Efficient photocatalytic oxidation sensitized by conjugated polymers in a batch reaction and microreactors under visible light

Article abstract of DOI:10.1039/c8ta03297a

We studied microfluidic reaction systems for the efficient catalytic oxidation of α-terpinene sensitized by conjugated polymers. Different microreactors, including flow-reaction-based mono- and dual-channel, as well as polymer-coated dual-channel microreactors, were designed and evaluated, which demonstrated improved reaction efficiency.

Full text of DOI:10.1039/c8ta03297a

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Kun Chang, Zhaorong Chang et al.
Bubble-template-assisted synthesis of hollow fullerene-like
MoS2 nanocages as a lithium ion battery anode material
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JPolueransael odfoMnaotetraiadljsuCsht emmairsgtriynsA
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DOI: 10.1039/C8TA03297A
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Efficient Photocatalytic Oxidation Sensitized by Conjugated
Polymers in Batch and Microreactors under Visible Light
Anqi Li,ab Chunyan Tan,*ab Tianying Yuan,ab Jiamei Liang,ab Dan Gao,*ab Ying Tanab and Yuyang
Received 00th January 20xx,
Accepted 00th January 20xx
Jiang*bc
DOI: 10.1039/x0xx00000x
www.rsc.org/
We studied microfluidic reaction systems for the efficient catalytic photosensitizers, including microporous polymers (MPs),14, 15
oxidation of α-terpinene sensitized by conjugated polymers. mesoporous graphitic carbon nitride,16, 17 silicon nano crystals,18
Different microreactors, including flow-reaction-based mono- and metal−organic frameworks (MOFs),19 and conjugated polymers
dual-channel, as well as polymer-coated dual-channel (CPs).20 CPs have attracted a great deal of attention due to their
microreactors, were designed and evaluated, which demonstrated potential applications in organic solar cells, chemical sensors,
improved reaction efficiency.
cell imaging, and a variety of other fields.21-23 It has been
reported that some CPs are able to generate singlet oxygen
upon light irradiation through intersystem crossing (ISC) leading
to CPs’ anti-bacteria and anti-tumor applications.24-30 However,
no studies have reported the use of CPs as 1O2 photosensitizers
in organic synthesis.
Singlet oxygen (1O2) is an important reactive oxygen species
(ROS) that plays an important role in many physiological
processes in living systems and acts as an excellent oxidizing
agent in various organic reactions.1-3 Due to its high oxidation
efficiency, sustainability, and convenience in separation, singlet
oxygen has been widely used in organic synthesis, including the
preparation of endoperoxides from Diels−Alder reactions,4
dioxetanes from [2+2] cycloadditions,5 hydroperoxides from
alkenes and phenols,6 sulfoxides from sulfides,7 phosphine
oxides from phosphines,8 and selective oxidation of aromatic
alcohols into corresponding aldehydes.9 Moreover, some
reactions involving singlet oxygen provide regio-specific and
stereo-specific introduction/insertion of oxygen into organic
substrates, such as in ene reactions with allylic alcohol
substrate.10, 11
1O2 is usually produced by photosensitization or chemical
reactions. Commonly used photosensitizers include transition
metal complexes, organic dyes and porphyrin derivatives,12, 13
which can transfer electronic energy from a triplet excited state
to ground state triplet oxygen. However, there are some
intrinsic drawbacks associated with these compounds, such as
toxicity and photo-bleaching problems. Recently, a growing
number of novel materials have been developed as
a.
Department of Chemistry, Tsinghua University, Beijing 100084, P. R. China.
b.The State Key Laboratory of Chemical Oncogenomics, the Graduate School at
Shenzhen, Tsinghua University, Shenzhen 518055, P. R. China. *E-mail:
tancy@sz.tsinghua.edu.cn
； gao.dan@sz.tsinghua.edu.cn
c. School of Pharmaceutical Sciences, Tsinghua University, Beijing 100084, P. R.
China. *E-mail: jiangyy@sz.tsinghua.edu.cn
†Electronic Supplementary Information (ESI) available: Experimental including
materials,
methods,
and
some
supplementary
figures.
See
DOI: 10.1039/x0xx00000x
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DOI: 10.1039/C8TA03297A
Scheme 1. Schematic illustration of PPET3 photosensitized oxidation of α-terpinene in a
batch, a dual-channel microreactor, and a polymer-coated microreactor.
Herein, we report an efficient photocatalytic oxidation of
α-terpinene sensitized by conjugated polymers, PPET3, in a
batch reaction and microreactors. Different microreactors were
designed, including flow-reaction-based microreactors as well
as a polymer-coated dual-channel microreactor (Scheme 1).
