NITROGEN CHEMICAL-STRUCTURE IN DNA AND RELATED MOLECULES BY X-RAY ABSORPTION-SPECTROSCOPY

被引:53
作者
KIRTLEY, SM
MULLINS, OC
CHEN, J
VANELP, J
GEORGE, SJ
CHEN, CT
OHALLORAN, T
CRAMER, SP
机构
[1] LAWRENCE BERKELEY LAB,BERKELEY,CA 94720
[2] UNIV CALIF DAVIS,DAVIS,CA 95616
[3] AT&T BELL LABS,MURRAY HILL,NJ 07974
[4] NORTHWESTERN UNIV,CHICAGO,IL 60611
关键词
X-RAY ABSORPTION SPECTROSCOPY; DNA STRUCTURE; HYDROGEN BONDING;
D O I
10.1016/0167-4781(92)90157-U
中图分类号
Q5 [生物化学]; Q7 [分子生物学];
学科分类号
071010 ; 081704 ;
摘要
The electronic environment of nitrogen in nucleic acid bases, nucleotides, polynucleotides and DNA has been studied, for the first time using X-Ray Absorption Near-Edge Spectroscopy (XANES). Generally, the spectra of these complex molecules consist of low energy bands corresponding to 1s --> pi* transitions and high energy bands corresponding to 1 s --> sigma* transition, as illustrated using several nitrogen model compounds. The 1s --> pi* transitions show particular sensitivity to the chemical environment of the nitrogen. Oxygen substitution on ring carbon atoms generally results in a significant blue shift of the lowest 1s --> pi* bands while halogen substitution results in a small blue shift. These observations illustrate the significance of the disturbance of the aromatic ring system produced by exocyclic carbonyl groups. Direct substitution on the nitrogen frequently results in significant spectral perturbations. Differences between the spectra of the polynucleotides and the sums of spectra of the individual nucleotides point to the effects of hydrogen-bonding in complementary double-helix structures. The XANES spectrum of a DNA sample with a known ratio of the polynucleotides is equivalent to the weighted sum of the spectra of individual polynucleotides, indicating that the difference in base stacking interactions produces negligible spectral effects. The variability of nitrogen K-edge spectra in these samples and in protein may be useful for chemically specific imaging using X-ray microscopes.
引用
收藏
页码:249 / 254
页数:6
相关论文
共 14 条
  • [1] PERFORMANCE OF THE DRAGON SOFT-X-RAY BEAMLINE
    CHEN, CT
    SETTE, F
    [J]. REVIEW OF SCIENTIFIC INSTRUMENTS, 1989, 60 (07) : 1616 - 1621
  • [2] CONCEPT AND DESIGN PROCEDURE FOR CYLINDRICAL ELEMENT MONOCHROMATORS FOR SYNCHROTRON RADIATION
    CHEN, CT
    [J]. NUCLEAR INSTRUMENTS & METHODS IN PHYSICS RESEARCH SECTION A-ACCELERATORS SPECTROMETERS DETECTORS AND ASSOCIATED EQUIPMENT, 1987, 256 (03) : 595 - 604
  • [3] K-SHELL PHOTOABSORPTION OF THE N2 MOLECULE
    CHEN, CT
    MA, Y
    SETTE, F
    [J]. PHYSICAL REVIEW A, 1989, 40 (11): : 6737 - 6740
  • [4] MOLECULAR EFFECTS ON INNER-SHELL PHOTOABSORPTION - K-SHELL SPECTRUM OF N-2
    DEHMER, JL
    DILL, D
    [J]. JOURNAL OF CHEMICAL PHYSICS, 1976, 65 (12) : 5327 - 5334
  • [5] QUANTITATIVE-ANALYSIS OF ALL MAJOR FORMS OF SULFUR IN COAL BY X-RAY ABSORPTION FINE-STRUCTURE SPECTROSCOPY
    HUFFMAN, GP
    MITRA, S
    HUGGINS, FE
    SHAH, N
    VAIDYA, S
    LU, FL
    [J]. ENERGY & FUELS, 1991, 5 (04) : 574 - 581
  • [6] CHEMISORPTION GEOMETRY OF PYRIDINE ON PT(111) BY NEXAFS
    JOHNSON, AL
    MUETTERTIES, EL
    STOHR, J
    SETTE, F
    [J]. JOURNAL OF PHYSICAL CHEMISTRY, 1985, 89 (19) : 4071 - 4075
  • [7] KELEMEN SR, 1990, FUEL, V69
  • [8] NITROGEN K-SHELL PHOTOEMISSION AND AUGER EMISSION FROM N2 AND NO
    LINDLE, DW
    TRUESDALE, CM
    KOBRIN, PH
    FERRETT, TA
    HEIMANN, PA
    BECKER, U
    KERKHOFF, HG
    SHIRLEY, DA
    [J]. JOURNAL OF CHEMICAL PHYSICS, 1984, 81 (12) : 5375 - 5378
  • [9] HIGH-RESOLUTION K-SHELL PHOTOABSORPTION MEASUREMENTS OF SIMPLE MOLECULES
    MA, Y
    CHEN, CT
    MEIGS, G
    RANDALL, K
    SETTE, F
    [J]. PHYSICAL REVIEW A, 1991, 44 (03): : 1848 - 1858
  • [10] SAENGER W, 1984, PRINCIPLES NUCLEIC A