• KIEE International Transactions on Electrophysics and Applications
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• 제11C권3호
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• pp.81-84
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• 2001

The trans and cis forms of N-alkyl-4-styrylpyridinium derivatives (CnSP: n= 4, 8, 12, 16) were successfully synthesized and purified. The derivatives of styrylpyridinium cause photoisomerization when they are illuminated with UV light. The pressure-area isotherms of CnSP and their derivatives were studied to reveal the effect of alkyl chain length. The photoisomerization of CnSP monolayers at the air/water interfaces was indirectly studied by measuring surface tension changes with photoirradiation on the water surface. The characteristics of CnSP were furthermore studied with UV-vis, surface pressure-area isotherms, surface potential-area isotherms, Brewster Angle Microscopy (BAM) at the air/water interface, and optical diffraction efficiency on the ultrathin films.

• Bulletin of the Korean Chemical Society
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• 제16권11호
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• pp.1019-1023
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• 1995

A light-emitting silicon material was prepared by electrochemical etching of n-Si single crystal wafers in a solution of hydrofluoric acid and ethanol. Visible photoluminescence from the silicon was inhomogeneous and decayed rapidly in the ambient laboratory conditions or with photoirradiation. Substantial improvements in photoluminescence which include little-dependent luminescence peak energy with excitation energy variation and longer-lasting room temperature visible photoluminescence were achieved when the surface of photoluminescent silicon material was derivatized with the surface modifier of octadecylmercaptan. Surface modification of the photoluminescent silicon was evidenced by the measurements of contact angles of static water drops, FT-IR spectra and XPS data, in addition to changed photoluminescence. Similar improvements in photoluminescence were observed with the light-emitting silicon treated with dodecylmercaptan, but not with octadecane. The present results indicate that sulfurs of octadecylmercaptans or dodecylmercaptans appear to coordinate the surface Si atoms of LESi and perturb the surface states to significantly change the luminescent characteristics of LESi.

• Journal of Photoscience
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• 제4권3호
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• pp.133-140
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• 1997

A system for studying oxidative hemolysis has been used by controling UV-irradiation and concentration of a novel molecular probe, N,N'-bis(2-hydroperoxy-2-methoxyethyl)-1,4,5,8-naphthalenetetra-carboxylic diimide (NP-III), which generates hydroxyl radical upon longer wavelength photoirradiation (> 350 nm). NP-III induces 25~30% of hemolysis at low concentration (50 $\mu$M) for 3h-irradiation of UVA. The simultaneous treatment of N-ethylmaleimide (NEM) with NP-IH completely hemotyzed erythrocytes under the same conditions as NP-III alone by both decreasing thiol group and increasing lipid peroxidation in erythrocyte membrane. However. thiol-reducing agents prevented the protein-crosslinking and lipid peroxidation on the NEM-synergistic hemolysis by partially scavenging hydroxyl radical and maintaining the thiol group of erythrocyte membrane in the reduced state. In addition, erythrocytes pretreated with 2,2,5,7,8-pentamethyl-6-hydroxychromane (PMC), vitamin E homologue was able to delay and decrease the lipid peroxidation when compared to cells pretreated with both NEM and PMC. We suggest that the presence of reduced thiols in inner membrane protein by GSH can prevent the protein-crosslinking and the lipid peroxidation, and eventually prevent the oxidative hemolysis of erythrocyte.

• Bulletin of the Korean Chemical Society
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• 제25권11호
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• pp.1635-1640
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• 2004

The cyclophanes 1a-d containing two benzo[b]furan rings connected by various bridges have been prepared and their binding behaviors with N-benzylphenethylammonium cation 2 were examined by NMR titration method. The successive alkylation reactions of 4-hydroxyl groups and then 2-hydroxyl groups of 2,4-dihydroxybenzophenonse gave macrocycles 5a-c. Photoirradiation of the macrocycles 5a-c with 350 nm mercury lamp followed by dehydration afforded the cyclophanes 1a-c. Hydrolysis of two ester groups pendant on a bridge of 1b produced the carboxyl group-containing cyclophane 1d. The cyclophane 1a having a p-xylene bridge showed 1 : 1 binding with 2 with the binding constant of $36{\pm}6M^{-1}$ in 3 : 1 $CDCl_3$/methanol-$d_4$ solvent, while 1b and 1c which have neutral flexible bridges exhibited no appreciable binding with 2. The disodium salt of 1d showed much higher binding affinity for 2 forming 1 : 1 and 1 : 2 complexes.

