Surface Topology of Redox- and Thermoresponsive Nanogel Droplets.

Hydrogels are usually depicted as a homogenous polymer block with a distinct surface. While defects in the polymer structure are looked into frequently, structural irregularities on the hydrogel surface are often neglected. In this work, thin hydrogel layers of ≈100 nm thickness (nanogels) are synthesized and characterized for their structural irregularities, as they represent the surface of macrogels. The nanogels contain a main-chain responsiveness (thermo responsive) and a responsiveness in the cross-linking points (redox responsive). By combining data from ellipsometry using box-model and two-segment-model analysis, as well as atomic force microscopy, a more defined model of the nanogel surface can be developed. Starting with a more densely cross-linked network at the silica wafer surface, the density of cross-linking gradually decreases toward the hydrogel-solvent interface. Thermo-responsive behavior of the main chain affects the entire network equally as all chain segments change solubility. Cross-linker-based redox-responsiveness, on the other hand, is only governed by the inner, more cross-linked layers of the network. Such dual responsive nanogels hence allow for developing a more detailed model of a hydrogel surface from free radical polymerization. It provides a better understanding of structural defects in hydrogels and how they are affected by responsive functionalities.

Nominally identical microplastic models differ greatly in their particle-cell interactions.

Due to the abundance of microplastics in the environment, research about its possible adverse effects is increasing exponentially. Most studies investigating the effect of microplastics on cells still rely on commercially available polystyrene microspheres. However, the choice of these model microplastic particles can affect the outcome of the studies, as even nominally identical model microplastics may interact differently with cells due to different surface properties such as the surface charge. Here, we show that nominally identical polystyrene microspheres from eight different manufacturers significantly differ in their ζ-potential, which is the electrical potential of a particle in a medium at its slipping plane. The ζ-potential of the polystyrene particles is additionally altered after environmental exposure. We developed a microfluidic microscopy platform to demonstrate that the ζ-potential determines particle-cell adhesion strength. Furthermore, we find that due to this effect, the ζ-potential also strongly determines the internalization of the microplastic particles into cells. Therefore, the ζ-potential can act as a proxy of microplastic-cell interactions and may govern adverse effects reported in various organisms exposed to microplastics.

Dynamic matrices with DNA-encoded viscoelasticity for cell and organoid culture.

Three-dimensional cell and organoid cultures rely on the mechanical support of viscoelastic matrices. However, commonly used matrix materials lack control over key cell-instructive properties. Here we report on fully synthetic hydrogels based on DNA libraries that self-assemble with ultrahigh-molecular-weight polymers, forming a dynamic DNA-crosslinked matrix (DyNAtrix). DyNAtrix enables computationally predictable and systematic control over its viscoelasticity, thermodynamic and kinetic parameters by changing DNA sequence information. Adjustable heat activation allows homogeneous embedding of mammalian cells. Intriguingly, stress-relaxation times can be tuned over four orders of magnitude, recapitulating mechanical characteristics of living tissues. DyNAtrix is self-healing, printable, exhibits high stability, cyto- and haemocompatibility, and controllable degradation. DyNAtrix-based cultures of human mesenchymal stromal cells, pluripotent stem cells, canine kidney cysts and human trophoblast organoids show high viability, proliferation and morphogenesis. DyNAtrix thus represents a programmable and versatile precision matrix for advanced approaches to biomechanics, biophysics and tissue engineering.

Dynamic wetting properties of PDMS pseudo-brushes: Four-phase contact point dynamics case.

We investigate the wetting properties of PDMS (Polydimethylsiloxane) pseudo-brush anchored on glass substrates. These PDMS pseudo-brushes exhibit a significantly lower contact angle hysteresis compared to hydrophobic silanized substrates. The effect of different molar masses of the used PDMS on the wetting properties seems negligible. The surface roughness and thickness of the PDMS pseudo-brush are measured by atomic force microscopy and x-ray reflectivity. The outcome shows that these surfaces are extremely smooth (topologically and chemically), which explains the reduction in contact angle hysteresis. These special features make this kind of surfaces very useful for wetting experiments. Here, the dynamics of the four-phase contact point are studied on these surfaces. The four-phase contact point dynamics on PDMS pseudo-brushes deviate substantially from its dynamics on other substrates. These changes depend only a little on the molar mass of the used PDMS. In general, PDMS pseudo-brushes increase the traveling speed of four-phase contact point on the surface and change the associated power law of position vs time.

