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The development of nanoscale composites with hierarchical architecture and complex anisotropies enables the fabrication of new classes of devices. Stretchable strain sensors have been developed in the past for applications in various fields such as wearable electronics and soft robotics, yet the sensing capacities of most of these sensors are independent of the direction of deformation. In the present work, we report on the preparation of a direction-sensitive strain sensor using the anisotropic optical properties of a monolayer of oriented plasmonic 1D nano-objects. Grazing incidence spraying (GIS) is used for depositing a monolayer of in-plane aligned silver nanowires with a controlled density on a deformable and transparent substrate. Using the selective excitation of transverse and longitudinal localized plasmon resonance modes of silver nanowires by polarized UV-visible-NIR spectroscopy, we show that the macroscopic anisotropic properties of the monolayer upon stretching are highly dependent on the stretching direction and light polarization. Measuring the polarized optical properties of the anisotropic thin films upon stretching thus allow for retrieving both the local strain and the direction of the deformation using a simple model.

Gold nanoparticles decorated with analyte recognition units can form the basis of colorimetric (bio)sensors. The presentation of those recognition units may play a critical role in determining sensor sensitivity. Herein, we use a model system to investigate the effect of the architecture of a polymeric linker that connects gold nanoparticles with the recognition units. Our results show that the number of the latter that can be adsorbed during the assembly of the colorimetric sensors depends on the linker topology. We also show that this may lead to substantial differences in colorimetric sensor performance, particularly in situations in which the interactions with the analyte are comparably weak. Finally, we discuss design principles for efficient colorimetric sensor materials based on our findings.

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 (

Over the past two decades, microfluidics has made significant contributions to material and life sciences, particularly via the design of nano-, micro- and mesoscale materials such as nanoparticles, micelles, vesicles, emulsion droplets, and microgels. Unmatched in control over a multitude of material parameters, microfluidics has also shed light on fundamental aspects of material design such as the early stages of nucleation and growth processes as well as structure evolution. Exemplarily, polymer hydrogel particles can be formed via microfluidics with exact control over size, shape, functionalization, compartmentalization, and mechanics that is hardly found in any other processing method. Interestingly, the utilization of microfluidics for material design largely focuses on the fabrication of single entities that act as reaction volume for organic and cell-free biosynthesis, cell mimics, or local environment for cell culturing. In recent years, however, hydrogel design has shifted towards structures that integrate a large variety of functions, e.g., to address the demands for sensing tasks in a complex environment or more closely mimicking architecture and organization of tissue by multiparametric cultures. Hence, this review provides an overview of recent literature that explores microfluidics for fabricating hydrogel materials that go well beyond common length scales as well as the structural and functional complexity of microgels necessary to produce hierarchical hydrogel structures. We focus on examples that utilize microfluidics to design microgel-based assemblies, on microfluidically made polymer microgels for 3D bioprinting, on hydrogels fabricated by microfluidics in a continuous fashion, like fibers, and on hydrogel structures that are shaped by microchannels.

Nanoparticle tracking analysis (NTA) is a widely used methodology to investigate nanoscale systems at the single species level. Here, we introduce the locally structured on-chip optofluidic hollow-core light cage, as a novel platform for waveguide-assisted NTA. This hollow waveguide guides light by the antiresonant effect in a sparse array of dielectric strands and includes a local modification to realize aberration-free tracking of individual nano-objects, defining a novel on-chip solution with properties specifically tailored for NTA. The key features of our system are (i) well-controlled nano-object illumination through the waveguide mode, (ii) diffraction-limited and aberration-free imaging at the observation site, and (iii) a high level of integration, achieved by on-chip interfacing to fibers. The present study covers all aspects relevant for NTA including design, simulation, implementation via 3D nanoprinting, and optical characterization. The capabilities of the approach to precisely characterize practically relevant nanosystems have been demonstrated by measuring the solvency-induced collapse of a nanoparticle system which includes polymer brush-based shells that react to changes in the liquid environment. Our study unlocks the advantages of the light cage approach in the context of NTA, suggesting its application in various areas such as bioanalytics, life science, environmental science, or nanoscale material science in general.