• Bulletin of the Korean Chemical Society
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• 제32권spc8호
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• pp.2981-2987
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• 2011

A comparative study of the photodynamic and antioxidant activities of methyl pheophorbide-a (MPa, 1) and its transition metal(II) complexes (2-5) is described. Four transition metal complexes (palladium(II): 2, zinc(II): 3, cobalt(II): 4 and copper(II): 5) of MPa were prepared by reaction between the corresponding transition metal and 1, respectively, and were characterized by $^1H$-NMR and UV-vis spectroscopic and mass spectrometric analyses. In vitro results show a photodynamic therapy (PDT) efficacy with A549 cells might be attributed to a heavy atom effect of the transition metal complexes of MPa. Among them, 4 and 5 showed higher photodynamic activity than that of 1 at the concentration of 5 ${\mu}M$ at 24 h incubation after photoirradiation. The images of morphological change for 2-5 show evidence for the PDT effect with A549 cells. And the all transition metal complexes of MPa showed higher antioxidant activity than that of MPa, in which 4 showed the highest antioxidant activity.

• Journal of Photoscience
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• 제1권1호
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• pp.31-37
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• 1994

Photoirradiation at > 300 nm onto a suspension of platinized TiO$_2$ (TiO$_2$-Pt) particles in an aqueous solution. of N$_{\varepsilon}$-carbamyI-L-lysine (Lys(CONH)$_2$) induced the selective N-cyclization of Lys(CONH$_2$) into almost optically pure L-pipecolinic acid (PCA) under argon atmosphere at ambient temperature. Among various TiO$_2$-Pt catalysts, a P-25 (Degussa) powder platinized via impregnation from chloroplatinic acid followed by hydrogen reduction at 753 K exhibited the highest photocatalytic activity for Lys(CONH$_2$) consumption and L-PCA production. GC-MS analyses of L-PCA obtained photocatalytically from $^{15}$N$\alpha$-Lys(CONH$_2$) revealed the selective formation $^{15}$N-substituted L-PCA. This implies that the mechanism for L-PCA production contains selective cleavage of C$_{\varepsilon}$-N bond and intramolecular alkylation at $\alpha$-amino group. Effect of pH on the rate of this photocatalytic reaction was investigated in detail and compared with the pH-dependent charge distribution in Lys(CONH$_2$) molecule. It is clarified that protonation-deprotonation of $\alpha$-amino group gives marked influence on the rate and selectivity of the photocatalytic reaction. On the basis of these results, it is concluded that the selective production of optically pure L-PCA, especially in an acidic suspension of TiO$_2$-Pt, was attributed to the enhanced protonation of $\alpha$-amino group to prevent undesirable oxidation by photogenerated positive holes and blocking of $\varepsilon$-amino group to yield racemic Schiff base intermediate.

• Bulletin of the Korean Chemical Society
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• 제31권9호
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• pp.2453-2458
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• 2010

Photochemical studies of N-[(trimethylsilyl)alkyl]saccharins were carried out to investigate their photochemical behavior. Depending on the nature of the substrate and the solvent system employed, reactions of these substances can take place by either SET-promoted silyl migration from carbon to either the amide carbonyl or sulfonyl oxygen or by a N-S homolysis route. The results of the current studies show that an azomethine ylide, arising from a SET-promoted silyl migration pathway, is generated in photoreactions of N-[(trimethylsilyl)methyl]saccharin and this intermediate reacts to give various photoproducts depending on the conditions employed. In addition, irradiation of N-[(trimethylsily)ethyl]saccharin produces an excited state that reacts through two pathways, the relative importance is governed by solvent polarity and protic nature. Finally, photoirradiation of N-[(trimethylsilyl)propyl]saccharin in a highly polar solvent system comprised of 35% aqueous MeOH gives rise to formation of a tricyclic pyrrolizidine and saccharin that generated via competitive SET-promoted silyl transfer and $\gamma$-hydrogen abstraction pathways.

• 대한화학회지
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• 제35권5호
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• pp.452-460
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• 1991

메탄올-물 혼합용매 및 수용성 CTAB, SDS 용액에서 2-에틸안트라센[2-EA]과 9-페닐안트라센[9-PA]에 빛을 조사하는 동안 1,3-디페닐이소벤조푸란[DPBF]이 감소되는 것으로부터 이 반응에 단일항 산소$(^1O_2)$가 관여된다는 화학적 증거를 얻었다. 용매의 극성에 민간함 UV 분광학적 특성을 이용하여 2-EA와 9-PA의 평균미세환경의 극성을 조사하였다. 2-EA와 9-PA가 수용성 CTAB, SDS 및 Brij 35 용액에 가용화될 때 그들의 평균 미세환경은 극성이었으며, 미세환경의 극성 파라미터는 미셀의 이온성에 영향을 받지 않았다. 2-EA의 평균 미세환경의 극성은 40%(w/w) 에탄올 수용액의 극성과 비슷했으며, 9-PA의 경우는 30%(w/w)와 40%(w/w) 사이의 에탄올 수용액의 극성과 비슷했다. 이들 화학종들이 수용성 미셀용액에 가용화될 때 대부분 미셀의 표면에 분포할 것이라는 것을 알았다. 여러 용매에서 2-EA와 9-PA의 광증감능을 검토하였다. 메탄올-물 혼합용매가 수용성 미셀용액보다 광산화반응에 유리한 것으로 나타났다.

• 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.