Imine-linked porous organic polymers showing mesoporous microspheres architectures with tunable surface roughness

Article abstract of DOI:10.1002/pola.28902

Different kinds of porous organic polymers (POPs) bearing 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (BDP) fluorophores have been developed to generate singlet oxygen upon light illumination. Herein, four imine-linked POPs were prepared by copolymerization of amine and aldehyde with different ratios of di-aldehyde A1 and A2. The POPs were investigated by a combination of techniques such as solid ¹³C NMR, FTIR, and nitrogen absorption–desorption isotherms and electronic microscopy. The results demonstrated that these POPs were prone to form hierarchical porous architectures. Scanning electron microscopy and transmission electron microscopy images revealed that the spherical morphologies showed different roughness, that is, BDP-POPs with more BDP aldehyde A2 presented rougher surface. Finally, these POPs were used to generate singlet oxygen (¹O₂) monitored by 1,3-diphenylisobenzofuran and bioimaging in HeLa cells. Our results indicated that the ability to generate ¹O₂ is dependent on the amount of BDP.

Full text of DOI:10.1002/pola.28902

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Imine-Linked Porous Organic Polymers Showing Mesoporous
Microspheres Architectures with Tunable Surface Roughness
1
Fan Song,1 He Zhang,2 De-Gao Wang,1 Tao Chen,2 Shen Yang,2 Gui-Chao Kuang
1State Key laboratory of Power metallurgy, Department of Polymer Materials and Engineering, Central South University,
Changsha, Hunan 410083, People’s Republic of China
2Chongqing Key Laboratory for Oral Diseases and Biomedical Sciences, College of Stomatology Chongqing Medical University,
Chongqing 400016, People’s Republic of China
Correspondence to: G.-C. Kuang (E-mail: gckuang@csu.edu.cn) or S. Yang (E-mail: ysdentist@hotmail.com)
Received 29 July 2017; accepted 21 October 2017; published online 00 Month 2017
DOI: 10.1002/pola.28902
ABSTRACT: Different kinds of porous organic polymers (POPs)
bearing 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (BDP) fluoro-
phores have been developed to generate singlet oxygen upon
light illumination. Herein, four imine-linked POPs were pre-
pared by copolymerization of amine and aldehyde with differ-
ent ratios of di-aldehyde A1 and A2. The POPs were
investigated by a combination of techniques such as solid 13C
NMR, FTIR, and nitrogen absorption–desorption isotherms and
electronic microscopy. The results demonstrated that these
POPs were prone to form hierarchical porous architectures.
Scanning electron microscopy and transmission electron
microscopy images revealed that the spherical morphologies
showed different roughness, that is, BDP-POPs with more BDP
aldehyde A2 presented rougher surface. Finally, these POPs
were used to generate singlet oxygen (1O2) monitored by 1,3-
diphenylisobenzofuran and bioimaging in HeLa cells. Our
results indicated that the ability to generate 1O2 is dependent
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on the amount of BDP. 2017 Wiley Periodicals, Inc. J. Polym.
Sci., Part A: Polym. Chem. 2017, 00, 000–000
KEYWORDS: armorphous; BODIPY; dyes; fluorescence; polyam-
ide; porous polymers; roughness; singlet oxygen; solid-state;
surface roughness
films based on multiple thiophene and carbazole units were
obtained to find application photovoltaic devices.25,26 The
photophysical properties of these POPs are tuned by the fol-
lowing three strategies: (1) introduction of low loading of
INTRODUCTION Great progress has been made in porous
organic polymers (POPs) area in the last several decades.1–4
These fascinating functional materials offer great advantages
due to their structural flexibility on molecular design and post
modification, thus show promising applications in various
fields such as gas adsorption and separation,5–8 organic cataly-
sis,9–11 environmental remediation,12 and chemical sens-
ing.13,14 According to the structural regularity, there are two
types of POPs. One type is crystalline POPs such as covalent
organic frameworks,15,16 which were obtained by dynamic
covalent chemistry. The other one is amorphous POPs, includ-
ing conjugated microporous polymers (CMPs),17–19 porous
aromatic frameworks,20 hyper crosslinked polymers,21 and so
on. These amorphous polymers were prepared by classic
organic coupling reactions.
