Heteroaromatic Hyperbranched Polyelectrolytes: Multicomponent Polyannulation and Photodynamic Biopatterning

Article abstract of DOI:10.1002/anie.202104709

We reported an efficient multicomponent polyannulation for in situ generation of heteroaromatic hyperbranched polyelectrolytes by using readily accessible internal diynes and low-cost, commercially available arylnitriles, NaSbF₆, and H₂

Full text of DOI:10.1002/anie.202104709

A Journal of the Gesellschaft Deutscher Chemiker
Angewandte
International Edition Chemie
www.angewandte.org
Accepted Article
Title: Heteroaromatic Hyperbranched Polyelectrolytes: Multicomponent
Polyannulation and Photodynamic Biopatterning
Authors: Xiaolin LIU, Minghui Xiao, Ke Xue, Mingzhao Li, Dongming
Liu, Yong Wang, Xinzhe Yang, Yubing Hu, Ryan T. K. Kwok,
Anjun Qin, Chunlei Zhu, Jacky W. Y. Lam, and Ben Zhong
Tang
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To be cited as: Angew. Chem. Int. Ed. 10.1002/anie.202104709
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Angewandte Chemie International Edition
10.1002/anie.202104709
RESEARCH ARTICLE
Heteroaromatic Hyperbranched Polyelectrolytes: Multicomponent
Polyannulation and Photodynamic Biopatterning
Xiaolin Liu,[
a],[c],
Minghui Xiao,[b], Ke Xue, Mingzhao Li, Dongming Liu, Yong Wang, Xinzhe
[b]
[d]
[d]
[a]
Yang, Yubing Hu, Ryan T. K. Kwok, Anjun Qin, Chunlei Zhu, Jacky W. Y. Lam,[a],[c],* and Ben
[
d]
[a]
[a]
[d]
[b],*
Zhong Tang[a],[c],[d],[e],[f],[g],*
Dedication: This study is dedicated to the 100th anniversary of Chemistry at Nankai University and the 30th anniversary of The Hong
Kong University of Science and Technology.
[
a]
X. Liu, Dr. Y. Wang, Dr. Y. Hu, Dr. R. T. K. Kwok, Dr. J. W. Y. Lam, Prof. B. Z. Tang
Department of Chemistry, Hong Kong Branch of Chinese National Engineering Research Center for Tissue Restoration and Reconstruction, Institute for
Advanced Study, Division of Biomedical Engineering, Division of Life Science, and State Key Laboratory of Molecular Neuroscience, The Hong Kong
University of Science and Technology, Clear Water Bay, Kowloon, Hong Kong, China
E-mail: chjacky@ust.hk, tangbenz@ust.hk
[
b]
M. Xiao, K. Xue, Prof. C. Zhu
Key Laboratory of Functional Polymer Materials of Ministry of Education, State Key Laboratory of Medicinal Chemical Biology, Institute of Polymer
Chemistry, College of Chemistry, Nankai University, Tianjin 300071, China
E-mail: chunlei.zhu@nankai.edu.cn
[
c]
d]
X. Liu, Dr. J. W. Y. Lam, Prof. B. Z. Tang
HKUST-Shenzhen Research Institute, No. 9 Yuexing 1st RD, South Area, Hi-tech Park, Nanshan, Shenzhen 518057, China
M. Li, D. Liu, X. Yang, A. Qin, Prof. B. Z. Tang
[
Center for Aggregation-Induced Emission, SCUT-HKUST Joint Research Institute, State Key Laboratory of Luminescent Materials and Devices, South
China University of Technology, Guangzhou 510640, China
[
[
[
e]
Prof. B. Z. Tang
AIE Institute, Guangzhou Development District, Huangpu, Guangzhou 510530, China
Prof. B. Z. Tang
Guangdong−Hong Kong−Macau Joint Laboratory of Optoelectronic and Magnetic Functional Materials
Prof. B. Z. Tang
f]
g]
Shenzhen Institute of Molecular Aggregate Science and Engineering, School of Science and Engineering, The Chinese University of Hong Kong,
Shenzhen, 2001 Longxiang Boulevard, Longgang District, Shenzhen City, Guangdong 518172, China
These authors contributed equally to this work.
#
Supporting information for this article is given via a link at the end of the document.
