Fusaro Massimo, Leś Andrzej, Stolarczyk Elżbieta U, Stolarczyk Krzysztof
Faculty of Chemistry, University of Warsaw, Pasteura 1, 02-093 Warsaw, Poland.
National Medicines Institute, Chełmska 30/34, 00-725 Warsaw, Poland.
Molecules. 2023 Oct 19;28(20):7167. doi: 10.3390/molecules28207167.
We derived a theory of biomolecule binding to the surface of Au clusters and of the Au plane based on the hard soft acid base (HSAB) principle and the free electron metallic surface model. With the use of quantum mechanical calculations, the chemical potential () and the chemical hardness () of the biomolecules are estimated. The effect of the gold is introduced via the empirical value of the gold chemical potential (-5.77 eV) as well as by using the expression (modified here) for the chemical hardness (). The effect of an aqueous environment is introduced by means of the ligand molecular geometry influenced by the PCM field. This theory allows for a fast and low-cost estimation of binding biomolecules to the AuNPs surface. The predicted binding of thiolated genistein and abiraterone to the gold surface is about 20 kcal/mol. The model of the exchange reaction between these biomolecules and citrates on the Au surface corresponds well with the experimental observations for thiolated abiraterone. Moreover, using a model of the place exchange of linear mercaptohydrocarbons on 12-mercaptododecane acid methyl ester bound to the Au surface, the present results reflect the known relation between exchange energy and the size of the reagents.
我们基于软硬酸碱（HSAB）原理和自由电子金属表面模型，推导了生物分子与金簇表面及金平面的结合理论。通过量子力学计算，估算了生物分子的化学势（）和化学硬度（）。金的影响通过金化学势的经验值（-5.77 eV）以及使用化学硬度（）的表达式（此处修改）来引入。水环境的影响通过受极化连续介质模型（PCM）场影响的配体分子几何结构来引入。该理论能够快速且低成本地估算生物分子与金纳米颗粒表面的结合情况。预测硫醇化染料木黄酮和阿比特龙与金表面的结合能约为20千卡/摩尔。这些生物分子与金表面柠檬酸盐之间的交换反应模型与硫醇化阿比特龙的实验观察结果吻合良好。此外，使用与金表面结合的12 - 巯基十二烷酸甲酯上线性巯基烃的位置交换模型，目前的结果反映了交换能与试剂大小之间的已知关系。
