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A simple hydrothermal method was employed to prepare the surface grafted 1-hydroxyethylidene-1,1-diphosphonic acid-hydroxyapatite (HEDP-HAP) composites, which were termed as 0.2HEDP-HAP, 0.5HEDP-HAP and 1HEDP-HAP respectively, according to the HEDP content. Adsorption experiments showed that the maximum adsorption capacity of 0.5HEDP-HAP for Cu 2+ reached 168.9 mg/g, which was 4.19 times that of HAP, while the maximum adsorption capacity of 1HEDP-HAP for Pb 2+ was as high as 1521 mg/g, which was approximately 10 times that of HAP. For the first time, the interaction mechanism of HEDP with HAP, or HEDP-HAP composite with the two heavy metal ions was illustrated by the combination of quantum chemistry (QC) calculation, quantitative analysis of molecular surface, Becke surface analysis and Independent Gradient Model (IGM) method. The active reaction sites, the types, relative strength and essence of the interactions were revealed based on the visual analysis of interactions. The results demonstrated that the phosphonic acid group (PO 3 H - ) of HEDP 2- can form hydrogen bonds with the phosphate group (PO 4 3- ) and the hydroxyl group (OH) of HAP. The oxygen atom of PO 3 H- provided lone pair electrons to form chelate with Ca 2+ of HAP, which resulted in the strong affinity of HEDP with HAP. Moreover, the significant improvements of uptake of surface grafted HEDP-HAP for Cu 2+ and Pb 2+ were due to the formation of the ternary surface complexes., (Copyright © 2020 Elsevier B.V. All rights reserved.)

In this paper, a new nanobiomaterial, alendronate hydroxyapatite (AL-HAP), was synthesized by the conventional co-precipitation method with alendronate (AL) as dopant, and applied in the removal of heavy metal contaminants for the first time. The characterization results showed that the crystallinity of the AL-HAP nanocomposite biomaterials after doping has been greatly deteriorated, and the pore volume and pore size increased. When the doping amount of AL was 10 %, the maximum adsorption capacity of AL-HAP for Pb 2+ , Cd 2+ and Cu 2+ can reach 1431.8, 469 and 226.6 mg/g, respectively, which was much higher than that reported in other literature. Meanwhile, the adsorption mechanism of AL-HAP for heavy metal ions was discussed from both the views of experimental and Multiwfn program theoretical calculation based on density functional theory (DFT). Quantitative molecular surface analysis was carried out for the first time to study the minimum points and the positions of electrostatic potential (ESP) and average local ionization energy(ALIE), as well as the exact values, giving more accurate and reliable analysis conclusions for the reaction sites and binding mode. In addition, the independent gradient model (IGM) method was also firstly applied to investigate the interactions between AL and HAP or AL-HAP nanocomposite with metal ions. AL-HAP is a potential adsorption material for heavy metal wastewater treatment and soil remediation because of its advantages such as convenient synthesis, excellent adsorption performance and no secondary pollution., (Copyright © 2020 Elsevier B.V. All rights reserved.)