Enhanced stability of complex coacervate core micelles following different core-crosslinking strategies.

Complex coacervate core micelles (C3Ms) are formed by mixing aqueous solutions of a charged (bio)macromolecule with an oppositely charged-neutral hydrophilic diblock copolymer. The stability of these structures is dependent on the ionic strength of the solution; above a critical ionic strength, the micelles will completely disintegrate. This instability at high ionic strengths is the main drawback for their application in, , drug delivery systems or protein protection.

Charged Polypeptide Tail Boosts the Salt Resistance of Enzyme-Containing Complex Coacervate Micelles.

Encapsulation of proteins can have advantages for their protection, stability, and delivery purposes. One of the options to encapsulate proteins is to incorporate them in complex coacervate core micelles (C3Ms). This can easily be achieved by mixing aqueous solutions of the protein and an oppositely charged neutral-hydrophilic diblock copolymer.

Effect of enzymatic cross-linking of naringenin-loaded β-casein micelles on their release properties and fate in in vitro digestion.

The microbial transglutaminase (mTG) was used to improve the stability of the naringenin-loaded β-casein micelles (CNMs). The formation of cross-linked CNMs was confirmed by SDS-PAGE electrophoresis, showing a decrease in monomeric β-CN levels with increasing crosslinking time. Dynamic light scattering (DLS) showed that after crosslinking the particle size distribution did not change upon dilution, suggesting occurrence of intra-crosslinking.

Formation and ripening of alginate-like exopolymer gel layers during and after membrane filtration.

The properties of biofilm EPS are determined by the multiple interactions between its constituents and the surrounding environment. Because of the high complexity of biofilm EPS, its constituents' characterisation is still far from thorough, and identification of these interactions cannot be done yet. Therefore, we use gels of bacterial alginate-like exopolysaccharides (ALEs) as a model component for biofilm EPS in this work.

Balancing Enzyme Encapsulation Efficiency and Stability in Complex Coacervate Core Micelles.

Encapsulation of charged proteins into complex coacervate core micelles (C3Ms) can be accomplished by mixing them with oppositely charged diblock copolymers. However, these micelles tend to disintegrate at high ionic strength. Previous research showed that the addition of a homopolymer with the same charge sign as the protein improved the stability of protein-containing C3Ms.

3D biofilm visualization and quantification on granular bioanodes with magnetic resonance imaging.

The use of microbial fuel cells (MFCs) for wastewater treatment fits in a circular economy context, as they can produce electricity by the removal of organic matter in the wastewater. Activated carbon (AC) granules are an attractive electrode material for bioanodes in MFCs, as they are cheap and provide electroactive bacteria with a large surface area for attachment. The characterization of biofilm growth on AC granules, however, is challenging due to their high roughness and three-dimensional structure.

FRET Reveals the Formation and Exchange Dynamics of Protein-Containing Complex Coacervate Core Micelles.

The encapsulation of proteins into complex coacervate core micelles (C3Ms) is of potential interest for a wide range of applications. To address the stability and dynamic properties of these polyelectrolyte complexes, combinations of cyan, yellow, and blue fluorescent proteins were encapsulated with cationic-neutral diblock copolymer poly(2-methyl-vinyl-pyridinium)- b-poly(ethylene-oxide). Förster resonance energy transfer (FRET) allowed us to determine the kinetics of C3M formation and of protein exchange between C3Ms.

An acidic model pro-peptide affects the secondary structure, membrane interactions and antimicrobial activity of a crotalicidin fragment.

In order to study how acidic pro-peptides inhibit the antimicrobial activity of antimicrobial peptides, we introduce a simple model system, consisting of a 19 amino-acid long antimicrobial peptide, and an N-terminally attached, 10 amino-acid long acidic model pro-peptide. The antimicrobial peptide is a fragment of the crotalicidin peptide, a member of the cathelidin family, from rattlesnake venom. The model pro-peptide is a deca (glutamic acid).

Adhesion of emulsified oil droplets to hydrophilic and hydrophobic surfaces - effect of surfactant charge, surfactant concentration and ionic strength.

