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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.
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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.
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Nanogéis , Oxirredução , Propriedades de Superfície , Nanogéis/química , Hidrogéis/química , Temperatura , Polietilenoglicóis/química , Tamanho da Partícula , Polietilenoimina/química , Microscopia de Força AtômicaRESUMO
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 (â¼65°) and state B with a small water contact angle (â¼25°). With the coaxial needle, we can demonstrate that the water contact angle of a sample in state B significantly increases by â¼30° 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.
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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.
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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.
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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.
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Microplásticos , Polímeros , Microscopia de Força Atômica , Plásticos , Propriedades de SuperfícieRESUMO
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.
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Ação Capilar , Elasticidade , Microscopia de Força Atômica/métodosRESUMO
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.
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Transferência Ressonante de Energia de Fluorescência , Polímeros , Polímeros/química , Soluções , Água , MolhabilidadeRESUMO
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.
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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.
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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.
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Oviductos , Espermatozoides , Animais , Bovinos , Meios de Cultura , Feminino , Humanos , Masculino , Reologia , ViscosidadeRESUMO
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.
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Despite strenuous research efforts for more than one century, identifying the magnitude and sign of the apparent line tension for a liquid-solid-gas system remains an elusive goal. Herein we accurately determine the apparent line tension from the size-dependent contact angle of sessile nanodrops on surfaces with different wetting properties via atomic force microscopy measurements and molecular dynamics simulations. We show that the apparent line tension has a magnitude of 10^{-11}-10^{-10} J/m, in good agreement with theoretical predictions. Furthermore, while it is positive and favors shorter contact lines for droplets on very lyophilic surfaces, the apparent line tension changes its sign and favors longer contact lines on surfaces with an apparent contact angle higher than a critical value. By analyzing the density and the potential energy of liquid molecules within the sessile droplet, we demonstrate that the sign of the apparent line tension is a thermodynamic property of the liquid-solid-gas system rather than the local effect of intermolecular interactions in the three-phase confluence region.
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Photoisomerization in some azobenzene-containing polymers (azopolymers) results in reversible solid-to-liquid transitions because trans- and cis-azopolymers have different glass transition temperatures. This property enables photoinduced healing and processing of azopolymers with high spatiotemporal resolution. However, a general lack of knowledge about the influence of the polymer structure on photoinduced reversible solid-to-liquid transitions hinders the design of such novel polymers. Herein, the synthesis and photoresponsive behavior of new azopolymers with different lengths of spacers between the polymer backbone and the azobenzene group on the side chain are reported. Azopolymers with no and 20 methylene spacers did not show photoinduced solid-to-liquid transitions. Azopolymers with 6 or 12 methylene spacers showed photoinduced solid-to-liquid transitions. This study demonstrates that spacers are essential for azopolymers with photoinduced reversible solid-to-liquid transitions, and thus, gives an insight into how to design azopolymers for photoinduced healing and processing.
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Controlling the organization of particles at liquid-gas interfaces usually relies on multiphasic preparations and external applied forces. Here, we show that micromolar amounts of a conventional cationic surfactant induce, in a single step, both adsorption and crystallization of various types of nanometer- to micrometer-sized anionic particles at the air-water interface, without any additional phase involved or external forces other than gravity. Contrary to conventional surfactant-induced particle adsorption through neutralization and hydrophobization at a surfactant concentration close to the critical micellar concentration (CMC), we show that in our explored concentration regime (CMC/1000-CMC/100), particles adsorb with a low contact angle and maintain most of their charge, leading to the formation of two-dimensional assemblies with different structures, depending on surfactant ( Cs) and particle ( Cp) concentrations. At low Cs and Cp, particles are repulsive and form disordered assemblies. Increasing Cp in this regime increases the number of adsorbed particles, leading to the formation of mm-sized, highly ordered polycrystalline assemblies because of the long-range attraction mediated by the collective deformation of the interface. Increasing Cs decreases the particle repulsion and therefore the interparticle distance within the monocrystalline domains. A further increase in Cs (≈CMC/10) leads to a progressive neutralization of particles accompanied by the formation of disordered structures, ranging from densely packed amorphous ones to loosely packed gels. These results emphasize a new role of the surfactant to mediate both adsorption and crystallization of particles at liquid-gas interfaces and provide a practical manner to prepare two-dimensional ordered colloidal assemblies in a remarkably robust and convenient manner.
