Biomedical subjects

Han Young Woo

Publications and source records attributed to Han Young Woo.

7 recordsLinked to original sources

PubMed2006

Silver nanocrystal-modified silicon nanowires as substrates for surface-enhanced Raman and hyper-Raman scattering.

Metal catalyzed, CVD-grown silicon nanowires decorated by chemical assembly of closely spaced Ag nanocrystals were modified with the well-known "silver mirror" reaction and investigated as substrates for surface-enhanced Raman (SERS) and hyper-Raman (SEHRS) spectroscopy. Four chromophores were examined: Rhodamine 6G, crystal violet, a cyanine dye, and a cationic donor-acceptor substituted stilbene. After soaking the substrates overnight in 10(-4) M aqueous chromophore solutions, all four chromophores gave good-quality SERS spectra in < or =60 s using <1 microW of 458-nm cw laser power, and SEHRS spectra are obtained in < or =120 s using <1 mW of mode-locked 916-nm laser power. Results from this substrate are compared with those on colloidal silver nanoparticles deposited as a film, as well as surfaces grown by the silver mirror reaction.

Microscopy, Electron, Scanning↗

PubMed2006

Solvent effects on resonant first hyperpolarizabilities and Raman and hyper-Raman spectra of DANS and a water-soluble analog.

The two-photon-resonant first hyperpolarizabilities associated with hyper-Rayleigh and hyper-Raman scattering are reported for 4-dimethylamino-4-nitrostilbene in 1,4-dioxane, dichloromethane, acetonitrile, and methanol, and for an ionic analog, 4-N,N-bis(6-(N,N,N-trimethylammonium)-hexyl)amino-4-nitrostilbene dibromide in methanol and water. Resonance Raman and hyper-Raman excitation profiles are also measured and modeled. The resonance Raman and hyper-Raman spectra show very similar relative intensities which do not vary much as the excitation frequency is tuned across the lowest-energy strong linear absorption band, suggesting that a single resonant electronic state dominates the one- and two-photon absorptions in this region. The absorption, resonance Raman, and hyper-Raman profiles can be simulated reasonably well with a common set of parameters. The peak resonant (absolute value of beta)2, measured by hyper-Rayleigh scattering, varies by about 50% over the range of solvents examined and shows a weak correlation with the linear absorption maximum, with the redder-absorbing systems exhibiting larger peak hyperpolarizabilities. The experimental hyper-Rayleigh intensities are higher than those calculated, possibly reflecting contributions from nonresonant electronic states.

Journal Article↗

PubMed2005

Solvent effects on the two-photon absorption of distyrylbenzene chromophores.

A series of organic- and water-soluble distyrylbenzene-based two-photon absorption (TPA) fluorophores containing dialkylamino donor groups at the termini was designed, synthesized, and characterized. The central core was systematically substituted to modulate intramolecular charge transfer (ICT). These molecules allow an examination of solvent effects on the TPA cross section (delta) and on the TPA action cross section. In toluene, the delta values follow the order of ICT strength. The effect of solvent on delta is nonmonotonic: maximum delta was measured in an intermediate polarity solvent (THF) and was lowest in water. We failed to find a correlation between the observed solvent effect and previous theoretical predictions. Hydrogen bonding to the donor groups and aggregation of the optical units in water, which are not included in calculational analysis, may be responsible for the discrepancies between experimental results and theory.

Absorption↗

PubMed2005

Two-photon absorption in aqueous micellar solutions.

Addition of the surfactant sodium dodecyl sulfate at concentrations above the critical micelle concentration increases the fluorescence quantum yield and the two-photon absorption cross-section of charged [2.2]paracyclophane chromophores containing pairs of D-pi-D chromophores. The resulting spectra in the micellar solutions are very similar to those obtained for neutral isostructural analogues in toluene. The measured etadelta values are 1300 GM for 1C and 1920 GM for 2C, which are comparable or larger to those in toluene. These results highlight possible misleading interpretation of two-photon-induced emission for evaluating the concentration of labeled substrates used in two-photon microscopy and provide guidelines for designing molecular structures with optimized two-photon action cross-sections in water.

Acetates↗

PubMed2005

Solvatochromism of distyrylbenzene pairs bound together by [2.2]paracyclophane: evidence for a polarizable "through-space" delocalized state.

