JBIC Journal of Biological Inorganic Chemistry
(d, 6H, OCH2CH2O), 3.91 (d, 6H, OCH2CH2O), 3.75 (q,
6H, –CH2CH3), 1.32(t, 6H, –CH2CH3), − 2.88 (s, 2H, NH).
Mass (ESI): calcd for C57H54N4O8 (M+H)+, 924.06; found
924.50.
Synthesis of palladium porphyrin complex (PdPor)
The indomethacin-conjugated porphyrin (Por) (56 mg,
0.042 mmol) and palladium acetate (11.31 mg, 0.050 mmol)
were dissolved in 10-mL dichloromethane and then heated
to 70 °C. The completion of metal insertion was verifed by
UV–Vis spectroscopy and TLC. The solvent was evaporated
in vacuo and the residue was washed with 3×100 mL brine
solution and 3× 100 mL H2O, respectively. The organic layer
was dried over Na2SO4 and evaporated in vacuo. The resi-
due was purifed by silica column chromatography (MeOH
in CH2Cl2: 0–2% v/v) to get 50-mg product, yield 82%. 1H
NMR (400 MHz, CDCl3) δ 8.81 (s, 8H, β-pyrrole), 8.16 (s,
2H, CH), 8.05 (d, 2H, CH), 7.94 (d, 6H, CH), 7.60 (d, 2H,
p-chlorobenzoyl, H-3, H-5), 7.39 (d, 2H, p-chlorobenzoyl,
H-2, H-6), 7.16 (m, 6H, benzyl), 6.79–6.94 (m, 3H, indolyl),
6.66 (m, 2H, –NHCH2–), 4.22 (d, 6H, OCH2CH2O), 3.87(d,
6H, OCH2CH2O), 3.79 (s, 3H, –OCH3), 3.72 (q, 6H,
–CH2CH3), 3.67 (s, 2H, –COCH2), 3.52 (t, 2H, –NHCH2–),
3.33 (t, 2H, –CH2NH–), 2.40 (s, 3H, CH3), 1.63 (s, 4H,
–CH2CH2–), 1.33 (t, 9H, –CH2CH3). Mass (ESI): calcd for
C80H76ClN7O10Pd (M+H)+, 1436.44; found 1436.72.
Synthesis of indomethacin‑conjugated porphyrin
(Por)
The compound 3 (483 mg, 0.523 mmol), Boc-protected
1,4-butanediamine (268.68 mg, 0.628 mmol), DMAP
(128.5 mg, 1.052 mmol) and EDCI (201.7 mg, 1.052 mmol)
were dissolved in 70-mL dichloromethane. The reaction
mixture was stirred overnight under a nitrogen atmosphere.
The solvent was evaporated in vacuo and the residue was
subjected to silica chromatography (MeOH in CH2Cl2,
1
1–2% v/v) to get 246.9-mg product, yield 35%. H NMR
(400 MHz, CDCl3) δ 8.75 (s, 8H, β-pyrrole), 8.12 (s, 2H,
CH), 8.02 (d, 2H, CH), 7.89 (d, 6H, CH), 7.50 (d, 2H,
p-chlorobenzoyl, H-3, H-5), 7.29 (d, 2H, p-chlorobenzoyl,
H-2, H-6), 7.13 (m, 6H, benzyl), 6.73–6.84 (m, 3H, indolyl),
6.58 (m, 2H, –NHCH2–), 4.22 (d, 6H, OCH2CH2O), 3.81
(d, 6H, OCH2CH2O), 3.69 (s, 3H, –OCH3), 3.60 (q, 6H,
–CH2CH3), 3.5 (s, 2H, –COCH2), 3.44 (t, 2H, –NHCH2–),
3.22 (t, 2H, –CH2NH–), 2.29 (s, 3H, CH3), 1.53 (s, 4H,
–CH2CH2–), 1.23 (t, 9H, –CH2CH3), − 2.85 (s, 2H, NH).
