• Bulletin of the Korean Chemical Society
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• 제26권8호
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• pp.1190-1196
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• 2005

Halopyrroles, N-substituted 2-halopyrroles were prepared by halogenation of N-substituted pyrroles with NBS, NCS, or surfuryl chloride. N-Substituted 3-halopyrroles were synthesized by acid-catalyzed thermal and photochemical isomerization reactions of N-substituted 2-halopyrroles. Both the thermal and photochemical reactions were acid-catalyzed. For the acid-catalyzed isomerization, a mechanism of [1,3] bromine shift followed by deprotonation is operated. For the acid-catalyzed photoisomerization, an excited triplet state of 2-protonated N-benzyl-2-halopyrrole produces an intermediate N-substituted pyrrole complex with halonium ion which is equilibrated with N-substituted pyrrole plus halonium ion, and then the halonium ion newly adds to 3-position of N-substituted pyrrole followed by deprotonation to afford N-benzyl-3-halopyrrole.

• Bulletin of the Korean Chemical Society
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• 제26권5호
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• pp.791-794
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• 2005

A visible photochemistry of maleic to fumaric acid adsorbed on silver nanoparticle surfaces was investigated as probed by SERS using a simple flow method. Photoisomerization of maleic to fumaric acid was consecutively observed in the condition of various flow rates, which varied the exposure time of laser beam. The sequential SERS spectra of maleic acid indicated that the photochemical isomerization and desorption took place simultaneously on silver nanoparticle surfaces as a function of laser fluency and wavelength. For 530.9nm laser line excitation, the rate constant coefficients were obtained with a = 5.9 $sec^{-1}$ mW for isomerization and b = 13.9 $sec^{-1}$ mW for desorption, which $k_1\;=\;aI^n\;and\;k_2\;=\;bI^m$. Both reactions were one photon process (n = 1, m = 1) of a visible light and relatively fast process whose decay time was in the range of milli-second for 50 mW laser power. The rate of photochemical reaction increased on going toward the blue and photodesorption was a dominant process. A simple flow method used in this study was very useful to study a relatively fast photochemical reaction of molecules adsorbed on silver nanoparticle surfaces.

• Journal of Photoscience
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• 제9권2호
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• pp.1-4
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• 2002

Hula-twist is a volume-conserving photoisomerization reaction mechanism postulated in 1985 to account for the rapid photoisomerization of the retinyl chromophore in rhodopsin. The requisite stereochemical consequence of simultaneous isomerization of a double bond and an adjacent single bond has recently been demonstrated in isomerization of pre-vitamin D in an organic glass and by many other examples of organic systems already reported in the literature This paper reports the consequence in applying the mechanism to the primary photochemical process of several photosensitive biopigments: bilirubin, photoactive yellow protein, bacteriorhodopsin and rhodopsin. It is shown that the anchored nature of the chromophores must first be taken into consideration.

• Bulletin of the Korean Chemical Society
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• 제29권4호
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• pp.761-766
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• 2008

Photoresponsive arylether dendrimers Bis-azo-Gn(3,5) 1a-1c and Bis-azo-Gn(3,4,5) 2a-2c (n = 1-3) with an azobenzene unit at the core and several vinyl groups (3,5-bis(but-3-enyloxy)phenyl groups or 3,4,5-tris(but-3- enyloxy)phenyl groups) at the periphery have been prepared. Their structures and reversible trans-cis isomerization behaviors have been investigated by $^1H$-NMR, $^{13}C$-NMR, MALDI-TOF-Mass, and UV-vis spectra. All six azobenzene-cored dendrimers carried out very fast trans $\rightarrow$ cis photoisomerization on irradiation of 350 nm light and reached to the photostationary state within 180 s. During the dark incubation, slow thermal back reversion from cis to trans form is observed for all six dendrimers and is completed within 3 days for 1a-1c and 1 day for 2a-2c. Isomerization efficiency decreases with increasing generation. However, the initial reaction rates of both trans $\rightarrow$ cis photochemical isomerization and cis $\rightarrow$ trans thermal isomerization increases significantly with increasing generation for dendrimers for 1a-1c but only slightly for 2a-2c.

