二氧化铈量子点纳米酶的制备及用于抗坏血酸比色检测的研究

doi:10.19964/j.issn.1006-4990.2024-0335

Abstract

Abstract:

The morphology and size of nanozymes significantly affect their mimetic enzyme catalytic activity.In order to improve the substrate catalytic activity of CeO₂ as a nanozyme and broaden its application range，using cerium nitrate as the precursor and citric acid as the structure-directing substance，CeO₂ quantum dots（CeO₂ QDs） with good crystallinity and small particle size were prepared by one-pot hydrothermal method.The small size effect and rich surface defects of CeO₂ QDs could expose more substrate contact active sites，thereby endowing it with oxidase-liked activity.The optimal CeO₂ quantum dot nanozyme，CeO₂ QDs-6，with the maximum particle size distribution at （4.0±0.6） nm，showed better oxidase enzyme kinetic characteristics than natural enzymes，with the Michaelis kinetic constant as low as 0.165 mmol/L and the maximum reaction rate up to 9.11×10^-8 mol/（L·s）.Based on the antioxidant activity of ascorbic acid，a rapid，sensitive and highly selective CeO₂ QDs-6 ascorbic acid colorimetric detection probe was constructed.Under the optimized conditions，this probe had good ascorbic acid detection performance in the linear range of 1.0~8.0 μmol/L，the lowest detection limit was 148 nmol/L，and showed certain feasibility in the detection of milk samples.

Key words: cerium dioxide, nanozyme, oxidase-liked activity, colorimetric analysis, ascorbic acid

CLC Number:

TQ133.3

TANG Qi, SUN Tao, XUE Bin. Study on preparation of cerium dioxide quantum dot nanozymes and their application in colorimetric detection of ascorbic acid[J]. Inorganic Chemicals Industry, 2025, 57(6): 35-42.

