Porphyrin-Hyperbranched Copolymer Films as Recyclable Photooxidation Catalysts for 1,5-Dihydroxynaphthalene

Article abstract of DOI:10.1002/cctc.201701219

Novel and stable films were easily assembled at the water–chloroform interface by noncovalent interaction between meso-tetrakis(4-sulfonatophenyl)porphyrins (H₂TPPS, FeTPPS, and ZnTPPS) and polypeptide-containing hyperbranched copolymers of various molecular weights. These films could be used as recyclable heterogeneous photocatalysts for the oxidation of 1,5-dihydroxynaphthalene. Conversion yields of 91 and 88 % were obtained for H₂TPPS and FeTPPS, respectively, and these values were much higher than those obtained for the corresponding porphyrin systems without polymers. These films could be easily utilized over 10 catalytic runs with only a slight decrease in the catalytic activity and low porphyrin loss. No separation or purification of either the catalyst or product was necessary, which proved that these porphyrin–hyperbranched copolymer films could be efficient, robust, and recyclable photooxidation catalysts.

Full text of DOI:10.1002/cctc.201701219

Accepted Article
Title: Porphyrin-hyperbranched copolymer films as recyclable
photooxidation catalysts for 1, 5-dihydroxynaphthalene
Authors: Qizhi Ren, kaifang sun, lintong guo, cheng cai, and
zongsheng hou
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To be cited as: ChemCatChem 10.1002/cctc.201701219
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Porphyrin-hyperbranched copolymer films as recyclable
photooxidation catalysts for 1, 5-dihydroxynaphthalene
Kaifang Sun, Lintong Guo, Cheng Cai, Zongsheng Hou and Qizhi Ren*
Dedication ((optional))
Abstract: Novel and stable films can be easily assembled at water-
on an efficient catalytic system in aqueous phase consisting of
FeTPPS and polyamidoamine dendrimers, which is efficient for
H O oxidation of trichlorophenol in water. All these examples
2 2
chloroform interface by noncovalent interaction between meso-
[
8]
2
tetrakis (4-sulfonatophenyl) porphyrins (H TPPS, FeTPPS and
ZnTPPS) and polypeptide-containing hyperbranched copolymers of
various molecular weights. These films can be used as recyclable
heterogeneous photocatalysts for 1, 5- dihydroxynaphthalene
oxidation. Conversion yields of 91% and 88% could be obtained for
suggested that the architecture of the designed dendritic
polymers such as hyperbranched polymers and dendrimers can
give rise to efficient recyclable catalytic systems for
2 2
photooxidation using H O as an environment-friendly oxidant.
H
2
TPPS and FeTPPS respectively which were much higher than for
The question was therefore whether it would be possible to
develop a porphyrin/dendritic polymer system involving rather a
heterogeneous system. This would be more advantageous for
the reuse and recycling of the water soluble porphyrin catalysts.
the corresponding porphyrin systems without polymers. These films
can be easily utilized over 10 catalytic runs with only a slight
decrease in catalytic activity and low porphyrin loss. No separation
and purification for both catalyst and products were necessary
proving that these porphyrin-hyperbranched copolymer films can be
efficient,robust and recyclable photooxidation catalysts.
We report here on a novel, stable film catalytic system,
which can be easily assembled at water-chloroform interface by
noncovalent
interaction
between
meso-tetrakis
(4-
sulfonatophenyl) porphyrins (H
2
TPPS, FeTPPS and ZnTPPS)
Porphyrin-containing proteins such as Cytochrome P450
monooxygenase (P450) have been investigated for several
decades due to their wonderful catalytic efficiency and other
important roles. Considerable attention has been focused on the
laboratory-synthesized porphyrins to mimic the wide range of
and polypeptide-containing hyperbranched polymers. These
films showed high retention for the photodegradation of 1, 5-
dihydroxynaphthalene. The reactant and product can be
distributed in different phases during the catalytic process, which
means convenient recycling of the catalytic system.
