Junyou Wang

Complex Coacervate Core Micelles from Iron-Based Coordination Polymers

Complex coacervate core micelles (C3Ms) from cationic poly(N-methyl-2-vinyl-pyridinium iodide)-b-poly(ethylene oxide) (P2MVP(41)-b-PEO(205)) and anionic iron coordination polymers are investigated in the present work. Micelle formation is studied by light scattering for both Fe(II)- and Fe(III)-containing C3Ms. At the stoichiometric charge ratio, both Fe(II)-C3Ms and Fe(III)-C3Ms are stable for at least 1 week at room temperature. Excess of iron coordination polymers has almost no effect on the formed Fe(II)-C3Ms and Fe(III)-C3Ms, whereas excess of P2MVP(41)-b-PEO(205) copolymers in the solution can dissociate the formed micelles. Upon increasing salt concentration, the scattering intensity decreases. This decrease is due to both a decrease in the number of micelles (or an increase in CMC) and a decrease in aggregation number. The salt dependence of the CMC and the aggregation number is explained using a scaling argument for C3M formation. Compared with Fe(II)-C3Ms, Fe(III)-C3Ms have a lower CMC and a higher stability against dissociation by added salt.

Controlled mixing of lanthanide(III) ions in coacervate

This article presents a facile strategy to combine Eu(3+) and Gd(3+) ions into coacervate core micelles in a controlled way with a statistical distribution of the ions. Consequently, the formed micelles show a high tunability between luminescence and relaxivity. These highly stable micelles present great potential for new materials, e.g. as bimodal imaging probes.

Effect of pH on complex coacervate core micelles from Fe(III)-based coordination polymer

The effect of pH on iron-containing complex coacervate core micelles [Fe(III)-C3Ms] is investigated in this paper. The Fe(III)-C3Ms are formed by mixing cationic poly(N-methyl-2-vinylpyridinium iodide)-b-poly(ethylene oxide) [P2MVP(41)-b-PEO(205)] and anionic iron coordination polymers [Fe(III)-L(2)EO(4)] at stoichiometric charge ratio. Light scattering and Cryo-TEM have been performed to study the variations of hydrodynamic radius and core structure with changing pH. The hydrodynamic radius of Fe(III)-C3Ms is determined mainly by the corona and does not change very much in a broad pH range. However, Cryo-TEM pictures and magnetic relaxation measurements indicate that the structure of the micellar cores changes upon changing the pH, with a more crystalline, elongated shape and lower relaxivity at high pH. We attribute this to the formation of mixed iron complexes in the core, involving both the bis-ligand and hydroxide ions. These complexes are stabilized toward precipitation by the diblock copolymer.

Protein Immobilization onto Cationic Spherical Polyelectrolyte Brushes Studied by Small Angle X-ray Scattering

The immobilization of bovine serum albumins (BSA) onto cationic spherical polyelectrolyte brushes (SPB) consisting of a solid polystyrene (PS) core and a densely grafted poly(2-aminoethyl methacrylate hydrochloride) (PAEMH) shell was studied by small-angle X-ray scattering (SAXS). The observed dynamics of adsorption of BSA onto SPB by time-resolved SAXS can be divided into two stages. In the first stage (tens of milliseconds), the added proteins as in-between bridge instantaneously caused the aggregation of SPB. Then BSA penetrated into the brush layer driven by electrostatic attractions, and reached equilibrium in the second stage (tens of seconds). The amount of BSA immobilized onto brush layer reached the maximum when pH was increased to about 6.1 and BSA concentration to 10 g/L. The cationic SPB were confirmed to provide stronger adsorption capacity for BSA compared to anionic ones.

Multi-responsive physical gels formed by a biosynthetic asymmetric triblock protein polymer and a polyanion

We report the design, production and characterization of a biosynthetic asymmetric triblock copolymer which consists of one collagen-like and one cationic block spaced by a hydrophilic random coiled block. The polymer associates into micelles when a polyanion is added due to the electrostatic interaction between the cationic block and the polyanion. The collagen-like block self-assembles into thermo-responsive triple helices upon cooling. When both end blocks are induced to self-assemble, a physical gel is formed via thermo-responsive association of the charge-driven micelles. The self-assembly of both end blocks and the effects of salt and temperature thereon were characterized by light scattering and rheology.

