Doseok Kim

Structures of Ionic Liquids with Different Anions Studied by Infrared Vibration Spectroscopy

We investigated the structures of ionic liquids (1-butyl-3-methylimidazolium iodide [BMIM][I] and 1-butyl-3-methylimidazolium tetrafluoroborate [BMIM][BF4]) and their aqueous mixtures using attenuated total reflection (ATR) infrared absorption and Raman spectroscopy. The ATR spectrum in the CHx (x = 1, 2, 3) vibration region from 2800 to 3200 cm-1 was very different between [BMIM][BF4] and [BMIM][I] even though all the spectral features in this region were from the butyl chain and the imidazolium ring of the same cation. The spectrum did not change appreciably irrespective of the water concentration for [BMIM][BF4], whereas the spectrum from [BMIM][I] showed significant changes as the water concentration was increased, especially in CH-vibration modes from the imidazolium ring. For very diluted solutions both aqueous mixtures of [BMIM][I] and [BMIM][BF4] showed very similar spectra. Mixing of [BMIM][I] with heavy water (D2O) facilitated the isotopic exchange of the proton attached to the most acidic carbon of the imidazolium ring into deuterium from D2O, whereas even prolonged exposure to D2O did not induce any isotopic exchange for [BMIM][BF4]. Raman spectra around 600 cm(-1) indicative of the butyl chain conformation also changed differently as the water concentration was increased between [BMIM][I] and [BMIM][BF4]. These differences are considered to come from the variation in the position of the anion, where I- is expected to be closer to the C(2) hydrogen of the imidazolium cation and interacting more specifically as compared to BF(4-).

Structural Change of 1-Butyl-3-methylimidazolium Tetrafluoroborate + Water Mixtures Studied by Infrared Vibrational Spectroscopy

Mixtures of ionic liquid (IL, 1-butyl-3-methylimidazolium tetrafluoroborate, [BMIM][BF4]) and water with varying concentrations were studied by attenuated total reflection infrared absorption and Raman spectroscopy. Changes in the peak intensities and peak positions of CHx (x = 1, 2, 3) vibration modes of the cation of the IL and OH vibration modes of the water molecules were investigated. Peaks from normal-mode stretch vibrations of CH bonds belonging to the imidazolium ring of the cation did not change their positions, while those from the terminal methyl group of the butyl chain blueshifted by approximately 10 cm-1 with the addition of water. On the other hand, change in the spectral shape in the OH stretch vibration region shows hydrogen-bonding network of water molecules breaking down rapidly as the IL is added. Trends in the change of the peak positions and the peak intensities suggested qualitative change of the intermolecular structure in the [BMIM][BF4] + H2O mixture at 32 +/- 2 and 45 +/- 2 mol/L of water concentration.

Anion Configuration at the Air/Liquid Interface of Ionic Liquid [bmim]OTf Studied by Sum-Frequency Generation Spectroscopy

The air/liquid interface of a room temperature ionic liquid, 1-butyl-3-methylimidazolium trifluoromethanesulfonate ([bmim]OTf), is investigated using infrared-visible sum frequency generation (SFG) spectroscopy. The SFG spectra clearly show low-frequency modes [CF3-symmetric stretching (ss) mode and SO3-symmetric stretching (ss) mode] of the OTf anion, demonstrating the existence of anions polar oriented at the interface. The amplitude of the CF3-ss peak of the OTf anion has the opposite sign with respect to that of the SO3-ss peak, indicating that OTf anions at the surface have polar ordering where the nonpolar CF3 group points away from the bulk into the air, whereas the SO3 group points toward the bulk liquid. The line width of the SFG peak from the submerged SO3 group is appreciably narrower than that from IR absorption, suggesting the environment of the surface OTf anions is much more homogeneous than that of the bulk. The vibrational calculations also suggest that the anions and the cations form a more specific aggregated configuration at the surface as compared to the bulk.

Gold Nanorod-Assembled PEGylated Graphene-Oxide Nanocomposites for Photothermal Cancer Therapy

Gold nanorod‐attached PEGylated graphene‐oxide (AuNR‐PEG‐GO) nanocomposites were tested for a photothermal platform both in vitro and in vivo. Cytotoxicity of AuNR was reduced after encapsulation with PEG‐GO along with the removal of cetyltrimethylammonium bromide (CTAB) from AuNR by HCl treatment. Cellular internalization of the CTAB‐eliminated AuNR‐PEG‐GO nanocomposites was examined using dark‐field microscopy (DFM), confocal Raman microscopy and transmission electron microscopy (TEM). To determine the photothermal effect of the AuNR‐PEG‐GO nanocomposites, A431 epidermoid carcinoma cells were irradiated with Xe‐lamp light (60 W cm−2) for 5 min after treatment with the AuNR‐PEG‐GO nanocomposites for 24 h. Cell viability significantly decreased by ~40% when the AuNR‐PEG‐GO‐encapsulated nanocomposites were irradiated with light as compared with the cells treated with only the AuNR‐PEG‐GO nanocomposites without any illumination. In vivo tumor experiments also indicated that HCl‐treated AuNR‐PEG‐GO nanocomposites might efficiently reduce tumor volumes via photothermal processes. Our graphene and AuNR nanocomposites will be useful for an effective photothermal therapy.