Adhesion of emulsified oil droplets to a surface plays an important role in processes such as crossflow membrane filtration, where the oil causes fouling. We present a novel technique, in which we study oil droplets on a model surface in a flow cell under shear force to determine the adhesive force between droplets and surface. We prepared an emulsion of hexadecane and used hydrophilic and hydrophobic glass slides as model surfaces.

Colorful Packages: Encapsulation of Fluorescent Proteins in Complex Coacervate Core Micelles.

Encapsulation of proteins can be beneficial for food and biomedical applications. To study their biophysical properties in complex coacervate core micelles (C3Ms), we previously encapsulated enhanced green fluorescent protein (EGFP) and its monomeric variant, mEGFP, with the cationic-neutral diblock copolymer poly(2-methyl-vinyl-pyridinium)--poly(ethylene-oxide) (P2MVP--PEO) as enveloping material. C3Ms with high packaging densities of fluorescent proteins (FPs) were obtained, resulting in a restricted orientational freedom of the protein molecules, influencing their structural and spectral properties.

The toxicity of plastic nanoparticles to green algae as influenced by surface modification, medium hardness and cellular adsorption.

To investigate processes possibly underlying accumulation and ecological effects of plastic nano-particles we have characterized their interaction with the cell wall of green algae. More specifically, we have investigated the influence of particle surface functionality and water hardness (Ca concentration) on particle adsorption to algae cell walls. Polystyrene nanoparticles with different functional groups (non-functionalized, -COOH and -NH) as well as coated (starch and PEG) gold nanoparticles were applied in these studies.

Nanoparticle-Templated Formation and Growth Mechanism of Curved Protein Polymer Fibrils.

We investigated the growth of biosynthetic protein polymers with templated curvature on pluronic nanospheres. The protein has a central silk-like block containing glutamic residues (S(E)) and collagen-like end-blocks (C). The S(E) blocks stack into filaments when their charge is removed (pH <5).

Reversible polypeptide hydrogels from asymmetric telechelics with temperature-dependent and Ni(2+)-dependent connectors.

An asymmetric ('hybrid') triblock polypeptide TR4H with two different, orthogonally self-assembling end blocks has been constructed by conjugating a long (37 kDa) random coil block (R4) with a triple helix former T = (Pro-Gly-Pro)9 at the N terminus, and a histidine hexamer ('Histag', H) at the C terminus. This molecule can form trimers at room temperature by assembly of the T blocks, which can in turn assemble upon addition of Ni(2+), by association of Ni complexes involving the H block. This results in reversible hydrogels with dual responsiveness.

Complex Coacervate Core Micelles with Spectroscopic Labels for Diffusometric Probing of Biopolymer Networks.

We present the design, preparation, and characterization of two types of complex coacervate core micelles (C3Ms) with cross-linked cores and spectroscopic labels and demonstrate their use as diffusional probes to investigate the microstructure of percolating biopolymer networks. The first type consists of poly(allylamine hydrochloride) (PAH) and poly(ethylene oxide)-poly(methacrylic acid) (PEO-b-PMAA), labeled with ATTO 488 fluorescent dyes. We show that the size of these probes can be tuned by choosing the length of the PEO-PMAA chains.

Encapsulation of GFP in Complex Coacervate Core Micelles.

Protein encapsulation with polymers has a high potential for drug delivery, enzyme protection and stabilization. Formation of such structures can be achieved by the use of polyelectrolytes to generate so-called complex coacervate core micelles (C3Ms). Here, encapsulation of enhanced green fluorescent protein (EGFP) was investigated using a cationic-neutral diblock copolymer of two different sizes: poly(2-methyl-vinyl-pyridinium)41-b-poly(ethylene-oxide)205 and poly(2-methyl-vinyl-pyridinium)128-b-poly(ethylene-oxide)477.

Competition between surface adsorption and folding of fibril-forming polypeptides.

