Water-solubilization of alkyloxo(methoxo)porphyrinatoantimony bromides

Article abstract of DOI:10.1039/b911227h

In order to develop water-soluble porphyrins, alkyloxo(methoxo) porphyrinatoantimony bromides (alkyl = hexyl (1a), decyl (1b), dodecyl (1c), tetradecyl (1d), octadecyl (1e)) were prepared. 1 had more than 1 mmol dm ^-3 of solubility in water. Fr

Full text of DOI:10.1039/b911227h

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PAPER
www.rsc.org/pccp | Physical Chemistry Chemical Physics
Water-solubilization of alkyloxo(methoxo)porphyrinatoantimony
bromidesw
Jin Matsumoto,* Shin-ichiro Tanimura, Tsutomu Shiragami and Masahide Yasuda
Received 8th June 2009, Accepted 18th August 2009
First published as an Advance Article on the web 27th August 2009
DOI: 10.1039/b911227h
In order to develop water-soluble porphyrins, alkyloxo(methoxo)porphyrinatoantimony
bromides (alkyl = hexyl (1a), decyl (1b), dodecyl (1c), tetradecyl (1d), octadecyl (1e)) were
prepared. 1 had more than 1 mmol dmꢀ3 of solubility in water. From the dependence of the
half-width of the bands in the absorption spectra and surface tension on the concentration of 1,
it was estimated that 1b–d were present as aggregates in concentrations higher than
10 mmol dmꢀ3. From the NMR analysis in D2O, it was deduced that the alkyloxo ligands
of 1 were arranged alternately in the aggregates. The diameter of the aggregates of
1 in water was determined to be around 100 nm by the dynamic light scattering method.
Since the solubilities of di(methoxo)tetraphenylporphyrinatoantimony bromide and
5-(40-decyloxyphenyl)-10,15,20-triphenylporphyrinato(dimethoxo)antimony(V) bromide were low,
it was calculated that the long alkyl axial ligands were requisite for the high solubility in water.
Introduction
Experimental
Porphyrins have been widely utilized as biochemical and
biological functional chromophores.1 Bioactive porphyrins have
received much attention in connection with photo-sterilization2
and photodynamic therapy.3 For these purposes, the porphyrins
are required to have high photostability, high quantum yield of
the formation of singlet oxygen (1O2) and selective incorporation
into specific microorganisms or cells sites.4 Also, the water
solubility of the porphyrins is an important characteristic in
handling bio molecules in an aqueous solution. The synthesis of
the water-soluble porphyrins has usually been achieved through
the introduction of ionic groups such as pyridinium,5 sulfonate,6
and phosphonium5b,7 in porphyrin rings, although these ionic
porphyrins have less lipophilicity. Recently we have prepared the
water-soluble alkyloxo(methoxo)tetraphenylporphyrinatoantimony
bromide (1) (Scheme 1) by easily deriving it from commercially
available tetraphenylporphyrin.8,9 The formation of aggregates
was expected, since the solubility of 1 in water increases with
an increase in the alkyl chain length of 1. Here, the aggregation
structure of 1 in water will be elucidated by the measurements
of surface tension, absorption spectra, and NMR spectra.
Instruments
1H NMR (400 MHz) and 13C NMR (100 MHz) spectra were
taken in the CDCl3 and CD3OD using SiMe4 as an internal
standard with a Bruker AV 400M spectrometer. The NMR
spectra in D2O and a D2O–CD3OD mixed solvent were taken
by a pre-saturation method using dioxane as an internal
standard (d = 3.575 ppm). Matrix-assisted laser desorption/
ionization mass spectra (MALDI-MS) were measured on a
Bruker Daltonics Autoflex III TOF/TOF in the positive ion
mode. Calibration of the mass number was performed by the
internal standard method using polyethyleneglycol. UV-Vis
spectra of the solutions were obtained with a JASCO V-550
spectrophotometer.
The surface tensions were measured on a Kyowa Kaimen
Kagaku CBVP-Z at 25 1C using a Wilhelmy Pt plate. Dynanic
light scattering (DLS) was measured for the aqueous solution
of 1 (1 mmol dmꢀ3) at 25 1C by an Otsuka Electronics
FPAR-1000 equipped with a probe for diluted solutions. For
these measurements, the 1 was dissolved in pure water purified
by Millipore Elix III and was filtered through a membrane
filter with a 1 mm pore size.
