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通过寡核铈氧络合物模型可视化纳米氧化铈催化氧化色氨酸的过程。

Visualizing Catalytic Oxidation of Tryptophan by Nanoceria via an Oligonuclear Cerium Oxo-Complex Model.

作者信息

Targonska Sara, Greenwell Francesca, Agback Tatiana, Seisenbaeva Gulaim A, Kessler Vadim G

机构信息

Department Of Molecular Sciences, Swedish University Of Agricultural Sciences, Box 7015, Uppsala 750 07, Sweden.

Department Of Chemistry, Uppsala University, Box 523, Uppsala 751 20, Sweden.

出版信息

Inorg Chem. 2025 Apr 21;64(15):7300-7310. doi: 10.1021/acs.inorgchem.4c05165. Epub 2025 Apr 10.

DOI:10.1021/acs.inorgchem.4c05165
PMID:40208753
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC12015816/
Abstract

Metal oxide species interact with biologically relevant molecules, which are crucial to the life cycle of plants and animals. Metal oxides can also act as catalysts in various reactions required for proper plant development. In this study, we investigated the hydrolysis of inorganic Ce(IV) precursors in the presence of carboxylic acids, leading to the formation of oligonuclear cerium oxo-complexes. The structure of the species was obtained by X-ray single-crystal studies and found to be hexanuclear, with the composition CeO(OH)(HO)(NO)(CHO)(CHNO) (Ce-BA-DMF). The catalytic properties of these complexes on the oxidation of amino acids have been investigated, aiming to establish a transformation mechanism providing insights into both molecular and surface interactions. A redox feature assigned to the CeIV/III couple in the cerium oxo-complex was observed by cyclic voltammetry and found to be sufficiently positive to oxidize tryptophan directly, without the need for intermediate generation of reactive oxygen species. Our findings provide new insights into the possible molecular mechanisms and open the door for more targeted applications of ceria nanoparticles in agriculture and biomedicine.

摘要

金属氧化物物种与生物相关分子相互作用,这些分子对植物和动物的生命周期至关重要。金属氧化物还可以在植物正常发育所需的各种反应中充当催化剂。在本研究中,我们研究了在羧酸存在下无机铈(IV)前体的水解反应,该反应导致形成多核铈氧配合物。通过X射线单晶研究获得了该物种的结构,发现其为六核结构,组成为CeO(OH)(HO)(NO)(CHO)(CHNO) (Ce-BA-DMF)。我们研究了这些配合物对氨基酸氧化的催化性能,旨在建立一种转化机制,以深入了解分子和表面相互作用。通过循环伏安法观察到铈氧配合物中归因于CeIV/III电对的氧化还原特征,发现其足够正,可以直接氧化色氨酸,而无需中间产生活性氧物种。我们的研究结果为可能的分子机制提供了新的见解,并为氧化铈纳米颗粒在农业和生物医学中的更有针对性的应用打开了大门。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/3d95/12015816/f5384b868997/ic4c05165_0009.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/3d95/12015816/9a9fe7eafa33/ic4c05165_0001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/3d95/12015816/953aa583bba5/ic4c05165_0002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/3d95/12015816/94f93496be41/ic4c05165_0003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/3d95/12015816/77b5d702c439/ic4c05165_0004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/3d95/12015816/fd15a46b0e41/ic4c05165_0005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/3d95/12015816/d0d2a26e7bd9/ic4c05165_0006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/3d95/12015816/2970ba04cd32/ic4c05165_0007.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/3d95/12015816/f0486852a17e/ic4c05165_0008.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/3d95/12015816/f5384b868997/ic4c05165_0009.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/3d95/12015816/9a9fe7eafa33/ic4c05165_0001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/3d95/12015816/953aa583bba5/ic4c05165_0002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/3d95/12015816/94f93496be41/ic4c05165_0003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/3d95/12015816/77b5d702c439/ic4c05165_0004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/3d95/12015816/fd15a46b0e41/ic4c05165_0005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/3d95/12015816/d0d2a26e7bd9/ic4c05165_0006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/3d95/12015816/2970ba04cd32/ic4c05165_0007.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/3d95/12015816/f0486852a17e/ic4c05165_0008.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/3d95/12015816/f5384b868997/ic4c05165_0009.jpg

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本文引用的文献

1
Molecular Mechanisms in Metal Oxide Nanoparticle-Tryptophan Interactions.金属氧化物纳米粒子-色氨酸相互作用的分子机制。
Inorg Chem. 2024 May 13;63(19):8556-8566. doi: 10.1021/acs.inorgchem.3c03674. Epub 2024 Apr 29.
2
Cerium Nanophases from Cerium Ammonium Nitrate.硝酸铈铵中的铈纳米相
Langmuir. 2024 Feb 27;40(8):4350-4360. doi: 10.1021/acs.langmuir.3c03611. Epub 2024 Feb 16.
3
Natural Silicates Encapsulated Enzymes as Green Biocatalysts for Degradation of Pharmaceuticals.天然硅酸盐包封酶作为用于药物降解的绿色生物催化剂
ACS ES T Water. 2024 Jan 30;4(2):751-760. doi: 10.1021/acsestwater.3c00811. eCollection 2024 Feb 9.
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Synthesis and Characterization of Cerium-Oxo Clusters Capped by Acetylacetonate.乙酰丙酮封端的铈氧簇合物的合成与表征
Inorg Chem. 2024 May 27;63(21):9406-9417. doi: 10.1021/acs.inorgchem.3c02141. Epub 2023 Oct 4.
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Biosynthetic Pathways of Hormones in Plants.植物激素的生物合成途径
Metabolites. 2023 Jul 25;13(8):884. doi: 10.3390/metabo13080884.
6
Exploiting Interactions between Polyoxometalates and Proteins for Applications in (Bio)chemistry and Medicine.利用多金属氧酸盐与蛋白质的相互作用在(生物)化学和医学中的应用
Angew Chem Int Ed Engl. 2023 Aug 1;62(31):e202303817. doi: 10.1002/anie.202303817. Epub 2023 May 15.
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Factors influencing stoichiometry and stability of polyoxometalate - peptide complexes.影响多金属氧酸盐-肽配合物化学计量和稳定性的因素。
Dalton Trans. 2022 Jun 21;51(24):9511-9521. doi: 10.1039/d2dt00717g.
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Redox Active Cerium Oxide Nanoparticles: Current Status and Burning Issues.氧化还原活性铈氧化物纳米粒子:现状与热点问题。
Small. 2021 Dec;17(51):e2102342. doi: 10.1002/smll.202102342. Epub 2021 Aug 6.
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Phys Chem Chem Phys. 2021 Mar 21;23(11):6641-6650. doi: 10.1039/d0cp06068b. Epub 2021 Mar 12.
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