• 천문학회지
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• 제51권1호
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• pp.5-16
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• 2018

We investigate the escape of $Ly{\beta}$ from emission nebulae with a significant population of excited hydrogen atoms in the level n = 2, rendering them optically thick in $H{\alpha}$. The transfer of $Ly{\beta}$ line photons in these optically thick regions is complicated by the presence of another scattering channel leading to re-emission of $H{\alpha}$, alternating their identities between $Ly{\beta}$ and $H{\alpha}$. In this work, we develop a Monte Carlo code to simulate the transfer of $Ly{\beta}$ line photons incorporating the scattering channel into $H{\alpha}$. Both $H{\alpha}$ and $Ly{\beta}$ lines are formed through diffusion in frequency space, where a line photon enters the wing regime after a fairly large number of resonance scatterings with hydrogen atoms. Various line profiles of $H{\alpha}$ and $Ly{\beta}$ emergent from our model nebulae are presented. It is argued that the electron temperature is a critical parameter which controls the flux ratio of emergent $Ly{\beta}$ and $H{\alpha}$. Specifically for $T\;=\;3{\times}10^4\;K$ and $H{\alpha}$ line center optical depth $\tau{\alpha}\;=\;10$, the number flux ratio of emergent $Ly{\beta}$ and $H{\alpha}$ is ~ 49 percent, which is quite significant. We propose that the leaking $Ly{\beta}$ can be an interesting source for the formation of $H{\alpha}$ wings observed in many symbiotic stars and active galactic nuclei. Similar broad $H{\alpha}$ wings are also expected in $Ly{\alpha}$ emitting halos found in the early universe, which can be potentially probed by the James Webb Telescope in the future.

• 대한화학회지
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• 제24권3호
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• pp.250-258
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• 1980

여러종류의 자유라디칼들이 이소니트릴에 첨가되어 중간체인 imidoyl 자유라디칼 RN=CR'을 형성한다. 이것은 또한 imine으로부터 imidoyl hydrogen 을 떼어 내는 다음과 같은 반응에 의해서도 생성될 수 있다. RN=C(H)R' ＋ R"${\cdot}{\rightarrow}$ RN=CR' ＋ R"-H 중간체인 imidoyl 자유라디칼은 ${\beta}$-cleavage 및 aton transfer 반응을 통해서 안정된 분자를 형성한다. ${\beta}$-cleavage는 imidoyl 자유라디칼의 구조에 따라서 두개의 다른 방향으로의 반응이 가능하다. Cyanide transfer와 소위 말하는 정상적인 ${\beta}$-cleavage가 그러한 반응들이다. t-Butoxy 자유라디칼이 t-butylisonitrile 7에 첨가되면 중간체인 t-Bu-N=C-O-Bu-t가 생성되는데, 이것은 ${\beta}$-cleavage반응을 통해서 t-butylisocyanate와 t-butyl 자유라디칼을 형성한다. Phenyl 자유라디칼은 7에 첨가되어 중간체인 t-Bu-N=$C-C_6H_5$를 형성하는데 이것은 cyanide transfer 반응을 통해서 benzonitrile과 t-butyl 자유라디칼로 분해된다. 여기서 생성되는 t-butyl 자유라디칼은 다시 7에 첨가하여 intermediate인 자유라디칼 t-Bu-N=C-Bu-t을 형성하고, 이것은 다시 pivalonlonitrile과 t-butyl 자유라디칼로 분해되는데 이러한 반응이 반복되므로 radical chain isomerization을 일으킨다. Silyl 자유라디칼은 7에 첨가되어 t-Bu-N=$C-Si(CH_3)_3$를 형성하고, 이것은 cyanide transfer 반응을 거쳐서 다시 $(CH_3)_3$SiCN과 t-butyl 자유라디칼로 분해된다.

