• 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.

• Bulletin of the Korean Chemical Society
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• 제28권4호
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• pp.647-651
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• 2007

In order to investigate the excited-state intramolecular proton transfer (ESIPT) process of dihydroxyanthraquinones (DHAQ; 1,5-DHAQ and 1,8-DHAQ) in organic-inorganic hybrid matrices, transparent SiO2, SiO2- Al2O3, and Al2O3 matrices chemically bonded with DHAQ were prepared using a sol-gel technique. The absorption maxima of 1,5- and 1,8-DHAQ in SiO2 matrices are observed at around 420 nm, whereas those of DHAQ in both SiO2-Al2O3 and Al2O3 matrices are markedly shifted to longer wavelength compared with those in SiO2 matrix. This indicates that DAHQ forms a chemical bond with an Al atom of Al2O3. The DHAQ in SiO2 matrix shows a markedly Stokes-shifted emission which is originated from the ESIPT in DHAQ. Based on the emission lifetimes of DHAQ, the ESIPT of DHAQ was found to be strongly affected by the chemical interaction with Al atom in the Al2O3-related matrices.

• 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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• 제30권10호
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• pp.2341-2344
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• 2009

Metallacyclodimers, [Ag(OTf)($L1)]_2$ and [Ag($L2)]_2(OTf)_2$ (L1 = 1,3-dibromo-2,2-bis[(isonicotinoyloxy)methyl] propane; L2 = 2,5-dimethyl-2,5-bis(isonicotinoyloxy)hexane) were constructed and characterized. The crystal structure of [Ag(OTf)($L1)]_2$ reveals a 32-membered cyclodimer, whereas that of [Ag($L2)]_2(OTf)_2$ shows a linked 34-membered cyclodimer chain via intercyclic argentophilic (Ag…Ag) interactions. [Ag(OTf)($(L1)]_2$ affords “intramolecular $\pi-\pi$ interaction cyclodimer” whereas [Ag($L2)]_2(OTf)_2$ produces a racemic mixture of “twisted cyclodimer”. Ring-conformation of the cyclodimers was affected via the competition of electrostatic interaction and argentophilic interaction.

• Bulletin of the Korean Chemical Society
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• 제22권6호
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• pp.575-580
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• 2001

Intramolecular ring-ring interactions in the model compounds, $8-methoxypsoralen-CH_2O(CH_2)n-adenine(MOPCH_2OCnAd$, n=2, 3, 5, and 6) in which 5' position of 8-methoxypsoralne (8-MOP) is linked by different polymethylene bridges to N9 of adenine, have been investigated by hypochromism measurements. Efficient ring-ring stacking interactions have been observed in $MOPCH_2CO2Ad$ (7) from the percent hypochromism(%H) and fluorescence spectra of the models and a reference molecule. The 8-methoxyposralen-adenine systems have shown stronger ring-ring stacking interaction than the psoralen-adenine system.

• Bulletin of the Korean Chemical Society
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• 제13권6호
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• pp.613-620
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• 1992

The solvent-dependent photophysical properties of 2-biphenylcarboxylic acid (2BPCA) and 4-biphenylcarboxylic acid(4BPCA), which have a pre-twisted conformation in the ground state, have been investigated. The fluorescence spectra of 4BPCA show vibrational structure with a non-mirror image to the absorption spectra in nonpolar solvent while those of 2BPCA show no structure even in nonpolar solvents. As the solvent polarity increases, the fluorescence spectra become diffuse and broad with a strong red shift resulting in the large Stokes shift. The large fluorescence Stokes shift of BPCA's in polar solvent is also partially due to an intramolecular charge transfer (ICT) interaction in the excited state, as demonstrated by the large dipole moment in the excited state (7.6-10.6 D). The fluorescence decay behaviors of BPCA's (decay-times and their pre-exponential factors) also depend on solvent polarity in agreement with the solvent-dependent properties of the steady-state fluorecence. The data have been discussed in terms of change in the excited-state potential energy surface with respect to change of the dihedral angle of biphenyl moiety.