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Soft elastic composite materials containing particulate rigid inclusions in a soft elastic matrix are candidates for developing soft actuators or tunable damping devices. The possibility to reversibly drive the rigid inclusions within such a composite together to a close-to-touching state by an external stimulus would offer important benefits. Then, a significant tuning of the mechanical properties could be achieved due to the resulting mechanical hardening. For a long time, it has been argued whether a virtual touching of the embedded magnetic particles with subsequent detachment can actually be observed in real materials, and if so, whether the process is reversible. Here, we present experimental results that demonstrate this phenomenon in reality. Our system consists of two paramagnetic nickel particles embedded at finite initial distance in a soft elastic polymeric gel matrix. Magnetization in an external magnetic field tunes the magnetic attraction between the particles and drives the process. We quantify our experimental results by different theoretical tools, i.e., explicit analytical calculations in the framework of linear elasticity theory, a projection onto simplified dipole-spring models, as well as detailed finite-element simulations. From these different approaches, we conclude that in our case the cycle of virtual touching and detachment shows hysteretic behavior due to the mutual magnetization between the paramagnetic particles. Our results are important for the design and construction of reversibly tunable mechanical damping devices. Moreover, our projection on dipole-spring models allows the formal connection of our description to various related systems, e.g., magnetosome filaments in magnetotactic bacteria.
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Supramolecular gels made from 2D building blocks are emerging as one of the novel multifunctional soft materials for various applications. This study reports on a class of supramolecular nanosheet gels formed through a reversible self-assembly process involving both intramolecular folding and intermolecular self-assembly of poly[oligo(ethylene glycol)-co-(phenyl-capped bithiophenes)]. Such hierarchical self-assembled structure allows the gels to switch between sol and gel states under either redox or thermostimulus. Moreover, the gels illustrate high Young's moduli, compared to their controls that are made from the same oligo(ethylene glycol) and phenyl-capped bithiophenes blocks but have highly covalent-crosslinked structures. The example might open a window for emerging supramolecular 2D materials to develop mechanically robust and stimuli-responsive soft materials without compromising their intrinsic functions.
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Nanoestruturas/química , Polímeros/química , Temperatura , Módulo de Elasticidade , Géis/química , Substâncias Macromoleculares/síntese química , Substâncias Macromoleculares/química , Estrutura Molecular , Oxirredução , Tamanho da Partícula , Polímeros/síntese química , Propriedades de SuperfícieRESUMO
To describe many-particle systems suspended in incompressible low-Reynolds-number fluids, effective hydrodynamic interactions can be introduced. Here, we consider particles embedded in elastic media. The effective elastic interactions between spherical particles are calculated analytically, inspired by the approach in the fluid case. Our experiments on interacting magnetic particles confirm the theory. In view of the huge success of the method in hydrodynamics, we similarly expect many future applications in the elastic case, e.g., for elastic composite materials.
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Stimuli-responsive microgels can be used as stabilizers for emulsions. However, the details of structure and the viscoelastic property of the microgel-laden interface are still not well-known. We synthesized fluorescently labeled microgels and used confocal microscopy to observe their arrangement at the water/oil interface. The microgels aggregated spontaneously at the interface, and the aggregated structure reorganized due to thermal motion. The structure of the interfacial layer formed by microgels depended on the microgel concentration at the interface. We suggest that the structure was controlled by the aggregation and adsorption of microgels at the interface. The interparticle separation between microgels at the interface decreased over time, implying a slow aging process of the microgels at the interface. Magnetic beads were introduced at the interface and used to trigger deformation of the microgel layer. Under compression and shear the microgels in the aggregated structure rearranged, leading to plastic deformation, and some elastic responses were also observed.
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We study the magneto-elastic coupling behavior of paramagnetic chains in soft polymer gels exposed to external magnetic fields. To this end, a laser scanning confocal microscope is used to observe the morphology of the paramagnetic chains together with the deformation field of the surrounding gel network. The paramagnetic chains in soft polymer gels show rich morphological shape changes under oblique magnetic fields, in particular a pronounced buckling deformation. The details of the resulting morphological shapes depend on the length of the chain, the strength of the external magnetic field, and the modulus of the gel. Based on the observation that the magnetic chains are strongly coupled to the surrounding polymer network, a simplified model is developed to describe their buckling behavior. A coarse-grained molecular dynamics simulation model featuring an increased matrix stiffness on the surfaces of the particles leads to morphologies in agreement with the experimentally observed buckling effects.