Search

The spatiotemporal pH-triggered controlled release of a hydrophilic probe in a pH-responsive PGUV system demonstrates its potential as a biomimetic system for drug delivery, microreactors and artificial cell mimics.

Flower-like particles (FLPs) with hierarchical surface architectures have recently attracted considerable attention due to their potentially wide application range. Hitherto, nearly all FLPs were fabricated using inorganic compounds, while versatile organic polymers have not received sufficient attention yet. Herein, we show the construction of novel organic, polymeric FLPs with diameters of 2.5-5 μm using cellulose stearoyl esters (CSEs) by means of the crystallization of side chains. CSEs with degrees of substitution of approximately 3 were transformed into FLPs during the gradual precipitation of polymer chains from the mixture of their solutions in dichloromethane (DCM) and a nonsolvent, which is driven by the evaporation of DCM. Ordered petal-like nanostructures were formed on the particle surface through the crystallization of side chains. Finally, partially crystalline FLPs containing lamellar structures were obtained. Moreover, the formation process was strongly affected by the molecular weight of CSE, concentrations of CSE solutions and the volume ratio between DCM and nonsolvents.

Liquid crystalline materials found numerous applications in modern technologies due to their ability to respond to external fields. In this context, ferronematic liquid crystals are fascinating because they offer a response to weak magnetic fields in addition to electrical fields. Nevertheless, the synthesis of stable ferronematic liquid crystals represents a challenge for colloidal and synthetic chemists. In this work, we present a straight-forward strategy for directly incorporating presynthesized magnetic nanoparticles into every other interlayer of synthetic 2 : 1 layered silicates, which subsequently can be swollen to nematic phases simply by immersion into water, offering almost infinite stability. The resulting ferronematic suspension shows a sensitive response to magnetic fields. Moreover, the synthetic strategy is highly modular, enabling for variations of the magnetic nanosheets that allow for tuning the interaction between nanosheets and blocking temperature.

The influence of plasticizers based on carboxylic acid esters on the Fourier transform infrared (FTIR) spectroscopic determination of biodiesel contamination [fatty acid methyl esters (FAMEs)] in a...

The segmental dynamics of one-component nanocomposites (OCNC) is significantly influenced by the molecular weight (Mw) of the grafted polymer. Neutron backscattering shows that compared to the neat polymer the OCNCs exhibit a shift from slower segmental dynamics at low Mw to faster dynamics at high Mw. We model the local relaxation as distribution of exponential diffusers. This approach reveals the presence of fast and slow segments in both OCNCs. However, their fractional contribution varies with Mw leading to different average relaxation times. Our results present important insights into the origin of segmental mobility in OCNC and address the inconsistencies in different literature reports.

Amphiphilic polymers show a rich self-assembly behavior in aqueous solutions. In experimental investigations statistical copolymer or block copolymer architectures are usually investigated, because of their ease of synthesis or their structural analogy to surfactants. A copolymer structure that links the two architectures are alternating copolymers, which are easily accessible by polycondensation reactions. Using alternating hydrophilic and hydrophobic building blocks with varying length allows a systematic variation between statistical and multi-block architectures. We synthesized alternating amphiphilic copolymers as polyesters using hydrophobic dicarboxylic acids (C4 – C20) and hydrophilic polyethylene glycol (PEG) units (EG3 – EG1000). Copolymers with long EG units were made accessible with the help of a newly developed esterification process. The solution properties of the amphiphilic copolymers feature a lower critical solution temperature (LCST) behavior in water, which can be systematically varied over a wide range from 3 – 83°C by adjusting the lengths of the Cn- and EGm–units. We find that the transition temperature depends linearly on the hydrophobic unit length Cm and logarithmically on the hydrophilic length EGn. In the one-phase region the PEG copolymer coils are more compact compared to the respective PEG homopolymers due to hydrophobic interactions between the hydrophobic units leading to loop formation. For shorter PEG-units the copolymers form micellar structures consisting only of a few copolymer chains. The micellar cores consist of hydrophobic regions containing only a few dicarboxylic acid units, embedded in a PEG-rich and water-poor matrix. The cores are surrounded by a rather diluted corona of PEG chains. Further decreasing the PEG unit length leads to the formation of highly swollen gels consisting of networks of interconnected micelles. These can self-assemble to form highly ordered liquid crystalline cubic phases. The study demonstrates how the structure of alternating amphiphilic copolymers can be systematically varied to adjust thermal solution properties such as the LCST over a wide range, as well as the self-assembly properties varying between single chain, micelle, gels and highly ordered lyotropic liquid crystals.

