• 대한화학회지
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• 제55권3호
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• pp.335-340
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• 2011

양이온성 수용성 5, 10, 15, 20-tetrakis(N-methylpyridinium-4-yl) porphyrin (TMPyP)의 존재 하에서 음이온 계면 활성제인 sodium n-dodecyl sulfate 의 용액 특성을 전도도법, UV-vis 및 공명 빛 산란 (RLS) 분광학적 방법을 이용하여 포괄적으로 연구하였다. 그 결과에 따르면 TMPyP 농도의 증가로 SDS 용액의 임계 미셀 농도는 감소하였는데, SDS 미셀의 안정화는 미셀 표면에 존재하는 음전하의 중화 때문이다. SDS용액 내에는 자유 포르피린 단량체, 미셀에 속박된 포르피린 단량체 또는 응집체, 그리고 nonmicellar porphyrin/계면 활성제 응집체와 같은 세 종류의 TMPy종이 분명히 존재하였다. 우리의 연구 결과는 SDS가 TMPyP의 응집을 유도한다는 것을 나타내었다. 실제로 두 종류의 J-aggregations이 관찰되었는데, 하나는 미셀에 속박된 포르피린 단량체 또는 응집체였으며, 다른 하나는 nonmicellar porphyrin/계면 활성제 응집체이다. 그러나, cmc이하에서는 TMPyP가 SDS 음이온과 정전기 상호작용을 나타내었다.

• Bulletin of the Korean Chemical Society
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• 제28권12호
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• pp.2203-2208
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• 2007

Three possible binding modes of cationic meso-tetrakis(N-methylpyridinium-4-yl)porphyrin (TMPyP) to d[(GCATATATGC)2] duplex were investigated by the molecular dynamics (MD) simulation. Among the three binding modes namely, “along the groove”, “across the groove” and “face on the groove”, the “across the groove” model exhibited the largest negative binding free energy and the DNA backbone remained as the B form. In this model, the molecular plain of the TMPyP tilts 45o with respect to the DNA helix axis and is largely exposed to the solvent. TMPyP was stabilized mainly by the interaction between the positively charged neighboring pyridinium moieties of TMPyP and negatively charged phosphate groups of DNA. The result obtained in this work by MD and the report (Jin, B. et al., J. Am. Chem. Soc. 2005, 127, 2417.) that the spectral properties of poly[d(A-T)2] bound TMPyP in the presence and absence of the minor groove binding drug 4',6- diamidino-2-phenylindole are similar, we propose that TMPyP bind across the minor groove of the AT rich- DNA.

• Bulletin of the Korean Chemical Society
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• 제32권8호
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• pp.2599-2606
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• 2011

The fluorescence of ethidium bound to DNA, poly[d(A-T)$_2$], and poly[d(G-C)$_2$] at a [ethidium]/[DNA] ratio of 0.005 was quenched by porphyrins when both ethidium and the porphyrins simultaneously bound to the same polynucleotide. The quenching was tested using the "inner sphere" and the "Forster resonance energy transfer" (FRET) models, with the latter found to contribute, at least in part, to the quenching. Meso-tetrakis(N-methylpyridinium-4-yl)porphyrin (TMPyP) exhibited a higher quenching and FRET efficiency than cis-bis(N-methylpyridinium-4-yl)porphyrin (BMPyP) for all of the tested DNA and polynucleotides, demonstrating that energy transfer efficiency is affected by the number of positive charges of porphyrins.

• Bulletin of the Korean Chemical Society
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• 제33권2호
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• pp.529-534
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• 2012

The fluorescence of 4',6-diamidino-2-phenylindole (DAPI) bound to DNA at a [DAPI]/[DNA base] ratio of 0.005 was quenched by meso-tetrakis(N-methylpyridinium-4-yl)porphyrin (TMPyP) or cis-bis(N-methylpyridinium-4-yl)porphyrin (BMPyP) when both DAPI and either porphyrin spontaneously bound to the same DNA strand. The quenching was investigated using the "one-dimensional inner sphere" and the "F$\ddot{o}$rster resonance energy transfer" (FRET) models. Total quenching occurred when DAPI and TMPyP were up to 19.3 base pairs or $66\AA$ apart. BMPyP could quench the fluorescence up to 13.9 base pairs or $47\AA$. TMPyP, which intercalated between the DNA base-pairs, appeared to be a better acceptor than BMPyP, which stacked along the DNA stem. The higher quenching and higher resonance energy transfer efficiency of TMPyP was due to the larger overlap integral between its absorption spectrum and the emission spectrum of DNA-bound DAPI.

• Bulletin of the Korean Chemical Society
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• 제33권4호
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• pp.1165-1169
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• 2012

The fluorescence intensity of DNA-intercalated ethidium with [ethidium]/[DNA base] being 0.005 was quenched upon the binding of another intercalating ligand, meso-tetrakis(N-methylpyridinium-4-yl)porphyrin (TMPyP). Addition of $Ca^{2+}$ enhanced the quenching efficiency. The range of separations between donor and acceptor molecules, within which total quenching occurs, was calculated using a one-dimensional resonance energy transfer mechanism to be 9.5 base-pairs or $32.3{\AA}$ in the absence of $Ca^{2+}$ ions. The distance increased to 18.7 base-pairs or about $63.6{\AA}$ in the presence $100{\mu}M$ $Ca^{2+}$. Considering that (1) $Ca^{2+}$ had little effect on the binding modes of ethidium and TMPyP, which was investigated by reduced linear dichroism and (2) spectral overlap between the emission spectrum of ethidium and the absorption spectrum of TMPyP was maintained in the presence of $Ca^{2+}$, contributions from orientation factor and spectral overlap to $Ca^{2+}$-induced enhancement in DNA mediated energy transfer was limited. Although there is no direct evidence, electron transfer along the DNA stem may accompany the observed fluorescence quenching. In this respect, DNA bound $Ca^{2+}$ act as a partially conducting medium.