Critical analysis of adhesion work measurements from AFM-based techniques for soft contact.

HYPOTHESIS: The work of adhesion is a thermodynamic quantity that is frequently measured by atomic force microscopy (AFM). Determination of the work of adhesion requires quasi-equilibrium measurements, where we address the question of to what extent atomic force microscopy qualifies for quasi-equilibrium measurements. EXPERIMENT: To measure the work of adhesion, we combined soft colloidal probe AFM (SCP AFM) with reflection interference contrast microscopy (RICM). This allowed us to extract the work of adhesion either from the pull-off force or from the contact radius. With these methods, we investigated the adhesion behavior of poly(N-isopropylacrylamide) (PNIPAM) polymer brushes in the swollen and solvent-induced collapsed state by systematically analyzing contact radii and adhesive forces. FINDINGS: In the swollen state, the adhesion to the PNIPAM brush was fivefold larger and exhibited significant time dependencies when measured with SCP AFM. A strong rate dependence of the pull-off force method was indicative of a non-equilibrium process. In order to reliably determine the equilibrium work of adhesion, the contact radius method was found to be the better because it is not rate dependent. Our work highlights the important benefits of using optical measurements to determine the contact radius when deriving the works of adhesion between colloidal probes and polymer brush surfaces.

Influence of the Atmosphere on the Wettability of Polymer Brushes.

Polymer brushes, i.e., end-tethered polymer chains on substrates, are sensitive to adaptation, e.g., swelling, adsorption, and reorientation of the surface molecules. This adaptation can originate from a contacting liquid or atmosphere for partially wetted substrates. The macroscopic contact angle of the aqueous drop can depend on both adaptation mechanisms. We analyze how the atmosphere around an aqueous droplet determines the resulting contact angle of the wetting droplet on polymer brush surfaces. Poly(N-isopropylacrylamide) (PNiPAAm)-based brushes are used due to their exceptional sensitivity to solvation and liquid mixture composition. We develop a method that reliably measures wetting properties when the drop and the surrounding atmosphere are not in equilibrium, e.g., when evaporation and condensation tend to contaminate the liquid of the drop and the atmosphere. For this purpose, we use a coaxial needle in the droplet, which continuously exchanges the wetting liquid, and in addition, we constantly exchange the almost saturated atmosphere. Depending on the wetting history, PNiPAAm can be prepared in two states, state A with a large water contact angle (∼65°) and state B with a small water contact angle (∼25°). With the coaxial needle, we can demonstrate that the water contact angle of a sample in state B significantly increases by ∼30° when a water-free atmosphere is almost saturated with ethanol, compared to an ethanol-free atmosphere at 50% relative humidity. For a sample in state A, the relative humidity has little influence on the water contact angle.

Repulsive Interactions of Eco-corona-Covered Microplastic Particles Quantitatively Follow Modeling of Polymer Brushes.

The environmental fate and toxicity of microplastic particles are dominated by their surface properties. In the environment, an adsorbed layer of biomolecules and natural organic matter forms the so-called eco-corona. A quantitative description of how this eco-corona changes the particles' colloidal interactions is still missing. Here, we demonstrate with colloidal probe-atomic force microscopy that eco-corona formation on microplastic particles introduces a compressible film on the surface, which changes the mechanical behavior. We measure single particle-particle interactions and find a pronounced increase of long-range repulsive interactions upon eco-corona formation. These force-separation characteristics follow the Alexander-de Gennes (AdG) polymer brush model under certain conditions. We further compare the obtained fitting parameters to known systems like polyelectrolyte multilayers and propose these as model systems for the eco-corona. Our results show that concepts of fundamental polymer physics, like the AdG model, also help in understanding more complex systems like biomolecules adsorbed to surfaces, i.e., the eco-corona.

Molecular Transport within Polymer Brushes: A FRET View at Aqueous Interfaces.

Molecular permeability through polymer brush chains is implicated in surface lubrication, wettability, and solute capture and release. Probing molecular transport through polymer brushes can reveal information on the polymer nanostructure, with a permeability that is dependent on chain conformation and grafting density. Herein, we introduce a brush system to study the molecular transport of fluorophores from an aqueous droplet into the external "dry" polymer brush with the vapour phase above. The brushes consist of a random copolymer of N-isopropylacrylamide and a Förster resonance energy transfer (FRET) donor-labelled monomer, forming ultrathin brush architectures of about 35 nm in solvated height. Aqueous droplets containing a separate FRET acceptor are placed onto the surfaces, with FRET monitored spatially around the 3-phase contact line. FRET is used to monitor the transport from the droplet to the outside brush, and the changing internal distributions with time as the droplets prepare to recede. This reveals information on the dynamics and distances involved in the molecular transport of the FRET acceptor towards and away from the droplet contact line, which are strongly dependent on the relative humidity of the system. We anticipate our system to be extremely useful for studying lubrication dynamics and surface droplet wettability processes.