acceptor comononer during the polymerization27,28
; (2)
change the solvent polarity or state29; (3) addition of new
fluorescent quencher compounds.30,31
Although great achievements have been made in the POPs area,
people still devote considerable effort to advance their under-
standing on topologies, dimensionality and kinetics.32 For exam-
ple, the luminescent POPs with tunable surface morphologies
have rarely been referred. We have been interested in fluorescent
amphiphilic 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (BDP)
derivatives since 2014.33–36 Very recently, a novel about dimeric
BDP molecules based POPs could be realized by using FeCl3 at
room temperature was reported.37,38 The BDP based CMP was
firstly demonstrated great ability to capture volatile iodine vapor
by physical and chemical adsorption.39 In implementing our
former work, in this contribution, four imine-linked POPs were
prepared by varying the BDP units’ fraction and their porosities
were investigated. Considering BODIPY fluorophores could
Luminescent POPs using fluorescent building blocks have
been well developed.22 For example, the color of POPs could
be tuned from green to near infrared red by adjusting the
comonomers molar ratio.23 Photoelectric POPs by three com-
ponents design strategy were prepared to explore the energy
conversion efficiency.24 Several interesting luminescent POPs
Additional Supporting Information may be found in the online version of this article.
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SCHEME 1 Synthetic route for A2. Condition: (a) I2, HIO3, THF, ethanol; (b) 4-formylphenyl boronic acid, Pd(PPh3)4.
generate singlet oxygen upon visible light irradiation, these POPs
were used in bioimaging test and pursue their application in the
photodynamic therapy.
solution was dropped onto the copper grid coated with car-
bon support films. Then the surface liquid on the copper
grid was evaporated at room temperature for 2 days. Powder
X-ray diffraction (XRD) patterns of the dried samples were
measured on Siemens D 500.
EXPERIMENTAL
Materials
Synthesis
All reagents were purchased from various commercial sour-
ces and used without further purification unless otherwise
stated. All reactions were carried out in oven dried glass-
ware under an inert atmosphere of nitrogen. Analytical thin-
layer chromatography (TLC) was performed using TLC plates
precoated with silica gel (TLC: 10–40 mm, 0.2 6 0.03 mm).
Flash column chromatography was performed using 40–
63 M (230–400 mesh) silica gel as the stationary phase.
Monomers
Synthesis of A1 are according to literature.40 Compound A1
was obtained as white power (100 mg, 70%). 1H NMR
(500 MHz, CDCl3, d): 10.07 (s, 2H, CH), 7.98 (d, 4H, CH),
7.78 (d, 4H, CH). Synthesis of Compound 1 and 2 are according
to literature.41 Compound 1 was obtained as orange-yellow
1
power (293 mg, 17%). H NMR (500 MHz, DMSO-d6, d): 1.37
(s, 6H, CH3), 2.55 (s, 6H, CH3), 5.97 (s, 2H, CH), 7.28 (t, 2H, CH),
7.48 (t, 3H, CH). Compound 2 was obtained as red crystals
(350 mg, 94%). H NMR (500 MHz, DMSO-d6, d): 1.33 (s, 6H,
CH3), 2.54 (s, 6H, CH3), 7.40 (t, 2H, CH), 7.59 (t, 3H, CH).
Characterization
NMR
1
1H and 13C NMR spectra were recorded at 500 and 125 MHz
at room temperature, respectively. All chemical shifts were
reported in units relative to tetramethylsilane (TMS). Solid-
state 13C MAS NMR spectra were recorded from an AVANCE
||| 500 MHz produced by Bruker.
