Time-Resolved Resonance Raman Study of the Exciplex Formed Between Excited Cu-Porphyrin and DNA

Sergei G. Kruglik, Peter Mojzes, Yasuhisa Mizutani, Teizo Kitagawa, Pierre-Yves Turpin

    Research output: Contribution to journalArticleAcademicpeer-review

    27 Citations (Scopus)

    Abstract

    The photoinduced reversible process of exciplex formation and decay between the water-soluble cationic metalloporphyrin 5,10,15,20-tetrakis[4-(N-methylpyridyl)]porphyrin (Cu(T4MPyP)) and calf-thymus DNA has been studied by a picosecond time-resolved resonance Raman (ps-TR3) technique. For a detailed analysis of the exciplex properties, the following model compounds have also been investigated: double-stranded polynucleotides poly(dA-dT)2, poly(dG-dC)2, and poly(dA-dC)·poly(dG-dT), single-stranded poly(dT), and the 32-mer d[(GC)7ATAT(GC)7]2. Additional Raman measurements have also been done in using cw and 20-ns laser sources. It is shown that this reversible exciplex is formed, with a yield depending on the nucleic base sequence, in less than 2 ps after photoexcitation, between photoexcited Cu(T4MPyP) and CO groups of thymine residues in all thymine-containing sequences of nucleic acids. Such a rapid exciplex building process implies that it involves porphyrin molecules initially located, in the steady state of this interaction, at AT sites of the nucleic acids. This has two main consequences, which contradict previously reported assumptions (Strahan et al., J. Phys. Chem. 1992, 96, 6450): (i) although the binding mode of the porphyrin actually depends on the base sequence, there is no preferential binding of Cu(T4MPyP) to the various sites of DNA, and (ii) there is no photoinduced ultrafast porphyrin translocation from GC to AT sites of DNA. In addition, it is shown that with surrounding water molecules an exciplex can also be formed in ∼1 ps, whose spectral characteristics are not distinguishable from those formed with thymine residues. However, these two exciplex species can be distinguished from each other by their relaxation kinetics: the lifetime of the exciplex formed with water lies in the 3−12 ps range, while that of the exciplex formed with nucleic acids lies in the nanosecond time domain (1−3 ns). A set of possible routes is discussed for each of the exciplex building/decay processes.
    Original languageEnglish
    Pages (from-to)5018-5031
    Number of pages14
    JournalJournal of physical chemistry B
    Volume105
    Issue number21
    DOIs
    Publication statusPublished - 2001

    Fingerprint

    Porphyrins
    porphyrins
    Thymine
    thymine
    Nucleic acids
    nucleic acids
    DNA
    deoxyribonucleic acid
    Nucleic Acids
    Water
    Metalloporphyrins
    Poly T
    water
    polynucleotides
    Thymus
    Polynucleotides
    calves
    Molecules
    Photoexcitation
    decay

    Keywords

    • METIS-201359

    Cite this

    Kruglik, Sergei G. ; Mojzes, Peter ; Mizutani, Yasuhisa ; Kitagawa, Teizo ; Turpin, Pierre-Yves. / Time-Resolved Resonance Raman Study of the Exciplex Formed Between Excited Cu-Porphyrin and DNA. In: Journal of physical chemistry B. 2001 ; Vol. 105, No. 21. pp. 5018-5031.
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    title = "Time-Resolved Resonance Raman Study of the Exciplex Formed Between Excited Cu-Porphyrin and DNA",
    abstract = "The photoinduced reversible process of exciplex formation and decay between the water-soluble cationic metalloporphyrin 5,10,15,20-tetrakis[4-(N-methylpyridyl)]porphyrin (Cu(T4MPyP)) and calf-thymus DNA has been studied by a picosecond time-resolved resonance Raman (ps-TR3) technique. For a detailed analysis of the exciplex properties, the following model compounds have also been investigated: double-stranded polynucleotides poly(dA-dT)2, poly(dG-dC)2, and poly(dA-dC)·poly(dG-dT), single-stranded poly(dT), and the 32-mer d[(GC)7ATAT(GC)7]2. Additional Raman measurements have also been done in using cw and 20-ns laser sources. It is shown that this reversible exciplex is formed, with a yield depending on the nucleic base sequence, in less than 2 ps after photoexcitation, between photoexcited Cu(T4MPyP) and CO groups of thymine residues in all thymine-containing sequences of nucleic acids. Such a rapid exciplex building process implies that it involves porphyrin molecules initially located, in the steady state of this interaction, at AT sites of the nucleic acids. This has two main consequences, which contradict previously reported assumptions (Strahan et al., J. Phys. Chem. 1992, 96, 6450): (i) although the binding mode of the porphyrin actually depends on the base sequence, there is no preferential binding of Cu(T4MPyP) to the various sites of DNA, and (ii) there is no photoinduced ultrafast porphyrin translocation from GC to AT sites of DNA. In addition, it is shown that with surrounding water molecules an exciplex can also be formed in ∼1 ps, whose spectral characteristics are not distinguishable from those formed with thymine residues. However, these two exciplex species can be distinguished from each other by their relaxation kinetics: the lifetime of the exciplex formed with water lies in the 3−12 ps range, while that of the exciplex formed with nucleic acids lies in the nanosecond time domain (1−3 ns). A set of possible routes is discussed for each of the exciplex building/decay processes.",
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    author = "Kruglik, {Sergei G.} and Peter Mojzes and Yasuhisa Mizutani and Teizo Kitagawa and Pierre-Yves Turpin",
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    Kruglik, SG, Mojzes, P, Mizutani, Y, Kitagawa, T & Turpin, P-Y 2001, 'Time-Resolved Resonance Raman Study of the Exciplex Formed Between Excited Cu-Porphyrin and DNA' Journal of physical chemistry B, vol. 105, no. 21, pp. 5018-5031. https://doi.org/10.1021/jp004207q

