Spatial Ordering of the Structure of Polymer-Capped Gold Nanorods under an External DC Electric Field.

We studied the alignment changes of polymer-capped gold nanorods (GNRs@PS) under an applied electric field by visible-near-infrared absorption and small-angle X-ray scattering (SAXS) measurements. Monodispersed GNRs with an aspect ratio of 4.0 were produced by the seed-mediated growth method using cetyltrimethylammonium bromide and sodium oleate binary surfactants. We investigated the phase transition between the ordered structure of GNRs@PS induced by the external electric field. At appropriate field strengths (>3 V/µm), the SAXS profiles of GNRs@PS showed a smectic ordered structure. Increasing the electric field strength densified the ordered structure and greatly increased the Raman signals (the 298 and 445 cm-1 bands) of the carbon tetrachloride (solvent) between the GNRs@PS. The insights gained are potentially applicable to catalysts, future displays, optical filters, and data storage devices.

Excited-state intramolecular proton transfer and conformational relaxation in 4'-N,N-dimethylamino-3-hydroxyflavone doped in acetonitrile crystals.

The effect of intermolecular interactions on excited-state intramolecular proton transfer (ESIPT) in 4'-N,N-dimethylamino-3-hydroxyflavone (DMHF) doped in acetonitrile crystals was investigated by measuring its temperature dependence of steady-state fluorescence excitation and fluorescence spectra and picosecond time-resolved spectra. The relative intensity of emission from the excited state of the normal form (N*) to that from the excited state of the tautomer form (T*) and spectral features changed markedly with temperature. Unusual changes in the spectral shift and spectral features were observed in the fluorescence spectra measured between 200 and 218 K, indicating that a solid-solid phase transition of DMHF-doped acetonitrile crystals occurred. Time-resolved fluorescence spectra suggested conformational relaxation of the N* state competed with ESIPT after photoexcitation and the ESIPT rate increased with temperature in the low-temperature phase of acetonitrile. However, the intermolecular interaction of N* with acetonitrile in the high-temperature phase markedly stabilized the potential minimum of the fluorescent N* state and slowed the ESIPT. This stabilization can be explained by reorganization of acetonitrile originating from the strong electric dipole-dipole interaction between DMHF and acetonitrile molecules.

External Electric Field Effects on Excited-State Intramolecular Proton Transfer in 4'-N,N-Dimethylamino-3-hydroxyflavone in Poly(methyl methacrylate) Films.

The external electric field effects on the steady-state electronic spectra and excited-state dynamics were investigated for 4'-N,N-(dimethylamino)-3-hydroxyflavone (DMHF) in a poly(methyl methacrylate) (PMMA) film. In the steady-state spectrum, dual emission was observed from the excited states of the normal (N*) and tautomer (T*) forms. Application of an external electric field of 1.0 MV·cm(-1) enhanced the N* emission and reduced the T* emission, indicating that the external electric field suppressed the excited-state intramolecular proton transfer (ESIPT). The fluorescence decay profiles were measured for the N* and T* forms. The change in the emission intensity ratio N*/T* induced by the external electric field is dominated by ESIPT from the Franck-Condon excited state of the N* form and vibrational cooling in potential wells of the N* and T* forms occurring within tens of picoseconds. Three manifolds of fluorescent states were identified for both the N* and T* forms. The excited-state dynamics of DMHF in PMMA films has been found to be very different from that in solution due to intermolecular interactions in a rigid environment.

Electric-field-induced changes in absorption and fluorescence of the green fluorescent protein chromophore in a PMMA film.

External electric field effects on absorption, fluorescence, and fluorescence decay of p-HBDI that is a model compound of the chromophore of GFP have been examined in a poly(methyl methacrylate) film. The electroabsorption spectrum is similar in shape to the first derivative of the absorption spectrum, which results from the difference in molecular polarizability between the ground state and the Franck-Condon excited state. The electrophotoluminescence spectrum is dominated by the corresponding fluorescence spectrum, indicating the enhancement of the fluorescence intensity in the presence of external electric fields. The direct measurements of the electric field effect on the fluorescence decay profile suggest that the field-induced deceleration of the nonradiative process contributes to the increase in the fluorescence intensity in the presence of electric fields.