[
1]
oxidation reactions of these enzymes. Among these artificial
porphyrin compounds, the synthesis of the water soluble
porphyrins is of vital importance in medicinal purposes such as
[2]
DNA cleavage catalysts, photosensitizers for photodynamic
[
3]
[4]
therapy and wastewater treatments. Water soluble sulfonated
porphyrins are of particular importance, they have been proven
to be excellent sensitizers for singlet oxygen generation that are
[
5]
currently used under homogeneous conditions. Although high
catalytic activity is the advantage for these homogeneous
porphyrin catalysts, these systems cannot be commercialized
because of the difficulties associated with the catalyst separation,
recovery and recycling. Immobilization of porphyrins on supports
such as synthetic polymers, silicon materials and carbon
nanotubes, is especially important to investigate in order to
[6]
develop efficient heterogeneous catalysts.
We have reported on a P450 biomimetic catalytic system
consisting of a water-soluble porphyrin FeTPPS and dendritic
polymers in CHCl
porphyrins which had been phase-transferred from the water
phase to the CHCl phase by hyperbranched polymers. Good
catalytic activities and recyclabilities were observed for styrene
3
phase. The catalysts were encapsulated
3
Scheme 1. Structures of (A) the porphyrins (H TPPS, FeTPPS and ZnTPPS),
2
and (B) the hyperbranched PEI-PZLys multiarm copolymers 1, 2 and 3, with
different n value.
[
7]
epoxidation and ethylbenzene hydroxylation. Later we reported
K. Sun, L. Guo, C. Cai, Z. Hou and Prof. Q. Ren
School of Chemistry and Chemical Engineering
Shanghai Jiaotong University
Shanghai 200240 (PR China)
Fax: (+86)21-54741297
Three hyperbranched amphiphilic multiarm PEI-PZLys
copolymers 1-3 have been synthesized with a number average
4
molecular weight of 2.6, 5.0 and 7.510 respectively (scheme
E-mail: qzren@sjtu.edu.cn
1). Their synthesis and characterization details are given in
Supporting information (SI). These polymers have hydrophilic
core - hydrophobic shell structures. Water-soluble porphyrins
Supporting information for this article is given via a link at the end of
the document.
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COMMUNICATION
H
2
TPPS, FeTPPS and ZnTPPS can be phase transferred and
encapsulated into the hydrophilic PEI core of the polymer in the
CHCl phase. As we expected, all porphyrins in water phase
could be successfully phase transferred to the CHCl phase by
aqueous phase quickly after shaking. The pH value and the
porphyrin concentration (determined by Uv-vis spectroscopy) in
both water and chloroform phase were measured and the
3
3
2
percentage of the porphyrin H TPPS in the water and chloroform
polymers 1-3, respectively. The corresponding phase transfer
abilities of polymers 1-3 for the porphyrins have been tested by
phases were plotted against the pH value (Figure 2). The most
interesting and fundamental point is that the porphyrin can not
be released to the aqueous phase under strong acid conditions
(pH  4.2), instead a purple floc formed at the water-chloroform
interface (Figure 1V) and both water and chloroform phases
were colorless. Similar results were observed for the phase
transfer systems formed from the other porphyrins (FeTPPS and
ZnTPPS) and polymers respectively 1 and 3.
measuring
porphyrin/polymer. For example, for H
1
2
the
molar
ratio
of
phase
TPPS, 11.6, 23.6 and
1.2 moles could be encapsulated into one mole of polymers 1,
and 3, respectively (see SI). The phase transfer abilities for
transferred
2
porphyrins FeTPPS and ZnTPPS have the same order: 1<3<2.
[
9]
Polymers 1-3 have the amphiphilic core-shell structure. For
polymer 1, its smallest molecular weight and the smallest
particle size means the least numbers of the hydrophobic PZLys
groups in the outer shell (see DLS results in SI). Its solubility in
The stable presentation of the porphyrin-polymer floc (>7
days) gave us the revelation that suitable porphyrin films might
be stably self-assembled at the interface of H
Four concentrations of encapsulated porphyrins 100, 50, 10 and
μM have been prepared first, then pH value 4.0 were adjusted
2 3
O-CHCl phase.