Self-assembly of polypeptides into fibrillar structures can be initiated by planar surfaces that interact favorably with certain residues. Using a coarse-grained model, we systematically studied the folding and adsorption behavior of a β-roll forming polypeptide. We find that there are two different folding pathways depending on the temperature: (i) at low temperature, the polypeptide folds in solution into a β-roll before adsorbing onto the attractive surface; (ii) at higher temperature, the polypeptide first adsorbs in a disordered state and folds while on the surface.

Coverage and disruption of phospholipid membranes by oxide nanoparticles.

We studied the interactions of silica and titanium dioxide nanoparticles with phospholipid membranes and show how electrostatics plays an important role. For this, we systematically varied the charge density of both the membranes by changing their lipid composition and the oxide particles by changing the pH. For the silica nanoparticles, results from our recently presented fluorescence vesicle leakage assay are combined with data on particle adsorption onto supported lipid bilayers obtained by optical reflectometry.

Multi-responsive ionic liquid emulsions stabilized by microgels.

We present a complete toolbox to use responsive ionic liquid (IL) emulsions for extraction purposes. IL emulsions stabilized by responsive microgels are shown to allow rapid extraction and reversible breaking and re-emulsification. Moreover, by using a paramagnetic ionic liquid, droplets can be easily collected in low magnetic fields.

Complex coacervate core micelles as diffusional nanoprobes.

Because of their ease of preparation and versatile modification opportunities, complex coacervate core micelles (C3Ms) may be a good alternative for expensive diffusional probes, such as dendrimers. However, C3Ms are unstable at high salt concentrations and may fall apart in contact with other polymers or (solid) materials. Therefore, we designed and characterized small (15 nm radius), stable fluorescent C3Ms.

Subtle charge balance controls surface-nucleated self-assembly of designed biopolymers.

We report the surface-nucleated self-assembly into fibrils of a biosynthetic amino acid polymer synthesized by the yeast Pichia pastoris. This polymer has a block-like architecture, with a central silk-like block labeled SH, responsible for the self-assembly into fibrils, and two collagen-like random coil end blocks (C) that colloidally stabilize the fibers in aqueous solution. The silk-like block contains histidine residues (pKa≈6) that are positively charged in the low pH region, which hinders self-assembly.

A liquid CO2-compatible hydrocarbon surfactant: experiment and modelling.

Surfactants soluble in liquid CO2 are rare and knowledge on interfacial and self-assembly behaviour is fragmented. We found that polyoxyethylene (5) isooctylphenyl ether is interfacially active at the water-liquid CO2 interface. Water-liquid CO2 interfacial tension was measured at various surfactant concentrations at 50 bar and 283 K using the pendant drop method, and a CMC like cusp was observed at a surfactant concentration of ~50 mM in the bulk liquid CO2.

Interfacial tension and wettability in water-carbon dioxide systems: experiments and self-consistent field modeling.

This paper presents experimental and modeling results on water-CO2 interfacial tension (IFT) together with wettability studies of water on both hydrophilic and hydrophobic surfaces immersed in CO2. CO2-water interfacial tension (IFT) measurements showed that the IFT decreased with increasing pressure and the negative slopes of IFT-pressure isotherms decreased with increasing temperature. Water contact angle on a cellulose surface (hydrophilic) immersed in CO2 increased with pressure, whereas the water contact angle on a hydrophobic surface such as hexamethyl disilazane (HMDS) coated silicon surface was almost independent of pressure.

Colloidal interactions in liquid CO2--a dry-cleaning perspective.

Liquid CO(2) is a viable alternative for the toxic and environmentally harmful solvents traditionally used in dry-cleaning industry. Although liquid CO(2) dry-cleaning is being applied already at a commercial scale, it is still a relatively young technique which poses many challenges. The focus of this review is on the causes of the existing problems and directions to solve them.

Effect of surface roughness and softness on water capillary adhesion in apolar media.

The roughness and softness of interacting surfaces are both important parameters affecting the capillary condensation of water in apolar media, yet are poorly understood at present. We studied the water capillary adhesion between a cellulose surface and a silica colloidal probe in hexane by AFM force measurements. Nanomechanical measurements show that the Young's modulus of the cellulose layer in water is significantly less (~7 MPa) than in hexane (~7 GPa).