• Bulletin of the Korean Chemical Society
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• 제32권spc8호
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• pp.3090-3093
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• 2011

Curcumin is a natural product with antioxidant, anti-inflammatory, antiviral and antifungal functions. As it is known that the excited state intramolecular hydrogen transfer of curcumin are related to its medicinal antioxidant mechanism, we investigated its excited state dynamics by using femtosecond transient absorption spectroscopy in an effort to understand the molecule's therapeutic effect in terms of its photophysics and photochemistry. We found that stronger intermolecular hydrogen bonding with solvents weakens the intramolecular hydrogen bonding and decelerates the dynamical process of the enolic hydrogen. Exceptions are found in methanol and ethylene glycol due to their nature as simultaneous hydrogen bonding donor-acceptor and high viscosity solvent, respectively.

• 한국고분자학회:학술대회논문집
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• 한국고분자학회 2006년도 IUPAC International Symposium on Advanced Polymers for Emerging Technologies
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• pp.35-36
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• 2006

Excited-state intramolecular proton transfer (ESIPT) is a phototautomerization occurring in the excited states of the molecules possessing a cyclic intramolecular or solvent-bridged hydrogen bond. Recently, we have developed novel ESIPT chromophores, molecules, dendrimers and polymers which show very high fluorescence quantum efficiency combined with the characteristic features of optical switching, fluorescence patterining, lasing, and electroluminescence. Broad overview of these topics will be given in this talk.

• Macromolecular Research
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• 제16권5호
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• pp.385-395
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• 2008

Synthesis and properties of novel excited-state intramolecular proton transfer (ESIPT) materials, recently developed in our group, are described. Highly efficient ESIPT reaction, achieved in polyquinolines, polybenzoxazoles, and oxadiazole and imidazole derivatives possessing an intramolecular tautomerizable hydrogen bond, has been investigated theoretically and experimentally. It is demonstrated that unique properties arising from the ESIPT process (large Stokes' shift, no self-absorption, and easy population inversion, etc.) make it possible to produce advanced polymer devices for lasing, optical storage, and electroluminescence.

• Bulletin of the Korean Chemical Society
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• 제19권9호
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• pp.980-985
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• 1998

The excited-state intramolecular proton transfer (ESIPT) emission has been observed for 0.01 mM p-aminosalicylic acid (AS) in nonpolar aprotic solvents as demonstrated by the large Stokes' shifted fluorescence emission around 440 nm in addition to the normal emission at 330 nm. However in aprotic polar solvent such as acetonitrile, the large Stokes' shifted emission band becomes broadened, indicating existence of another emission band originated from intramolecular charge transfer (ICT). It is noteworthy that in protic solvents such as methanol and ethanol the normal and ICT emissions are quenched as the AS concentration decreases, followed by the appearance of new emission at 380 nm. These results are interpreted in terms of ESIPT coupled charge transfer in AS. Being consistent with these steady-state spectroscopic results, the picosecond time-resolved fluorescence study unravelled the decay dynamics of the ESIPT and ICT state ca. 300 ps and ca. 150 ps, respectively with ca. 40 ps for the relaxation time to form the ICT state.

• Bulletin of the Korean Chemical Society
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• 제34권1호
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• pp.211-220
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• 2013

The characteristic fluorescence properties of quercetin (QCT) and apigenin (API) were studied in various $CH_3OH-H_2O$ and $CH_3CN-H_2O$ mixed solvents. The structure of QCT is completely planar. API is not planar at the ground state but becomes nearly planar at the excited state. If the molecules are excited to the $S_1$ state in organic solvents, QCT exhibits no fluorescence due to excited state intramolecular proton transfer (ESIPT) between the -OH and the carbonyl oxygen, but API shows significant fluorescence because ESIPT occurs slowly. If the molecules are excited to the $S_2$ state, both QCT and API exhibit strong $S_2{\rightarrow}S_o$ emission without any dual fluorescence. As the $H_2O$ composition of both solvents increases, the fluorescence intensity decreases rapidly due to the intermolecular hydrogen bonding interaction. The theoretical calculation further supports these results. The change in fluorescence properties as a function of the solvatochromic parameters was also studied.

• Bulletin of the Korean Chemical Society
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• 제22권2호
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• pp.219-227
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• 2001