Synthesis of A2
Under N2 atmosphere, a mixture of compound 2 (85 mg,
0.148 mmol), 4-formylphenyl boronic acid (48 mg, 0.33
mmol), and K2CO3 (200 mg, 1.45 mmol) was dissolved in 1,
4-dioxane (10.0 mL), and the mixture was bubbled with N2
for 15 min. Pd(PPh3)4 (12 mg, 0.30 mmol) was added, and
the mixture was refluxed for 12 h. Then the mixture was
cooled to room temperature, water was added (30 mL)
(Scheme 1). The mixture was extracted with dichloromethane
(3 3 30 mL). The combined organic layer was dried over
Na2SO4. After removal of the solvent under reduced pressure,
the crude product was purified by column chromatography
(silica gel, DCM) to give wine red solid (49 mg, 62%).
High-resolution mass spectrometry experiments were per-
formed with a Bruker Daltonics Apex IV spectrometer. The
monomer in methanol was analyzed in negative model. UV-
vis adsorption spectra were measured by a Hitachi U-5100.
Fluorescence measurements were carried out by Hitachi F-
2700 with a Xenon discharge lamp excitation. FTIR spectra
were collected on a V Nicolet 6700 FTIR (scimitar series)
spectrometer in the 400–4000 cm21 region. Samples were
prepared by dispersing in anhydrous KBr. Thermogravimetric
analysis (TGA) was performed at a heating rate of 10 K/min
under N2. The cumulative apparent surface areas for N2
were calculated on Micro ASAP 2020 using the Brunauer-
Emmett-Teller (BET) model range from 0.01 to 0.1 bar for
all samples. Microporous volumes were calculated using the
t-plot method, while the total porous volumes were obtained
from the N2 isotherm at P/P0 5 0.99. Pore size distributions
were derived from the N2 adsorption isotherms using DFT
methods. Mass spectrum was obtained by using Tsq quan-
tum access max from Thermo. Scanning electron microscope
(SEM) images were carried out on a FEI SIRION200 micro-
scope. Before measurement, all the samples should be coated
with gold before test. Transmission electron microscopy
1H NMR (500 MHz, CDCl3, d): 1.33 (s, 6H, CH3), 2.57 (s, 6H,
CH3), 7.34 (d, 6H, CH), 7.52 (t, 3H, CH), 7.91 (d, 4H, CH),
10.03 (s, 2H, CH). 13C NMR (500 MHz, CDCl3, d): 191.8,
154.3, 140.2, 139.7, 135.1, 130.8, 130.0, 129.5, 129.3, 127.8,
53.4, 29.7, 22.7, 14.1, 13.5, 12.8. HRMS (ESI): m/z calcd for
C33H26BF2N2O2, [M-H]-: 531.2055, found: 531.1930.
BDP-POPs
The procedures for preparation of POPs are similar. This
series of POPs were prepared by the Schiff-based reaction
between di-aldehyde (A1 and A2 with different molar ratios)
and 1,3,5-tris(4-aminophenyl)benzene
B
in 1,4-dioxane
(2 mL) with acetic acid (6.0 M, 0.2 mL) as catalyst (Scheme
2). The BDP di-aldehyde A2 content increased from 0% to
100% for the BDP-POP-n (n 5 5, 6, 7, and 8). The reaction
(TEM) images were performed on
microscope. For the preparation of the sample, a drop of the
a JEOL JEM-2100F
2
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photographed by a Zeiss LSM 710 Spectral Confocal Laser
Scanning Microscope (CLSM).
