• 제목/요약/키워드: Photocleavage

검색결과 7건 처리시간 0.036초

Synthesis, DNA Photocleavage and Singlet Oxygen Measurement of Cationic Bisporphyrins

  • Wang, Kai;Jin, Qi;Zhang, Xiulan;Song, Shuai-Hua
    • 대한화학회지
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    • 제57권2호
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    • pp.246-251
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    • 2013
  • With -$OCH_2CO$- as a linker, a non ${\beta}$-substituted cationic bisporphyrin (4a) and a ${\beta}$-substituted cationic bisporphyrin (4b) were prepared through methylation of the intermediate which was obtained from ${\beta}$-amino-5,10,15,20-tetra (4-cyanophenyl) porphyrin or 5-hydroxylphenyl-10,15,20-tris(4-cyanophenyl) reacting with 5-hydroxy-10,15,20-trispyridinylporphyrin. Their structures were confirmed by $^1H$ NMR, IR, UV-vis, MS and elemental analysis. DNA photocleavage ability and the singlet oxygen ability of those cationic bisporphyrins were investigated. DNA photocleavage activity of ${\beta}$-substituted cationic bisporphyrin was significantly weaker than that of $H_2TMPyP$, but similar to that of non ${\beta}$-substituted cationic bisporphyrin. While 4a and 4b showed substantial photocleavage activities toward DNA, with 68% and 66% observed at 10 ${\mu}M$. The assessment of indirectly measured $^1O_2$ production rates against $H_2TMPyP$ were described and the relative singlet oxygen production yields were: free cationic bisporphyrins > $H_2TMPyP$. The results showed the cationic bisporphyrins with ${\beta}$-substitution and non ${\beta}$-substitution could be developed as potential photodynamic agents.

Photocleavage of DNA by 4'-Bromoacetophenone Analogs

  • Jeon, Ra-Ok;Pual A.Wender
    • Archives of Pharmacal Research
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    • 제24권1호
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    • pp.39-43
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    • 2001
  • 4'-Bromoacetophenone analogs, which are able to generate monophenyl radicals capable of hydrogen atom abstraction, were investigated as possible photoinducible DNA cleaving agents. The potential of 4'-Bromoacetophenone as a possible new DNA cleaver is explored. Pyrrolecarboxatmid conjugated 4'-Bromoacetophenone, in particular, DNA cleaving activity and sequence-selectivity on the contiguous AT base pair sites.

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Photocleavage of DNA by 4′-Bromoacetophenone- Pyrrole Carboxamides

  • Jeon, Raok
    • 한국응용약물학회:학술대회논문집
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    • 한국응용약물학회 2001년도 추계학술대회 및 정기총회
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    • pp.79-79
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    • 2001
  • Genotoxic chemotherapeutics are irreversible DNA targeting agents, which can act as anticancer and antiviral drugs. Natural antibacterial and anticancer enediynes function through the formation of free radicals formed by Bergman-type cycloaromatization and being capable of cleavage of DNA strand. They have been focused primarily on the design and syntheses of simple enediyne structures, which can be mimic their mechanistic feature. Recently. I have been reported the possible application of 4'-bromoacetophenone as a simple photoactivatable DNA cleaving agent, which could be readily prepared and exhibit potent and selective DNA cleaving activity. Herein, we further investigated the activity of 4'-bromoacetophenone-pyrrolecarboxamides, which consist of both DNA cleaving element and recognition unit under various conditions in order to get more understanding of the mechanism of the action and find a broad spectrum of application.

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Photoinduced Electron Transfer Reactions of Aryl Benzyl Sulfides Promoted by 2,4,6-Triphenylpyrilium Tetrafluoroborate (TP+BF4-)

  • Memarian, Hamid Reza;Ira, Mohammadpoor Baltork;Bahrami, Kiumars
    • Bulletin of the Korean Chemical Society
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    • 제27권1호
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    • pp.106-110
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    • 2006
  • Photocatalytic electron transfer reactions of aryl benzyl sulfides using 2,4,6 triphenylpyrilium tetrafluoroborate ($TP^+BF_4^-$) resulted in the oxidation of these sulfides to the corresponding sulfoxides and also in most cases in the C-S bond cleavage of them along with formation of aromatic aldehydes. In these reactions, the formation of sulfide radical cation has been proposed, which undergoes either oxidation to the corresponding sulfoxide or C-S bond cleavage to the formation of aromatic aldehydes. The further oxidation of sulfoxides to sulfones has not been observed. The influence of substrate structures on the reaction pathways as well as the role of $O_2$ in this respect is discussed.

