In Situ Synthesis of Photoactive Polymers on a Living Cell Surface via Bio-Palladium Catalysis for Modulating Biological Functions

Article abstract of DOI:10.1002/anie.202015247

Cell surface engineering with functional polymers is an effective strategy to modulate cell activity. Here, a bio-palladium catalyzed polymerization strategy was developed for in situ synthesis of conjugated polymers on living cell surfaces. Through Sonagashira polymerization, photoactive polyphenyleneethynylene (PPE) is synthesized on the cell surface via cell-generated bio-Pd catalyst. The in situ formed PPE is identified by excellent light-harvest capacity and blue fluorescence on the surfaces of E. coli and C. pyrenoidosa. Besides imaging microbes for tracing the polymerization process, PPE also exhibits enhanced antibacterial activity against E. coli. It can also augment the ATP synthesis of C. pyrenoidosa through enlarging the light absorption and accelerating the cyclic electron transport of the algae. With this bio-metal catalyzed polymerization method, functional polymers can be synthesized in situ on the living cell surface.

Full text of DOI:10.1002/anie.202015247

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Accepted Article
Title: In-Situ Synthesis of Photoactive Polymers on Living Cell Surface
via Bio-Palladium Catalysis for Modulating Biological Functions
Authors: Shu Wang
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To be cited as: Angew. Chem. Int. Ed. 10.1002/anie.202015247
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In-Situ Synthesis of Photoactive Polymers on Living Cell Surface
via Bio-Palladium Catalysis for Modulating Biological Functions
Ruilian Qi,a Hao Zhao,a Xin Zhou,a Jian Liu,a Nan Dai,a Yue Zeng,a Endong Zhang,a Fengting Lv,a*
Yiming Huang,a Libing Liu,a,c Yilin Wang,b,c* and Shu Wang a,c*
[a]
Prof. S. Wang, Prof. F. T. Lv, Prof. L. B. Liu, Prof. Y. M. Huang, Dr. R. L. Qi, H. Zhao, Dr. X. Zhou, Dr. J. Liu, N. Dai, Y. Zeng, E. D. Zhang, Key Laboratory
of Organic Solids, Beijing National Laboratory for Molecular Sciences, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, P. R. China
E-mail: wangshu@iccas.ac.cn; lvft@iccas.ac.cn
[b]
[c]
Prof. Y. L. Wang, Key Laboratory of Colloid, Interface and Chemical Thermodynamics, Institute of Chemistry, Chinese Academy of Sciences, Beijing
100190, P. R. China. Email: yilinwang@iccas.ac.cn
Prof. S. Wang, Prof. L. B. Liu, Prof. Y. L. Wang, College of Chemistry, University of Chinese Academy of Sciences. Beijing, 100049, P. R. China
Supporting information for this article is given via a link at the end of the document.
Abstract: Cell surface engineering with functional polymers is an
effective strategy to modulate cell activity. In this work, we develop a
new bio-palladium catalyzed polymerization strategy for in-situ
synthesis of conjugated polymers on living cell surfaces. Through
carboxyl, amino and phosphate groups, which favor the
formation of Pd nanoparticles. In addition, Pd nanoparticles
formed on bacterial surface (bio-Pd) displayed higher catalytic
activity in Heck reaction than colloid Pd.[13] In this work, we
design and construct a new in-situ polymerization system to
modify cell surface with photoactive polyphenyleneethynylene
(PPE), in which the Sonagashira polymerization is catalyzed by
the in-situ formed surface bio-Pd catalysts (Scheme 1a). The
synthesized PPE on cell surface is positively charged, therefore
the electrostatic interactions facilitate the binding to the
negatively charged cell surface. Since PPE emits blue
fluorescence, the polymer formation process on cell surface can
be easily traced and characterized. As shown in Scheme 1b, by
virtue of the excellent light-harvesting ability of conjugated
polymers,[14] their antibacterial activity against E. coli and the
improvement of ATP synthesis of C. pyrenoidosa make this
novel in-situ polymerization a promising strategy in cell surface
engineering with simultaneous modulation of biological functions.
