Peptide sequence mediated self-assembly of molybdenum blue nanowheel superstructures

Abstract

Peptide sequence can be used to control the self-assembly and structures of nanoscale molybdenum blue polyoxometalate (POM) wheel-shaped clusters.

Robotic synthesis of peptides containing metal-oxide-based amino acids

“…27 However, due to the complex synthetic processes for inorganic amino acids, which is limited to specific amino acids, 28,29 no general routes exist to incorporate anionic inorganic amino acid residues into a peptide chain automatically under robotic control. To achieve this goal, we chose polyoxometalates (POMs), a large group of clusters built from multiple transition metal ions linked by shared oxo or hydroxo anions; 30 their molecular nature means they introduce higher charge densities, 31 redox activity, 32,33 and additional coordination/catalytic sites into the peptide chain, 34 leading to exciting new opportunities for protein biochemistry and inorganic medicinal chemistry. [35][36][37][38] Incorporation of redox-active POMs into sequences may further impart POM peptides with tuneable redox responsiveness, which is useful in redox bio-catalysis, redox-mediated self-assembly, and hybrid flow battery.…”

“…[35][36][37][38] Incorporation of redox-active POMs into sequences may further impart POM peptides with tuneable redox responsiveness, which is useful in redox bio-catalysis, redox-mediated self-assembly, and hybrid flow battery. To date there are two major methodologies to introduce POMs into peptide chains: non-covalent assembly 34,39,40 or covalent conjugation. 28,29,[36][37][38] However, the bespoke conditions required, unpredictable reactions, and the potential for many by-products greatly limit the exploration of biochemical activity of hybrid inorganic peptides (see Figure 1).…”

Lanthanides Singing the Blues: Their Fascinating Role in the Assembly of Gigantic Molybdenum Blue Wheels

“…Organic ligands for the synthesis of hybridized inorganic–organic MBs/Ln-MBs should have a carboxyl group in order to be able to attach to {Mo 2 } units (always depicted as red polyhedra in all the figures). Furthermore, amino groups in ligands (e.g., amino acids and peptides) are of essential importance particularly in Ln-MB syntheses when it comes to (a) stabilization of templates inside the rings, (b) introduction of chirality, and (c) modulation of the shape and size of Ln-MBs …”

Synthesis and characterization of the `Japanese rice-ball'-shaped Molybdenum Blue Na4[Mo2O2(OH)4(C6H4NO2)2]2[Mo120Ce6O366H12(OH)2(H2O)76]∼200H2O

“…Furthermore, BVS was carried out to calculate the number of Mo V centres within the Ln-MB and UV-Vis-NIR spectroscopy was performed to determine the contribution of each Mo V centre to the overall reduction state of the nanocluster. Due to the low water solubility of {Mo 2 (C 6 H 4 NO 2 ) 2 } 2 {Mo 120 Ce 6 }, which is a frequently encountered problem in the case of hybridized Ln-MBs (Xuan et al, 2019;She et al, 2021), redox titration to determine the number of reduced electrons in {Mo 2 (C 6 H 4 NO 2 ) 2 } 2 {Mo 120 Ce 6 } was not feasible.…”