Sweet Janus Particles: Multifunctional Inhibitors of Carbohydrate-Based Bacterial Adhesion.

Escherichia coli and other bacteria use adhesion receptors, such as FimH, to attach to carbohydrates on the cell surface as the first step of colonization and infection. Efficient inhibitors that block these interactions for infection treatment are multivalent carbohydrate-functionalized scaffolds. However, these multivalent systems often lead to the formation of large clusters of bacteria, which may pose problems for clearing bacteria from the infected site. Here, we present Man-containing Janus particles (JPs) decorated on one side with glycomacromolecules to target Man-specific adhesion receptors of E. coli. On the other side, poly(N-isopropylacrylamide) is attached to the particle hemisphere, providing temperature-dependent sterical shielding against binding and cluster formation. While homogeneously functionalized particles cluster with multiple bacteria to form large aggregates, glycofunctionalized JPs are able to form aggregates only with individual bacteria. The formation of large aggregates from the JP-decorated single bacteria can still be induced in a second step by increasing the temperature and making use of the collapse of the PNIPAM hemisphere. This is the first time that carbohydrate-functionalized JPs have been derived and used as inhibitors of bacterial adhesion. Furthermore, the developed JPs offer well-controlled single bacterial inhibition in combination with cluster formation upon an external stimulus, which is not achievable with conventional carbohydrate-functionalized particles.

Hybrid Janus Particles: Challenges and Opportunities for the Design of Active Functional Interfaces and Surfaces.

Janus particles are a unique class of multifunctional patchy particles combining two dissimilar chemical or physical functionalities at their opposite sides. The asymmetry characteristic for Janus particles allows them to self-assemble into sophisticated structures and materials not attainable by their homogeneous counterparts. Significant breakthroughs have recently been made in the synthesis of Janus particles and the understanding of their assembly. Nevertheless, the advancement of their applications is still a challenging field. In this Review, we highlight recent developments in the use of Janus particles as building blocks for functional materials. We provide a brief introduction into the synthetic strategies for the fabrication of JPs and their properties and assembly, outlining the existing challenges. The focus of this Review is placed on the applications of Janus particles for active interfaces and surfaces. Active functional interfaces are created owing to the stabilization efficiency of Janus particles combined with their capability for interface structuring and functionalizing. Moreover, Janus particles can be employed as building blocks to fabricate active functional surfaces with controlled chemical and topographical heterogeneity. Ultimately, we will provide implications for the rational design of multifunctional materials based on Janus particles.

Reconfigurable assembly of charged polymer-modified Janus and non-Janus particles: from half-raspberries to colloidal clusters and chains.

Understanding the dynamic and reversible assembly of colloids and particles into complex constructs, inspired by natural phenomena, is of fundamental significance for the fabrication of multi-scale responsive and reconfigurable materials. In this work, we investigate the pH-triggered and reconfigurable assembly of structures composed of binary mixtures of oppositely charged polyacrylic acid (PAA)-modified non-Janus and poly(2-dimethylamino)ethyl methacrylate (PDMAEMA)/poly(N-isopropylacrylamide) (PNIPAM)-modified Janus particles driven by electrostatic interactions. Three different target structures are visible both in dispersions and in dry state: half-raspberry structures, colloidal clusters and colloidal chains depending on the mass, numerical and particle size ratio. All formed structures are well-defined and stable in a certain pH range. Half-raspberry-like structures are obtained at pH 6 and numerical ratios N JP/PAA-HP of 1 : 500 (for 200-PAA-HP), 1 : 44 (for 450-PAA-HP) and 1 : 15 (for 650-PAA-HP), respectively, due to electrostatic interactions between the central JP and the excessive PAA-HP. Colloidal chains and cluster-like structures are generated at numerical ratios N JP/PAA-HP of 4 : 5 (for 200-PAA-HP), 4 : 3 (for 450-PAA-HP), and 4 : 1 (for 650-PAA-HP). Moreover, the smaller the size of a "connecting" PAA colloid, the larger is the average length of a colloidal chain. Depending on the particle size ratio S JP/PAA-HP, some of the observed structures can be disassembled on demand by changing the pH value either close to the IEP of the PDMAEMA (for half-raspberries) or PAA (for colloidal clusters and chains) and then reassembled into new stable structures many times. The obtained results open a pathway to pH-controlled reconfigurable assembly of a binary mixture composed of polymeric-modified non-Janus and Janus particles, which allow the reuse of particle building blocks.