Sonagashira
polymerization
reaction,
photoactive
polyphenyleneethynylene (PPE) is synthesized on the cell surface
via cell-generated bio-Pd catalyst. The in-situ formed PPE is
identified by excellent light-harvest capacity and blue fluorescence
on the surfaces of E. coli and C. pyrenoidosa. Besides imaging
microbes for tracing the polymerization process, PPE also exhibits
enhanced antibacterial activity against E. coli. Moreover, it can
augment the ATP synthesis of C. pyrenoidosa through enlarging the
light absorption and accelerating the cyclic electron transport of the
algae. By using this bio-metal catalyzed polymerization method,
functional polymers can be in-situ synthesized on the living cell
surface, which paves a new way for modulating cell functions.
Cell surface engineering is an important methodology for
regulating cell functions, such as protecting cells against harsh
environments,[1] improving biosynthesis efficiency,[2] and
endowing cells with more functionalities.[3] Inspired by this
promising method, several functional materials such as
metal/semiconductor nanoparticles,[4] polymers,[5] and metal–
organic complexes[6] have been explored as coating materials
on the cellular surface. Up to date, considerable research has
been focused on cell surface modification by functional polymers
due to the increased availability of secondary interactions and
derivation from grafted polymers.[7] However, due to the
repulsion-caused low conjugation efficiency of polymer to cell
surface, this modification usually need a large excess of reactive
polymers.[8] To increase the utilization of polymers, an in-situ
polymerization strategy has recently been applied to live cells.
Besides the high grafting density, the structure of in-situ formed
polymers also matches well with the charge distribution and
biologically functional regions on cell surface, leading to a high
binding affinity between polymers and living cells.[9] The present
in-situ polymerization studies mainly focus on the radical
polymerization,[10] however, the inherent free radicals generated
from initiators and monomers will induce potential cytotoxicity to
cells. Moreover, the detection of polymer formation process on
the surface is also difficult. It is urgent to develop novel surface
polymerization methods to solve these key issues.
Pd-mediated cross-coupling reactions for labeling and drug
synthesis has been realized in living cell systems,[11] which
ensure the feasibility of this strategy on cell surface. Cell surface
generally possesses multiple Pd binding sites,[12] including
Scheme 1. (a) Synthesis of PPE through bio-Pd catalyzed Sonogashira
polymerization. (b) In-situ synthesis of PPE on the cell surface and its
antibacterial activity against E. coli and improvement of ATP synthesis in C.
pyrenoidosa.
1
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Figure 1. (a) Schematic illustration of PPE synthesis using Sonogashira coupling via Pd catalysis in aqueous solution. (b) NMR and (c) IR spectra of
polymerization solution ([M1] = 100 μM, [M2]/[M1] = 1.3). (d) Conversion efficiency as a function of monomer concentrations after reaction for 2 h and 5 h.
Cationic
bromide)-2,5-diiodobenzene
hexamethylene-trimethylammonium
1,4-bis(oxy-hexamethylene-trimethylammonium
of fluorescence intensity of the reaction solution further indicated
the formation of PPE (Figure S5).