Size-Sorting and Pattern Formation of Nanoparticle-Loaded Micellar Superstructures in Biconcave Thin Films

Biconcave thin water layers represent a template to induce organization of supramolecular structures into ordered monolayers. Here we show how micelles form extensive micrometer-sized pseudo-2D superstructures that reveal size-sorting and geometric pattern formation, as shown by cryo-transmission electron microscopy (cryoTEM). Electron-rich gold particles inside the micelles facilitate direct visualization and determination of size, composition, and ordering of the micellar assemblies over multiple length scales. Some of the patterns observed show intriguing geometric patterns for superstructures, including Fibonacci-like, double-spiral domains that also appear in, for example, sunflower seed head patterns.

Ternary supramolecular quantum-dot network flocculation for selective lectin detection

We present a versatile, tuneable, and selective nanoparticle-based lectin biosensor, based on flocculation of ternary supramolecular nanoparticle networks (NPN), formed through the sequential binding of three building blocks. The three building blocks are β-cyclodextrin-capped CdTe quantum dots, tetraethylene glycol-tethered mannose-adamantane cross-linkers (ADTEGMan), and the tetravalent lectin Concanavalin A (ConA). The working principle of this selective sensor lies in the dual orthogonal molecular interactions of the linker, uniting adamantane-β-cyclodextrin and mannose-lectin interaction motifs, respectively. Only when the lectin is present, sequential binding takes place, leading to in situ self-organization of the sensor through the formation of ternary supramolecular networks. Monitoring the loss of fluorescence signal of the quantum dots in solution, caused by controlled network formation and consecutive flocculation and sedimentation, leads to selective, qualitative, and quantitative lectin detection. Fluorescent sedimented networks can be observed by the naked eye or under UV illumination for a lectin concentration of up to 10−8 M. Quantitative detection is possible at 100 min with a lower detection limit of approximately 5 × 10−8 M.

Lanthanide-Dipicolinic Acid Coordination Driven Micelles with Enhanced Stability and Tunable Function

Lanthanide-incorporated polymer micelles have been prepared driven by the lanthanide-dipicolinic acid (Ln-DPA) coordination. The terdentate DPA ligand is grafted to the PVP block of a diblock copolymer poly(4-vinylpyridine)-b-poly(ethylene oxide) (P4VP48-b-PEO193). Upon addition of Eu(III) ions to a solution of the DPA16-g-P4VP48-b-PEO193 block copolymer, intermolecular cross-links form and the ligand-carrying blocks assemble, leading to the formation of micelles, stabilized by the hydrophilic PEO blocks. The DPA exhibits a dual function in this study. First, the chelate group strongly coordinates to Eu(III) in a three to one ratio, and leads to high stability of the formed micelles, as proven by light scattering and luminescence spectroscopy. Second, DPA acts as an antenna that transfers energy to the Eu(III) ion and dramatically enhances the luminescence emission. The Eu(III) emission is moreover most sensitive for local environment and allows to shine light on the internal structure of this class of self-assembled 36 nm size soft nanoparticles. With the same strategy gadolinium(III) can be incorporated providing micelles which show enhanced magnetic relaxation rates. Micelles capping a mixture of Eu(III) and Gd(III) show both enhanced luminescence emission and magnetic relaxation rates, and the functions can be tuned by regulating the mixing ratio of Eu(III) and Gd(III), showing great potential for developing multimodal imaging agents for diagnostic as well as therapeutic applications.

Supramolecular Virus‐Like Nanorods by Coassembly of a Triblock Polypeptide and Reversible Coordination Polymers

We investigate a new case of a self-assembly-stimulated self-assembly in which a triblock polypeptide is combined with a anionic coordination polymer of a dipicolinic acid bis-ligand, and d- or f- block metal ions like ZnII or EuIII . The polypeptide not only has a silk-like domain that can fold and stack, but also a C-terminal cationic sequence by which it can interact with the supramolecular (coordination) polyanion. In the presence of all three ingredients (polypeptide, bis-ligand, and metal ions), we observe the initiation and slow growth of well-defined metal-containing nanorods of up to 150 nm in length, proving that self-assembly of the polypeptide is triggered by the self-assembly of the coordination polyelectrolyte and vice versa. The particles, which have a striking resemblance to rod-like viruses, are stable up to 1.2 m NaCl, and can be made fluorescent when lanthanides like EuIII are used, showing the potential to exploit functional properties and applications of virus-like supramolecular structures.