Control of the aggregation properties of Tris(maltohexaose)-linked porphyrins with an alkyl chain

Article abstract of DOI:10.1002/ejoc.200900940

A series of porphyrins with three maltohexaose units and one alkyl chain (ethyl, butyl, hexyl, decyl, and hexadecyl) has been synthesized. Aggregation properties were investigated by absorbance and circular dichroism (CD) spectra. These trismaltohexaosylated tetraphenylporphyrins exhibited high water solubility. Although these porphyrins exhibited sharp Soret bands in DMSO solution, the Soret band broadened in a concentration-dependent manner in aqueous solution. This is the result of the aggregation of porphyrin molecules in aqueous solution. Interestingly, trismaltohexaosylated porphyrins with long alkyl chains of a certain length exhibited a broad. Soret band in water without concentration dependency due to the stability of such, aggregates. The CD spectra were silent in DMSO solution in all porphyrin derivatives, indicating that the maltohexaose moiety does not interact with the porphyrin chromophore in the monomelic state. However, in water, a splitting Cotton effect was observed at the Soret band. Intensity of this CD signal decreased as the length of the alkyl chain was extended. These observations show the formation of a chiral, face-to-face aggregate, in which the porphyrin rings are in close proximity to each other for short; alkyl chain derivatives. The porphyrin derivatives with long alkyl chains exhibit edge-to-edge aggregation, where hydrophobic interaction of the alkyl chains separates the porphyrin chromophores.

Full text of DOI:10.1002/ejoc.200900940

FULL PAPER
DOI: 10.1002/ejoc.200900940
Control of the Aggregation Properties of Tris(maltohexaose)-Linked
Porphyrins with an Alkyl Chain
[
a]
[b]
[b]
[c]
Yuji Mikata,* Taichi Sawaguchi, Toyoji Kakuchi,* Michael Gottschaldt,
Ulrich S. Schubert,[ Hiromi Ohi, and Shigenobu Yano*
c,d]
[e]
[e]
Keywords: Carbohydrates / Porphyrinoids / Aggregation / Noncovalent interactions / Circular dichroism
A series of porphyrins with three maltohexaose units and one
alkyl chain (ethyl, butyl, hexyl, decyl, and hexadecyl) has
been synthesized. Aggregation properties were investigated
by absorbance and circular dichroism (CD) spectra. These
trismaltohexaosylated tetraphenylporphyrins exhibited high
water solubility. Although these porphyrins exhibited sharp
Soret bands in DMSO solution, the Soret band broadened in
a concentration-dependent manner in aqueous solution. This
is the result of the aggregation of porphyrin molecules in
aqueous solution. Interestingly, trismaltohexaosylated por-
phyrins with long alkyl chains of a certain length exhibited
a broad Soret band in water without concentration depen-
dency due to the stability of such aggregates. The CD spectra
were silent in DMSO solution in all porphyrin derivatives,
indicating that the maltohexaose moiety does not interact
with the porphyrin chromophore in the monomeric state.
However, in water, a splitting Cotton effect was observed at
the Soret band. Intensity of this CD signal decreased as the
length of the alkyl chain was extended. These observations
show the formation of a chiral, face-to-face aggregate, in
which the porphyrin rings are in close proximity to each
other for short alkyl chain derivatives. The porphyrin deriva-
tives with long alkyl chains exhibit edge-to-edge aggrega-
tion, where hydrophobic interaction of the alkyl chains sepa-
rates the porphyrin chromophores.
Introduction
amphiphilic porphyrins tend to aggregate in solu-
[
9,12,17–21]
tion.
Thus, introduction of a wide variety of alkyl
Porphyrin derivatives play important roles in biological
systems. In recent years, photodynamic therapy (PDT)
using porphyrin derivatives as a photosensitizing biological
chromophore is considered as a clean, effective cancer ther-
chains to the porphyrin derivatives enables us to control the
[22–25]
aggregation state by hydrophobic forces.
It is also of
significant interest to organize porphyrins in nanoscale or-
[26–29]
der.
The present research is established on the basis
[
1–3]
apy.
For clinical use, it is important to make porphyrin
of the above consideration, creating a hybrid material with
biological similarity to regulate aggregation properties by
cooperative effects between the carbohydrates and the alkyl
chains.
derivatives soluble in aqueous solution. From the viewpoint
of biological applications, non-ionic, cell-permeable carbo-
hydrates that exist abundantly in nature are considered to
be attractive materials for hydrophilic functionalities.
Carbohydrates play many important roles such as energy
sources for living systems, construction materials, and ad-
Results
hesion between cells.[
4,5]
Thus, hybrid materials of carbo-
hydrates and porphyrins may become a photofunctional
Synthesis
molecule with biological similarity.[
6–16]
On the other hand,
A series of porphyrins with three maltohexaose units and
one alkyl chain (3MalTPP, 1E3MalTPP, 1B3MalTPP,
[
a] KYOUSEI Science Center, Nara Women’s University,
Nara 630-8506, Japan
1H3MalTPP, 1D3MalTPP, and 1HD3MalTPP) was syn-
Fax: +81-742-20-3095
E-mail mikata@cc.nara-wu.ac.jp
thesized from 3-iodopropyl nonadeca-O-acetyl-β--mal-
[
30–32]
[
[
[
[
b] Graduate School of Engineering, Division of Biotechnology tohexaoside (S-I)
and 5,10,15,20-tetrakis(4-hydroxy-
and Macromolecular Chemistry, Hokkaido University,
Sapporo 060-8628, Japan
[33,34]
phenyl)porphyrin (p-THPP)
according to Schemes 1,
2, and 3. For the synthesis of acetyl-protected derivatives of
c] Friedrich-Schiller-University Jena, Laboratory of Organic and
Macromolecular Chemistry,
Humboldtstr. 10, 07743 Jena, Germany
d] Eindhoven University of Technology, Laboratory of Macromo-
lecular Chemistry and Nanoscience,
P. O. Box 513, 5600 MB Eindhoven, The Netherlands
e] Innovative Collaboration Center, Kyoto University, Kyoto Dai-
gaku Katsura,
3MalTPP, 1B3MalTPP, 1H3MalTPP, and 1HD3MalTPP,
p-THPP was treated with S-I, and thus obtained trismal-
tohexaosylated porphyrin 1 (3MalTPP) was subjected to
further alkylation (Scheme 1). As shown in Scheme 2, an
alkyl chain was in advance introduced to p-THPP to obtain
9 and 14, and then, these monoalkylated porphyrins were
Nishikyo-ku, Kyoto 615-8520, Japan
Eur. J. Org. Chem. 2010, 663–671
© 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
663

Y. Mikata,T. Kakuchi, S. Yano et al.
FULL PAPER
Scheme 1.
treated with S-I for the synthesis of 1E3MalTPP and these porphyrins exist as a monomer in this solution. In
1
D3MalTPP. The acetyl groups of maltohexaose-conju- aqueous solution, however, strong exciton coupling signals
[
35–37]
gated porphyrins 1, 6–8, 19, and 20 were removed by so- in the region from 380 to 460 nm
were observed (Fig-
dium methoxide in CHCl /MeOH to give the desired am- ure 2, solid lines). Thus, the trismaltohexaosylated por-
3
phiphilic porphyrins (Scheme 3).
phyrins with an alkyl chain form aggregates with chirality
around the porphyrin chromophore in aqueous solution.
