CO2-Folded Single-Chain Nanoparticles as Recyclable, Improved Carboxylase Mimics

Article abstract of DOI:10.1002/anie.202006842

Emulating the function of natural carboxylases to convert CO₂ under atmospheric condition is a great challenge. Herein we report a class of CO₂-folded single-chain nanoparticles (SCNPs) that can function as recyclable, function-intensified carboxylase mimics. Lewis pair polymers containing bulky Lewis acidic and basic groups as the precursor, can bind CO₂ to drive an intramolecular folding into SCNPs, in which CO₂ as the folded nodes can form gas-bridged bonds. Such bridging linkages highly activate CO₂, which endows the SCNPs with extraordinary catalytic ability that can not only catalyze CO₂-insertion of C(sp³)-H for imitating the natural enzyme's function, it can also act on non-natural carboxylation pathways for C(sp² and sp)-H substrates. The nanocatalysts are of highly catalytic efficiency and recyclability, and can work at room temperature and near ambient CO₂ condition, inspiring a new approach to sustainable C₁ utilization.

Full text of DOI:10.1002/anie.202006842

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Accepted Article
Title: CO2-Folded Single-Chain Nanoparticles as Recyclable,
Intensified Carboxylase Mimics
Authors: Qiang Yan, Rongjin Zeng, and Liang Chen
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CO -Folded Single-Chain Nanoparticles as Recyclable, Intensified
2
Carboxylase Mimics
Rongjin Zeng, Liang Chen and Qiang Yan*
3
2
Abstract: Emulating the function of natural carboxylases to convert
multiform C(sp /sp /sp)─H carboxylation using atmospheric CO
in highly efficient and continual manner.
2
CO
2
under atmospheric condition is a grand challenge. Here we report
-folded single-chain nanoparticles (SCNPs) that can
a class of CO
2
function as recyclable, function-intensified carboxylase mimics. Using
Lewis pair polymer containing bulky Lewis acidic and basic groups as
the precursor, it can bind CO
SCNP, in which CO as the folded nodes can form gas-bridged bonds.
Such bridging linkages highly activate CO , which endows the SCNPs
2
to drive an intramolecular folding into
2
2
with extraordinary catalytic ability that can not only catalyze CO
2
-
3
insertion of C(sp )─H for imitating natural enzyme’s function, and also
2
act on non-natural carboxylation pathways for C(sp and sp)─H
substrates. The nanocatalysts are of highly catalytic efficiency and
recyclability, and can work at room temperature and near ambient
2 1
CO condition, inspiring a new vista on sustainable C utilization.
2
Scheme 1. Frustrated Lewis pair polymer precursor (P1) and its CO -driven
chain-folding into the single-chain nanoparticle (SCNP, NP1) for recyclable CO
2
catalytic carboxylation.
Carboxylases play a pivotal role in natural carbon sequestration,
as they can directly use atmospheric CO to catalyze
carboxylation of inert C─H bonds. To achieve this process in
2
[
1]
Natural carboxylase depends on a binding center formed by four
[
2]
vitro, a variety of synthetic catalysts such as transition metals,
[
9]
residues to trap CO
should contain particular functionalities capable of collectively
binding and activating CO . For this, we introduce complementary
frustrated Lewis acidic and basic monomers, triarylborane and
triarylphosphine, to the polymer side chain. Frustrated Lewis pair
refers to sterically hindered Lewis acid–base that can prohibit
Lewis adduct formation yet offer binding ability to gases,
2 2
especially CO -
.[10] With this principle, small-molecule- or CO
cross-linked Lewis networks have been constructed. Herein we
2
.
In a similar fashion, the designed SCNP
metal-organic frameworks,[ and covalent organic frameworks,[4]
have been exploited to replace the function of carboxylases.
Nevertheless, due to lack of the enzyme’s complex 3D structures
and specialized substrate binding sites, these catalysts have not
yet surpassed the natural ones in efficacy, atom economy,
reaction mildness, and reutilization. Engineering ideal
carboxylase mimics with biomimetic catalytic cavities and simple
3]
2
molecular scaffolds for green, sustainable CO
remains challenges.
