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감광제 광산화에 의한 Bisphenol A 안정성 감소 (Decreased Stability of Bisphenol A by Photosensitization)

  • 박찬억;이재환
    • 한국식품과학회지
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    • 제42권3호
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    • pp.277-280
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    • 2010
  • 내분비교란물질인 BPA는 식품의 포장용기나 젖병 등의 제조에 이용되며, 라이보플라빈 광산화에 의해 안정성이 감소하는 것으로 보고된 바 있다. 본 연구에서는 광산화 시 메틸렌블루, 로즈벵갈, 라이보플라빈, 또는 이산화티타늄 등의 감광제 종류에 따른 BPA안정성을 비교하였고, sodium azide($NaN_3$) 농도에 따른 BPA안정성을 확인하였다. BPA 농도는 라이보플라빈, 로즈벵갈, 메틸렌블루 순서로 유의적으로 감소하였지만(p<0.05), 이산화티타늄 첨가 시료와 대조구인 감광제 무첨가군의 BPA 농도는 유의적인 차이가 없었다(p>0.05). BPA의 안정성은 메틸렌블루 농도 의존적으로 감소하였으며, $NaN_3$ 농도가 증가할수록 BPA 안정성은 증가하였다. 이는 메틸렌블루 광산화에 의한 BPA농도 감소에 일중항산소가 관여함을 의미한다.

Relaxation Process of the Photoexcited State and Singlet Oxygen Generating Activity of Water-soluble meso-Phenanthrylporphyrin in a DNA Microenvironment

  • Hirakawa, Kazutaka;Ito, Yusuke;Yamada, Takashi;Okazaki, Shigetoshi
    • Rapid Communication in Photoscience
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    • 제3권4호
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    • pp.81-84
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    • 2014
  • To examine the microenvironmental effect of DNA on the photosensitized reaction, the electron-donor-connecting porphyrin, meso-(9-phenanthryl)-tris(N-methyl-p-pyridinio) porphyrin (Phen-TMPyP), was synthesized. Phen-TMPyP can bind to oligonucleotides with two binding modes, depending on the DNA concentration. The fluorescence lifetime measurement of Phen-TMPyP shows a shorter component than that of the reference porphyrin without the phenanthryl moiety. However, the observed value is much longer than those of previously reported similar types of electron-donor-connecting porphyrins, suggesting that electron-transfer quenching by the phenanthryl moiety is not sufficient. The fluorescence quantum yield of Phen-TMPyP ($5{\mu}M$) decreased with an increase in DNA concentration of up to $5{\mu}M$ base pair (bp), possibly due to self-quenching through an aggregation along the DNA strand, increased with an increase in DNA concentration of more than $5{\mu}M$ bp and reached a plateau. The fluorescence quantum yield of Phen-TMPyP with a sufficient concentration of DNA was larger than that of the reference porphyrin. The singlet oxygen ($^1O_2$) generating activity of Phen-TMPyP was confirmed by the near-infrared emission spectrum measurement. The quantum yield of $^1O_2$ generation was decreased by a relatively small concentration of DNA, possibly due to the aggregation of Phen-TMPyP, and recovered with a sufficient concentration of DNA. The recovered quantum yield was rather smaller than that without DNA, indicating the quenching of $^1O_2$ by DNA. These results show that a DNA strand can stabilize the photoexcited state of a photosensitizer and, in a certain case, suppresses the $^1O_2$ generation.

Photochemical Property and Photodynamic Activity of Tetrakis(2-naphthyl) Porphyrin Phosphorus(V) Complex

  • Hirakawa, Kazutaka;Aoki, Shunsuke;Ueda, Hiroyuki;Ouyang, Dongyan;Okazaki, Shigetoshi
    • Rapid Communication in Photoscience
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    • 제4권2호
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    • pp.37-40
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    • 2015
  • To examine the photosensitized biomolecules damaging activity, dimethoxyP(V)tetrakis(2-naphthyl)porphyrin (NP) and dimethoxyP(V)tetraphenylporphyrin (PP) were synthesized. The naphthyl moiety of NP hardly deactivated the photoexcited P(V)porphyrin ring in ethanol. In aqueous solution, the naphthyl moiety showed the quenching effect on the photoexcited porphyrin ring, possibly through electron transfer and self-quenching by a molecular association. Binding interaction between human serum albumin (HSA), a water soluble protein, and these porphyrins could be confirmed by the absorption spectral change. The apparent association constant of NP was larger than that of PP. It is explained by that more hydrophobic NP can easily bind into the hydrophobic pockets of HSA. The photoexcited PP effectively induced damage of the tryptophan residue of HSA, through electron transfer-mediated oxidation and singlet oxygen generation. NP also induced HSA damage during photo-irradiation and the contributions of the electron transfer and singlet oxygen mechanisms were speculated. The electron transfer-mediated mechanism to the photosensitized protein damage should be advantageous for photodynamic therapy in hypoxic condition. The quantum yield of the HSA photodamage by PP was significantly larger than that of NP. The quenching effect of the naphthyl moiety is considered to suppress the photosensitized protein damage. In conclusion, the naphthalene substitution to the P(V)porphyrins can enhance the binding interaction with hydrophobic biomacromolecules such as protein, however, this substitution may reduce the photodynamic effect of P(V)porphyrin ring in aqueous media.