The intensity of this CD signal decreased as the length of
the alkyl chain was extended. For porphyrins with longer
alkyl chains, in contrast to the smooth and sharp negative
Cotton effect at the long-wavelength region, a broad posi-
tive Cotton effect at the short-wavelength region exhibits
broad, structureless features. The examination of concen-
tration dependency in the CD spectra resulted in very com-
plicated characteristics and further study was avoided at the
present stage. Figure 3 summarizes the differences in the
CD and absorption spectra at the Soret band of all por-
phyrin derivatives in aqueous solution at a concentration of
Absorbance Spectra
The absorbance spectra of all maltohexaosylated por-
phyrin derivatives exhibit a Soret band and four Q bands
around 425 nm and 500–680 nm, respectively (Figure 1).
The Soret band is very sharp in DMSO solution, indicating
that these porphyrins exist as a monomer in this solution.
In contrast, in aqueous solution, the absorbance spectra be-
come broad, and the half-height width widened when the
concentration was increased from 10 to 10  (Figure 1).
This observation suggests the formation of porphyrin ag-
gregates in water solution with a variety of absorption en-
ergy levels. It should be noted that, for porphyrin deriva-
tives with long alkyl chains, the shape of the Soret band
–
7
–5
1
.0ϫ10–5 .
–7
Discussion
was unchanged in the concentration range from 10 to
–
5
10
. This indicates that the porphyrins form stable aggre-
A series of porphyrins with three acetyl-protected mal-
tohexaose units and one alkyl chain has been synthesized
by two synthetic routes shown in Schemes 1 and 2. The ra-
tio of alkylating agent and hydroxyporphyrin were opti-
mized from several trials considering the product yield and
separation efficiency. For the series of compounds studied
in this work, Scheme 1 would be a better synthetic route
because laborious separation by column chromatography is
gates without a concentration dependency. Table 1 summa-
rizes the Soret band absorption properties of the porphyrin
derivatives in DMSO and water at a concentration of
–
5
1
.0ϫ10 .
CD Spectra
In DMSO solution, no active Cotton effect was observed common for all compounds. In this case, however, a con-
at the Soret band (Figure 2, broken lines), indicating that siderable amount of S-I is necessary. In addition, the syn-
664
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© 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Org. Chem. 2010, 663–671

Aggregation Properties of Tris(maltohexaose)-Linked Porphyrins
Scheme 2.
Scheme 3.
thesis of 1E3MalTPP according to Scheme 1 was problem- to increase in proportion to the alkyl chain length, and it
atic because of the difficulty in separating compounds 19 became constant for longer alkyl chains than 1B3MalTPP
and 1 (starting material of the second step) due to their and decreased for 1HD3MalTPP (Table 1). The increase in
small differences in polarity or molecular size. As evidenced half-height width for other compounds is due to the shoul-
by the synthesis of 1D3MalTPP, the present paper demon- der around 410 nm. Considering that this shoulder as a
strates that both syntheses can be used to prepare the tris- splitting peak, the edge-to-edge type aggregate (Figure 4a)
maltohexaosylated porphyrins with a long alkyl chain.
seems to be predominant for 1B3MalTPP, 1H3MalTPP,
The peak-top wavelength in the absorbance spectra are and 1D3MalTPP, as alkyl chains interact with each other
almost unchanged for all porphyrin derivatives; however, by hydrophobic interactions in aqueous solution. The
the half-height width (W1/2) in aqueous solution was found 1HD3MalTPP derivative, which has an extremely long alkyl
Eur. J. Org. Chem. 2010, 663–671
© 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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665

Y. Mikata,T. Kakuchi, S. Yano et al.
FULL PAPER
Figure 2. CD spectra of 3MalTPP, 1E3MalTPP, 1B3MalTPP,
1
H3MalTPP, 1D3MalTPP, and 1HD3MalTPP in DMSO and
–
5
water (1.0ϫ10  concentration).
Figure 1. UV/Vis spectra of 3MalTPP, 1E3MalTPP, 1B3MalTPP,
1
H3MalTPP, 1D3MalTPP, and 1HD3MalTPP in DMSO and
water with normalized intensity.
chain, exists also as an edge-to-edge aggregate with a de-
creased half-height width, because the porphyrin rings are Figure 3. Overlay plot of CD and absorption spectra of trismal-
–
5
separated from each other.
tohexaosylated porphyrins in water (1.0ϫ10  concentration).
Table 1. Soret band absorbance spectral data for 3MalTPP, 1E3MalTPP, 1B3MalTPP, 1H3MalTPP, 1D3MalTPP, and 1HD3MalTPP in
[
a]
DMSO and water.
Compound
in DMSO
in Water
Soret band / nm
W
1/2 / nm (ε / –1 cm–1)
Soret band / nm
W
1/2 / nm (ε / –1 cm–1)
3
1
1
1
1
1
MalTPP
424
424
424
424
424
424
13.5 (383000)
14 (447000)
13.5 (485000)
14 (433000)
13.5 (422000)
13.5 (546000)
426
427
427
427
426
428
22.5 (219000)
25.5 (227000)
29 (216000)
29.5 (206000)
28 (221000)
E3MalTPP
B3MalTPP
H3MalTPP
D3MalTPP
HD3MalTPP
25.5 (240000)
[
a] Concentration: 1.0ϫ10–5 .
666
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Eur. J. Org. Chem. 2010, 663–671

Aggregation Properties of Tris(maltohexaose)-Linked Porphyrins
Figure 4. Schematic diagram representing the aggregation properties with (a) edge-to-edge association and (b) face-to-face association.
