DNA Binding and Catalytic Properties of Positively Charged Corroles
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For the original syntheses of triarylcorroles see:
Nardis S., 2005, Mini‐Rev. Org. Chem., 2
For modifications of triarylcorroles see:
I. Aviv Z. Gross Chem. Commun.2007 DOI:.
Aviezer D., 2000, Cancer Res., 60, 2793
Synthesis of5: The required dipyrromethane (1.03 g) was prepared as in Ref. 15 (yield=49 %) but purified by two chromatographic treatments (alumina dichloromethane/ethyl acetate 5:1 followed by silica gel dichloromethane/ethyl acetate 10:0→10:1).
Synthesis of4: Pentafluorobenzaldehyde (50 μL 0 4 mmol) was added to a 10‐mL solution of5(178 mg 0.8 mmol) in propionic acid and the mixture was heated to reflux for 50 min. The residue obtained after solvent evaporation was washed with hot water neutralized with ammonium hydroxide (25 %) and washed again with hot water. The solid material was dissolved in methanol basic alumina was added and the solvent was evaporated. Separation between4and the analogous porphyrin2was achieved by column chromatography (silica CH2Cl2followed by 0.5 % methanol) followed by separation by preparative thin‐layer chromatography (silica plate CHCl3/MeOH 50:1) affording pure4(18 mg 8 %).4:Rf=0.15 (CH2Cl2/ethyl acetate 1:1). UV/Vis (CH2Cl2/MeOH (2:1)):λmax(ε10−3)=416 (104.99) 576 (16.14) 610 (9.40) 640 (5.34). MS (MALDI‐TOF):m/z(%): 619 (100) [M+].1H NMR (200 MHz C6D6):δ=8.93 (br s 4 H) 8.67 (d J=4 Hz 4 H) 8.26 (m 4 H) 7.90 ppm (br. s 4 H).19F (188 MHz):δ=−138.79 (d J=23.5 Hz 2 F) −153.22 (t J=21.9 Hz 1 F) −162.37 ppm (t J=22.5 Hz 1 F).2:Rf=0.37 (CH2Cl2/ethyl acetate 1:1). UV/Vis (CH2Cl2):λmax(ε10−3)=414 (233.34) 510 (15.51) 542 (3.17) 586 (4.69). MS (MALDI‐TOF LD+):m/z(%): 796 (100) [M+].1H NMR (200 MHz CDCl3):δ=9.05 (d J=5.2 Hz 4 H) 8.87 (m 8 H) 8.15 (d J=5.4 Hz 4 H) −2.94 ppm (s 2 H).19F (188 MHz):δ=−137.22 (dd 3J=23.3 Hz 4J=7.9 Hz 4 F) 151.96 (t J=20.9 Hz 2 F) −161.88 ppm (td 3J=22.6 Hz 4J=8.3 Hz 4 F).
3: 4‐Pyridinecarboxaldehyde (38 μL 0.40 mmol) was added to a 10‐mL solution of5(178 mg 0.8 mmol) in propionic acid and the mixture was heated at reflux for 70 min. The residue obtained after solvent evaporation was washed with hot water neutralized with ammonium hydroxide (25 % ammonia) and washed again with hot water. The solid material was dissolved in methanol basic alumina was added and the solvent was evaporated. Separation of3was achieved by column chromatography (silica CH2Cl2followed by 0.5 % methanol) followed by separation on PTLC (silica plate CHCl3/MeOH 100:1). The faster eluting fraction was comprised of the brownish red porphyrin (1) and the next slightly fluorescent dark‐green‐colored fraction afforded the desired corrole3(6 % 12 mg). Alternatively good chromatographic separation could be achieved by eluting with ethyl acetate to which methanol was gradually added.Rf=0.73 (CH2Cl2/MeOH 5:1). UV/Vis (CH2Cl2):λmax(ε10−3)=418 (61.15) 576 (9.85) 614 (5.62); MS (MALDI‐TOF LD+):m/z(%): 530 (100) [M+H].1H NMR (300 MHz) (C6D6):δ=7.87 (d J=5.1 Hz 2 H) 7.99 (d J=5.1 Hz 4 H) 8.35 (d J=4.8 Hz 2 H) 8.43 (d J=4.2 Hz 2 H) 8.66 (d J=4.8 Hz 2 H) 8.78 (d J=4.2 Hz 2 H) 9.02 ppm (br s 6 H).