The translocation of biologically active macromolecules through cell membranes is of vital importance for cells and is a key process for drug delivery. Proteins exploit specific conformational changes in their secondary structure to facilitate membrane translocation. For the large class of biological and synthetic macromolecules, where such conformational adaptions are not possible, guidelines to tailor the structure of monomers and macromolecules to aid membrane translocation and cross-membrane drug delivery would be highly desirable. Here, we use alternating amphiphilic macromolecules to systematically investigate the relation between polarity, polymer chain length, lipid chain length, polymer concentration, and temperature on membrane partition and translocation rate. We employed pulse field gradient NMR and confocal fluorescence microscopy to determine membrane adsorption and desorption rate constants and partitioning coefficients. We find that translocation is a two-step process involving a fast adsorption and membrane insertion process and a slower desorption process. Membrane insertion is a key step that determines the molecular weight, concentration, and temperature dependences. Passive translocation is possible on time scales from minutes to hours. Macromolecules with different adapted hydrophilic/hydrophobic comonomer sequences show the same translocation rate, indicating that common optimized translocation conditions can be realized with a variety of monomer chemical structures. The investigated copolymers are biocompatible, biodegradable, and capable of transporting a hydrophobic payload through the lipid membrane. This detailed understanding of the macromolecular translocation mechanism enables to better tailor the delivery of active agents using macromolecular carriers.

Stimuli-responsive materials change their state in response to external triggers. Switching between different states enables information to be written, stored, and read, if the transition between the states exhibits hysteresis. Thermally responsive polymers exhibit an intrinsic hysteresis for the volume phase transition between the swollen and de-swollen solution state. Here, it is shown that this hysteresis can be used to realize bistability, remanence, and reversible write/read information storage. This is demonstrated for the simplest and most widely used thermoresponsive polymer, poly(N-isopropylacrylamide) (PNIPAM), as well as for PNIPAM block copolymers, which widens the hysteresis window. The hysteresis is shown to be related to cluster domain assembly/disassembly during the phase transition. Information can be written thermally using a laser, or using heated or cooled pen tips on a thin-film backscattering display. The bistable state can additionally be switched by pH, enabling an AND logic gate function. Furthermore, an unusual memory state is discovered, where information is visible in the hysteresis window and invisible at higher temperatures, allowing encoded information to be hidden. Since hysteresis is a very common intrinsic phenomenon for responsive materials, this principle to encode and store information is potentially applicable to a broad range of responsive materials.

Bioprinting has evolved into a thriving technology for the fabrication of cell-laden scaffolds. Bioinks are the most critical component for bioprinting. Recently, microgels have been introduced as a very promising bioink enabling cell protection and the control of the cellular microenvironment. However, their microfluidic fabrication inherently seemed to be a limitation. Here we introduce a direct coupling of microfluidics and 3D-printing for the microfluidic production of cell-laden microgels with direct in-flow bioprinting into stable scaffolds. The methodology enables the continuous on-chip encapsulation of cells into monodisperse microdroplets with subsequent in-flow cross-linking to produce cell-laden microgels, which after exiting a microtubing are automatically jammed into thin continuous microgel filaments. The integration into a 3D printhead allows direct in-flow printing of the filaments into free-standing three-dimensional scaffolds. The method is demonstrated for different cross-linking methods and cell lines. With this advancement, microfluidics is no longer a bottleneck for biofabrication.

Thiols play an important role in the synthesis of well-defined nanoparticles (NPs) with tailored properties, but their effects on the formation kinetics of NPs are still under investigation. Here, we used in situ small-angle X-ray scattering (SAXS)/UV-vis spectroscopy and time-dependent transmission electron microscopy (TEM) to elucidate the role of thiols in the formation process of gold NPs (AuNPs) by changing the adding sequence between thiol ligand and reducing agent. Through quantitative analysis of in situ SAXS/UV-vis and TEM, detailed information on size, size distribution, the number of particles, optical properties, and the size evolution was obtained. Two different growth mechanisms of monodisperse AuNPs controlled by thiol ligand are exhibited: (i) thiol plays a dual role as a digestive ripening etchant and as a stabilizing ligand in the presence of a weak phosphine ligand. The digestive ripening mechanism involving the dissolution of bigger particles and subsequent deposition of monomers onto existing small NPs is responsible for producing narrowly dispersed NPs. (ii) Thiol acts as a strong stabilizing agent; in this case, the formation rate constant is quite slow, thus limiting the growth rate of NPs. Therefore, diffusion-limited growth mechanism is proposed for obtaining narrowly dispersed NPs with a diameter of 5.6 nm (12%). Our findings demonstrate that the formation of nearly monodisperse AuNPs with controllable size distribution could be realized by different growth mechanisms in the presence of thiol ligand.

