A nOveL WAter-SOLubLe neAr-InFrAreD gLuCOSe-COnJugAteD POrPhyrIn
221
4.297 (dd, 1H, J = 5.1 Hz, J = 6.9 Hz), 4.183 (dd, 1H,
(d, 4H, J = 4.6 Hz), 8.139 (d, 4H, J = 8.4 Hz), 7.507
(d, 4H, J = 8.4 Hz), 5.753 (s, 8H), 0.011 (s, 18H), -2.45
(2H -NH).
J = 2.4 Hz, J = 9.9 Hz), 3.935 (m, 1H), 2.165 (s, 3H,
CH3), 2.107 (s, 3H, CH3), 2.070 (s, 3H, CH3), 2.050 (s,
3H, CH3).
4-(2,3,4,6-tetra-O-acetyl-β-D-glucopyranosyl)phe-
nyl-2,2'-dipyrromethane (5). TFA (76 mL) was added
to a stirring solution of compound 4 (4.5 g, 20 mmol) in
pyrrole (20 mL) solution. Then the resulting solution was
stirred for 2 h at the room temperature. The solution was
concentrated under reduced pressure and purified by flash
column chromatography (ethyl acetate:petroleum = 1:2 in
v/v) to give the desired white solid compound (5). Yield
3.8 g (68%), mp 146–148 °C. ESI-MS: m/z (C29H32N2O10)
In vivo imaging and distribution of glucose conjugated
alkyl porphyrin
Athymic nude mice (seven weeks old, 20–25g) were
used. All the animal experiments were performed in com-
pliance with the Guiding Principles for the Care and Use
of Laboratory Animals, Peking Union Medical College,
China. Animals can access free to food and water. Tumor-
bearing mice were prepared by injecting a suspension of
1 × 106 liver tumor cells in physiological saline (100 mL)
into the subcutaneous left flank. Tumors develop within
a period of 1 week. Athymic nude mice were randomly
assigned to perform as follows: glucose conjugated
alkyl porphyrin, control group (n = 6 for each group). In
experimental group, near infrared fluorescence agent was
injected into the tail vein of the liver tumor-bearing mice
at 200 ml of 2 × 10-4 M. Images were taken using a Kodak
Image Station in vivo FX (filters: excitation 625 m, emis-
sion 700 nm) with an exposure time of 1 min. At the end
of the imaging, anesthetized mice were sacrificed and
images of organs were made to evaluate the distribution
of near infrared fluorescence agent. Fluorescence image
of organ was analyzed using the Kodah Image Analysis
Software.
1
569.00 (calcd. for [M + H]+ 569.21). H NMR (CDCl3,
300MHz):, ppm7.938(s, 2H), 7.115(d, 2H, J=4.5Hz),
6.903 (d, 2H, J = 2.1 Hz), 6.668 (dd, 2H, J = 1.5 Hz,
J = 2.7 Hz), 6.129 (dd, 2H, J = 2.4 Hz, J = 3.3 Hz), 5.869
(m, 2H), 5.415 (s, 1H), 5.191 (m, 1H), 5.051 (dd, 1H, J =
2.7 Hz), 4.268 (dd, 2H, J = 5.4 Hz, J = 6.9 Hz), 4.116 (m,
1H), 3.831 (m, 1H), 2.088 (m, 12H).
5,15-bis[(trimethylsilyl)ethynyl]-10,20-bis[4-(2,3,4,6-
tetra-O-acetyl-β-D-glucopyranosyl)phenyl]porphyrin
(6). TFA (8 mL) was added to a stirring solution of com-
pound 5 (113.6 mg, 0.2 mmol) and 3-(trimethylsilyl)pro-
pynal (25.2 mg, 0.2 mmol) in CH2Cl2 (20 mL) under N2
for 30 min. Then DDQ (90 mg) was added, and stirred for
2 h at room temperature. The reaction was quenched with
20 mL triethyl amine, and the mixture was concentrated
under reduced pressure and purified by flash column
chromatography (ethyl acetate:petroleum = 1:1 in v/v)
to give a greenish purple solid 6. Yield 69 mg (51.2%),
mp > 300 °C. MALDI-TOF-HRMS: m/z (C70H74N4O20Si2)
Acknowledgements
This work is supported by the National Basic Research
Program of China (No. 2006CB705703) and the PhD
Programs Foundation of Ministry of Education of China
(Nos. 20101106120052, 20070023020).
1
1347.4527 (calcd. for [M + H]+ 1347.4508). H NMR
(CDCl3, 300 MHz): , ppm 9.587 (d, 4H, J = 4.5 Hz),
8.806 (d, 4H, J = 4.5 Hz), 8.102 (d, 4H, J = 8.1 Hz), 7.405
(d, 4H, J = 8.4 Hz), 5.441–5.521 (m, 6H), 5.303–5.359
(m, 2H), 4.449 (dd, 2H, J = 5.4 Hz, 6.9 Hz), 4.331 (dd,
2H, J = 2.4 Hz, 9.9 Hz), 4.058–4.116 (m, 2H), 2.251 (s,
6H, 2CH3), 2.162 (s, 6H, 2CH3), 2.124–2.137 (m, 12H,
4CH3), 0.620 (s, 18H, 6CH3).
Supporting information
1H NMR and MS data of compound 4, 5, 6 and 1 are
given in the supplementary material. This material is
worldscinet.com/jpp/jpp.shtml.
5,15-bis[(trimethylsilyl)ethynyl]-10,20-bis[4-β-D-
glucopyranosyl)phenyl]porphyrin (1). Compound (6)
(60 mg, 0.044 mmol) was suspended in dry MeOH
(10 mL). NaOMe (300 ml, 1.0 M) was added and the solu-
tion was stirred for 4–5 h at room temperature. Cationic
ionic exchanger 001 × 7 was added to neutralize the solu-
tion. The ion exchanger was then filtered off and the sol-
vent was evaporated to dry, then the residue was dissolved
in a minimal amount of water, and acetone was added to
recrystallize the product, the solid was filtered, and dis-
solved again in a minimal amount of water, recrystallized
by acetone and collected after filtration. Finally the water
soluble target compound (1) was obtained as a greenish
purple solid 1.Yield 41 mg (89%), mp > 300 °C. MALDI-
TOF-HRMS: m/z [M + H]+ (C54H58N4O12Si2) 1011.3658
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Copyright © 2011 World Scientific Publishing Company
J. Porphyrins Phthalocyanines 2011; 15: 221–222