1 (PC) (Photodynamic therapy of cancer; PDT) PDT 600 850 nm 1) PDT PC PDT 2 - 4) PDT HOMO-LUMO * Soret 450nm PDT PDT 600 850 nm 5, 6) PC PDT PC Q HOMO-LUMO * 600 850 nm 5, 6) PC PDT 1 - 8) PDT (1,4- ) (3,4- ) (3,4-PP) 3,4-PP PDT 9, 10) 3,4-PP 3,4-PP PDT 8, 11) PDT PC 11 - 15) PC PC PDT DNA PC 16) PC 4, 12, 15)
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1
(PC)
(Photodynamic therapy of cancer; PDT)
PDT 600 850
nm
1)
PDT
PC
PDT 2 - 4)
PDT
HOMO-LUMO * Soret
450nm
PDT
PDT 600 850 nm
5, 6)
PC PDT
PC Q HOMO-LUMO *
600 850 nm
5, 6)
PC PDT
1 - 8)
PDT
(1,4- )
(3,4- ) (3,4-PP)
3,4-PP PDT
9, 10) 3,4-PP
3,4-PP
PDT
8, 11)
PDT PC
11 - 15)
PC
PC
PDT DNA
PC
16) PC
4, 12, 15)
2
PC PC
PDT
PDT
PC
PC
Zn-PC
PC
Zn-PC
Zn-PC
PC
PC Zn-PC
PDT
PC
PC ( )
16) 3,3’-
3,3’- 3,3’-
t-
t-Boc) N-(t-Boc)
N-(t-Boc)
G-1.0)
(Scheme 1)
NC
NH
CN HOOC
NH
COOH
HOOC
N
COOH
BOC
NH
NH2
N
NH
NH2
COB
O
O
3,3'- Iminodipropionitrile 3,3'-Iminodipropionic acid
N-(t-Boc)iminodipropionic acid G1
S h 1Scheme 1
G-1.0
1.5 (G-1.5)
2 G-2 2.5 (G2.5)
PC
PC
Zn-PC
Wyler Zn-PC
2 8
Type 1
Scheme 2
Type 2
Scheme 3
N
N N
N
N
N
N
N
Zn
COOH
COOHHOOC
HOOC
O
O
O
O
O
O
HOOC
+
Phthalic anhydride Trimellic anhydrideType 1 compound
Mole ratio between phthalic and trimellic anhydride Number of carboxylic acid
3:1 1 1:1 2 1:3 3 0:4 4
S h 2
Scheme 2
Zn-PC Type 1 Type 2
3
N
N N
N
N
N
N
N
Zn
COOH
COOH
COOH
COOHCOOH
HOOC
HOOC
COOH
O OO
O
O
O
O
O
O
Mole ratio between phthalic anhydride and pyromellic dianhydride Number of carboxylic acid
3:1 2 1:1 4 1:3 6 0:4 8
S h 3
Phtalic anhydride Pyromellic dianhydride
Type 2 compound
+
Scheme 3
4:0 3:1 1:1 3:1
(II) 1,2,4-
[5.4.0]-7-
6 mol dm-3
2 Zn-PC
PC
Type 1 Type 2
T1 T2 T3 T4 P2 P4 P6
P8
PC
PC
Type 1 Type 2 8
Zn-PC
1H-NMR) 15 mg cm-3
Bruker
AM-400
IR) FTIR-8100A
UV-Vis)
UV-2400PC
(DMSO) 1.0 x 104 mol dm-3
F-4500
JASCO FP-6600
DMSO
1.0 x 104 mol dm-3
(ESR)
JFS-FA200
Perkin-Elmer 2400CHN
PDT
PDT
5% 37 5% CO2
80%
Vero
PC 3
Vero
Casesin AM Propidium
lodode Hoechst staining
Array scan Cy5
PC
H2-PC Zn-PC Zn-PC
00 00 00 00%
Table 1 UV-Vis log
UV-Vis PC 690 nm 770
nm HOMO-LUMO - Q
Zn-PC H2-PC
4
Zn-PC Zn-PC
log
PC log
Table 1 UV-Vis spectral data and molar
absorption coefficientof H2-PC, Zn-PC, and
Zn-PCtetracarboxylic and octacarboxylic acids
Compound max/nm log
H2-PC 624.5 2.46
654.0 2.10
687.5 2.03
Zn-PC 607.0 4.54
655.5 4.58
Zn-PC tetracarboxylic acid 690.5 3.60
772.5 4.22