• 대한화학회지
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• 제54권4호
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• pp.437-442
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• 2010

수용액 속에서 $NaHSO_4$, TBAB (phase transfer catalyst), ionic liquid (IL) (1-butyl-3-methyl imidazolium hydrogen sulphate [bmim]$HSO_4$)를 사용하여, formalin, ${\beta}$-naphthol, aromatic amines을 반응시켜서 대응하는 2,3-dihydro-2-phenyl-1Hnaphtho-[1,2-e] [1,3] oxazine 유도체를 합성할 수 있는 보다 친환경적이고, 수율이 좋고, 크로마토그래피 분리 방법을 사용하지 않는 합성 방법을 개발하였다.

• Journal of Photoscience
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• 제4권2호
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• pp.61-67
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• 1997

The model based on the idea that the p$_y$-orbital of the carbonyl oxygen is responsible to receiving hydrogen was devised for simulation of intramolecular hydrogen transfer. A Monte Carlo method was applied to free rotation of a molecular chain performed by changing the dihedral angles, and a "hit" was defined as the case when the migrating hydrogen comes within the region defined as the p$_y$-orbital and satisfies all the geometrical requirements for abstraction. A set of parameters was employed for defining the region and the requirements; $\tau$ was defined as the angle formed between O...H vector and its projection on the mean plane of the carbonyl group (- 43$\circ$ < $\tau$ < + 43$\circ$), $\Delta$ as the C=O...H angle (90 -15$\circ$ < $\Delta$ < 90 + 15$\circ$), $\theta$ as the O...H - C angle ( 180 - 80$\circ$< 0 < 180 + 80$\circ$), d as the distance from the center of the lobe of the p$_y$-orbital to hydrogen (0 < d < 1.04 ${\AA}$). The minimum value for the distance between carbonyl oxygen (O$_1$) and the migrating hydrogen (H$_i$) and for that between non-bonded atoms except the pair of O$_1$ and H$_i$ were assumed to be 0.52 ${\AA}$ and 1.54 ${\AA}$, respectively. The apphcation of this model to intramolecular $\beta$-, $\gamma$-, $\delta$-, $\epsilon$-, and $\zeta$-hydrogen abstraction in ketones and $\eta$- and $\theta$- proton transfer in oxoesters gave good results reflecting their photochemical behavior. The model was also used for prediction of photoreactivities of 2-(N,N-dibenzylamino)ethyl 2-, 3- and 4-benzoylbenzoate (1a - c). (1a - c).

• Bulletin of the Korean Chemical Society
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• 제22권4호
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• pp.383-387
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• 2001

The kinetics and mechanism of the reactions of thiophenyl dimethylacetates (TDA) and trimethylacetates (TTA) with benzylamines in acetonitrile are studied. The reactions are first order in both the amine and the substrate. Relatively large values of ${\beta}X(\betanuc$ = 1.1-1.5; TDA and 1.1-1.5; TTA) and ${\beta}Z({\beta}lg$ = -1.8~-2.0; DTA and -1.3~-1.6; TTA) for benzylamines, significantly large kH/kD values (=1.2-1.5; DTA and 1.2-1.5; TTA) involving deuterated benzylamines, and large ${\rho}XZ$ (=0.82; TDA and 1.05; TTA) values are interpreted to indicate stepwise acyl transfer mechanism, but with the hydrogen bonded four center type transition state for benzylamine. The relatively greater magnitudes of ${\rho}XZ$ and the secondary kinetic isotope effects involving deuterated nucleophiles are in line with the proposed mechanism.

• Bulletin of the Korean Chemical Society
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• 제33권3호
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• pp.833-838
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• 2012

The thermal degradation products of polytrimethylene terephthalate (PTT) obtained by heating the sample in the temperature range of $250-360^{\circ}C$ under non-oxidative conditions was characterized using MALDI-TOF (matrix assisted laser desorption/ionization) mass spectrometry. The structures of the degradation products were determined and the relative compositions were estimated. The MALDI-TOF mass spectra of the thermally degraded PTT sample showed three main series of oligomer products with different end groups, which were carboxyl/carboxyl, carboxyl/allyl, and allyl/allyl. In contrast to the thermal degradation of polyethylene terephthalate (PET), the oligomers containing terephthalic anhydrides were not detected, whereas the formation of oligomers containing the unsaturated allyl ester group was confirmed by mass assignment. From these results, it was concluded that the thermal degradation of PTT proceeds exclusively through the ${\beta}$-CH hydrogen transfer mechanism, which is in accordance with the proposed reaction mechanism for the thermal degradation of polybutylene terephthalate (PBT).