인삼 틸라코이드에서 Singlet Oxygen($^1$O$_2$) 생성에 미치는 전자전달계의 영향 (Effects of Light and Photosynthetic Electron Transport System on the Generation of Singlet Oxygen ($^1$O$_2$) in Ginseng Thylakoid Membrane)

  • 양덕조;채쾌;이성종;김용해;강영희
    • Journal of Ginseng Research
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    • 제14권1호
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    • pp.57-62
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    • 1990
  • In order to Investigate the mechanism of the leaf-burning disease of ginseng (Panax ginseng C.A. Meyer), studies on the generation of singlet oxygen (1O2) and the photooxidation of the pigments were carried out in comparison with the ones of soybean (G1ycine max L). The studies were mainly focalized on the effects of light intensity, light intensity, inhibitor and electron donor/acceptor of the Photosynthetic electron transport system. When we measured the amounts of 1O2 generated in the thylakoids of ginseng and soybean by the irradiation of light (300 w/m2) as a function its time. It was identified that a higher amount of 1O2 was formed in the ginseng thylakoid than the case of soybean. A generation ratio of lO2 between ginseng and soybean sltbstantially identical in the range of light intensities 50∼150w/m2 However much higher amount of 1O2 was generated in ginseng by irradiation of strong intensity of light (200 500w/m2). Wave length dependency on the generation of 1O2 and the pigment photooxidation was observed on ginseng thylakoids; red light (600-700 nm) gave a maximum effect in the contrast with blur green light (400-60 nm). When the ginseng thylalioid was treated with the electron donor (Mn2+) and acceptors (DCPIP, FeCy) of the photosynthetic electron transport system. a drastic inhibition of 1O2 generation was observed. However, treatment with its inhibitors (DCMU, KCW) activated 1O2 generation. An interesting fact that an electron donor or acceptor of the photosystem II(P680) Inhibited 1O2 generation, suggests an intimate relationship between 1O2 generation and photosystem II.

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Application of Chemical Probes to Detect Superoxide Anion and Singlet Oxygen in Biological Systems during Gamma Irradiation

  • Lee, Min Hee;Cho, Eun Ju;Kim, Ji Hong;Kim, Ji Eun;Chung, Byung Yeoup;Cho, Jae-Young;Lee, Kang-Soo;Kim, Jin-Hong
    • 방사선산업학회지
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    • 제5권3호
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    • pp.221-225
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    • 2011
  • To detect superoxide anion ($O_2{\cdot}^-$) or singlet oxygen ($^1O_2$) in biological systems during gamma irradiation, specific chemical probes, 4,5-dihydroxy-1,3-benzene disulfonic acid (Tiron) or 2,2,6,6-tetramethyl-piperidine (TEMP), were evaluated. Tiron or TEMP spin adducts was structurally stable in aqueous solution during gamma irradiation up to 500 or 1,000 Gy, respectively. The signal of Tiron semiquinone radical, a spin adduct of Tiron upon reaction with $O_2{\cdot}^-$, was slightly increased by gamma irradiation. This trend was dose-dependently manifested in $O_2$-saturated aqueous solution using nitro blue tetrazolium (NBT), a common probe for both hydrated electron ($e{^-}_{aq}$) and $O_2{\cdot}^-$. In contrast, a spin adduct of TEMP, was never inducible by gamma irradiation, while its signal was substantially enhanced by photosensitization of riboflavin. These results suggest that Tiron and NBT or TEMP could be utilized to detect $O_2{\cdot}^-$ or $^1O_2$ in biological systems during gamma irradiation, although $O_2{\cdot}^-$ or $^1O_2$ are not the main reactive oxygen species produced by water radiolysis.

