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.

Donor:Acceptor Janus Nanoparticle-Based Films as Photoactive Layers: Control of Assembly and Impact on Performance of Devices.

Water-processable organic semiconductor nanoparticles (NPs) are considered promising materials for the next-generation of optoelectronic applications due to their controlled size, internal structure, and environmentally friendly processing. Reasonably, the controllable assembly of donor:acceptor (D:A) NPs on large areas, quality, and packing density of deposited films, as well as layer morphology, will influence the effectiveness of charge transfer at an interface and the final performance of designed optoelectronic devices.This work represents an easy and effective approach for designing self-assembled monolayers of D:A NPs. In this self-assembly procedure, the NP arrays are prepared on a large scale (2 × 2 cm2 ) at the air/water interface with controlled packing density and morphology. Due to the unique structure of individual D:A Janus particles and their assembled arrays, the Janus nanoparticle (JNP)-based device exhibits an 80% improvement of electron mobility and more balanced charge extraction compared to the conventional core-shell NP-based device. An outstanding performance of polymer solar cells with over 5% efficiency is achieved after post-annealing treatment of assembled arrays, representing one of the best results for NP-based organic photovoltaics. Ultimately, this work provides a new protocol for processing water-processable organic semiconductor colloids and future optoelectronic fabrication.

Fibrous Scaffolds for Muscle Tissue Engineering Based on Touch-Spun Poly(Ester-Urethane) Elastomer.

Development of fiber-spinning technologies and materials with proper mechanical properties is highly important for the manufacturing of aligned fibrous scaffolds mimicking structure of the muscle tissues. Here, the authors report touch spinning of a thermoplastic poly(1,4-butylene adipate)-based polyurethane elastomer, obtained via solvent-free polymerization. This polymer possesses a combination of important advantages such as 1) low elastic modulus in the range of a few MPa, 2) good recovery ratio and 3) resilience, 4) processability, 5) nontoxicity, 6) biocompatibility, and 7) biodegradability that makes it suitable for fabrication of structures mimicking extracellular matrix of muscle tissue. Touch spinning allows fast and precise deposition of highly aligned micro- and nano-fibers without use of high voltage. C2C12 myoblasts readily align along soft polymer fibers and demonstrate high viability as well as proliferation that make proposed combination of polymer and fabrication method highly suitable for engineering skeletal muscles.

Impact of surface charge on the motion of light-activated Janus micromotors.

Control over micromotors' motion is of high relevance for lab-on-a-chip and biomedical engineering, wherein such particles encounter complex microenvironments. Here, we introduce an efficient way to influence Janus micromotors' direction of motion and speed by modifying their surface properties and those of their immediate surroundings. We fabricated light-responsive Janus micromotors with positive and negative surface charge, both driven by ionic self-diffusiophoresis. These were used to observe direction-of-motion reversal in proximity to glass substrates for which we varied the surface charge. Quantitative analysis allowed us to extract the dependence of the particle velocity on the surface charge density of the substrate. This constitutes the first quantitative demonstration of the substrate's surface charge on the motility of the light-activated diffusiophoretic motors in water. We provide qualitative understanding of these observations in terms of osmotic flow along the substrate generated through the ions released by the propulsion mechanism. Our results constitute a crucial step in moving toward practical application of self-phoretic artificial micromotors.

4D Biofabrication Using a Combination of 3D Printing and Melt-Electrowriting of Shape-Morphing Polymers.

We report the fabrication of scroll-like scaffolds with anisotropic topography using 4D printing based on a combination of 3D extrusion printing of methacrylated alginate, melt-electrowriting of polycaprolactone fibers, and shape-morphing of the fabricated object. A combination of 3D extrusion printing and melt-electrowriting allows programmed deposition of different materials and fabrication of structures with high resolution. Shape-morphing allows the transformation of a patterned surface of a printed structure in a pattern on inner surface of a folded object that is used to align cells. We demonstrate that the concentration of calcium ions, the environment media, and the geometrical shape of the scaffold influences shape-morphing that allows it to be efficiently programmed. Myoblasts cultured inside a scrolled bilayer scaffold demonstrate excellent viability and proliferation. Moreover, the patterned surface generated by PCL fibers allow a very high degree of orientation of cells, which cannot be achieved on the alginate layer without fibers.

Shape-Morphing Fibrous Hydrogel/Elastomer Bilayers Fabricated by a Combination of 3D Printing and Melt Electrowriting for Muscle Tissue Regeneration.

This paper reports an approach for the fabrication of shape-changing bilayered scaffolds, which allow the growth of aligned skeletal muscle cells, using a combination of 3D printing of hyaluronic acid hydrogel, melt electrowriting of thermoplastic polycaprolactone-polyurethane elastomer, and shape transformation. The combination of the selected materials and fabrication methods allows a number of important advantages such as biocompatibility, biodegradability, and suitable mechanical properties (elasticity and softness of the fibers) similar to those of important components of extracellular matrix (ECM), which allow proper cell alignment and shape transformation. Myoblasts demonstrate excellent viability on the surface of the shape-changing bilayer, where they occupy space between fibers and align along them, allowing efficient cell patterning inside folded structures. The bilayer scaffold is able to undergo a controlled shape transformation and form multilayer scroll-like structures with cells encapsulated inside. Overall, the importance of this approach is the fabrication of tubular constructs with a patterned interior that can support the proliferation and alignment of muscle cells for muscle tissue regeneration.