Zn-PC octacarboxylic acid 747 4.21
769.0 4.26
Type 1 Type 2 Zn-PC
Type 1 Zn-PC
59 44 53 29%
Type 2 Zn-PC
22
16 22 35%
PC
PC
12, 15)
PC
Type 1 Type 2
PC
Type 1 Zn-PC
Type 2 Zn-PC
8
(Zn-PC)
16)
Zn-PC
Q
Q PC
(HOMO)- (LUMO) *
max 650 nm
log 4.5
Q
Fmax
PC
Q
Q max Type 1 Zn-PC
Type
2
Type 1 Zn-PC Q
max
Fmax PC
Storks
Type 1 Zn-PC
Type 2
5
A
B
P
A A A
A A A
A
AB
B B
B
B
B
B
B
A A
A
A
A
AB B
B
B B
BP P P P
P
P
P
P
P
P
P
P
P
P
P
P
A
A
A A
A AB
B
B
B
B
B
BA P
P P P
P
P
Fig.1 Schematic dyagram of phthalocyanine isomers synthesized from trimellic anhydride and phthlic anhydride.
A
P
A A
A A
A A
A P
P
P
P
P
A
A
A
A
A P
P P
Fig.2 Schematic dyagram of phthalocyanine isomers synthesized from pyromellic anhydride and phthlic anhydride.
(Figs. 1 & 2)
Type 1 Type 2
Zn-PC
3,3’- 3,3’-
3,3’-
t- t-Boc)
N-(t-Boc)
N-(t-Boc)
G-1.0
G-1.5
3,3’- 3,3’-
88%
3,3’- t-
t-Boc) N-(t-Boc)
13%
N-(t-Boc)
G-1.0 70%
G-1.5 93%
3,3’- N-(t-Boc)
G-1.0 G-1.5 1H-NMR IR
PC
Type 1 Zn-PC Zn-PC
G1 Zn-PC
(Scheme 4)
N
N N
NN
N
N
N
Zn
COOH
COOHHOOC
HOOC
NH
NH2
N
NH
NH2
COB
O
O
N
N N
NN
N
N
N
Zn
HN
H2N
N
HN
H2N
O
O
NH
NH2
N
HN
NH2
O
O
NH NH2
N
NH
NH2
O
O
HN
H2N
N
NHH2N
O
O
+
Scheme 4
Type 2 Zn-PC Zn-PC
G-1.0 (Scheme 5)
G-1.5
NH
NH2
N
NH
NH2
COB
O
O
+
N
N N
NN
N
N
N
Zn
COOH
COOH
COOH
COOHCOOH
HOOC
HOOC
COOH
N
N N
N
N
N
N
N
Zn
NH
NH2
N
NH
NH2
O
O
NH
NH2
N
HNNH2O
O
NH
NH2N
NH
NH2
O
O
HN
NH2
N
NH
NH2
OO
HN
NH2
N
NH
NH2
OO
NH
H2N
N
HN
NH2
O O
HN
H2N
N
HNH2N
O
O
HNH2N
N
HNH2N
O
O
Scheme 5
Type 1 G-1.0-Zn-PC 25%
6
Type 2 Zn-PC
G-1.0 G-1.5 18% 9%
3 Zn-PC
Q 690 nm
715 nm
3 Zn-PC
PC
PC Type 1 T1G1.0 T1G1.5 T1G2.0
T1G-2.5 T4G1.0 T4G1.5 T4G2.0 T4G2.5
Type 2 P8G1.0 P8G1.5 P8G2.0 P8G2.5
PC IR MS
PC UV-Vis ESR
(Table 2)
PC DMSO
Q 680nm 695nm
PC
(Figs. 3-5)
PC Q PC
1
PC 690 710 nm
Storks UV-Vis
PC
ESR PC g =
2.00240 2.00365
g
PC PC
PC g
Table 2 Characterization data of dendritic Zn-Pcs. Compound yield / % log max max / nmF max / nm g value
T1G1.0 2 4.594 679.5 690.0 2.00262T1G1.5 13 4.480 687.0 690.0 2.00260T1G2.0 12 4.579 678.5 690.0 2.00243T1G2.5 7 4.521 678.5 690.0 2.00260T4G1.0 17 5.339 686.5 705.0 2.00276T4G1.5 12 5.512 680.5 700.0 2.00278T4G2.0 13 5.745 687.5 700.0 2.00283T4G2.5 10 5.965 687.0 700.0 2.00278P8G1.0 6 4.207 696.0 710.0 2.00275P8G1.5 5 4.664 694.0 710.0 2.00302P8G2.0 3 2.00364P8G2.5 0.4 4.630 699.0 710.0 2.00287
Fig. 3 UV-Vis and fluoresce spectra of Type1 T1
dendritic Pcs in DMSO.
