A Zinc Coordination Complex Mimicking Carbonic Anhydrase for CO2 Hydrolysis and Sequestration

Article abstract of DOI:10.1021/acs.inorgchem.9b01059

Carbonic anhydrase (CA) mimicking is an effective and environmentally friendly strategy for carbon dioxide sequestration. Herein, we developed a nonanuclear CA-mimetic zinc coordination complex (1) which possesses a coordination environment similar to tha

Full text of DOI:10.1021/acs.inorgchem.9b01059

Article
Cite This: Inorg. Chem. XXXX, XXX, XXX−XXX
pubs.acs.org/IC
A Zinc Coordination Complex Mimicking Carbonic Anhydrase for
CO Hydrolysis and Sequestration
2
‡
,⊥
†,§,⊥
‡
,‡
,†,∥
Yueyun Huang, Sainan Zhang,
Haixin Chen, Limin Zhao,* Zhenjie Zhang,*
Peng Cheng,∥ and Yao Chen*
,†,§
†
State Key Laboratory of Medicinal Chemical Biology, Nankai University, Tianjin 300071, People’s Republic of China
Department of Chemistry and Chemical Engineering, Guangdong Pharmaceutical University, Guangzhou 510000, People’s
‡
Republic of China
§
Department of Pharmacy, Nankai University, Tianjin 300071, People’s Republic of China
Department of Chemistry, Nankai University, Tianjin 300071, People’s Republic of China
∥
*
S Supporting Information
ABSTRACT: Carbonic anhydrase (CA) mimicking is an effective and
environmentally friendly strategy for carbon dioxide sequestration. Herein, we
developed a nonanuclear CA-mimetic zinc coordination complex (1) which
possesses a coordination environment similar to that of CA’s catalytically active
zinc sites. Complex 1 exhibited excellent reusability, solvent and thermal
stability, and gram-scale synthesis, which are essential for practical applications.
It was found that complex 1 exhibited outstanding catalytic performance that is
much better in comparison to that of the popular CA-mimetic compound Zn-
cyclen and comparable to that of the reported metal−organic frameworks (e.g.,
CFA-1). Moreover, we found that its catalytic activity can be significantly
−
−
improved via OAc /OH exchange and particle size reduction treatment. This
study provides important guidance for the design of highly efficient CA-mimetic
materials.
INTRODUCTION
construct Zn-based coordination complexes with the same Zn
■
14−17
coordination environments as CA.
For instance, Klaui et
̈
Emission of carbon dioxide (CO ) has led to severe climate
problems such as an increase in earth’s surface temperature
due to the greenhouse effect. Among the technologies utilized
2
al. reported the use of tris(imidazolyl)phosphane as a ligand to
synthesize a variety of stable zinc coordination complexes to
1
1
8
mimic CA. Ichikawa’s group also synthesized a Zn
to mitigate CO emissions, biological CO sequestration by
2
2
19
coordination complex for CA mimicking. Our group has
long focused on employing coordination complexes, especially
metal−organic frameworks (MOFs), to mimic natural enzymes
carbonic anhydrases (CA) has demonstrated great promise due
to its environmentally friendly nature and outstanding catalytic
efficiency in converting CO into HCO .
‑
2−5
However, the
2
3
20−22
application of CA is limited by its inherent deficiency such as
for advanced applications.
Recently, we demonstrated
high sensitivity to pH, low thermal and chemical stability, and
high cost. Although many efforts have been made to use solid
that a series of MOFs can mimic CA, and they exhibited
6
6
excellent efficiency on CO in situ conversion. However, the
2
porous materials to immobilize CA to improve its stability
small-scale synthesis and high cost hinder the further
application of current CA-mimetic coordination complexes.
Herein, we developed a CA-mimetic coordination complex,
7
−12
against perturbation environments and harsh conditions,
this strategy still faces drawbacks such as low immobilization
efficiency and unavoidable reduction of enzymatic activity.
Thus, exploring new strategies to overcome these short-
comings is of great significance and urgently needed.