Microfluidic methods allowing fast mixing allow studying fast chemical reactions on the millisecond time scale. Here the kinetics of nucleation and growth of thioglycerol- and l -cysteine-capped CdS quantum dots is investigated using a continuous-flow microfluidic device in combination with in situ microscopy and spectroscopic techniques. A microfluidic device is developed to three-dimensionally focus a central aqueous Cd2+-stream, which is completely enclosed by a water buffer layer, into a stream of aqueous S2−. Diffusion-limited nucleation and growth of CdS nanoparticles occurs in the buffer layer downstream the reaction channel which can be followed by in situ confocal laser scanning microscopy and UV-Vis absorption spectroscopy on the time scale of the first 1–100 ms, giving direct and unique insights into early colloidal crystal nucleation and growth processes.

We demonstrate how to directly transform a close-packed hexagonal colloidal monolayer into nonclose-packed particle arrays of any two-dimensional symmetry at the air/water interface. This major advancement in the field of nanoparticle self-assembly is based on a simple one-dimensional stretching step in combination with the particle array orientation. Our method goes far beyond existing strategies and allows access to all possible two-dimensional Bravais lattices. A key element of our work is the possibility to macroscopically stretch a particle array in a truly one-dimensional manner, which has not been possible up to now. We achieve this by stretching the nanoparticle array at an air/water interface during the transfer process. The degree of stretching is simply controlled by the wettability of the transfer substrate. To retain the symmetry of the transferred structure, the capillary forces upon drying have to be circumvented. We demonstrate two concepts based on thermal fixation for this. It allows for the first time to fabricate nonclose-packed, nonhexagonal colloidal monolayers on a macroscopic length scale.

Heat-up synthesis routes are very commonly used for the controlled large-scale production of semiconductor and magnetic nanoparticles with narrow size distribution and high crystallinity. To obtain fundamental insights into the nucleation and growth kinetics is particularly demanding, because these procedures involve heating to temperatures above 300 °C. We designed a sample environment to perform

The defined assembly of nanoparticles in polymer matrices is an important precondition for next‐generation functional materials. Here we demonstrate that a defined three‐dimensional nanoparticle assembly within the unit cells can be realized by directly linking the nanoparticles to block copolymers. We show that for a range of nearly symmetric to unsymmetric block copolymers there are only two formed structures, a hexagonal lattice of P6/mmm‐symmetry, where the nanoparticles are located in 1D‐arrays within the cylindrical domains, and a cubic lattice of Im3m‐symmetry, where the nanoparticles are located in the octahedral voids of a BCC‐lattice, corresponding to the structure of ferrite steel. We observe the block length ratio and thus the interfacial curvature to be the most important parameter determining the lattice type. This is rationalized in terms of minimal chain extension such that domain topologies with large positive curvature are highly preferred. Already volume fractions of only one percent are sufficient to destabilize a lamellar structure and favor the formation of highly curved interfaces. The study thus demonstrates how nanoparticles can be located on well‐defined positions in three‐dimensional unit cells of block copolymer nanocomposites. This opens the way to functional 3D‐nanocomposites where the nanoparticles need to be located on defined matrix positions., By directly linking nanoparticles to block copolymers, defined three‐dimensional nanoparticle assemblies can be realized within domain unit cells. The block length ratio is the most important parameter determining the lattice type. Volume fractions of domains with large positive curvature of only one percent are already sufficient to destabilize lamellar structure and favor the formation of highly curved interfaces.

