• Title/Summary/Keyword: Photochemical Reaction Mechanism

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Photochemical Synthesis of Aspartylphenylalanyl Methyl Ester (광 알킬화 반응에 의한 Aspartylphenylalanyl Methyl Ester의 합성)

  • Sang Chul Shim;Kyu Ho Chae
    • Journal of the Korean Chemical Society
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    • v.19 no.5
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    • pp.367-374
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    • 1975
  • Glycine residue in N-X-glycylphenylalanine methyl ester(X = trifluoroacetyl or acetyl) was converted into aspartic acid derivative by a photoalkylation reaction. The reaction was induced with 350 nm lamp using a combination of diacetyl/di-t-butyl peroxide (DBP) as the photoinitiator, and acetic anhydride as the alkylating agent. In the thermal reaction with DBP and acetic anhydride, the same alkylation reaction of the dipeptide was observed. From this thermal alkylation reaction the photoalkylation reaction is also thought to undergo via free radical mechanism.

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Photodynamically induced endothelial cell injury and neutrophil-like HL-60 adhesion

  • Takahashi, Miho;Nagao, Tomokazu;Matsuzaki, Kazuki;Nishimura, Toshihiko;Minamitani, Haruyuki
    • Journal of Photoscience
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    • v.9 no.2
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    • pp.518-520
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    • 2002
  • Photodynamic therapy (PDT) is a treatment modality based on photochemical reaction and the resultant cytotoxic reactive oxygen species. The platelet thrombus formation leading to stasis observed in vivo during PDT is called vascular shut down (VSD) effect. To investigate the mechanism of the VSD effect, we observed Human Umblical Vein Endothelial Cell (HUVEC) injury induced by photochemical reaction. We observed cell retraction and blebbing after PDT. It seems that the injury was not fetal and only morphological change. Then, the cytoplasm was stained by Calcein-AM and subendothelial area was evaluated from fluorescence microscopy. The rate of subendothelial area after PDT increased significantly. Second, we investigated interaction between neutrophils and HUVEC. Human promyelocytic leukemia cells (HL-60) were differentiated into neutrophil by incubation with all-trans retinoic acid. Calcein-AM labeled neutrophil adhesion to HUVEC was evaluated from fluorescence microscopy. PDT-induced neutrophil adhesion to HUVEC depended more on the exposure of subendothlial area than on neutrophil activation. This result suggests that there is a certain interaction between neutrophil and HUVEC during PDT.

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Photochemical Changes of Malonaldehyde by the Presence of Aflatoxins in Model Systems (Aflatoxin 존재하에서의 수용액중 Malonadehyde 의 광화학적 변화)

  • Kwon,, Tai-Wan
    • Korean Journal of Food Science and Technology
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    • v.1 no.1
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    • pp.45-50
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    • 1969
  • On the basis of UV spectral changes and TBA reaction, malonaldehyde (MA) in aqueous solution receives considerable photochemical modification by UV light of short wavelengths around $260m{\mu}$. When aflatoxin is added in the solution, UV light of long wavelengths around $360m{\mu}$ induces such changes quite rapidly and although the rate of change is rather slow, it is also true even with ordinary laboratory illumination(fluorescent). The modification is irreversible in nature and the role of aflatoxin in this reaction is identified as a photosensitizer. The mechanism involved in this modification is apparently due to the parallel dimerization of MA molecules, but not by head to tail combination of the molecules.

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Selective nucleation of copper on fluorocarbon-resin surface by Nd:YAG laser-induced chemical reaction (레이저 유도 화학반응을 이용한 fluorocarbon 수지표면 위의 선택적 구리핵의 형성)

  • Lee, Hong-Kyu;Lee, Kyoung-Cheol;Ahn, Min-Young;Lee, Cheon
    • Proceedings of the KIEE Conference
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    • 1999.07d
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    • pp.1535-1537
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    • 1999
  • Photochemical defluorination and substitution of fluorocarbon-resin surfaces using a pulsed Nd:YAG laser(266 nm) and copper-sulfate$(CuSO_4)$ aqueous solution were discussed. Interface of copper nuclei and fluorocabon-resin was chemically bonded through oxygen which was photodissociated from water in copper-sulfate aqueous solution under the laser irradiation. The reaction mechanism for chemical surface modification is discussed on the basis of x-ray photoelectron spectroscopy and atomic force microscope analyses.