Solid lines show UV-Vis spectra. Broken lines
show fluoresce spectra. :T1G1.0 :T1G1.5
Fig. 4 UV-Vis and fluoresce spectra of Type1 T1
dendritic Pcs in DMSO.
Solid lines show UV-Vis spectra. Broken lines show
fluoresce spectra. :T4G1.0 :T4G1.5 :T4G2.0
:T4G2.5
7
PDT
PDT
1O23O2
(S0)
(S1)
S1 S0
(T1) S1
T1 10-6 10-2 s
T1
T1
T1
T1 S0
PC Q 650 nm
Stokes
PC
PC
PC
PDT PC
Vero 10
PC
Vero (Fig. 6)
PC PDT
(A) (B)
Fig. 6 Fluorescence image of IU-002 cells.
(A) Control, (B) Incubated with dendritic PC and irradiated
with halogen light for 10 minutes.
PC
PC
PC T1G1.0
T4G1.0 P8G1.0 P8G1.5 Vero
PDT (Fig. 7)
Fig. 5 UV-Vis and fluoresce spectra of Type1 T1
dendritic Pcs in DMSO.
Solid lines show UV-Vis spectra. Broken lines show
fluoresce specra. :P8G1.0 :P8G1.5 :P8G2.5
8
2%
4%
PC G-1.0
20%
25% G-1.5
1.4%
PC
PC
4.
PC Type 1 Type 2
Zn-PC
PC Q PC
1
PC Zn-PC PDT
PC
PDT
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(1996).
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Fridrich, W. Maier-Borst, P. Schlag: Photochem.
Photobiol., 51, 351 (1990).
4) K. Fukushima, K. Tabata, I. Okura: J. Porphyrins
Phthalocyanines, 2, 219 (1998).
5) K. Tabata, K. Fukushima, K. Oda, I. Okura: J.
Porphyrins Phthalocyanines, 4, 278 (2000).
6) T. J. Dougherty: J. Photochem. Photobiol., 58, 895
(1993).
7) M. J. Cook, I. Chambrier, S. J. Cracknell, D.A. Mayes,
D. A. Russel: Photochem. Photobiol., 62, 542 (1995).
8) M. P. De Dilippis, D. Dei, L. Fantetti, G. Roncucci:
Tetrahedron Lett., 41, 9149 (2002).
9) K. Sakamoto, E. Ohno-Okumura, T. Kato: J. Jpn. Soc.,
Colour Mater., 76, 342 (2003).
10) , : , 75, 214 (2002).
11) I. Seotsanyana-Mokhosi, N. Kuznetsova, T. Nyokong:
J. Photochem. Photobiol. A: Chem., 140, 215 (2001).
12)
2004 .
13) K. Sakamoto, E. Ohno-Okumura, Taku Kato, Recent Rsearch
Development of Inorganic Chemistry, 5, 1 (2006).
14) K. Sakamoto E. Ohno-Okumura Current Topics in
Electrochemistry 9 117 (2003).
15)
(1997).
16) D.R.Boston J.C.Bailar.Jr Inorganic Chemistry 11,
1578 (1972).
Fig. 7 Photocytoxity of dendritic Pcs.
:T1G1.0 :T4G1.0 :P8G1.0 :P8G1.5
0
5
10
15
20
25
30
0 0.001 0.002 0.003 0.004 0.005
Concenctration / mg ml -1
Let
hal
cel
l per
cent
/ %
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