Colorimetric/Fluorometric Detection of Adenosine-5′-Triphosphate Based on Metal-Organic Framework Cu@Sc-MOF Nanozyme

doi:10.19894/j.issn.1000-0518.240028

Chinese Journal of Applied Chemistry ›› 2024, Vol. 41 ›› Issue (5): 728-738.DOI: 10.19894/j.issn.1000-0518.240028

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Colorimetric/Fluorometric Detection of Adenosine-5′-Triphosphate Based on Metal-Organic Framework Cu@Sc-MOF Nanozyme

Xiao-Jing CHAI¹, Rui-Rui ZHAO¹, Yuan ZHANG², Chuan DONG²(), Shao-Min SHUANG¹()

^1.School of Chemistry and Chemical Engineering，Shanxi University，Taiyuan 030006，China
^2.Institute of Environmental Science，Shanxi University，Taiyuan 030006，China

Received:2024-01-28 Accepted:2024-04-14 Published:2024-05-01 Online:2024-06-03
Contact: Chuan DONG,Shao-Min SHUANG
About author:smshuang@sxu.edu.cn
Supported by:
the National Natural Science Foundation of China(22274090)

Abstract

Abstract:

A copper/scandium metal-organic framework （Cu@Sc-MOF） nanozyme was prepared by solvothermal method. The Cu@Sc-MOF nanozyme could oxidize substrate 3，3′，5，5′-tetramethylbenzidine （TMB） to produce blue oxTMB which showed absorption at 652 nm in the presence of H₂O₂. Similarly， Cu@Sc-MOF was used to catalyze o-phenylenediamine （OPD） to generate diminophenazine （DAP） with fluorescence emission at 570 nm. The colorimetric/fluorometric dual-mode sensor for the detection of adenosine-5′-triphosphate （ATP） was developed owing to the peroxidase-like characteristics of the Cu@Sc-MOF. Upon the addition of ATP in the Cu@Sc-MOF/H₂O₂ mixture， the peroxidase-like activity of Cu@Sc-MOF was inhibited due to the strong interaction between ATP and Cu²⁺ ion， causing weakened absorbance at 652 nm and less fluorescence intensity at 570 nm. The respective values of linear ranges for the colorimetric and fluorometric method were 2.50~40.0 μmol/L and 1.00~22.5 μmol/L， and the limits of detection （LOD） were 0.600 and 1.87μmol/L. The colorimetric/fluorescence dual-mode analysis method could realize to detect ATP in HepG2 cell lysate with recoveries ranged from 92.0%~101% and 93.2%~97.9%， respectively， showing good application prospects in the detection of ATP.

Key words: Cu@Sc-MOF, Nanozyme, Peroxidase-like activity, Colorimetric/Fluorometric, Adenosine-5??- triphosphate

CLC Number:

O655

Xiao-Jing CHAI, Rui-Rui ZHAO, Yuan ZHANG, Chuan DONG, Shao-Min SHUANG. Colorimetric/Fluorometric Detection of Adenosine-5′-Triphosphate Based on Metal-Organic Framework Cu@Sc-MOF Nanozyme[J]. Chinese Journal of Applied Chemistry, 2024, 41(5): 728-738.

Figures/Tables 11

Fig.1 Illustration of the application of Cu@Sc-MOF for detection of ATP via fluorometric and colorimetric dual-mode

Fig.2 SEM image （A） and elemental mapping （B-F） of Cu@Sc-MOF

Fig.3 （A） XRD pattern，（B） FT-IR spectra，（C） nitrogen adsorption and desorption isotherm curves，（D） XPS spectra of Cu@Sc-MOF and Sc-MOF， and （E） C1s，（F） O1s，（G） Sc2p （H） Cu2p and （I） N1s high-resolution spectrum of Cu@Sc-MOF

Fig.4 Dependence of relative catalytic activity of Cu@Sc-MOF toward oxidation of TMB/OPD by H2O2 on （A） concentration of Cu@Sc-MOF，（B） pH，（C） temperature，（D） reaction time，（E） concentration of H2O2，（F） concentration of Cu@Sc-MOF，（G） concentration of OPD and （H） pH

Fig.5 （A） UV-Vis absorption spectra of TMB in different reaction systems；（B） The Fluorescence emission spectra of OPD in different reaction systems

Fig.6 Steady-state kinetic assay of （A） H2O2 and （B） TMB inset： double reciprocal plot

Table 1 Steady-State Kinetics of the Cu@Sc-MOF， HRP and other POD-like mimics

Material	K_m/（mmol·L^-1）		10⁸v_max/（mol·L^-1·s^-1）		Ref.
Material	TMB	H₂O₂	TMB	H₂O₂	Ref.
HRP	0.434	3.70	10.0	8.71	［21］
Cu-BDCPPI	0.890	0.290	3.36	1.29	［22］
Cu-MOF	0.047 7	2.65	0.312	0.126	［23］
Fe-BTC	0.261	0.033 4	7.95	2.65	［24］
Fe₃Ni-MOF-NH₂	0.241	0.156	1.13	1.27	［25］
Mo-CDs	0.245	3.20	0.176	4.76	［26］
Cu@Sc-MOF	0.040	0.086	1.74	4.69	This work

Fig.7 （A） The relative absorption of DPBF with different treatments；（B） The relative activity of Cu@Sc-MOF catalytic system with ROS scavengers （PBQ， His and Thiourea）；（C） ESR spectra of Cu@Sc-MOF catalytic systems；（D） Fluorescence spectra of TA in different systems

Table 2 Comparison of sensitivity between Cu@Sc-MOF and other ATP sensors

Materials	Method	Linear range/（μmol·L^-1）	Limit of detection/（nmol·L^-1）	Ref.
Tb/Eu-MOF	Fluorescence	0~8	121.4	［29］
UiO-66@COF	Fluorescence	0~10	38.0	［30］
Cy5@UiO-67	Fluorescence	0.008~1	0.503	［31］
Thioflavin T	Fluorescence	0~5	24.8	［32］
CDs/OPD-Cu²⁺	Fluorescence	1.0~100	430	［33］
N-GQDs	Fluorescence	0~10	1.16	［34］
Cu@Sc-MOF	Colorimetry	2.5~40	600	This work
Cu@Sc-MOF	Fluorescence	1.0~22.5	270	This work

Table 3 Detection results of ATP in HepG2 cell lysate

Testing mode	Sample/（μmol·L^-1）	Added/（μmol·L^-1）	Found/（μmol·L^-1）	Recovery/%	RSD/%（n=6）
Colorimetric mode	2.83	10.00	11.81	92.0	2.9
		15.00	17.53	98.3	2.7
		35.00	38.18	101	2.3
Fluorescence mode	2.91	5.00	7.38	93.2	3.4
		15.00	17.54	97.9	2.8
		20.00	21.87	95.4	1.3

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Colorimetric/Fluorometric Detection of Adenosine-5′-Triphosphate Based on Metal-Organic Framework Cu@Sc-MOF Nanozyme

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