Figures/Tables 12

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References 30

1	ROCCHITTA G， SPANU A， BABUDIERI S，et al.Enzyme biosensors for biomedical applications：Strategies for safeguarding analytical performances in biological fluids［J］.Sensors，2016，16（6）：780.
2	ZHANG Ruofei， FAN Kelong， YAN Xiyun.Nanozymes：Created by learning from nature［J］.Science China.Life Sciences，2020，63（8）：1183-1200.
3	GAO Lizeng， ZHUANG Jie， NIE Leng，et al.Intrinsic peroxidase-like activity of ferromagnetic nanoparticles［J］.Nature Nanotechnology，2007，2（9）：577-583.
4	WANG Ruixue， DU Yuanyuan， FU Ying，et al.Ceria-based nanozymes in point-of-care diagnosis：An emerging futuristic approach for biosensing［J］.ACS Sensors，2023，8（12）：4442-4467.
5	MA Yuanyuan， TIAN Zhimin， ZHAI Wenfang，et al.Insights on catalytic mechanism of CeO₂ as multiple nanozymes［J］.Nano Research，2022，15（12）：10328-10342.
6	金声势，刘凯杰，刘秋文，等.磷酸改性CeO₂纳米棒负载Pt催化剂催化丙烷燃烧性能的研究［J］.无机盐工业，2024，56（1）：141-148.
	JIN Shengshi， LIU Kaijie， LIU Qiuwen，et al.Study on catalytic performance of phosphoric acid modified CeO₂ nanorod supported Pt catalyst for propane combustion［J］.Inorganic Chemicals Industry，2024，56（1）：141-148.
7	李向果，郭淼，姚会敏，等.菱形二氧化铈的水热合成及发光机理研究［J］.无机盐工业，2020，52（6）：30-35，40.
	LI Xiangguo， GUO Miao， YAO Huimin，et al.Research on hydrothermal synthesis and photoluminescence mechanism of rhombus CeO₂ ［J］.Inorganic Chemicals Industry，2020，52（6）：30-35，40.
8	郝晓东，冯心怡，徐阳，等.二氧化铈纳米催化剂可控合成及超微观构效关系研究［J］.无机盐工业，2022，54（3）：7-17.
	HAO Xiaodong， FENG Xinyi， XU Yang，et al.Study on controllable synthesis and ultramicroscopic structure-activity relationship of cerium oxides nanocatalysts［J］.Inorganic Chemicals Industry，2022，54（3）：7-17.
9	WANG Zhiqiao， ZHANG Mingjian， HU Xiaobing，et al.CeO_2- _x quantum dots with massive oxygen vacancies as efficient catalysts for the synthesis of dimethyl carbonate［J］.Chemical Communications，2020，56（3）：403-406.
10	黄振旭，何欢欢，贾潘潘，等.水热法制备石墨烯及对抗坏血酸电催化性能的研究［J］.无机盐工业，2020，52（11）：29-32.
	HUANG Zhenxu， HE Huanhuan， JIA Panpan，et al.Synthesis of graphene by hydrothermal method and its electrocatalytic property on ascorbic acid［J］.Inorganic Chemicals Industry，2020，52（11）：29-32.
11	CHEN Qi， ESPEY M G， SUN A Y，et al.Pharmacologic doses of ascorbate act as a prooxidant and decrease growth of aggressive tumor xenografts in mice［J］.Proceedings of the National Academy of Sciences of the United States of America，2008，105（32）：11105-11109.
12	DADAKHANI S， DEHGHAN G， KHATAEE A.A robust and facile label-free method for highly sensitive colorimetric detection of ascorbic acid in fresh fruits based on peroxidase-like activity of modified FeCo-LDH@WO₃ nanocomposite［J］.Spectrochimica Acta Part A：Molecular and Biomolecular Spectroscopy，2023，302：123016.
13	YAN Zhaoxiong， WANG Nenghuan， ZHANG Meng，et al.Indoor light boosted formaldehyde abatement over electrostatic self-assembled graphitic carbon nitride/ceric oxide at ambient temperature［J］.Journal of Environmental Chemical Engineering，2021，9（5）：106174.
14	HASSAN M S， KHAN R， AMNA T，et al.The influence of synthesis method on size and toxicity of CeO₂ quantum dots：Potential in the environmental remediation［J］.Ceramics International，2016，42（1）：576-582.
15	NGUYET N T， TUAN C V， NGAN D T T，et al.Electrodeposited fabrication of CeO₂ branched-like nanostructure used for nonenzymatic glucose biosensor［J］.Crystals，2023，13（9）：1315.
16	CHEN Xiaoxue， YU Fengqiu， GONG Fuzhong，et al.Preparation of 3D porous CeO₂/g-C₃N₄ photocatalyst via facile one-step calcination for rapid removing of tetracycline［J］.Vacuum，2023，213：112090.
17	TAGUCHI M， TAKAMI S， ADSCHIRI T，et al.Supercritical hydrothermal synthesis of hydrophilic polymer-modified water-dispersible CeO₂ nanoparticles［J］.CrystEngComm，2011，13（8）：2841-2848.
18	IKRAM M， HAYAT S， IMRAN M，et al.Novel Ag/cellulose-doped CeO₂ quantum dots for efficient dye degradation and bactericidal activity with molecular docking study［J］.Carbohydrate Polymers，2021，269：118346.
19	GENG Xiaoyu， XUE Ruisong， LIANG Feng，et al.Synergistic effect of silver nanoclusters and graphene oxide on visible light-driven oxidase-like activity：Construction of a sustainable nanozyme for total antioxidant capacity detection［J］.Talanta，2023，259：124565.
20	YANG Jin， CHENG Shiqi， QIN Shangying，et al.CeO₂-Co₃O₄ nanocomposite with oxidase-like activity for colorimetric detection of ascorbic acid［J］.RSC Advances，2023，13（15）：9918-9923.
21	QIN Wenjie， SU Li， YANG Chen，et al.Colorimetric detection of sulfite in foods by a TMB-O₂-Co₃O₄ nanoparticles detection system［J］.Journal of Agricultural and Food Chemistry，2014，62（25）：5827-5834.
22	LIU Haiyan， LIU Juewei.Self-limited phosphatase-mimicking CeO₂ nanozymes［J］.ChemNanoMat，2020，6（6）：947-952.
23	SHANG Hongyuan， ZHANG Xiaofei， DING Meili，et al.A smartphone-assisted colorimetric and photothermal probe for glutathione detection based on enhanced oxidase-mimic CoFeCe three-atom nanozyme in food［J］.Food Chemistry，2023，423：136296.
24	ZHAO Ning， SONG Jianqiang， ZHAO Longshan.Metallic deep eutectic solvents-assisted synthesis of Cu，Cl-doped carbon dots as oxidase-like and peroxidase-like nanozyme for colorimetric assay of hydroquinone and H₂O₂ ［J］.Colloids and Surfaces A：
	Physicochemical and Engineering Aspects，2022，648：129390.
25	ZHU Mingyun， WEN Yifeng， SONG Shugui，et al.Synergistic effects between polyvinylpyrrolidone and oxygen vacancies on improving the oxidase-mimetic activity of flower-like CeO₂ nanozymes［J］.Nanoscale，2020，12（37）：19104-19111.
26	HUANG Lunjie， ZHANG Wentao， CHEN Kai，et al.Facet-selective response of trigger molecule to CeO₂｛110｝for up-regulating oxidase-like activity［J］.Chemical Engineering Journal，2017，330：746-752.
27	SONG Guangchun， ZHANG Qi， LIANG Shuang，et al.Oxidation activity modulation of a single atom Ce-N-C nanozyme enabling a time-resolved sensor to detect Fe³⁺ and Cr⁶⁺ ［J］.Journal of Materials Chemistry C，2022，10（41）：15656-15663.
28	BHAGAT S， SRIKANTH VALLABANI N V， SHUTTHANANDAN V，et al.Gold core/ceria shell-based redox active nanozyme mimicking the biological multienzyme complex phenomenon［J］.Journal of Colloid and Interface Science，2018，513：831-842.
29	CHENG Qin， YANG Yong， PENG Yusi，et al.Pt nanoparticles with high oxidase-like activity and reusability for detection of ascorbic acid［J］.Nanomaterials，2020，10（6）：1015.
30	PENG Dong， QUE Mingming， DENG Xiulong，et al.Mn₃O₄ nanoparticles decorated porous reduced graphene oxide with excellent oxidase-like activity for fast colorimetric detection of ascorbic acid［J］.Mikrochimica Acta，2023，190（6）：243.