From the CD spectra, 3MalTPP exhibits a large Cotton exist as a monomer in DMSO solution but as an aggregate
effect with a splitting pattern, suggesting that this com- in water. The alkyl chain length is the important factor that
pound mainly exists as a face-to-face aggregate with nega- governs the aggregation mode, namely, long alkyl chain in-
tive helicity (Figure 4b), where the porphyrin rings are in creases the half-height width for the Soret band and de-
close proximity to each other. 1E3MalTPP, which has an creases the intensity in the CD spectrum. Both parameters,
ethyl group, has a decreased CD intensity compared to however, were unaffected by derivatives that have alkyl
that of 3MalTPP, exhibiting a new, negative Cotton effect chains longer than a hexyl group. This indicates that a face-
in the long-wavelength region (around 436 nm). These ob- to-face aggregate was formed for short alkyl chain deriva-
servations are considered as a mixture of two Cotton ef- tives where the porphyrin rings are twisted, whereas an
fects, indicating the formation of edge-to-edge aggregates edge-to-edge aggregate was formed for long alkyl chain de-
in addition to face-to-face aggregates by the ethyl-substit- rivatives. Especially, the UV spectrum of the derivative with
uent effect. The porphyrin derivatives with alkyl chains decyl and maltohexaose substituents was unchanged in
–5
–7
longer than butyl exhibit a decreased CD intensity and a water at all concentrations tested (10 –10 ). This is
redshifted peak-top. These observations suggest that probably because the edge-to-edge aggregate was formed by
1
B3MalTPP, 1H3MalTPP, and 1D3MalTPP exist mainly hydrophobic interaction of the decyl chains. The present
as an edge-to-edge aggregate. The porphyrin ring itself information could help us to create novel photofunctional
tends to form an aggregate, however, repulsive forces from nanomaterials.
electrostatic interactions in charged water-soluble por-
phyrins such as TPPS [5,10,15,20-tetrakis(4-sulfonyl-
phenyl)porphyrin] separates them. In contrast, the present
porphyrin derivatives with oligosaccharide and alkyl chain
are non-ionic, forming the stable aggregates with negative
helicity by attached maltohexaose group. Moreover, intro-
duction of alkyl chains of certain length into these por-
phyrins affords a stable edge-to-edge association without
concentration-dependency. Preliminary estimation of ag-
gregation number for 1D3MalTPP by SLS measurement
suggests that the aggregation number is Ͼ2,000 in low and
Experimental Section
Reagents: DMF was dried with 4 Å molecular sieves. THF was
4
distilled from LiAlH . Water was obtained from a Milli-Q system
(
Millipore). Other dry solvents, spectrometry grade solvents were
used as received. Potassium carbonate was dried at 100 °C under
reduced pressure. Other reagents were used as received. Column
chromatography was performed by using Cica Silica Gel 10N 40–
50 µm. Recycle column chromatography was performed by JAI LC-
908 using a JAIGEL-3H column and THF as the eluent. Dialysis
high concentrations and the rotational square radius is was performed using SPECTRAM Spectra/Por 7 Membrane
small, indicating the formation of stable, micelle-like, high- MW1000.
density aggregate.
5
,10,15-Tris[4-(3-nonadeca-O-acetyl-β-D-maltohexaosyloxy)propyl-
oxy]phenyl-20-(4-hydroxyphenyl)porphyrin (1): 5,10,15,20-Tetra-
kis(4-hydroxyphenyl)porphyrin (p-THPP)[
was treated with 1-iodopropyl nonadeca-O-acetyl-β--maltohexao-
side (S-I) (577 mg, 295 µmol) in the presence of K CO (202 mg,
.47 mmol) in DMF (30 mL) at room temperature for 2 d and at
0 °C for 2 h. After filtration, the material was extracted with ethyl
33,34]
(100 mg, 147 µmol)
Conclusion
2
3
A hydrophobic porphyrin chromophore was solubilized
in water by attaching three maltohexaose units. All of the
porphyrins exhibit sharp Soret bands and an inactive CD
in DMSO solution. In contrast, in water solution, the Soret
1
6
acetate, washed with water and brine, and dried with sodium sul-
fate. The solvent was removed under reduced pressure, and the por-
band was broadened and active CD Cotton effects were ob- phyrin derivatives having one to four maltohexaose units were sepa-
served. These observations indicate that these porphyrins rated by column chromatography. Yield: 112.8 mg (12%). R
f
= 0.15
Eur. J. Org. Chem. 2010, 663–671
© 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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667

Y. Mikata,T. Kakuchi, S. Yano et al.
FULL PAPER
1
(toluene/acetone, 2:1). H NMR (300 MHz, CDCl
3
): δ = 8.85 (d, 8
(200 mg, 32.4 µmol), 1-bromohexane (24.2 m in DMF, 2.0 mL,
H, pyr), 8.09 (m, 8 H, 2,6-H aryl), 7.26 (m, 8 H, 3,5-H aryl), 5.42–
2 3
48.6 µmol), and K CO (45.0 mg, 0.32 mmol) in DMF (10 mL) was
3
2
C
.92 (m, 3ϫ42 H, maltohexaose), 4.07 (t, 3ϫ4 H, 1,3-H propyl),
.24–1.99 (m, 3 ϫ 57 H, acetyl), –2.77 (br. s, 2 H, NH) ppm.
stirred for 5 d at room temperature. After filtration, the material
was extracted with ethyl acetate, washed with water and brine, and
dried with sodium sulfate. The solvent was removed under reduced
275
H
342
N
4
O154 (6167.66): calcd. C 53.55, H 5.59, N 0.91; found
C 53.09, H 5.67, N 0.90.
pressure, and the residue was purified by column chromatography.
1
Yield: 168.6 mg (83%). R
300 MHz, CDCl
f
= 0.21 (toluene/acetone, 2:1). H NMR
): δ = 8.84 (m, 8 H, pyr), 8.11 (m, 8 H, 2,6-H
5
,10,15-Tris(4-hydroxyphenyl)-20-{4-[3-(nonadeca-O-acetyl-β-D-
(
3
maltohexaosyl)propoxy]phenyl}porphyrin (2): Compound 2 was ob-
tained as a byproduct in the synthesis of 1. Yield: 132.9 mg (36%).
aryl), 7.27 (m, 8 H, 3,5-H aryl), 5.47–3.78 (m, 3ϫ42 H, mal-
tohexaose), 4.06 (m, 14 H, 1,3-H propyl, 1-H hexyl), 2.24–1.98 (m,
1
R
f
= 0.30 (toluene/acetone, 2:1). H NMR (300 MHz, CDCl
3
): δ =
3
ϫ57 H, acetyl), 1.59 (m, 6 H, 2-H propyl), 1.47 (m, 4 H, 3,4-H
hexyl), 1.26 (m, 2 H, 5-H hexyl), 0.99 (t, 3 H, 6-H hexyl), –2.76
br. s, 2 H, NH) ppm. C281 154 (6251.82): calcd. C 53.98,
H 5.71, N 0.90; found C 54.09, H 5.91, N 0.91.