Polymer brush surfaces that alter their physical properties in response to chemical stimuli have the capacity to be used as new surface‐based sensing materials. For such surfaces, detecting the polymer conformation is key to their sensing capabilities. Herein, we report on FRET‐integrated ultrathin (, FRET chemistry was integrated within stimuli‐responsive polymer brush layers on planar substrates for spatial sensing of changing polymer conformations. Sensing was demonstrated for a variety of liquid mixture compositions, including high‐resolution observation of lateral differences in polymer conformation at immiscible liquid interfaces (see picture), thus offering great potential to be leveraged for new surface‐based sensing devices.

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. Stacked elastomeric arrays containing plasmonic nanoparticles show efficient chiral responses that can be fully controlled by mechanical compression and stack rotation. These simple layered materials may be useful modulators for photonic applications.

Functional elastomers with incredible toughness and stretchability are indispensable for applications in soft robotics and wearable electronics. Furthermore, coupled with excellent electrical and thermal properties, these materials are at the forefront of recent efforts toward widespread use in cutting-edge electronics and devices. Herein, we introduce a highly deformable eutectic-GaIn liquid metal alloy-embedded natural rubber (NR) architecture employing, for the first time, industrially viable solid-state mixing and vulcanization. Standard methods of rubber processing and vulcanization allow us to fragment and disperse liquid metals into submicron-sized droplets in cross-linked NR without compromising the elastic properties of the base matrix. In addition to substantial boosts in mechanical (strain at failure of up to ∼650%) and elastic (negligible hysteresis loss) performances, the tearing energy of the composite was enhanced up to 6 times, and a fourfold reduction in the crack growth rate was achieved over a control vulcanizate. Moreover, we demonstrate improved thermal conductivity and dielectric properties for the resulting composites. Therefore, this work provides a facile and scalable pathway to develop liquid metal-embedded soft elastomeric composites that could be instrumental toward potential applications in soft-matter engineering.

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.

We report on the surprising observation of a unique perforated lamellar (PL) morphology in a mixture of an asymmetric polystyrene-block-poly(4-vinylpyridine) (PS-b-P4VP) block copolymer and CdSe–Cd...

Electrofluorochromic (EFC) materials have gained extensive attention owing to their interesting modulations of fluorescence by an electric stimulus. However, the limited performances, especially th...

A scalable method for the assembly of oriented bacterial cellulose (BC) films is presented based on using wrinkled thin silicone substrates of meter-square size as templates during biotechnological...

The design of colloidal nanostructures as surface-enhanced Raman scattering (SERS) substrates requires control over both structural and optical characteristics. A widespread expectation is that the SERS efficiency depends crucially on whether the plasmonic excitation matches the exciting laser wavelength. However, also the balance between radiative (scattering) and non-radiative (absorbing) properties plays a major role, regarding both the efficiency of near field enhancement and the experimentally observed signal intensity. We present a study of the influence of mode-excitation matching and extinction characteristics for core/satellite superstructures, comprising gold nanotriangles decorated with small gold nanospheres. The variation of the core size and aspect ratio allowed tuning the main coupled mode between 700 and 800 nm, from off-resonant through resonant at 785 nm, as well as tuning extinction contributions, from dominantly absorbing to dominantly scattering. We observed additional gains of 1-2 orders of magnitude in signal enhancement, which were correlated to core size and diffuse optical properties. Our findings indicate a competition between SERS enhancement and increased scattering losses in larger assemblies. Thus, a balance of optical parameters is required for efficient SERS and the development of assemblies as advanced sensing devices.

Cononsolvency occurs if a mixture of two good solvents causes the collapse or demixing of polymers into a polymer-rich phase in a certain range of compositions of these two solvents. The better sol...

Because of its multiresponsive behavior upon variation of pH value, temperature, and ionic strength, poly­(N,N-dimethylaminoethyl methacrylate) (PDMAEMA) is an attractive candidate for adaptive surface coatings, especially in the field of biomedical sensors. In the presented article, PDMAEMA Guiselin brushes (5–12 nm, dry thickness) were prepared by the grafting-to approach, and the thermoresponsive UCST-type (upper critical solution temperature) behavior of the generated films, induced by [Fe­(CN)6]3–, was demonstrated for the first time. To clarify the specific mechanism of the temperature responsiveness, the molecular interactions between polymer chains and complex ions were studied by in situ infrared spectroscopy and in situ ellipsometry, showing wavenumber shifts of the ν­(CN) band due to ion pairing as well as changes of the ν­(OH) band intensity due to swelling. Conclusively, experimental data suggest that the electrostatic interaction between the two components plays a significant role in the thermoresponsive behavior of PDMAEMA films. Using this knowledge, the UCST of the PDMAEMA Guiselin brushes could be adjusted between 34.0 ± 1.2 °C at pH 8 and 40.7 ± 2.0 °C at pH 5.

