Angewandte Chemie International Edition
10.1002/anie.202103165
COMMUNICATION
Pd@SiJAR for intracellular catalysis for aldol reaction between a
fluorescent 9-antracenecarboxaldehyde with acetone to form a
aldol product (4) with shifted fluorescence response (Figure S33).
The intracellular aldol reaction (details in SI) was monitored by
fluorescence microscopy and flow cytometry (Figure 4g-i). The
initial strong green fluorescence inside the cells started fading
within 8 h and disappeared after 24 h due to the formation of the
aldol product 4 (Figure 4f). We isolated the aldol product 4 from
the cell lysate and analyzed to show high ee (ca. 79%) (Figure
S34). The absence of Cal-Pd-SiJAR or acetone showed
consistent fluorescence signals until 24 h (Figure S35), validating
that disappearance of fluorescence could only occur through the
intracellular aldol reaction. After incubating with MCF-7 cells for
R. Goers, A. Najer, M. Spulber, O. Onaca-Fischer, J. Huwyler, C. G.
Palivan, Nat. Commun. 2018, 9, 1127.
[
3]
a) M. Sancho-Albero, B. Rubio-Ruiz, A. M. Pérez-López, V. Sebastián,
P. Martín-Duque, M. Arruebo, J. Santamaría, A. Unciti-Broceta, Nat.
Catal. 2019, 2, 864–872; b) M. A. Miller, B. Askevold, H. Mikula, R. H.
Kohler, D. Pirovich, R. Weissleder, Nat. Commun. 2017, 8, 15906; c) J.
Clavadetscher, E. Indrigo, S. V. Chankeshwara, A. Lilienkampf, M.
Bradley, Angew. Chem. Int. Ed. 2017, 56, 6864–6868; Angew. Chem.
2017, 129, 6968–6972.
[4]
a) S. Dutta, N. Kumari, S. Dubbu, S. W. Jang, A. Kumar, H. Ohtsu, J.
Kim, S. H. Cho, M. Kawano, I. S. Lee, Angew. Chem. Int. Ed. 2020, 59,
3
416 3422; Angew. Chem. 2020, 132, 3444–3450; b) V. Smeets, W.
–
Baaziz, O. Ersen, E. M. Gaigneaux, C. Boissière, C. Sanchez, D. P.
Debecker, Chem. Sci. 2020, 11, 954–961; c) K. Engström, E. V.
Johnston, O. Verho, K. P. J. Gustafson, M. Shakeri, C. W. Tai, J. E.
Bäckvall, Angew. Chem. Int. Ed. 2013, 52, 14006–14010; Angew. Chem.
2013, 125, 14256–14260.
24 h, we retrieved the Cal-Pd@SiJAR through cell-lysis and
affirmed their preserved nanostructure (by TEM) and catalytic
performance using a standard colorimetric assay kit and aldol
reaction (Figure S36-39). In comparison, Cal-Glt-Pd-NH SiO did
2 2
not induce any intracellular aldol reaction because of severe
nanostructre deformation and deactivation (details in SI, Figure
S40).[24]
[5]
a) Z. Du, C. Liu, H. Song, P. Scott, Z. Liu, J. Ren, X. Qu, Chem. 2020, 6,
1–13; b) J. J. Soldevila-Barreda, N. Metzler-Nolte, Chem. Rev. 2019, 119,
8
29–869; c) J. P. C. Coverdale, I. Romero-Canelón, C. Sanchez-Cano,
G. J. Clarkson, A. Habtemariam, M. Wills, P. J. Sadler, Nat. Chem. 2018,
0, 347–354.
1
[
[
6]
7]
a) A. Sousa-Castillo, J. R. Couceiro, M. Tomás-Gamasa, A. Mariño-
López, F. López, W. Baaziz, O. Ersen, M. Comesaña-Hermo, J. L.
Mascareñas, M. A. Correa-Duarte, Nano Lett. 2020, 20, 7068–7076; b)
J. Lee, S. Dubbu, N. Kumari, A. Kumar, J. Lim, S. Kim, I. S. Lee, Nano
Lett. 2020, 20, 6981–6988; c) W. Fang, J. Yang, J. Gong, N. Zheng, Adv.
Funct. Mater. 2012, 22, 842–848.
In conclusion, we developed a solid-state NC-conversion
strategy to selectively modify the controllable arc-section of h-
SiO with metal-silicate for installing a chemically responsive
2
circular lid, which endowed noble metal decoration and size-
controlled mouth-opening for the co-localization of catalytic metal
NCs and enzymes inside SiJARs. As a key step, MnO-yolk acted
as metal reservoir which docked and fused as Mn2+ into shell-
section; the resulting lid-on-jar Janus shell was isolated as the
intermediate structure before transitioning to symmetric biphasic-
shell. These open-mouth chemo-enzymatic nanoreactors
rendered high enantioselectivity for asymmetric aldol reaction
through a cooperating transition state stabilization role of Pd and
Cal-A co-supported on negatively curved silica-interior. Sub-100
nm sized SiJARs were highly biocompatible and easily
internalized with living cells creating an organelle-like confined
catalytic compartments inside cytoplasm. In future, these highly
customizable hybrid chemoenzymatic nanodevices can be
utilized for synthesizing active therapeutics and bioimging probes
locally inside cells in order to develop next generation biomedical
tools.
a) H. Che, S. Cao, J. C. M. van Hest, J. Am. Chem. Soc. 2018, 140,
5356–5359; b) P. Gobbo, A. J. Patil, M. Li, R. Harniman, W. H. Briscoe,
S. Mann, Nat. Mater. 2018, 17, 1145–1153; c) L. -C. Lee, J. Lu, M. Weck,
C. W. Jones, ACS Catal. 2016, 6, 784–787.
[8]
a) G. Prieto, H. Tüysüz, N. Duyckaerts, J. Knossalla, G. -H. Wang, F.