The silver colloidal effects on the excited-state structure and intramolecular charge transfer (ICT) of p-N,N-dimethylaminobenzoic acid (DMABA) in aqueous cyclodextrin (CD) solutions have been investigated by UV-VIS absorption, steady-state and time-resolved fluorescence, and transient Raman spectroscopy. As the concentration of silver colloids increases, the ratio of the ICT emission to the normal emission (Ia /Ib) of DMABA in the aqueous $\alpha-CD$ solutions are greatly decreased while the Ia /Ib values in the aqueous B-CD solutions are significantly enhanced. It is also noteworthy that the ICT emission maxima are red-shifted by 15-40 nm upon addition of silver colloids, implying that DMABA encapsulated in $\alpha-CD$ or B-CD cavity is exposed to more polar environment. The transient resonance Raman spectra of DMABA in silver colloidal solutions demonstrate that DMABA in the excited-state is desorbed from silver colloidal surfaces as demonstrated by the disappearance of νs (CO2-)(1380 cm-1 ) with appearance of ν(C-OH)(1280 cm -1) band, respectively. Thus, in the aqueous B-CD solutions the carboxylic acid group of DMABA in the excited-state can be readily hydrogen-bonded with the secondary hydroxyl group of B-CD while in aqueous and $\alpha-CD$ solutions the carboxylic acid group of DMABA has the hydrogen-bonding interaction with water. Consequently, in the aqueous B-CD solutions the enhancement of the Ia /Ia value arises from the intermolecular hydrogen-bonding interaction between DMABA and the secondary hydroxyl group of B-CD as well as the lower polarity of the rim of the B-CD cavity compared to bulk water. This is also supported by the increase of the association constant for DMABA/ B-CD complex in the presence of silver colloids.

• 한국섬유공학회:학술대회논문집
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• 한국섬유공학회 2003년도 The Korea-Japan Joint Symposium
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• pp.27-28
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• 2003

Synthesis and properties of novel excited-state intramolecular proton transfer (ESIPT) materials recently developed in our group are described. Highly efficient ESIPT in polymeric system has been investigated theoretically and experimentally with a semi-rigid polyquinoline (PQH, PQDH) possessing an intramolecular tautomerizable hydrogen bond. Poly(aryl ether) dendrimers of three different generations that are cored with photo-tautomerizable quinoline (QGn, n=1,2,3) were also synthesized and characterized to investigate the effect of dendritic architecture on the ESIPT activity. Stimulated emission and amplified spontaneous emission in these organic materials system are discussed in terms of ESIPT activity.

• Bulletin of the Korean Chemical Society
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• 제32권3호
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• pp.981-987
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• 2011

The anomalous spectroscopic properties of quercetin-3-O-rhamnoside (QCRM) and quercetin-3-O-rutinoside (QCRT) in AOT reverse micelle were studied. The excited state intramolecular proton transfer (ESIPT) occurs through the strong hydrogen bond between the -OH at position 5 and the carbonyl oxygen. Because the ESIPT can only happens in the $S_1$ state and the Franck-Condon factor involved in the $S_2\;{\rightarrow}\;S_1$ internal conversion is small, the $S_2\;{\rightarrow}\;S_o$ emission alone appears. Because the molecular planarity is improved at the interior of the micelle, the excited state intramolecular charge transfer in the $S_1$ state is extended, and the excited state is more tolerable for any quenching effects in the micelle. Therefore, an $S_1\;{\rightarrow}\;S_o$ emission was newly discovered under this micelle microenvironment. For the $S_2\;{\rightarrow}\;S_o$ emission, the quantum yields increase but the quantum yield of the $S_1\;{\rightarrow}\;S_o$ emission approximately decreases as the water concentration in the micelle increases.

• Journal of Photoscience
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• 제2권1호
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• pp.13-18
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• 1995

The steady-state emission spectra of dicoumarol (DC) in ethanol and EPA have been examined at various temperatures (77-298 K). At room temperature, a fluorescence spectrum of DC in ethanol shows a emission maximum at 350 nm. In EPA a Stokes-shifted emission band appears around 470 nm in addition to the 350 nm emission, and its intensity is enhanced as temperature decreases. This emission is attributed to a zwitterionic tautomer of DC formed by a single excited-state intramolecular proton transfer (ESIPT) along the internal hydrogen-bonding. The fluorescence lifetimes have been measured at 350 and 450 nm as a function of temperature. The fluorescence decay at 350 nm is single exponential at any temperature, whereas the one at 450 nm becomes biexponential at temperatures below 250 K. These results are discussed in terms of a conformational change followed by the ESIPT. The activation energy barrier for the conformational change has been determined to be 3.7 $\pm$ 0.2 kJ/mole.

• Bulletin of the Korean Chemical Society
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• 제13권2호
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• pp.140-145
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• 1992

The excited state intramolecular proton transfer and physical properties of 7-hydroxyquinoline are studied in various solutions and heterogeneous systems by measuring steady state and time-resolved fluorescence, reflection and NMR spectra. Proton transfer is observed only in protic solvents owing to its requirement of hydrogen-bonded solvent bridge for proton relay transfer. The activation energies of the proton transfer are 2.3 and 5.4 kJ/mol in $CH_3OH$ and in $CH_3OD$, respectively. Dimers of normal molecules are stable in microcrystalline powder form and undergo an extremely fast concerted double proton transfer upon absorption of a photon, consequently forming dimers of tautomer molecules. In the supercage of zeolite NaY, its tautomeric form is stable in the ground state and does not show any proton transfer.