Concentration gradients in evaporating binary droplets probed by spatially resolved Raman and NMR spectroscopy.

Understanding the evaporation process of binary sessile droplets is essential for optimizing various technical processes, such as inkjet printing or heat transfer. Liquid mixtures whose evaporation and wetting properties may differ significantly from those of pure liquids are particularly interesting. Concentration gradients may occur in these binary droplets. The challenge is to measure concentration gradients without affecting the evaporation process. Here, spectroscopic methods with spatial resolution can discriminate between the components of a liquid mixture. We show that confocal Raman microscopy and spatially resolved NMR spectroscopy can be used as complementary methods to measure concentration gradients in evaporating 1-butanol/1-hexanol droplets on a hydrophobic surface. Deuterating one of the liquids allows analysis of the local composition through the comparison of the intensities of the C­H and C­D stretching bands in Raman spectra. Thus, a concentration gradient in the evaporating droplet was established. Spatially resolved NMR spectroscopy revealed the composition at different positions of a droplet evaporating in the NMR tube, an environment in which air exchange is less pronounced. While not being perfectly comparable, both methods­confocal Raman and spatially resolved NMR experiments­show the presence of a vertical concentration gradient as 1-butanol/1-hexanol droplets evaporate.

Mechanofluorescent Polymer Brush Surfaces that Spatially Resolve Surface Solvation.

Polymer brushes, consisting of densely end-tethered polymers to a surface, can exhibit rapid and sharp conformational transitions due to specific stimuli, which offer intriguing possibilities for surface-based sensing of the stimuli. The key toward unlocking these possibilities is the development of methods to readily transduce signals from polymer conformational changes. Herein, we report on single-fluorophore integrated ultrathin (<40 nm) polymer brush surfaces that exhibit changing fluorescence properties based on polymer conformation. The basis of our methods is the change in occupied volume as the polymer brush undergoes a collapse transition, which enhances the effective concentration and aggregation of the integrated fluorophores, leading to a self-quenching of the fluorophores' fluorescence and thereby reduced fluorescence lifetimes. By using fluorescence lifetime imaging microscopy, we reveal spatial details on polymer brush conformational transitions across complex interfaces, including at the air-water-solid interface and at the interface of immiscible liquids that solvate the surface. Furthermore, our method identifies the swelling of polymer brushes from outside of a direct droplet (i.e., the polymer phase with vapor above), which is controlled by humidity. These solvation-sensitive surfaces offer a strong potential for surface-based sensing of stimuli-induced phase transitions of polymer brushes with spatially resolved output in high resolution.

Elasticity-to-Capillarity Transition in Soft Substrate Deformation.

Whereas capillarity controls fluid dynamics at submillimeter scale and elasticity determines the mechanics of rigid solids, their coupling governs elastocapillary deformations on soft solids. Here, we directly probed the deformations on soft substrates induced by sessile nanodroplets. The wetting ridge created around the contact line and the dimple formed underneath the nanodroplet were imaged with a high spatial resolution using atomic force microscopy. The ridge height nonmonotonically depends on the substrate stiffness, and the dimple depth nonlinearly depends on the droplet size. The capillarity of the substrate overcomes the elasticity of the substrate in dominating the deformations when the elastocapillary length is approximately larger than the droplet contact radius, showing an experimental observation of the elasticity-to-capillarity transition. This study provides an experimental approach to investigate nanoscale elastocapillarity, and the insights have the potential to kick-off future work on the fundamentals of solid mechanics.

Flow profiles near receding three-phase contact lines: influence of surfactants.

