A hollow microshuttle-shaped capsule covalent organic framework for protein adsorption

Article abstract of DOI:10.1039/c8tb02870b

Covalent organic frameworks (COFs) are a class of crystalline porous materials utilized in various potential applications. However, the development of hollow-structured COFs with defined morphology is important for their further applications, which is rar

Full text of DOI:10.1039/c8tb02870b

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Guoping Chen et al.
Regulating the stemness of mesenchymal stem cells by tuning
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DOI: 10.1039/C8TB02870B
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A hollow microshuttle-shaped capsule covalent organic framework
for protein adsorption
Received 00th January 20xx,
Accepted 00th January 20xx
Zhixiang Lu, Yanxiong Liu, Xiaolan Liu, Shuhan Lu, Yuan Li, Shaoxiong Yang, Yu Qin, Liyan Zheng*
and Hongbin Zhang*
DOI: 10.1039/x0xx00000x
www.rsc.org/
Covalent organic frameworks (COFs) have emerged as crystalline porous materials for various potential applications.
However, the development of hollow structure COFs with defined morphology is important for their further application and
rare. Herein, COF with unique hollow shuttle morporlogy was prepared by a Schiff condensation reaction between 4- (4-
aldehyde phenyl) ethylene (TPE) and tetra-(4-aminophenyl) porphyrin (TAP). A detailed mechanistic investigation reveals
initial self-assembly and following similar inside-out Ostwald ripening processes is responsible for the hollow capsule
formation. The hollow microshuttle-shaped capsule COF is used for hemoglobin adsorption study, which shows an uptake
of 550.82 mg· g -1 of hemoglobin. These studies could foreshadow new avenues for development of porous materials with
defined morphology for biomolecules adsorption.
of expensive enzymes, but also promotes the stability of enzymes
under extreme conditions. Therefore, the use of COF materials to
1. Introduction
load enzymes has great potential applications in the field of
biomolecule [24-26]. So far, for most COFs with hollow structures
mainly rely on template strategies. Zeolites, metals oxides and
metals organic frameworks (MOFs) are commonly used as removable
organic and inorganic templates [27-30]. However, removing templates
to form the hollow structures will introduce other toxic components
and cause the shell collapse, which restrict the scope of applications,
especially in biological aspects [31-32]. This template-assisted method
is cumbersome and time-consuming [33-35]. Moreover, the shape of
COFs was limited into cubes, sheets, fibres, belts, spheres and
Covalent organic frameworks (COFs) are a class of crystalline porous
materials with regular pore structure, high surface area, thermal
stability and controlled properties [1], which have been successfully
utilized in various fields, such as photoconductive devices, catalysis,
energy storage, separation, adsorption, drug delivery, sensing and
confined-space chemical reactions, etc [2-9]. COFs can be synthesized
under relatively mild conditions through a reversible dynamic
nucleation-elongation process, generally including boronic acid
trimerization, boronate eater formation, the trimerization of nitriles,
and Schiff base reaction [10-13]. The reversibility of the reaction allows
the self-assembly of the structural units until they achieve long-range
periodicity, which leads to the crystallization of the COFs and further
forms a variety of morphologies for COFs [14]. However, COFs are
usually synthesized into microcrystalline powders with irregular
morphologies in most cases.
The morphology of the materials is crucial for its applications in
many fields. Especially, hollow structural materials have received
much attention in recent years because of their potential
applications in drug delivery, catalysis, molecular recognition,
proteins and energy storage, etc [15-22]. Enzyme loading is an
important research field in biomedicine and pharmaceutical industry
[23]. The immobilization process not only improves the recoverability
platelets morphologies [36-41]
.
Self-assembly is a powerful and elegant eternal theme for
fabricating various architectures. This technique has been
successfully applied to the preparation of hollow COFs without the
assistant of templates [42]. Rahul Banerjee’ research group has
successfully synthesized chemically stable COFs hollow spheres by
Ostwald ripening procedure [43]. Florian Beuerle’s group prepared
COFs with microtubes shape via a bottom-up self-assembly process
based on rolled-up crystallite sheets. Despite these advances for the
preparation of COFs with defined morphology via template-free
methods, the development of COFs with other defined morphologies
has rarely been explored [44]
.