Two poly (p-phenylene ethynylene terthiophenes)
(PPET3s), PPET3-N+ and PPET3-COOR (structures are shown in
Scheme 1), were designed and synthesized. Conjugated
polymer backbones have been known to contribute to light-
harvesting properties. Meanwhile, the terthiophenes units
were introduced in backbones, which have been reported to
enhance ISC efficiency due to heavy atom effect of sulfur.31-37 In
particular, improved singlet oxygen generation of PPET3-N+ and
its photocytotoxicity to tumor cells were observed,38 which
motivated our further exploration of these polymers in
photocatalytic reactions.
Figure 1. (a) Oxidation of α-terpinene by singlet oxygen via the Diels-Alder [4+2] reaction;
(b) Photosensitized conversion of α-terpinene into ascaridole in batch reaction; (c)
Comparison of the photocatalytic efficiency between PPET3-N+ and methylene blue
(MB). Conversion was analyzed using UV/Visible spectroscopic measurements. Reaction
conditions: 0.1 M α-terpinene with different concentrations of PPET3-N+ or 80 μM
methylene blue in 5 mL ethanol under 120 W white LED light irradiation for different
lengths of time periods.
To investigate the activity of PPET3-N+ as a photosensitizer
to produce singlet oxygen, photo-oxidation of α-terpinene to
ascaridole (Figure 1) in the presence of PPET3-N+ was evaluated
under white LED light. Photocatalytic reaction mechanism of α-
terpinene has been reported and studied in details. Generally
speaking, singlet oxygen can catalyze a [4+2] photooxidation of
α-terpinene to form the main product as ascaridole, and
byproducts including p-cymene and allylic epoxides of α-
terpinene, which might be formed due to likely successor
reactive oxygen intermediates.2, 39, 40 In our study, absorbance
at a maximum wavelength of 265 nm was used to quantify the
remaining α-terpinene during the photo-oxidation process in
both ethanol and acetonitrile (Figure S1 in the Supporting
Information). To intuitively reflect the capability of PPET3-N+,
this reaction was carried out with methylene blue (MB), a
commercially available small molecular photosensitizer, as a
reference substance in the same conditions. As depicted in
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Figure 1b and 1c, with 80 μM PPET3-N+ after 3 h of reation time control. Therefore, polydimethylsiloxane (VPieDwMArStic)l,e Onlainne
DOI: 10.1039/C8TA03297A
(entry 9 in Table 1), 95% α-terpinene was converted into inexpensive, transparent and accessible material, was used to
ascaridole with a yield of about 93%, as revealed by NMR replace the glass plate to attach glass substrates following
spectroscopy. It is noteworthy to point out that no other plasma treatment. Nonetheless, the mono-channel
significant by-product was found, which indicates the high microreactor presents the inherent problem of controlling the
specificity of the reaction and further confirms that the heterogeneous gas-liquid reaction to supply sufficient gas for
oxidizing agent was singlet oxygen rather than other reactive the reaction. To overcome these shortcomings, a dual-channel
oxygen species like ·OH or H2O2.9 Comparatively, only about microreactor was prepared according to a previous report.53
70% conversion of α-terpinene using MB as the photosensitizer
was obtained after 3.0 h, suggesting that PPET3-N+ exhibits glass chip for the reaction and a lower PDMS chip for air flow,
higher photo-catalytic activity than MB under visible light. which are separated by a gas-permeable PDMS membrane. The
The dual-channel microreactor is composed of an upper
Reaction conditions were optimized using different PDMS membrane affords sufficient air for the reaction and
concentrations of PPET3-N+ and different light intensities enhances gas-liquid phase contact. In our study, the PDMS
(Figure S2 in the Supporting Information). When the membrane was prepared by a spin coating with a rotation speed
concentration of PPET3-N+ increased from 10 to 60 μM, the of 1200 rpm for 30 s to obtain a PDMS film at thickness of 49
conversion of α-terpinene went up correspondingly. However, μm (Figure S4).
as the concentration increased past 60 μM, subtle differences
in the reaction rate were observed. As mentioned previously,
the production of singlet oxygen is related to the energy
transfer process from the triplet photosensitizer to triplet
oxygen. As concentration ascends, the probability of
intermolecular collisions of excited state PPET3-N+ also increase
and influence ISC and the production of the triplet
photosensitizer.41, 42 One possibility of this phenomenon is that
higher concentrations of photosensitizers result in an increased
scattering effect, which reduces the UV light penetration.43
Light intensity demonstrated to be another influencing factor,
where the conversion of α-terpinene with 80 μM PPET3-N+ was
improved from 0% to 60% and to 94%, as from the non-
flashlight irradiation to the light intensity of 70 W and 120 W,
respectively, using a white LED light. Thus, the stronger light
source promoted higher photosensitization efficiency.44
Meanwhile, the photostability experiments (Figure S3)
suggested that both polymers, PPET3-N+ and PPET3-COOR,
were quite stable in the batch reaction under white LED light
with only about 10% intensity variations.