(M1)
and
1,4-bis(oxy-
bromide)-2,5-
For in-situ synthesis of PPE on cell surface, a bio-Pd catalyst
on E. coli surface was constructed. The binding affinity between
Pd (II) ions and E. coli was measured by isothermal titration
microcalorimetry (ITC). The derived binding constant (Ka) was
1.43 × 106 M-1 suggested the strong electrostatic binding
between Pd (II) ions and E. coli (Figure 2a). After Pd (II) ions
binding on the bacterial surface, sodium formate (HCOONa) was
added to initiate the reduction of Pd (II) by molybdoenzymes on
cell surface of E. coli.[16] The EDS mapping revealed the
presence of Pd element on E. coli surface (Figure 2b). Pd
nanoparticles with inter-planar spacing of 1.93 Å (200) for the
diethynylbenzene (M2) were chosen as monomers for
polymerization (Figure 1a). The characteraization of M1 and M2
were given in Figure S1 and S2. The positive charges of M1
and M2 can greatly increase their water solubility to ensure them
polymerization in aqueous environment. In addition, the positive
charges also favor the process of binding to negatively charged
cell surface via electrostatic interactions, which put them in close
proximity of the bio-Pd catalyst on the surface. Firstly, the
Sonogashira polymerizations of M1 and M2 (molar ratio of
M1/M2 = 1/1.3) in aqueous solution were studied. The polymer
conversion efficiencies (relative to M2) were calculated by HPLC. lattice fringe were observed on the surface of E. coli in the high-
As shown in Figure 1b, the polymer conversion efficiency was
increased along with the increas of reaction time. At low
monomer concentration ([M1] = 100 μM), the conversion was
relatively high and reached 32% and 49% after reaction for 2 h
and 5 h, respectively. While increasing monomer concentration
up to 500 μM, the conversion efficiency decreased to 21% at 2 h
and 29% at 5 h. After polymerization, the hydrogen (Hc) and the
peak of C-H stretch (3220 cm-1) in the terminal acetylene were
obviously decreased (Figure 1c and 1d), which indicated the
consumption of M2. Meanwhile, the peak of C C stretch shift
from 2098 cm-1 to 2276 cm-1, which suggested the formation of
bis-substituted alkynyl[15]. Both NMR and IR results confirmed
the polymerization took place in the aqueous solution. Derived
from the GPC (Figure S3), the molecular weight of the resulting
polymers formed at 100 and 500 μM monomer concentrations
are both about 3.5×103 (~9 repeat units). In addition, the HPLC-
MS analysis demonstrated the formation of conjugated polymers
on cell surface (Figure S4). Since the synthesized PPE emits
blue fluorescence rather than monomers, the siginificant increas
resolution TEM images, which is consistent with Pd (0) crystal
(Figure 2c). To further confirm the generation of Pd (0)
nanoparticles, XPS analysis of the Pd-E. coli sample treated
with HCOONa was performed (Figure 2d). The peaks at 335.4
(Pd 3d5/2) and 340.6 eV (Pd 3d3/2) revealed the loading of Pd (0)
species on E. coli surface. It is noted that the characteristic
peaks of Pd (II) at 337.8 and 342.8 eV were also found in the
XPS spectrum possibly due to the surface oxidation.
Following the formation of bio-Pd nanoparticles, the in-situ
polymerization reaction was subsequently carried out by adding
monomers M1 and M2 to the solution of E. coli coated with bio-
Pd. The polymerization process was traced by confocal laser
scanning microscopy (CLSM). A significant and dose-dependent
increase in fluorescence intensity was observed on the surface
of E. coli but not on E. coli only treated with monomers (Figure
2e and 2f). Combined with the significant enhancement of
fluorescent intensity on cell surface, it can be concluded that Pd-
catalyzed Sonogashira polymerization took place on E. coli
surface. Considering that the synthesized PPE possesses
cationic charge and hydrophobic moieties that contributed to
2
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Figure 2. Pd catalyzed Sonogashira polymerization on E. coli surface. (a) The binding affinity between palladium ion and E. coli. (b) EDS map of palladium
elements observed by TEM. (c) TEM image of Pd nanoparticles formed on the surface of E. coli. The inset picture is high resolution of TEM images for measuring
the lattice distance of formed palladium nanoparticles. (d) XPS spectrum of palladium nanoparticles formed on E. coli surface. (e) CLSM images, (f) Relative
fluorescence intensity analysis, and (g) E. coli viability after polymerization at different monomer concentrations.
bactericidal ability,[17] the bacterial viability and cell morphology
before and after polymerization reaction were tested and shown
in Figure 2g and Figure S6. The control groups in the presence
of Pd catalyst or monomers only had very less influence on the
viability of E. coli (90%). With the monomer concentration
increase from 100 μM to 500 μM, the bacterial viability after
polymerization decreased to 28%. Obvious membrane damages
were also observed for this case (Figure S6). The increased
bactericidal ability at high monomer concentration might ascribe
to the formation of polymers with high polymerization degree.