-(4-Hexadecanoxyphenyl)-10,15,20-tris{4-[3-(nonadeca-O-acetyl-β-
-maltohexaosyl)propoxy]phenyl}porphyrin (8): A mixture of 1
153.5 mg, 24.9 µmol), 1-bromohexadecane (18.7 m in acetone,
.0 mL, 37.3 µmol), and K CO (34.4 mg, 0.25 mmol) in acetone
30 mL) was stirred for 5 d at room temperature. After filtration,
8
2
.84 (s, 4 H, pyr), 8.79 (d, J = 4.8 Hz, 2 H, pyr), 8.73 (d, J = 4.8 Hz,
H, pyr), 7.99 (m, 6 H, 2,6-H aryl), 7.90 (d, J = 8.5 Hz, 2 H, 2,6-
(
354 4
H N O
H aryl), 7.08 (m, 6 H, 3,5-H aryl), 7.01 (d, J = 8.5 Hz, 2 H, 3,5-H
aryl) 5.45–3.77 (m, 42 H, maltohexaose), 4.07 (t, 4 H, 1,3-H pro-
pyl), 2.23–1.99 (m, 57 H, acetyl), –2.77 (br. s, 2 H, NH) ppm.
5
D
121 134 4
C H N O54 (2508.38): calcd. C 57.94, H 5.38, N 2.23; found C
(
57.83, H 5.45, N 2.11.
2
2
3
5
,10-Bis(4-hydroxyphenyl)-15,20-bis{4-[3-(nonadeca-O-acetyl-β-D-
(
maltohexaosyl)propoxy]phenyl}porphyrin (3): Compound 3 was ob-
tained as a byproduct in the synthesis of 1. Yield: 94.9 mg (15%).
the material was extracted with ethyl acetate, washed with water
and brine, and dried with sodium sulfate. The solvent was removed
under reduced pressure, and the residue was purified by column
1
R
f
= 0.21 (toluene/acetone, 2:1). H NMR (300 MHz, CDCl
3
): δ =
8.82 (m, 8 H, pyr), 8.06 (d, J = 8.1 Hz, 8 H, 2,6-H aryl), 7.21 (m,
8 H, 3,5-H aryl), 5.47–3.80 (m, 2ϫ42 H, maltohexaose), 4.06 (t,
2ϫ4 H, 1,3-H propyl), 2.24–1.99 (m, 2ϫ57 H, acetyl), –2.78 (br.
chromatography. Yield: 80.9 mg (51%). R
f
= 0.29 (toluene/acetone,
): δ = 8.84 (m, 8 H, pyr), 8.11 (d,
J = 7.7 Hz, 8 H, 2,6-H aryl), 7.27 (d, J = 7.7 Hz, 8 H, 3,5-H aryl),
.47–3.78 (m, 3ϫ42 H, maltohexaose), 4.07 (m, 14 H, 1,3-H pro-
1
2:1). H NMR (300 MHz, CDCl
3
s, 2 H, NH) ppm. C198
H
238
N
4
O
104 (4338.02): calcd. C 54.82, H
5
5.53, N 1.29; found C 54.68, H 5.67, N 1.30.
pyl, 1-H hexadecyl), 2.25–1.99 (m, 3ϫ57 H, acetyl), 1.78 (m, 3ϫ2
H, 2-H propyl), 1.61 (m, 2 H, 3-H hexadecyl), 1.46–1.25 (m, 24
H, 4,5,6,7,8,9,10,11,12,13,14,15-H, hexadecyl), 0.88 (t, 3 H, 16-H
5
,15-Bis(4-hydroxyphenyl)-10,20-bis{4-[3-(nonadeca-O-acetyl-β-D-
maltohexaosyl)propoxy]phenyl}porphyrin (4): Compound 4 was ob-
tained as a byproduct in the synthesis of 1. Yield: 40.9 mg (6%).
374 4
hexadecyl), –2.77 (br. s, 2 H, NH) ppm. C291H N O154 (6392.09):
1
R
f
= 0.36 (toluene/acetone, 2:1). H NMR (300 MHz, CDCl
3
): δ = calcd. C 54.68, H 5.90, N 0.88; found C 54.55, H 5.92, N 0.81.
8
.85 (dd, J = 4.8, 7.5 Hz, 8 H, pyr), 8.07 (m, 8 H, 2,6-H aryl), 7.22
5
-(4-Ethoxyphenyl)-10,15,20-tris(4-hydroxyphenyl)porphyrin (9): p-
(
(
(
m, 8 H, 3,5-H aryl), 5.47–3.80 (m, 2ϫ42 H, maltohexaose), 4.07
t, 2ϫ4 H, 1,3-H propyl), 2.24–1.99 (m, 2ϫ57 H, acetyl), –2.78
br. s, 2 H, NH) ppm. C198H N O104 (4338.02): calcd. C 54.82,
238 4
[33,34]
THPP
(300 mg, 0.44 mmol) was treated with ethyl iodide
0.88 mmol) in the presence of K CO (608 mg, 4.4 mmol) in DMF
30 mL) at room temperature for 2 d. After filtration, the material
(
(
2
3
H 5.53, N 1.29; found C 54.92, H 5.68, N 1.23.
,10,15,20-Tetrakis{4-[3-(nonadeca-O-acetyl-β-
propoxy]phenyl}porphyrin (5): Compound 5 was obtained as a by-
product in the synthesis of 1. Yield: 41.2 mg (4%). R = 0.09 (tolu-
): δ = 8.84 (s, 8 H,
was extracted with chloroform, washed with water and brine, and
dried with sodium sulfate. The solvent was removed under reduced
pressure, and porphyrin derivatives having one to four ethyl groups
5
D-maltohexaosyl)-
were separated by column chromatography. Yield: 66.3 mg (21%).
f
1
1
R = 0.13 (chloroform/methanol, 20:1). H NMR (300 MHz, [D ]-
ene/acetone, 2:1). H NMR (300 MHz, CDCl
3
f
6
DMSO): δ = 8.87 (m, 8 H, pyr), 8.10 (d, J = 8.5 Hz, 2 H, 2,6-H
aryl), 8.05 (d, J = 8.3 Hz, 6 H, 2,6-H aryl), 7.26 (d, J = 8.5 Hz, 2
H, 3,5-H aryl), 7.21 (d, J = 8.3 Hz, 6 H, 3,5-H aryl), 4.32 (t, 2 H,
pyr), 8.11 (d, J = 7.5 Hz, 8 H, 2,6-H aryl), 7.27 (d, J = 7.5 Hz, 8
H, 3,5-H aryl), 5.47–3.93 (m, 4 ϫ 42 H, maltohexaose), 4.07 (t,
4
ϫ4 H, 1,3-H propyl), 2.25–1.99 (m, 4ϫ57 H, acetyl), –2.77 (br.
s, 2 H, NH) ppm. C352 204 (7997.30): calcd. C 52.87, H
.62, N 0.70; found C 52.77, H 5.74, N 0.67.