We further explored the behavior of PPET3-N+ in different
Figure 2. (a) Picture of the dual-channel reactor, which is manufactured with an upper
microreactors. The use of microreactors for chemical reactions
glass chip, lower PDMS chip, and PDMS membrane; (b) Schematic representations of
mono-channel and dual-channel microreactors.
46
has received considerable attention in recent years.45,
Compared to traditional batch systems, microreactors have
been reported to have large surface area to volume ratios to
ensure thermal homogeneity, have improved heat and mass
transfer to produce faster reactions, and maintain safe and
convenient reactions.47, 48 Several properties of microreactors
have made them excellent candidates for photoreactions,
including good spatial illumination homogeneity, gas
permeability, light transmission, and high-illuminated surface
area per unit volume.49-51 Both mono- and dual-channel
microreactors were designed and fabricated, as shown in Figure
2. A mono-channel microreactor was fabricated on glass
substrates due to its excellent compatibility and stability with
organic solvents.52 The channel consisted of a circular mixer and
long serpentine section to ensure maximum mixing and
increase utilization of space. Typically, the glass substrates are
irreversible bonded with another glass plate by means of a
thermally annealed method to obtain an integrated device;
however, this method requires high temperatures and precise
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classified into two major types: physical and chemical
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modifications. Using the physical modificDaOtiIo: n10l.1ik0e39d/Cip8-TcAo0a3t2i9n7gA,
drop-casting, spray-coating etc.,59 catalysts are adhered to the
surface of channels via electrostatic interaction or Van der
Waals’ force, whereas chemical modifications are obtained by
grafting catalysts on the surface by chemical bonding over a
number of chemical processes.60 It has been revealed that lipid-
soluble conjugate polymers exhibit excellent film forming
properties and can be applied in sensors and in optoelectronic
devices.61 PPET3-COOR, which has alkyl ester side chains, was
used to drop cast a film on a glass channel, due to its good
solubitity in organic solvent and excellent spreadability on glass.
The polymer film was formed by drop-cast the polymer solution
on the glass channel surface. The excess polymer film outside
the channel was gently cleaned off, then a PDMS membrane
was irreversible bonded between the modified glass and
another PDMS piece with channel feature using oxygen plasma
treatment. Atomic force microscope (AFM) was used to
characterize the morphology of the polymer film.
Figure 3. Photosensitized conversion of -terpinene into ascaridole in the mono-channel
and dual-channel microreactors. Conversion was analyzed using UV/Visible
spectroscopic measurements. Reaction conditions: 0.1 M α-terpinene with 80 μM
PPET3-N+ at different gas flow rates under 61.5 W/cm2 white LED light irradiation for
different lengths of time periods.
Photo oxidation of α-terpinene was conducted at different
reaction conditions and analyzed in mono- and dual-channel.
According to literature reports, acetonitrile is a better solvent
than ethanol for PDMS based microreactors due to swelling
problems in organinc solvents.54 Thus, acetonitrile was further
used in reactions on microreactors in our study. The
concentrations of α-terpinene and PPET3-N+ were 0.1 M and 80
μM, respectively, and the retention time was adjusted by
changing the injection rate. The results are presented in Figure
3. While both mono- and dual-channel microreactors could
improve photocatalytic efficiency, dual-channel provided better
performance than the mono-channel in terms of conversion at
the same retention time. When the conversion in the dual-
channel microreactors was over 90% after 5 minutes (entry 3)
under an air flow rate of 150 μL/min, only 45% of α-terpinene
was oxidized in the mono-channel (entry 1) within the same
time period, and much longer time as 3 hours was needed for
the similar conversion in batch experiment (entry 9). Moreover,
the air flow rate also plays an important role in determining the
reaction conversion. When the air flow rate increased from 80
to 150 μL/min, the conversion increased from 80% to 94%
within 306 s (entry 3). However, a subtle decreased was
observed when the air rate further increased to 220 μL/min
(entry 4), which is mostly likely attributed to air saturation in the
channels. Furthermore, when O2 replaced air flow, the
conversion reached 90% in 252 s (entry 5). These results clearly
demonstrate that dual-channel microreactors profoundly
improve the reaction efficiency compared to the mono-channel
and batch system. It has also been reported that amplificative
microreactors provide excellent conversion and output,55
suggesting that our proposed method may have further
applicability in scale-up reactions.