• Bulletin of the Korean Chemical Society
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• 제27권4호
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• pp.495-502
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• 2006

Intramolecular energy flow and C-$H_{methyl}$ and C-$H_{ring}$ bond dissociations in vibrationally excited toluene in the collision with HF have been studied by use of classical trajectory procedures. The energy lost by the vibrationally excited toluene upon collision is not large and it increases slowly with increasing total vibrational energy content between 20,000 and 45,000 $cm ^{-1}$. Above the energy content of 45,000 $cm ^{-1}$, however, energy loss decreases. Furthermore, in the highly excited toluene, toluene gains energy from incident HF. The temperature dependence of energy loss is negligible between 200 and 400 K. Energy transfer to or from the excited methyl C-H bond occurs in strong collisions with HF transferring relatively large amount of its translational energy (>> $k_BT$) in a single step, whereas energy transfer to the ring C-H bond occurs in a series of small steps. When the total energy content $E_T$ of toluene is sufficiently high, either C-H bond can dissociate. The C-$H_{methyl}$ dissociation probability is higher than the C-$H_{ring}$ dissociation probability. The dissociation of the ring C-H bond is not the result of the intermolecular energy flow from the direct collision between the ring C-H and HF but the intramolecular flow of energy from the methyl group to the ring C-H stretch. The C-$H_{ring}$${\cdot}{\cdot}{\cdot}$HF interaction is not important in transferring energy and in turn bond dissociation.

• 한국응용과학기술학회지
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• 제21권3호
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• pp.238-245
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• 2004

The interaction between anion and zwitterionic surfactants was investigated by means of surface tension, NMR spectroscopy, and fluorescence studies. These systems are N-tetradecyloxymethyl-N,N-dimethyl betaine ($C_{14}$, TDB), N-octadecyloxymethyl-N,Ndimethyl betaine ($C_{18}$, ODB), and sodium dodecylethoxy sulfate (SDE). These systems show a composition dependency in micellar properties. When the molar fraction of TDB and ODB was about 0.6, the cmc values of these systems showed minima, whereas the solubilized amount of a water insoluble dye, NMR line width showed maxima. These changes comes from the intramolecular complexes formed in the mixed micelles. The complexes are due to the electrostatic interaction of oppositely charged head groups of betaine and sodium dodecylethoxy sulfate. A comparison of betaine and SDE alkyl methylene group line widths to those of n-methyl group indicates that the interior of the micelle in the restricted region is more immobile than the head group.

• Bulletin of the Korean Chemical Society
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• 제22권6호
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• pp.597-604
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• 2001

The reaction of [(2-N,N-dimethylaminomethyl) pheny] methylvinychlorosiane with t-BuLi in hexane solvent gave dimers, five isomeric 1,3-disilacyslobutanes which were weparated and charaterized. In trapping experiments with various trapping agents, no corresponding silene-trapping aduct was observed. We suggest that more important species for the formation of five isomeric dimers might be the zwitterionic species generated by virtue of intramolecular donor atom rather than the silene.

• Bulletin of the Korean Chemical Society
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• 제24권7호
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• pp.901-905
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• 2003

The lower critical solution temperature (LCST) of thermosensitive poly(organophosphazenes) with methoxypoly(ethylene glycol) (MPEG) and amino acid esters as side groups was studied as a function of saccharide concentration in aqueous solutions of mono-, di-, and polysaccharides. Most of the saccharides decreased the LCST of the polymers, and the LCST decrease was more prominently observed by saccharides containing a galactose ring, such as D-galactose, D-galactosamine and D-lactose, and also the polysacccharide, 1-6-linked D-dextran effectively decreased the LCST of the polymers. Such an effect was discussed in terms of intramolecular hydrogen bonding of saccharides in polymer aqueous solution. The saccharide effect was found to be almost independent on the kinds of the amino acid esters and MPEG length of the polymers. Such a result implies that the polymer-saccharide interaction in aqueous solution is clearly influenced by the structure of sacchardes rather than by that of the polymers. The acid saccharides such as D-glucuronic and D-lactobionic acid increased the LCST, which seems to be due to their pH effect.