Biomimetic catalysis has emerged as an alternative of
enzyme immobilization due to its high stability, recyclability,
[
Zn (Me bta) (OAc) ]·3DMF (1; Me bta = 5,6-dimethyl-
9 2 12 6 2
1,2,3-benzotriazole), consisting of a nonanuclear Zn cluster in
which the Zn atoms possess a coordination environment
similar to the Zn active site in CA (Figure 1), and evaluated its
CA-biomimetic activity and catalytic kinetics using model
and cost efficiency. Biological CO sequestration by CA mostly
2
substrates and direct CO conversion. Notably, this biomi-
2
relies on the tetrahedral catalytic center in which the Zn ion
coordinates with three histidine imidazole moieties and a
single hydroxide ion. The catalytic mechanism of CO2
sequestration by CA is the nucleophilic attack of a Zn-
metic coordination complex can be easily prepared on a gram
−
−
scale. In addition, we found that OAc /OH exchange and
hydroxyl group toward CO and subsequent formation of
Received: April 11, 2019
2
2
,13
bicarbonate anions.
An efficient strategy to mimic CA is to
©
XXXX American Chemical Society
A
DOI: 10.1021/acs.inorgchem.9b01059
Inorg. Chem. XXXX, XXX, XXX−XXX

Inorganic Chemistry
Article
diffused in 1.5 mL of DMF was mixed with 13.5 mL of HEPES buffer
(
50 mM, pH 8.0). First, CO was introduced to the reaction system
2
and the pH value of the solution was recorded at the same time.
Finally, the reaction was stopped when the pH value stayed at a
plateau.
CO Sequestration. Conversion of CO to CaCO was carried
2
2
3
out to evaluate the CO sequestration, which was performed in 11.0
2
mL of a reaction solution containing 1.0 mL of DMF with 2.0 mg of
catalyst, 5.0 mL of HEPES buffer with 400 mM CaCl , and an
2
additional 5.0 mL of 50 mM HEPES buffer (pH 8.0). The solution
was stirred for 1 h with bubbling CO gas. CaCO was collected by
2
3
Figure 1. (a) Coordination environment of the Zn active site in CA.
centrifugation and then dried. Finally, the mass of formed CaCO was
3
(
b) Nonanuclear Zn cluster of compound 1 in which the coordination
weighed to calculate the yield.
geometry of the peripheral Zn with coordination environment similar
3
to that of the active site in CA is shown.
RESULTS AND DISCUSSION
A colorless crystalline powder of 1 was afforded via slow
evaporation of a reaction mixture of Me bta with zinc acetate
dihydrate in DMF solvent at room temperature. The powder
X-ray diffraction (PXRD) pattern of the as-synthesized
compound agreed well with the simulated pattern of 1 (Figure
■
particle size reduction treatment can significantly improve its
catalytic activity.
2
EXPERIMENTAL SECTION
■
Synthesis of [Zn (Me bta) (OAc) ]·3DMF (1) and 1-nano.
9
2
12
6
2
a). In addition, an inverted fluorescence microscope (Figure
The zinc coordination compound [Zn (Me bta) (OAc) ]·3DMF
9
2
12
6
(
1) was synthesized according to a procedure reported by Volkmer et
23
al. Zn(OAc) ·2H O (0.102 g, 0.46 mmol) and Me bta (0.614 g,
2
2
2
3
.72 mmol) were dissolved in 10.0 mL of DMF, respectively. Then,
these two solutions were mixed and stirred at room temperature for
0 min. After the solvent was slowly evaporated for 3 days, colorless
3
and block-shaped crystals of 1 were filtered and dried under vacuum
to remove DMF. Nanosized particles were obtained via grinding. The
particle size of 1-nano was measured using a nanoparticle size
analyzer.
Preparation of 1* and 1-nano*. Compound 1* and 1-nano*
were obtained via soaking 250 mg of 1 or 1-nano in 20.0 mL of
NaOH solution (pH 9.0−10.0) for 2.5 h. The NaOH solution was
24,25
replaced every 30 min.
The complex was collected by filtration,
washed with water three times, and then dried at room temperature.
About 15−20 mg samples of 1 and 1* were digested in 0.5 mL of
Figure 2. (a) PXRD patterns of 1, 1*, 1-nano, and 1-nano*. (b)
Microscope image of 1. (c) TEM image of 1-nano. (d) TEM image of
1*. (e) TEM image of 1-nano*.