2
conversion
[
11]
postulated that the polymer P1 would maintain a loose chain
One possible solution is to adopt single-chain technology.[5] This
approach allows that a linear polymer forms, via an external
trigger, intramolecular linkages and folds into a compact single-
chain nanoparticle (SCNP).[ Such controlled crosslinkings of the
single polymer chain result in the formation of compartmentalized
structure, which enables active site isolation. This structural
feature, which is reminiscent of those contributing to the
effectiveness of enzymes, can be used for the construction of
enzyme-like functional objects.[7] Successes in emulation of the
conformation in the absence of CO
upon CO the frustrated Lewis pair units would be together bound
tightly with CO , driving a polymer chain folding into SCNP, NP1
Scheme 1, right). Moreover, CO species in the binding domain
are possible to lie in high-active state. This is potential to motivate
inert C─H bonds and further achieve CO catalytic insertion (R─H
to R─COOH) that cannot be achieved under mild conditions. If
the active CO is depletion, the SCNPs would unfold and revert to
2
(Scheme 1, left), whereas
2
6]
2
(
2
2
2
chain relaxation, temporarily losing the catalytic activity (dormant
state). With alternating aeration and catalysis cycle, such SCNPs
could be viewed as reusable carboxylase mimics for sustainable
catalytic centers of metalloenzymes utilizing metal-folded
SCNPs[ give us inspiration to create CO
8]
2
-fixing-enzyme mimics
by this way. Here we address this unmet issue and report an
unprecedented CO -folded SCNP system that can function as
recyclable, function-enhanced carboxylase mimics to catalyze
1
C utilization.
2
The linear copolymer precursor P1 was synthesized via
reversible addition-fragmentation chain transfer polymerization
(
RAFT). Three kinds of monomers, styrene, 4-styryl-
di(pentafluorophenyl)borane and 4-styryl-dimesitylphosphine,
were statistically copolymerized at the feed ratio of 0.8:0.1:0.1, in
which the bulky borane and phosphine units served as the
frustrated Lewis acceptors and donors (Detailed synthesis and
characterization in the Supporting Information, Scheme S1 and
Figure S1-S7). Size exclusion chromatography (SEC) trace
[
a]
R. J. Zeng, Dr. L. Chen, and Prof. Dr. Q. Yan
State Key Lab of Molecular Engineering of Polymers
Department of Macromolecular Science, Fudan University
Shanghai 200433, CHINA
E-mail: yanq@fudan.edu.cn
Supporting information for this article is given via a link at the end of
the document.
showed that the molecular weight of P1 (M
g/mol with a dispersity index of Ð = 1.18 (Figure 1a, black line).
w
SEC) can attain 60800
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To facilitate intramolecular collapse and minimize unwanted
interchain coupling, the chain folding process was carried out at
diluted chloroform solution (0.1 mg/mL) and room temperature
2
chains in unfolding state. Upon addition of CO , they transformed
to well-defined spherical geometry with mean diameter of 11 nm
(Figure 1d and inset height profile), which coincides well with the
practical (R
DLS) and theoretical data (R SEC). More valuable
h h
upon exposure to CO
2
(10 kPa). After CO
2
treatment, in
comparison to P1, the SEC trace was shifted towards longer
retention time with a shoulder at low retention region (Ð = 1.26,
Figure 1a, red dash line), suggesting a reduction of hydrodynamic
radius due to chain compaction. Dynamic light scattering (DLS)
further evidenced this change from linear polymer into a more
information on the SCNP morphological transition was obtained
by small-angle neutron scattering measurement (SANS) in
deuterated solvent. Figure 1d exhibited the Kratky plots for the
unfolded polymer and folded nanoparticles. Clearly, the Kratky
curve of NP1 had a maximum, and declined as the scattering
vector (Q) increased at high Q region, which is qualitatively similar
to the characteristic profile of multidomain folded proteins and
rather different from that of compact globular proteins.[12b,13] In
addition, the form factor of NP1 was compared to P1 precursor by
compact structure. P1 gave a mean hydrodynamic diameter of
DLS
1
7.6 nm (R
h
= 8.8 nm; Figure 1b, black line); however, their
DLS
size reduced ~35% (R
upon addition of CO
polymers driven by CO
h
= 5.7 nm; Figure 1b, red dash line)
2
. A main reason is the intra-chain folding of
, leading to their phase transition from
-
2/ν
2
Ornstein−Zernike regime, I(Q) ~ Q
(ν is scaling exponent,
Figure S9).[ The exponent value for P1 is fitting to be 1.10, near
the typical value of a Gaussian chain state (ν = 1); whereas the
calculated ν for NP1 is 0.82, which lies between the given values
for the chain structure (ν = 1) and the globular protein (ν = 0.66),
indicating the chain collapse of NP1 but not reach a fully
compacted globular state.