Herein, COF with hollow capsule morphology was prepared by a
Schiff condensation reaction between 4- (4- aldehyde phenyl)
[45]
ethylene (TPE)
and tetra-(4-aminophenyl) porphyrin (TAP). A
Key Laboratory of Medicinal Chemistry for Natural Resource (Yunnan University),
Ministry of Education, Functional Molecules Analysis and Biotransformation key
laboratory of Universities in Yunnan Province, School of Chemical Science and
Technology, Yunnan University, Kunming, Yunnan 650091, China
*E-mail: zhengliyan@ynu.edu.cn (L. Zheng), zhanghb@ynu.edu.cn (H. Zhang)
Electronic Supplementary Information (ESI) available: [details of any supplementary
information available should be included here]. See DOI: 10.1039/x0xx00000x
detailed time-dependent study for the formation of hollow shuttle
reveals that initial self-assembly and following similar inside-out
Ostwald ripening processes are responsible for the formation of
hollow capsule. To the best of our knowledge, this is the first example
of COFs materials with shuttle-shaped hollow capsule by template-
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Emmett-Teller
(BET)
method
using
nitrogen
gas
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adsorption/desorption at 77 K (BET, MicromeDrOitIi:c1s0A.1S0A39P/C280T2B00,2U8S7A0)B.
The Fourier transform infrared (FT-IR) spectra were obtained on a FT-
IR spectrophotometer (Thermo Nicolet 365). The UV-Vis absorption
was characterized by a UV/Vis/NIR spectrophotometer (Shimadzu,
Japan).
2.3 Synthesis of TPE-TAP-COF
The synthesis of 4- (4- aldehyde phenyl) ethylene refers to our
previous article. Synthesis of TPE-TAP-COF was carried out by the
Schiff base reaction between 4- (4-aldehyde phenyl) ethylene (TPE,
50 mg) and tetra-(4-aminophenyl)porphyrin (TAP, 40 mg) in toluene-
dioxane (1 mL:1 mL) solvent combination with a catalytic amount of
0.2 mL (6 M) acetic acid has been under static heating at 150 ℃ for 5
days and then can obtain solid. The precipitates were washed with
anhydrous THF and acetone and then were dried for 24 h under high
vacuum at 120 ℃ to provide TPE-TAP-COF as a dark purple powder
in ~56 % yield.
2.4 Structural simulation and power X-ray diffraction analysis
The Pawley refinements were performed within the Material Studio
Reflux module to infer the crystalline structure and the unit cell
parameters. Certainly, the structures were optimized in the Dmol3
module of Materials Studio package, which can help to provide a
more rational layer morphology and higher consistency with the
experimental PXRD pattern. Furthermore, the simulation of two
possible structures AA (eclipsed), AB (staggered) modes were also
constructed by using an optimized P1 spaced group.
Fig. 1 (A) Synthesis scheme of 4- (4- aldehyde phenyl) ethylene (TPE);
(B) Synthetic scheme of TPE-TAP-COF; (C) Top view and (D) side view
of AA (eclipsed) stacking of TPE-TAP-COF (gray, carbon; blue,
nitrogen)
free method. Moreover, the COF with shuttle-shaped hollow capsule
an uptake amount of 550.82 mg· g -1 of hemoglobin, which is the
highest adsorption capacity among known COFs.
