title: Enzyme-Triggered Defined Protein Nanoarrays: Efficient Light-Harvesting Systems to Mimic Chloroplasts.
abstract: The elegance and efficiency by which chloroplasts harvest solar energy and conduct energy transfer have been a source of inspiration for chemists to mimic such process. However, precise manipulation to obtain orderly arranged antenna chromophores in constructing artificial chloroplast mimics was a great challenge, especially from the structural similarity and bioaffinity standpoints. Here we reported a design strategy that combined covalent and noncovalent interactions to prepare a protein-based light-harvesting system to mimic chloroplasts. Cricoid stable protein one (SP1) was utilized as a building block model. Under enzyme-triggered covalent protein assembly, mutant SP1 with tyrosine (Tyr) residues at the designated sites can couple together to form nanostructures. Through controlling the Tyr sites on the protein surface, we can manipulate the assembly orientation to respectively generate 1D nanotubes and 2D nanosheets. The excellent stability endowed the self-assembled protein architectures with promising applications. We further integrated quantum dots (QDs) possessing optical and electronic properties with the 2D nanosheets to fabricate chloroplast mimics. By attaching different sized QDs as donor and acceptor chromophores to the negatively charged surface of SP1-based protein nanosheets via electrostatic interactions, we successfully developed an artificial light-harvesting system. The assembled protein nanosheets structurally resembled the natural thylakoids, and the QDs can achieve pronounced FRET phenomenon just like the chlorophylls. Therefore, the coassembled system was meaningful to explore the photosynthetic process in vitro, as it was designed to mimic the natural chloroplast.
authors.affiliation: State Key Laboratory of Supramolecular Structure and Materials, College of Chemistry, Jilin University , 2699 Qianjin Street, Changchun 130012, China.
authors.forename: Linlu
authors.initials: L
authors.lastname: Zhao
authors.affiliation: State Key Laboratory of Supramolecular Structure and Materials, College of Chemistry, Jilin University , 2699 Qianjin Street, Changchun 130012, China.
authors.forename: Haoyang
authors.initials: H
authors.lastname: Zou
authors.affiliation: State Key Laboratory of Supramolecular Structure and Materials, College of Chemistry, Jilin University , 2699 Qianjin Street, Changchun 130012, China.
authors.forename: Hao
authors.identifier: 0000-0002-2373-1100
authors.initials: H
authors.lastname: Zhang
authors.affiliation: State Key Laboratory of Supramolecular Structure and Materials, College of Chemistry, Jilin University , 2699 Qianjin Street, Changchun 130012, China.
authors.forename: Hongcheng
authors.initials: H
authors.lastname: Sun
authors.affiliation: State Key Laboratory of Supramolecular Structure and Materials, College of Chemistry, Jilin University , 2699 Qianjin Street, Changchun 130012, China.
authors.forename: Tingting
authors.initials: T
authors.lastname: Wang
authors.affiliation: State Key Laboratory of Supramolecular Structure and Materials, College of Chemistry, Jilin University , 2699 Qianjin Street, Changchun 130012, China.
authors.forename: Tiezheng
authors.initials: T
authors.lastname: Pan
authors.affiliation: State Key Laboratory of Supramolecular Structure and Materials, College of Chemistry, Jilin University , 2699 Qianjin Street, Changchun 130012, China.
authors.forename: Xiumei
authors.initials: X
authors.lastname: Li
authors.affiliation: State Key Laboratory of Supramolecular Structure and Materials, College of Chemistry, Jilin University , 2699 Qianjin Street, Changchun 130012, China.
authors.forename: Yushi
authors.initials: Y
authors.lastname: Bai
authors.affiliation: State Key Laboratory of Supramolecular Structure and Materials, College of Chemistry, Jilin University , 2699 Qianjin Street, Changchun 130012, China.
authors.forename: Shanpeng
authors.initials: S
authors.lastname: Qiao
authors.affiliation: State Key Laboratory of Supramolecular Structure and Materials, College of Chemistry, Jilin University , 2699 Qianjin Street, Changchun 130012, China.
authors.forename: Quan
authors.initials: Q
authors.lastname: Luo
authors.affiliation: State Key Laboratory of Supramolecular Structure and Materials, College of Chemistry, Jilin University , 2699 Qianjin Street, Changchun 130012, China.
authors.forename: Jiayun
authors.initials: J
authors.lastname: Xu
authors.affiliation: State Key Laboratory of Supramolecular Structure and Materials, College of Chemistry, Jilin University , 2699 Qianjin Street, Changchun 130012, China.
authors.forename: Chunxi
authors.initials: C
authors.lastname: Hou
authors.affiliation: State Key Laboratory of Supramolecular Structure and Materials, College of Chemistry, Jilin University , 2699 Qianjin Street, Changchun 130012, China.
authors.forename: Junqiu
authors.identifier: 0000-0002-8922-454X
authors.initials: J
authors.lastname: Liu
mesh_terms: D055162:Biocatalysis; D002736:Chloroplasts / Q000737:chemistry / Q000378:metabolism*; D031541:Fluorescence Resonance Energy Transfer; D006735:Horseradish Peroxidase / Q000378:metabolism*; D045342:Light-Harvesting Protein Complexes / Q000378:metabolism*; D018716:Molecular Mimicry; D036103:Nanotechnology; D010957:Plasmids; D040081:Protein Array Analysis; D045663:Quantum Dots / Q000737:chemistry / Q000378:metabolism; D016329:Sp1 Transcription Factor / Q000378:metabolism*; D014443:Tyrosine / Q000378:metabolism
chemical_list: D045342:Light-Harvesting Protein Complexes; D016329:Sp1 Transcription Factor; D014443:Tyrosine; D006735:Horseradish Peroxidase
keywords: chloroplast mimic; light-harvesting; protein assembly; protein nanostructures; quantum dot