Preparation of methoxo(octadecyloxo)tetraphenylporphyrinato-
antimony(V) bromide (1e). The preparation of 1e was
performed by a reaction of bromo(methoxo)tetraphenyl-
porphyrinatoantimony bromide (123 mg)10 with 1-octadecanol
(2.0 g) in MeCN–pyridine (40 : 3, 43 cm3) under heating at
80 1C until the Soret band shifted from 423 to 419 nm. After
the reaction mixture cooled to room temperature, the excess
alkanol was removed by filtration and reprecipitation with
hexane. After the evaporation of the solvents, 1e was isolated
by column chromatography on SiO2 (Fuji Silysia BW 300)
with CHCl3–MeOH (9 : 1 v/v) as the eluent.
Scheme 1 Alkyloxo(methoxo)porphyrinatoantimony bromides (1).
Department of Applied Chemistry, Faculty of Engineering,
University of Miyazaki, Gakuen-Kibanadai, Miyazaki 889-2192,
Japan. E-mail: jmatsu@cc.miyazaki-u.ac.jp
w Electronic supplementary information (ESI) available: NMR and
NOESY spectra. See DOI: 10.1039/b911227h
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1e. Yield 28%. 1H NMR (CDCl3) d = ꢀ2.57 (t, J = 6.2 Hz,
2H), ꢀ2.19 (s, 3H), ꢀ2.01–ꢀ1.94 (m, 2H), ꢀ1.63 (quint, J =
7.6 Hz, 2H), ꢀ0.34 (quint, J = 7.6 Hz, 2H), 0.32 (quint, J =
7.6 Hz, 2H), 0.68 (quint, J = 7.6 Hz, 2H), 0.88 (t, J = 6.9 Hz, 3H),
0.91 (quint, J = 7.6 Hz, 2H), 1.01–1.08 (m, 2H), 1.01–1.32
(m, 18H), 7.91–8.02 (m, 12H), 8.28–8.29 (m, 4H), 8.35–8.37
(m, 4H), 9.56 (s, 8H); 13C NMR (CDCl3) d = 14.09, 22.67,
23.20, 27.70, 28.28, 28.85, 29.13, 29.34, 29.41, 29.52,
29.60, 29.64, 29.64, 29.68, 29.68, 29.68, 31.90, 45.82, 58.02,
122.98, 127.90, 127.95, 128.03, 128.11, 130.03, 133.86,
134.72, 134.83, 138.15, 146.03; UV-Vis (in MeOH)
7.98–8.05 (m, 9H), 8.33 (d, J = 8.5 Hz, 2H), 8.41–8.43 (m, 6H),
9.70 (s, 4H), 9.70 (d, J = 5.1 Hz, 2H), 9.78 (d, J = 5.1 Hz, 2H).
5-(40-Decyloxyphenyl)-10,15,20-triphenylporphyrinato(dimeth-
1
oxo)antimony(V) bromide (2). Yield 36%. H NMR (CD3OD)
d = ꢀ2.13 (s, 6H), 0.93 (t, J = 6.9 Hz, 3H), 1.35–1.46
(m, 10H), 1.48–1.55 (m, 2H), 1.63–1.70 (m, 2H), 1.97–2.04
(m, 2H), 4.33 (t, 2H), 7.50 (d, J = 8.7 Hz, 2H), 7.95–8.04
(m, 9H), 8.30 (d, J = 8.7 Hz, 2H), 8.38–8.40 (m, 6H), 9.65
(d, J = 5.0 Hz, 2H), 9.65 (s, 4H), 9.72 (d, J = 5.0 Hz, 2H); 13
C
NMR (CD3OD) d = 14.46, 23.75, 27.30, 30.49, 30.49, 30.58,
30.74, 30.80, 33.09, 46.12, 69.62, 115.14, 124.12, 124.32,
124.90, 129.03, 129.03, 130.96, 130.96, 131.69, 134.98,
135.02, 135.10, 135.34, 135.99, 135.99, 137.52, 139.79,
139.80, 139.80, 147.42, 147.49, 147.59, 147.92; UV-Vis
(in MeOH) lmax/nm (e/104 dm3 molꢀ1 cmꢀ1) 420 (20.7)
554 (1.42) 596 (1.08); Exact mass (MALDI-MS) calcd. for
C56H54N4O3Sb [M+]: 951.3234. Found: 951.3268.
l
max/nm (e/104 dm3 molꢀ1 cmꢀ1) 419 (48.4) 551 (1.78) 591
(1.01); Exact mass (MALDI–MS) calcd. for C63H68N4O2Sb
[M+]: 1033.4380. Found: 1033.4302.
