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Thin films made of deformable micro- and nano-units, such as biological membranes, polymer interfaces, and particle-laden liquid surfaces, exhibit a complex behavior during drying, with consequences for various applications like wound healing, coating technologies, and additive manufacturing. Studying the drying dynamics and structural changes of soft colloidal films thus holds the potential to yield valuable insights to achieve improvements for applications. In this study, we employ interfacial monolayers of core-shell microgels with varying degrees of softness as model systems and investigate their drying behavior on differently modified solid substrates (hydrophobic vs. hydrophilic). By leveraging on video microscopy, particle tracking, and thin film interference, we shed light on the interplay between microgel adhesion to solid surfaces and the immersion capillary forces that arise in the thin liquid film. We discovered that a dried replica of the interfacial microstructure can be more accurately achieved on a hydrophobic substrate relative to a hydrophilic one, particularly when employing softer colloids as opposed to harder counterparts. These observations are qualitatively supported by experiments with a thin film pressure balance which allows mimicking and controlling the drying process and by computer simulations with coarse-grained models., Comment: 36 pages of main manuscript with 9 figures and 1 table, 22 pages of Supporting Information with 21 figures and 4 tables

Microgels are often discussed as well-suited model system for soft colloids. In contrast to rigid spheres, the microgel volume and, coupled to this, the volume fraction in dispersion can be manipulated by external stimuli. This behavior is particularly interesting at high packings where phase transitions can be induced by external triggers such as temperature in case of thermoresponsive microgels. A challenge, however, is the determination of the real volume occupied by these deformable, soft objects and consequently, to determine the boundaries of the phase transitions. Here we propose core-shell microgels with a rigid silica core and a crosslinked, thermoresponsive poly-N-isopropylacrylamide (PNIPAM) shell with a carefully chosen shell-to-core size ratio as ideal model colloids to study fluid-solid transitions that are inducible by millikelvin changes in temperature. Specifically, we identify the temperature ranges where crystallization and melting occur using absorbance spectroscopy in a range of concentrations. Slow annealing from the fluid to the crystalline state leads to photonic crystals with Bragg peaks in the visible wavelength range and very narrow linewidths. Small-angle X-ray scattering is then used to confirm the structure of the fluid phase as well as the long-range order, crystal structure and microgel volume fraction in the solid phase. Thanks to the scattering contrasts and volume ratio of the cores with respect to the shells, the scattering data do allow for form factor analysis revealing osmotic deswelling at volume fractions approaching and also exceeding the hard sphere packing limit., Comment: 65 pages, 29 pages main manuscript (6 figures), 36 pages supporting information (26 figures)

Molecular chirality plays fundamental roles in biology. The chiral response of a molecule occurs at a specific spectral position, determined by its molecular structure. This fingerprint can be transferred to other spectral regions via the interaction with localized surface plasmon resonances of gold nanoparticles. Here, we demonstrate that molecular chirality transfer occurs also for plasmonic lattice modes, providing a very effective and tunable means to control chirality. We use colloidal self-assembly to fabricate non-close packed, periodic arrays of gold nanoparticles, which are embedded in a polymer film containing chiral molecules. In the presence of the chiral molecules, the SLRs become optically active, i.e. showing handedness-dependent excitation. Numerical simulations with varying lattice parameters show circular dichroism peaks shifting along with the spectral positions of the lattice modes, corroborating the chirality transfer to these collective modes. A semi-analytical model based on the coupling of molecular and plasmonic resonances rationalizes this chirality transfer., Comment: 13 pages, 6 Figures, full paper submitted, removed errors caused by word

The assembly of colloidal particles at liquid/liquid or air/liquid interfaces is a versatile procedure to create microstructured monolayers and study their behavior under compression. When combined with soft and deformable particles such as microgels, compression is used to tune not only the interparticle distance but also the underlying microstructure of the monolayer. So far, the great majority of studies on microgel-laden interfaces is conducted ex situ after transfer to solid substrates, for example, via Langmuir-Blodgett deposition. This type of analysis relies on the stringent assumption that the microstructure is conserved during transfer and subsequent drying. In this work, we couple a Langmuir trough to a custom-built small-angle light scattering setup to monitor colloidal monolayers in situ during compression. By comparing the results with ex situ and in situ microscopy measurements, we conclude that Langmuir-Blodgett deposition can alter the structural properties of the colloidal monolayers significantly., Comment: 44 pages in total, 33 pages of main manuscript with 10 figures

Micron-sized hard core-soft shell hybrid microgels are promising model systems for studies of soft matter as they enable in-situ optical investigations and their structures/morphologies can be engineered with a great variety. Yet, protocols that yield micron-sized core-shell microgels with a tailorable shell-to-core size ratio are rarely available. In this work, we report on the one-pot synthesis protocol for micron-sized silica-poly(N-isopropylacrylamide) core-shell microgels that has excellent control over the shell-to-core ratio. Small-angle light scattering and microscopy of 2- and 3-dimensional assemblies of the synthesized microgels confirm that the produced microgels are monodisperse and suitable for optical investigation even at high packing fractions., Comment: 32 pages, 12 figures, 22 pages and 5 figures for main manuscript

To explore dense packings of soft colloids, scattering experiments are ideal to access the structure factor. However, for soft microgels determination of the structure factor is difficult because of the low contrast of the polymer network and potential microgel interpenetration and deformation that change the form factor contribution. Here, we employ small-angle X-ray scattering (SAXS) to study soft, thermoresponsive microgels with poly-N-isopropylacrylamide (PNIPAM) shells and gold nanoparticle cores. The scattering of the gold cores dominates the scattering patterns and allows precise determination of the microgel volume fraction over a broad range of concentrations. At high volume fractions we find distinct patterns with sharp Bragg peaks allowing extraction of the structure factor and characterization of the phases combined with UV-Vis spectroscopy. The unique scattering contrast of our core-shell microgels combined with SAXS opens up new ways to investigate dense packings of soft microgels including in situ studies of phase transitions.

