European Journal of Inorganic Chemistry
10.1002/ejic.201800898
FULL PAPER
Ester hydrolysis reactions. Ester hydrolysis experiments were
carried out at 60 °C. UiO-66 (5 mg, 6 mol%, 0.003 mmol based
on formula weight) was added to PBS buffer (2 mL; pH 8.5) in a
Keywords: Enzyme mimics • Heterogeneous catalysis • Lipase
•
Metal-organic frameworks • Nanoparticles
5
mL vial. The resulting mixture was stirred for 20 min to
[
[
1]
a) N. L. Rosi, J. Eckert, M. Eddaoudi, D. T. Vodak, J. Kim, M. O’Keeffe,
O. M. Yaghi, Science 2003, 300, 1127–1129; b) J. R. Long, O. M.
Yaghi, Chem. Soc. Rev. 2009, 38, 1213–1214; c) H.-C. Zhou, J. R.
Long, O. M. Yaghi, Chem. Rev. 2012, 112, 673–674.
disperse the UiO-66 completely. To this suspension was then
added p-nitrophenyl acetate (PNPA) (0.05 mmol). The vial was
then placed in a preheated oil bath at 60 °C under stirring.
Periodic monitoring was carried out by removing a 20 μL aliquot
from the reaction mixture and diluting it with a PBS buffer (2 mL).
The suspension was filtered to remove the UiO-66 solid prior to
UV/Vis measurements. Progress of the reaction was monitored
2]
a) L. Schlapbach, A. Zuttel, Nature 2001, 414, 353–358; b) O. K. Farha,
ö. Y. A. I. Eryazici, C. D. Malliakas, B. G. Hauser, M. G. Kanatzidis, S.
T. Nguyen, R. Q. Snurr, J. T. Hupp, Nat. Chem. 2010, 2, 944–948; c) S.
Ma, H.-C. Zhou, Chem. Commun. 2010, 46, 44–53. d) Y. Liu, J. F.
Eubank, A. J. Cairns, J. Eckert, V. C. Kravtsov, R. Luebke, M.
Eddaoudi, Angew. Chem. Int. Ed. 2007, 46, 3278–3283; e) Z. Niu, S.
Fang, X. Liu, J.-G. Ma, S.-Q. Ma, P. Cheng, J. Am. Chem. Soc. 2015,
137, 14873-14876; f) S. Ma, D. Sun, D. Yuan, X.-S. Wang, H.-C. Zhou,
J. Am. Chem. Soc. 2009, 131, 6445–6451.
[
10b]
by detection of the p-nitro-phenoxide absorbance at 405 nm.
No spectral evidence for the p-nitrophenol was observed at this
pH. The contrast reaction was carried out under the same
conditions without the catalyst.
[
3]
a) J. Lee, O. K. Farha, J. Roberts, K. A. Scheidt, S. T. Nguyen, J. T.
Hupp, Chem. Soc. Rev. 2009, 38, 1450–1459; b) C.-Y. Sun, S.-X. Liu,
D.-D. Liang, K.-Z. Shao, Y.-H. Ren, Z.-M. Su, J. Am. Chem. Soc. 2009,
Transesterification reactions. Transesterification experiments
were carried out at 60 °C. UiO-66 (5 mg, 6 mol%, 0.003 mmol
based on formula weight) was added to an aliquot of methanol
or ethanol (2 mL) in a 5 mL vial. The resulting mixture was
stirred for 20 min to disperse the UiO-66 completely. To this
suspension was then added p-nitrophenyl acetate (PNPA) (0.05
mmol). The vial was then placed in a preheated oil bath at 60 °C
under stirring. Periodic monitoring was carried out by removing a
1
31, 1883–1888; c) L. Ma, J. M. Falkowski, C. Abney, W. Lin, Nat.
Chem. 2010, 2, 838–846; d) C.-D. Wu, W. Lin, Angew. Chem. Int. Ed.
007, 46, 1075–1078; e) X. Liu, W. Qi, Y. Wang, R. Su, Z. He,
2
Nanoscale 2017, 9, 17561-17570.
[4]
a) S.-H. Cho, B. Ma, S. T. Nguyen, J. T. Hupp, T. E. Albrecht-Schmitt,
Chem. Commun. 2006, 24, 2563–2565; b) A. C. McKinlay, R. E. Morris,
P. Horcajada, G. Férey, R. Gref, P. Couvreur, C. Serre, Angew. Chem.
Int. Ed. 2010, 49, 6260–6266; c) K. M. L. Taylor-Pashow, J. D. Rocca,
Z. Xie, S. Tran, W. Lin, J. Am. Chem. Soc. 2009, 131, 14261–14263; d)
P. Horcajada, C. Serre, M. Vallet-Regí, M. Sebban, F. Taulelle, G.
Férey, Angew. Chem. Int. Ed. 2006, 45, 5974–5978.
2
0 μL aliquot from the reaction mixture and diluting it with
methanol or ethanol (2 mL). The suspension was filtered to
remove the UiO-66 solid prior to UV/Vis measurements.
Progress of the reaction was monitored by detection of the p-
[
10b]
nitrophenol absorption at 315 nm.
The contrast reaction was
[
5]
a) D. Zhao, S. Tan, D. Yuan, W. Lu, Y. H. Rezenom, H. Jiang, L.-Q.
Wang, H.-C. Zhou, Adv. Mater. 2011, 23, 90–93; b) G. Lu, J. T. Hupp, J.
Am. Chem. Soc. 2010, 132, 7832–7833; c) A. Lan, K. Li, H. Wu, D. H.