Hairy Particles with Immobilized Enzymes: Impact of Particle Topology on the Catalytic Activity.

Enzymes are described as ideal green biocatalysts because they are highly specific and selective. However, their practical application is hampered because of the low stability and missing reusability of free enzymes. One method to overcome these problems is the immobilization of enzymes onto carriers. Although numerous publications discuss different immobilization strategies, optimization of these carriers for the highest enzyme activity and loading capacity, enzyme selectivity, reusability, and reactor system configuration still remains a challenging task. In this contribution, we aim to address the role of the core-shell particle design with respect to their geometry as well as the polymer shell thickness on the immobilization of biomolecules. We discovered that spherical particles with a core diameter of 200 nm and intermediate shell thickness as well as platelet-like particles exhibited excellent results with a maximum immobilization yield of laccase from Trametes versicolor of up to 92% and an activity on the carrier material of 5.722 U/(g particle). Especially, the platelet-like particles offered a scalable and convenient alternative for the immobilization of laccase. Circular dichroism measurements proved that the secondary structure of the enzyme is not impaired by immobilization onto all kinds of carrier particles. Moreover, the immobilized laccase was successfully used for the decolorization of Cibacron blue P-3R in up to 18 cycles. Finally, particle separation was achieved via citrate-induced flocculation within 10 min. This detailed study contributes to the understanding of rational design of catalytically active hybrid materials and their effective performance at interfaces for applications in textile industry and environmental technologies.

"On Water" Surface-initiated Polymerization of Hydrophobic Monomers.

We present the "on water" surface-initiated Cu-mediated controlled radical polymerization ("on water" SI-CuCRP) that converts hydrophobic monomers in aqueous reaction medium to polymer brushes at unparalleled speed and efficiency. The method allows the facile conversion of a variety of common monomers under most simple reaction conditions and with minimal monomer amounts to thick and homogeneous polymer brushes. The highly living character of the "on water" SI-CuCRP allowed the preparation of decablock (homo)polymer brushes and opens the pathway to sequentially controlled polymer brushes on solids.

Detachment of Rough Colloids from Liquid-Liquid Interfaces.

Particle surface roughness and chemistry play a pivotal role in the design of new particle-based materials. Although the adsorption of rough particles has been studied in the literature, desorption of such particles remains poorly understood. In this work, we specifically focus on the detachment of rough and chemically modified raspberry-like microparticles from water/oil interfaces using colloidal-probe atomic force microscopy. We observe different contact-line dynamics occurring upon particle detachment (pinning vs sliding), depending on both the particle roughness and surface modification. In general, surface roughness leads to a reduction of the desorption force of hydrophobic particles into the oil and provides a multitude of pinning points that can be accessed by applying different loads. Our results hence suggest future strategies for stabilization and destabilization of Pickering emulsions and foams.

Universal emulsion stabilization from the arrested adsorption of rough particles at liquid-liquid interfaces.

Surface heterogeneities, including roughness, significantly affect the adsorption, motion and interactions of particles at fluid interfaces. However, a systematic experimental study, linking surface roughness to particle wettability at a microscopic level, is currently missing. Here we synthesize a library of all-silica microparticles with uniform surface chemistry, but tuneable surface roughness and study their spontaneous adsorption at oil-water interfaces. We demonstrate that surface roughness strongly pins the particles' contact lines and arrests their adsorption in long-lived metastable positions, and we directly measure the roughness-induced interface deformations around isolated particles. Pinning imparts tremendous contact angle hysteresis, which can practically invert the particle wettability for sufficient roughness, irrespective of their chemical nature. As a unique consequence, the same rough particles stabilize both water-in-oil and oil-in-water emulsions depending on the phase they are initially dispersed in. These results both shed light on fundamental phenomena concerning particle adsorption at fluid interfaces and indicate future design rules for particle-based emulsifiers.

