Liquid phase behavior of ionic liquids with alcohols: experimental studies and modeling

Ionic liquids (ILs) have been suggested as potential "green" solvents to replace volatile organic solvents in reaction and separation processes due to their negligible vapor pressure. To develop ILs for these applications, it is important to gain a fundamental understanding of the factors that control the phase behavior of ionic liquids with other liquids. In this work, we continue our study of the effect of chemical and structural factors on the phase behavior of ionic liquids with alcohols, focusing on pyridinium ILs for comparison to imidazolium ILs from our previous studies. The impact of different alcohol and IL characteristics, including alcohol chain length, cation alkyl chain length, anion, different substituent groups on the pyridinium cation, and type of cation (pyridinium vs imidazolium) will be discussed. In general, the same type of behavior is observed for pyridinium and imidazolium ILs, with all systems studied exhibiting upper critical solution temperature behavior. The impacts of alcohol chain length, cation chain length, and anion, are the same for pyridinium ILs as those observed previously for imidazolium ILs. However, the effect of cation type on the phase behavior is dependent on the strength of the cation-anion interaction. Additionally, all systems from this study and our previous work for imidazolium ILs were modeled using the nonrandom two-liquid (NRTL) equation using two different approaches for determining the adjustable parameters. For all systems, the NRTL equation with binary interaction parameters with a linear temperature dependence provided a good fit of the experimental data.     

Organized assemblies of single wall carbon nanotubes and porphyrin for photochemical solar cells: charge injection from excited porphyrin into single-walled carbon nanotubes

Photochemical solar cells have been constructed from organized assemblies of single-walled carbon nanotubes (SWCNT) and protonated porphyrin on nanostructured SnO2 electrodes. The protonated form of porphyrin (H4P2+) and SWCNT composites form 0.5-3.0 microm-sized rodlike structures and they can be assembled onto nanostructured SnO2 films [optically transparent electrode OTE/SnO2] by an electrophoretic deposition method. These organized assemblies are photoactive and absorb strongly in the entire visible region. The incident photon to photocurrent efficiency (IPCE) of OTE/SnO2/SWCNT-H4P2+ is approximately 13% at an applied potential of 0.2 V versus saturated calomel electrode. Femtosecond pump-probe spectroscopy experiments confirm the decay of the excited porphyrin in the SWCNT-H4P2+ assembly as it injects electrons into SWCNT. The dual role of SWCNT in promoting photoinduced charge separation and facilitating charge transport is presented.     

Harvesting infrared photons with tricarbocyanine dye clusters

The absorption of 4,5-benzoindotricarbocyanine dye (IR125) in the infrared can be tuned by controlling the type of aggregation in different media. Molecular clusters of this dye formed in a mixed solvent show broad absorption in the 550-950 nm region as compared to the absorption bands of J- and H-type aggregates. The molecular clusters of the carbocyanine dye are electrophoretically deposited as thin film on optically transparent electrodes using a dc electric field. These tricarbocyanine dye cluster films are photoactive in the infrared region and produce cathodic current when employed as photocathode in a photoelectrochemical cell. Transient absorption spectroscopy of the molecular clusters show short-lived singlet state in the picosecond time scale (lifetime 6 ps) and a charge separated state in the nanosecond time scale. Implication of such dye cluster films for harvesting infrared photons in a photoelectrochemical cell is discussed.     

Click chemistry inspired synthesis of ferrocene amino acids and other derivatives

This work reports the synthesis of a wide range of ferrocenyl-amino acids and other derivatives in excellent yield. Diverse amino acid containing azides were synthesized and ligated to ferrocene employing click reaction to access ferrocenyl amino acids. Chiral alcohols, esters, diols, amines containing azido group were tagged to ferrocene via click reaction to generate ferrocene derived chiral derivatives. A novel strategy for direct incorporation of ferrocene into a peptide and a new route to 1, 1′disubstituted ferrocene amino acid derivative are reported.     

Density, Excess Volume, and Viscosity of Vinyl Acetate or?Benzyl Acetate with (o-, m-, p-)Xylenes and?Ethylbenzene at T=(303.15 and 313.15) K

Viscosity η, and density ρ, of binary liquid mixtures of vinyl acetate or benzyl acetate with o-xylene, m-xylene, p-xylene and ethyl benzene have been determined at (303.15 and 313.15) K for the entire composition range. From the experimental values excess molar volume and deviations in viscosity have been calculated. These excess quantities were fitted to the Redlich-Kister polynomial equation. The viscosity data have been correlated using the Grunberg-Nissan, Tamura and Kurata, Auslander, and Jouyban-Acree models.