CF COOH and gently heated until they completely dissolved.
3
Subsequently, ∼0.1 mL of DMSO-d was added to the solution for
6
1
H NMR analysis (Figure S3).
Assay of Activities of Zinc Coordination Compounds. The
activities of the catalysts were measured at 25 °C via monitoring the
concentration changes of p-NP at 402 nm, which is a hydrolysis
product of p-NPA and p-NPB. To draw a calibration curve of p-NP,
various concentrations of p-NP (5−60 μM) in HEPES buffer (50
mM, pH 8.0) including 1% acetonitrile and 10% DMF was scanned
by a UV/vis/NIR spectrometer (Lambda 950). First, 2.67 mL of
HEPES buffer (50 mM, pH 8.0) and 0.3 mL of zinc coordination
compound (0.21 μmol) which was dispersed in DMF were placed in a
cuvette. Then, p-NPA (0.03 mL, 50 mM) or p-NPB (0.03 mL, 50
mM), dissolved in acetonitrile, was placed in the cuvette (the final
molar percent of zinc coordination compound catalyst was 14%). The
amount of hydrolysate p-NP was measured by a UV/vis/NIR
spectrometer at 1 s intervals for 1800 s. Meanwhile, to study the effect
of self-decomposition of p-NPA and p-NPB, a blank control without
addition of zinc coordination compound was also studied under the
same conditions.
2
b) showed colorless, block-shaped microscale crystals. Single-
crystal data revealed that compound 1 contains a nonanuclear
cluster of [Zn L ] (L = 1,2,3-benzotriazolate). Notably,
complex 1 can be easily synthesized on a gram scale in a one-
pot reaction, which surpasses reported CA-mimetic coordina-
6+
9
12
2
,26−29
tion complexes.
As shown in Figure 1b, Zn1 and Zn2 are
the central metal atoms of 1 that are coordinated with six
nitrogen atoms, while Zn3 is the peripheral metal atom that
coordinates with three nitrogen atoms and one carboxylate
oxygen atom. Compound 1 shows great potential to mimic CA
for CO2 sequestration, because the peripheral Zn3 atom
possesses a coordination environment similar to that of the
active Zn center in CA.
High stability toward various solvents, acids and bases, and
thermal treatment is essential for biomimetic catalysts. We
found that complex 1 showed high stability under harsh
conditions such as organic solvents, high temperatures, and
solutions with a broad spectrum of pH values. After 1 was
soaked in DMF, methanol, ethanol, acetonitrile and HEPES
buffer (50 mM, pH = 8.0), its PXRD patterns agreed with the
simulated pattern (Figure S1a), indicative of its high stability.
Meanwhile, PXRD data also showed that compound 1 can be
stable in HEPES solutions at pH ranging from 4 to 12 (Figure
S1b). In addition, the thermal stability of 1 was tested via
heating at different temperatures (∼80−200 °C). From PXRD
results, we found complex 1 still can retain its crystallinity at
Reusability of Zinc Coordination Compounds. The recycla-
bility of zinc coordination compound for substrate hydrolysis was
evaluated. p-NPA (0.5 mM) was added to 40.0 mL of HEPES buffer
(
50 mM, pH 8.0) containing 0.21 μmol of catalyst. The reaction
mixture was stirred at room temperature for 1 h to hydrolyze p-NPA.
Subsequently, the zinc coordination compounds were separated and
washed three times with deionized water by centrifugation. Zinc
coordination compounds were dried at room temperature for the next
catalytic cycle.
CO Hydration in the Change of pH Value. During the CO
2
2
+
hydration process, bicarbonate ions and H were generated to form an
acidic solution. The change in pH value of the reaction solution was
monitored by real-time detection. A 0.21 μmol portion of catalyst
B
DOI: 10.1021/acs.inorgchem.9b01059
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Inorganic Chemistry
Article
Scheme 1. Hydrolysis Reactions of p-NPA and p-NPB
Figure 3. (a) Catalytic kinetic traces of different catalysts on hydrolysis of p-NPA. (b) Catalytic kinetic traces of different catalysts on hydrolysis of
p-NPB. (c) 6 h conversion of p-NPA hydrolyzed by different catalysts. (d) Recyclability of 1-nano* on hydrolysis of p-NPA for five cycles.
