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M. Chen, Z.-H. Jiang and W.-H. Chen, Bioorg. Med. Chem.
Lett., 2012, 22, 7056–7059.
12 C.-Q. Zhou, Y.-L. Lin, J.-X. Chen, L.-S. Wang, N.-N. Yang,
W. Zeng and W.-H. Chen, Bioorg. Med. Chem. Lett., 2012,
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Biodiversity, 2012, 9, 1125–1132.
4H), 3.65 (s, 8H), 3.20 (m, 4H); ESI MS m/z: 401.9 ([M ꢁ
2Clꢁ]2+) and HRMS for C46H46N2O11 ([M ꢁ 2Cl]2+) calc.:
401.1545, found: 401.1538. Compound 2 (173 mg, 79%)
was synthesized in a similar way from the reaction of
berberrubine 3 (134 mg, 0.4 mmol) with tetraethylene
glycol monomethyl ether tosylate 5 (148 mg, 0.4 mmol), as
a yellow powder having 1H-NMR (400 MHz, DMSO-d6) d
9.78 (s, 1H), 8.96 (s, 1H), 8.20 (d, J ¼ 9.2 Hz, 1H), 8.02 (d,
J ¼ 9.2 Hz, 1H), 7.81 (s, 1H), 7.10 (s, 1H), 6.18 (s, 2H), 4.94
(t, J ¼ 6.2 Hz, 2H), 4.43–4.41 (m, 2H), 4.07 (s, 3H), 3.82–
3.80 (m, 2H), 3.61–3.58 (m, 2H), 3.54–3.51 (m, 2H), 3.47–
3.42 (m, 6H), 3.36–3.35 (m, 2H), 3.22 (t, J ¼ 6.2 Hz, 2H),
3.16 (s, 3H); ESI MS m/z: 512.9 ([M ꢁ Clꢁ]+) and HRMS for
14 M. Chen, M.-Z. Chen, C.-Q. Zhou, W.-E. Lin, J.-X. Chen,
W.-H. Chen and Z.-H. Jiang, Inorg. Chim. Acta, 2013, 405,
461–469.
15 J.-X. Chen, W.-E. Lin, C.-Q. Zhou, L. F. Yau, J.-R. Wang,
C
28H34NO8 ([M ꢁ Clꢁ]+) calc.: 512.2284, found: 512.2279.
2ꢁ
B. Wang, W.-H. Chen and Z.-H. Jiang, Inorg. Chim. Acta, 21 As stated in the text, Cu2Cl6 dianion was not detected in
2011, 376, 389–395.
16 S. Mazzini, M. C. Bellucci and R. Mondelli, Bioorg. Med.
Chem., 2003, 11, 505–514.
17 J. H. Griffin and P. B. Dervan, J. Am. Chem. Soc., 1987, 109,
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18 E. Arunkumar, A. Ajayaghosh and J. Daub, J. Am. Chem. Soc.,
2005, 127, 3156–3164.
19 C. A. Traina, R. C. Bakus II and G. C. Bazan, J. Am. Chem. Soc.,
2011, 133, 12600–12607.
20 Synthetic procedures for compounds 1 and 2: to a solution of 23 First-order rate constant for the cleavage of a phosphodiester
the negative ESI mass spectrum. Therefore, CuCl2 rather
than the salts of Cu2Cl6 was used as a control.
2ꢁ
22 Under the condition of 5 mM Tris–HCl buffer (5 mM NaCl, pH
7.0), the binding constants with calf-thymus DNA that were
obtained by means of spectrouorimetric titrations were
(8.99 ꢃ 0.04) ꢀ 103 Mꢁ1 for berberine, (1.15 ꢃ 0.18) ꢀ 105
Mꢁ1 for compound I, (1.51 ꢃ 0.15) ꢀ 104 Mꢁ1 for
compound 1, (2.38 ꢃ 0.11) ꢀ 104 Mꢁ1 for 1@Cu2+ and
(1.46 ꢃ 0.01) ꢀ 103 Mꢁ1 for compound 2, respectively.
berberrubine 3 (320 mg, 1.0 mmol) in MeCN (20 mL) was
added 1,11-ditosyl-3,6,9-trioxaundecane 4 (243 mg, 0.48
mmol). The resulting mixture was reuxed for 6 days, and
then concentrated under reduced pressure. The obtained
bond in double-stranded DNA was reported to be 3.6 ꢀ 10ꢁ8
hꢁ1 under physiological conditions. See: J. Eigner,
H. Boedtker and G. Michaels, Biochim. Biophys. Acta, 1961,
51, 165–171.
residue was subjected to anion exchange into chloride 24 A. Sreedhara and J. A. Cowan, J. Biol. Inorg. Chem., 2001, 6,
form, and subsequently puried by chromatography on a 337–347.
reverse-phase column, eluting with a gradient of methanol 25 X. Sheng, X. M. Liu, Y. T. Chen, G. Y. Lu, J. J. Zhang, Y. Shao,
in water (0–10%), to give compound 1 (360 mg, 86%) as a F. Liu and Q. Xu, Chem.–Eur. J., 2007, 13, 9703–9712.
yellow powder having H-NMR (400 MHz, DMSO-d6) d 9.66 26 M. S. A. Begum, S. Saha, M. Nethaji and A. R. Chakravarty,
(s, 2H), 8.85 (s, 2H), 8.05 (d, J ¼ 9.6 Hz, 2H), 7.88 (d, J ¼ J. Inorg. Biochem., 2010, 104, 477–484.
9.2 Hz, 2H), 7.69 (s, 2H), 7.05 (s, 2H), 6.15 (s, 4H), 4.95– 27 F. Mancin, P. Scrimin, P. Tecilla and U. Tonellato, Chem.
4.92 (m, 4H), 4.28–4.26 (m, 4H), 3.89 (s, 6H), 3.78–3.76 (m, Commun., 2005, 2540–2548.
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1404 | Med. Chem. Commun., 2013, 4, 1400–1404
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