Preparation of 5-(40-decyloxyphenyl)-10,15,20-triphenyl-
porphyrinato(dimethoxo)antimony(V) bromide (2). According
to the Lindsey method,11 benzaldehyde (0.92 cm3; 9.0 mmol)
and BF3ꢂOEt2 (0.20 cm3) were added to a CHCl3 solution
(500 cm3) of 4-decyloxybenzaldehyde (0.79 g; 3.0 mmol).
A CHCl3 solution (300 cm3) of pyrrole (0.83 cm3; 12.0 mmol)
was added to the solution and stirred at room temperature
until the color of the solution turned from a pale orange
to a red–violet. NEt3 (0.67 cm3; 9 mmol) and chloranil
(2.20 g; 9.0 mmol) were added to the solution and then heated
at 80–90 1C for 1 h under dark conditions. After evaporation,
the condensed solution was filtered and extracted with
CH2Cl2–hexane (2 : 1). The crude product was subjected to
column chromatography on SiO2 using CH2Cl2–hexane
(1 : 3 v/v) to yield 5-(40-decyloxyphenyl)-10,15,20-triphenyl-
porphyrin (3).
A pyridine solution (15 cm3) of SbBr3 (0.80 g) was added to
a dry pyridine (15 cm3) solution of 3 (0.10 g). The mixture was
heated at 130 1C under dry conditions until the Soret band
shifted from 413 to 466 nm. The solution was treated with Br2
(1 cm3) at room temperature for 30 min to give dibromo-
antimony(V) 5-(40-decyloxyphenyl)-10,15,20-triphenylporphyrin
bromide (4). A MeOH solution (20 cm3) of 4 (50 mg;
0.044 mmol) was heated at 80 1C until the Soret band shifted
from 429 to 420 nm. After evaporation, the crude 2 was
purified by column chromatography on SiO2 using
CH2Cl2–MeOH (20 : 1–10 : 1 v/v).
Results and discussion
Preparation and solubility of
tetraphenylporphyrinatoantimony(V) bromides
In our previous report,8 cationic tetraphenylporphyrinato-
antimony(V) (Sbtpp) complexes having axial hydroxo and
methoxo ligands were found to be to some extent water-
soluble. The methoxo-Sbtpp type had a higher water-solubility
than the hydroxo-Sbtpp type. Therefore, our attention is
focused on 1 ([Sb(OMe)(OR)(tpp)]Br).
The preparations of 1 started from the partial solvolysis of
Br ligand of dibromotetraphenylporphyrinatoantimony bromide
([SbBr2(tpp)]Br) with MeOH to give [Sb(OMe)Br(tpp)]Br,
which underwent the Br-ligand exchange with alcohols
(ROH) in the presence of pyridine (Scheme 2).8,9 1 (5 mg)
was suspended in pure water (1 cm3) and was left to stand for
3 days. The supernatant solution (40 ꢃ 10ꢀ3 cm3) was moved
to another vessel and was diluted with MeOH (50 cm3) to
measure the absorption spectra. The molar amounts of 1 in
MeOH solution were measured using absorbance and molar
absorption coefficient (e) with a Soret band in MeOH listed in
Table 1. The measured molar amounts was converted to the
saturated concentration of original aqueous solution of 1
which was defined as the solubility (Cs). The values of Cs are
summarized in Table 1. The Cs values of 1a–e were determined
5-(40-Decyloxyphenyl)-10,15,20-triphenylporphyrin (3). Yield
18%. 1H NMR (CD3OD) d = ꢀ2.76 (s, 2H), 0.91 (t, J = 6.7
Hz, 3H), 1.26–1.49 (m, 12H), 1.58–1.65 (m, 2H), 1.94–2.01
(m, 2H), 4.23 (t, J = 6.5 Hz, 2H), 7.26 (d, J = 8.6 Hz, 2H),
7.79–7.72 (m, 9H), 8.10 (d, J = 8.5 Hz, 2H), 8.20–8.22
(m, 6H), 8.83 (m, 6H), 8.88 (d, J = 4.7 Hz, 2H); 13C NMR
d = 14.15, 22.72, 26.24, 29.38, 29.51, 29.54, 29.64, 29.68,
31.95, 68.34, 112.74, 119.92, 120.05, 120.21, 126.66, 126.66,
127.67, 127.67, 130.98, 134.56, 134.56, 135.60, 142.21, 142.24,
142.24, 159.02; Exact mass (MALDI–MS) calcd. for
C54H50N4O [M+]: 770.3985. Found: 770.4033.
