二氧化铈纳米颗粒上磷酸盐吸附的红外和拉曼诊断模型,The Journal of Physical Chemistry C

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二氧化铈纳米颗粒上磷酸盐吸附的红外和拉曼诊断模型
The Journal of Physical Chemistry C ( IF 3.3 ) Pub Date : 2023-10-04 , DOI: 10.1021/acs.jpcc.3c05409
Khoa Minh Ta ₁ , David J Cooke ₁ , Lisa J Gillie ₁ , Stephen C Parker ₂ , Sudipta Seal _{3,

4} , Philippe B Wilson ₅ , Roger M Phillips ₆ , Jonathan M Skelton ₇ , Marco Molinari ₁

Affiliation

二氧化铈（CeO ₂；二氧化铈）纳米颗粒（CeNP）是一种很有前途的纳米酶，具有多种生物活性。有效的纳米酶需要在生物环境中面对表面形态形成时保持其活性，因此表征表面形态对于理解和控制 CeNP 的治疗能力至关重要。特别地，吸附的磷酸盐可以影响用于将磷酸盐前药转化为体内治疗剂的酶活性，并且还限定导致活性CeO ₂转化为非活性CePO ₄的磷酸盐清除过程的早期阶段。在这项工作中，我们利用从头开始晶格动力学计算来研究磷酸盐与二氧化铈三个主要表面的相互作用，并预测吸附磷酸盐物质的红外（IR）和拉曼光谱特征。我们发现磷酸盐以一系列稳定的结合构型强烈吸附在CeO _{2表面，其中三角双锥配位中的5重配位的P物种可能代表磷酸盐清除早期阶段的稳定中间体。}我们发现磷酸盐物质在 500 至 1500 cm ^–1之间显示出特征光谱指纹，而裸露的 CeO ₂表面在 600 cm ^–1以上没有显示出活性模式，并且 5 倍配位的 P 物质特别显示出潜在的诊断性 P–O红外光谱和拉曼光谱中的拉伸模式均在 650 至 700 cm ^{–1之间。}这种对磷酸盐在 CeO ₂上的不同结合模式和一组参考光谱的全面探索，为磷酸盐形态的实验表征以及最终控制其对二氧化铈纳米酶性能的影响迈出了重要的一步。

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Infrared and Raman Diagnostic Modeling of Phosphate Adsorption on Ceria Nanoparticles

Cerium dioxide (CeO₂; ceria) nanoparticles (CeNPs) are promising nanozymes that show a variety of biological activity. Effective nanozymes need to retain their activity in the face of surface speciation in biological environments, and characterizing surface speciation is therefore critical to understanding and controlling the therapeutic capabilities of CeNPs. In particular, adsorbed phosphates can impact the enzymatic activity exploited to convert phosphate prodrugs into therapeutics in vivo and also define the early stages of the phosphate-scavenging processes that lead to the transformation of active CeO₂ into inactive CePO₄. In this work, we utilize ab initio lattice-dynamics calculations to study the interaction of phosphates with the three major surfaces of ceria and to predict the infrared (IR) and Raman spectral signatures of adsorbed phosphate species. We find that phosphates adsorb strongly to CeO₂ surfaces in a range of stable binding configurations, of which 5-fold coordinated P species in a trigonal bipyramidal coordination may represent a stable intermediate in the early stages of phosphate scavenging. We find that the phosphate species show characteristic spectral fingerprints between 500 and 1500 cm^–1, whereas the bare CeO₂ surfaces show no active modes above 600 cm^–1, and the 5-fold coordinated P species in particular show potential diagnostic P–O stretching modes between 650 and 700 cm^–1 in both IR and Raman spectra. This comprehensive exploration of different binding modes for phosphates on CeO₂ and the set of reference spectra provides an important step toward the experimental characterization of phosphate speciation and, ultimately, control of its impact on the performance of ceria nanozymes.

更新日期：2023-10-04

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