Study of wet treatment of polyimide by sum-frequency vibrational spectroscopy

A polyimide surface treated with a strong NaOH solution for improvement of adhesion with metals was investigated using ultraviolet absorption and sum-frequency vibrational spectroscopy. Conversion of imide groups to amide groups at the polyimide surface was observed. This conversion and subsequent etching of the polyimide film by the solution seems to be more effective in the amorphous part of the film. Drying of the film converts the surface amides back to imides.

Stability of the Si-H bond on the hydrogen-terminated Si(111) surface studied by sum frequency generation

Stability of the Si-H bonds on the hydrogen terminated Si(III) surface has been investigated by sum frequency generation (SFG) spectroscopy in air at room temperature. The SFG observation showed that the Si(III)surface is terminated by a monolayer of monohydride (Si-H) after etching in a concentrated ammonium fluoride (NH4F)solution. The number of Si-H bonds decreased with laser irradiation time and the abstraction rate of hydrogen atoms on Si increased with the increase of input energy of

Nonlinear absorption of Cr4+:YAG studied with lasers of different pulsewidths

A saturable absorber Cr4+:YAG, used for a passive Q switching of Nd:YAG laser was studied in order to understand the physical mechanism of nonlinear absorption (photobleaching). An optical bleaching experiment was carried out using the two pulsed lasers with duration of pico- and nanoseconds at 1.064 μm wavelength. Experimental results were compared with numerical analysis of theoretical rate equations with all relevant energy levels. The inclusion of intersystem crossing between singlet- and triplet-excited states with reasonable rate of transition kisc was necessary to explain the difference in the saturation behaviors for nanosecond and picosecond laser pulses.

Detection of the mycotoxin citrinin using silver substrates and Raman spectroscopy.

We detected a trace amount of the mycotoxin citrinin using surface-enhanced Raman scattering (SERS) on silver nanoparticle (Ag NP) surfaces. The SERS substrate on hydrophobic Teflon films was also introduced to observe the citrinin peaks. A broad band at ∼1382cm(-1), which was ascribed to the symmetric carboxylate stretching mode, was observed in addition to an antisymmetric carboxylate stretching mode at ∼1568cm(-1) in the Raman spectra. The spectral feature indicated that citrinin would adsorb on Ag NPs via its carboxylate form. Based on density functional theory (DFT) calculations, vibrational mode analysis was performed to compare the Raman spectra of citrinin. DFT calculations also predicted that a bidentate bridge configuration through O15 and O16 atoms in citrinin would be the most stable on three Ag atoms. After treating with Ag NPs, observation of citrinin peaks was attempted in fungal cells of Penicillium citrinum. This work may provide useful insights into the direct observation of the hazardous citrinin mycotoxin using SERS by understanding its adsorption behaviors on Ag surfaces.

Comparison of Photophysical Properties of the Hemicyanine Dyes in Ionic and Nonionic Solvents

The fluorescence properties of 4-[4-(dimethylamino)styryl]-1-n-alkylpyridinium bromide (hemicyanine) dissolved in solvents of different polarities and viscosities (methanol, ethylene glycol, tetra-ethylene glycol, glycerol, benzyl alcohol, pyridine, and two ionic liquids, 1-butyl-3-methylimidazolium tetrafluoroborate, [BMIM]BF4, and 1-butyl-3-methylimidazolium hexafluorophosphate, [BMIM]PF6) were investigated. Significant increase in the fluorescence quantum yield and the fluorescence decay lifetime was observed with the increase in the viscosity of the solvent medium. It is because the intramolecular rotational motion of the molecule becomes more difficult in viscous liquid, which leads to a decrease in the nonradiative decay processes. The fluorescence quantum yields for all of the solutions followed a semiempirical law that depends only on the solvent viscosity. The correlation function C(t) was obtained for each solution by joining fluorescence decay curves measured at different wavelengths. From the fitted results of C(t), we observed the distinctive feature unique to the ionic liquids, in which the correlation functions for ionic liquid solutions are fitted to be biphasic, while they are monophasic for other solvents. The fluorescence maximum of hemicyanine dissolved in these ionic liquids red-shifted following the increase in the excitation wavelength.

Characteristics of Visible Fluorescence from Ionic Liquids

The observation of fluorescence in the visible spectral range in imidazolium-based ionic liquids, in which the peak of the fluorescence spectrum shifts with the change in the excitation wavelength by over 200 nm, was reported by Samanta and co-workers (Paul et al. J. Phys. Chem. B 2005, 109, 9148; Chem. Phys. Lett. 2005, 402, 375), and the aggregate structure in the bulk ionic liquid was suggested to explain this unique phenomenon. In this work, by employing 2D-scan fluorescence spectroscopy, we identified the long- and short-wavelength fluorescence components of the fluorescence spectrum of 1-butyl-3-methylimidazolium tetrafluoroborate ([C4MIM][BF4]), of which only the long-wavelength fluorescence component was found to be responsible for the reported fluorescence properties. The fluorescence intensity of the long-wavelength component decreased much faster upon dilution in aqueous mixtures than the short-wavelength component, supporting the conclusion that the long-wavelength fluorescence is from molecular aggregates in the bulk ionic liquid. Fluorescence correlation spectroscopy (FCS), which was used to accurately account for the number density of the long-wavelength fluorescent species in aqueous solutions of the ionic liquid, also suggested that the fluorescence came from aggregate structures of molecules in ionic liquids.