to be more than 1.0 mmol dmꢀ3
.
The bio affinity of 1 has already been elucidated through
photochemical sterilization toward Saccharomyces cerevisiae,
showing that 1 was required to be amphiphilic for efficient
sterilization.9 Moreover, the quantum yields for the formation
1
of O2 have been reported to be 0.48–0.65 for 1.9
5-(40-Decyloxyphenyl)-10,15,20-triphenylporphyrinato(dibromo)-
antimony(V) bromide (4). Yield 86%. 1H NMR (CDCl3) d = 0.93
(t, J = 7.0 Hz, 3H), 1.28–1.52 (m, 12H), 1.67 (m, 2H), 2.01
(m, 2H), 4.35 (t, J = 6.3 Hz, 2H), 7.54 (d, J = 8.5 Hz, 2H),
Scheme 2 Synthetic routes of 1.
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Table 1 The properties of 1a–e
CAC/10ꢀ5
HWd
M
Dd (ppm)f
ge
Me
MeO
MWa
eb/105 Mꢀ1 cmꢀ1
Cs/mMc
d/nmg
h
h
1a
1b
1c
1d
1e
946.6
1002.7
1030.7
1058.8
1114.9
3.98
4.61
3.74
4.08
4.84
1.09
2.10
2.21
2.40
1.92
—
—
ꢀ1.36
ꢀ1.94
ꢀ1.88
ꢀ1.73
ꢀ1.45
ꢀ0.29
ꢀ0.04
ꢀ0.02
0.06
115.0
155.4
119.4
187.6
118.3
2.0
1.0
2.0
1.0
1.0
2.0
h
—
h
—
0.11
Molecular weight. Molar absorption coefficient of Soret band in Mꢀ1 cmꢀ1 (M = mol dmꢀ3) determined in MeOH. Saturated concentration
a
b
c
d
e
in water. Critical aggregation concentrations (CAC) were determined from HW. CAC were determined from surface tension (g) measurement.
Dd of Me group on alkyl chain (Me) and axial MeO ligand (MeO) determined from 1H NMR spectra in CD3OD and D2O (see the ESIw). The
f
g
average size of aggregates (d) measured by the DLS. Not observed at the concentration of 1.0 ꢃ 10ꢀ6–1.0 ꢃ 10ꢀ4 M.
h
Measurements of absorption spectra and surface tension for
an aqueous solution of 1
Usually, the aggregation of porphyrins results in a shift of
the maximum absorption wavelength and/or broadening of
the Soret band.5a,12 Absorption spectra were measured for
the aqueous and MeOH solutions at various concentrations of
1 ([1]). An example of the absorption spectra of 1b in water
is shown in Fig. 1, where the spectra are normalized by
their maximum absorbance at the Soret band. This shows
that the broadening of the spectra took place with an
increase in [1b], but the maximum absorption wavelength
was scarcely shifted. The peak widths at the half height
(HW) were changed in a step-wise manner by [1], as shown
in Fig. 2. The HW of 1b in water remained constant at 14 nm
when [1b] o 8 ꢃ 10ꢀ6 mol dmꢀ3. With an increase of [1b] up to
2.0 ꢃ 10ꢀ5 mol dmꢀ3, HW increased from 14 to 17.4 nm.