Schüth, Chem. Rev. 2016, 116, 14056–14119; b) Y. Li, J. Shi, Adv. Mater.
2
014, 26, 3176–3205.
C. Gao, F. Lyu, Y. Yin, Chem. Rev. 2020, 121, 834–881.
10] a) S. Gao, Z. Wang, L. Ma, Y. Liu, J. Gao, Y. Jiang, ACS Catal. 2020, 10,
375–1380; b) Q. Wang, X. Zhang, L. Huang, Z. Zhang, S. Dong, Angew.
Chem. Int. Ed. 2017, 56, 16082–16085; Angew. Chem. 2017, 129,
6298–16301.
[
[
9]
1
1
[
[
[
11] a) Z. Teng, W. Li, Y. Tang, A. Elzatahry, G. Lu, D. Zhao, Adv. Mater.
2019, 31, 1707612; b) Y. Chen, H. –R. Chen, J. –L. Shi, Acc. Chem. Res.
2014, 47, 125–137.
12] a) T. W. Kwon, K. -W. Jeon, S. Dutta, I. S. Lee, Chem. Mater. 2018, 30,
8070–8078; b) T. -L. Ha, J. G. Kim, S. M. Kim, I. S. Lee, J. Am. Chem.
Soc. 2013, 135, 1378–1385.
13] a) J. G. Kim, A. Kumar, S. J. Lee, J. H. Kim, D. -G. Lee, T. Kwon, S. H.
Cho, I. S. Lee, Chem. Mater. 2017, 29, 7785–7793; b) S. M. Kim, M.
Jeon, K. W. Kim, J. Park, I. S. Lee, J. Am. Chem. Soc. 2013, 135, 15714–
Acknowledgements
15717.
[
[
14] a) D. Yi, Q. Zhang, Y. Liu, J. Song, Y. Tang, F. Caruso, Y. Wang, Angew.
Chem. Int. Ed. 2016, 55, 14733–14737; Angew. Chem. 2016, 128,
This work was supported by the Basic Science Research Program
through the National Research Foundation of Korea (NRF)
funded by the Ministry of Science, ICT & Future Planning (MSIP)
14953–14957; b) X. Li, L. Zhou, Y. Wei, A. M. El-Toni, F. Zhang, D. Zhao,
J. Am. Chem. Soc. 2015, 137, 5903–5906; c) M. Alarcón-Correa, T.-C.
Lee, P. Fischer, Angew. Chem. Int. Ed. 2015, 54, 6730–6734; Angew.
Chem. 2015, 127, 6834–6838; d) D. A. Wilson, R. J. M. Nolte, J. C. M.
van Hest, J. Am. Chem. Soc. 2012, 134, 9894–9897.
(
2
NRF-2016R1A3B1907559)
020R1I1A1A01071721) (A.K.).
(I.S.L.)
and
(NRF-
15] a) J. Chen, F. Jiang, Y. Yin, Acc. Chem. Res. 2021, 54, 1168–1177; b)
X. Wang, J. Liu, ChemNanoMat 2020, 6, 1437–1448; c) D. Wang, X.
Wang, Z. Li, M. Chi, Y. Li, Y. Liu, Y. Yin, ACS Nano 2018, 12, 10949–
Keywords: open-mouth nanoreactor • nanocrystal conversion
chemistry • chemo-enzyme hybrid • nanocatalyst •
enantioselective catalysis
1
0956.
16] K. W. Kim, S. M. Kim, S. Choi, J. Kim, I. S. Lee, ACS Nano 2012, 6,
122–5129.
[
[
5
[
[
1]
2]
A. F. Mason, N. A. Yewdall, P. L. W. Welzen, J. Shao, M. Stevendaal, J.
17] a) B. G. Cha, J. H. Jeong, J. Kim, ACS Cent. Sci. 2018, 4, 484–492; b)
D. H. Han, H. -K. Na, W. H. Choi, J. H. Lee, Y. K. Kim, C. Won, S. -H.
Lee, K. P. Kim, J. Kuret, D. -H. Min, M. J. Lee, Nat. Commun. 2014, 5,
C. M. van Hest, D. S. Williams, L. K. E. A. Abdelmohsen, ACS Cent. Sci.
2019, 5, 1360–1365.
a) K. Y. Lee, S. J. Park, K. A. Lee, S. H. Kim, H. Kim, Y. Meroz, L.
5
633.
18] I. Avramov, T. Vassilev, I. Penkov, J. Non-Cryst. Solids 2005, 351, 472–
76.
Mahadevan, K. H. Jung, T. K. Ahn, K. K. Parker, K. Shin, Nat. Biotechnol.
[
2018, 36, 530–535; b) T. Einfalt, D. Witzigmann, C. Edlinger, S. Sieber,
4
5
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