title: Dual-Metal Centered Zirconium-Organic Framework: A Metal-Affinity Probe for Highly Specific Interaction with Phosphopeptides.
abstract: The highly specific affinity between probes and phosphopeptides is the fundamental interaction for selective identification of phosphoproteomes that uncover the mechanisms of signal transduction, cell cycle, enzymatic regulation, and gene expression in biological systems. In this study, a metal-affinity probe possessing both interactions of metal oxide affinity chromatography (MOAC) and immobilized metal ion affinity chromatography (IMAC) was facilely prepared by immobilizing zirconium(IV) on a zirconium-organic framework of UiO-66-NH2, which holds dual-metal centers of not only the inherent Zr-O cluster but also the immobilized Zr(IV) center. This dual-metal centered zirconium-organic framework (DZMOF) demonstrates as a highly specific metal-affinity probe toward the extraction of phosphopeptides due to the metal-affinity interactions of MOAC and IMAC toward either mono-phosphorylated or multi-phosphorylated peptides. The binding energies of zirconium 3d5/2and 3d3/2in this DZMOF are 183.07 and 185.47 eV, respectively, which are higher than those of the intact UiO-66-NH2(182.84 and 185.17 eV, respectively), confirming the higher metal-affinity interaction between the DZMOF and phosphopeptides. This high metal-affinity probe presents an unprecedented strong performance in anti-nonspecific interference during the capturing of phosphopeptides of β-casein with the molar ratio of β-casein vs bovine serum albumin up to ca. 1:5000. The enrichment of phosphopeptides from a human saliva sample by DZMOF further confirms the great potential of DZMOF in the extraction of low-abundance phosphopeptides for real complex biological samples.
authors.affiliation: CAS Key Lab of Separation Sciences for Analytical Chemistry, National Chromatographic R&A Center, Dalian Institute of Chemical Physics, Chinese Academy of Sciences , Dalian, 116023, China.|University of Chinese Academy of Sciences , Beijing, 100049, China.
authors.forename: Jiaxi
authors.identifier: http://orcid.org/0000-0003-0439-824X
authors.initials: J
authors.lastname: Peng
authors.affiliation: CAS Key Lab of Separation Sciences for Analytical Chemistry, National Chromatographic R&A Center, Dalian Institute of Chemical Physics, Chinese Academy of Sciences , Dalian, 116023, China.|University of Chinese Academy of Sciences , Beijing, 100049, China.
authors.forename: Hongyan
authors.initials: H
authors.lastname: Zhang
authors.affiliation: CAS Key Lab of Separation Sciences for Analytical Chemistry, National Chromatographic R&A Center, Dalian Institute of Chemical Physics, Chinese Academy of Sciences , Dalian, 116023, China.|University of Chinese Academy of Sciences , Beijing, 100049, China.
authors.forename: Xin
authors.initials: X
authors.lastname: Li
authors.affiliation: CAS Key Lab of Separation Sciences for Analytical Chemistry, National Chromatographic R&A Center, Dalian Institute of Chemical Physics, Chinese Academy of Sciences , Dalian, 116023, China.|University of Chinese Academy of Sciences , Beijing, 100049, China.
authors.forename: Shengju
authors.initials: S
authors.lastname: Liu
authors.affiliation: CAS Key Lab of Separation Sciences for Analytical Chemistry, National Chromatographic R&A Center, Dalian Institute of Chemical Physics, Chinese Academy of Sciences , Dalian, 116023, China.|University of Chinese Academy of Sciences , Beijing, 100049, China.
authors.forename: Xingyun
authors.initials: X
authors.lastname: Zhao
authors.affiliation: Wenzhou Institute of Biomaterials and Engineering, Chinese Academy of Sciences , Wenzhou, 325000, China.
authors.forename: Jing
authors.initials: J
authors.lastname: Wu
authors.affiliation: CAS Key Lab of Separation Sciences for Analytical Chemistry, National Chromatographic R&A Center, Dalian Institute of Chemical Physics, Chinese Academy of Sciences , Dalian, 116023, China.
authors.forename: Xiaohui
authors.initials: X
authors.lastname: Kang
authors.affiliation: CAS Key Lab of Separation Sciences for Analytical Chemistry, National Chromatographic R&A Center, Dalian Institute of Chemical Physics, Chinese Academy of Sciences , Dalian, 116023, China.
authors.forename: Hongqiang
authors.identifier: http://orcid.org/0000-0002-7508-0872
authors.initials: H
authors.lastname: Qin
authors.affiliation: College of Chemical Engineering and Materials Science, Zhejiang University of Technology , Hangzhou, 310014, China.
authors.forename: Zaifa
authors.initials: Z
authors.lastname: Pan
authors.affiliation: CAS Key Lab of Separation Sciences for Analytical Chemistry, National Chromatographic R&A Center, Dalian Institute of Chemical Physics, Chinese Academy of Sciences , Dalian, 116023, China.
authors.forename: Ren'an
authors.initials: R
authors.lastname: Wu
mesh_terms: D002364:Caseins; D002846:Chromatography, Affinity; D006801:Humans; D007477:Ions; D010748:Phosphopeptides; D015040:Zirconium / Q000737:chemistry*
chemical_list: D002364:Caseins; D007477:Ions; D010748:Phosphopeptides; D015040:Zirconium
keywords: immobilized metal ion affinity; metal oxide affinity; metal-affinity probe; metal−organic framework; phosphorylated peptide