HW remained constant at 17.4 nm when [1b] 4 2.0 ꢃ
10ꢀ5 mol dmꢀ3. Similar behaviors were observed for 1c and
1d. Therefore, it is suggested that 1b–d behave as aggregates
in water. In the case of 1a and 1e, HW kept nearly constant
values of 13 nm for 1a and 20 nm for 1e, showing that a
Fig. 2 Dependence of HW on [1]: 1a (.), 1b (J), 1c (n), 1d (&),
and 1e (E) in water and 1b (+) in MeOH.
g decreased until [1] reached 1 ꢃ 10ꢀ5 mol dmꢀ3 where the
breakpoint appeared. In the cases of 1a and 1e, however, a
clear breakpoint did not appear. It is well known that the
breakpoint corresponds to the critical micelle concentration
required for the aggregation of various surfactants.13
Therefore, 1b–d formed aggregates in the aqueous solutions
of more than the critical aggregation concentrations (CAC)
obtained from HW and g (Table 1).
breakpoint
did
not
appear
in
the
range
of
1 ꢃ 10ꢀ6 mol dmꢀ3 to 1 ꢃ 10ꢀ4 mol dmꢀ3. On the other
hand, HW in MeOH remained constant at 11.7 nm irrespective
of the increase of [1], as shown in Fig. 2 as a typical example
of 1b. This suggests that 1 did not aggregate in MeOH.
The surface tensions (g) were measured for given concentrations
of aqueous solutions of 1 (Fig. 3). In the cases of 1b–d,
Fig. 1 Spectral changes in UV-Vis of 1b in water. Spectra are
Fig. 3 Plots of surface tension (g) against [1] in water: 1a (.), 1b (J),
1c (n), 1d (&), and 1e (E).
normalized at maximum absorbance.
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1
Measurements of H NMR spectra of 1 in water
in same side of MeO ligand and in the opposite side of MeO
ligand, respectively (see the ESI, Fig. S2w). The peaks of one
ortho proton (Ho0) and one meta proton (Hm0) shifted to a
higher field, and those of another ortho and meta protons
(Ho and Hm) kept their original positions. The selected values
of Dd are listed in Table 1.
High Cs of 1 enabled us to estimate the aggregation structure
1
of 1 by the H NMR spectra in D2O. The NMR spectra of 1
were remarkably broadened in D2O, as shown in a typical
example of 1b of Fig. 4. The NMR spectra of 1 other than 1b
were shown in Fig. S1 (see the ESIw). In order to assign the
spectra in D2O, the NMR spectra were measured in a mixed
D2O–CD3OD solvent with various solvent ratios. The 1H
NMR spectrum of 1b in CD3OD was correctly assigned by
the comparison with the spectra of the analogous complex,10
and by the 1H–1H COSY technique. By shielding effects of the
porphyrin ring, the methylene protons (Ha–Hi) on the axial
alkyloxo ligand appeared in a higher field (ꢀ2.51–1.25 ppm)
compared with normal alcohols. As an increase in content of
D2O in CD3OD–D2O, the peak of the terminal methyl group
(Hj) largely shifted to a higher field compared with other
methylene protons. The anisotropic shifts were evaluated by
the difference of the chemical shifts (Dd) in CD3OD and D2O.
Fig. 5 shows the plots of Dd against the D2O contents. The Dd
values of the terminal methyl group (Hj) and the methylene
protons (Hf–Hi) located close to the terminal were large,
whereas the Dd of the methylene protons (Ha) located close
to the antimony atom were smaller. Also the MeO protons
(Hk) kept their original positions. Moreover, two ortho
(Ho and Ho0) and two meta (Hm and Hm0) protons of the
phenyl group were unequivalently observed around 8.4 and
7.9 ppm, respectively, showing that the peripheral phenyl
groups were twisted to the porphyrin ring. By NOESY
spectra, the Ho and Ho0 were assigned to be the protons located
Structure of aggregate
From the anisotropic shift in the NMR spectra, we estimated
the structure of the aggregate where the terminal Me group of
1 was located on the position close to another porphyrin ring
but the MeO ligand was located on the opposite side to make a
bilayer structure, as shown in Scheme 3. Therefore, the
cationic porphyrin moiety overlapped each other in an
edge-to-edge manner, accompanying the hydrophobic inter-
action of alkyl chains to form an aggregate. This can reasonably
explain the extremely high field-shift of Hj protons and
anisotropic high field shifts of Hm0 and Ho0 protons. The
bilayer structure was repeatedly accumulated to form aggregates.
