Taiha Joo

Coumarin-Derived Cu2+-Selective Fluorescence Sensor: Synthesis, Mechanisms, and Applications in Living Cells

A novel coumarin-based fluorogenic probe bearing the 2-picolyl unit (1) was developed as a fluorescent chemosensor with high selectivity and suitable affinity in biological systems toward Cu(2+) over other cations tested. The fluorescence on-off mechanism was studied by femtosecond time-resolved fluorescence (TRF) upconversion technique and ab initio calculations. The receptor can be applied to the monitoring of Cu(2+) ion in aqueous solution with a pH span 4-10. To confirm the suitability of 1 for biological applications, we also employed it for the fluorescence detection of the changes of intracellular Cu(2+) in cultured cells. The results indicate that 1 should be useful for the fluorescence microscopic imaging and the study on the biological functions of Cu(2+).

Third‐order nonlinear time domain probes of solvation dynamics

Several closely related third‐order nonlinear time‐resolved spectroscopic techniques, pump/probe transient absorption, transient grating, and three pulse stimulated photon echo peak shift measurements, are investigated theoretically and experimentally. It is shown in detail, through the consideration of response functions and numerical simulations including both finite pulse durations and detuning from exact resonance, how the solvation dynamics are manifested in these third‐order nonlinear time‐resolved spectroscopies. It is shown that the three pulse stimulated photon echo peak shift measurement and the transient grating measurement can give accurate dynamical information, whereas transient absorption may not be a reliable technique for a study of solvation dynamics in some cases. The contribution of very slow or static (inhomogeneous) components to the dynamics, however, can only be obtained from the three pulse echo peak shift measurements. Comprehensive experimental measurements are presented to illu...

A two-photon fluorescent probe for lipid raft imaging : C-laurdan

The lipid‐rafts hypothesis proposes that naturally occurring lipid aggregates exist in the plane of membrane that are involved in signal transduction, protein sorting, and membrane transport. To understand their roles in cell biology, a direct visualization of such domains in living cells is essential. For this purpose, 6‐dodecanoyl‐2‐(dimethylamino)naphthalene (laurdan), a membrane probe that is sensitive to the polarity of the membrane, has often been used. We have synthesized and characterized 6‐dodecanoyl‐2‐[N‐methyl‐N‐(carboxymethyl)amino]naphthalene (C‐laurdan), which has the advantages of greater sensitivity to the membrane polarity, a brighter two‐photon fluorescence image, and reflecting the cell environment more accurately than laurdan. Lipid rafts can be visualized by two‐photon microscopy by using C‐laurdan as a probe. Our results show that the lipid rafts cover 38 % of the cell surface.

Time-resolved and time-integrated photoluminescence in ZnO epilayers grown on Al2O3(0001) by metalorganic vapor phase epitaxy

We report on photoluminescence (PL) spectra of ZnO films grown by low pressure metalorganic vapor phase epitaxy. For PL measurements, high quality ZnO thin films were epitaxially grown on Al2O3(0001) substrates. Time-integrated PL spectra of the films at 10 K clearly exhibited free A and B excitons at 3.376 and 3.382 eV and bound exciton peaks at 3.360, 3.364, and 3.367 eV. With increasing temperature, intensities of the bound exciton peaks drastically decreased and a free exciton peak was dominant above 40 K. Furthermore, time-resolved PL measurements at the free exciton peak were carried out at room temperature. The decay profiles were of double-exponential form, and the decay time constants of 180 ps and 1.0 ns were obtained using a least-square fit of the data.

Size‐Controlled Soft‐Template Synthesis of Carbon Nanodots toward Versatile Photoactive Materials

Size-controlled soft-template synthesis of carbon nanodots (CNDs) as novel photoactive materials is reported. The size of the CNDs can be controlled by regulating the amount of an emulsifier. As the size increases, the CNDs exhibit blue-shifted photoluminescence (PL) or so-called an inverse PL shift. Using time-correlated single photon counting, ultraviolet photoelectron spectroscopy, and low-temperature PL measurements, it is revealed that the CNDs are composed of sp² clusters with certain energy gaps and their oleylamine ligands act as auxochromes to reduce the energy gaps. This insight can provide a plausible explanation on the origin of the inverse PL shift which has been debatable over a past decade. To explore the potential of the CNDs as photoactive materials, several prototypes of CND-based optoelectronic devices, including multicolored light-emitting diodes and air-stable organic solar cells, are demonstrated. This study could shed light on future applications of the CNDs and further expedite the development of other related fields.

Two-Photon Fluorescent Turn-On Probe for Lipid Rafts in Live Cell and Tissue

We report a new two-photon fluorescence turn-on probe 6-[(E)-3-oxo-1-dodecenyl]-2-[N-methyl-N-(carboxymethyl)amino]naphthalene (CL2) that is designed specifically for visualizing lipid rafts in living cells and tissues. This probe emits much brighter two-photon excited fluorescence in lipid rafts than in non-raft domains and allows direct visualization of the lipid rafts in the live cells and pyramidal neuron layer of the CA1 region at a depth of 100-250 mum in live tissues using two-photon microscopy.

