TY - JOUR
T1 - Enzyme-Loaded Hemin/G-Quadruplex-Modified ZIF-90 Metal–Organic Framework Nanoparticles
T2 - Bioreactor Nanozymes for the Cascaded Oxidation of N-hydroxy-l-arginine and Sensing Applications
AU - Chen, Chaochao
AU - Vázquez-González, Margarita
AU - O'Hagan, Michael P.
AU - Ouyang, Yu
AU - Wang, Zhanhui
AU - Willner, Itamar
N1 - Publisher Copyright:
© 2022 Wiley-VCH GmbH
PY - 2022/3/17
Y1 - 2022/3/17
N2 - Biocatalytic cascades are challenging to operate in homogeneous solution, where diffusional mass transport hinders efficient communication between the reactive components. There is great interest in developing devices to perform such transformations in confined environments, which increase the efficiency of the cascaded process by generating high local concentrations of the reactive species. Herein, a bioreactor-nanozyme assembly is introduced for the cascaded aerobic oxidation of N-hydroxy-l-arginine (NOHA) to citrulline in the presence of glucose. The reaction mimics a key step in the nitric oxide synthase oxidation of l-arginine in nature. The system consists of glucose oxidase (GOx)-loaded hemin/G-quadruplex (hemin/G4)-modified ZIF-90 metal–organic framework nanoparticles. The aerobic oxidation of glucose by GOx yields H2O2 that fuels the hemin/G4-catalyzed oxidation of NOHA into citrulline. The process driven by the bioreactor-nanozyme system is ≈sixfold enhanced compared to the homogeneous mixture of the biocatalysts, due to its operation in the confined environment of the nanoparticles. Extension to a three-step cascade is then demonstrated using a bioreactor composed of β-galactosidase/GOx-loaded hemin/G4-modified ZIF-90 nanoparticles activating the cascaded oxidation of NOHA to citrulline, in the presence of lactose. Moreover, the bioreactor-nanozyme hybrid is applied as a functional optical sensor of glucose, using fluorescence or chemiluminescence as readout signals.
AB - Biocatalytic cascades are challenging to operate in homogeneous solution, where diffusional mass transport hinders efficient communication between the reactive components. There is great interest in developing devices to perform such transformations in confined environments, which increase the efficiency of the cascaded process by generating high local concentrations of the reactive species. Herein, a bioreactor-nanozyme assembly is introduced for the cascaded aerobic oxidation of N-hydroxy-l-arginine (NOHA) to citrulline in the presence of glucose. The reaction mimics a key step in the nitric oxide synthase oxidation of l-arginine in nature. The system consists of glucose oxidase (GOx)-loaded hemin/G-quadruplex (hemin/G4)-modified ZIF-90 metal–organic framework nanoparticles. The aerobic oxidation of glucose by GOx yields H2O2 that fuels the hemin/G4-catalyzed oxidation of NOHA into citrulline. The process driven by the bioreactor-nanozyme system is ≈sixfold enhanced compared to the homogeneous mixture of the biocatalysts, due to its operation in the confined environment of the nanoparticles. Extension to a three-step cascade is then demonstrated using a bioreactor composed of β-galactosidase/GOx-loaded hemin/G4-modified ZIF-90 nanoparticles activating the cascaded oxidation of NOHA to citrulline, in the presence of lactose. Moreover, the bioreactor-nanozyme hybrid is applied as a functional optical sensor of glucose, using fluorescence or chemiluminescence as readout signals.
KW - biocatalytic cascades
KW - chemiluminescence
KW - DNA nanotechnology
KW - DNAzymes
KW - nitric oxide
KW - sensors
UR - http://www.scopus.com/inward/record.url?scp=85122731953&partnerID=8YFLogxK
U2 - 10.1002/smll.202104420
DO - 10.1002/smll.202104420
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C2 - 35037383
AN - SCOPUS:85122731953
SN - 1613-6810
VL - 18
JO - Small
JF - Small
IS - 11
M1 - 2104420
ER -