Heat-up synthesis routes are very commonly used for the controlled large-scale production of semiconductor and magnetic nanoparticles with narrow size distribution and high crystallinity. To obtain fundamental insights into the nucleation and growth kinetics is particularly demanding, because these procedures involve heating to temperatures above 300 °C. We designed a sample environment to perform in situ SAXS/WAXS experiments to investigate the nucleation and growth kinetics of iron oxide nanoparticles during heat-up synthesis up to 320 °C. The analysis of the growth curves for varying heating rates, Fe/ligand ratios, and plateau temperatures shows that the kinetics proceeds via a characteristic sequence of three phases: an induction Phase I, a final growth Phase III, and an intermediate Phase II, which can be divided into an early phase with the evolution and subsequent dissolution of an amorphous transient state, and a late phase, where crystalline particle nucleation and aggregation occurs. We extended classical nucleation and growth theory to account for an amorphous transient state and particle aggregation during the nucleation and growth phases. We find that this nonclassical theory is able to quantitatively describe all measured growth curves. The model provides fundamental insights into the underlying kinetic processes especially in the complex Phase II with the occurrence of a transient amorphous state, the nucleation of crystalline primary particles, particle growth, and particle aggregation proceeding on overlapping time scales. The described in situ experiments together with the extension of the classical nucleation and growth model highlight the two most important features of nonclassical nucleation and growth routes, i.e., the formation of intermediate or transient species and particle aggregation processes. They thus allow us to quantitatively understand, predict, and control nanoparticle nucleation and growth kinetics for a wide range of nanoparticle systems and synthetic procedures.

We study the dynamics of pure oleic acid and grafted oleic acid synthesized by decomposing iron oleate into oleic acid grafted iron oxide nanoparticles. Our quasielastic neutron scattering study shows that oleic acid dominantly performs translational diffusion at room temperature. On the other hand, in nanocomposites, constraints imposed by grafting and crowding of neighboring chains restrict the grafted oleic acid to uniaxial rotation. Interestingly, it also manifests mobility in grafted oleic acid below the crystallization temperature of pure oleic acid. The data from grafted oleic acid could be effectively described using a uniaxial rotational diffusion model with an additional elastic scattering contribution. This kind of elastic scattering arises due to the restricted bond mobility and increases with decreasing temperature. The radius of rotation obtained from the fitted data agrees very well with the geometry of the molecule and grafting density. These results open possibilities of research on the confined surfactant systems, which could be analyzed using the approach described here.

Polymer hexosomes are block copolymer solution morphologies that adopt an internal structure composed of an inverse hexagonal (HII) phase. To date, most polymer hexosomes are reportedly rotationally symmetric solid structures that possess a common feature where hexagonally ordered inverted cylinders rotate along a central axis of symmetry to form circular hoops. Here, we report on the formation of polymer hexosomes whose inverted cylinders orient in an unusual manner, forming hoops that are noncircular. For topological reasons, this led to the generation of four defects in the resulting hexosome structure. We find that these defect-bearing hexosomes are hollow, thereby resembling polymer vesicles or polymersomes with an inverse hexagonal cylindrical morphology in the shell. The topological defects of these so-called "vesicular hexosomes" are enticing as they could serve as a platform to spatially anchor targeting ligands or biomolecules on the surface, while the hollow cylindrical shell and the vesicular lumen could spatially accommodate cargoes within the different domains. We propose that these vesicular hexosomes do not form via a conventional nucleation-growth self-assembly pathway, but rather via a two-step process involving first liquid-liquid phase separation followed by polymer microphase separation.

Scientific reports 10(1), 16691 (2020). doi:10.1038/s41598-020-73671-3, Published by Macmillan Publishers Limited, part of Springer Nature, [London]

Delamination by osmotic swelling of layered materials is generally thought to become increasingly difficult, if not impossible, with increasing layer charge density because of strong Coulomb interactions. Nevertheless, for the class of 2:1 layered silicates, very few examples of delaminating organo-vermiculites were reported in literature. We propose a mechanism for this repulsive osmotic swelling of highly charged vermiculites based on repulsive counterion translational entropy that dominates the interaction of adjacent layers above a certain threshold separation. Based on this mechanistic insight, we were able to identify several organic interlayer cations appropriate to delaminate highly charged, vermiculite-type clay minerals. These findings suggest that the osmotic swelling of highly charged organoclays is a generally applicable phenomenon rather than the odd exemption.

We investigate the properties of polymer nanocomposites consisting of narrow disperse spherical nanoparticles that are coated with narrow disperse polymers. These nanoparticles can be homogeneously dispersed in a polymer matrix. The structure of the polymer-coated nanoparticles was examined by using small angle X-ray scattering (SAXS) and transmission electron microscopy (TEM), and was related to the viscoelastic properties of the nanocomposites. We observe a systematic retardation of the polymer relaxation dynamics with increasing particle loading. Nanoparticle aggregation leading to the formation of chain-like structures causes a strong reinforcement effect.

