Radicals formed by electron transfer from cytosine and 1-methylcytosine to the triplet state of anthraquinone-2,6-disulfonic acid. A Fourier-transform EPR study
文献信息
K. Hildenbrand, S. Naumov
Radicals generated by electron transfer from cytosine and 1-methylcytosine to the laser-induced triplet state of anthraquinone-2,6-disulfonic acid were studied by time-resolved Fourier-transform (FT) EPR in H2O and D2O at 10°C. The main products observed on the nanosecond timescale were successors of the base radical cations. Their hyperfine couplings were determined by computer simulation of the experimental spectra. Assignment of the radical structures was supported by density functional theory (DFT) quantum mechanical calculations. The experiments with cytosine deprotonation at N1 resulted in the cytosin-1-yl radical 1 with high spin density at N1 and C5 whereas, for 1-methylcytosine, deprotonation at the exocyclic amino group yielded the aminyl radical 2. For both parent compounds, cytosine and 1-methylcytosine, two additional long-lived radicals (3 and 4) with unknown structure were detected on the nanosecond to microsecond timescale. Their spectral parameters were independent of the N1 substituent.
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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.













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