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Photochemical Behavior of Carbon Monoxide in Aqueous Suspension of ZnO (ZnO 수용액중에서 일산화탄소의 광화학적 거동)

  • Chul-Ho Park;Woo-Suk Chang;Yong-Sung Kim;Hyoung-Ryun Park
    • Journal of the Korean Chemical Society
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    • v.47 no.3
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    • pp.213-219
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    • 2003
  • The photochemical transformation of carbon monoxide in aqueous solution has been investigated at $25{\pm}0.1^{\circ}C$using ZnO as a photocatalyst. After irradiation of 253.7 nm UV light in the solution, carboxylation and carbonylation processes were carried out, and the formation of formic acid, oxalic acid, glyoxylic acid, formaldehyde and glyoxal was observed. The formation of the products depended on the pH values in the solution. The yield of formaldehyde and glyoxal increased in acidic solution whereas it decreased in basic solution. When the pH values in the solution increased above 11.5, the yield of formic acid increased rapidly. The initial quantum yields of the products were determined and the probable mechanisms for the reactions were presented on the basis of the products analysis.

Comparison of Photoaddition Reactions of Aromatic Carbonyl Compounds with Silyl Thioketene Acetal vs. Silyl Ketene Acetal

  • Lee, In Ok;Yoon, Ung Chan;Cho, Dae Won
    • Rapid Communication in Photoscience
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    • v.2 no.3
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    • pp.76-78
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    • 2013
  • Photoaddition reactions of aromatic carbonyl compounds with silyl thioketene acetals have been explored. The results of this study show that the acetonphenone react with dimethyl substituted silyl thioketene acetal competitively via either single electron transfer (SET)-desilylation or [2+2]-cycloaddition pathways to produce b-hydroxyester and oxetanes. In contrast, photochemical reactions of the benzaldehyde with dimethyl substituted silyl thioketene acetal mainly lead to the formation of oxetanes arising by [2+2] cycloaddition. A comparison of the results with those of silyl ketene acetal revealed that replacement of sulfur atom in ${\alpha}$-silyl donor substrate bring about dramatic changes in chemoselectivities as well as excited state reaction mechanism.

판상형 산화아연의 합성 및 응용에 관한 연구 동향

  • Jang, Ui-Sun
    • Ceramist
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    • v.20 no.4
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    • pp.55-73
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    • 2017
  • As one of the most versatile semiconductors, zinc oxide (ZnO) with one-dimensional (1-D) nanostructures has been significantly developed for the application of ultraviolet (UV) lasers, photochemical sensors, photocatalysts, and so on. Such 1-D nanowires could be easily achieved due to the anisotropic growth rate along the [0001] direction. However, such typical growth habit leads to decrease the surface area of the (0001) plane, which plays a central role in not only UV lasing action but also photocatalytic reaction. This fact lead us to develop ZnO crystal with enhanced polar surface area through crystal growth control. The purpose of this review is to provide readers a simple route to plate-type ZnO crystal with highly enhanced polar surfaces and their applications for UV-laser, photocatalyst, and antibacterial agents. In addition, we will highlight the recent study on pilot-scale synthesis of plate-type ZnO crystal for industrial applications.