• Journal of Photoscience
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• 제4권2호
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• pp.49-52
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• 1997

Irradiation (300 nm) of 1, 2-benzoquinones 1 and diphenylacetylene 2 in dichloromethane yielded two isomeric quinone methides, 6 and 7. The same types of quinone methides, 9 and 10 (or 12 and 13) were obtained from the photocycloadditions of 9, 10-phenanthrenequinone 8 (or acenaphthenequinone 11) to diphenylacetylene 2. One-way photoisomerizations were observed between each isomeric adducts, (6, 7), (9, 10) and (12, 13).

• 한국인쇄학회지
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• 제18권2호
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• pp.41-54
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• 2000

가시광을 선택적으로 반사하는 광 응답성 코레스테릭 액정을 조제하고, 그 선택적 반사파장의 광화학적 변조를 시도함으로서 포토닉스(Photonices) 재료로서의 가능성을 검토했다. 고유의 선택 반사파장의 변조는 아조벤젠 유도체의 트란스(trans)·시스(cis)간의 광이성화에 의해 상전이 온도와 칼라의 변화와 함께 가역적으로 제어되어질 수 있었다. 또한 선택 반사파장의 변화에 수반되는 반사율의 변화는 코레스테릭 액정과 검출광의 광학적 성질에 의해 크게 좌우되어 지고, 반사율의 가역적인 스위칭에 있어서는 검출광에 대한 코레스테릭 액정의 초기 반사파장의 위치는 상반된 스위칭 모드(normal and reverse modes)를 산출하기에 매우 중요한 역할을 담당했다.

• Bulletin of the Korean Chemical Society
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• 제19권11호
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• pp.1179-1184
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• 1998

Mesogenic and azo monomers were synthesized and copolymerized to obtain two copolymers composed of methacrylate and itaconate backbone. Glass transition temperatures of the copolymers were found to be slightly higher than ambient temperature. Both the copolymers showed liquid crystalline properties. Trans-cis isomerization in film state was observed under UV-irradiation with a light of 365 nm. Regarding the photochemical phase transition behavior, the transition rate of nematic-to-isotropic state was slightly faster in the methacrylate copolymer during irradiation at 365 nm and the rate of the reverse transition was much faster in itaconate copolymer under thermal effect.

• 폴리머
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• 제36권6호
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• pp.776-788
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• 2012

셀로비오스, 말토오스 그리고 락토오스를 1-{4-(4'-시아노페닐아조)펜옥시}옥틸브롬 혹은 1-{4-(4'-시아노페닐아조)펜옥시카보닐}헵타노일 클로라이드와 반응시켜 옥타[8-{4-(4'-시아노페닐아조)펜옥시}]옥틸 그리고 옥타[8-{4-(4'-시아노페닐아조)펜옥시카보닐}]헵타노화 이당류 유도체들을 합성함과 동시에 이들의 열방성 액정과 광화학적 상전이 거동을 검토하였다. 모든 {(시아노페닐아조)펜옥시}옥틸 이당류 에테르들(CADETs)은 단방성 네마틱(N) 상들을 형성하는 반면 모든 {(시아노페닐아조)펜옥시카보닐}헵타노화 이당류 에스터들(CADESs)은 양방성 N 상들을 형성하였다. CADETs에 비해, CADESs는 높은 액체(I) 상에서 N 상으로의 전이 온도들을 나타냈다. 유리 셀 혹은 러빙된 폴리이미드(PI) 배향막을 지닌 셀 중에서 N 상을 형성하고 있는 이당류 유도체에 광을 조사시킬 경우, 아조벤젠기의 trans-cis 이성화에 의해 N 상은 I 상으로 변하였다. 한편, 광 조사시켜 얻은 시료를 광을 차단한 상태로 방치할 경우 열에 의한 cis-trans 이성화와 trans 아조벤젠기들의 재배열로 인하여 I 상은 최초의 N 상으로 변하였다. 유리 셀의 경우에 비해 러빙된 PI 배향막을 지닌 셀의 경우가 이당류 유도체들의 광화학적 N-I 그리고 열적 I-N 상전이 속도들은 빠르며 시아노아조벤젠기를 지닌 monomesogenic 화합물들 그리고 4-{4'-(시아노페닐아조)펜옥시}옥틸 글루코오스 그리고 셀룰로오스 에테르들에 대해 관찰되는 결과들에 비해 현저히 달랐다. 이러한 결과를 주사슬의 유연성, 반복단위당에 도입된 메소겐기들의 수 그리고 아조벤젠기들간의 거리에 기인한 아조벤젠기들의 협동효과의 차이의 견지에서 검토하였다.