1-H ethyl), 1.59 (t, 3 H, 2-H ethyl), –2.76 (br. s, 2 H, NH) ppm.
H N O
446 4
5
5,10-Bis(4-ethoxyphenyl)-15,20-bis(4-hydroxyphenyl)porphyrin (10):
Compound 10 was obtained as a byproduct in the synthesis of 9.
5
-(4-Butoxyphenyl)-10,15,20-tris{4-[3-(nonadeca-O-acetyl-β-D-mal-
f
Yield: 74.9 mg (23%). R = 0.27 (chloroform/methanol, 20:1). The
tohexaosyl)propoxy]phenyl}porphyrin (6): A mixture of 1 (148.7 mg,
2
synthesis of 10 was described previously.[
38]
4.1 µmol), 1-iodobutane (41.0 µmol), and K
2 3
CO (33.3 mg,
0.24 mmol) in DMF (10 mL) was stirred for 5 d at room tempera-
5,15-Bis(4-ethoxyphenyl)-10,20-bis(4-hydroxyphenyl)porphyrin (11):
Compound 11 was obtained as a byproduct in the synthesis of 9.
ture. After filtration, the material was extracted with ethyl acetate,
washed with water and brine, and dried with sodium sulfate. The
solvent was removed under reduced pressure, and the residue was
Yield: 25.7 mg (8%). R
synthesis of 11 was described previously.[
,15,20-Tris(4-ethoxyphenyl)-20-(4-hydroxyphenyl)porphyrin (12):
Compound 12 was obtained as a byproduct in the synthesis of 9.
f
= 0.33 (chloroform/methanol, 20:1). The
38]
f
purified by column chromatography. Yield: 129.1 mg (86%). R =
5
1
0.19 (toluene/acetone, 2:1). H NMR (300 MHz, CDCl
3
): δ = 8.84
(m, 8 H, pyr), 8.11 (d, J = 8.3 Hz, 8 H, 2,6-H aryl), 7.23 (d, J =
1
Yield: 77.9 mg (23%). R
NMR (300 MHz, CDCl
f
= 0.50 (chloroform/methanol, 20:1). H
8
4
.3 Hz, 8 H, 3,5-H aryl), 5.47–3.76 (m, 3ϫ42 H, maltohexaose),
.06 (m, 14 H, 1,3-H propyl, 1-H hexyl), 2.24–1.98 (m, 3ϫ57 H,
3
): δ = 8.84 (d, 8 H, pyr), 8.06 (m, 6 H,
2
3
1
,6-H aryl), 7.98 (d, J = 8.5 Hz, 2 H, 2,6-H aryl), 7.19 (m, 6 H,
,5-H aryl), 7.01 (d, J = 8.5 Hz, 2 H, 3,5-H aryl), 4.23 (m, 3ϫ2 H,
-H ethyl), 1.56 (t, 3ϫ3 H, 2-H ethyl), –2.73 (br. s, 2 H, NH) ppm.
acetyl), 1.63 (m, 4 H, 2,3-H hexyl), 1.11 (t, 3 H, 4-H hexyl), –2.76
br. s, 2 H, NH) ppm. C279 154 (6223.77): calcd. C 53.84,
H 5.67, N 0.90; found C 53.37, H 5.58, N 0.87.
(
350 4
H N O
5,10,15,20-Tetrakis(4-ethoxyphenyl)porphyrin (13): Compound 13
5
-(4-Hexanoxyphenyl)-10,15,20-tris{4-[3-(nonadeca-O-acetyl-β-
D
-
was obtained as a byproduct in the synthesis of 9. Yield: 29.5 mg
(9%). The synthesis of 13 was described previously.[
39]
maltohexaosyl)propoxy]phenyl}porphyrin (7): mixture of
A
1
668
www.eurjoc.org
© 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Org. Chem. 2010, 663–671

Aggregation Properties of Tris(maltohexaose)-Linked Porphyrins
-(4-n-Decanoxyphenyl)-10,15,20-tris(4-hydroxyphenyl)porphyrin 5.47–3.76 (m, 3ϫ42 H, maltohexaose), 4.06 (m, 14 H, 1,3-H pro-
5
[
33,34]
(
14): p-THPP
decane (0.4  in DMF, 2.2 mL, 0.88 mmol) in the presence of
CO (608 mg, 4.40 mmol) in DMF (30 mL) at room temperature
(300 mg, 0.44 mmol) was treated with 1-bromo-
pyl, 1-H ethyl), 2.24–1.98 (m, 3ϫ57 H, acetyl), 1.62 (t, 3 H, 2-H
ethyl), –2.77 (br. s, 2 H, NH) ppm. C277 154 (6195.71):
calcd. C 53.70, H 5.63, N 0.90; found C 53.88, H 5.70, N 0.97.
H
346 4
N O
K
2
3
for 1 d and at 70 °C for 2 h. After filtration, the material was ex-
tracted with chloroform, washed with water and brine, and dried
with sodium sulfate. The solvent was removed under reduced pres-
sure, and the porphyrin derivatives having one to four decyl groups
5
-(4-Decanoxyphenyl)-10,15,20-tris{4-[3-(nonadeca-O-acetyl-β-
D-
maltohexaosyl)propoxy]phenyl}porphyrin (20): A mixture of 14
(
(
89.6 mg, 109.4 µmol), S-I (642.5 mg, 0.33 mmol), and K
150.6 mg, 1.09 mmol) in DMF (10 mL) was stirred for 5 d at room
2 3
CO
were separated by column chromatography. Yield: 118.3 mg (33%).