Abstract: The development of facile methods for the synthesis of
properties and multiple charges to interact with oppositely
charged species via electrostatic attraction.[1] Among various
natural polyelectrolytes, polysaccharides are the largest
functional hyperbranched polyelectrolytes plays a pivotal role for
biomimicry and the creation of new materials. In this study, we
reported an efficient multicomponent polyannulation for in situ
generation of heteroaromatic hyperbranched polyelectrolytes by
using readily accessible internal diynes and low-cost, commercially
component of biomass, exemplified by
a
[3]
variety of
[
2]
[4]
hyperbranched species, such as amylopectin, glycogen,
arabinoxylan,[5] xanthan gum,[6] and PTR-EPS1.[7] In general,
these hyperbranched polysaccharides are rich in hydroxyl
groups, while some of them contain additional amino groups,
carboxyl groups, and sulfonate groups, which can be ionized
6 2
available arylnitriles, NaSbF , and H O/AcOH. The polymers were
obtained in excellent yields (up to 99%) with extraordinary high
6
molecular weights (M
w
up to 1.011 × 10 ) and low polydispersity
indices. The resulting polymers showed good processibility and high
quantum yields with tunable emission in the solid state, making them
ideal materials for highly ordered fluorescent photopatterning. These
hyperbranched polyelectrolytes also possessed strong ability to
generate reactive oxygen species, which allowed their applications
in efficient bacterial killing and customizable photodynamic
patterning of living organisms in a simple and cost-effective way. In
view of the unique properties and functionalities, these
hyperbranched polyelectrolytes hold great promise to be used in a
plethora of follow-up studies, such as photoelectronic materials,
disease theranostics, biochips, and tissue engineering.
under
certain conditions to become hyperbranched
polyelectrolytes to fulfill certain biological functions. Despite
hyperbranched polyelectrolytes play a pivotal role in organisms,
their exact chemical structures are hardly identified due to the
structural complexity.[2] In addition, the contents of some species
are low in nature.[7] Thus, understanding their detailed formation
mechanisms and biological functions become difficult. In this
regard, synthetic polymers can serve as largely accessible
substitutes to mimic the structures and functions of
[8]
biomacromolecules. It is thus of great importance to design
and synthesize novel hyperbranched polyelectrolytes and
explore their potential applications.
Owing to the limited synthetic approach, the research
progress of hyperbranched polyelectrolytes is stagnant.
Typically, hyperbranched polymers are synthesized via the
Introduction
polycondensation of AB
2
monomers,[9] which lack chemical
Polyelectrolytes, such as DNA, RNA, and proteins, are
widespread in natural living systems, and possess biological
stability, require nontrivial synthetic efforts, and suffer from
unsatisfactory functionality.[10] Another most widely used method
1
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Angewandte Chemie International Edition
10.1002/anie.202104709
RESEARCH ARTICLE
is the copolymerization of A
3
and B
2
monomers,[11] which
which low-cost, commercially available arylnitriles and readily
generally requires strictly controlled conditions to avoid gelation,
large dispersity (Đ), and/or the formation of oligomeric
products.[12] On the other hand, the main strategy for the
synthesis of polyelectrolytes is the post-modification of nonionic
polymers,[13] which is hard to achieve 100% conversion
efficiency and leaves patches along the polymer chains. Some
coupling reactions (e.g., Heck and Sonogashira) are also
employed for the synthesis of polyelectrolytes, but they typically
accessible internal diynes were reacted via rhodium(III)-
catalyzed three-fold C−H activation in the presence of NaSbF
6
2
and H O/acetic acid (AcOH) to in situ generate heteroaromatic
hyperbranched polyelectrolytes (Scheme 1).[ These polymers
24]
were generated in excellent yields (up to 99%) with
6
extraordinary high molecular weights (M
w
up to 1.011 × 10 ) and
low Đ values. Surprisingly, these hyperbranched polyelectrolytes
were luminescent in the solid state with tunable emission
wavelength, high quantum yield, and good processibility, which
made them ideal materials for fluorescent photopatterning.
Because of their net positive charges and strong ROS
generation ability, these polymers could serve as effective
photosensitizers for photodynamic killing of bacteria. More
interestingly, we, for the first time, achieved the photodynamic
patterning of living organisms in a customizable fashion and
investigated the dynamic changes of the resulting biopatterns.
require
expensive
ionic
monomers.[14]
Besides,
the
aforementioned polymerizations are one or two-component
systems, which greatly restrict the structural and functional
diversity of polymers. In contrast with these “few-body” systems,
the “many-body” systems are commonly adopted by natural
polymerizations because the permutations and combinations of
multiple components can bring in rich biodiversity and infinite
possibilities.[15] As such, it is essential to develop
multicomponent polymerizations for the facile synthesis of
hyperbranched polyelectrolytes from stable monomers.
The development of novel hyperbranched polyelectrolytes
with unique structures and multifunctionalities is still in strong
demand. Although many hyperbranched polyelectrolytes have
been studied during the past several decades,[16] most of them
are commodity polymers with aliphatic backbones and no
advanced functionalities.[17] In addition, the investigation of
aromatic hyperbranched polymers often suffers from low
molecular weight, poor processability and poor solubility due to
π–π stacking, which discourage their real-world applications. In
this regard, the introduction of positively charged heteroaromatic
fused rings into the hyperbranched polymers can probably
address these issues and provide more opportunities. First, the
heteroaromatic fused rings can endow the polymers with unique
photophysical properties. Since the positively charged
heteroaromatic rings are highly electron-deficient, they can act
as appropriate donors to facilitate the formation of
donor−acceptor (D−A) structures to tune the emission
wavelength of polymers. On the other hand, the charges on the
aromatic rings also help suppress intermolecular and/or
intramolecular π–π stacking[18] to increase the solubility and
processibility of polymers.
