule. The analogous fusion process is difficult in case of EmimOs and DAH because of their comparatively smaller alkyl (octyl and hexanoate) chain. However, the direction of C-343 migration is reversed with the decrease of pH of the SB-16 micellar medium. An increase in the average solvation and rotational relaxation time of the probe in acidic medium has been observed. Since experimental conditions are maintained such that the probe molecules and the zwitterionic SB-16 micelles remain oppositely charged, the observed results can be attributed to the increased electrostatic interaction (attractive) between them. Temperature dependent study also supports this finding.

Photophysics of 3,3'-diethyloxadicarbocyanine iodide (DODCI) in ionic liquid micelle and binary mixtures of ionic liquids: effect of confinement and viscosity on photoisomerization rate.

The dynamics of photoisomerization of 3,3'-diethyloxadicarbocyanine iodide (DODCI) has been investigated inside micellar environment formed by a surfactant-like ionic liquid, 1-butyl-3-methylimidazolium octyl sulfate ([C(4)mim][C(8)SO(4)]) and also in binary mixture of another ionic liquid, N,N,N-trimethyl-N-propyl ammonium bis(trifluoromethanesulfonyl) imide, ([N(3111)][Tf(2)N]) with methanol, acetonitrile, and n-propanol by using steady-state and picosecond time-resolved fluorescence spectroscopy. The entrapment of DODCI into the [C(4)mim][C(8)SO(4)] micellar environment led to the enhanced fluorescence intensity along with ~13 nm red shift in the emission maxima. A sharp increase in the fluorescence quantum yield (Φ) and the lifetime (τ(f)) near the critical micelle concentration (cmc) range is observed followed by saturation at higher concentration. As a result of partitioning of the probe molecules in the micellar phase from water, the nonradiative rate constant (k(nr)) of DODCI decreases 2.7 times than in water. The retardation of isomerization rate is due to high microviscosity of the micellar system compared to bulk water. In order to understand how the rate of isomerization depends on polarity as well as viscosity, we have measured isomerization rate in neat [N(3111)][Tf(2)N] and its mixtures with polar solvents, like methanol, acetonitrile, and n-propanol. The addition of methanol and n-propanol increases the polarity, but viscosity of the medium decreases. The nonradiative rate constant that represents the rate of photoisomerization decreases with the addition of the polar solvent in [N(3111)][Tf(2)N]. Complete analysis of all the experimental results indicate that viscosity is the sole parameter that regulates the rate of photoisomerization. Temperature-dependent k(nr) are used to determine the activation energy (E(a)) in 100 mM [C(4)mim][C(8)SO(4)] solution and neat [N(3111)][Tf(2)N] system.

Ionic liquid-in-oil microemulsions composed of double chain surface active ionic liquid as a surfactant: temperature dependent solvent and rotational relaxation dynamics of coumarin-153 in [Py][TF2N]/[C4mim][AOT]/benzene microemulsions.

In the recent past, nonaqueous microemulsions containing ionic liquids (ILs) have been utilized for performing chemical reactions, preparation of nanomaterials, and synthesis of nanostructured polymers and in drug delivery systems. The most promising fact about IL-in-oil microemulsions is their high thermal stability compared to that of aqueous microemulsions. In our earlier publication (Rao, V. G.; Ghosh, S.; Ghatak, C.; Mandal, S.; Brahmachari, U.; Sarkar, N. J. Phys. Chem. B 2012, 116, 2850-2855), we presented for the first time the possibility of creating huge number of IL-in-oil microemulsions, just by replacing the inorganic cation, Na(+), of NaAOT by any organic cation and using different ionic liquids as the polar core. In this manuscript we are interested in exploring the effect of temperature on such systems. We have characterized the phase diagram of the [Py][TF2N]/[C4mim][AOT]/benzene ternary system at 298 K. We have shown that in the experimental temperature range employed in this study, the microemulsions remain stable and a slight decrease in the size of the microemulsions is observed with increasing temperature. We have reported the detailed study of solvent and rotational relaxation of coumarin 153 (C-153) in neat IL, N-methyl-N-propylpyrrolidinium bis((trifluoromethyl)sulfonyl)imide ([Py][TF2N]), and in [Py][TF2N]/[C4mim][AOT]/benzene microemulsions using steady state and picosecond time-resolved spectroscopy. We have monitored the effect of (i) varying the [Py][TF2N]/[C4mim][AOT] molar ratio (R value) and (ii) temperature on solvent and rotational relaxation of C-153. The features observed in absorption and emission spectra clearly indicate that (i) the probe molecules reside at the polar interfacial region of the [Py][TF2N]/[C4mim][AOT]/benzene microemulsions and (ii) with increasing R value the probe molecules move toward the polar IL-pool of the microemulsion. We have shown that the increase in solvation time on going from neat [Py][TF2N] to [Py][TF2N]-containing microemulsions is very small compared to the increase in solvation time on going from pure water to water-containing microemulsions. The average solvation time decreases with increasing R values at 298 K, but it shows only a small R dependence compared to microemulsions containing solvents capable of forming hydrogen bonds. We have also shown that the temperature has substantial effect on the solvent and rotational relaxation of C-153 in neat [Py][TF2N] compared to that of [Py][TF2N]/[C4mim][AOT]/benzene microemulsions at R = 0.69.

