Gadolinium Doping Modulates the Enzyme-like Activity and Radical-Scavenging Properties of CeO2 Nanoparticles

被引:10
作者
Sozarukova, Madina M. [1 ]
Kozlova, Taisiya O. [1 ]
Beshkareva, Tatiana S. [1 ,2 ]
Popov, Anton L. [3 ]
Kolmanovich, Danil D. [3 ]
Vinnik, Darya A. [3 ]
Ivanova, Olga S. [4 ]
Lukashin, Alexey V. [2 ]
Baranchikov, Alexander E. [1 ]
Ivanov, Vladimir K. [1 ]
机构
[1] Russian Acad Sci, Kurnakov Inst Gen & Inorgan Chem, Moscow 119991, Russia
[2] Lomonosov Moscow State Univ, Dept Mat Sci, Moscow 119234, Russia
[3] Russian Acad Sci, Inst Theoret & Expt Biophys, Pushchino 142290, Russia
[4] Russian Acad Sci, Frumkin Inst Phys Chem & Electrochem, Moscow 119071, Russia
基金
俄罗斯科学基金会;
关键词
nanozyme; nanoceria; gadolinium; conjugate; antioxidant; prooxidant; radical scavenger; chemiluminescence; CERIUM OXIDE NANOPARTICLES; HORSERADISH-PEROXIDASE; DIOXIDE NANOPARTICLES; GD2O3; NANOPARTICLES; MIMETIC ACTIVITY; NANOZYME; ANTIOXIDANT; NANOCERIA; BEHAVIOR; REDUCTION;
D O I
10.3390/nano14090769
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Their unique physicochemical properties and multi-enzymatic activity make CeO2 nanoparticles (CeO2 NPs) the most promising active component of the next generation of theranostic drugs. When doped with gadolinium ions, CeO2 NPs constitute a new type of contrast agent for magnetic resonance imaging, possessing improved biocatalytic properties and a high level of biocompatibility. The present study is focused on an in-depth analysis of the enzyme-like properties of gadolinium-doped CeO2 NPs (CeO2:Gd NPs) and their antioxidant activity against superoxide anion radicals, hydrogen peroxide, and alkylperoxyl radicals. Using an anion-exchange method, CeO2:Gd NPs (similar to 5 nm) with various Gd-doping levels (10 mol.% or 20 mol.%) were synthesized. The radical-scavenging properties and biomimetic activities (namely SOD- and peroxidase-like activities) of CeO2:Gd NPs were assessed using a chemiluminescent method with selective chemical probes: luminol, lucigenin, and L-012 (a highly sensitive luminol analogue). In particular, gadolinium doping has been shown to enhance the radical-scavenging properties of CeO2 NPs. Unexpectedly, both bare CeO2 NPs and CeO2:Gd NPs did not exhibit SOD-like activity, acting as pro-oxidants and contributing to the generation of reactive oxygen species. Gadolinium doping caused an increase in the pro-oxidant properties of nanoscale CeO2. At the same time, CeO2:Gd NPs did not significantly inhibit the intrinsic activity of the natural enzyme superoxide dismutase, and CeO2:Gd NPs conjugated with SOD demonstrated SOD-like activity. In contrast to SOD-like properties, peroxidase-like activity was observed for both bare CeO2 NPs and CeO2:Gd NPs. This type of enzyme-like activity was found to be pH-dependent. In a neutral medium (pH = 7.4), nanoscale CeO2 acted as a prooxidant enzyme (peroxidase), while in an alkaline medium (pH = 8.6), it lost its catalytic properties; thus, it cannot be regarded as a nanozyme. Both gadolinium doping and conjugation with a natural enzyme were shown to modulate the interaction of CeO2 NPs with the key components of redox homeostasis.
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页数:20
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