14]
random-coil (P1) to sphere-like SCNP state (NP1). SEC in-line
multiangle laser light scattering (SEC-MALLS) exhibited that the
actual molecular weight of NP1 was 35800 g/mol, consistent with
that of the corresponding P1 precursor of 36400 g/mol (Figure S8
and Table S1), further pointing to a successful formation of SCNP.
According to the empirical formula between hydrodynamic radius
[
12]
-2
0.561
and molecular weight,
R
h
= 1.44 × 10 ·M
w
, the calculated
SEC
DLS).
R
h
of NP1 was 5.2 nm, close to the experimental value (R
h
Figure 2. (a) 11B and (b) 31P NMR spectral changes of P1 and NP1 structures.
Inset: formed [P─CO ─B] bridging structure.
2
After proving CO
understand the CO
insight on the polymeric structural alteration, their B and
2
-induced SCNP formation, we next wanted to
2
-folded molecular mechanism. To gain deep
11
31
P
Figure 1. SEC traces (a), DLS results (b), and SANS Kratky plots of P1 (black)
and NP1 (red) before and after CO treatment. (c-d) The AFM image showing
the morphologies of (c) P1 precursor (worm-like individual polymer chain, as
indicated by arrows) and (d) compact SCNPs of NP1 (inset, height profile).
2
NMR spectroscopy before and after CO stimulation were studied.
2
11B NMR spectra of P1 displayed a broad
In the absence of CO ,
2
resonance around 72 ppm, ascribed to the three-coordination
boron signal of triarylborane moieties. However, the addition of
CO
-78 ppm, Figure 2a), indicating a characteristic transition to form
four-coordination borane species with CO
.[15] Furthermore, 31
NMR spectra of P1 showed a sharp peak at -23 ppm, whereas in
the presence of CO this peak shifted oppositely to downfield
2
gave rise to a significant upfield shift from 72 to -6 ppm (Δδ
=
The morphological transition of P1 precursor to NP1 in solution
was visualized by atomic force microscopy (AFM). From Figure
2
P
1c, P1 showed loose, worm-like structure, indicating their polymer
2
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region of 46 ppm (Δδ = +69 ppm, Figure 2b), pointing to the
the products, and automatically return to the P1 form; iv) A new
generation of P─C bond. These data accord with the case of
2
round of catalytic cycle can be reset through CO re-purging.
-based frustrated Lewis complex.[
10b]
known small-molecule CO
CO
out (Figure S10). From these findings, we inferred that CO
associate with the borane and phosphine groups to produce
unique CO -bridged structures (P─CO ─B), which drive the
2
Table 1. Catalytic carboxylation of diverse C(sp , sp2 and sp)─H bonds using
3
2
-concentration-dependent NMR monitoring was also carried
can
2
CO -folded SCNPs as nanocatalysts.
2
2
2
cross-linking within the polymer to yield SCNP. Infrared (FT-IR)
and 19F NMR spectra supported this conclusion (Figure S11-S12).
Moreover, this gas binding reaction is almost complete except for
2
traces of unsaturated P─CO species remained.
Further investigation found that this coil-to-globule transition is
o
reversible. When the temperature exceeds 60 C, NP1 will unfold
the chain due to the dissociation of bridging bonds. If adding CO
again, a refolding process of P1 is accessible. Even over 10
rounds of alternating stimuli, such thermally-unfolded and CO
folded cycle can be sustained (Figure S13-S14). This means that
2
2
-
the gas bridges are dynamic, presaging the high activity of CO
2
species bound in the SCNPs.
Figure 3. The polymer morphological transition between in active folding (NP1)
and dormant unfolding state (P1) for recyclable CO utilization and catalytic
2
carboxylation.