temperature. After filtration, the material was extracted with ethyl
acetate, washed with water and brine, and dried with sodium sul-
fate. The solvent was removed under reduced pressure, and the resi-
1
R
f
= 0.22 (chloroform/methanol, 20:1). H NMR (300 MHz, [D
6
]-
DMSO): δ = 8.89 (m, 8 H, pyr), 8.06 (d, J = 8.4 Hz, 2 H, 2,6-H
aryl), 7.98 (d, J = 8.3 Hz, 6 H, 2,6-H aryl), 7.27 (d, J = 8.4 Hz, 2
H, 3,5-H aryl), 7.21 (d, J = 8.3 Hz, 6 H, 3,5-H aryl), 4.20 (t, 2 H,
due was purified by column chromatography. Yield: 246.8 mg
1
(
36 %). R
f
= 0.23 (toluene/acetone, 2:1). H NMR (300 MHz,
1
3
-H decyl), 1.91 (m, 2 H, 2-H decyl), 1.58–1.19 (m, 14 H,
,4,5,6,7,8,9-H decyl), 0.90 (t, 3 H, 10-H decyl), –2.85 (br. s, 2 H,
CDCl
3
): δ = 8.84 (m, 8 H, pyr), 8.11 (d, J = 8.5 Hz, 8 H, 2,6-H
aryl), 7.27 (d, J = 8.5 Hz, 8 H, 3,5-H aryl), 5.47–3.76 (m, 3ϫ42
H, maltohexaose), 4.06 (m, 14 H, 1,3-H propyl, 1-H decyl), 2.24–
1.98 (m, 3ϫ57 H, acetyl), 1.60 (m, 3ϫ2 H, 2-H propyl), 1.32–1.21
(m, 14 H, 3,4,5,6,7,8,9-H decyl), 0.91 (t, 3 H, 10-H decyl), –2.77
(br. s, 2 H, NH) ppm. C285H362N O (6307.93): calcd. C 54.27,
NH) ppm.
,10-Bis(4-decanoxyphenyl)-15,20-bis(4-hydroxyphenyl)porphyrin
15): Compound 15 was obtained as a byproduct in the synthesis
of 14. Yield: 82.9 mg (20 %). R = 0.31 (chloroform/methanol,
0:1). H NMR (300 MHz, CDCl
d, J = 8.3 Hz, 4 H, 2,6-H aryl), 7.99 (d, J = 8.1 Hz, 4 H, 2,6-H
5
(
f
4
154
1
2
3
): δ = 8.84 (m, 8 H, pyr), 8.08 H 5.78, N 0.89; found C 54.15, H 5.88, N 0.90.
(
5
-(4-Hydroxyphenyl)-10,15,20-tris{4-[3-(β-D-maltohexaosyl)-
aryl), 7.23 (d, J = 8.3 Hz, 4 H, 3,5-H aryl), 7.03 (d, J = 8.1 Hz, 4
H, 3,5-H aryl), 4.19 (t, 2ϫ2 H, 1-H decyl), 1.95 (m, 2ϫ2 H, 2-H
decyl), 1.60–1.25 (m, 2ϫ14 H, 3,4,5,6,7,8,9-H decyl), 0.91 (t, 2ϫ3
H, 10-H decyl), –2.77 (br. s, 2 H, NH) ppm.
propoxy]phenyl}porphyrin (3MalTPP): Sodium methoxide in dry
methanol (2.0 mL, 2 wt.-%) was added to a solution of 1 (241.2 mg,
3
3
9.1 µmol) in dry THF (10.0 mL). After desalting by dialysis,
1
MalTPP was purified by freeze drying (126.5 mg, 86%). H NMR
5
,15-Bis(4-decanoxyphenyl)-10,20-bis(4-hydroxyphenyl)porphyrin
16): Compound 16 was obtained as a byproduct in the synthesis
of 14. Yield: 45.4 mg (11 %). R = 0.38 (chloroform/methanol,
): δ = 8.79 (d, J = 4.9 Hz, 4 H,
(
6
300 MHz, [D ]DMSO): δ = 9.97 (br. s, 1 H, -OH phenol), 8.81 (s,
(
8
2
=
4
–
H, pyr), 8.05 (d, J = 8.1 Hz, 6 H, 2,6-H aryl), 7.94 (d, J = 8.3 Hz,
H, 2,6-H aryl), 7.33 (d, J = 8.1 Hz, 6 H, 3,5-H aryl), 7.15 (d, J
8.3 Hz, 2 H, 3,5-H aryl), 5.80–2.96 (m, 3ϫ42 H, maltohexaose),
f
1
2
0:1). H NMR (300 MHz, CDCl
3
pyr), 8.77 (d, J = 4.9 Hz, 4 H, pyr), 8.01 (d, J = 8.6 Hz, 4 H, 2,6-
H aryl), 7.97 (d, J = 8.4 Hz, 4 H, 2,6-H aryl), 7.17 (d, J = 8.6 Hz,
.33 (m, 3ϫ4 H, 1,3-H propyl), 2.14 (m, 3ϫ2 H, 2-H propyl),
2.96 (br. s, 2 H, NH) ppm. MS (ESI): m/z = 3771.41. UV/Vis
4
H, 3,5-H aryl), 7.07 (d, J = 8.4 Hz, 4 H, 3,5-H aryl), 4.14 (t, 2ϫ2
–1
–1
(DMSO): λ (ε /  cm ) = 424 (383000), 520 (13900), 558 (11300),
H, 1-H decyl), 1.90 (m, 2ϫ2 H, 2-H decyl), 1.51–1.18 (m, 2ϫ14
H, 3,4,5,6,7,8,9-H decyl), 0.85 (t, 2ϫ3 H, 10-H decyl), –2.86 (br.
s, 2 H, NH) ppm.
–1
–1
5
2
95 (4500), 652 (6100) nm. UV/Vis (H O): λ (ε /  cm ) = 426
(
219000), 519 (12300), 558 (8500), 590 (4800), 649 (5100) nm.
5
-(4-Ethoxyphenyl)-10,15,20-tris{4-[3-(β- -maltohexaosyl)-
D
5
,15,20-Tris(4-decanoxyphenyl)-20-(4-hydroxyphenyl)porphyrin
17): Compound 17 was obtained as a byproduct in the synthesis
of 14. Yield: 85.3 mg (18 %). R = 0.58 (chloroform/methanol,
0:1). H NMR (300 MHz, CDCl ): δ = 8.86 (m, 8 H, pyr), 8.09
d, J = 8.5 Hz, 6 H, 2,6-H aryl), 8.05 (d, J = 8.4 Hz, 2 H, 2,6-H
propoxy]phenyl}porphyrin (1E3MalTPP): Sodium methoxide in dry
methanol (2.0 mL, 2 wt.-%) was added to a solution of 19
(
f
(
163.6 mg, 26.4 µmol) in dry THF (10.0 mL). After desalting by
1
2
3
dialysis, 1E3MalTPP was purified by freeze drying (91.2 mg, 91%).
(
1
H NMR (300 MHz, [D
J = 8.1 Hz, 8 H, 2,6-H aryl), 7.38 (d, J = 8.1 Hz, 8 H, 2,6-H aryl),
.61–3.03 (m, 3ϫ42 H, maltohexaose), 4.39–4.31 (m, 14 H, 1,3-H
propyl, 1-H ethyl), 2.20 (br. m, 3ϫ2 H, 2-H propyl), 1.54 (t, 3 H,
-H ethyl), –2.89 (br. s, 2 H, NH) ppm. MS (ESI): m/z = 3800.35.
