التفاصيل البيبلوغرافية
| العنوان: |
Efficient Artificial Nucleases for Mediating DNA Cleavage Based on Tuning the Steric Effect in the Pyridyl Derivatives of Tripod Tetraamine‐Cobalt(II) Complexes. |
| المؤلفون: |
Kettenmann, Sebastian Doniz, Louka, Febee R., Marine, Elise, Fischer, Roland C., Mautner, Franz A., Kulak, Nora, Massoud, Salah S. |
| المصدر: |
European Journal of Inorganic Chemistry; 6/7/2018, Vol. 2018 Issue 20/21, p2322-2338, 17p |
| مصطلحات موضوعية: |
ARTIFICIAL nucleases, DNA damage, PYRIDYL compounds, STERIC isotope effects, COMPLEX compounds synthesis, COBALT compounds, THERAPEUTICS |
| مستخلص: |
Four cobalt(II) complexes [Co(L1)Cl]PF6/ClO4 (C1‐PF6/C1‐ClO4), [Co(L2)Cl]PF6 (C2‐PF6), [Co(L3)Cl]PF6/ClO4·H2O·CH3OH (C3‐PF6/C3‐ClO4·H2O·CH3OH) and [Co(L4)Cl]PF6·2H2O (C4‐PF6·2H2O), in which L1–L4 refer to [(3,5‐dimethyl‐4‐methoxy‐2‐pyridylmethyl)bis(2‐pyridylmethyl)]amine, [(3,4‐dimethoxy‐2‐pyridylmethyl)‐(2‐pyridylmethyl)]amine, [bis(3,5‐dimethyl‐4‐methoxy‐2‐pyridylmethyl)‐(2‐pyridylmethyl)]amine and {[bis(3,4‐dimethoxy‐2‐pyridyl)methyl]‐(2‐pyridylmethyl)}amine, respectively, were synthesized and structurally characterized. Single‐crystal X‐ray crystallography confirmed the trigonal bipyramidal geometries of the complexes. In aqueous acetonitrile solution, the green complexes dissolve with the formation of a yellow solution with biphasic kinetic behavior. In 60 % H2O/CH3CN (by volume) and 25 °C, the first step corresponds to the rapid formation of [Co(L)(CH3CN)]2+ (ka = 0.16–2.0 min–1) followed by a slow conversion into [Co(L)(H2O)]2+ (kb = 6.3 × 10–3–0.10 min–1), where the two species exist in equilibrium. The spectrophotometric and conductometric titrations of the complexes were consistent with the proposed equilibrium. The coordinated H2O in the aqua complexes, [Co(L)(H2O)]2+ have pKa values ranging from 8.3 to 8.5 at 25 °C. All complexes cleaved plasmid DNA at micromolar concentrations within 2 h at 37 °C and pH 7.0 under hydrolytic conditions. Compared to the uncatalyzed cleavage of DNA, rate enhancements of up to 100 million were achieved in case of complex C4‐PF6. [ABSTRACT FROM AUTHOR] |
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| قاعدة البيانات: |
Complementary Index |
