• Title/Summary/Keyword: Excited-state proton transfer

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Study of rganized Assemblies and Surfaces Using Picosecond Lasers

  • Bhattacharyya, Kankan
    • Journal of Photoscience
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    • v.6 no.3
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    • pp.123-128
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    • 1999
  • Dynamics of many ultrafast processes are markedly slowed down in various organized molecular assemblies compared to ordinary liquids. We will show that the solvation dynamics of water molecules is affected amost dramatically and is retarded by 3 ∼4 orders of magnitude in microemulsions, micells and lipids. We will also discuss how the access to fewer water molucules and the drastically altered local pH in an organized asembly affected the excited state proton transfer processes. Finally, we will show how surface second haromonic generation can be used to study the air-water surface.

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Ketyl radical formation of excited 1, 8-naphthalimides in protic polar solvent

  • Cho, Dae Won;Cho, Dae Won;Park, Hea Jung;Yoon, Ung Chan;Lee, Myoung Hee;Im, Chan
    • Rapid Communication in Photoscience
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    • v.1 no.2
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    • pp.35-37
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    • 2012
  • Photoinduced electron-transfer process of 1,8-naphthalimide-linker-trimethylsilane (NI-O3-TMS, O3 = 3,6,9-trioxaundecyl) and NI-O3 has been investigated using the transient absorption measurements in $CH_3CN$ and $CH_3CN/H_2O$. The excitation of NI-O3-TMS in $CH_3CN$ produced the NI radical anion ($NI^{{\cdot}-}$) with a transient absorption band around 413 nm, via the intermolecular electron-transfer between NI moieties in the excited singlet state. In contrast, in a protic polar solvent mixture of $CH_3CN/H_2O$, a proton abstraction process occurred from $NI^{{\cdot}-}$ to generate the NI ketyl radical ($NIH^{\cdot}$), which showed a transient absorption band around 405 nm. The decay time constants of $NIH^{\cdot}$ were quite long compared to those of $NI^{{\cdot}-}$ in $CH_3CN$.

Proton Transfer Equilibria in The Excited State of Piroxicam and Its Analog in Aqueous Solution

  • Yoon, Min-Joong;Kim, Yong-Hee
    • Bulletin of the Korean Chemical Society
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    • v.10 no.5
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    • pp.434-437
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    • 1989
  • The pH dependence of the absorption and fluorescence of 4-hydroxy-2-methyl-1,2-benzothiazinenecarboxylat es, piroxicam and HMBDC have been measured and compared with the solvent dependence of the spectra reported previously. Four different prototropic species are observed in both ground and excited states of piroxicam ; the cation, the neutral, the anion and the dianion, while three different species such as the cation, the neutral and the anion are observed in HMBDC. The $pK_a$ and $pK_a^{\ast}$ have been determined by absorptiometric titration and Forster cycle method, respectively. The probable structure of each species has been proposed on the basis of the intramolecular phototautomerism.

Solvent Dependence of Absorption and Fluorescence Spectra of Piroxicam. A Possible Intramolecular Proton Transfer in the Excited State

  • Yoon, Min-Joong;Choi, Hyong-Nae;Kwon, Hwang-Won;Park, Koon-Ha
    • Bulletin of the Korean Chemical Society
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    • v.9 no.3
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    • pp.171-175
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    • 1988
  • The spectral properties of piroxicam in different solvents are similar to those of its skeletal precursor, HMBDC. The maximum absorption and emission wavelengths strongly depend on the hydrogen bonding ability of the solvent, and it is shown that intramolecular hydrogen bonding between the -OH and the ortho carbonyl group of the parent benzothiazine ring plays an important role in the solvent-dependence of their spectroscopic properties. The fluorescence spectra in aprotic nonpolar solvent exhibit abnormally large Stokes-shifted (${\sim}9,000cm^{-1}$) emission bands in contrast to the spectra in water. In ethanol, dual emission bands with two different fractional components of lifetimes have been observed. These results suggest that the abnormally red-shifted emission is attributed to the proton transferred form of an intramolecularly hydrogen-bonded closed conformer.

Micellar Effects on Intramolecular Charge Transfer Emission from Biphenylcarboxylic Acids

  • Yoon, Min-Joong;Cho, Dae-Won;Kang, Seong-Gwan;Lee, Min-Yung
    • Bulletin of the Korean Chemical Society
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    • v.14 no.6
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    • pp.704-708
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    • 1993
  • The intramolecular charge transfer (ICT) phenomena of the photoexcited 2-biphenylcarboxylic acid (2BPCA) and 4-biphenylcarboxylic acid (4BPCA) have been investigated in some surfactant micellar solutions. The ICT emission of 4BPCA and 2BPCA in aqueous solution at sufficiently low pH (1-3) has been observed to be markedly quenched and blue-shifted upon addition of a cationic surfactant, cetyltrimethylammonium chloride (CTAC) in contrast to little change in anionic sodium dodecyl sulfate (SDS) and neutral Brij 35. An anionic emission band has been observed to be enhanced at expense of the ICT emission as a function of the concentration of CTAC. These results with the micellar effects on the fluorescence decay kinetics of 4BPCA suggest that formation of the ICT state of the excited acids is inhibited by CTAC-induced proton transfer as well as the decrease in the polarity and/or hydrogen-bonding ability of the micellar microenvironment entrapping the acids.