Results and Discussion
Polymerization. All monomers used in this work were
easily acquired and chemically stable under ambient conditions.
Arylnitriles 1a−g, sodium hexafluoroantimonate(V) (NaSbF ),
6
and AcOH were low-cost and commercially available, and were
directly used without further purification. The internal diynes
2
a−c involved in this work were facilely synthesized in high
yields according to the previously reported procedures (Scheme
[25]
2 2 2
S1). All polymerizations were catalyzed by [Cp*RhCl ] , Ag O
6
and AgSbF in a one-pot manner.
To obtain soluble hyperbranched polyelectrolytes in high
yields and high molecular weights, we systematically
investigated the polymerization conditions using 1a, 2a, NaSbF
6
,
and AcOH/H O as monomers. Several key reaction parameters
2
were set as variables to examine their impacts on the resulting
polymers, including solvent type, monomer concentration,
monomer ratio, catalyst loading, reaction atmosphere, and
reaction time (Table 1). The effect of solvents on the
polymerization was first studied (Table1, entries 1−3). By
comparing the polymerization reactions in 1,2-dichloroethane
The heteroaromatic hyperbranched polyelectrolytes with
unique physiochemical properties are expected to open new
frontiers in their applications. On the one hand, the compact
hyperbranched structure helps rigidify the luminescent units,
which impedes the nonradiative decay by restricting
intramolecular motions to result in fluorescent emission and
intersystem crossing (ISC).[19] Such polymers are anticipated to
show high fluorescence quantum yields desired for fluorescence
imaging.[20] On the other hand, the polymers may undergo
(
DCE),
dimethylsulfoxide
(DMSO),
and
dichloromethane/methanol (DCM/MeOH, v/v, 1/1), the best
result was obtained in pure DCE, which gave a polymer with a
weight-average molecular weight (M
entry 1). Increasing the concentration of 2a from 50 to 100 mM
led to a sharp decrease in both M and yield due to the
w
) of 260 600 in 57% yield
(
w
incomplete dissolution of 2a (entry 4). However, when the
concentration of 2a was decreased from 50 to 30 mM, the
polymerization proceeded smoothly without gel formation even
when the reaction time was extended from 12 to 18 h, affording
1
efficient ISC to a long-lived T state and interact with adjacent
triplet oxygen to produce reactive oxygen species (ROS) for
photodynamic therapy (PDT).[21] Further, given the high charge
density in the backbone, these polymers may exhibit affinity to
negatively charged species in biological systems, such as DNA
and bacterial membrane.[14, 22] Besides, due to the eco-friendly
and non-invasive attributes as well as the high spatiotemporal
resolution of light,[23] PDT is promising for the precise patterning
of living organisms, which offer an opportunity to build various
kinds of bio-architectures in a cost-efficient way.
w
a polymer with M of 231 400 in 84% yield (entry 5). It was found
that the monomer ratio and catalyst loading also played crucial
roles in the polymerization (entries 5−9). When the theoretical
monomer loading ratio of [1a]:[2a] = 3:2 was adopted, a polymer
with a high M was obtained in a high yield (entry 5). However,
w
further increasing the amount of arylnitrile 1a or internal diyne 2a
led to a sharp decrease in yield (entries 6−7). On the other hand,
decreasing the loading of [Cp*RhCl
afforded a polymer with a higher M in a higher yield (entry 8).
However, both M and yield were sharply decreased by further
2 2
] from 10 to 5% mol
w
In this paper, we developed a four-component (AB
2 2
+ C +
w
D + E), seven-functional group polymerization approach, in
2
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Angewandte Chemie International Edition
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RESEARCH ARTICLE
Scheme 1. In-Situ Generation of Heteroaromatic Hyperbranched Polyelectrolytes by Polyannulation of Arylnitriles, Internal Diynes, NaSbF
AcOH/H O.
6
, and
2
Table 1. Optimization of the Polyannulation Reactiona
b
M
w
Đb
entry
solvent
DCE
[1a] (mM)
33
[2a] (mM)
50
[Rh] (%)
time (h)
12
yield (%)
57
1
2
3
4
5
6
7
8
9
10
10
10
10
10
10
10
5
260 600
2.1
DCM/MeOH
DMSO
DCE
33
50
12
Trace
Trace
Trace
84
33
50
12
67
100
30
12
DCE
20
18
231 400
208 300
1.9
6.7
DCE
20
40
18
24
DCE
25
30
18
Trace
97
DCE
20
30
18
307 100
46 400
29 700
417 800
2.1
1.7
1.3
1.6
DCE
20
30
2.5
5
18
65
1
1
0c
1
DCE
20
30
18
61
DCE
20
30
5
24
99
aUnless otherwise noted, the polymerizations were carried out at 120 °C in N
20 mol%), and Ag
O (6 equiv.). bEstimated by GPC in DMF on the basis of a linear polystyrene calibration. Đ = dispersity = M
in air.