Transforming atmospheric CO
ambitious dream of sustainable chemistry. Carboxylase can
easily realize this goal because its key CO -binding pocket can
weaken the inert double bond of CO and its precise folded
conformation can offer the ideal catalytic cavity. In our SCNP, the
P─CO ─B binding bridge, like the enzyme's binding site, can
efficiently activate CO , while the chain folding architecture,
2
into value-added chemicals is an
2
2
2
2
mimicking the enzyme's 3D geometry, can afford optimal catalytic
compartments. Based on these, we speculated that the SCNPs
2
With SCNPs in hand, we first investigated CO carboxylation of
acetophenone. In organisms, this process is finished by
acetophenone carboxylase, which is essential for the metabolism
could be used as recyclable carboxylase mimics for CO
conversion. The overall design is depicted as Figure 3: i) Free
chain P1 purging with CO can form NP1 SCNP; ii) Adding various
substrates containing C(sp , sp or sp)─H bonds, they can react
with the highly active CO bound in the SCNP and convert into the
2
of aromatic toxicants.[ However, in laboratory, it is extremely
16]
3
hard to perform CO
2
insertion on this saturated C(sp )─H bond.
2
3
2
The only examples require concerted photo-/organocatalysis
working at high pressure.[17] Using the SCNPs as nanocatalysts,
2
o
corresponding carboxylation products under room temperature; iii) we surveyed their catalytic ability for this reaction at 25 C. All
After the reaction ends, NP1 that loses CO
2
will unfold and release
acetophenones with different substituents can be almost
quantitatively carboxylated within 2–6 h, as attested by H NMR
1
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and mass spectra (Entry 1-4, Table 1; Supporting Information).
Among them, introduction of electron-donating groups (e.g.
methyl- and methoxyl-) have negative effect on the catalysis
synthetic nanocatalysts that are formed from CO
chain nanoparticles (SCNPs). Installing frustrated Lewis partners
on the polymer, CO can intramolecularly collapse the polymer
chain through dynamic CO -bridged bonds, in which the CO
folding domains conformationally and functionally emulate the
CO -binding cavity of carboxylases. Since CO bound in the
2
-folded single-
2
(
(
longer time, 6 h). On the contrary, electron-withdrawing group
e.g. nitro-) favor this reaction owing to the increased acidity of
2
2
-
C─H bond (within shorter time, 2 h). After verifying the excellent
2
2
3
catalysis to C(sp )─H, we then expected to expand the scope of
SCNPs are highly activated, they can efficiently catalyze the
carboxylation of diversiform C─H bonds under mild conditions
substrates. It is known that carboxylases have no activity to C(sp2
and sp)─H bonds. Interestingly, we discovered that styrene-type
using atmospheric CO
between the folding and unfolding states, these SCNPs can be
recycled for continuous CO conversion. This study will open a
new avenue for gas catalysis and provide a new outlook to
sustainable CO valorization.
2 1
as C source. Switching the polymers
2
derivatives with C(sp )─H can also be well catalyzed by the
SCNPs (Entry 5-9, Table 1). The influence of push-pull electron
effect of substitution on conversion is still valid (Entry 6-7).
Notably, even for N-heterocyclic double bonds (e.g. benzopyrrole
and benzoxazole), the results remained delightful (~70% yield,
Entry 8-9). The reason for the small decline in conversion is that
N-heterocycles as Lewis bases can competitively bind the borane
2
2
Acknowledgements
2
moieties in SCNP, leading to CO premature deactivation. For the
case of C(sp)─H bonds, the catalytic rates are faster (<1 h) owing
to their higher hydrocarbon acidity. Regardless of the alkyne
substrates with aromatic, aliphatic or alicyclic scaffolds, high
yields of 82–94% can be attained (Entry 10-15, Table 1). These
facts overall demonstrate that our SCNP nanocatalysts can not
only imitate the function of natural carboxylases, and also beyond
their function, mediating non-natural C─H carboxylation pathways.
The authors thank the support of National Natural Science
Foundation of China (21674022 and 51703034) and Shanghai
Rising-Star Program (19QA1400700).
Keywords: single-chain nanoparticles • enzyme mimics • CO
2
conversion • Lewis pair • sustainable C1 chemistry
[
1]
2]
S. M. Glueck, S. Gümüs, W. M. F. Fabian, K. Faber, Chem. Soc. Rev.
010, 39, 313-328.
a) J. T. Hong, M. Li, J. N. Zhang, B. Q. Sun, F. Y. Mo, ChemSusChem
019, 12, 6-39; b) L. Fu, S. D. Li, Z. H. Cai, Y. Z. Ding, X.-Q. Guo, L.-P.
2
[
2
Zhou, D. Yuan, Q.-F. Sun, G. Li, Nat. Catal. 2018, 1, 469-478; c) Q.-Y.
Meng, S. Wang, G. S. Huff, B, König, J. Am. Chem. Soc. 2018, 140,
3198-3201; d) M. Gaydou, T. Moragas, F. Juliá-Hernández, R. Martin, J.