• Journal of Photoscience
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• 제3권3호
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• pp.153-158
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• 1996

The effects of $\alpha$- and $\beta$-cyclodextrins (CD) on the twisted intramolecular charge transfer (TICT) behavior of p-N,N'-dimethylaminobenzoic acid (DMABA) in buffered aqueous solution have been investigated by examining formation and decay behaviors of the TICT-typical dual fluorescence. The ratio of the TICT emission to the normal emission (I$_a$/I$_b$) increases linearly $\alpha$-CD concentration increases, while in the presence of $\beta$-CD it shows nonlinear dependences on the CD concentration. The analysis of the CD-dependent changes of the I$_a$/I$_b$ and absorption spectra demonstrates formation of 1:1 inclusion complexes between DMABA and CDs. The decay time of the normal emission (ca. 700 ps) is little affected by the formation of $\alpha$-CD inclusion complex, whereas it increases upto ca. 1.6 ns upon formation of $\beta$-CD inclusion complex. The TICT emission for the $\beta$-CD inclusion complex exhibits two decay components while it shows a single component for the $\alpha$-CD inclusion complex, indicating formation of one or two types of inclusion complex in the presence of $\alpha$-CD or $\beta$-CD, respectively. These results are attributed to the CD cavity size dependence on patterns of complexation between CDs and DMABA. The CD size dependences of the TICT fluorescence properties with the orientation of the guest molecule demonstrate that the specific hydrogen bonding between the carboxylic acid group and water plays an important role in the excited-state TICT.

• 천문학회지
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• 제23권1호
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• pp.71-82
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• 1990

Theoretical calculations of the combined radiative transfer and statistical equilibrium equation including the charge-particle conservations have been earned out for a multilevel hydrogen atom in quiescent prominences. Cool and dense models show the steep changes of population and radiation field in the vicinity of the surface, while these physical quantities remain unchanged for models with temperature of 7,300K, regardless of total densities. Ionization rate of hydrogen atom related with metallic line formation varies in considerable amounts from the surface to the center of model prominences cooler than 6,300K. However, such cool models cannot release enough hydrogen line emissions to explain observed intensities. Prominence models with a temperature higher than 8,000K can yield the centrally reversed Lyman line profiles confirmed by satellite EUV observations. We find that queiscent prominence with a density between $2{\times}10^{11}$ and $10^{12}cm^{-3}$ should be in temperature range between 6,300K and 8,300K, in order to explain consistently observed H alpha, beta line emissions and $n_p/n_l$ ratio.

• Bulletin of the Korean Chemical Society
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• 제31권10호
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• pp.2801-2805
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• 2010

A nucleophilic substitution reaction of 4-chloro-7-nitrobenzofurazan (NBF-Cl) with anilines in MeOH-MeCN mixtures was conducted at 25, 35, and $45^{\circ}C$. Based on the higher $\beta_{nuc}$ values (1.0 - 1.6) of the reaction and a good correlation of the rate constants with the reduction potentials of the aniline nucleophiles, the present reaction was initiated by a single electron transfer (SET). After this step, the reaction proceeds through a transition state similar to the normal $S_NAr$-Ad.E pathway.

• Journal of Photoscience
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• 제1권1호
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• pp.53-59
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• 1994

Molecular orientation and polarity of solubilization site of dipolar azobenzenes solubilized in micellar solutions are discussed. The polarity of solubilization was estimated by using Taft $\pi$$^*$ scale with linear solvation energy relationship, $\Delta$E=$\Delta$E$_0$ + S($\pi$$^*$ + d$\delta$)+a$\alpha$ + b$\beta$. Hydrogen bonding effects were taken into account for the estimation of micropolarity. The polarity that azobenzenes experienced in the miceliar solutions was close to water which represented that the azobenzenes were mostly solubilized at the interface. For the orientations of azobenzenes were concerned, the nitro group of NPNOH faced the interface and the hydroxy group of NPNO$^-$ located at the interfacial area.