2. Experimental section
2.1 Chemicals and materials
4, 4'-dimethylbenzophenone, titanium tetrachloride (TiCl4),
pyridine,N-bromobutanimide (NBS), dibenzoyl peroxide (BPO) were
purchased from Aladdin.Anhydrous tetrahydrofuran, silver nitrate,
sodium acetate trihydrate, 1, 4-dioxane, acetic acid, hemoglobin,
chloroform-d, 99.8 atom % D were purchased from Energy Chemical.
silver nanoparticles (about 10 nm) purchased from sigma. All other
reagents were analytical grade and used as received. Ultrapure water
was prepared using a Milli-Q water purification system. The
phosphate buffer solution was prepared by dibasic sodium
phosphate with sodium dihydrogen phosphate to the required pH
values.
2.5 Loading of Hb in TPE-TAP-COF
For the loading studies, 5 mg of the TPE-TAP-COF was firstly
sonicated in 4 mL of the phosphate buffer (pH=7.4) for 5 min in order
to get a homogeneous dispersion. This buffer solution was treated
with different concentrations (0.1~1 mg·ml-1) and stirred at 4 ℃ for
24 h. Then the solution was centrifuged and recorded using UV–vis
spectrometer, and then the isothermal adsorption curve is obtained.
The adsorption dynamic curve shows the adsorption capacity of the
COF to Hb of 0.8 mg·ml-1at different time.
2.2 Apparatus
The NMR spectra were recorded by AVANCEDRX400 NMR
spectrometer (Bruker, Germany) operated at 400 MHz. X-ray powder
diffraction patterns were taken using a D/max-TTR III X-ray
diffractometer (Rigaku, Japan) with a scan speed of 0.1 s per step and
a step size of 0.01°. High resolution solid-state NMR spectra were
recorded at ambient pressure on a Bruker AVANCE III 400 M
spectrometer using a standard CP-TOSS pulse sequence (cross
polarization with total suppression of sidebands) probe with 4 mm
(outside diameter) zirconia rotors. Cross-polarization with TOSS was
used to acquire 13C data at 100.37 MHz. The 13C ninety-degree pulse
widths were 4 µs. The decoupling frequency corresponded to 72 kHz.
The TOSS sample-spinning rate was 5 kHz. Recycle delays was 2 s. The
13C chemical shifts are given relative to glycine as 176.03 ppm. The
morphology of TPE-TAP-COF were characterized by scanning
electron microscopy (SEM) (Quanta, FEI) and a JEM 2100 high
resolution transmission electron microscope (HRTEM, JEOL, Japan).
The specific surface areas of TPE-TAP-COF were tested by Brunauer-
Fig. 2 (A) 13C solid-state CP-MAS NMR of TPE-TAP-COF; (B)IR spectra
of TPE-TAP-COF; (C) SEM image of TPE-TAP-COF; (D)Transmission
electron microscopy of TPE-TAP-COF.
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down to room temperature. For the adsorption studies, 5 mg TPE-
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TAP-COF was added into aqueous solutionDcOoIn: t1a0i.n10e3d9/ACu8TNB0P2s8a7n0Bd
stirred at room temperature for 12 h. Then the solution was
centrifuged at 8000 rpm for 1 minute and the UV-vis spectra of the
supernatant were recorded. The sample for TEM imaging was
without centrifugal treatment. The experiment process of the
adsorption of Ag NPs is the same as the experiment process of Au
NPs (5 mg COF, 1 mL Ag NPs solution and 3 mL water.).
3. Results and discussion
3.1 Preparation and Characterization of TPE-TAP-COF
The TPE-TAP-COF was synthesized by solvothermal reactions (Fig.
