Nucleic acid base spectra

The previous section outlined the typical e loss and e gain products observed in the nucleic acid bases in the solid state. These studies can be applied to the study of the radiation chemistry of DNA. The relevance of the study of model systems is shown by considering the following remarkable observations. Years ago, Ehrenberg et al. showed the EPR spectra of the 5,6-dihydrothymine-5-yl radical observed in thymine, thymidine, and DNA. The spectra are nearly identical [46]. The reduction product observed in cytosine monohydrate is the N3 protonated anion. In solution, this reduction product gives rise to a 1.4-mT EPR doublet. The same feature is present in irradiated DNA at 77 K. Likewise, the result of e loss in guanine bases is characterized by a broad EPR singlet. The same feature is also evident in the EPR spectrum of DNA irradiated and observed at 77 K. 

Another method is to produce EPR basis spectra by irradiating various nucleic acid bases. The EPR spectrum of DNA is simulated by taking various combinations of the... 

These compounds contain alkyl groups that form strong, covalent bonds with the nucleic acid bases of DNA, especially guanine. This interferes with DNA transcription and replication, inhibiting mitosis (Figure 16.1). They have a broad spectrum of antitumour activity and are used in the treatment of lymphoma, breast and ovarian carcinoma, melanoma and multiple myeloma. 

Spectral data (Amax and AE, and e x 10 3) for the pyrimidine bases investigated in a few representative papers are collected in Table XXVIII. The absorption bands are denoted by the capital letters A, B, C, etc. In Table XXVIII we have listed the results of the vacuum ultraviolet measurements by Yamada and Fukutome428 (cf. also ref. 429), who measured the spectra of sublimed films of cytosine, thymine, uracil (and also of guanine and adenine) down to 120 nm at room temperature. Several remarkable absorption peaks were found below 190 nm in addition to the already known ones near 260 and 200 nm. A weak absorption at 230-240 nm in cytosine was not indicated in the sublimed films of the molecule,428 but was visible in the stretched polyvinyl alcohol film spectrum.432 Crewe et al.i3° studied the interactions of fast electrons with the five nucleic acid bases and measured the energy-loss spectra of 20 keV electrons transmitted through thin films of these bases. These last data are also listed in Table XXVIII for comparison with the other spectral findings. 

The substitution of a bromine atom on a nucleic acid base (e.g. 8Br-adenosine) provides the base with significant absorption in the 300 nm region. The RR spectrum of the brominated species can then be specifically excited by 300 nm irradiation [59]. The brominated bases are in effect RR labels but there are rare naturally occurring bases with significant absorption in the near UV, these are sulfur substituted analogs absorbing from 300-360 nm. For example Nishimura, Tsuboi and coworkers [60] obtained RR spectra of the single 4-thiouridine which occurs in a number of tRNAs. 

The discovery of the base-paired, double-helical structure of deoxyribonucleic acid (DNA) provides the theoretic framework for determining how the information coded into DNA sequences is replicated and how these sequences direct the synthesis of ribonucleic acid (RNA) and proteins. Already clinical medicine has taken advantage of many of these discoveries, and the future promises much more. For example, the biochemistry of the nucleic acids is central to an understanding of virus-induced diseases, the immune re-sponse, the mechanism of action of drugs and antibiotics, and the spectrum of inherited diseases. 

Infrared and Raman spectroscopy are in current use fo r elucidating the molecular structures of nucleic acids. The application of infrared spectroscopy to studies of the structure of nucleic acids has been reviewed,135 as well as of Raman spectroscopy.136 It was noted that the assignments are generally based on isotopic substitution, or on comparison of the spectrum of simple molecules that are considered to form a part of the polynucleotide chain to that of the nucleic acid. The vibrational spectra are generally believed to be a good complementary technique in the study of chemical reactions, as in the study76 of carbohydrate complexation with boric acid. In this study, the i.r. data demonstrated that only ribose forms a solid complex with undissociated H3B03, and that the complexes are polymeric. 

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