6
]DMSO): δ = 8.87 (s, 8 H, pyr), 8.12 (d,
aryl), 7.25 (d, J = 8.5 Hz, 6 H, 3,5-H aryl), 7.15 (d, J = 8.4 Hz, 2
H, 3,5-H aryl), 4.23 (t, 3ϫ2 H, 1-H decyl), 1.98 (m, 3ϫ2 H, 2-H
decyl), 1.64–1.25 (m, 3ϫ14 H, 3,4,5,6,7,8,9-H decyl), 0.91 (t, 3ϫ3
H, 10-H decyl), –2.75 (br. s, 2 H, NH) ppm.
5
2
–
1
–1
5,10,15,20-Tetakis(4-decanoxyphenyl)porphyrin (18): Compound 18
UV/Vis (DMSO): λ (ε /  cm ) = 424 (447000), 520 (16200), 557
(12100), 596 (4900), 651 (6400) nm. UV/Vis (H O): λ (ε /  cm )
2
= 427 (227000), 521 (13600), 559 (9300), 595 (4800), 651 (5300)
nm.
–
1
–1
was obtained as a byproduct in the synthesis of 14. Yield: 28.9 mg
1
(
5%). R
f
= 0.19 (hexane/chloroform, 1:1). H NMR (300 MHz,
CDCl ): δ = 8.87 (m, 8 H, pyr), 8.08 (d, J = 8.5 Hz, 8 H, 2,6-H
3
aryl), 7.23 (d, J = 8.5 Hz, 8 H, 3,5-H aryl), 4.20 (t, 4ϫ2 H, 1-
H decyl), 1.95 (m, 4ϫ2 H, 2-H decyl), 1.50–1.25 (m, 4ϫ14 H,
5
-(4-Butoxyphenyl)-10,15,20-tris{4-[3-(β-D-maltohexaosyl)-
propoxy]phenyl}porphyrin (1B3MalTPP): Sodium methoxide in dry
methanol (2.0 mL, 2 wt.-%) was added to a solution of 6 (109.4 mg,
1
3,4,5,6,7,8,9-H decyl), 0.91 (t, 5ϫ3 H, 10-H decyl), –2.74 (br. s, 2
H, NH) ppm.
7.6 µmol) in dry THF (8.0 mL). After desalting by dialysis,
1
5
-(4-Ethoxyphenyl)-10,15,20-tris{4-[3-(nonadeca-O-acetyl-β-
D
-mal-
1B3MalTPP was purified by freeze drying (67.1 mg, 99%). H
NMR (300 MHz, [D ]DMSO): δ = 8.87 (s, 8 H, pyr), 8.10 (m, 8
2 3
CO (125.0 mg, H, 2,6-H aryl), 7.38 (m, 8 H, 2,6-H aryl), 5.57–3.06 (m, 3ϫ42 H,
tohexaosyl)propoxy]phenyl}porphyrin (19): A mixture of 9 (64.0 mg,
6
9
0
0.6 µmol), S-I (531.8 mg, 271.8 µmol), and K
.91 mmol) in DMF (20 mL) was stirred for 7 d at room tempera-
maltohexaose), 4.39–4.31 (m, 14 H, 1,3-H propyl, 1-H butyl), 2.20
(br. m, 3ϫ2 H, 2-H propyl), 1.91 (m, 2 H, 2-H butyl), 1.60 (m, 2
H, 3-H butyl), 1.07 (t, 3 H, 4-H butyl), –2.90 (br. s, 2 H, NH) ppm.
ture. After filtration, the material was extracted with ethyl acetate,
washed with water and brine, and dried with sodium sulfate. The
solvent was removed under reduced pressure, and the residue was
–
1
–1
MS (ESI): m/z = 3828.31. UV/Vis (DMSO): λ (ε /  cm ) = 424
purified by column chromatography. Yield: 215.5 mg (38%). R
f
=
(485000), 519 (18000) 557 (14400), 595 (5900), 652 (7600) nm. UV/
1
–1
–1
0.16 (toluene/acetone, 2:1). H NMR (300 MHz, CDCl
3 2
): δ = 8.84 Vis (H O): λ (ε /  cm ) = 427 (216000), 521 (14100), 560 (11100),
(m, 8 H, pyr), 8.11 (m, 8 H, 2,6-H aryl), 7.26 (m, 8 H, 3,5-H aryl), 594 (5600), 652 (5300) nm.
Eur. J. Org. Chem. 2010, 663–671
© 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
669

Y. Mikata,T. Kakuchi, S. Yano et al.
FULL PAPER
5
-(4-Hexanoxyphenyl)-10,15,20-tris{4-[3-(β-
D
-maltohexaosyl)-
ported by the Deutsche Forschungsgemeinschaft–Japan Society for
the Promotion of Science (DFG-JSPS) joint project (GZ: 446 JAP
113/347/0-1).
propoxy]phenyl}porphyrin (1H3MalTPP): Sodium methoxide in dry
methanol (2.0 mL, 2 wt.-%) was added to a solution of 7 (145.6 mg,
2
1
3.3 µmol) in dry THF (10.0 mL). After desalting by dialysis,
1
H3MalTPP was purified by freeze drying (89.6 mg, 100%).
H
[
[
1] R. Bonnett, Chem. Soc. Rev. 1995, 24, 19–33.
NMR (300 MHz, [D
6
]DMSO): δ = 8.80 (s, 8 H, pyr), 8.05 (m, 8
2] M. Ochsner, J. Photochem. Photobiol. B: Biology 1997, 39, 1–
H, 2,6-H aryl), 7.32 (m, 8 H, 3,5-H aryl), 5.55–2.96 (m, 3ϫ42 H,
maltohexaose), 4.33 (m, 3ϫ4 H, 1,3-H propyl) 4.20 (m, 2 H, 1-H
hexyl), 2.13 (br. m, 6 H, 2-H propyl), 1.84 (m, 2 H, 2-H hexyl),
18.
[3] E. S. Nyman, P. H. Hynninen, J. Photochem. Photobiol. B: Bio-
logy 2004, 73, 1–28.
[
4] D. M. Ratner, E. W. Adams, M. D. Disney, P. H. Seeberger,
1
6
.52 (m, 2 H, 3-H hexyl), 1.36 (m, 4 H, 4,5-H hexyl), 0.90 (t, 3 H,
-H hexyl), –2.96 (br. s, 2 H, NH) ppm. MS (ESI): m/z = 3855.66.
ChemBioChem 2004, 5, 1375–1383.
–1
–1
[5] K. Ohtsubo, J. D. Marth, Cell 2006, 126, 855–867.