3
CHCl phase was indeed the lowest, the low phase transfer
ability for porphyrins might be due to its own unstable state in
the organic phase; For polymer 3, the increased PZLys groups
in the outer shell part might cause the increase of the steric
hindrance for the porphyrin approaching into its hydrophilic core;
For one mole of polymer 2, about 23.6 molars of H TPPS can be
2
encapsulated, its biggest phase transfer ability might be related
to the suitable amphiphilic structure, which can balance the
1
for the upper aqueous layer, the well assembled films were
gradually formed (Figure 3). It is shown that all of the porphyrins
can stay well at the interface of water-chloroform phase. The
higher the concentration of the porphyrins, the thicker the
interface films. These observations provide the proof that
various well assembled films can be well designed by adjusting
porphyrin concentrations and pH value and formation time.
polymer solubility in CHCl
PZLys groups.
3
and the steric hindrance caused by
Figure 1. pH-sensitive release and encapsulation of H
2
TPPS by polymer 2.
Figure 3. Photos of assembly H TPPS-polymer 2 film at water-chloroform
2
phase, the concentrations of encapsulated porphyrin is 100，50，10，1uM,
from left to right. pH value of the water phase is 4.0.
I
1
00
1
[10]
The porphyrin-polymer films were analyzed using HNMR,
IV
1
IR, Uv-vis and TEM. Figure S8 in SI shows the HNMR spectra
5
0
II
for the H
CDCl and DMSO-d6:CDCl
to find the suitable D-reagent to dissolve the porphyrin-polymer
film, a 1:1 mixture of CDCl and DMSO-d6 was used to partially
2
TPPS, polymer 2 and H
2
TPPS-2 film in DMSO-d6,
V
0
3
3
=1:1 solvents. Since it was difficult
-50
3
III
dissolve these films. Inspite of the weak peak intensities and
high baseline, the 1.1-1.5, 3.1 and 5.0ppm signals show the
existence of different proton peaks of the polymer, the 8.2 ppm
signals belong to the phenyl protons of the porphyrin.
-100
0
2
4
6
8
10 12 14
pH
Figure 2. The percentage of H
TPPS-2 systems during the pH triggering. The representations of I-V
reference Figure 1.
2
TPPS in water and chloroform phases in
The IR spectra for H TPPS, 2 and H TPPS-2 are shown in
2
2
H
2
-1
Figure S9 in SI, the strong 1650, 1536 and 1453 cm belonging
-1
to the acid amide bonds of amino acids; 3057cm belonging to
-
1
stretching vibration peak of aromatic hydrogen, 1850-1950cm
[
11]
peaks are assigned to phenyl vibration peak of amino acide;
It is worth noting that all of the encapsulated porphyrins in
the chloroform phase could be released back to the water phase
by adjusting the pH value of the water phase. This pH-triggered
release is shown in Figures 1 and 2. Upon addition of acid or
alkali solutions into the vial, the porphyrin could be partially or
completely released from the PEI-PZLys and diffused to the
-1
the 1040 and 1190 cm strong peaks belong to the C-N and C-H
stretching vibration of porphyrin pyrrole ring respectively. Uv-vis
spectra are shown in Figure S10 in SI. There are no obvious
absorption peaks for polymer, the porphyrin-polymer composite
remains the strong Soret peak at 420nm and Q band at
5
20~650nm. Apparently a slight red-shift for the Soret band took
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ChemCatChem
10.1002/cctc.201701219
COMMUNICATION
place which means that the interaction occurred between the
porphyrin and the polymer. Besides, the intensity ratio for the
Soret/Q band decreased from 5:1 to 2:1. All these confirmed that
the interaction between the porphyrin and polymer. Figure 4
shows the TEM images of the film when the concentration of the
monitoring the decrease of its Uv-vis adsorption at its sharpest
peak, at 329nm. The conversion yields are given in Table 1. The
blank experiment was tested in the absence of porphyrin
photosensitizer and a 1,5-dihydroxynaphthalene conversion of
19% was observed (entry 0).