Modulation of photophysics and photodynamics of 1'-hydroxy-2'-acetonaphthone (HAN) in bile salt aggregates: a study of polarity and nanoconfinement effects.

The modulation of the photophysical properties of 1'-hydroxy-2'-acetonaphthone (HAN) upon encapsulation into the hydrophobic nanocavities of different bile salt aggregates has been investigated for the first time using steady-state and time-resolved fluorescence spectroscopy. Because HAN is very sensitive to the polarity of the microenvironment in which it is confined, we performed a comparative study on the excited-state binding dynamics of HAN using three different bile salts of varying hydrophobicity. The encapsulation of HAN into the bile salt aggregates led to an enhanced fluorescence intensity along with a significant blue shift in the emission maxima that was highly sensitive to the confined microenvironment. Using HAN as a sensitive fluorophore to probe the nanocavities of bile salt aggregates in aqueous solution, we found different mechanisms of probe encapsulation depending on the degree of hydrophobicity of the nanocavities, which results in a difference in the alteration of the spectral behavior. A sharp increase in the fluorescence quantum yield near the cmc was observed, followed by saturation for all three bile salt aggregates. However, maximum fluorescence quantum yield in NaDC aggregates can be rationalized by maximum partitioning of HAN into the more hydrophobic and rigid environment provided by NaDC aggregates. Moreover, the alteration of the spectral behavior with increasing concentration of bile salts strikingly differs from that observed previously in the presence of conventional surfactants. Time-resolved fluorescence measurements further elucidated how the probe molecules interact with the aggregates. Longer fluorescence lifetime and anisotropy values clearly indicate the caging of the tautomers of HAN into the hydrophobic nanocavities of bile salt aggregates. This work further demonstrates the changes in the fluorescence properties of HAN with structural changes of bile salt aggregates induced by the addition of salt and organic cosolvent.

Ionic-liquid-induced changes in the properties of aqueous zwitterionic surfactant solution: solvent and rotational relaxation studies.

In the recent past, the chameleon-like nature of zwitterionic micelles has been utilized for performing electrophilic, nucleophilic, base, and acid catalyzed reactions. But the use of simple salts to induce the zwitterionic character limits the variation to inorganic cations and anions only. To overcome this problem, we have used room temperature ionic liquids (RTILs), which can be tailored according to need. More precisely, we have shown the effect of added RTILs on the nature of water molecules in the palisade layer of a zwitterionic (N-hexadecyl-N,N-dimethylammonio-1-propanesulfonate (SB-16)) micelle using solvation and rotational relaxation studies of C-153 dye. We have carried out a comparative study of changes in the solvent and rotational relaxation parameters of C-153 in an aqueous solution of SB-16 upon addition of three different ionic liquids (ILs): 1-ethyl-3-methylimidazolium ethyl sulfate [C(2)mim][C(2)SO(4)], 1-ethyl-3-methylimidazolium n-butyl sulfate [C(2)mim][C(4)SO(4)], and 1-ethyl-3-methylimidazolium n-hexyl sulfate [C(2)mim][C(6)SO(4)]. It has been observed that in the presence of added RTILs the solvation dynamics become faster and the change in solvation dynamics is more pronounced in the case of [C(2)mim][C(6)SO(4)] compared to that for [C(2)mim][C(4)SO(4)] and [C(2)mim][C(2)SO(4)]. This can be accounted for by considering the increased water penetration (increased microfluidity) with the addition of ILs. In accordance with solvation dynamics results, fluorescence anisotropy studies also indicate an increase in microfluidity of the palisade layer of the SB-16 micelle with the added RTILs. The average rotational relaxation time in 28 mM SB-16 was found to be 1.12 ns. With the addition of 800 mM [C(2)mim][C(2)SO(4)], the average rotational relaxation time remains the same (1.12 ns), whereas with the addition of 800 mM [C(2)mim][C(6)SO(4)] it decreases to 0.40 ns. This observation is in agreement with our earlier report on the microfluidity of SB-16 solution with the addition of [C(2)mim][C(2)SO(4)] and [C(2)mim][C(6)SO(4)] (Rao, V. G.; Ghatak, C.; Ghosh, S.; Mandal, S.; Sarkar, N. Chem. Phys. Chem. DOI: 10.1002/cphc.201100866).