Olson, T. J. Emge, W. Ki, M. Hong, J. Li, Angew. Chem. Int. Ed. 2009,
carried out under the same conditions without the catalyst.
Esterification reactions. Esterification reactions were carried
out at 60 °C for methanol and 78 °C for ethanol. 1mmol of n-
hexylic acid, and the desired amount of alcohol were mixed with
UiO-66 (5 mg, 0.3 mol%, 0.003 mmol based on formula weight)
in a vial and placed in a preheated oil bath. The reaction was
detected by a gas chromatograph (GC, Agilent 7890B) with a
4
8, 2334–2338; d) L.-G. Qiu, Z.-Q. Li, Y. Wu, W. Wang, T. Xu, X. Jiang,
Chem. Commun. 2008, 31, 3642–3644; e) B. V. Harbuzaru, A. Corma,
F. Rey, P. Atienzar, J. L. Jorda, H. Garcia, D. Ananias, L. D. Carlos, J.
Rocha, Angew. Chem. Int. Ed. 2008, 47, 1080–1083.
[
6]
a) K. Mina, J. Kim, K. Park, Y. J. Yoo, J. Mol. Catal. B-Enzym. 2012, 83,
3
0m long and 0.25mm diameter capillary column HP-5 (5%
8
7-93; b) B. Krajewska, ZnzymeMicrob. Tech. 2004, 35, 126–139.
phenylmethylpolysiloxane). The suspension was centrifuged and
filtered to remove the UiO-66 solid prior to GC detection.
Retention times were compared with those of commercial
standards when available.
[7]
a) H. Wei, E. Wang, Chem. Soc. Rev. 2013, 42, 6060–6093; b) Y. H.
Lin, J. S. Ren, X. G. Qu, Adv. Mater. 2014, 26, 4200-4217; c) H. Y.
Shin, T. J. Park, M. Il Kim, J. Nanomater. 2015, 2015, 7. d) B.Liu, J. Liu,
Nano Res. 2017, 10,1125–1148.
[
[
8]
9]
I. Nath, J. Chakraborty, F. Verpoort, Chem. Soc. Rev. 2016, 45, 4127-
4170.
Materials characterization
a) K. Wang, D. Feng, T.-F. Liu, J. Su, S. Yuan, Y. -P. Chen, M. Bosch,
X. Zou, H. C. Zhou, J. Am. Chem. Soc. 2014, 136, 13983–13986; b) K.
Sasan, Q. Lin, C.-Y. Mao, P. Feng, Chem. Commun. 2014, 50, 10390–
Powder X-ray diffraction (XRD) patterns of the as-prepared
products were recorded using an X-ray diffractometer (Bruker
-
1
1
0393; c) C. Zou, T. Zhang, M.-H. Xie, L. Yan, G.-Q. Kong, X.-L. Yang,
D8 advance) with Cu Kα irradiation at a scan rate of 4 °C min
A. Ma, C.-D. Wu, Inorg. Chem. 2013, 52, 3620–3626; d) A. M. Shultz,
O. K. Farha, J. T. Hupp, S. T. Nguyen, J. Am. Chem. Soc. 2009, 131,
and a step size of 0.02°. The morphology and crystal structure of
the as-prepared products were examined by field-emission
scanning electron microscopy (SEM, Hitachi S4800). The
particle diameter distribution was determined by dynamic light
scattering (DLS, Malvern Zetasizer Nano ZS90).
4
204–4205. e) O. K. Farha, A. M. Shultz, A. A. Sarjeant, S. T. Nguyen,
J. T. Hupp, J. Am. Chem. Soc. 2011, 133, 5652–5655; f) L. Meng, Q.
Cheng, C. Kim, W.-Y. Gao, L. Wojtas, Y.-S. Chen, M. J. Zaworotko, X.-
P. Zhang, S. Ma, Angew. Chem. Int. Ed. 2012, 51, 10082–10085.
[
10] a) F.-X. Qin, S.-Y. Jia, F.-F. Wang, S.-H. Wu, J. Song, Y. Liu, Catal. Sci.
Technol. 2013, 3, 2761-2768; b) H. Cheng, L. Zhang, J. He, W. Guo,
Z.-Y. Zhou, S.-M. Nie, H. Wei, Anal. Chem. 2016, 88, 5489-5497; c) S.
Xie, J. Ye, Y. Yuan, Y. Chai, R. Yuan, Nanoscale 2015, 7, 18232-
Acknowledgements
1
8238; d) F. Luo, Y. Lin, L. Zheng, X. Lin, Y. Chi, ACS Appl. Mat.
Interfaces 2015, 7, 11322-11329; e) F. Liu, J. He, M. Zeng, J. Hao, Q.
Guo, Y. Song, L. Wang, J. Nanopart. Res. 2016, 18, 1-9.
This work was supported by the National Natural Science
Foundation of China (Nos. 21621004, 21476165, 21606166,
[11] a) B. Li, D. Chen, J. Wang, Z. Yan, L. Jiang, D. Duan, J.He, Z.-R. Luo,
J.-P. Zhang, F. Yuan, Sci. Rep. 2014, 4, 6759; b) M. J. Katz, J. E.
Mondloch, R. K. Totten, J. K. Park, S. T. Nguyen, O. K. Farha, J. T.
Hupp, Angew. Chem. Int. Ed. 2014, 53, 497-501; c) M. J. Katz, S. Y.
Moon, J. E. Mondloch, M. H. Beyzavi, C. J. Stephenson, J. T. Hupp, O.
5
1773149), the Beiyang Young Scholar of Tianjin University
(
(
2012) and the State Key Laboratory of Chemical Engineering
Nos. SKL-ChE-08B01).
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