H
2
TPPS was 10 μM. It reveals that a large number of spheric
Table 1. Photooxidation of 1, 5-dihydroxynaphthalene catalyzed by
porphyrin/polymer systems using H O as oxidant.
2 2
particles with a diameter of 250nm are evenly distributed.
Values of
porphyrin
Conversion
Rate
[%]
Residual
porphyrin
[%]
Entry
Catalyst
Blank
Cycle
[
a]
[b]
[c]
[μmol/g]
0
1
2
3
4
5
6
7
8
9

2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
50.0
50.0
1
1
1
1
1
1
1
1
1
2
3
4
5
10
2
3
4
5
10
1
1
19
92
89
91
87
51
83
88
80
90
89
87
85
74
87
85
84
82
70
91
90

Figure 4. TEM image of H
hours. The concentration of H
2
TPPS-2 film grown at the H
TPPS was 10 μM.
2 3
O-CHCl phase after 4
36
2
H
H
H
H
2
2
2
2
TPPS
95
TPPS-1
TPPS-2
TPPS-3
Photooxygenation of 1, 5-dihydroxynaphthalene is an
attractive route for the synthesis of 5-hydroxy-1, 4-naphtho-
quinone (juglone), a naturally occurring compound which plays
96
94
[
12]
an important role in the pharmaceutical and dye industries.
FeTPPS
7
Besides, degradation of 1, 5-dihydroxynaphthalene has also
been greatly investigated because of the importance for
removing the phenolic and naphtholic pollutants from
wastewater. Homogeneous sensitizers such as porphyrins have
been described for the photooxidative approaches, but the main
problem with the photochemical route is the deactivation of the
porphyrins caused, especially for iron porphyrins, by their
FeTPPS-1
FeTPPS-2
FeTPPS-3
93
93
90
94
92
89
87
75
92
90
88
85
72
80
75
2
H TPPS-2
[
13]
photolysis.
10
11
12
13
14
15
16
17
H
H
H
H
2
TPPS-2
2
TPPS-2
2
TPPS-2
2
TPPS-2
FeTPPS-2
FeTPPS-2
FeTPPS-2
FeTPPS-2
FeTPPS-2
Figure 5. Photographs of the color changing in the two-phase solution before
and after the reaction.
Thus, film catalysts consisting of porphyrin/polymer systems
were investigated as heterogeneous catalysts for the
photooxidation of 1, 5-dihydroxynaphthalene with a catalyst/
18
1
9
0
H
2
TPPS-2
2 2
substrate ratio of 1:100 using H O as oxidant and a 100W
2
FeTPPS-2
Iodine Tungsten Lamp (ITL). A water-dichloromethane biphasic
system was used to rapidly remove the main product 5-hydroxy-
[
a] Values for porphyrin incorporation (μmol/g) in the polymer. [b] Reaction
1
, 4- naphthoquinone from the upper aqueous phase to the
time is 60min and the reaction is monitored by Uv-vis and GC. [c] 24h
photolysis in absence of substrate.