2
(
50 °C (Figure S1c). Moreover, thermogravimetric analysis
TGA) results showed that there were two distinct weight loss
steps for 1. The first one was a 10% weight loss occurring at
successfully replace the acetate anions via simply soaking 1 in
NaOH solution (pH 10). PXRD (Figure 2a) and TEM (Figure
2d) analysis revealed that the formed 1* did not show
−
−
4
0−140 °C that was attributed to the solvent molecules and
structural or morphology changes. The successful OAc /OH
then a 40% mass loss began around 400 °C. These results
further indicated that complex 1 possessed good thermal
stability (Figure S1d).
exchange (Figure S2a) was confirmed by the FTIR spectrum of
1 and 1*. In the FTIR spectrum of complex 1, there is a strong
−1
band at 1669 cm assigned to the asymmetric stretching
vibration of the coordinated acetate anions, but it is a weak
The biomimetic catalysis activity of complex 1 was first
evaluated via monitoring the concentration change of p-
nitrophenol (p-NP) produced from the hydrolysis of p-
nitrophenylacetate (p-NPA) and p-nitrophenylbutyrate (p-
NPB) (Scheme 1). In addition, a popular CA-mimetic
1
response signal in the spectrum of 1*. Furthermore, the H
NMR spectrum of the digested complex 1* showed almost no
−
residue of acetate anions (Figure S3). After successful OAc /
−
OH exchange, the initial rate of p-NPA hydrolysis was (4.59
30−34
−2
compound, Zn-cyclen, was selected as a positive control.
± 0.29) × 10 μM/s for 1*, which is 1.5 times better than
Self-decomposition of p-NPA and p-NPB without addition of
catalysts was set as the blank control. The catalysis results
revealed that 1 exhibited good catalytic performance toward
the hydrolysis of p-NPA and p-NPB (Figure 3a,b). For the
that of the untreated 1. Similarly, the initial rate of p-NPB
−
2
hydrolysis for 1*, (3.75 ± 0.15) × 10 μM/s, is also
approximately 1.7 times better than that of 1. The results
revealed the improved biomimetic catalysis due to the anion-
exchange strategy.
−
2
hydrolysis of p-NPA, the initial rate of 1 is (3.0 ± 0.26) × 10
μM/s, which is more than 3 times better than that of the blank
reaction, (0.94 ± 0.05) × 10− μM/s, and much higher than
that of Zn cyclen, (1.65 ± 0.04) × 10− μM/s. For the
hydrolysis of p-NPB, the initial rate of 1 is (2.25 ± 0.25) ×
We further investigated whether the catalytic activity
originated from the surface or inside of the complex 1. The
2
2
CO adsorption isotherm collected at 195 K unveiled the
2
nonporous structure of 1, which is consistent with the
structural analysis. Thus, the catalytic reactions should occur
on the surface of the material. Reducing the particle size could
promote the catalytic activity due to increased material surface.
We prepared nanosized particles (1-nano, ∼160 nm) via
grinding (Figure 2c and Figure S4a). The initial rates of p-NPA
and p-NPB hydrolysis were increased to (4.39 ± 0.29) × 10−
−
2
1
0
μM/s, which is about 5-fold better than its self-
−
2
decomposition, (0.46 ± 0.07) × 10 μM/s, and also much
higher than that of Zn-cyclen, (0.98 ± 0.04) × 10− μM/s.
Inspired by the structure of CA, we tried to exchange the
acetate anions with hydroxide anions to further promote the
catalytic activity of 1. It was found that hydroxide anions can
2
2
C
DOI: 10.1021/acs.inorgchem.9b01059
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Inorganic Chemistry
Article
Figure 4. (a) Conversion of CO evaluated via weighing the formed CaCO . (b) Real-time monitoring of pH change for different compounds.