, with the addition of NaSbF
(4 equiv.), H
O (12 equiv.), AcOH (9 equiv.), AgSbF
/M
. cThe reaction was conducted
2
6
2
6
(
2
w
n
Table 2. Polyannulation Results with Different Monomersa
reducing the amount of [Cp*RhCl
polymerization could also proceed in air without inert gas
protection, affording a polymer with M of 29 700 in 61% yield
entry 10). A time of 18 h was eventually adopted as the optimal
reaction time, as prolonging the reaction time to 24 h did not
give rise to much higher M and yield (entry 11).
Under the optimized polymerization conditions, different
arylnitriles and internal diynes were combined to evaluate the
robustness and universality of this polymerization (Table 2), in
which arylnitriles 1a−g possessed substituent groups with
different electron densities and steric hindrance, and internal
diynes 2a−c carried rigid conjugated or flexible spacers. As
shown in Table 2, arylnitriles 1a−g all reacted efficiently with
internal diynes 2a−c to give hyperbranched polyelectrolytes in
2
]
2
(entry 9). The
b
(MALLS)c
307 100
Đb
entry
monomer
1a/2a
1c/2a
1d/2a
1e/2a
1a/2b
1b/2c
1e/2c
1f/2c
yield (%)
97
M
w
w
1
2
3
4
5
6
7
8
9
2.1
2.3
2.2
1.6
1.5
1.5
1.7
1.3
1.3
(
87
198 800
124 000
482 200
35 300
96
w
94
83
84
35 400 (328 200)
51 300 (719 800)
25 800 (652 800)
26 000 (1011 000)
91
93
1g/2c
76
aUnless otherwise noted, the polymerizations were carried out at 120 °C in
DCE under N
12 equiv.), AcOH (9 equiv.), AgSbF
Ag
polystyrene calibration. Đ = dispersity = M
laser light scattering (MALLS) technique in THF.
2
for 18 h, with [1] = 20 mM, [2] = 30 mM, NaSbF
6
(4 equiv.), H
(5 mol%), and
linear
2
O
excellent yields with high molecular weights (M
1
w
up to 1.011 ×
(
6
(20 mol%), [Cp*RhCl ]
2
2
06). It is noteworthy that, the molecular weight of
a
(6 equiv.). bEstimated by GPC in DMF on the basis of
2
O
a
hyperbranched polymer is often underestimated when measured
by GPC using linear polystyrene as a standard, which is
attributed to the contracted conformation and the reduced free
volume of the globular hyperbranched polymer.[26] Indeed, when
the molecular weight of the hyperbranched polyelectrolytes were
measured by a multiangle laser light-scattering method, their
. cValue measured by multiangle
w
/M
n
calibrated ones (Table 2, entries 6−9). Surprisingly, although
hyperbranched materials synthesized by conventional
polymerization approaches typically exhibited very broad Đ
absolute M values were 9−38 times of the polystyrene-
w
3
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Angewandte Chemie International Edition
10.1002/anie.202104709
RESEARCH ARTICLE
often exceeding 5−10),[27] the Đ values of the present polymers
difficult to be derived from H, 13C or 19F NMR spectra because
of the overlapping of the resonances and broad signals arising
from structural isomerism.
1
(
were all lower than 2.3. The low Đ values were probably caused
by the large steric fused-rings, which significantly suppressed
the random cross-linking and gelation during the polymerization.
Based on the mechanism of a previously reported organic
reaction,[24] we proposed
a reaction mechanism for this
multicomponent polyannulation (Scheme S3). Thanks to the
C−H activation, two C−H bonds of the arylnitriles served as the
hidden functional groups to participate in the polymerization
process, and the three-fold C−H activation/annulation cascade
of monomers allowed the polyelectrolytes to grow in three
directions, to give hyperbranched polyelectrolytes with eight
possible isomers in the chemical structures (Figure S1 in the
Electronic Supporting Information).
All
the
obtained
heteroaromatic
hyperbranched
polyelectrolytes showed good solubility in commonly used
organic solvents, such as DCM, chloroform, DCE, acetone,
DMSO, and N,N-dimethylformamide (DMF), regardless of their
molecular weights and the size of the fused-ring moieties. The
thermal property of these polymers was evaluated by
thermogravimetric analysis. The decomposition temperature at
5
% weight loss under nitrogen was in the range of 201−257 °C
(
Figure S2), suggesting the high thermal stability of the present
polymers. It is noteworthy that P1d/2a retained more than 60%
of its initial weight even after heated to 800 °C, enabling it an
ideal ceramic material.
Figure 1. FT-IR spectra of (A) 1a, (B) 2b, (C) Model 3, and (D) P1a/2b.