Compared with the surface modification by coating with pre-
formed or in-situ polymerization using sodium ascorbate as
electron donor (Figure S7), the coating efficiency of in-situ
polymerization in the presence of HCOONa was slightly lower,
but it exhibited a significantly difference to two kinds of bacteria
(E. coli and P. aeruginosa). Obvious blue fluorescence and high
bacteria killing was observed on E. coli with strong reductive
ability[18], while rarely no fluorescence and low bacteria killing
was shown on P. aeruginosa without reductive ability. Based on
the above results, it can be concluded that the in-situ
synthesized polymers can not only image the E. coli for tracing
the polymerization process, but also exhibit good antibacterial
capacity.
pyrenoidosa mainly through electrostatic interactions (Figure
3a), same to that of E. coli. After sodium ascorbate reduction,
the presence of Pd elements on C. pyrenoidosa surface was
identified by the EDS map (Figure 3b), and the nanoparticles
with lattice space of 1.95 Å (200) were also observed (Figure
3c). XPS further confirmed the generation of Pd (0) species
(Figure S8). Then Pd-catalyzed Sonogashira polymerization
was monitored by CLSM after adding monomers M1 and M2
(Figure 3d). With bio-Pd catalyst on C. pyrenoidosa surface,
blue fluorescence was observed around the perimeter of red
emission of C. pyrenoidosa. It is noted that the intensity of blue
fluorescence increased by 10 and 40 times than that of C.
pyrenoidosa treated with 100 μM and 500 μM monomers,
respectively (Figure S9). These results indicated that the Pd-
catalyzed Sonogashira polymerization successfully took place
on C. pyrenoidosa surface. The in-situ polymerization had slight
influence on the viability of C. pyrenoidosa (Figure S10). As
ATP is an important product of photosynthesis, the influence of
bio-Pd catalyzed Sonogashira polymerization on C. pyrenoidosa
surface on ATP biological synthesis was studied. After
polymerization reaction for 2 h, the C. pyrenoidosa solution was
then irradiated under white light for 30 min, and then the
produced ATP was measured and the result was summarized in
Figure 4a. Compared to C. pyrenoidosa without any treatment,
42% and 115% increase of ATP production were observed for
the Pd-loaded C. pyrenoidosa treated with 100 μM monomer
and 500 μM monomer, respectively. For C. pyrenoidosa without
Pd loading, upon treatment with 100 μM monomer
After successfully realizing the Sonogashira coupling on the
surface of E. coli, we extended the in-situ strategy to modify the
surface of C. pyrenoidosa. The exothermic process of titrating
Pd (II) ions into C. pyrenoidosa and large binding constant (Ka =
3.28 × 105 M-1) suggested that Pd (II) ions strongly bind with C.
3
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Figure 3. Pd catalyzed Sonogashira polymerization on C. pyrenoidosa surface. (a) The binding affinity between palladium ion and C. pyrenoidosa. (b) EDS map
and (c) TEM image of palladium nanoparticles. (d) CLSM images after polymerization at different monomer concentrations.
and 500 μM monomer, only 11% and 22% ATP production
increase were observed, respectively, which verified that the in-
situ synthesized polymers augmented the ATP synthesis of C.
pyrenoidosa. The augmentation mechanism of ATP synthesis of
C. pyrenoidosa was further investigated. Our previous work has
proved that conjugated polymer nanoparticles (CPNs) can
augment the photosynthetic activity of chloroplast by broadening
the light capture range and accelerating the electron transport
rates in photosystem II (PS II) of chloroplast.[19] As shown in
Figure 4b, the fluorescence emission spectra of reaction
mixture overlapped well with the absorption of C. pyrenoidosa,
which indicated that the light transformed from the in-situ
synthesized polymers could be utilized by C. pyrenoidosa for
photosynthesis. The increase of absorption and trapped light
energy per reaction center, ABS/RC and TR/RC, did confirm the
enlarged light absorption and capture in the C. pyrenoidosa with
surface coupling (Figure 4c and 4d). To further confirm the
effect of light harvesting by the in-situ formed polymers, the ATP
production of C. pyrenoidosa under the irradiation of red light
(which cannot excite the polymers) was measured (Figure S11).