Am. Chem. Soc. 2017, 129, 12161-12164; e) K. Sasano, J. Takaya, N.
Iwasawa, J. Am. Chem. Soc. 2013, 135, 10954-10957.
[
3]
a) H. T. D. Nguyen, Y. B. N. Tran, H. N. Nguyen, T. C. Nguyen, P. T. K.
Nguyen, Inorg. Chem. 2018, 57, 13772-13782; b) S. Shyshkanov, T. N.
Nguyen, F. M. Ebrahim, K. C. Stylianou, P. J. Dyson, Angew. Chem. Int.
Ed. 2019, 58, 5371-5375; Angew. Chem. 2019, 131, 5425-5429; c) J. L.
Shi, L. Zhang, N. Sun, D. Hu, Q. Shen, F. Mao, Q. Gao, W. Wei, ACS
Appl. Mater. Interfaces 2019, 11, 28858-28867.
Figure 4. (a) Catalytic activity of CO
various categories of C─H substrates. (b) Catalytic and regenerative time of the
SCNPs using CO /N mixing gas with varied CO pressures.
2
-bound SCNPs after reaction cycles for
[
[
[
4]
5]
6]
a) Q.-Q. Dang, C.-Y. Liu, X. M. Wang, X.-M. Zhang, ACS Appl. Mater.
Interfaces 2018, 10, 27972-27978; b) X. Lan, C. Du, L. Cao, T. T. She,
Y. Li, G. Y. Bai, ACS Appl. Mater. Interfaces 2018, 10, 38953-38962.
a) M. Ouchi, N. Badi, J.-F. Lutz, Nat. Chem. 2011, 3, 917-924; b) M.
Gonzalez-Burgos, A. Latorre-Sanchez, J. A. Pomposo, Chem. Soc. Rev.
2
2
2
Besides reaction efficiency, we also cared about the reusability
of nanocatalysts and reaction mildness. To assess the reusage of
nanocatalysts, we regenerated the SCNPs for at least 5 times by
2015, 44, 6122-6142.
a) T. S. Fischer, D. Schulze-Sünninghausen, B. Luy, O. Altintas, C.
Barner-Kowollik, Angew. Chem. Int. Ed. 2016, 55, 11276-11280; Angew.
Chem. 2016, 128, 11446-11450; b) R. K. Roy, J.-F. Lutz, J. Am. Chem.
Soc. 2014, 136, 12888-12891; c) T. Mes, R. van der Weegan, A. R. A.
Palmans, E. W. Meijer, Angew. Chem. Int. Ed. 2011, 50, 5085-5089;
Angew. Chem. 2011, 123, 5191-5195.
exerting CO
diverse categories of C─H bonds still retained 90% (Figure 4a).
On the other hand, we studied the influence of CO partial
pressure on the catalytic cycle. The tests were carried out in
various CO /N mixing gases. It was found that reducing CO
2
. It was found that their catalytic activity towards
2
2
2
2
[7]
a) H. Rothfuss, N. D. Knöfel, P. W. Roesky, C. Barner-Kowollik, J. Am.
Chem. Soc. 2018, 140, 5875-5881; b) Y. L. Liu, T. Pauloehrl, S. I.
Presolski, L. Albertazzi, A. R. A. Palmans, E. W. Meijer, J. Am. Chem.
Soc. 2015, 137, 13096-13105; c) Y. L. Liu, S. Pujals, P. J. M. Stals, T.
Paulöhrl, S. I. Presolski, E. W. Meijer, L. Albertazzi, A. R. A. Palmans, J.
Am. Chem. Soc. 2018, 130, 3423-3433; d) R. Lambert, A.-L. Wirotius, D.
Taton, ACS Macro Lett. 2017, 6, 489-494; e) I. Perez-Baena, F. Barroso-
Bujans, U. Gasser, A. Arbe, A. J. Moreno, J. Colmenero, J. A. Pompso,
ACS Macro Lett. 2013, 2, 775-779.
pressure (from 10 to 0.1 kPa) had no obvious negative effect on
the catalytic rates, only prolonging the regenerative time of
SCNPs (Figure 4b). Gratifyingly, even under 100 Pa of CO
the ambient CO pressure (30 Pa), the catalytic activities were
maintained (Figure S15). These suggest the recyclability of SCNP
2
, near
2
nanocatalysts and their potency in direct use of atmospheric CO
as C feedstock.