Structural Characterization. To facilitate the structural
characterization of the hyperbranched polyelectrolytes, model
compound 3 was prepared by rhodium(III)-catalyzed cascade
annulation of 4-fluorobenzonitrile and diphenylacetylene under
the same synthetic conditions for the polymers (Scheme S2),
Photophysical and Optical Properties. Motivated by the
unique heteroaromatic fused-ring moieties in the molecular
structures, we systematically studied the photophysical
properties of the model compound and polymers. The
absorption spectra of the model compound and polymers in
chloroform (10 μM) were shown in Figure S32. Their maximum
absorption peaks were found in the range of 480−548 nm. By
incorporating different substituent groups to the strong electron-
withdrawing heteroaromatic fused rings, the maximum emission
wavelength of the polymers could be facilely tuned from 575 to
652 nm (Figure 2A). In particular, by introducing
tetraphenylethylene (TPE) into the polymer skeletons, the
resulting polymers P1a/2a and P1c−e/2a showed aggregation-
enhanced emission. Taking P1e/2a as an example, its
chloroform solution fluoresced weakly at 619 nm. Upon the
addition of hexane, a nonpolar poor solvent for the polymer, into
the chloroform solution, the emission intensity gradually
increased accompanied with a slight blueshift in the emission
maximum to 612 nm (Figure 2B and Figure S33). We further
examined the solid fluorescence of the as-synthesized model
compound and polymers. The emission of 3 and P1/2 powders
covered the spectral range from yellow, orange, and red to deep
red with a gradual shift in maximum emission wavelength from
and its spectral properties were in good accordance with the
literature.[24] Typical FT-IR, 1H NMR, 13C NMR and 19F NMR
spectra of model compound 3, polymer P1a/2b, and its
corresponding monomers 1a and 2b were collected for
comparative illustration. In the FT-IR spectra (Figure 1), the C≡N
stretching vibrations of 1a and the C≡C stretching vibrations of
-1
2
b occurred at 2233 and 2220 cm , respectively. However,
these peaks were not observed in the spectra of 3 and P1a/2b.
Meanwhile, new peaks associated with the delocalized C=O,
C=N, and Sb−F stretching vibrations emerged in the spectra of
-1
P1a/2b at 1741, 1641, and 657 cm , respectively, indicating the
occurrence of the polymerization. Similar observations were also
found in the FT-IR spectra of other polymers (Figure S3 and S4).
The H NMR and 13C NMR spectra of monomers 1a and 2b,
1
model compound 3 and P1a/2b in CD Cl were compared and
2
2
shown in Figure S6. New peaks emerged at δ 7.76 in the
spectra of 3 and P1a/2b, corresponding to the aromatic proton
absorptions from the newly formed heteroaromatic fused rings
Figure S6C−D). Besides, the 13C NMR spectra further verified
(
5
70 to finally 662 nm (Figure 2C and Figure S34). In general, the
our hypothesis on the chemical structure of the resulting polymer
synthesis of conventional red/deep red luminogens require
tedious synthetic steps because of the inclusion of π-conjugated
macrocyclic units. In addition, the resulting polymers often suffer
from aggregation-caused quenching to result in a low quantum
yield in the solid state.[ Notably, the thin films of P1/2 showed
high photoluminescence quantum yields (PLQY) of up to 14.3%
(
Figure S6E−H). The characteristic peak of C≡N in 1a was not
observed in the polymer spectrum, and, meanwhile, the intensity
of the characteristic C≡C peak in 2b was sharply decreased in
the polymer spectrum as a result of polyannulation. Instead, the
aromatic carbons at positions “d” resonated at δ 170.69 and
28]
1
70.71 in the spectra of 3 and P1a/2b, respectively. Similar
features were also observed in the spectra of other polymers
Figure S7−S31), confirming the successful synthesis of
(
Table S1). Particularly, the red-emissive P1e/2a film exhibited a
PLQY of 6.7% with CIE coordinates of (0.63, 0.36) (Figure S35).
The photostability study showed that the P1e/2a film retained
(
polymers with structures as shown in Scheme 1. However, the
degree of branching of the hyperbranched polyelectrolytes was
4
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RESEARCH ARTICLE
Figure 2. Photophysical and optical properties of model 3 and P1/2. (A) Emission spectra of P1/2 and model 3 in chloroform. Concentration: 10 μM. Excitation
wavelength: 365 nm. (B) Plot of relative emission intensity (I/I ) versus the composition of hexane/chloroform mixtures of P1e/2a. Inset: Photographs of P1e/2a in
hexane/chloroform mixtures with different hexane fractions (f ) taken under UV irradiation from a handheld UV lamp. Concentration: 1 μM. I = PL intensity in pure
chloroform. Excitation wavelength: 365 nm. (C) Luminescent photographs of polymer P1/2 and model 3 in the solid state. (D) Wavelength dependence of
refractive index of thin films of P1c/2a and P1e/2a. Abbreviation: n = refractive index, ν ’ = modified Abbé number = (n1319 – 1)/(n1064 – n1559), D’ = chromatic
dispersion 1/ν ’. (E) Two-dimensional fluorescent photopatterns generated by photolithography of films of P1c/2a. (F) Two-dimensional fluorescent
photopatterns generated by photolithography of films of P1e/2a with zoom-in form (left) and the grayscale intensity profile of the arrowed area (right).