The formation of a biomolecular corona around engineered particles determines, in large part, their biological behavior in vitro and in vivo. To gain a fundamental understanding of how particle design and the biological milieu influence the formation of the "hard" biomolecular corona, we conduct a series of in vitro studies using microfluidics. This setup allows the generation of a dynamic incubation environment with precise control over the applied flow rate, stream orientation, and channel dimensions, thus allowing accurate control of the fluid flow and the shear applied to the proteins and particles. We used mesoporous silica particles, poly(2-methacryloyloxyethylphosphorylcholine) (PMPC)-coated silica hybrid particles, and PMPC replica particles (obtained by removal of the silica particle templates), representing high-, intermediate-, and low-fouling particle systems, respectively. The protein source used in the experiments was either human serum or human full blood. The effects of flow, particle surface properties, incubation medium, and incubation time on the formation of the biomolecular corona formation are examined. Our data show that protein adhesion on particles is enhanced after incubation in human blood compared to human serum and that dynamic incubation leads to a more complex corona. By varying the incubation time from 2 s to 15 min, we demonstrate that the "hard" biomolecular corona is kinetically subdivided into two phases comprising a tightly bound layer of proteins interacting directly with the particle surface and a loosely associated protein layer. Understanding the influence of particle design parameters and biological factors on the corona composition, as well as its dynamic assembly, may facilitate more accurate prediction of corona formation and therefore assist in the design of advanced drug delivery vehicles.

Efficient hydrogelators will gel water fast and at low concentrations. Small molecule gelling agents that assemble into fibers and fiber networks are particularly effective hydrogelators. Whereas it is straightforward to determine their critical concentration for hydrogelation, the kinetics of hydrogelation is more difficult to study because it is often very fast, occurring on the subsecond time scale. We used a 3D focusing microfluidic device combined with fluorescence microscopy and in situ small-angle X-ray scattering (SAXS) to study the fast pH-induced gelation of a model small molecule gelling agent at the millisecond time scale. The gelator is a 1,3,5-benzene tricarboxamide which upon acidification assembles into nanofibrils and fibril networks that show a characteristic photoluminescence. By adjusting the flow rates, the regime of early nanofibril formation and gelation could be followed along the microfluidic reaction channel. The measured fluorescence intensity profiles were analyzed in terms of a diffusion-advection-reaction model to determine the association rate constant, which is in a typical range for the small molecule self-assembly. Using in situ SAXS, we could determine the dimensions of the fibers that were formed during the early self-assembly process. The detailed structure of the fibers was subsequently determined by cryotransmission electron microscopy. The study demonstrates that 3D focusing microfluidic devices are a powerful means to study the self-assembly on the millisecond time scale, which is applied to reveal early state of hydrogelation kinetics. In combination with in situ fluorescence and X-ray scattering, these experiments provide detailed insights into the first self-assembly steps and their reaction rates.

Liquid microjets play a key role in fiber spinning, inkjet printing, and coating processes. In all of these applications, the liquid jets carry dispersed particles whose spatial and orientational distributions within the jet critically influence the properties of the fabricated structures. Despite its importance, there is currently no knowledge about the orientational distribution of particles within microjets and droplets. Here, we demonstrate a microfluidic device that allows to determine the local particle distribution and orientation by X-ray scattering. Using this methodology, we discovered unexpected changes in the particle orientation upon exiting the nozzle to form a free jet, and upon jet break-up into droplets, causing an unusual biaxial particle orientation. We show how flow and aspect ratio determine the flow orientation of anisotropic particles. Furthermore, we demonstrate that the observed phenomena are a general characteristic of anisotropic particles. Our findings greatly enhance our understanding of particle orientation in free jets and droplets and provide a rationale for controlling particle alignment in liquid jet-based fabrication methodologies.

We present a microfluidic nozzle device for the controlled continuous solution blow spinning of ultrafine fibers. The device is fabricated by soft lithography techniques and is based on the principle of a gas dynamic virtual nozzle for precise three-dimensional gas focusing of the spinning solution. Uniform fibers with virtually endless length can be produced in a continuous process while having accurate control over the fiber diameter. The nozzle device is used to produce ultrafine fibers of perfluorinated copolymers and of polycaprolactone, which are collected and drawn on a rotating cylinder. Hydrodynamics and mass balance quantitatively predict the fiber diameter, which is only a function of flow rate and air pressure, with a small correction accounting for viscous dissipation during jet formation, which slightly reduces the jet velocity. Because of the simplicity of the setup, the precise control of the fiber diameter, the positional stability of the exiting ultrafine fiber and the potential to implement arrays of parallel channels for high throughput, this methodology offers significant benefits compared to existing solution-based fiber production methods.