Cell Viability Assay
The HeLa cells (ATCC) were cultured in 96-well cluster (Corning
Inc, NY, USA) at a density of 1 3 103 cells per well with 100 lL
of minimum essential medium (MEM)/EBSS (Hyclone Laborato-
ries, GE Healthcare Life Sciences, Logan) for 24 h. After the cells
completely adhered to the plate, the medium was changed with
new suspensions contained 0.012 mg/mL POPs. Then, the cells
were incubated for another 24 h. After washed three times with
Dulbecco’s phosphate-buffered saline, and 100 lL of fresh
MEM/EBSS and 10 lL of test reagent were added. The absor-
bance of the supernatant at 450 nm was quantified after 2 h
using a multi-well plate reader (BioTek Instruments Inc, Winoo-
ski) to evaluate cell viability. The relative viability was calcu-
lated by using the following formula: relative viability5 [(As–
Ab)/(Ac–Ab)] 3 100%, where As is the experimental OD, Ac is
the control OD, and Ab is the blank OD.
SCHEME 2 Synthesis of BDP-POPs. Condition: acetic acid,
1,4-dioxane, 120 8C, 72 h. [Color figure can be viewed at
wileyonlinelibrary.com]
RESULTS AND DISCUSSION
The BDP-POPs were investigated by FTIR and solid NMR
first. FTIR results demonstrated that the absorption from
aldehyde at 1700 cm21 disappeared and new peak assigned
to imine linkage at 1622 cm21 appeared [Fig. 1(a)]. In addi-
tion, the peaks intensity ascribed to BDP increased gradually
as the content of BDP di-aldehyde A2 increased. For exam-
ple, the characteristic peaks of BDP at 1000, 1165, and
1508 cm21 were pretty weak for BDP-POP-5, but became
obvious when 1 mol% of A2 was copolymerized for BDP-
POP-6, and further enhanced for BDP-POP-7 and BDP-POP-
8.42 This result indicated that the content of BDP in the pol-
ymers was consistent with the molar ratio for the monomers
A1 and A2. In contrast, the solid NMR spectra results were
not sensitive to the content of BDP in the polymers [Fig.
1(b)]. The solid NMR spectra are similar for BDP-POP-n
(n 5 5, 6, and 7) when the copolymerized BODIPY molar
ratio was lower than 10 mol%. However, BDP-POP-8 NMR
spectrum shows a characteristic peak at 10 ppm, which was
attributed to the methyl substituents on the BDP units. On
the other hand, the peaks band in 113–151 ppm region
became broader, which might indicate that the BDP and the
phenyl rings formed highly extended conjugated architec-
tures. These POPs are thermal stable and would not decom-
pose until 300 8C. In addition, the temperatures for these
polymers remained 90 wt % were dependent on the BDP
fraction, that is, more copolymerized BDP units lead to low
thermal stability (Supporting Information Fig. S1). The pro-
cedure to prepare the porous polymers was not strict, and
thus the powder is amorphous without crystallinity as evi-
denced by the XRD (Supporting Information Fig. S2).
yields were determined by gravity. Detailed synthesis and
characterizations are described in Supporting Information.
Herein, the synthesis of BDP-POP-8 was used as an example:
A2 (36 mg, 0.07 mmol) and 1,3,5-tris(4-aminophenyl) benzene
(16 mg, 0.05 mmol) were added into a reaction tube (volume
10 mL with a body length of 10 cm and a neck length of 5 cm)
and then dissolved in of 1,4-dioxane (2.0 mL). Then aqueous
acetic acid (0.2 mL, 6.0 mol/L) was added to the mixture. The
solution was degassed with three freeze–pump–thaw cycles.
After filled of nitrogen, the tube was warmed up to room tem-
perature, and then placed in an oven at 120 8C for 72 h without
disturbance. After that, a red solid along the tube was isolated
by filtration. The crude product was washed with N,N-dime-
thylformamide (3 3 10 mL) and tetrahydrofuran (3 3 10 mL),
and dried at 80 8C under vacuum for 12 h to yield BDP-POP-
8 as a red powder (28 mg, 87%). BDP-POP-5, BDP-POP-6, and
BDP-POP-7 were synthesized by the similar route with yield
75%, 65%, and 72% respectively.