0
H
0
D
=
D
more than 70% of its initial absorbance when irradiated by white
light at a power density of 100 mW/cm for 60 min, indicating its
good photostability (Figure S36). The efficient solid-state
emission of the polymers indicated their great potential as light-
emitting coating materials and fluorescent sensors.
which were higher than those of some inorganic gems, such as
emerald (n1079.5 = 1.566 and n1341.4 = 1.560), and much higher
than those of the commercial optical polymers, such as
polycarbonate (n632.8 = 1.581), poly(methyl methacrylate) (n632.8
2
= 1.489 and n1550 = 1.481), and polydimethylsiloxane (n632.8
1.428).[31]
=
High-refractive-index polymers are promising candidate
materials for optical engineering applications, such as optical
chips, prisms, optical waveguides, and holographic image
recording systems.[29] Polarizable aromatic rings and
heteroatoms, particularly halogen elements are well-known
The generation of highly ordered macro- and micro-
fluorescent patterns by photolithography is of great significance
for the construction of optical display devices, optical writing and
reading, and anti-counterfeiting applications.[32] Thanks to the
excellent film-forming ability and efficient solid-state emission of
the present polymers, it is possible to fabricate their uniform
fluorescent films without defects on silica wafers by a simple
spin-coating technique. Upon exposing the polymer thin films to
UV light at room temperature for 40 min under a customizable
photomask, the fluorescence of the exposed regions was
completely quenched due to the photo-oxidation of the
[30]
contributors for enhancing the refractive index (n). In view of
the unique chemical structure, we measured the n values of the
synthesized polymers with polarized heteroaromatic fused rings
by using P1c/2a and P1e/2a for demonstration. As summarized
in Figure 2D, both polymers showed high n values with small
chromic dispersion. Interestingly, P1e/2a possessed high n
values of 1.686−1.600 in the spectral region of 575−1690 nm,
5
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RESEARCH ARTICLE
chromophores,40 whereas the non-irradiative regions remained
intact and highly emissive (Figure 2E), which favored the
generation of a fluorescent QR code pattern. In addition to
macro-pattern, other sophisticated patterns with varying sizes
and contents could also be readily generated by changing the
scale and shape of the photomask. As shown in Figure 2F, a
fluorescent rose-shaped macro-pattern was easily created.
When examining the enlarged image of a selected location, it
was found that each region in the macro-pattern was actually
composed of gridlike micro-pattern with sharp edges, indicating
the high resolution and structural complexity. The facile, rapid,
and precise generation of highly emissive patterns demonstrated
the promise of the present polymers in photonic and electronic
applications.
Figure S38). For comparison, the performance of Rose Bengal,
1
a most widely used photosensitizer for O
2
generation, was also
tested under the same condition. In the presence of
polyelectrolytes and white-light irradiation, a noticeable decrease
of ABDA absorption at 378 nm was observed. Specifically, the
1O
generation efficiency of P1e/2a was much higher than Rose
2
1
Bengal. P1c/2a and P1d/2a were also able to generate
O
2
more effectively than Rose Bengal, but P1e/2c showed inferior
performance. According to a method reported in previous
studies,[35] the 1
O
quantum yields of P1c/2a, P1d/2a, P1e/2a
and P1e/2c were determined to be 0.943, 0.899, 0.975, and
0.375, respectively (Figure S39). The strong 1O
generation
2
2
efficiency of P1c−e/2a was probably ascribed to its conjugated
D−A structure, which significantly reduced the singlet–triplet
energy gap and promoted the intersystem crossing (ISC)
process. On the other hand, the compact hyperbranched
structures of P1c−e/2a rigidified the intramolecular motions of
the polymer backbones, which suppressed the nonradiative
decay and facilitated the ISC process. Although P1e/2c also
Reactive
Oxygen
Species
(ROS)
Generation.
Heteroaromatic cations such as pyridinium salts and
quinolizinium salts have been reported to be typical acceptor
groups for efficient generation of ROS.[19b, 33] In this regard, the
novel heteroaromatic, carbocationic moieties in the present
polyelectrolytes encouraged us to explore their ROS generation
ability. Two commercial ROS indicators, including 2',7′-
possessed strong D−A pairs in the polymer structure, its 1
O
2
generation ability was quite low due to the active intramolecular
motions induced by the flexible oligo(ethylene glycol) chains,
which consumed the excited-state energy nonradiatively.
dichlorofluorescin
(DCFH)
and
9,10-anthracenediyl-
bis(methylene)dimalonic acid (ABDA), were used to evaluate
ROS generation of the P1c/2a, P1d/2a, P1e/2a and P1e/2c as
demonstration. DCFH is a nonfluorescent probe, but can be
Bacterial Killing and Photodynamic Biopatterning. The
1
strong O
2
generation ability of the polymers encouraged us to
converted
to
the
highly
fluorescent
form
(2′,7′-
further explore their potential in photodynamic killing of bacteria.
