Protein

Nucleic acid interactions. I. Electronic structures of cytosine, indole, and guanine complexes

P. Ilich, F. G. Prendergast

Research output: Contribution to journalArticle

8 Citations (Scopus)

Abstract

Low singlet transition energies and line strengths were calculated for the cytosine : indole : guanine complex by the INDO/1S-CI method. The chromophores were arranged in three sets of 270 intercalating geometries. Calculations were executed in the supermolecule model with single excited configurations. Errors due to basis set extension and incomplete configuration representation were assessed, for all chromophore pairs, by full BSSE correction calculations and inclusion of double-excited configurations. The intercalation-induced perturbations of the principal transitions are characterized by but not limited to (a) a decrease in strength of {π*,π} transitions, (b) increase in strength in {π*,n} transitions, (c) splitting of {π*,π} transitions into components of unequal strength, and (d) energy and strength dependence in mixed transitions on rise and shift movements of the nucleic acid bases. These predictions are in accord with absorption, fluorescence emission, and scattering, and resonance Raman spectroscopic data on oligonucleotides and analogous aromatic complexes. The calculations suggest that major differences in intercalating coordinations are discernible in the near-uv spectroscopic domain of proteins and nucleic acids.

Original languageEnglish (US)
Pages (from-to)667-694
Number of pages28
JournalBiopolymers
Volume32
Issue number6
DOIs
StatePublished - Jun 1992

Fingerprint

Cytosine
Nucleic acids
Guanine
Nucleic Acids
Electronic structure
Chromophores
Proteins
Raman Spectrum Analysis
Oligonucleotides
Fluorescence
Intercalation
Scattering
Geometry
indole
Protein Domains

ASJC Scopus subject areas

  • Biochemistry, Genetics and Molecular Biology(all)
  • Biochemistry
  • Biophysics

Cite this

Protein : Nucleic acid interactions. I. Electronic structures of cytosine, indole, and guanine complexes. / Ilich, P.; Prendergast, F. G.

In: Biopolymers, Vol. 32, No. 6, 06.1992, p. 667-694.

Research output: Contribution to journalArticle

@article{74e710599e1441e290429fb985a7bbd4,
title = "Protein: Nucleic acid interactions. I. Electronic structures of cytosine, indole, and guanine complexes",
abstract = "Low singlet transition energies and line strengths were calculated for the cytosine : indole : guanine complex by the INDO/1S-CI method. The chromophores were arranged in three sets of 270 intercalating geometries. Calculations were executed in the supermolecule model with single excited configurations. Errors due to basis set extension and incomplete configuration representation were assessed, for all chromophore pairs, by full BSSE correction calculations and inclusion of double-excited configurations. The intercalation-induced perturbations of the principal transitions are characterized by but not limited to (a) a decrease in strength of {π*,π} transitions, (b) increase in strength in {π*,n} transitions, (c) splitting of {π*,π} transitions into components of unequal strength, and (d) energy and strength dependence in mixed transitions on rise and shift movements of the nucleic acid bases. These predictions are in accord with absorption, fluorescence emission, and scattering, and resonance Raman spectroscopic data on oligonucleotides and analogous aromatic complexes. The calculations suggest that major differences in intercalating coordinations are discernible in the near-uv spectroscopic domain of proteins and nucleic acids.",
author = "P. Ilich and Prendergast, {F. G.}",
year = "1992",
month = "6",
doi = "10.1002/bip.360320609",
language = "English (US)",
volume = "32",
pages = "667--694",
journal = "Biopolymers",
issn = "0006-3525",
publisher = "John Wiley and Sons Inc.",
number = "6",

}

TY - JOUR

T1 - Protein

T2 - Nucleic acid interactions. I. Electronic structures of cytosine, indole, and guanine complexes

AU - Ilich, P.

AU - Prendergast, F. G.

PY - 1992/6

Y1 - 1992/6

N2 - Low singlet transition energies and line strengths were calculated for the cytosine : indole : guanine complex by the INDO/1S-CI method. The chromophores were arranged in three sets of 270 intercalating geometries. Calculations were executed in the supermolecule model with single excited configurations. Errors due to basis set extension and incomplete configuration representation were assessed, for all chromophore pairs, by full BSSE correction calculations and inclusion of double-excited configurations. The intercalation-induced perturbations of the principal transitions are characterized by but not limited to (a) a decrease in strength of {π*,π} transitions, (b) increase in strength in {π*,n} transitions, (c) splitting of {π*,π} transitions into components of unequal strength, and (d) energy and strength dependence in mixed transitions on rise and shift movements of the nucleic acid bases. These predictions are in accord with absorption, fluorescence emission, and scattering, and resonance Raman spectroscopic data on oligonucleotides and analogous aromatic complexes. The calculations suggest that major differences in intercalating coordinations are discernible in the near-uv spectroscopic domain of proteins and nucleic acids.

AB - Low singlet transition energies and line strengths were calculated for the cytosine : indole : guanine complex by the INDO/1S-CI method. The chromophores were arranged in three sets of 270 intercalating geometries. Calculations were executed in the supermolecule model with single excited configurations. Errors due to basis set extension and incomplete configuration representation were assessed, for all chromophore pairs, by full BSSE correction calculations and inclusion of double-excited configurations. The intercalation-induced perturbations of the principal transitions are characterized by but not limited to (a) a decrease in strength of {π*,π} transitions, (b) increase in strength in {π*,n} transitions, (c) splitting of {π*,π} transitions into components of unequal strength, and (d) energy and strength dependence in mixed transitions on rise and shift movements of the nucleic acid bases. These predictions are in accord with absorption, fluorescence emission, and scattering, and resonance Raman spectroscopic data on oligonucleotides and analogous aromatic complexes. The calculations suggest that major differences in intercalating coordinations are discernible in the near-uv spectroscopic domain of proteins and nucleic acids.

UR - http://www.scopus.com/inward/record.url?scp=0026881172&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0026881172&partnerID=8YFLogxK

U2 - 10.1002/bip.360320609

DO - 10.1002/bip.360320609

M3 - Article

VL - 32

SP - 667

EP - 694

JO - Biopolymers

JF - Biopolymers

SN - 0006-3525

IS - 6

ER -