Live Cell Imaging
In vitro cytotoxicity was tested by means of a Tecan Infinite
M200 monochromator based multifunction microplate reader.
Confocal fluorescence imaging was performed on an inverted
microscope (1 3 81, Olympus) equipped with a confocal scan-
ning unit (FV1000, Olympus).The HeLa cells were grown to
70%–80% confluence before being trypsinized and plated on
24-well plate with sterilized round coverslips at a density of 1
3 104 cells per well with Dulbecco’s modified Eagle’s medium
(Gibco) containing 10% fetal bovine serum (Gibco). After being
incubated for 24 and 48 h, respectively, the cells were fixed
with cold 4% paraformaldehyde for 10 min and washed with
phosphate-buffered saline (PBS) three times on orbiter rotator.
Then the cells were sealed with prolong gold mounting
med/4’,6-diamidino-2-phenylindole (DAPI) (Invitrogen) and
The permanent porosity of the BDP-POPs was investigated
by nitrogen adsorption–desorption isotherms at 77 K. The
samples were activated at 120 8C for 6 h before measure-
ment. All the four isotherms show fully reversible adsorp-
tion–desorption curves. For BDP-POP-5 at low relative
pressure (P/P0 < 0.05), the nitrogen isotherms presented
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different sizes, which was dependent on the BODIPY units’
molar ratio in the polymers. For example, the BDP-POP-
8 shows the particle size with the diameter is less than 0.4
lM, while the other three microspheres diameters are in the
range of 1–2 lM. What impressed us more is that the sur-
face roughness of the microspheres is related to the BODIPY
content. For the polymer BDP-POP-5, which was prepared
just by A1 and B, the surface of corresponding microsphere
turns to be smooth [Fig. 3(a)]. BDP-POP-6 with only 1
mol % of BODIPY unit incorporated in the polymer, the
microspheres surface became a little bit rougher [Fig. 3(b)].
While the surface of BDP-POP-7 microspheres, which copo-
lymerized 10 mol % of BODIPY unit, turned to be much
rougher [Fig. 3(c)]. The microsphere size and surface rough-
ness dependence on the BDP molar ratio were further veri-
fied by TEM (Fig. 4). Consistent results were obtained for
the four polymers.
High resolution TEM (HRTEM) revealed the porous struc-
tures (Fig. 5).
FIGURE 1 (a) FTIR and (b) solid-state 13C MAS NMR spectra
of four porous polymers. [Color figure can be viewed at
wileyonlinelibrary.com]
some enhancement, indicating that a characteristic micropo-
rous nature. This porosity might be ascribed to type I iso-
therm character according to IUPAC classification. At relative
high pressure (P/P0 5 0.05–0.9), the nitrogen adsorption of
the polymers increased gradually. Sharp increase in BDP-
POP-5 and BDP-POP-8 adsorption was observed when the
pressure was in the range of P/P0 5 0.9–1.0 with apparent
hysteresis in this region. The porosities were further ana-
lyzed by nonlocal density functional theory (NLDFT) model,
which revealed that only BDP-POP-5 presented small micro-
pores (pore size smaller than 2 nm), while the other three
polymers showed mesopores (Fig. 2). Therefore, the pore
size would change to be larger one after induction of BOD-
IPY building blocks. This result is consistent with Zhang’s
observation that pore size distribution is dependent on the
size of building blocks43 (Table 1).