P1e/2a, the strongest photosensitizer for ROS generation, was
chosen for subsequent biological experiments. We first
characterized the particle size and zeta potential of P1e/2a
aggregates upon addition of its solution to phosphate buffered
saline (PBS). The hydrodynamic diameter of P1e/2a aggregates
ranged from 70−150 nm with a zeta potential of 7.79 ± 0.75 mV
(Figure 4A). In addition, we also performed transmission
electron microscopy (TEM) characterization to confirm the
particle size (Figure 4A inset). Because of its positive charge,
P1e/2a tended to accumulate on the negatively charged
bacterial membrane through electrostatic interactions. Such
property enabled fluorescent labeling of methicillin-resistant
Staphylococcus aureus (MRSA) by P1e/2a within 60 min (Figure
dichlorofluorescein; DCF) when oxidized by various ROS. As
shown in Figure 3A and Figure S37, in the absence of polymers,
DCFH remained nonfluorescent even upon white-light irradiation
2
(
8 mW/cm ). In contrast, in the presence of polymers and white-
light irradiation, the emission associated with DCF at 524 nm
was significantly increased, indicating that thees polymers could
be used to sensitize the generation of ROS.
4
B). Next, we evaluated the quantitative inactivation of MRSA by
P1e/2a in the presence or absence of white-light irradiation
Figure S40 and Figure 4C). In the dark, there was a moderate
(
concentration-dependent inhibition on the bacterial viability,
which was attributed to the membrane-damaging effect of the
positively charged polymers. In contrast, the viability significantly
decreased by two orders of magnitude in the presence of white-
light irradiation due to the additional destructive effect by the
produced ROS by P1e/2a. When the concentration of P1e/2a
reached 30 g/mL, the bacterial killing efficiency was determined
to be 99.2%, which indicated the outstanding photodynamic
effect of P1e/2a. To visualize the antibacterial effect of P1e/2a,
live/dead dual-color fluorescent staining was performed. As
shown in Figure 4D, a large proportion of MRSA incubated with
P1e/2a for 30 min were stained with green fluorescence in the
absence of light irradiation, indicating the relatively large survival
rate and weak antibacterial effect. In contrast, the ratio of red
fluorescence was remarkably increased in the presence of light
irradiation, and no green fluorescence could be found. These
results were in accordance with the aforementioned quantitative
study. Furthermore, the morphology of MRSA upon different
treatments was characterized by scanning electron microscopy
Figure 3. Reactive oxygen species (ROS) generation of P1/2. (A) Changes of
fluorescence intensity at 524 nm of 2’,7’-dichlorofluorescin (DCFH) in the
presence or absence of P1c/2a, P1d/2a, P1e/2a, and P1e/2c in aqueous
suspension with white-light irradiation for different time periods. (B) The
decomposition rates of 9,10-anthracenediyl-bis(methylene)dimalonic acid
0
(ABDA) by P1c/2a, P1d/2a, P1e/2a, P1e/2c, and Rose Bengal, where A and
A are the absorbance of ABDA in the presence of photosensitizers at 378 nm
before and after white-light irradiation, respectively.
1
Singlet oxygen ( O
2
) is one of the important ROS species
with significant applications in several fields, including organic
synthesis and photodynamic therapy.[34] It is thus essential to
measure the 1O
presence of O
generation ability of these polymers. In the
2
, the absorption of ABDA became weakly due to
2
1
its conversion to endoperoxide. Thus, under white-light
irradiation, we recorded the absorbance spectra of ABDA in the
presence of P1e/2a, P1c/2a, P1d/2a and P1e/2c (Figure 3B and
6
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Angewandte Chemie International Edition
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RESEARCH ARTICLE
Figure 4. Antibacterial behaviors of P1e/2a. (A) Size distribution of P1e/2a measured by dynamic light scattering. Inset: A TEM image of P1e/2a aggregates.
Concentration: 30 μg/mL. Scale bar: 100 nm. (B) CLSM images of bacteria incubated with P1e/2a for different time, where P1e/2a was shown in red. (C)
Statistical analyses of the bacterial viability by the logarithm number in the absence and presence of white-light irradiation. (D) Live/dead staining of bacteria with
different treatments, where live and dead bacteria were shown in green and red, respectively. (E) SEM images of bacteria with different treatments.
(
SEM, Figure 4E). After treated with P1e/2a in the absence of
group incubated with P1e/2a and irradiated with white light, a
clear gridlike pattern could be identified, which became denser
in the masked region (i.e. grid) and coarser in the unmasked
region (i.e. slit) over time. In contrast, no evident gridlike
patterns were created for the control groups without the addition
of P1e/2a. Such results were also confirmed by the
corresponding fluorescence images taken under a 365-nm UV
lamp (Figure S41). To gain more insight into the details of
bacterial growth, we employed confocal laser scanning
microscopy (CLSM) to characterize the three-dimensional (3D)
structure of the living bacterial patterns (Figure 5C). At 12-h
post-incubation, a representative grid was sparse in shape,
which was characterized by a typical size of 1796  7 m  1795
 4 m with a height of 138  5 m. Upon extending the
incubation time, the grid gradually expanded, and the
corresponding dimensional parameters changed to 2183  3 m
 2199  6 m  407  3 m at 36-h post incubation. Meanwhile,
the fluorescence in the slit started to emerge and eventually
merged with the grid, and the spacing distance between
adjacent grids was narrowed from 960  2 m at 12-h post
incubation to 551  8 m (Figure S42). As photodynamic
biopatterning provided a simple and cost-effective way to
fabricate 3D living biopatterns, the present results thus
demonstrated the potential of these hyperbranched
polyelectrolytes in photo-manipulating the biological behaviors of
living organisms.
light irradiation, the smooth membrane surface of the bacteria
became rough and was partially collapsed. When irradiated with
white light, the bacteria were damaged with serious membrane
splitting and deformation due to the photodynamic effect of
P1e/2a.