1A, B). Fourier transform Infrared (FTIR) and 13C cross polarized (CP)
solid-state MAS are commonly applied as proof of the detection
strategy for the formation of imine bond (C=N). The structural
integrity of the framework was confirmed by solid-state CP-MAS
NMR, which displays the resonance signal around 156.7 ppm for the
carbon of C=N bond (Fig. 2A). In the FTIR spectrum (Fig. 2B), the
absorption band near 1696 cm-1 for the C=N bond stretching modes
indicates that the presence of the imine group forming from the
tetraphenylethene and porphyrin moiety. As shown in Fig. S1, the
thermogravimetric analysis (TGA) results revealed a weight loss of
around 36.07 % until the temperature reach to 450 ℃, suggesting
the TPE-TAP-COF with high thermal stability. By measuring the
capacity N2 adsorption/desorption experiment at 77 K, the
permanent porosity of the TPE-TAP-COF was determined, this result
shows a type I isotherm, which is the characteristic of the intrinsic
microporosity characteristics of the TPE-TAP-COF (Fig. S2). The
Brunauer−Emmett−Teller surface area is ∼218 m2 g−1. The sample
was activated at 150 °C to remove the solvent molecule from the
lattice for sorption analysis. The distribution of the pore diameter
based on the theory of non-local density functional shown a single
peak porosity at 1.6 nm (Fig. S3).
Fig. 3 (A) Experimental PXRD (black curve); theoretical eclipsed (red
curve); stacked (blue curve); (B) top view of simulated AA stacking (C)
Pawley refinement of PXRD; (D) AB stacking.
2.6 Loading of nanoparticles in TPE-TAP-COF
Au NPs synthesis method [46]: before the experiment, all the
instruments were soaked in aqua regia and cleaned with ultrapure
water. 100 mL HAuCl4 ·3H2O with a mass fraction of 0.01 % was
stirred and heated to 130 ℃, and then 3.6 mL sodium citrate with a
mass fraction of 1 % was added
，remaining heating. It can be
observed the color of solution turned from pale yellow to purple and
then to bright red. Stop heating and remain stirred till it was cooled
Fig. 4 (A) SEM and (B) TEM images of TPE-TAP-COF recorded at different intervals of time, respectively; (C) Mechanism of the formation of
COF hollow microshuttle.
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The possible crystal structure of TPE-TAP-COF was obtained by shaped structure which assembled from nanorods can be observed
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experimental XRD measurement and theoretical structure at the third day. The anisotropy structure DrOevI:e1a0l.e1d03t9h/Cat8TtBh0e28fi7n0aBl
simulation. The crystalline nature of TPE-TAP-COF was revealed that shuttle-shaped hollow capsule was original from the following
by powder X-ray diffraction (PXRD) analysis. Considering the growth process, rather than packaging of the hollow capsule during
construction type (4+4) is similar to SB-PORPy-COF [47], TPE-TAP-COF the drying process (Fig S8). However, the surface of the microcapsule
was constructed from TPE and TAP by using Materials Studio formed at 3 days is rough. As the reaction progress, the SEM images
Software package (see table S2). The strong PXRD peaks at the recorded that the surface of microcapsule gradually became smooth
position 2θ = 5.4, and 7.9°, which can be assigned to the (100) and and the TEM images revealed that inner of microcapsule is solid
(010) facets, respectively. The hump centered at ∼22° may be caused (hollow microcapsule, HMS). Finally, TEM images recorded for TPE-
by zigzag π−π stacking of 2D layers. The appearance of (100) facet in TAP-COF after a reaction time of 4 days showed the formation of
the XRD pattern is a convincing evidence to validate the layer-by- hollow cavities inside the microshuttle. According to the literature
layer structures arranged by the manner of typical 2D COFs. reference, our COF self-assembly should belong to the template-free
Therefore, TPE-TAP-COF is a typical 2D COFs with layer-by layer methods in the formation of many hollow structures, at present,
arrangement. The theoretical 2D eclipsed structure (AA) and the there are few reports on the self-assembly of COFs. We speculate