Diameters of the aggregates of 1 in water were determined
to be around 100 nm by the DLS method (Fig. 6, Table 1).
Therefore, the aggregates of 1 were not normal spherical
micelles found for typical surfactants.13
Free base meso-tetraphenylporphyrin is poorly soluble, even
in organic solvents, because of the formation of aggregates
through p–p stacking (J- and H-aggregations) between the
porphyrin rings.14 1a–e having MeO and alkyloxo ligands
were soluble not only in water, but also in some organic
solvents such as dioxane, CHCl3, MeCN, and MeOH.8
Fig. 4 1H NMR spectra of 1b in mixed solvents of CD3OD and D2O. The symbols * and # denote the peak of impurities and TMS, respectively.
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Fig. 5 Dependence of Dd for (A) the axial ligands and (B) the peripheral phenyl groups on the contents of D2O in the mixed solvent in the
1H NMR spectra of 1b.
Scheme 4
face-to-face dimer structure, rather than
a micelle-like
structure, presumably due to hydrogen bonding formed
between the HO ligands or OH–p interactions between the
HO ligands and the porphyrin rings. Also di(methoxo)tetra-
phenylporphyrinatoantimony bromide (1g) was poorly soluble
in water: Cs(1g) = 0.13 mmol dmꢀ3. Therefore, a long
alkyl chain is requisite for the high Cs. However, the Cs of
5-(40-decyloxyphenyl)-10,15,20-triphenylporphyrinato(dimethoxo)-
antimony(V) bromide (2) was poorly soluble in water; CS(2) =
0.42 mmol dmꢀ3. Thus, the long alkyl chain substituted on a
peripheral phenyl group did not operate effectively to enhance
the Cs. Therefore, the formation of edge-to-edge aggregation
and the breaking up of face-to-face aggregation is favorable
for the water-solubilization of porphyrin. Thus, controlling
the aggregation structure is important for solubility in water.
Scheme 3 Plausible structure of aggregate of 1.
Conclusion
The photostability and photocatalytic activity of Sbtpp
chromophore has been confirmed by dechlorination15 and
epoxidation16 under visible light irradiation. Bioaffinity of
Sbtpp has been confirmed by photochemical sterilization of
Escherichia coli,17 Legionella pneumophila,18 and Saccharomyces
cerevisiae.9 The hydrophobic/hydrophilic properties of the
porphyrins strongly affected the binding capability to micro-
organisms.3 So far the amphiphilic porphyrin derivatives have
Fig. 6 Distribution of aggregate size of 1 measured by the DLS method.
However, the Cs of hexyloxo(hydroxo)tetraphenylporphyrinato-
antimony bromide (1f) was low (0.08 mmol dmꢀ3) (Scheme 4).
Therefore, the hydroxo ligand of 1f accelerated to form a
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been prepared by the introduction of a sugar,19 polyethylene-
oxide20 or peptide21 into non-ionic porphyrins, or that of alkyl
moieties22 into ionic porphyrins to use in photodynamic therapy.
We can easily synthesize the water-soluble porphyrins from
commercially available tetraphenylporphyrin. Thus, compounds
such as the series 1, with hydrocarbon chains of various lengths,
are good candidates as bioactive photosensitizers.
12 K. Kano, K. Fukuda, H. Wakami, R. Nishiyabu and
R. F. Pasternack, J. Am. Chem. Soc., 2000, 122, 7494–7502.
13 M. J. Rosen, Surfactants and Interfacial Phenomena, Wiley,
New York, 2nd edn, 1989.
14 (a) P. Hambright, The Porphyrin Handbook, ed. K. M. Kadish,
K. M. Smith and R. Guilard, Academic Press, New York, 2000,
vol. 3, ch. 18, pp. 129–210; (b) S. Okada and H. Segawa, J. Am.
Chem. Soc., 2003, 125, 2792–2796.
15 T. Shiragami, Y. Shimizu, K. Hinoue, Y. Fueta, K. Nobuhara,
I. Akazaki and M. Yauda, J. Photochem. Photobiol., A, 2003, 156,
115–119.
16 T. Shiragami, R. Makise, Y. Inokuchi, J. Matsumoto, H. Inoue
and M. Yasuda, Chem. Lett., 2004, 33, 736–737.
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