Figure 4. (a) Photosensitized conversion of a-terpinene into ascaridole in PPET3-COOR
film coated dual-channel microreactors; (b) Evaluation of the reusability of PPET3-COOR
film coated dual-channel microreactors. Conversion was analyzed using UV/Visible
spectroscopic measurements. Reaction conditions: 0.1 M α-terpinene, 150 μL/min air
flow rate and 5 min of retention time under 61.5 W/cm2 white LED light irradiation.
Recently, there has been an increasing interest in the
immobilization of catalysts on microreactors, which show
numerous advantageous like uniform dispersion of catalytic
active components, prevention of nanocatalysts from
deactivation by avoiding aggregation, and simplified workup
procedures.56-58 The strategies of immobilization could be
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a
Table 1. Photo-oxidation of α-terpinene in 3 different systems
.
In conclusion, we have developed CP-based microreactors
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to generate 1O2 in photosensitized oxiDdOatI:io10n..10C39o/mC8pTaAr0e3d29t7oA
traditional small molecule photosensitizers, PPET3-N+ exhibited
better photocatalytic performance under visible light
irradiation. Significant reaction efficiency was achieved by
conducting reaction with PPET-N+ in designed dual-channel
microreactors. The PPET3-COOR films were sufficiently
deposited on the surface of channels to obtain an integrated
Entry
1
Reactorb
Air
/
Time
Convc
45%
Mono-channel
5 min
2
3
4
5
6
7
8
9
Dual-channel
Dual-channel
80 μL/min
150 μL/min
220 μL/min
5 min
5 min
5 min
4.2 min
5 min
5 min
5 min
3 h
80%
94%
89%
90%
41%
68%
68%
95%
Dual-channel
polymer-coat
microreactor,
which
presented
good
d
Dual-channel
O2
photocatalytic abilities. In addition, we anticipate to further
improve the properties of the polymer-coated microreactor in
future studies as a mean to promote its application in
continuous photocatalytic organic synthesis systems.
1 layer polymer-coated
3 layers polymer-coated
5 layers polymer-coated
Batch
150 μL/min
150 μL/min
150 μL/min
/
Conflicts of interest
There are no conflicts to declare.
a Reaction conditions: 0.1 M α-terpinene, 120 W white LED light in batch and 61.5
W/cm2 white light in microreactor , room temperature, ethanol in batch system
b
and acetonitrile in microreactors as the solvent; Concentration of PPET3-N+ in
c
experiment were 80 μM; Conversions were recorded with UV/Vis spectra Acknowledgements
analysis; d Flow with O2.
This research was supported by National Natural Science
Foundation of China (No. 21572115) and Shenzhen Municipal
Government (JCYJ20160301153959476 and
Figure 4a shows that the polymer-coated microreactor
exhibited excellent photocatalytic capability. From obtained
data, when channels were coated with 1 layer of polymer film,
the conversion of α-terpinene was about 41% in a retention
time of 5 min (entry 6). The oxidant efficiency of PPET3-COOR
deposited film kept an upward tendency as thickness increased
from 1 to 3 layers (entry 7). However, there were no significant
changes in the reaction efficiency between 3 and 5 layers. The
conversion of α-terpinene with 5 layers of film was slightly
higher than that with 3 layers within 5 min, but both
conversions were approximately 68% in a retention time of 5
min (entry 8). AFM results (Figure S5) showed that many pores
are evenly distributed on the films with increasing pore size
from 0.8 to 4 μm as the layers build up. Based on the sectional
height figures (Fig. S5 d-f), the thickness of the polymer-
deposited film show an upward trend and are 95, 250, and 350
μm for 1, 3 and 5 layers, respectively. The results suggest that
the increasing thickness and larger pore size of PPET3-COOR
film enhance the photo-oxidation, which might be due to
increasing contact of the reactant with the polymer, as well as
more efficient singlet oxygen production.
To demonstrate the reusability of polymer-deposited
microreactors, repeated experiments were conducted in the
same conditions: 0.1 M α-terpinene, retention time of 5 min,
and air flow rate of 150 μL/min. The results in Figure 4b show
that as the number of tests increased, the reaction conversion
showed a descending trend, and the conversion of 1 layer film
decreased from 40% to 22% after six experiments. Similarly, the
conversion of 3 layers and 5 layers both declined from 70% to
about 50% and 55%, respectively. In fact, the effluent reaction
solution from the outlet was slightly yellow, as observed by the
naked eye. This result should be mainly attributed to the
physical adsorption and desorption of polymer film on the glass
surface.
JCYJ20160324163734374).
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Journal of Materials Chemistry A
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DOI: 10.1039/C8TA03297A
A table of contents entry
Conjugated polymer photosensitized oxidation of αꢀterpinene in batch and different microreactors
including monoꢀ and dualꢀchannel,and polymerꢀcoated dualꢀchannel microreactors, were studied.