The Photochemical Reactivities of Benzenes Tethered to Haloarene

  • 박용태;김영희;황철균;성대동
    • Bulletin of the Korean Chemical Society
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    • v.17 no.6
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    • pp.506-510
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    • 1996
  • The syntheses and photoreactions of haloarenes, in which the aryl and haloaryl moieties are tethered by a simple alkyl group, were studied. For 2-benzyl-1-halobenzene, in which two aryl moieties were connected by methylene group, photoreduced product, diphenylmethane, was obtained along with the minor formation of the photocyclized product, fluorene, in acetonitrile solvent. For 1-halo-2-phenethylbenzene, in which two aryl moieties were connected by ethylene group, photocyclized products, 9,10-dihydrophenanthrene and phenanthrene, were obtained along with the minor formation of photoreduced product, bibenzyl, in acetonitrile solvent. The photoreaction selectivities in several solvent systems were studied: In cyclohexane, 2-benzyl-1-chlorobenzene was photoreduced more effective than 2-benzyl-1-bromobenzene; In the presence of NaOH, 1-halo-2-phenethylbenzenes gave 9,10-dihydrophenanthrene and, in the presence of toluene, they gave phenanthrene. A radical reaction mechanism is proposed for the explanation of the reactions. This study shows that the photoreaction of haloarene, in which haloaryl and aryl moieties are tethered by ethylene group, can be used for ring formation of 9,10-dihydrophenanthrene otherwise difficultly accessible.

Reaction and Characterization of Silylene and its Precusor (Silylene과 Silylene 전구체의 반응 특성 연구)

  • Kong, Young Kun;Ahn, Young Man
    • Analytical Science and Technology
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    • v.7 no.3
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    • pp.321-327
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    • 1994
  • The mild thermal decomposition of 7, 7-dimethyl-1, 2, 3, 4, 5-pentaphenyl-7-silanorbornadiene with excess methyl alcohol proceeds to give 1-methoxydimethylsilyl-1, 2, 3, 4, 6-pentaphenylcyclohexa-2, 5-diene which is colorless needle crystal. The cophotolysis of the solution of 7-silanorbornadiene in the excess ethyl alcohol proceeds with loss of silylenes to give ethoxydimethylsilane which is insertion reaction product of silylene with O-H bond of ethyl alcohol. According to above results, it is presumed that the mechanism of photochemical decomposition and that of mild thermochemical decomposition of 7-silanorbornadiene are different.

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Photophysical and Electrochmical Studies of N,N-Bis (2,5-di-tert-butylphenyl) - 3,4,9,10 perylenebis (dicarboximide) (DBPI)

  • El-Hallag, Ibrahim S.;El-Daly, Samy A.
    • Bulletin of the Korean Chemical Society
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    • v.31 no.4
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    • pp.989-998
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    • 2010
  • The titled dye of DBPI gives amplified spontaneous emission (ASE) with maximum at 580 nm upon pumping by nitrogen laser (${\lambda}_{ex}\;=\;337.1\;nm$). The ground state absorption cross section (${\sigma}_A$) and emission cross section (${\sigma}_E$) as well as effective emission cross section(${\sigma}^*_E$) have been determined. The electronic absorption spectra of DBPI were measured in ethanol and tetrahydrofuran at room and low temperature. DBPI displays molecular aggregation in water. The photochemical reactivity of DBPI was also studied in carbon tetrachloride upon irradiation with 525 nm light. The electrochemical investigation of DBPI dye has been carried out using cyclic voltammetry and convolution deconvolution voltammetry combined with digital simulation technique at a platinum electrode in 0.1 mol/L tetrabutyl ammonium perchlorate (TBAP) in two different solvents acetonitrile ($CH_3CN$) and dimethylformamide (DMF). The species were reduced via consumption of two sequential electrons to form radical anion and dianion (EE mechanism). In switching the potential to positive direction, the compound was oxidized by loss of two sequential electrons, which were followed by a fast dimerization and/or aggregation process i.e $EC_{dim1}EC_{dim2}$ mechanism. The electrode reaction pathway and the chemical and electrochemical parameters of the investigated compound were determined using cyclic and convolutive voltammetry. The extracted electrochemical parameters were verified and confirmed via digital simulation method.