    Time-Resolved Resonance Raman Study of the Exciplex Formed Between Excited Cu-Porphyrin and DNA. / Kruglik, Sergei G.; Mojzes, Peter; Mizutani, Yasuhisa; Kitagawa, Teizo; Turpin, Pierre-Yves.

    In: Journal of physical chemistry B, Vol. 105, No. 21, 2001, p. 5018-5031.

    Research output: Contribution to journalArticleAcademicpeer-review

    TY - JOUR

    T1 - Time-Resolved Resonance Raman Study of the Exciplex Formed Between Excited Cu-Porphyrin and DNA

    AU - Kruglik, Sergei G.

    AU - Mojzes, Peter

    AU - Mizutani, Yasuhisa

    AU - Kitagawa, Teizo

    AU - Turpin, Pierre-Yves

    PY - 2001

    Y1 - 2001

    N2 - The photoinduced reversible process of exciplex formation and decay between the water-soluble cationic metalloporphyrin 5,10,15,20-tetrakis[4-(N-methylpyridyl)]porphyrin (Cu(T4MPyP)) and calf-thymus DNA has been studied by a picosecond time-resolved resonance Raman (ps-TR3) technique. For a detailed analysis of the exciplex properties, the following model compounds have also been investigated: double-stranded polynucleotides poly(dA-dT)2, poly(dG-dC)2, and poly(dA-dC)·poly(dG-dT), single-stranded poly(dT), and the 32-mer d[(GC)7ATAT(GC)7]2. Additional Raman measurements have also been done in using cw and 20-ns laser sources. It is shown that this reversible exciplex is formed, with a yield depending on the nucleic base sequence, in less than 2 ps after photoexcitation, between photoexcited Cu(T4MPyP) and CO groups of thymine residues in all thymine-containing sequences of nucleic acids. Such a rapid exciplex building process implies that it involves porphyrin molecules initially located, in the steady state of this interaction, at AT sites of the nucleic acids. This has two main consequences, which contradict previously reported assumptions (Strahan et al., J. Phys. Chem. 1992, 96, 6450): (i) although the binding mode of the porphyrin actually depends on the base sequence, there is no preferential binding of Cu(T4MPyP) to the various sites of DNA, and (ii) there is no photoinduced ultrafast porphyrin translocation from GC to AT sites of DNA. In addition, it is shown that with surrounding water molecules an exciplex can also be formed in ∼1 ps, whose spectral characteristics are not distinguishable from those formed with thymine residues. However, these two exciplex species can be distinguished from each other by their relaxation kinetics: the lifetime of the exciplex formed with water lies in the 3−12 ps range, while that of the exciplex formed with nucleic acids lies in the nanosecond time domain (1−3 ns). A set of possible routes is discussed for each of the exciplex building/decay processes.

    AB - The photoinduced reversible process of exciplex formation and decay between the water-soluble cationic metalloporphyrin 5,10,15,20-tetrakis[4-(N-methylpyridyl)]porphyrin (Cu(T4MPyP)) and calf-thymus DNA has been studied by a picosecond time-resolved resonance Raman (ps-TR3) technique. For a detailed analysis of the exciplex properties, the following model compounds have also been investigated: double-stranded polynucleotides poly(dA-dT)2, poly(dG-dC)2, and poly(dA-dC)·poly(dG-dT), single-stranded poly(dT), and the 32-mer d[(GC)7ATAT(GC)7]2. Additional Raman measurements have also been done in using cw and 20-ns laser sources. It is shown that this reversible exciplex is formed, with a yield depending on the nucleic base sequence, in less than 2 ps after photoexcitation, between photoexcited Cu(T4MPyP) and CO groups of thymine residues in all thymine-containing sequences of nucleic acids. Such a rapid exciplex building process implies that it involves porphyrin molecules initially located, in the steady state of this interaction, at AT sites of the nucleic acids. This has two main consequences, which contradict previously reported assumptions (Strahan et al., J. Phys. Chem. 1992, 96, 6450): (i) although the binding mode of the porphyrin actually depends on the base sequence, there is no preferential binding of Cu(T4MPyP) to the various sites of DNA, and (ii) there is no photoinduced ultrafast porphyrin translocation from GC to AT sites of DNA. In addition, it is shown that with surrounding water molecules an exciplex can also be formed in ∼1 ps, whose spectral characteristics are not distinguishable from those formed with thymine residues. However, these two exciplex species can be distinguished from each other by their relaxation kinetics: the lifetime of the exciplex formed with water lies in the 3−12 ps range, while that of the exciplex formed with nucleic acids lies in the nanosecond time domain (1−3 ns). A set of possible routes is discussed for each of the exciplex building/decay processes.

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    EP - 5031

    JO - Journal of physical chemistry B

    JF - Journal of physical chemistry B

    SN - 1520-6106

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