Learning from natural CO
artificial CO
2
1
2
-fixation enzymes is crucial to realizing
catalysis. In this work, we first demonstrate a kind of
[8]
a) J. F. Chen, J. Wang, Y. G. Bai, K. Li, E. S. Garcia, A. L. Ferguson, S.
C. Zimmerman, J. Am. Chem. Soc. 2018, 140, 13695-13702; b) Y. Y.
2
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Zhang, W. Y. Wang, W. Q. Fu, M. J. Zhang, Z. Y. Tang, R. Tan, D. H.
Yin, Chem. Commun. 2018, 54, 9430-9433; c) N. D. Knöfel, H. Rothfuss,
J. Willenbacher, C. Barner-Kowollik, P. W. Roesky, Angew. Chem. Int.
Ed. 2017, 56, 4950-4954; Angew. Chem. 2017, 129, 5032-5036; d) A.
Sanchez-Sanchez, A. Arbe, J. Colmenero, J. A. Pomposo, ACS Macro
Lett. 2014, 3, 439-443.
[12] a) L. J. Fetters, N. Hadijchristidis, J. S. Lindner, J. W. Mays, J. Phys.
Chem. Ref. Data 1994, 23, 619-640; b) J. A. Pomposo, I. Perez-Baena,
F. Lo Verso, A. J. Moreno, A. Arbe, J. Colmenero, ACS Macro Lett. 2014,
3, 767-772.
[13] a) L. Pollack, M. W. Tate, N. C. Darnton, J. B. Knight, S. M. Gruner, E.
A. Eaton, R. H. Austin, Proc. Natl. Acad. Sci. USA 1999, 96, 10115-
10117; b) D. Durand, C. Vives, D. Cannella, J. Perez, E. Pebay-Peyroula,
P. Vachette, F. Fieschi, J. Struct. Biol. 2010, 169, 45-53.
[14] M. Rubinstein, R. H. Colby, Polymer Physics; Oxford University Press:
New York, 2003.
[
[
9]
G. M. M. Stoffel, D. A. Saez, H. DeMirci, B. Vögeli, Y. Rao, J. Zarzycki,
Y. Yoshikuni, S. Wakatsuki, E. Vöhringer-Martinez, T. J. Erb, Proc. Natl.
Acad. Sci. USA 2019, 116, 13964-13969.
10] a) D. W. Stephan, G. Erker, Chem. Sci. 2014, 5, 2625-2641; b) C. M.
Mömming, E. Otten, G. Kehr, R. Fröhlich, S. Grimme, D. W. Stephan, G.
Erker, Angew. Chem. Int. Ed. 2009, 48, 6643-6646; Angew. Chem. 2009,
[15] B. Wrackmeyer, Annu. Rep. NMR Spectrosc. 1988, 20, 61-200.
[16] S. Weidenweber, K. Schühle, U. Demmer, E. Warkentin, U. Ermler, J.
Heider, Sci. Rep. 2017, 7, 39674.
121, 6770-6773.
[
11] a) M. Wang, F. Nudelman, R. R. Matthes, M. P. Shaver, J. Am. Chem.
Soc. 2017, 139, 14232-14236; b) L. Chen, R. J. Liu, X. Hao, Q. Yan,
Angew. Chem. Int. Ed. 2019, 58, 264-268; Angew. Chem. 2019, 131,
[17] a) N. Ishida, Y. Masuda, Y. Imamura, K. Yamazaki, M. Murakami, J. Am.
Chem. Soc. 2019, 141, 19611-19615; b) Q. Meng, T. E. Schirmer, A. L.
Berger, K. Donabauer, B. König, J. Am. Chem. Soc. 2019, 141, 11393-
11397.
270-274; c) F. Vidal, J. Gomezcoello, R. A. Lalancette, F. Jäkle, J. Am.
Chem. Soc. 2019, 141, 15963-15971.
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CO -Folded Single-Chain
Nanoparticles as Recyclable,
Intensified Carboxylase Mimics
Text for Table of Contents
Folding polymer by CO
2
. Frustrated Lewis pair polymers can be folded into single-chain nanoparticles with CO
2 2
gas. The CO -
bridged connections can weaken the inert CO
2
and directly catalyze CO -carboxylation of diverse C-H bonds under room
2
2
temperature and near atmospheric conditions, functioning as carboxylase mimic for sustainable CO conversion.
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