PREPARATION OF POLYMERIC PHOTOSTABILIZERS CONTAINING HALS GROUPS AND THEIR PHOTOSTABILIZATION EFFECTS ON POLYSTYRENE

  • Chae, Kyu Ho;Oh, Jae-Seong;Ham, Heui Suk
    • Journal of Photoscience
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    • 제3권3호
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    • pp.167-169
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    • 1996
  • Absorption of UV light induces photocleavage of polymer chains to produce free radicals which initiate photodegradation of the polymer molecules. Discoloration, cracking of surface, stiffening, and decreasing of mechanical properties of polymeric products occur as a result of photodegradation of the polymers. Photostabilizers are added to the polymer systems in order to minimize the unwanted effects of UV light. It is well known that Hindered Amine Light Stabilizers (HALS) are one of the most effective photostabilizer for polymers.' HALS have been used in a large number of commercial polymers and predominantly used in styrenic and engineering plastics. They are efficient and cost-effective in many applications despite their high prices. However, low molecular weight HALS vaporize easily, emitting harmful amines, and have poor extraction resistance, decreasing their photostabilization effect. They also decompose during processing and migrate within the polymers resulting in deposition on the polymer surfaces called 'blooming". These drawbacks of low molecular HALS can be overcome by use of the polymeric HALS. We have been studying photochemical reactions of the polymer systems. The present paper reports the preparation of a new polymeric photostabilizer containing HALS groups and their stabilization effects on photooxidation of polystyrene. The synthetic scheme for the preparation of polymeric photostabilizers containing HALS groups were shown at Scheme 1. N-[(Chloroformyl) phenyl]maleimide (CPMI) and N-[4-(chlorocarbonyl) phenyl]maleimide (CPMIC) were prepared by the known procedure. N[4-N'-(2,2,6,6-tetramethyl-4-piperidinyl)aminocarbonyl-phenyl] maleimide (TMPI) was prepared by the reaction of CPMI with 4-amino-2,2,6,6-tetramethylpiperidine (ATMP).

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광촉매(光觸媒) 산화(酸化) 반응(反應)을 이용한 클로로페놀 분해(分解)에 관한 연구(硏究) (A Study on the Removal of Chloro-Phenols by Photocatalytic Oxidation)

  • 이상협;박주석;박중현
    • 상하수도학회지
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    • 제9권4호
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    • pp.87-96
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    • 1995
  • The Electron/Hole Pair is generated when the activation energy produced by ultraviolet ray illuminates to the semiconductor and OH- ion produced by water photocleavage reacts with positive Hole. As a results, OH radical acting as strong oxidant is generated and then Photocatalytic oxidation reaction occurs. The photocatalytic oxidation can oxidate the non-degradable and hazardous organic substances such as pesticides and aromatic materials easier, safer and shorter than conventional water treatment process. So in this study, many factors influencing the oxidation of chlorophenols, such as inorganic electrolytes addition, change of oxygen and nitrogen atmosphere, temperature, pH, oxygen concentration, chlorophenol concentration, were throughly examined. According to the experiments observations, it is founded that the rate of chlorophenol oxidation follows a first-order reaction and the modified Langmuir-Hinshelwood relationship. And the photocatalytic oxidation occurs only when activation energy acting as Electron/Hole generation, oxygen acting as electron acceptor to prevent Electron/Hole recombination, $TiO_2$ powder acting as photocatalyst are present. The effects of variation of dissolved oxygen concentration, temperature and inorganic electrolytes concentration on 2-chlorophenol oxidation are negligible. And the lower the organic concentration, the higher the oxidation efficiency becomes. Therefore, the photocatalytic oxidation is much effective to oxidation of hazardous substances at very low concentration. The oxidation is effective in the range of 0.1 g/L-10 g/L of $TiO_2$. Finally when the ultra-violet ray is illuminated to $TiO_2$, the surface characteristics of $TiO_2$ change and Adsorption/Desorption reaction on $TiO_2$ surface occurs.

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