bottom chloroform phase (Figure 5). The formation of juglone
was determined by HNMR spectra, elemental analysis and
mass spectrometric data (see SI, Figure S12 and Table S3). The
conversion of 1, 5-dihydroxynaphthalene was calculated by
1
Entry 2-4 show that the activity of H
2
TPPS-polymer systems
TPPS (entry 1). The
were 87-91%, similar to the 92% of free H
2
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COMMUNICATION
catalytic activities for three film catalysts decrease in the order of
1
0
0
0
.0
.8
.6
.4
H TPPS
2
FeTPPS
H
2
TPPS-2> H
2
TPPS-1> H
2
TPPS-3. The photooxidation of 1, 5-
a
c
b
d
dihydroxynaphthalene catalyzed by iron porphyrin/polymer films
had also been investigated (entry 6-8), and yields 80-88% were
obtained for the FeTPPS-polymer systems. It is well known that
iron porphyrin is an unstable catalyst for this reaction because of
0.2
[
14]
its easy photolysis,
a 51% yield has been obtained for
0.0
1.2
FeTPPS alone (entry 5). Thus FeTPPS-polymer systems can
efficiently improve the naphthoquinone formation. There is the
same activity order for FeTPPS-polymer as H TPPS-polymer
2
systems. This order 2>1>3 also coincides with phase transfer
ability for 1-3 polymers (see page 2 left), which demonstrates
that for these polymers, the higher phase transfer ability causes
the higher catalytic activity.
H TPPS-2
2
FeTPPS-2
0
0
.9
.6
0.03
0.02
0.01
0
.020
.015
0
0.010
.005
0
0.00
4
21
423
0.3
.0
0
300
350
400
450
300
350
400
450
Wavelength/nm
Wavelength/nm
H TPPS-2
2
Figure 8. UV-vis spectra observed during the photodegradation of 1,5-
dihydroxynaphthalene catalyzed by (a) H TPPS (b) FeTPPS (c) H TPPS-2 (d)
FeTPPS-2 (Reaction time recording of spectra up to bottom for a and b were 0,
, 10, 15, 20, 25 and 30min; for c and d were 0, 5, 10, 15, 20, 25, 30, 45 and
60min).
1
00
2
2
FeTPPS-2
8
6
4
2
0
0
0
0
0
5
H TPPS
FeTPPS
30
2
Thus these film catalysts existing at the interfaces between
the two liquid phases are very stable during the irradiation.
Importantly, they can be reused easily in new H oxidations of
, 5-dihydroxynaphthalene for several cycles. The recycling of
0
60
90
120
150
180
2
O
2
Illumination time / min
1
these catalytic systems is quite simple, no product separation
and catalyst filtration are necessary. To restart a new cycle, a
new substrate aqueous phase and pure chloroform phase can
be added to the same catalytic batch after the former two
phases have been removed respectively (Scheme S3 in SI).
Figure 6. Photostabilities of H
2
TPPS, FeTPPS, H
2
TPPS-2 and FeTPPS-2.
H
2
TPPS
FeTPPS
TPPS-2
FeTPPS-2
1.0
0.8
0.6
0.4
0.2
0.0
Entries 9-18 show the activities of 2-5 and 10 runs of H
and FeTPPS-2. Only a slight decrease in both catalytic systems
was observed, the catalytic activities by H TPPS-2 (FeTPPS-2)
2
TPPS-2
H
2
2
th
from second to 5 runs were 90% (87%) to 85% (82%).
th
Activities 74% (70%) were even obtained at the 10 run for
these two catalytic systems, respectively (entry 13 & 18). The
slight decrease of the activities of the catalysts in the aqueous
phase might be mainly caused by the loss of the catalysts during
the recycling of the catalytic system preparation process. The
efficient catalytic activities of these porphyrin/ polymer films can
be explained by the nature of the active site, the polymers might
provide suitable and flexible cavities for the substrate and the
singlet oxygen approach to the porphyrin center. The activity
decrease for FeTPPS film catalysts were similar to that of
0
10 20 30 40 50 60
Reaction time / min
Figure 7. Conversion rate of 1, 5-dihydroxynaphthalene catalyzed by H
FeTPPS, H TPPS-2 and FeTPPS-2.