2
3
and (4.28 ± 0.09) × 10− μM/s for 1-nano, respectively,
2
the weight of formed CaCO is 2.6-fold higher than that of
3
which are ∼1.5 times better than those of the microsized 1
blank control. Moreover, the amount of CaCO generated by
3
(
∼50 μm, Figure 3a,b). These results revealed that reducing
1-nano* is higher than that generated by Co-BBP and Co-
36
particle size could enhance the catalytic activity, because the
increased particle surface allowed more active sites to contact
with reaction substrates.
BBP@Tb-MOF, which were reported by Sahoo et al. (Table
S1). In addition, during the CO hydration process,
2
+
bicarbonate ions and H were generated to form an acidic
−
−
Finally, combining the OAc /OH exchange and particle
size reduction treatment, we obtained a superior CA-
biomimetic catalyst, 1-nano*, which showed the best catalytic
ability (Figure 2a). For the hydrolysis of p-NPA and p-NPB,
the initial rates of reactions catalyzed by 1-nano* were
solution. The pH change of the reaction solution was
monitored by real-time detection. Catalysts (0.21 μmol)
were diffused in 15.0 mL of HEPES buffer (50 mM, pH 8.0)
containing 10% DMF. The pH value of the solution was
recorded and meanwhile CO was introduced into the reaction
2
improved to (6.28 ± 0.05) × 10− and (5.51 ± 0.09) × 10
2
−2
system. Finally, the reaction was stopped when the pH value
did not change. According to the real-time monitoring of pH
change, the pH value rapidly dropped from 7.9 to 6.5 within 2
min in the presence of 1-nano*. According to the pH change,
we observed the order 1-nano* > 1* ≈ 1-nano ≈ 1 > Zn-
cyclen > blank control, which is in agreement with the results
for hydrolysis of p-NPA (Figure 4b). These results indicated
that compound 1-nano* showed the best catalysis effect on
μM/s, respectively, which are more than 2 times better than
those of the untreated 1. Moreover, the catalytic activity of 1-
nano* is comparable to that of the reported CA-biomimetic
metal−organic framework CFA-1 (initial rate: 6.42 × 10
μM/s). In addition, the conversion of p-NPA was also detected
−
2
to illustrate the catalytic activity of biomimetic catalysts
(
Figure 3c). Notably, 1-nano* showed the highest conversion
of 70.7 ± 1.1% after reaction for 6 h, while the conversions of
CO conversion.
2
blank control, Zn-cyclen, 1, 1-nano, and 1* were 12.29 ±
0
.4%, 28.0 ± 2.6%, 53.8 ± 4.4%, 63.6 ± 2.6%, and 66.9 ± 2.9%,
CONCLUSION
■
respectively (Table S1). Furthermore, the recyclability of 1-
nano* was also evaluated. We found that 1-nano* still retained
high catalytic activity after five consecutive catalysis cycles
In conclusion, we demonstrated that a nonanuclear Zn
coordination complex 1 possesses high CA-biomimetic
catalytic activity, attributed to the similarity of its coordination
environment to the zinc active centers in CA. Complex 1 can
be easily prepared on a gram scale and had good thermal,
solvent, and pH stability. The biomimetic catalytic activity of
complex 1 was comprehensively studied via evaluation of
(
∼
Figure 3d). After five catalytic cycles, 1-nano* still retained
82% of the conversion of the first cycle. Moreover, the Zn
salts (Zn(OAc) and Zn(OH) ) and the physical mixtures of
these Zn salts and the ligand were also selected as controls.
There is no obvious catalytic activity for Zn(OAc) , while
2
2
2
Zn(OH) cannot dissolve in the reaction solution and also
hydrolysis of p-NPA and p-NPB and conversion of CO into
2
2
showed no catalytic activity. We further mixed Zn(OAc) with
CaCO . In order to improve the catalytic activity, except for
2
3
−
−
Me bta in solution and found that the mixture showed much
using an OAc /OH exchange strategy, we also developed a
new approach via reducing particle size to improve its catalytic
efficiency. The formed 1-nano* catalyst showed boosted
catalytic activity, which is more than 2 times better than that of
the untreated 1. Moreover, the biomimetic catalysts exhibited
good reusability. This study paves a new avenue to design
2
lower catalytic activity in comparison to 1-nano* (Figure S6).
These results further indicated Zn centers with a coordination
environment similar to that of to CA is crucial to the high
catalytic activity.