Manganese insertion:2‐Mn and4‐Mn were prepared by heating the porphyrin/corrole pyridine solution at reflux with 15 equivalents of Mn(OAc)2⋅4 H2O followed by chromatographic separation (silica starting with CH2Cl2and gradually adding methanol) affording 92 % and 81 % yield respectively.2‐Mn: UV/Vis (MeOH):λmax(ε10−3)=328 (12.6) 370 (22.5) 392 (19.5) 458 (49.7) 554 (5.2) 766 (0.84). MS (MALDI‐TOF LD+):m/z(%): 849 (100) [M+].19F (MeOD) (188 MHz):δ=−134.49 (br s 4 F) −148.20 (s 2 F) −157.08 ppm (s 4 F).4‐Mn: UV/Vis (MeOH):λmax(ε10−3)=368 (16.7) 402 (26.7) 420 (4.8) 458 (18.4) 484 (16.2) 634 (9.4). MS (MALDI‐TOF LD+):m/z(%): 670 (100) [M+].19F (C5D4N) (188 MHz):δ=−136.58 (br s 2 F) −155.16 (s 1 F) −161.23 ppm (s 2 F)
N‐methylation:2‐Mn and4‐Mn were dissolved in hot THF and excess methyl iodide was added to the solutions which were then left at 40 °C until complete precipitation. The solid material was collected by centrifugation and washed with THF and diethyl ether until the solvent was colorless. [(2′)Mn(X)]2+: UV/Vis (phosphate buffer solution; pH 6.8):λmax(ε10−3)=372 (22.4) 394 (19.7) 460 (56.4) 558 (5.7). MS (MALDI‐TOF LD+)m/z(%): 879 (10) [M+] 864 (100) [M−15] 849 (50) [M−30].19F (MeOD) (188 MHz):δ=−137.87 (br s 4 F) −151.28 (s 2 F) −160.04 ppm (s 4 F). [(4′)Mn]2+: UV/Vis (KH2PO40.3 M pH 6.8):λmax(ε10−3)=488 (49.4) 556 (8.4) 598 (10.3) 660 (15.9); MS (MALDI‐TOF LD+):m/z(%): 700 (10) [M+] 685 (100) [M−15]. ESI (CH3CN/H2O 70/30)m/z(%): 685 (40) [M+−15] 370.5 (85) [M++CH3CN]/2 350.0 (100) [M+]/2.19F (MeOD) (188 MHz):δ=−129.08 (br s 2 F) −152.51 (s 1 F) −158.68 ppm (s 2 F). The product was crystallized by slow diffusion of ann‐hexane/diethyl ether mixture into concentrated methanol solution.
[(4′)Mn]2+was crystallized as a methanol and water solvate. Crystal data: 2(C37H22F5MnN6)2+⋅4 I−⋅5 CH4O⋅H2O M=2086.92 triclinic space groupP$\bar 1$ a=16.1423(4) b=16.5311(4) c=16.6329(5) Å α=115.329(1) β=90.631(1) γ=94.626(1)° V=3993.6(2) Å3 Z=2 ρcalcd=1.735 g cm−3 45 552 reflections measured 15 503 unique (Rint=0.061 2θmax=52.0°) final R=0.069 (wR=0.177) for 10 085 reflections withI>2σ(I) and R=0.112 (wR=0.203) for all data. CCDC‐634668 contains the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.
Zheng G., 1992, Chem. J. Chin. Uni. (in Chinese), 13, 727
Stock solutions were prepared by dissolving calf‐thymus DNA (1 mg Sigma Aldrich) in 1 mL of doubly distilled water and were left overnight at 4 °C. Experiments were carried out at 24 °C and pH 6.8 (5 mMNaH2PO4 2.5 mMNa2HPO4 and either 0.01 Mor 0.2 MNaCl); DNA concentrations were calculated by usingε262nm=1.32×104 M−1 cm1.[21]
Szabó C., 2002, Mol. Med., 8
[(2′)Mn(X)]2+and [(4′)Mn]2+were dissolved in 10 mL of water (aided by 1 mL of methanol for the latter) 1.5 g of freshly HCl‐regenerated ion‐exchange resin (Dowex 1:8 chloride form) was added and the vessels were slowly shaken over night. The resin was filtrated and the solvent was lyophilized
Peroxynitrite was prepared according to published procedures [33]and the experimental procedures were identical to those reported in Ref. [31].