催化剂	米氏动力常数/ （mmol·L^-1）	最大反应速率/ （10^-8 mol·L^-1·s^-1）
HPR^［3］	0.434	10.00
CeO₂ NCs^［25］	0.960	6.00
CeO₂ NRs^［26］	0.350	0.14
Ce–N/C^［27］	0.200	1.14
Au/CeO₂ CSNPs^［28］	0.290	3.90
CeO₂ QDs-6	0.165	9.11

材料	线性范围/（μmol·L^-1）	检测限/（nmol·L^-1）
Pt NPs^［29］	1.0~20.0	144
Mn₃O₄@p-rGO^［30］	0.5~80.0	278
CeO₂-Co₃O₄ NC^［20］	1.0~500.0	250
CeO₂ QDs-6	1.0~8.0	148

[1]	Huang Zhenxu,He Huanhuan,Jia Panpan,Chen Tiwei,Wei Shiqian. Synthesis of graphene by hydrothermal method and its electrocatalytic property on ascorbic acid [J]. Inorganic Chemicals Industry, 2020, 52(11): 29-32.
[2]	HAN Jian-Hong, LIU 派, XU Hai-Sheng, GUO Ting. Experimental research for purification of cerium dioxide from rock crystal waste with ammonia as precipitator [J]. INORGANICCHEMICALSINDUSTRY, 2012, 44(7): 44-.
[3]	Li Zhilin;Hua Pengmin. Preparation of nano-sized selenium by sodium dodecyl sulfate template method [J]. INORGANICCHEMICALSINDUSTRY, 2009, 0(7): 0-0.
[4]	Fan Fangqiang;Yu Lin;Sun Ming;Diao Guiqiang;Miao Fei. Preparation of nano-sized cerium dioxide by single reverse microemulsion method and study on dispersion and morphology [J]. INORGANICCHEMICALSINDUSTRY, 2009, 0(3): 0-0.
[5]	Kong Yajie;Han Lijuan;Li Haimin. Exploratory experiment of absorbing boron from hot brine by hydrated cerium dioxide [J]. INORGANICCHEMICALSINDUSTRY, 2008, 0(10): 0-0.

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Study on preparation of cerium dioxide quantum dot nanozymes and their application in colorimetric detection of ascorbic acid

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