Planet-satellite-type supracolloidal clusters represent a comparably young class of nanomaterials, which are unique with regard to structural order. In this prospective article, different approaches for their synthesis are discussed and compared. These synthetic methods enable the engineering of supracolloidal structural and adaptive properties, which in turn enables different emerging applications, such as in sensing and catalysis. These possibilities are explored on the basis of selected recent examples. A perspective about possible future developments is given at the end of this article.

The utilization of plasmonic energy in the form of heat, resonance energy, and/or hot carriers offers unique possibilities for various applications, like in catalytic and medical applications, due to their simple recyclability or administration. A common strategy to make this plasmonic energy available to the direct environment is to introduce conductive polymer coatings to transfer the energy and to increase the excitons lifetime. However, their practical use is limited due to the limited spectral match of gold with commonly used polymeric materials and semiconductors, the oxidation vulnerability of silver, and the short range of the required strong plasmonic interactions. To overcome these challenges, we developed the synthesis of conjugated polymer–gold–silver hybrid colloids that simultaneously enable silver as the central plasmonic material and prolong the internal relaxation by a heterojunction with a conductive polymer shell. The introduced thin gold layer focuses the plasmonic energy to the metal surface, enhancing and enabling the photocatalyzed polymerization of polypyrrole (PPy) while maintaining the plasmonic properties of silver. Hence, the introduced hybrid particles allow the foreseeable use of plasmonic energy in real-world applications via the strong plasmonics of silver and compatible conductive polymer shells as mediators.

Janus particles represent a unique group of patchy particles combining two or more different physical or chemical functionalities at their opposite sides. Especially, individual Janus particles (JPs) with both chemical and geometrical anisotropy as well as their assembled layers provide considerable advantages over the conventional monofunctional particles or surfactant molecules offering (a) a high surface-to-volume ratio; (b) high interfacial activity; (c) target controlling and manipulation of their interfacial activity by external signals such as temperature, light, pH, or ionic strength and achieving switching between stable emulsions and macro-phase separation; (d) recovery and recycling; (e) controlling the mass transport across the interface between the two phases; and finally (f) tunable several functionalities in one particle allowing their use either as carrier materials for immobilized catalytically active substances or, alternatively, their site-selective attachment to substrates keeping another functionality active for further reactions. All these advantages of JPs make them exclusive materials for application in (bio-)catalysis and (bio-)sensing. Considering “green chemistry” aspects covering biogenic materials based on either natural or fully synthetic biocompatible and biodegradable polymers for the design of JPs may solve the problem of toxicity of some existing materials and open new paths for the development of more environmentally friendly and sustainable materials in the very near future. Considering the number of contributions published each year on the topic of Janus particles in general, the number of contributions regarding their environmentally friendly and sustainable applications is by far smaller. This certainly pinpoints an important challenge and is addressed in this review article. The first part of the review focuses on the synthesis of sustainable biogenic or biocompatible Janus particles, as well as strategies for their recovery, recycling, and reusability. The second part addresses recent advances in applications of biogenic/biocompatible and non-biocompatible JPs in environmental and biotechnological fields such as sensing of hazardous pollutants, water decontamination, and hydrogen production. Finally, we provide implications for the rational design of environmentally friendly and sustainable materials based on Janus particles.

We investigated the temperature-dependent optical response of ordered lattices of noninteracting gold-core/poly(N-isopropylacrylamide)-shell nanoparticles (NPs), a system with proven photothermal a...

β-Sheets in natural spider dragline silk proteins are typically formed by polyalanine (An) as well as alanine-glycine (AG) and GGA sequences flanking these An regions. The hydrophobic β-sheet-rich ...

Noble metal hydro- and aerogels exhibit a variety of unique properties, including large surface areas, ultralow densities, and high porosities. While their potential use in various applications ran...