Performance of Nitrogen-doped Hollow Carbon Spheres as Oxidase Mimic

doi:10.15541/jim20200396

Abstract

Abstract:

Due to efficient performance and stability, nanozymes have recently attracted much attention in bioreaction. In this work, a facile approach for preparing N-doped hollow carbon sheres (N-HCSs) by using CaCO₃ spheres as green template and polydoamine as nitrogen and carbon sources was reported. Morphologies and structures of the samples were characterized. Using TMB (3,3,5,5° tetramethylbenzidine) as a substrate, UV spectra photometry was used to investigate its oxidase-like activity and catalytic mechanism. The results showed that N-HCSs displayed oxidase-like activity. The oxidase-like activity of N-HCSs increased by three times after activation by KOH. These enzymes conform to the Michaelis-Menten kinetic equation, and the K_m constant before and after activation were 0.105 and 0.083, respectively, indicating good affinity for substrates. The data demonstrate that it is superoxide anion (O₂? ^-) that plays a major role in catalytic reaction. This work data provides a theoretical basis for the design and preparation of high activity oxidase-mimicking enzymes.

Key words: N-doped hollow carbon sheres, oxidase-like enzyme, reaction mechanism

CLC Number:

TQ174

ZHENG Yanning, JI Junrong, LIANG Xueling, LAI Zhengjie, CHENG Qifan, LIAO Dankui. Performance of Nitrogen-doped Hollow Carbon Spheres as Oxidase Mimic[J]. Journal of Inorganic Materials, 2021, 36(5): 527-534.

Figures/Tables 10

Fig. 1 Morphologies and element mappings of N-HCSs

Fig. 2 SEM images of (a) N-HCS and (b) N-HCS-1, and TEM images of (c) CaCO3@PDA and (d) N-HCS

Fig. 3 (a) XPS full spectra of N-HCS and N-HCS-1; N1s spectra of (b) N-HCS and (c) N-HCS-1; (d) N species contents of N-HCS and N-HCS-1

Fig. 4 (a) Nitrogen absorption-desorption isotherm curves of N-HCS and N-HCS-1, (b) HK model corresponding pore size distribution curves of N-HCS and N-HCS-1

Table 1 Pore structure parameters of N-HCS and N-HCS-1

Sample	Specfic suface/(m²•g^-1)		V_t/ (cm³•g^-1)	V_m/ (cm³•g^-1)	S_m/ (m²•g^-1)	(S_m/S_t)/ %
Sample	Langmuir	BET	V_t/ (cm³•g^-1)	V_m/ (cm³•g^-1)	S_m/ (m²•g^-1)	(S_m/S_t)/ %
N-HCS	685.6	490.1	0.651	0.109	230.51	45.49
N-HCS-1	730.0	518.4	0.732	0.111	228.16	44.01

Fig. 5 (a) UV-Vis absorption spectra of different systems, and effects of (b) catalyst concentration, (c) pH and (d) temperature on the oxidase-like activity of N-HCSs

Fig. 6 Steady-state kinetic assay of N-HCS and N-HCS-1

Table 2 Comparison of the Km and Vmax between N-HCSs and other oxidase-like

Catalyst	Substrate	K_m/ (mmol•L^-1)	V_max/(×10^-8, mol•L^-1•s^-1)	Ref.
N-PCS	TMB	0.095	5.20	[4]
His@AuNCs	TMB	0.041	6.21	[31]
Pt Au DNPs	TMB	0.22	2.82	[32]
Acr⁺-Mes	TMB	0.129	2.68	[33]
N-HCS	TMB	0.1049	4.69	This work
N-HCS-1	TMB	0.0825	5.98	This work

Fig. 7 (a) Absorption spectra of the solution containing TMB and N-HCS and N-HCS-1 under N2-saturated conditions, and effect of scavengers (b) IPA, (c) CAT and (d) SOD on the catalytic oxidation of TMB by the N-HCS and N-HCS-1

Fig. 8 (a) ESR spectra and (b) catalytic mechanism diagram for the oxidase-like activity of the N-HCSs

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