The dynamics of wetting and dewetting is largely determined by the velocity field near the contact lines. For water drops it has been observed that adding surfactant decreases the dynamic receding contact angle even at a concentration much lower than the critical micelle concentration (CMC). To better understand why surfactants have such a drastic effect on drop dynamics, we constructed a dedicated setup on an inverted microscope, in which an aqueous drop is held stationary while the transparent substrate is moved horizontally. Using astigmatism particle tracking velocimetry, we track the 3D displacement of the tracer particles in the flow. We study how surfactants alter the flow dynamics near the receding contact line of a moving drop for capillary numbers in the order of 10-6. Even for surfactant concentrations c far below the critical micelle concentration (c ≪ CMC) Marangoni stresses change the flow drastically. We discuss our results first in a 2D model that considers advective and diffusive surfactant transport and deduce estimates of the magnitude and scaling of the Marangoni stress from this. Modeling and experiment agree that a tiny gradient in surface tension of a few µN m-1 is enough to alter the flow profile significantly. The variation of the Marangoni stress with the distance from the contact line suggests that the 2D advection-diffusion model has to be extended to a full 3D model. The effect is ubiquitous, since surfactant is present in many technical and natural dewetting processes either deliberately or as contamination.

Memory effects in polymer brushes showing co-nonsolvency effects.

Densely packed polymer chains grafted to a substrate, especially polymer brushes, have been studied intensively. Of special interest are systems that react to changes in external conditions or"remember" previous conditions. With this focus, we explore the properties of PNiPAAm brushes and relate published work to own results. The co-nonsolvency effect leads to a collapse of a PNiPAAm brush for a certain mixing ratio of ethanol in water. This also influences the wetting behavior of PNiPAAm brushes. We show that through prewetting of a brush with different liquids (water and ethanol), the contact angle of subsequent water drops changes significantly. To explain this change, the swelling of the brush was investigated with spectroscopic ellipsometry and the orientation of the molecules at the surface with sum-frequency generation (SFG). Only little change in swelling was found. The SFG measurements reveal in the ethanol prewetted case a well ordered hydrophobic methyl layer at the interface, which is consistent with the contact angle measurement.

Mechano-tunable chiral metasurfaces via colloidal assembly.

Dynamic control of circular polarization in chiral metasurfaces is being used in many photonic applications. However, simple fabrication routes to create chiral materials with considerable and fully tunable chiroptical responses at visible and near-infrared wavelengths are scarce. Here, we describe a scalable bottom-up approach to construct cross-stacked nanoparticle chain arrays that have a circular dichroism of up to 11°. Due to their layered design, the strong superchiral fields of the inter-layer region are accessible to chiral analytes, resulting in a tenfold enhanced sensitivity in a chiral sensing proof-of-concept experiment. In situ restacking and local mechanical compression enables full control over the entire set of circular dichroism characteristics, namely sign, magnitude and spectral position. Strain-induced reconfiguration opens up an intriguing route towards actively controlled pixel arrays using local deformation, which fosters continuous polarization engineering and multi-channel detection.

What Can Probing Liquid-Air Menisci Inside Nanopores Teach Us About Macroscopic Wetting Phenomena?

Solid surfaces with excellent nonwetting ability have drawn significant interest from interfacial scientists and engineers. While much effort was devoted to investigating macroscopic wetting phenomena on nonwetting surfaces, the otherwise microscopic wetting has received less attention, and the surface/interface properties at the microscopic scale are not well resolved and correlated with the macroscopic wetting behavior. Herein, we first characterize the nanoscopic morphology and effective stiffness of liquid-air interfaces inside nanopores (nanomenisci) on diverse nonwetting nanoporous surfaces underneath water droplets using atomic force microscopy. Detailed three-dimensional imaging of the droplet-surface contact region reveals that water only slightly penetrates into the nanopores, allowing for quantitative prediction of the macroscopic contact angle using the Cassie-Baxter model. By gradually increasing the scanning force, we observe incrementally wetting of nanopores by water, and dewetting occurs when the force is lowered again, exhibiting reversible wetting-dewetting transitions. Further, nanoindentation measurements demonstrate that the nanomenisci show apparent elastic deformation and size-dependent effective stiffness at small indenting forces. Finally, we correlate the effective stiffness of the nanomenisci with the transition from complete rebound to partial rebound for impinging droplets on nanoporous surfaces. Our study suggests that probing the physical properties of the liquid-air menisci at the nanoscale is essential to rationalize macroscopic static and dynamic wetting phenomena on structured surfaces.

Embedment of Quantum Dots and Biomolecules in a Dipeptide Hydrogel Formed In Situ Using Microfluidics.