2
TPPS,
2
The photostabilities of these catalysts under the same
conditions as those for photooxidations have been tested. Data
are presented in table 1 and Figure 6. Under the same condition,
2
H TPPS film catalysts, which proved that the severe photolysis
of FeTPPS can be efficiently restrained, which was consistent
with the results obtained in Figure 6. The activities of thicker
porphyrin film catalysts (50mol/g ) have also been tested (entry
19 & 20), the activity increase for both porphyrins were quite
limited, which might be caused by the sterically crowded cavities
of these high porphyrin concentration catalysts. However the
residual porphyrins still maintained 80% and 75%, much higher
than those for homogeneous porphyrin catalyst. The electron
densities on the iron(III) in catalysts were examined by X-ray
Photoelectron spectroscopy (XPS), the Fe (2P3/2) binding
energies 710.2ev and 711.4ev were obtained for FeTPPS and
FeTPPS-2 respectively, the slight higher binding energy
indicates the decrease of the electron density of iron, which
9
0% of FeTPPS had been decomposed within 10 mins, which is
consistent with the sudden decrease of the activities after 5 min
Figure 7 & 8). The photostability of H TPPS is better than that
of FeTPPS, while most of the H TPPS had been decomposed
within 120 min. Comparing the poor photostabilites of FeTPPS
and H TPPS, it is clear that the corresponding polymer systems
(
2
2
2
keep considerable stabilities. This means that these film
photosensitizers can efficiently avoid the photolysis and
prolongate the photostabilites.
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ChemCatChem
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means the existence of the electronic effect for the film
[8]
Q. Ren, Z. Hou, Y. Wang, H. Zhang, S. Yang, ChemSusChem 2011, 4,
[15]
1063-1067.
catalysts. All these results reconfirms that the new catalytic
system is efficient and robust for 1, 5-dihydroxynaphthalene
oxidation.
[
9]
M. Kramer, J. Stumby, H. Turk, S. Krause, A. Komp, L. Delineau, S.
Prokhorova, H. Kautz, R. Haag, Angew. Chem. Int. Ed. 2002, 41, 4252-
4256.
In summary, a novel and stable film can be easily assembled at
the water-chloroform interface by noncovalent interaction
between porphyrins and polypeptide-containing hyperbranched
polymers. These films can act as heterogeneous catalysts for
the photooxidation of 1, 5-dihydroxynaphthalene. Because of the
electronic effect and steric hindrance, they have the advantage
of high stability, good recyclability and little photolysis. Moreover,
no product and catalyst separation were necessary during the
catalytic process. Further experiments are being carried out for
more substrates and catalytic mechanisms.
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Experimental Section
The synthesis and characterization of the porphyrins and the
hyperbranched polymers 1-3 are given in SI and the previous
[
7]
report. The synthesized porphyrins were efficiently purified with
the accurate dialytic bag. The Molar mass calculation and the
yields of grafting of the polymers, the experimental data of the
characterization of the porphyrin-polymer films, the calculation of
the phase transfer ability of polymers for porphyrins, and the
oxidation catalysis studies are given in SI.
Acknowledgements
We gratefully acknowledge the financial support of this work by
the National Natural Science Foundation of China (21371120 &
20871082).
Keywords: sulfonated porphyrins • hyperbranched polymers•
photooxidation • film • heterogenous
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ChemCatChem
10.1002/cctc.201701219
COMMUNICATION
Entry for the Table of Contents
COMMUNICATION
Kaifang Sun, Lintong Guo,
Cheng Cai, Zongsheng Hou
and Qizhi Ren*
Page No. – Page No.
Porphyrin-hyperbranched
copolymer films as
H O
2
2
recyclable photooxidation
catalysts for 1, 5-
dihydroxynaphthalene
Novel and stable films can be easily assembled at water-chloroform interface by noncovalent
interaction between meso-tetrakis (4-sulfonatophenyl) porphyrins and polypeptide-containing
hyperbranched copolymers. These films can act as efficient recyclable heterogeneous
catalysts for the photooxidation of 1, 5-dihydroxynaphthalene. They have advantages of high
stability, good recyclability and little photolysis. No separation and purification for both
catalyst and products were necessary during the catalytic process
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