Time-resolved photoluminescence of the size-controlled ZnO nanorods

Size dependence of the time-resolved photoluminescence (TRPL) has been investigated for the ZnO nanorods fabricated by catalyst-free metalorganic chemical vapor deposition. The nanorods have a diameter of 35 nm and lengths in the range of 150 nm to 1.1 μm. The TRPL decay rate decreases monotonically as the length of the nanorods increases in the range of 150 to 600 nm. Decrease of the radiative decay rate of the exciton-polariton has been invoked to account for the results.

Comprehensive Studies on an Overall Proton Transfer Cycle of the ortho-Green Fluorescent Protein Chromophore

Initiated by excited-state intramolecular proton transfer (ESIPT) reaction, an overall reaction cycle of 4-(2-hydroxybenzylidene)-1,2-dimethyl-1H-imidazol-5(4H)-one (o-HBDI), an analogue of the core chromophore of the green fluorescent protein (GFP), has been investigated. In contrast to the native GFP core, 4-(4-hydroxybenzylidene)-1,2-dimethyl-1H-imidazol-5(4H)-one (p-HBDI), which requires hydrogen-bonding relay to accomplish proton transfer in vivo, o-HBDI possesses a seven-membered-ring intramolecular hydrogen bond and thus provides an ideal system for mimicking an intrinsic proton-transfer reaction. Upon excitation, ESIPT takes place in o-HBDI, resulting in a ∼600 nm proton-transfer tautomer emission. The o-HBDI tautomer emission, resolved by fluorescence upconversion, is comprised of an instantaneous rise to a few hundred femtosecond oscillation in the early relaxation stage. Frequency analysis derived from ultrashort pulse gives two low-frequency vibrations at 115 and 236 cm(-1), corresponding to skeletal deformation motions associated with the hydrogen bond. The results further conclude that ESIPT in o-HBDI is essentially triggered by low-frequency motions and may be barrierless along the reaction coordinate. Femtosecond UV/vis transient absorption spectra also provide supplementary evidence for the structural evolution during the reaction. In CH(3)CN, an instant rise of a 530 nm transient is resolved, which then undergoes 7.8 ps decay, accompanied by the growth of a rather long-lived 580 nm transient species. It is thus concluded that following ESIPT the cis-proton transfer isomer undergoes cis-trans-isomerization. The results of viscosity-dependent dynamics are in favor of the one-bond-flip mechanism, which is in contrast to the volume-conserving isomerization behavior for cis-stilbene and p-HBDI. Further confirmation is given by the picosecond-femtosecond transient IR absorption spectra, where several new and long-lived IR bands in the range of 1400-1500 cm(-1) are assigned to the phenyl in-plane breathing motions of the trans-proton transfer tautomer. Monitored by the nanosecond transient absorption, the 580 nm transient undergoes a ∼7.7 μs decay constant, accompanied by the growth of a new ∼500 nm band. The latter is assigned to a deprotonated tautomer species, which then undergoes the ground-state reverse proton recombination to the original o-HBDI in ∼50 μs, achieving an overall, reversible proton transfer cycle. This assignment is unambiguously supported by pump-probe laser induced fluorescence studies. On these standpoints, a comparison of photophysical properties among o-HBDI, p-HBDI, and wild-type GFP is discussed in detail.

Electronic dephasing studies of molecules in solution at room temperature by femtosecond degenerate four wave mixing

Abstract The electronic dephasing of two oxazine dyes dissolved in ethylene glycol at room temperature is investigated by femtosecond degenerate four wave mixing (DFWM) experiments. Both two-pulse and three-pulse DFWM with simultaneous detection of the signals at two distinct phase-matching directions permits detailed investigation of dephasing dynamics in a room temperature liquid. At least two stochastic processes are responsible for the observed electronic dephasing: one is treated empirically as an exponential decay; the second is regarded in the full analytic form of the Kubo relaxation function. Both fast and slow (inhomogeneous) dynamics are recovered. The slow dynamics is found to bring about spectral diffusion over the inhomogeneous distribution on the time scale around a picosecond.

Ultrafast liquid dynamics studied by third and fifth order three pulse photon echoes

We report a new spectroscopic measurement based on fifth order nonlinear response from a molecule in a room temperature liquid. In conjunction with conventional three pulse stimulated photon echo, detailed information on solvent–solute dynamics for a wide range of time scales has been obtained. Both the ultrafast inertial components and much slower dynamics of the solvent are found to make important contributions to the solvent relaxation. The potential of the fifth order measurements is discussed via numerical calculations using model solvent spectral densities.