FIGURE 2 (a) The porosity of the BDP-POPs was investigated
by nitrogen adsorption–desorption isotherm. (b) Pore size dis-
tribution for BDP-POP-5, BDP-POP-6, BDP-POP-7, and BDP-POP-
8 calculated by NLDFT measured at 77 K. [Color figure can be
viewed at wileyonlinelibrary.com]
SEM and TEM were performed to investigate these four
porous polymers BDP-POPs morphologies. The SEM images
revealed that these polymers were spherical particles with
4
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TABLE 1 Porosity Parameters of POPs Studied in This Work
Polymer
BDP Ratio (mol)
SBET (m2/g)a
Vtotal (cm3/g)b
Vmicro (cm3/g)
V
micro/Vtotal
Dpore (nm)
BDP-POP-5
BDP-POP-6
BDP-POP-7
BDP-POP-8
0%
50.8
18.5
36.7
39.3
0.15
0.05
0.08
0.11
0.02
0.01
0.01
0.01
0.13
0.20
0.13
0.09
2.0, 6.2, 11.8
5.8, 11.4
5.3, 8.2
1%
10%
100%
5.3, 11.2
a
b
Surface area calculated from the nitrogen adsorption based on BET model.
The value were determined at P/P0 5 0.99.
As mentioned above, the surface textures of the microsphere
can be tunable by simply varying the content BODIPY deriva-
tives A2. We are not sure the detailed mechanism responsi-
ble for the microspheres with different surface toughness.
But the kinetics controlled process might be used to support
the microspheres formation. When three components A1,
A2, and B condensation reaction occurred, heterogeneous
nucleation happened because of the bigger size of BODIPY
derivative and thus the reaction rate would be promoted.44
Eventually, the POPs microspheres with relative rough surfa-
ces were observed. In fact, the POPs precipitate would be
detected earlier in the bottom of the tube for the BODIPY
derivatives containing polymerization.
2- ethoxyethanol.41 A series of POPs with numerous BDP
units were developed and their abilities to generated 1O2
were dependent on the molecular isomerization and spacer
between the dimeric BDP building block.38,39 While the
surface areas showed little effect on this ability. Therefore,
we are wondering whether the BDP units’ content in the
1
POPs would affect the O2 generation ability. 1,3-Diphenyli-
sobenzo- furan (DPBF) was selected as 1O2 capturer.45
Upon a low power green LED lamp (wavelength: 480–
510 nm, 25 W) irradiation, the BDP-POPs in DMF would
generate 1O2, which were absorbed by DPBF in DMF solu-
tion. Therefore, the abilities to generate 1O2 could be com-
pared by monitoring the decay curve at the characteristic
peak value at 414 nm. As shown in Figure 6, for each
porous polymer, the absorption intensity at the 414 nm
decreased gradually after irradiation. The decay rates were
summarized in Figure 7. Porous polymers are beneficial in
providing accessibility for adsorption some oxygen due to
The BDP containing POPs might be good candidates to gen-
erate singlet oxygen (1O2) under visible light. In fact, the
BDP based CMP have been reported as good photocatalyst
for oxidation of thioanisoles to methylphenyl sulfoxide in
FIGURE 3 SEM images of four porous polymers (a) BDP-POP-5, (b) BDP-POP-6, (c) BDP-POP-7, and (d) BDP-POP-8.
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FIGURE 4 TEM image of POPS: (a) BDP-POP-5, (b) BDP-POP-6, (c) BDP-POP-7, and (d) BDP-POP-8.
FIGURE 5 HRTEM image of POPs: (a) BDP-POP-5, (b) BDP-POP-6, (c) BDP-POP-7, and (d) BDP-POP-8.

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FIGURE 6 Time-dependent absorption spectra of DPBF (in DMF) upon irradiation with a low power green LED lamp in the pres-
ence of POPs: (a) BDP-POP-5, (b) BDP-POP-6, (c) BDP-POP-7, and (d) BDP-POP-8. Test conditions: DPBF (4 3 1025 M) in DMF
(2.5 mL) solution with 0.1 mg BDP-POP for (a), (b), (c), and (d), respectively. [Color figure can be viewed at wileyonlinelibrary.com]
the pore size and structure, thus resulting in some ability
to generate singlet oxygen after excitation. The O2 genera-
These microspheres were used for cell imaging. The geome-
tries, size, and surface roughness have shown great effect on
the cell uptake properties, probably because the rough sur-
face exhibits high adhesion ability to the cell membrane and
thus fast cell uptake rate.46 To exclude the cellular uptake
rate effect, HeLa were performed, which were incubated at
37 8C for as long as 48 h (for 12, 24 h time interval, cell
imaging study of these microspheres the confocal laser scan-
ning microscope images were not good). DAPI was used as
blue dye for compassion. Control experiment revealed that
the untreated cells showed no background fluorescence.