인삼 Light Harvesting Chlorophyll Protein의 특성 및 엽소병에서 Singlet Oxygen($^1O_2$) Quenching (Characteristics of Light Harvesting Chlorophyll-Protein Complex and Singlet Oxygen ($^1O_2$) Quenching in Leaf-burning Disease from Panax ginseng C. A. Meyer)

  • 양덕조;이성택
    • Journal of Ginseng Research
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    • 제13권2호
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    • pp.158-164
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    • 1989
  • 인삼엽소병(leaf-burning disease) 원인과 light-harvesting chlorophyll-protein(LHCP) complex의 solar energy 분배능력과의 상호 연관성을 조사하기 위한 기초 연구로써 인삼 thylakoid의 chlorophyll-protein(CP) complex의 조성 및 특징을 조사하였다. 인삼의 CP-complex는 non-denaturing SDS-PAGE 방법에 의해 4개 bands로 분리되었으며 각 band는 Bassi와 Dunahay의 결과에 따라 CPI(PSI의 reaction center와 LHCP I antennae), CP I(PSI reaction center), LHCP II(LHCP II)의 oligoform), 그리고 LHCP II(PS II antennae; CP29, CP26)로 확인되었다. 인삼의 LHCP II 는 양지식물인 spinach, soybean과 비교해 볼 때 오히려 인삼의 band intensity가 더 높았으며, CP I band는 인삼에서만 분리되었다. 인삼 CP-complex band의 absorption 및 fluorescence spectra, chlorophyll a.b ratio 에서도 비교식물과 차이를 나타내었다. Thylakoid membrane의 polypeptide 함량은 인삼에서 비교식물에 비해 현저히 낮은 polypeptide 함량은을 나타내었다. SDS-PAGE에 의한 polypeptide pattern은 band의 수나 band intensity에서 비교식물과 차이를 나타내었으며, 특히 29-35 kD, 55 kD과 60 kD 근치에서 현저한 band intensity 차이를 확인하였다. Specific $^1O_2$에 의해 chl. a가 60%, chl.b는 90%, 그리고 carotenoid는 70%가 파괴되는 것으로 확인되었다.

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뫼스바우어 분광법을 이용한 LuFe2O4의 자발분극과 철 이온의 거동과의 상관관계에 대한 연구 (The Research about the Correlation Between the Spontaneous Polarization of LuFe2O4 and Behavior of Iron by Mössbauer)

  • 방봉규;김철성;김성백
    • 한국자기학회지
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    • 제17권1호
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    • pp.10-13
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    • 2007
  • [ $LuFe_2O_4$ ] 단결정 시료를 floating zone법을 이용하여 합성, 결정학적 및 자기구조를 연구하였다. 결정 구조는 $R\={3}mh$의 능면체로 결정되었고, 격자 상수는 각각 $a_0=3.440(2)\;{\AA},\;c_0=25.263(2)\;{\AA}$이었다. 진동 시료 자화율 측정기(VSM) 실험결과와 $M\"{o}ssbauer$ 분석 실험결과 자기적 $N\'{e}el$ 온도($T_N$)는 250 K로 결정되었다. 12 K에서의 $M\ddot{o}ssbauer$ 스펙트럼을 결정구조에서 기인한 4개 세트의 6라인 공명흡수선으로 분석하였으며, 상온에서의 $M\"{o}ssbauer$ 스펙트럼은 3개의 single과 1개의 doublet이 중첩된 형태를 보였다. 상온에서 singlet들의 이성질체 이동치는 $Fe^{3+}$의 이온 상태를 나타내는 $0.20{\pm}0.01mm/s$ 전후의 값을, doublet은 $Fe^{2+}$의 이온 상태를 나타내는 $0.70{\pm}0.01mm/s$의 값을 갖는 것을 알 수 있었다. 상온에서의 $Fe^{3+}$$Fe^{2+}$간의 면적비율은 1:1로 나타났으나, 온도가 상승함에 따라 doublet 형태가 점차 사라지다가 360 K에서는 singlet 형태의 단일 흡수선으로 나타났다. 이는 $LuFe_2O_4$물질에서 나타내는 자발분극현상이 철 이온이 가지고 있는 거동의 변화 때문인 것으로 해석된다.

산소 존재하에서 UVB에 의한 페플록사신의 광화학적 반응의 특성 (Characteristics of Photochemical Reaction of Pefloxacin Irradiated by UVB in an Aerobic Condition)

  • 최윤수;이경선
    • 약학회지
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    • 제44권1호
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    • pp.36-40
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    • 2000
  • The photodegradation of pefloxacin, photolabile fluoroquinolone antibacterial agent, was studied. In the presence of $N_2$, photodegradation of pefloxacin was suppressed. The singlet oxygen and free radical generated in the reaction media proceeded photochemical reaction. The photodegradation of peflxacin was sensitized by benzophenone, a triplet state sensitizer.

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The Link Between Stereoselectivity and Spin Selectivity in Intermolecular and Intramolecular Photochemical Reactions

  • Griesbeck, Axel G.
    • Journal of Photoscience
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    • 제10권1호
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    • pp.49-60
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    • 2003
  • How stereo selectivity in singlet and triplet photocycloaddition and photocyclization reactions, respectively, is linked to spin selectivity and how this link affects our understanding of photochemical reaction mechanisms, is described in this review. As illustrative examples, the Paterno-Buchi reaction and the Norrish-Yang cyclization are described with emphasis on triplet biradical structure and dynamics.

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