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On the radiation chemistry of some pyrimidine-electron adducts: reaction of pyrimidine negative ions with t-butanol radicals.

The rates of decay of the electron adducts of thymine, thymidylic acid and of uracil at pH approximately 8-5 and at wave-lengths of 340 or 350 nm in the presence of t-butanol as scavenger for OH radicals are not influenced significantly by the addition of 0-1 M NaClO4. It follows that the decay reactions do not take place between negatively-charged species. The best explanation seems to be an efficient reaction of the electron adducts with the t-butanol radicals formed by reaction of OH radicals with the t-butanol.

Butanols↗

Efficient pyrimidine N-1-alkylation via activation of electron rich olefins with oxoammonium salts: synthesis of methoxy TEMPO substituted pyrimidine nucleoside analogs.

Our work outlines the use of oxoammonium salts in a formal 1,2 addition process to olefins giving nucleoside analogs as products. Specifically, oxoammonium salts can be added to a solution of olefin and silylated heterocycle to give Methoxy TEMPO substituted nucleoside analogs after hydrolytic workup and chromatographic purification.

Alkenes↗

Bis-intercalation of a homodimeric thiazole orange dye in DNA in symmetrical pyrimidine-pyrimidine-purine-purine oligonucleotides.

One- and two-dimensional 1H NMR spectroscopy were used to characterize the binding of a homodimeric thiazole orange dye, 1,1'-(4,4,8,8-tetramethyl-4,8-diazaundecamethylene)-bis-4-(3 -methyl-2,3-dihydro-(benzo- 1,3-thiazole)-2-methylidene)-quinolinium tetraiodide (TOTO), to various double-stranded DNA oligonucleotides containing symmetric (5'-pyr-pyr-pu-pu-3')2 or (5'-pu-pu-pyr-pyr-3')2 sequences. It was found that TOTO binds preferentially to oligonucleotides containing a (5'-CTAG-3')2 or a (5'-CCGG-3')2 sequence. Binding to the (5'-CCGG-3')2 sequence is less favored than to the (5'-CTAG-3')2 sequence. The complexes of TOTO with d(CGCTAGCGCTAGCG)2 (10) and d(CGCTAGCCGGCG):d(CGCCGGCTAGCG) (11) oligonucleotides, each containing two preferential binding sites, was also examined. In both cases TOTO forms mixtures of 1:1 and 1:2 dsDNA-TOTO complexes in ratios dependent on the relative amount of TOTO and the oligonucleotides in the sample. Binding of TOTO to the two oligonucleotides is sequence selective at the (5'-CTAG-3')2 and (5'-CCGG-3')2 sites. The 1H NMR spectra of both the 1:2 complexes and the three different 1:1 complexes have been assigned. A slight negative cooperativity is observed in formation of the 1:2 complexes. The ratio between the two different 1:1 complexes formed with oligonucleotide 11 is 2.4 in favor of binding to the (5'-CTAG-3')2 site. This is very similar to results obtained when the two sites are in different oligonucleotides. Thus the distribution of TOTO among the (5'-CTAG-3')2 and (5'-CCGG-3')2 sites is independent of whether the two sites are in the same or two different oligonucleotides.

Base Sequence↗