UV/Vis (DMSO): λ (ε /  cm ) = 424 (433000), 519 (15500), 557
[
[
[
6] M. Momenteau, D. Oulmi, P. Maillard, A. Croisy, SPIE, Pho-
–
1
–1
(
11700), 596 (4600), 651 (6500) nm. UV/Vis (H
427 (206000), 521 (13300), 561 (9500), 594 (4600), 652 (5300)
nm.
2
O): λ (ε /  cm )
todynamic Therapy of Cancer II 1994, 2325, 13–23.
7] Y. Mikata, Y. Onchi, K. Tabata, S. Ogura, I. Okura, H. Ono,
S. Yano, Tetrahedron Lett. 1998, 39, 4505–4508.
=
8] Y. Mikata, Y. Onchi, M. Shibata, T. Kakuchi, H. Ono, S. Og-
ura, I. Okura, S. Yano, Bioorg. Med. Chem. Lett. 1998, 8, 3543–
5
-(4-Decanoxyphenyl)-10,15,20-tris{4-[3-(β-D-maltohexaosyl)-
propoxy]phenyl}porphyrin (1D3MalTPP): Sodium methoxide in dry
methanol (5.0 mL, 2 wt.-%) was added to a solution of 20
3548.
[
9] G. Csík, E. Balog, I. Voszka, F. Tölgyesi, D. Oulmi, P. Mail-
(797.8 mg, 126.5 µmol) in dry THF (30.0 mL). After desalting by
lard, M. Momenteau, J. Photochem. Photobiol. B: Biology
dialysis, 1D3MalTPP was purified by freeze drying (487.1 mg,
1998, 44, 216–224.
9
8
3
2
8%). 1H NMR (300 MHz, [D
.06 (m, 8 H, 2,6-H aryl), 7.32 (m, 8 H, 3,5-H aryl), 5.80–2.96 (m,
ϫ42 H, maltohexaose), 4.32 (m, 3ϫ4 H, 1,3-H propyl) 4.20 (m,
H, 1-H decyl), 2.13 (m, 3ϫ2 H, 2-H propyl), 1.84 (m, 2 H, 2-H
6
]DMSO): δ = 8.81 (s, 8 H, pyr),
[10] G. Zheng, A. Graham, M. Shibata, J. R. Missert, A. Oseroff,
T. J. Dougherty, R. K. Pandey, J. Org. Chem. 2001, 66, 8709–
8716.
[
11] X. Chen, L. Hui, D. A. Foster, C. M. Drain, Biochemistry 2004,
43, 10918–10929.
decyl), 1.51 (m, 2 H, 3-H decyl), 1.24 (m, 12 H, 4,5,6,7,8,9-H de-
[
12] M. Obata, S. Hirohara, K. Sharyo, H. Alimoto, K. Kajiwara,
S. Ogata, M. Tanihara, C. Ohtsuki, S. Yano, Biochem. Biophys.
Acta 2007, 1770, 1204–1211.
cyl), 0.82 (t, 3 H, 10-H decyl), –2.96 (br. s, 2 H, NH) ppm. MS
ESI): m/z = 3911.28. UV/Vis (DMSO): λ (ε / –1 cm ) = 424
422000), 519 (15400), 557 (12200), 594 (4800), 651 (6600) nm. UV/
–1
(
(
[
13] L. Flamigni, A. M. Talarico, B. Ventura, C. Sooambar, N. Sol-
O): λ (ε / –1 cm ) = 426 (211000), 521 (12700), 559 (9700),
–1
Vis (H
2
ladié, Eur. J. Inorg. Chem. 2006, 2155–2165.
595 (4100), 652 (5000) nm.
[14] R. Ballardini, B. Colonna, M. T. Gandolfi, S. A. Kalovidouris,
L. Orzel, F. M. Raymo, J. F. Stoddart, Eur. J. Org. Chem. 2003,
5
-(4-Hexadecanoxyphenyl)-10,15,20-tris{4-[3-(β-D-maltohexaosyl)-
288–294.
propoxy]phenyl}porphyrin (1HD3MalTPP): Sodium methoxide in
dry methanol (1.0 mL, 2 wt.-%) was added to a solution of 8
[
15] V. Sol, J. C. Blais, V. Carré, R. Granet, M. Guilloton, M. Spiro,
P. Krausz, J. Org. Chem. 1999, 64, 4431–4444.
16] G. Li, S. K. Pandey, A. Graham, M. P. Dobhal, R. Mehta, Y.
Chen, A. Gryshuk, K. Rittenhouse-Olson, A. Oseroff, R. K.
Pandey, J. Org. Chem. 2004, 69, 158–172.
[17] A. Iosif, U.-W. Grummt, J. Prakt. Chem. 1997, 339, 420–425.
18] I. Voszka, R. Galántai, P. Maillard, G. Csík, J. Photochem.
(47.3 mg, 7.4 µmol) in dry THF (5.0 mL). After desalting by dialy-
[
sis, 3HD1MalTPP was purified by freeze drying (21.4 mg, 72%).
1
H NMR (300 MHz, [D
H, 2,6-H aryl), 7.38 (m, 8 H, 3,5-H aryl), 5.60–3.07 (m, 3ϫ42
H, maltohexaose), 4.39 (m, 3ϫ4 H, 1,3-H propyl) 4.27 (m, 2 H,
-H hexadecyl), 2.20 (m, 3ϫ2 H, 2-H propyl), 1.88 (m, 2 H, 2-
H hexadecyl), 1.58 (m, 2 H, 3-H hexadecyl), 1.21–1.09 (m, 24 H,
,5,6,7,8,9,10,11,12,13,14,15-H hexadecyl), 0.82 (t, 3 H, 16-H hexa-
6
]DMSO): δ = 8.87 (s, 8 H, pyr), 8.12 (m,
8
[
Photobiol. B: Biology 1999, 52, 92–98.
1
[
[
19] C. Schell, H. K. Hombrecher, Chem. Eur. J. 1999, 5, 587–598.
20] S. M. Andrade, S. M. B. Costa, Chem. Eur. J. 2006, 12, 1046–
4
1057.
decyl), –2.89 (br. s, 2 H, NH) ppm. UV/Vis (DMSO): λ (ε /
[
21] S. Hirohara, M. Obata, S. Ogata, K. Kajiwara, C. Ohtsuki, M.
Tanihara, S. Yano, J. Photochem. Photobiol. B: Biology 2006,
84, 56–63.
–1
–1

cm ) = 424 (546000), 519 (20200), 557 (16100), 595 (6700), 651
8400) nm. UV/Vis (H
2
O): λ (ε / –1 cm ) = 428 (240000), 522
–1
(
(
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Acknowledgments
[
This research was supported by a Grant-in-Aid for Scientific Re-
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Received: August 18, 2009
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Published Online: December 17, 2009
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© 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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