Depending on the volume fraction and interparticle interactions, colloidal suspensions can form different phases, ranging from fluids, crystals, and glasses to gels. For soft microgels that are made from thermoresponsive polymers, the volume fraction can be tuned by temperature, making them excellent systems to experimentally study phase transitions in dense colloidal suspensions. However, investigations of phase transitions at high particle concentration and across the volume phase transition temperature in particular, are challenging due to the deformability and possibility for interpenetration between microgels. Here, we investigate the dense phases of composite core-shell microgels that have a small gold core and a thermoresponsive microgel shell. Employing Ultra Small Angle X-ray Scattering, we make use of the strong scattering signal from the gold cores with respect to the almost negligible signal from the shells. By changing the temperature we study the freezing and melting transitions of the system in-situ. Using Bragg peak analysis and the Williamson-Hall method, we characterize the phase transitions in detail. We show that the system crystallizes into an rhcp structure with different degrees of in-plane and out-of-plane stacking disorder that increase upon particle swelling. We further find that the melting process is distinctly different, where the system separates into two different crystal phases with different melting temperatures and interparticle interactions.

By circumventing the optical diffraction limit, super-resolved fluorescence microscopies enable the study of larger cellular structures and molecular assemblies. However, fluorescence nanoscopy currently lacks the spatiotemporal resolution to resolve distances on the size of individual molecules and reveal the conformational fine structure and dynamics of molecular complexes. Here we establish FRET nanoscopy by combining colocalization STED microscopy with multiparameter FRET spectroscopy. We simultaneously localize donor and acceptor dyes of single FRET pairs with nanometer resolution and quantitatively measure intramolecular distances with sub-nanometer precision over a large dynamic range. While FRET provides isotropic 3D distance information, colocalization measures the projected distance onto the image plane. The combined information allows us to directly determine its 3D orientation using Pythagoras's theorem. Studying two DNA model systems and the human guanylate binding protein hGBP1, we demonstrate that FRET nanoscopy unravels the interplay between their spatial organization and local molecular conformation in a complex environment., Comment: Main Text (34 pages, 6 figures) with Supporting Information (90 pages, 29 figures, 20 tables)

We investigate the conformation, position, and dynamics of core-shell nanoparticles (CSNPs) composed of a silica core encapsulated in a cross-linked poly-N-isopropylacrylamide shell at a water-oil interface for a systematic range of core sizes and shell thicknesses. We first present a free-energy model that we use to predict the CSNP wetting behavior at the interface as a function of its geometrical and compositional properties in the bulk phases, which gives good agreement with our experimental data. Remarkably, upon knowledge of the polymer shell deformability, the equilibrium particle position relative to the interface plane, an often elusive experimental quantity, can be extracted by measuring its radial dimensions after adsorption. For all the systems studied here, the interfacial dimensions are always larger than in bulk and the particle core resides in a configuration wherein it just touches the interface or is fully immersed in water. Moreover, the stretched shell induces a larger viscous drag at the interface, which appears to depend solely on the interfacial dimensions, irrespective of the portion of the CSNP surface exposed to the two fluids. Our findings indicate that tailoring the architecture of CSNPs can be used to control their properties at the interface, as of interest for applications including emulsion stabilization and nanopatterning., Comment: 38 pages, 12 figures

The self-assembly of two nonionic surfactants, pentaethylene glycol monododecyl ether (C12E5) and n-dodecyl-{\ss}-maltoside ({\ss}-C12G2), in the presence of a purpose-synthesized silica sol of uniform particle size (diameter 16 nm) has been studied by adsorption measurements, dynamic light scattering and small-angle neutron scattering (SANS) using a H2O/D2O mixture matching the silica, in order to highlight the structure of the surfactant aggregates. For C12E5 strong aggregative adsorption onto the silica beads, with a high plateau value of the adsorption isotherm above the CMC was found. SANS measurements were made at a series of loadings, from zero surfactant up to maximum surface coverage. It is found that the spherical core-shell model nicely reproduces the SANS data up to and including the local maximum at q = 0.42 nm-1 but not in the Porod region of high q, indicating that the surface area of the adsorbed surfactant is underestimated by the model of a uniform adsorbed layer. A satisfactory representation of the entire scattering profiles is obtained with the model of micelle-decorated silica beads, indicating that C12E5 is adsorbed as spherical micellar aggregates. This behaviour is attributed to the high surface curvature of the silica which prevents an effective packing of the hydrophobic chains of the amphiphile in a bilayer configuration. For the maltoside surfactant {\ss}-C12G2 very weak adsorption on the silica beads was found. The SANS profile indicates that this surfactant forms oblate ellipsoidal micelles in the silica dispersion, as in the absence of the silica beads.