The control of the distribution of colloidal particles in microfluidic flows plays an important role in biomedical and industrial applications. A particular challenge is to induce cross-streamline migration in laminar flows, enabling the separation of colloidal particles according to their size, shape or elasticity. Here we show that viscoelastic fluids can mediate cross-streamline migration of deformable spherical and cylindrical colloidal particles in sinusoidal microchannels at low Reynolds numbers. For colloidal streams focused into the center of the channel entrance this leads to a symmetric stream-splitting and separation into four substreams. The degree of stream splitting and separation can be controlled via the flow rates, viscoelasticity of the focusing fluid, and the spatial microchannel modulation with an upper limit when reaching the microchannel walls. We demonstrate that this effect can be used to separate flexible particles of different size and shape. This methodology of cross-stream migration has thus great potential for the passive separation of colloids and cells in microfluidic channels.

The aim of this work was to predict composition and nine selected physicochemical properties of fossil/synthetic aviation fuel blends by chemometric analysis of mid-infrared spectra. Therefore, infrared spectra of various mixtures with six different synthetic hydrocarbon fuels were recorded and comprehensively interpreted, supported by data from comprehensive two-dimensional gas chromatography–mass spectrometry analysis of these fuels. Deep insight has been gained on how individual blend components are differentiated in principal component analysis and how they influence physicochemical properties by means of partial least squares regression. A chemometric model has been established to determine the amount of an individual synthetic fuel in a blend with a precision of

Nanorattles are metallic core-shell particles with core and shell separated by a dielectric spacer. These nanorattles have been identified as a promising class of nanoparticles, due to their extraordinary high electric-field enhancement inside the cavity. Limiting factors are reproducibility and loss of axial symmetry owing to the movable metal core; movement of the core results in fluctuation of the nanocavity dimensions and commensurate variations in enhancement factor. We present a novel synthetic approach for the robust fixation of the central gold rod within a well-defined box, which results in an axisymmetric nanorattle. We determine the structure of the resulting axisymmetric nanorattles by advanced transmission electron microscopy (TEM) and small-angle X-ray scattering (SAXS). Optical absorption and scattering cross-sections obtained from UV-vis-NIR spectroscopy quantitatively agree with finite-difference time-domain (FDTD) simulations based on the structural model derived from SAXS. The predictions of high and homogenous field enhancement are evidenced by scanning TEM electron energy loss spectroscopy (STEM-EELS) measurement on single-particle level. Thus, comprehensive understanding of structural and optical properties is achieved for this class of nanoparticles, paving the way for photonic applications where a defined and robust unit cell is crucial.

The stabilization of water/air, water/oil and water/solid interfaces by Janus particles with polystyrene (PS) and poly(methacrylic acid) (PMAA) hemispheres was systematically investigated. The stabilization of these interfaces is of relevance for the formulation of foams, emulsions and dispersions. The Janus particles were prepared from micellar solutions of polystyrene-b-polyisoprene-b-poly(tert-butyl methacrylate) (PS-PI-PtBMA) triblock terpolymers by selective cross-linking of the polyisoprene domain on a multi-gram scale, followed by hydrolysis of the PtBMA block. For the investigation of water/oil-emulsions a series of hydrophobic oils (paraffin oil, xylene, peanut oil, isopropyl myristate) with increasing polarity was selected. We found that the Janus particles do not stabilize the air/water interface and efficiently suppress foaming. The Janus particles showed a pronounced selectivity in their efficiency to stabilize w/o-emulsions. Isopropyl myristate water/oil emulsions could be stabilized up to several months with only 0.2 wt.-% of Janus particles. In general, interfaces with air and very hydrophobic oils and pigments were not stabilized, indicating that a certain polarity and interfacial mobility is necessary for an efficient stabilization by Janus particles. The Janus particles can be used as sole stabilizers in the soap-free emulsion polymerization of styrene/n-butyl acrylate or methyl methacrylate/n-butyl acrylate under commercially relevant semi-batch reaction conditions. Polymer coatings prepared from Janus particle-stabilized acrylate and styrene/acrylate dispersions showed a significantly reduced surface hydrophobicity as compared to surfactant-stabilized dispersions.