4D Biofabrication of fibrous artificial nerve graft for neuron regeneration.

In this paper, we describe the application of the 4D biofabrication approach for the fabrication of artificial nerve graft. Bilayer scaffolds consisting of uniaxially aligned polycaprolactone-poly(glycerol sebacate) (PCL-PGS) and randomly aligned methacrylated hyaluronic acid (HA-MA) fibers were fabricated using electrospinning and further used for the culture of PC-12 neuron cells. Tubular structures form instantly after immersion of fibrous bilayer in an aqueous buffer and the diameter of obtained tubes can be controlled by changing bilayer parameters such as the thickness of each layer, overall bilayer thickness, and medium counterion concentration. Designed scaffolds showed a self-folded scroll-like structure with high stability after four weeks of real-time degradation. The significance of this research is in the fabrication of tuneable tubular nerve guide conduits that can simplify the current existing clinical treatment of neural injuries.

Tuning the Interactions in Multiresponsive Complex Coacervate-Based Underwater Adhesives.

In this work, we report the systematic investigation of a multiresponsive complex coacervate-based underwater adhesive, obtained by combining polyelectrolyte domains and thermoresponsive poly(N-isopropylacrylamide) (PNIPAM) units. This material exhibits a transition from liquid to solid but, differently from most reactive glues, is completely held together by non-covalent interactions, i.e., electrostatic and hydrophobic. Because the solidification results in a kinetically trapped morphology, the final mechanical properties strongly depend on the preparation conditions and on the surrounding environment. A systematic study is performed to assess the effect of ionic strength and of PNIPAM content on the thermal, rheological and adhesive properties. This study enables the optimization of polymer composition and environmental conditions for this underwater adhesive system. The best performance with a work of adhesion of 6.5 J/m2 was found for the complex coacervates prepared at high ionic strength (0.75 M NaCl) and at an optimal PNIPAM content around 30% mol/mol. The high ionic strength enables injectability, while the hydrated PNIPAM domains provide additional dissipation, without softening the material so much that it becomes too weak to resist detaching stress.

Thermo-Responsive Polymer Brushes with Side Graft Chains: Relationship Between Molecular Architecture and Underwater Adherence.

During the last few decades, wet adhesives have been developed for applications in various fields. Nonetheless, key questions such as the most suitable polymer architecture as well as the most suitable chemical composition remain open. In this article, we investigate the underwater adhesion properties of novel responsive polymer brushes with side graft chain architecture prepared using "grafting through" approach on flat surfaces. The incorporation in the backbone of thermo-responsive poly(N-isopropylacrylamide) (PNIPAm) allowed us to obtain LCST behavior in the final layers. PNIPAm is co-polymerized with poly(methyl ethylene phosphate) (PMEP), a poloyphosphoester. The final materials are characterized studying the surface-grafted polymer as well as the polymer from the bulk solution, and pure PNIPAm brush is used as reference. PNIPAm-g-PMEP copolymers retain the responsive behavior of PNIPAm: when T > LCST, a clear switching of properties is observed. More specifically, all layers above the critical temperature show collapse of the chains, increased hydrophobicity and variation of the surface charge even if no ionizable groups are present. Secondly, effect of adhesion parameters such as debonding rate and contact time is studied. Thirdly, the reversibility of the adhesive properties is confirmed by performing adhesion cycles. Finally, the adhesive properties of the layers are studied below and above the LCST against hydrophilic and hydrophobic substrates.

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.

Enabling the synthesis of homogeneous or Janus hairy nanoparticles through surface photoactivation.

Nanoparticles (NPs) homogeneously covered with polymer chains or with chains of two different polymers segregated in distinct domains ("Janus" particles) possess remarkable features. Their unique colloidal properties can be finely tuned by the grafted polymers while the characteristics of the nano-core remain unaffected. Herein, a simple and robust photochemical approach is reported to synthesize, from 50 nm cores, homogeneous and Janus "hairy" nanoparticles with hydrophilic and amphiphilic properties, respectively. This is achieved by using a surface-anchored bis(acyl)phosphane oxide photoinitiator which allows a spatially controlled surface-initiated photopolymerization at room temperature. Homogeneous and Janus hairy nanoparticles dispersed in water have very different interaction behaviours which are directly visualized by in situ liquid cell transmission electron microscopy and confirmed by small angle X-ray scattering from a statistically relevant number of particles.

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.

Programmed assembly of oppositely charged homogeneously decorated and Janus particles.

The exploitation of colloidal building blocks with morphological and functional anisotropy facilitates the generation of complex structures with unique properties, which are not exhibited by isotropic particle assemblies. Herein, we demonstrate an easy and scalable bottom-up approach for the programmed assembly of hairy oppositely charged homogeneously decorated and Janus particles based on electrostatic interactions mediated by polyelectrolytes grafted onto their surface. Two different assembly routes are proposed depending on the target structures: raspberry-like/half-raspberry-like or dumbbell-like micro-clusters. Ultimately, stable symmetric and asymmetric micro-structures could be obtained in a well-controlled manner for the homogeneous-homogeneous and homogeneous-Janus particle assemblies, respectively. The spatially separated functionalities of the asymmetric Janus particle-based micro-clusters allow their further assembly into complex hierarchical constructs, which may potentially lead to the design of materials with tailored plasmonics and optical properties.

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.