A Spectrophotofluorometer for Measuring Very Weak Fluorescences From Biological Molecules

Vigny, Paul; Duquesne, M.

doi:10.1111/j.1751-1097.1974.tb06542.x

Cited by 83 publications

(31 citation statements)

References 20 publications

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“…Direct comparison of theoretical and experimental excimer characteristics is impossible due to their absence for the systems studied. However, experimental study of similar compounds (dinucleoside monophosphates) shows the existence of an excimer fluorescence shift for ApA, GpG, CpC, and ApG both at low and room temperature [44,45]. This is in agreement with the theoretical results.…”

Section: (A)supporting

confidence: 82%

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Electronic absorption and emission spectra of nucleic acids and their components: Some questions of theory and experiment

Danilov

Pechenaya

Zheltovsky

1980

Int J of Quantum Chemistry

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The results of calculations of the transition energies and polarization in nucleotide bases performed by the CNDO/S CI method are compared with experimental data for long-wavelength and vacuumabsorption bands. The calculations and the analysis of experimental data testify to the existence of n -T* transitions in the first absorption bands of the bases. The study of double-stranded polynucleotides and DNA hypochromism based on the theoretical electronic characteristics of the bases and perturbation theory is performed. The role of stacking and complementary interactions within the hypochromic effect is cleared up. Two mechanisms for the shift of the fluorescence band maximum are investigated: two-proton transfer along H bonds and excimer formation. The study of H-bond potential curves shows the disadvantage of two-proton phototautomerism in the nucleotide base pairs in contrast to model systems. The possibility of excimer state formation in stacked homo-and heterodimers of nucleotide bases is shown within the extended-Huckel treatment. The nature of excimer minimum for the excited-state potential curve is analyzed.To understand the absorption and luminescence spectra of DNA and also the nature of the related phenomena (hypochromism, energy migration, excimer states formation, etc.), a quantum-mechanical study of electronic structure of nucleotide bases is necessary. A series of important spectroscopic features points out that the knowledge of velectronic wave functions is not sufficient. In this connection the study of the excited singlet and triplet states of the bases with the help of the C N D O /~ method, which permits us to directly take into account the interaction of all valence electrons, has recently been undertaken [l, 21. To obtain detailed information on the electronic structure of the bases, the calculations of the ground and excited states of adenine (A), thymine (T), uracil (U), guanine (G), and The calculated energies of electronic transitions into singlet excited states A E and their oscillator strengths (f) are given in Tables I and 11. Experimental data for the absorption band maxima of the bases in the water solutions [5-81 and sublimated films of the bases [9,10] are also given. In can be seen that the *

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Section: (A)supporting

confidence: 82%

“…Recently measured fluorescence spectra of polynucleotides at room temperature show a similar shift [45,461. Two mechanisms explaining this effect have been suggested in the literature: (1) excimer formation between two neighboring bases within one polynucleotide strand, and (2) two-proton tautomerism within a Watson-Crick base pair.…”

Section: 59mentioning

confidence: 84%

Electronic absorption and emission spectra of nucleic acids and their components: Some questions of theory and experiment

Danilov

Pechenaya

Zheltovsky

1980

Int J of Quantum Chemistry

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“…In order to test this hypothesis, Mrs. Daudel had the idea to use a highly sensitive spectrophotofluorometer that incorporates a photon-counting device. This apparatus has been built by Vigny and Duquesne at the Fondation Curie, lnstitut du Radium [3].…”

Section: Interaction Of Carcinogens With the Dna Resulting Damagesmentioning

confidence: 99%

Recent progress in chemical carcinogenesis

Daudel¹

2009

Int. J. Quantum Chem.

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“…Due to a high quenching, the quantum yields are low (4 N and effort in the technique is necessary to be able to record the spectra [93]. In addition to the monomer like fluorescence, a longwavelength emission has been detected in some dinucleotides and polynucleotides and attributed to an excimer emission [92,95,94].…”

Section: Spectroscopy Of Nucleic Acidsmentioning

confidence: 99%

Excited States of Nucleic Acids

Favre

Vigny

1975

Photochem & Photobiology

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The literature on the electronic excited states of nucleic acids is reviewed covering the period approximately of mid 1973-mid 1975. Our interest focuses on the nucleic acids themselves as well as on their components and derivatives from two points of view which are closely related: (i) their spectroscopic properties, and (ii) their photochemical properties. The photobiological aspects of nucleic acids will not be considered here, however. Spectroscopy of nucleic acidsVery few papers have been concerned with the investigation of the excited singlet states of nucleic acid bases at high resolution. Sharp absorption and emission spectra are reported for crystalline purine at 4 K and an interpretation of the pattern of the excited singlet states is given using molecular orbital calculations and correlations with pyrimidine and aza substituted derivatives [63]. A study of the polarized singlecrystal reflection spectra of 6-azauracil shows that the 260 nm absorption band can be resolved into two bands [S]. Higher excited singlet states of nucleic acid bases have been investigated in thin films 1911 and the energy diagrams have been evaluated both in the neutral and ionized state [SS]. Theoretical calculations of the energies of the lower-out-of-plane transitions of the nucleic acid bases, their tautomers and ions have been made using the CNDO-CI method [35]. The CND0/2 method has also been used for these molecules [ 1011 and thiouracils [25].Studies of the fluorescence and phosphorescence emission of nucleic acids in water-alcohol glasses at low temperature, where the quantum yields are high, have received less emphasis than previously. In the case of the dinucleotide C3fP5C, the fluorescence polarimtion has been interpreted in terms of a charge resonance in the excimer state [lo]. Further work has been reported on the triplet emission of DNA [45] and yeast tRNAPhe [34]. In that case, the triplet emission of Ado can be observed at 1.2 K, but not at 77 K, partially due to energy transfer to the "Y" base. Energy transfer in Ado frozen aggregates to appropriate traps has been demonstrated [49] as well as triplet-triplet energy transfer from the bases to tryptophan in oligopeptide, poly rA (or DNA) complexes [33]. The large previously observed enhancement in the phosphorescence of DNA when Agf

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A Spectrophotofluorometer for Measuring Very Weak Fluorescences From Biological Molecules

Cited by 83 publications

References 20 publications

Electronic absorption and emission spectra of nucleic acids and their components: Some questions of theory and experiment

Electronic absorption and emission spectra of nucleic acids and their components: Some questions of theory and experiment

Recent progress in chemical carcinogenesis

Excited States of Nucleic Acids

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