Interestingly, the fluorescence intensity in the cell was corre-
lated with the BODIPY molar ratio as well. The BDP-POP8
showed highest red emission intensity among the four
porous polymers (Fig. 8). The overlay of the blue image and
red image showed purple color, which indicated that these
polymers were localized in the cytoplasm. Unfortunately,
there were still some polymers adhere to the cell surface,
though we had tried our best to remove the free micro-
spheres outside the cells with PBS for three time (each time
was 10 min), that might attributed to the strong interaction
between the rough surface of the particle and the cells. Over
the course of our test, no apparent toxicity of these porous
polymers was observed based on no significant change for
the cell morphologies, which is consistent with Wang’s
report that the porous polymers have excellent stability and
low toxicity.47
1
tion abilities were highly related to the BODIPY content,
that is, BDP-POP-8 showed the best abilities to generate
1O2. It is reasonable that, at such low concentration
(0.1 mg/2.5 mL), BDP-POP-8 have much more BODIPY
units than other porous polymer to capture photo to
1
generate O2.
FIGURE 7 Comparison of decay rate of DPBF in presence of BDP-
POPs. [Color figure can be viewed at wileyonlinelibrary.com]
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FIGURE 8 (a, e, i, m, q) Confocal images of HeLa cells with DAPI. (b, f, j, n, r) Bright-field images and (c, g, k, o, s) confocal images of HeLa cells
with control, BDP-POP5, BDP-POP6, BDP-POP7, BDP-POP8, respectively. (d, h, i, p, t) Corresponding merged images of confocal images (a, c),
(e, g), (i, k), (m, o), and (q, s) (c5 0.012 mmg/mL, 48 h, 37 8C). The scale bar is 25 mm. [Color figure can be viewed at wileyonlinelibrary.com]
CONCLUSIONS
polymers showed microspheres with different roughness.
In summary, four imine-linked porous polymers BDP-POPs
with different BODIPY content were developed. These porous
The surface difference might be attributed to the fast hetero-
geneous nucleation rates when BODIPY derivatives were
8
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1
20 T. Ben, H. Ren, S. Ma, D. Cao, J. Lan, X. Jing, W. Wang, J.
Xu, F. Deng, J. Simmons, S. Qiu, G. S. Zhu, Angew. Chem.,
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introduced. These BDP-POPs generation O2 abilities showed
strong correlation with the BODIPY content. Further work
along this line to study these POPs biological application is
underway in our laboratory.
21 L. X. Tan, B. E. Tan, Chem. Soc.Rev. 2017, 46, 3322.
22 J. W. Crowe, L. A. Baldwin, P. L. McGrier, J. Am. Chem.
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23 L. Guo, D. P. Cao, J. Mater. Chem. A. 2015, 3, 8490.
ACKNOWLEDGMENTS
24 L. Chen, K. Furukawa, J. Gao, A. Nagai, T. Nakamura, Y. P.
Dong, D. L. Jiang, J. Am. Chem. Soc. 2014, 136, 9806.
This work was supported by the State Key Laboratory of
Powder Metallurgy, Central South University, the National Nat-
ural Science Foundation of China (21204047 and 81500894),
the Specialized Research Fund for the Doctoral Program of
China (SRFDP20125503120009), and the Funds for Outstanding
Young Scholars of Chongqing Medical University (CYYQ201506)
(to Dr. S.Y.)
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