As low-molecular-weight hydrogelators, dipeptide hydrogel materials are suited for embedding multiple organic molecules and inorganic nanoparticles. Herein, a simple but precisely controllable method is presented that enables the fabrication of dipeptide-based hydrogels by supramolecular assembly inside microfluidic channels. Water-soluble quantum dots (QDs) as well as premixed porphyrins and a dipeptide in dimethyl sulfoxide (DMSO) were injected into a Y-shaped microfluidic junction. At the DMSO/water interface, the confined fabrication of a dipeptide-based hydrogel was initiated. Thereafter, the as-formed hydrogel flowed along a meandering microchannel in a continuous fashion, gradually completing gelation and QD entrapment. In contrast to hydrogelation in conventional test tubes, microfluidically controlled hydrogelation led to a tailored dipeptide hydrogel regarding material morphology and nanoparticle distribution.

Sperm-Driven Micromotors Moving in Oviduct Fluid and Viscoelastic Media.

Biohybrid micromotors propelled by motile cells are fascinating entities for autonomous biomedical operations on the microscale. Their operation under physiological conditions, including highly viscous environments, is an essential prerequisite to be translated to in vivo settings. In this work, a sperm-driven microswimmer, referred to as a spermbot, is demonstrated to operate in oviduct fluid in vitro. The viscoelastic properties of bovine oviduct fluid (BOF), one of the fluids that sperm cells encounter on their way to the oocyte, are first characterized using passive microrheology. This allows to design an artificial oviduct fluid to match the rheological properties of oviduct fluid for further experiments. Sperm motion is analyzed and it is confirmed that kinetic parameters match in real and artificial oviduct fluids, respectively. It is demonstrated that sperm cells can efficiently couple to magnetic microtubes and propel them forward in media of different viscosities and in BOF. The flagellar beat pattern of coupled as well as of free sperm cells is investigated, revealing an alteration on the regular flagellar beat, presenting an on-off behavior caused by the additional load of the microtube. Finally, a new microcap design is proposed to improve the overall performance of the spermbot in complex biofluids.

Versatile high-speed confocal microscopy using a single laser beam.

We present a new flexible high speed laser scanning confocal microscope and its extension by an astigmatism particle tracking velocimetry (APTV) device. Many standard confocal microscopes use either a single laser beam to scan the sample at a relatively low overall frame rate or many laser beams to simultaneously scan the sample and achieve a high overall frame rate. The single-laser-beam confocal microscope often uses a point detector to acquire the image. To achieve high overall frame rates, we use, next to the standard 2D probe scanning unit, a second 2D scan unit projecting the image directly onto a 2D CCD-sensor (re-scan configuration). Using only a single laser beam eliminates crosstalk and leads to an imaging quality that is independent of the frame rate with a lateral resolution of 0.235 µm. The design described here is suitable for a high frame rate, i.e., for frame rates well above the video rate (full frame) up to a line rate of 32 kHz. The dwell time of the laser focus on any spot in the sample (122 ns) is significantly shorter than those in standard confocal microscopes (in the order of milli- or microseconds). This short dwell time reduces phototoxicity and bleaching of fluorescent molecules. The new design opens up further flexibility and facilitates coupling to other optical methods. The setup can easily be extended by an APTV device to measure three dimensional dynamics while being able to show high resolution confocal structures. Thus, one can use the high resolution confocal information synchronized with an APTV dataset.

Gas-Phase Induced Marangoni Flow Causes Unstable Drop Merging.

The merging of drops plays a key role in many processes from simple rain to complex coating applications. In technical applications, often liquids with different surface tensions merge on a substrate like inkjet printing. For a suitable set of surface tensions, one drop can form a stable wetting film that is covering the other drop. Here, we explore the dynamics of driven wetting films and show a route toward their instability when these wetting films are driven by an external source of energy, which is Marangoni stress in our case. The wetting becomes unstable via a fingering instability and can be observed in various liquid combinations. The vapor of the liquid with the lower surface tension induces a Marangoni driven flow inside the other drop that pulls the wetting film. The concentration of the driving vapor can be controlled through the spreading velocity of the corresponding drop. We use this dependence to map out the characteristics of the instability. For very high or very low spreading velocities, no instability is observed. This is summarized in a stability diagram, which has three different regimes. A detailed analysis reveals a strong coupling of the characteristics of the fingering instability to the spreading velocity. The use of the spreading velocity as a control parameter is justified by a simplified 1D model that motivates how the spreading velocity controls the concentration profile of the second liquid vapor before and at contact. The strength of the Marangoni flow that drives the instability depends on the exposure time of the sitting drop to the vapor concentration profile around the spreading drop.