experimental peak position of PXRD, whereas the AB stacking model that the formation mechanism of hollow capsules structures is
(blue, Fig. 3A) is totally different. A simulated PXRD pattern shows similar to the Ostwald ripening process in outward diffusion [48]. As
good agreement with the one of the XRD measurement result. The the reaction proceeds, the internal microcrystals have high surface
Pawley refinement yielded a PXRD that is well consistent with the energy, and the surface energy can be reduced to the minimum by
experimentally surveyed pattern, as the evidence by their negligible dissolving or migrating the crystals from the inner core. This
differences and very staggered structure (AB) as shown in the Fig. 3D. speculation was supported by the shell thickness of 5 days is thinner
The theoretical model of PXRD for TPE-TAP-COF AA stacking model than that of 4 days (shown as Fig. 4A, S9). Moreover, Schiff base is a
(red, Fig. 3B) is almost exactly the same as the of Rwp=9.45 % and reversible dynamic bond, which is benefit for recrystallize/self-
Rp=6.41 % (Fig. 3C, refined and difference spectra). A 3D triclinic unit assemble. As mentioned earlier, this happens as a result of inside out
cell (P1 space group) with the parameters of a =31.9982 Å, b=31.5291 Ostwald ripening. Identical FTIR and PXRD patterns of the TPE-TAP-
Å, c = 4.28402 Å, α = 90.4039°, γ = 89.9188° and β= 92.4525° was COF at different time intervals (Fig. S6, S7) indicate that the C=N bond
derived from the theoretical optimization of TPE-TAP-COF. Based on and COF crystallite formation is complete even at shorter reaction
these results, the diameter of TPE-TAP-COF is about 16.645 Å, which time and the following self-assembly and Ostwald ripening processes
is consistent with the one of the BET result. Interestingly, scanning of these crystallites did not disturb the internal ordering in the COF.
electron microscopy (SEM) images showed that TPE-TAP-COF Based on these observations, we postulate that the formation of
remarkably assembles into well-defined microcapsule structures hollow shuttle of TPE-TAP-COF underwent several processes
(Fig. 2C, Fig. S4) with 5 µm in length. As shown in Fig. 2C and Fig. 4A, including fusing nanosphere into nanorods, nanorods self-
some microcapsule with partly broken structures have been circled assembling towards microshuttle and inside-out Ostwald ripping
in red in the SEM image. The SEM images with larger magnification (Fig. 4C).
of intact and broken microcapsule were shown in Fig. S4 A and B, 3.3 Loading of Hb
respectively. These results revealed the microcapsule was hollow
structure. The statistic about the size distribution could be presented
in Fig. S5 and the length of the TPE-TAP-COF most is 5 µm.
Transmission electron microscopy (TEM) images further confirmed
that these microcapsule COF is hollow (Fig. 2D).
3.2 The behavior of self-assembly
To study the mechanism of the formation of shuttle-shaped
hollow capsule, we have studied the synthesis and morphological
changes of TPE-TAP-COF at different time intervals (1-, 2-, 3-, 4- and
5 days). TPE-TAP-COF synthesis was quenched by removing the
reaction tubes from the oven at those specific time intervals.
Furthermore, we have analyzed the TPE-TAP-COF samples isolated
after 1-, 2-, 3-, 4- and 5-days reaction time using SEM, TEM, FTIR and
PXRD measurements. Fig. 4A and B display SEM and TEM images of
the self-assembly process at different time intervals of the TPE-TAP-
COF. SEM and TEM images of the one-day sample show dense
spherical agglomerates of small individual crystallites (nanosphere,
NS). Starting from this spherical agglomerates with hundreds
Fig. 5 (A) UV absorption spectra of TPE-TAP-COF before and after
nanometers in diameter, the TPE-TAP-COF self-assemble into
adsorption of Hb; (B) Images of TPE-TAP-COF before and after
nanorod structure with hundreds nanometers in diameter and
adsorption of Hb daily light; (C) Adsorption isotherms of Hb on TPE-
micrometer in length after 2 days (nanorod, NR).
Thereafter, these nanorods gradually fuse to form microcapsule
morphology after 3 days (dense microcapsule, DMS). The shuttle-
TAP-COF; (D) Adsorption dynamic curves of TPE-TAP-COF.