A series of compounds were designed and synthesized to examine how through-space and through-bond electron delocalization respond to solvent effects. The general strategy involves the study of "dimers" of the distyrylbenzene chromophore held in close proximity by the [2.2]paracyclophane core and a systematic dissection of the chromophore into components with through-space and through-bond electronic delocalization. Steady state and time-resolved fluorescence spectroscopy in a range of solvents reveals a red-shift in emission and an increase in the intrinsic fluorescence lifetime for the emitting state in polar solvents when donor substituents are absent. We propose that through-space delocalization across the [2.2]paracyclophane core is more polarizable in the excited state, relative to the through-bond (distyrylbenzene based) excited state. When strong donors are attached to the distyrylbenzene chromophore, the charge transfer character of the distyrylbenzene-based excited state dominates fluorescence properties.

Journal Article↗

PubMed2005

Water-soluble [2.2]paracyclophane chromophores with large two-photon action cross sections.

A series of alpha,omega-donor-substituted distyrylbenzene dimers held together by the [2.2]paracyclophane core were designed, synthesized, and characterized. Different substituents were chosen to modulate the strength of the donor nitrogen groups and to allow the molecules to be either neutral and soluble in nonpolar organic solvents or charged and water-soluble. The specific neutral structures are (in order of decreasing donor strength) 4,7,12,15-tetra[N,N-bis(6' '-chlorohexyl)-4'-aminostyryl]-[2.2]paracyclophane (1N), 4,7,12,15-tetra[(N-(6' '-chlorohexyl)carbazol-3'-yl)vinyl]-[2.2]paracyclophane (2N), and 4,7,12,15-tetra[N,N-bis(4' '-(6' ''-chlorohexyl)phenyl)-4'-aminostyryl]-[2.2]paracyclophane (3N). The charged species are 4,7,12,15-tetra[N,N-bis(6' '-(N,N,N-trimethylammonium)hexyl)-4'-aminostyryl]-[2.2]paracyclophane octaiodide (1C), 4,7,12,15-tetra[(N-(6' '-(N,N,N-trimethylammonium)hexyl)carbazol-3'-yl)vinyl]-[2.2]paracyclophane octaiodide (2C), and 4,7,12,15-tetra[N,N-bis(4' '-(6' ''-(N,N,N-trimethylammonium)hexyl)phenyl)-4'-aminostyryl]-[2.2]paracyclophane octaiodide (3C). Two-photon excitation spectra, measured using the two-photon induced fluorescence technique, show in toluene the following trend for the two-photon cross sections (delta): 3N > 2N > 1N. In water the delta values follow the same order, 3C approximately 2C > 1C, but are smaller (approximately one-third). Significantly, the fluorescence quantum yield (eta) in water decreases much more for 1, relative to 2 and 3. The two-photon action cross sections (deltaeta) of 2C and 3C are 294 GM and 359 GM, respectively. These values are among the highest reported thus far. These results show that, to maximize the deltaeta in this class of chromophores, one needs to fine-tune the magnitude of the charge transfer character of the excited state, to minimize fluorescence quenching in polar media.

Benzene Derivatives↗

PubMed2004

Electronic modulation of dithienothiophene (DTT) as pi-center of D-pi-D chromophores on optical and redox properties: analysis by UV-Vis-NIR and Raman spectroscopies combined with electrochemistry and quantum chemical DFT calculations.

In this paper, we study three symmetrical D-pi-D chromophores containing dithieno[3,2-b:2',3'-d]thiophene (DTT) as the pi-center and various donor end moieties, by means of UV-vis-NIR and FT-Raman spectroscopy and in situ spectroelectrochemistry. The compounds display dual redox properties: all exhibited two oxidations and single stable reduction peaks contrarily to the one or two oxidations and none reduction which could be anticipated in view of their chemical structures. We analyze the possible electronic modulation by the pi-conjugated DTT relay in the redox process and electronic coupling between the two electron donor (D) units attached through conjugation to opposite sides of the pi-linker. To this end, the UV-vis-NIR and FT-Raman spectra of the neutral compounds and of the charged species generated upon in situ p- or n-doping have been recorded and interpreted with the help of Density Functional Theory (DFT) calculations. The analysis of the peculiar Raman features of these pi-conjugated chromophores is guided by the formalism of the Effective Conjugation Coordinate (ECC) theory. This research shows that the Raman spectroscopic characterization of this type of D-pi-D structures is a powerful tool to derive information about their pi-conjugational properties in the pristine and doped states.

Journal Article↗