The slight decrease of ATP under red light irradiation and 115%
increase of ATP production under white light irradiation indicated
that the enlarged light harvesting induced by the polymers play a
major role in the increase of ATP production. However, the
electron transport rate (ETR) of PS II was largely declined by the
in-situ polymerization (Figure S12a) and the corresponding
opening degree of PS II reaction centers (qP) was also
decreased (Figure S12b). This was associated with the PS II
photoinhibition caused by the in-situ synthesized polymers which
enlarged the light absorption of C. pyrenoidosa.[20] Since both
the activities of PS II and PS I contribute to the photosynthesis
efficacy, the energy conversion efficiency of PS I was measured.
The effective quantum yield Y(I) of the bio-Pd loaded C.
pyrenoidosa exhibited obvious increase when tread with 500 μM
monomer (Figure 4e). This result suggested that the increased
ATP synthesis was related to the augmentation in PS I activity.
4
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Figure 4. Enhanced ATP synthesis by Pd catalyzed Sonogashira polymerization on C. pyrenoidosa surface. (a) ATP production of C. pyrenoidosa, C.
pyrenoidosa/Pd, C. pyrenoidosa/monomer, and C. pyrenoidosa/Pd/monomer under light irradiation after polymerization. (b) Normalized UV-vis and fluorescence
spectra of C. pyrenoidosa and reaction mixture. (c) Absorption energy and (d) captured energy per reaction center measured by FMS-2 pulse modulated
fluorometer. (e) Photosystem I efficiency (Y(I)) of C. pyrenoidosa after polymerization. (f) Proposed mechanism of enhanced ATP synthesis induced by
polymerization.
The mechanism of enhanced ATP synthesis was illustrated in
Figure 4f. Generally, light induced ATP synthesis is coupled
with two pathways of electron transport: linear electron transport
from PS II to PS I (H2O → PS II → plastoquinone, Q →
cytochrome b6f → plastocyanin, Pc → PS I → ferredoxin, Fd →
NADP+) and cyclic electron transport around PS I (PS I → Fd →
Q → b6f → Pc → PS I). The decreased PS II activity and
increased PS I activity indicated that the C. pyrenoidosa with
surface coupling had an elevated cyclic electron transport which
usually drove more ATP production. That is to say, the in-situ
polymerization on C. pyrenoidosa surface regulated the
electron-transport pathways to produce more ATP.
In conclusion, we developed a new in-situ polymerization
strategy to modify cell surface with conjugated polymers for
regulating cell activity. Taking advantage of the negative charge
of cell surfaces, bio-Pd nanoparticles were loaded on cell
surface after reduction by the surface enzyme or reductant. The
in-situ polymerization reaction on cell surface was catalyzed by
the bio-Pd catalyst and the polymerization process was easily
traced by fluorescence imaging technique. Besides exhibiting
good antibacterial activity towards E. coli, the in-situ formed
photoactive conjugated polymers can also enhance the ATP
synthesis of C. pyrenoidosa by enlarging the light absorption
and accelerating the cyclic electron transport. The proposed bio-
Pd catalyzed polymerization provides a new avenue for cell
surface engineering to regulate cell activity for desirable
biological applications with in-situ synthesized functional
polymers.
We are grateful for financial support from the Strategic Priority
Research Program of the Chinese Academy of Sciences
(XDA16020804) and the National Natural Science Foundation of
China (Nos. 21533012, 21661132006, 21988102).
Keywords: cell surface engineering • in-situ polymerization •
bio-Pd catalysis• cell activity regulation
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10.1002/anie.202015247
Angewandte Chemie International Edition
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In this work, a new in-situ polymerization strategy to modify cell surface with conjugated polymers was developed by bio-Pd
nanoparticles catalyst on cell surface. The in-situ formed PPE can not only trace the polymerization process, but also exhibit
enhanced antibacterial activity against E. coli and augment the ATP synthesis of C. pyrenoidosa. The in-situ polymerization strategy
on the living cell surface paves a new way for modulating cell functions for desirable biological applications.
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This article is protected by copyright. All rights reserved.