Considering the high photokilling efficiency of P1e/2a
toward bacteria, it is possible to explore its new application in
photo-patterning of living organisms, which allows for the
creation of adaptive, customizable, and dynamic bio-
architectures to investigate their potential in cell migration, tissue
engineering, and biochips.[36] Because light is a low-cost and
noninvasive manipulation tool with high spatiotemporal
resolution, we decided to fabricate living bacterial patterns by
means of the photodynamic effect of P1e/2a, in which green
fluorescent protein (GFP)-expressing S. aureus was employed
to visualize the dynamic change of the resulting biopatterns. As
shown in Figure 5A, the dilute bacterial solution mixed with
P1e/2a was irradiated by white light through a pre-printed
gridlike adhesive mask for 20 min. The ROS generated by the
polymers efficiently killed the bacteria in the unmasked region,
while the bacterial viability in the masked region remained
unaffected. Further incubation of the whole set-up in the dark
favored the rapid growth and proliferation of the GFP-expressing
S. aureus in the masked region, leading to the formation of an
array of bacterial grids that were replicated from the mask. We
then monitored the dynamic change of the produced biopatterns
at 12, 18, 24, and 36-h post-incubation (Figure 5B). For the
7
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Angewandte Chemie International Edition
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RESEARCH ARTICLE
Figure 5. Photodynamic patterning of bacteria with P1e/2a. (A) Schematic illustration showing the bacterial patterning with a white light source and a pre-printed
adhesive mask. (B) Photographs of the bacterial pattern taken under a sun lamp at 12, 18, 24, and 36-h post white-light irradiation. “Polymer/Light” and
“PBS/Light” represent the groups that were incubated with P1e/2a and PBS, respectively, followed by white-light irradiation, while “PBS/Dark” indicates the group
that was incubated with PBS only. The yellow dashed rectangles outline the region of interest presented in the CLSM images. (C) Three-dimensional CLSM
images of a bacterial grid viewed from top and side views. The yellow dashed lines outline the border of the bacterial grid, while the red line indicates the bottom
plane of the bacterial grid. The bacteria were shown in green.
concurrently endowed the polymers with tunable emission. The
compact hyperbranched architecture of the polymers restricted
their intramolecular motions to suppress the nonradiative decay
to result in high fluorescence quantum yields (up to 14.3%) in
Conclusion
the solid state, which enabled the polymers to fabricate highly
ordered fluorescence photopatterns at different scales. Upon
white-light irradiation, these polymers could produce considerate
ROS for the efficient inactivation of bacteria. Furthermore, we,
for the first time, demonstrated the possibility of the
hyperbranched polyelectrolytes for the creation of customizable
living bacterial patterns via PDT. The efficient multicomponent
polymerization introduced here provided a facile strategy for the
synthesis of hyperbranched polyelectrolytes to enrich their family
members. The unique properties and functionalities of the
resulting polymers offered great opportunities for a multitude of
follow-up studies, such as photoelectronic materials, disease
theranostics, biochips, and tissue engineering.
In summary, we developed an efficient multicomponent
polymerization to in situ generate functional heteroaromatic
hyperbranched polyelectrolytes using readily accessible internal
diynes and low-cost, commercially available arylnitriles, NaSbF
6
,
and O/AcOH in one-pot manner. Compared with
H
2
a
conventional synthetic approaches, the present strategy
involved neither unstable and expensive monomers nor strictly
controlled conditions. The polymerization could proceed
efficiently with
a broad spectrum of monomers, affording
functional polymers in excellent yields (up to 99%) and
up to 1.011 × 106).
extraordinary high molecular weights (M
w
Notably, all the polymers showed low Đ values and high
solubility in common organic solvents, regardless of their
molecular weights and fused aromatic units. The positively
charged heteroaromatic rings were highly electron-deficient,
which facilitated the formation of D−A structures and
8
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RESEARCH ARTICLE
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1
0
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Entry for the Table of Contents
Insert graphic for Table of Contents here.
A multicomponent polymerization for the efficient synthesis of heteroaromatic hyperbranched polyelectrolytes was developed. These
hyperbranched polymers showed excellent solubility, high quantum yields, tunable emission, and strong ROS generation ability,
allowing for their widespread applications in highly ordered fluorescent photopatterning, efficient bacterial killing, and customizable
photodynamic patterning of living organisms.
Institute and/or researcher Twitter usernames: BenZhongTANG1; piter_tree
1
1
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