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The chemical stability of the hollow microcapsule TPE-TAP-COF in further prove that silver nanoparticles are adsorbed on the surface
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DOI: 10.1039/C8TB02870B
water and phosphate buffer (pH=7.4) was firstly investigated by of COF (Fig. S21). These results indicated that gold nanoparticles and
submerging the 40 mg material in 10 mL solution for 3 days. The silver nanoparticles can be adsorbed onto the surface of TPE-TAP-
unchanged position and intensity of peaks in the PXRD pattern and COF, and the size of these particles is much larger than the pore size
non-alteration of FTIR peak after the solution treatment show the of the COF. Therefore, they are very difficult to enter COF through
structural stability of this COF in phosphate buffer and water (Fig. the pore. Therefore, the previous adsorption mechanism is
S10, 11).
problematic. Moreover, Zeta potentials of Au NPs, Ag NPs, Hb and
The adsorption of proteins from aqueous solutions is of practical the TPE-TAP-COF were measured. As shown in Fig. S23, the zeta
and fundamental significance. The TPE-TAP-COF was applied to the potential of the TPE-TAP-COF was positively charged, while the Hb,
adsorption of hemoglobin (Hb) by monitoring the UV-vis absorption Au NPs and Ag NPs were negatively charged, indicating that the
spectrum. As shown in Fig. 5A, TPE-TAP-COF has an obvious absorption process of TPE-TAP-COF with Hb, Au NPs and Ag NPs
adsorption of Hb, and the UV absorption spectrum shows that the could occur through electrostatic attraction. In addition, as shown in
absorption at 410 nm is significantly decreased after the 0.8 mg·mL- Fig. S22, the TEM image of TPE-TAP-COF after adsorption Hb clearly
1
Hb and 5 mg COF are mixed in the phosphate buffer after stirring shows that the COF surface is covered with film-like complex.
12 h. The solution of Hb mixed with TPE-TAP-COF after the Therefore, the previous diffusion transfer into the COF mechanism is
centrifugation was turn to colorless (Fig. 5B). The adsorption dynamic wrong, and surface adsorption by electrostatic attraction should be
curves revealed that the adsorption was finished within 8 h (Fig. 5D). apprved.
The amount of Hb absorbed in TPE-TAP-COF was calculated to be 4. Conclusions
550.82 mg · g-1 from the adsorption isotherms (Fig. 5C). To the best
In summary, for the first time, a microshuttle-shaped capsule
of our knowledge, this value is the highest adsorption capacity for Hb structure COF was developed and underwent initial self-assembly
among known COFs. and following similar inside-out Ostwald ripening processes. The
Moreover, the adsorption behavior of different shapes of TPE- hollow microcapsule TPE-TAP-COF was applied to the adsorption of
TAP-COF were investigated. As shown in the Fig. 5C, D and Table S1, the Hb, which displayed the highest adsorption capacity among all
these results indicated that the morphology of TPE-TAP-COF had COFs. This work will inspire more insight into the development of
much affection on the maximum adsorption capacity and adsorption porous materials with defined morphology for biomolecules
equilibrium time. The maximum adsorption capacity was increased adsorption.
from 52.25 to 166.12, 488.16, 550.82 mg · g-1 when the morphology 5. Acknowledgements
changes from nanosphere, nanorod, dense microcapsule to hollow
This work was financially supported by the National Natural
microcapsule. Simultaneously, the adsorption equilibrium time was Science Foundation of China (NSFC, 21765024) and program for
decreased from 16 to 14, 10 and 8 h, respectively. These results changjiang scholars and innovative research team in university (IRT
indicated that the high adsorption capacity and fast adsorption ▁17R94)
equilibrium were benefited from the unique hollow microcapsule 6. Notes and references
structure of TPE-TAP-COF.
In order to investigate the interaction of Hb with TPE-TAP-COF, we
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nanoparticles and silver nanoparticles for the adsorption studies, As
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Page 7 of 7
Journal of Materials Chemistry B
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DOI: 10.1039/C8TB02870B
A hollow microshuttle-shaped capsule COF was prepared with template-
free procedure for the first time and has demonstrated the highest
adsorption capacity (550.82 mg• g -1) for hemoglobin so far.