Controlled and tunable design of polymer interface for immobilization of enzymes: does curvature matter?

Control and tuning of surface properties is indispensable for the programmed and rational design of materials. Particularly, polymeric brush-modified colloids can be used as carrier materials for enzyme immobilization. Although it is of prime importance to control the brush architecture, there is still a lack of systematic investigations concerning the impact of grafting density on the properties of the designed interface, as well as on the immobilization of biomolecules. In this work, we investigate the surface properties of polymer brushes with different grafting densities prepared using a "grafting from" approach on flat and on colloidal particle substrates by varying the density of initiator groups. In this way, we control and tune interfacial properties of the carrier material such as swelling, charge, adhesion as well as adsorption of laccase from Trametes versicolor on the grafted polyelectrolyte layer. We show that there is no direct transferability of the results received from planar to curved substrates regarding the swelling behavior in dependence on the grafting density. The maximum of swelling degree of PDMAEMA layers is achieved at 0.34 nm-2 and at 0.1 nm-2 grafting density for planar and curved particle substrates, respectively. The adhesion properties of the polymeric layer on both substrates are also strongly influenced by the grafting density, i.e. a decrease of the grafting density causes a transition from the adhesive to non-adhesive state. As proven by the cryo-TEM and AFM force distance measurements, an immobilization of laccase from Trametes versicolor causes a decrease of the polymer swelling and therefore leads to the changes in the surface morphology, charge and adhesion performance of final polymer-enzyme layer. Moreover, the higher effectiveness and activity of laccase were observed for the intermediate grafting densities which seem to be preferable over the maximum brush densities.

Hybrid Hairy Janus Particles as Building Blocks for Antibiofouling Surfaces.

Herein, we report a new strategy for the design of antifouling surfaces by using hybrid hairy Janus particles. The amphiphilic Janus particles possess either a spherical or a plateletlike shape and have core-shell structures with an inorganic core and hydrophilic/hydrophobic polymeric shells. Subsequently, these bifunctional Janus particles enable the fabrication of surfaces with modularity in chemical composition and final surface topography, which possess antifouling properties. The antifouling and fouling-release capability of the composite Janus particle-based surfaces is investigated using the marine biofilm-forming bacteria Cobetia marina. The Janus particle-based coatings are robust and significantly reduce bacterial retention under both static and dynamic conditions independent of the particle geometry. The plateletlike (kaolinite-based) Janus particles represent a scalable system for the rational design of antifouling coatings as well as their large-scale production and application in the future.

Postsynthetic Inner-Surface Functionalization of the Highly Stable Zirconium-Based Metal-Organic Framework DUT-67.

A postsynthetic functionalization approach was used to tailor the hydrophobicity of DUT-67, a metal-organic framework (MOF) consisting of 8-connected Zr6O6(OH)2 clusters and 2,5-thiophenedicarboxylate as the ligand, using postsynthetic exchange of the modulator by fluorinated monocarboxylates. Water adsorption isotherms demonstrated that, by the incorporation of such hydrophobic molecules, the hydrophobicity of the inner surface of the network can be tuned. Furthermore, tolerance of the material toward the removal of adsorbed water can be significantly enhanced compared to the parent DUT-67 MOF.

Patterned Polypeptoid Brushes.

Patterned polypeptoid brushes on gold and oxide substrates are synthesized by surface-initiated polymerization of N-substituted glycine N-carboxyanhydrides. Their biofouling resistance is shown by protein and cell adhesion experiments. The accessibility of the system to common patterning protocols is demonstrated by UV-lithography and a µCP approach. Moreover, the terminal secondary amine group of the polypeptoid brushes is functionalized with different fluorescent dyes to demonstrate their chemical accessibility.