Effectively eliminating CO is of great significance for CA’s
2
35
catalytic performance and application. Thus, the conversion
of CO into CaCO was conducted to evaluate the biomimetic
coordination complexes to mimic CA for CO treatment.
2
2
3
Moreover, new strategies have also been developed to promote
solid material biomimetic efficiency.
applicability of compound 1. The weight of formed CaCO3
converted from CO can be used to assess the CO hydration
2
2
and sequestration efficiency. We observed that the weights of
the formed precipitate generated by blank control, Zn-cyclen,
ASSOCIATED CONTENT
■
*
S
Supporting Information
1
, 1*, 1-nano and 1-nano* are 21.4, 27.8, 36.9, 66.0, 71.8, and
7
9.4 mg, respectively (Figure 4a). SEM/EDX images and
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acs.inorg-
chem.9b01059.
PXRD patterns proved that the formed precipitate after
bubbling CO was CaCO (Figures S7 and S8). For 1-nano*,
2
3
D
DOI: 10.1021/acs.inorgchem.9b01059
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Inorganic Chemistry
Materials and general methods, PXRD, TEM images,
Article
(
12) Abdelrahim, M. Y. M.; Martins, C. F.; Neves, L. A.; Capasso,
̃
C.; Supuran, C. T.; Coelhoso, I. M.; Joao, G. C.; Barboiu, M.
Supported ionic liquid membranes immobilized with carbonic
1
TGA, H NMR, particle size and SEM/EDX images
PDF)
(
anhydrases for CO transport at high temperatures. J. Membr. Sci.
2
2
017, 528, 225−230.
AUTHOR INFORMATION
Corresponding Authors
E-mail for L.Z.: zhaolimin@gdpu.edu.cn.
E-mail for Z.Z.: zhangzhenjie@nankai.edu.cn.
E-mail for Y.C.: chenyao@nankai.edu.cn.
(13) Satcher, J. H., Jr; Baker, S. E.; Kulik, H. J.; Valdez, C. A.;
Krueger, R. L.; Lightstone, F. C.; Aines, R. D. Modeling, synthesis and
characterization of zinc containing carbonic anhydrase active site
mimics. Energy Procedia 2011, 4, 2090−2095.
■
*
*
*
(
14) Echizen, T.; Ibrahim, M. M.; Nakata, K.; Izumi, M.; Ichikawa,
K.; Shiro, M. Nucleophilic reaction by carbonic anhydrase model zinc
ORCID
compound: characterization of intermediates for CO hydration and
2
phosphoester hydrolysis. J. Inorg. Biochem. 2004, 98, 1347−1360.
Zhenjie Zhang: 0000-0003-2053-3771
Peng Cheng: 0000-0003-0396-1846
Yao Chen: 0000-0002-3465-7380
(15) Lee, D.; Kanai, Y. Biomimetic carbon nanotube for catalytic
CO hydrolysis: first-principles investigation on the role of oxidation
2
state and metal substitution in porphyrin. J. Phys. Chem. Lett. 2012, 3,
1369−1373.
Author Contributions
⊥
Y.H. and S.Z. contributed equally.
(16) Sahoo, P. C.; Jang, Y. N.; Suh, Y. J.; Lee, S. W. Bioinspired
design of mesoporous silica complex based on active site of carbonic
anhydrase. J. Mol. Catal. A: Chem. 2014, 390, 105−113.
Notes
The authors declare no competing financial interest.
(17) Herr, U.; Spahl, W.; Trojandt, G.; Steglich, W.; Thaler, F.; Van
Eldik, R. Zinc (II) complexes of tripodal peptides mimicking the zinc
(II)-coordination structure of carbonic anhydrase. Bioorg. Med. Chem.
1999, 7, 699−707.
ACKNOWLEDGMENTS
■
The authors acknowledge the financial support from the
National Natural Science Foundation of China (31800793 and
1871153) and Tianjin Natural Science Foundation of China
18JCZDJC37300).
(18) Klaui, W.; Piefer, C.; Rheinwald, G.; Lang, H. Biomimetic Zinc
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complexes with a new tripodal nitrogen-donor ligand: tris [2-(1-
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