Wheel-Shaped Polyoxotungstate [Cu₂₀Cl(OH)₂₄(H₂O)₁₂(P₈W₄₈O₁₈₄)]^25- Macroanions Form Supramolecular “Blackberry” Structure in Aqueous Solution

Abstract

The hydrophilic polyoxotungstate [Cu20Cl(OH)24(H2O)12(P8W48O184)]25- ({Cu20P8W48}) self-assembles into single-layer, hollow, spherical "blackberry"-type structures in aqueous solutions, as studied by dynamic light scattering (DLS), static light scattering (SLS), zeta potential analysis, and scanning electron microscopy (SEM) techniques. This represents the first report of blackberry formation for a non-Mo-containing polyoxometalate. There is no obvious change in the shape and size of the blackberries during the slow blackberry formation process, neither with macroionic concentration nor with temperature. Our results suggest that the blackberry-type structure formation is most likely a general phenomenon for hydrophilic macroions with suitable size and charge in a polar solvent, and not a specific property of polyoxomolybdates and their derivatives. The {Cu20P8W48} macroions are thus far the smallest type of macroions to date (equivalent radius < 2 nm) showing the unique self-assembly behavior, helping us to move one step closer toward identifying the transition point from simple ions (can be described by the Debye-Hückel theory) to macroions in very dilute solutions. Moreover, by using {Cu20P8W48} blackberry-type structures as the model system, the electrophoretic properties of macroionic supramolecular structures are studied for the first time via zeta-potential analysis. The mobility of blackberry-type structures is determined and used for understanding the state of small cations in solution. We notice that the average charge density on each {Cu20P8W48} macroanion in a blackberry is much lower than that of discrete "free" {Cu20P8W48} macroions. This result suggests that some small alkali counterions are closely associated with, or even incorporated into, the blackberry-type structures and thus do not contribute to solution conductivity. This model is fully consistent with our speculation that monovalent counterions play an important role in the self-assembly of macroions, possibly providing an attractive force contributing to blackberry formation.

Chitosan-Polyoxometalate Nanocomposites: Synthesis, Characterization and Application as Antimicrobial Agents

“…S2). Such broad range may be due to counterion-mediated attraction between the polyanions, which results in a partial charge shielding [61]. In addition, the wider f-potential range observed for V 10 is likely to result from equilibria involving the formation of lower nuclearity oxovanadates (V 1 -V 5 ) at higher pH [62].…”

Polyoxometallate als Bausteine für funktionelle Nanosysteme

“…Nanometergroße wasserlösliche Makroionen wie {Mo 132 }, {Mo 154 }, {Mo 72 Fe 30 } und andere neigen in verdünnten Lösun-gen zur Bildung von stabilen gleichmäßigen, einschichtigen "Brombeer"-Strukturen von 20-1000 nm Größe über nichtkovalente Wechselwirkungen. [104,105] Für "Brombeer"-Strukturen aus dem Keplerat {Mo 72 Fe 30 } sind zwei interessante Eigenschaften zu beobachten: 1) sie erzeugen eine mikroskopische, vergleichsweise isolierte Wasserumgebung (mit über 3 Millionen Wassermolekülen), und 2) die "Brombeer"-Membran ist für kleine Kationen durchlässig, nicht jedoch für Anionen. Der passive Transport von Kationen durch die Membran ist vergleichsweise langsam, er benötigt aber weder einen Träger noch zusätzliche Energie.…”

“SOFT OXOMETALATES” (SOMs): A VERY SHORT INTRODUCTION

“…highlights few examples of relatively recent works and those of author's own which may be classified Early works on SOMs can be traced back to the times of Berzelius [5] [7] Recently a linear dependence between the radii of such SoFoSOM-blackberries with inverse of dielectric constant of the medium using {Mo 72 Fe 30 } and {Mo 132 } as model systems was observed. [8] To explain such observation a simple model was proposed.…”