7392
M.E. Bakleh et al. / Tetrahedron 65 (2009) 7385–7392
´
mixture for 3 h at rt. After concentration under reduced pressure
the residue was precipitated from cold diethyl ether and filtered.
The product was loaded onto a preparative Hibar Purosphere C18
column. The elution was achieved under the following conditions:
eluent A, 0.05% TFA in water; eluent B, 0.05% TFA in CH3CN/H2O
(70:30); A/B gradient 60/40 to 0/100 over 40 min; flow rate, 4 mL/
min; detection was performed at 214 nm and 438 nm for 16 or
431 nm for 17.
Dr. Celine Frochot and Pierre Couleaud for determination of singlet
oxygen quantum yield.
References and notes
1. (a) Detty, M. R.; Gibson, S. L.; Wagner, S. J. J. Med. Chem. 2004, 47, 3897; (b)Hamblin,
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4.2.16.1. Compound 16. Reaction with 13 (20 mg, 24 mmol,
1.1 equiv) has afforded the crude (96 mg) as a purple solid. After
deprotection, RP-HPLC (detections at 214 and 438 nm, retention
time 34 min) and lyophilization, 14 mg (23%) of the expected
compound 16 were obtained as a purple solid.
UV/visible (H2O):
(1.9), 646 (1.4).
l
(
e
ꢃ10ꢀ3) 438 (181.1), 519 (6.7), 556 (3.0), 589
1H NMR (400 MHz, DMSO-d6, 25 ꢁC)
d: ꢀ2.90 (br s, 2H, NH), 2.59
(s, 9H, CH3 tolyl), 1.20–8.50 (m, H spacer and H amino acids), 7.20–
8.85 (m, 24H, H tolyl, H Ar, Hb pyr).
SM (MALDI): mass spectrometry analysis shows the expected
molecular mass (theoretical value: 2854.28 Da; experimental
value: 2855.67 Da).
4.2.16.2. Compound 17. Reaction with 15 (25 mg, 24 mmol,1.1 equiv)
has afforded the crude (110 mg) as a purple solid. After deprotection,
RP-HPLC (detections at 214 and 431 nm, retention time 37 min) and
lyophilization, 19 mg (26%) of the expected compound 17 were
obtained as a purple solid.
´ ´
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l
(
e
ꢃ10ꢀ3) 431 (334.3), 517 (19.8), 554 (12.4),
592 (6.7), 655 (6.0).
1H NMR (400 MHz, DMSO-d6, 25 ꢁC)
d: ꢀ2.96 (br s, 2H, NH), 2.59
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4.3. Determination of singlet oxygen quantum yield
F
(1O2)
Quantum yield of 1O2 production was determined by direct
analysis of the 1O2 near-infrared luminescence at 1270 nm. Exci-
tation occurred with a Xe-arc, the light was separated in a SPEX
Fluorolog-3 F222, 0.22 mm double monochromator. A high pass
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trogen-cooled Ge-detector model (EO-817L, North Coast Scientific
Co). The absorbance of the reference solution (Bengal pink in EtOH
FF (1O2)¼0.68)26 and the sample solution (at 415 nm) were set
equal (between 0.2 and 0.5) by dilution.
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Acknowledgements
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´
We thank the ‘Conseil Regional du Limousin’, ‘La Ligue contre le
cancer’ and the ‘Conseil Re´gional d’Aquitaine’ for financial support.
The authors are indebted to Dr. Michel Guilloton for help in writing
the manuscript, Dr. Sandra Alves for routine MS MALDI analysis and
26. De Rosa, M. C.; Crutchley, R. J. Coord. Chem. Rev. 2002, 233–234, 351.