Mass (ESI): calcd for C80H78ClN7O10 (M + H)+, 1333.97;
found 1334.17.
Synthesis of platinum porphyrin complex (PtPor)
To a 10 mL flask, indomethacin-conjugated porphyrin
(Por) (70 mg, 0.053 mmol), potassium tetrachloroplatinate
(43.62 mg, 0.105 mmol), and 5 mL benzonitrile were added.
The mixture was then heated to refux for 48 h. The comple-
tion of metal insertion was verifed by UV–Vis spectros-
copy and TLC. The solvent was evaporated in vacuo and
the residue was subjected to silica column chromatography
(MeOH in CH2Cl2: 0–2% v/v). The pure fraction was col-
lected and concentrated to give the product 46 mg, yield
78%. 1H NMR (400 MHz, CDCl3) δ 8.77 (s, 8H, β-pyrrole),
8.20 (s, 2H, CH), 8.11 (d, 2H, CH), 8.02 (d, J =8 Hz, 6H,
CH), 7.65 (d, 2H, p-chlorobenzoyl, H-3, H-5), 7.42 (d, 2H,
p-chlorobenzoyl, H-2, H-6), 7.27 (m, 6H, benzyl), 6.69-
6.95 (m, 3H, indolyl), 6.82 (m, 2H, –NHCH2–), 4.37 (d,
6H, OCH2CH2O), 3.97 (d, 6H, OCH2CH2O), 3.81 (s, 3H,
–OCH3), 3.72 (q, 6H, –CH2CH3), 3.69 (s, 2H, –COCH2),
3.56 (t, 2H, –NHCH2–), 3.36 (t, 2H, –CH2NH–), 2.43 (s,
3H, CH3), 1.61 (s, 4H, -CH2CH2-), 1.35 (t, 9H, –CH2CH3).
Mass (ESI): calcd for C80H76ClN7O10Pt (M+H)+, 1525.50;
found 1525.83.
Synthesis of zinc porphyrin complex (ZnPor)
The indomethacin-conjugated porphyrin (Por) (55 mg,
0.041 mmol) was dissolved in 10 mL dichloromethane and
then heated to 40 °C, followed by addition of zinc acetate
dihydrate (181.14 mg, 0.825 mmol) in 4-mL MeOH. The
solution was refuxed for 3 h, and the completion of metal
insertion was verifed by UV–Vis spectroscopy and TLC.
The solvent was evaporated in vacuo and the residue was
subjected to silica column chromatography (40% hexane in
CH2Cl2, v/v). The pure fractions were collected and con-
centrated under reduced pressure, which was then dissolved
in a minimal amount of dichloromethane and precipitated
1
in hexane to get 47-mg desired complex, yield 77%. H
NMR (400 MHz, CDCl3) δ 8.81 (s, 8H, β-pyrrole), 8.16 (s,
2H, CH), 8.05 (d, 2H, CH), 7.94 (d, 6H, CH), 7.60 (d, 2H,
p-chlorobenzoyl, H-3, H-5), 7.39 (d, 2H, p-chlorobenzoyl,
H-2, H-6), 7.16 (m, 6H, benzyl), 6.79–6.94 (m, 3H, indolyl),
6.66 (m, 2H, –NHCH2–), 4.22 (d, 6H, OCH2CH2O), 3.87
(d, 6H, OCH2CH2O), 3.79 (s, 3H, –OCH3), 3.72 (q, 6H,
–CH2CH3), 3.67 (s, 2H, –COCH2), 3.52 (t, 2H, –NHCH2–),
3.33 (t, 2H, –CH2NH–), 2.40 (s, 3H, CH3), 1.63 (s, 4H,
–CH2CH2–), 1.33 (t, 9H, –CH2CH3). Mass (ESI): calcd for
C80H76ClN7O10Zn (M+H)+, 1397.33; found 1397.57.
UV–Vis absorption and fuorescence spectra
The UV–Vis absorption spectrum and fuorescence spec-
trum of four porphyrin conjugates were measured in DMSO
solution.
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