Smart microgels investigated by super-resolution fluorescence microscopy: influence of the monomer structure on the particle morphology.

In a recent publication [Bergmann et al. Phys. Chem. Chem. Phys., 2018, 20, 5074-5083] we presented a method which enables to investigate the morphology of microgels by superresolution fluorescence microscopy. Here, this method is applied to three microgel species, based on N-isopropylmethacrylamide (NIPMAM), N-n-propylacrylamide (NNPAM) and N-n-propylmethacrylamide (NNPMAM)) with 5, 7.5 and 10 mol% cross-linker, respectively. Super-resolution microscopy reveals differences of the network morphology of the synthesized particles showing the importance of the monomer structure.

Contrast variation SANS measurement of shell monomer density profiles of smart core-shell microgels.

The radial density profile of deuterated poly(N,n-propyl acrylamide) shell monomers within core-shell microgels has been studied by small-angle neutron scattering in order to shed light on the origin of their linear thermally-induced swelling. The poly(N-isopropyl methacrylamide) core monomers have been contrast-matched by the H2O/D2O solvent mixture, and the intensity thus provides a direct measurement of the spatial distribution of the shell monomers. Straightforward modelling shows that their structure does not correspond to the expected picture of a well-defined external shell. A multi-shell model solved by a reverse Monte Carlo approach is then applied to extract the monomer density as a function of temperature and of the core crosslinking. It is found that most shell monomers fill the core at high temperatures approaching synthesis conditions of collapsed particles, forming only a dilute corona. As the core monomers tend to swell at lower temperatures, a skeleton of insoluble shell monomers hinders swelling, inducing the progressive linear thermoresponse.

Resolving the internal morphology of core-shell microgels with super-resolution fluorescence microscopy.

We investigate the internal morphology of smart core-shell microgels by super-resolution fluorescence microscopy exploiting a combination of 3D single molecule localization and structured illumination microscopy utilizing freely diffusing fluorescent dyes. This approach does not require any direct chemical labeling and does not perturb the network structure of these colloidal gels. Hence, it allows us to study the morphology of the particles with very high precision. We found that the structure of the core-forming seed particles is drastically changed by the second synthesis step necessary for making the shell, resulting in a core region with highly increased dye localization density. The present work shows that super-resolution microscopy has great potential with respect to the study of soft colloidal systems.

Hydration and Solvent Exchange Induced Swelling and Deswelling of Homogeneous Poly(N-isopropylacrylamide) Microgel Thin Films.

The investigation of the response kinetics of smart colloidal microgel films is crucial for their optimization to enable advanced applications. We study the classical thermoresponsive microgel model system N-isopropylacrylamide cross-linked with N,N'-methylenebisacrylamide. Without the typically used polyelectrolyte coating of the substrate, thin microgel films are prepared in a single spin-coating step. Atomic force microscopy measurements reveal an extremely dense packing, resulting in a homogeneous compact thin film of microgel particles. The hydration kinetics of these films in H2O and D2O atmospheres as well as the kinetics of the solvent exchange between both water species are investigated with in situ time-of-flight neutron reflectometry (TOF-NR) and in situ Fourier-transform infrared (FTIR) spectroscopy. With accounting for a nonconstant humid atmosphere, the intrinsic diffusion dynamics of water molecules into the thin microgel film are modeled and the specific time constant τ and the effective Flory-Huggins interaction parameter χeff are determined. Comparing the results in H2O and D2O atmospheres, TOF-NR and FTIR spectroscopy results show an increased affinity of the microgel films toward H2O as compared to D2O. From the FTIR spectroscopy data, we further identify different kinetics of intermolecular processes and order them according to their temporal evolution.

Spatial distribution of core monomers in acrylamide-based core-shell microgels with linear swelling behaviour.

The peculiar linear temperature-dependent swelling of core-shell microgels has been conjectured to be linked to the core-shell architecture combining materials of different transition temperatures. Here the structure of pNIPMAM-core and pNNPAM-shell microgels in water is studied as a function of temperature using small-angle neutron scattering with selective deuteration. Photon correlation spectroscopy is used to scrutinize the swelling behaviour of the colloidal particles and reveals linear swelling. Moreover, these experiments are also employed to check the influence of deuteration on swelling. Using a form-free multi-shell reverse Monte Carlo approach, the small-angle scattering data are converted into radial monomer density profiles. The comparison of 'core-only' particles consisting of identical cores to fully hydrogenated core-shell microgels, and finally to H-core/D-shell architectures unambiguously shows that core and shell monomers display gradient profiles with strong interpenetration, leading to cores embedded in shells which are bigger than their isolated 'core-only' precursor particles. This surprising result is further generalized to different core cross-linker contents, for temperature ranges encompassing both transitions. Our analysis demonstrates that the internal structure of pNIPMAM-core and pNNPAM-shell microgels is heterogeneous and strongly interpenetrated, presumably allowing only progressive core swelling at temperatures intermediate to both transition temperatures, thus promoting linear swelling behaviour.

Dynamics of proteins confined in non-ionic bicontinuous microemulsions: a FCS study.

In our present work we present an approach which allows one to confine proteins in structurally nearly identical bicontinuous microemulsions with systematically decreasing water domain size. It is shown that sub-diffusive behaviour occurs already at water domain sizes below 13 nm. However, above 13 nm normal diffusion is seen. Moreover, we compare protein diffusion in microemulsions to the transport of a much smaller fluorescent dye.

Temperature dependent self-organization of DMPC membranes promoted by intermediate amounts of the saponin aescin.

The plant-derived biosurfactant aescin is naturally present in many plants and is used for treatment of disorders such as varicose veins and inflammation of veins. The hemolytic activity of this saponin is attributed to its interaction with cholesterol in the red blood cell membrane. This work investigates the phase and aggregation behavior of saponin-containing model membranes consisting of the phospholipid 1,2-dimyristoyl-sn-glycero-3-phosphocholine (DMPC). The aescin concentrations studied range from 1 mol% to 7 mol% with respect to the total lipid content. The methods of choice to elucidate the structural picture are small-angle scattering of X-rays (SAXS) and neutrons (SANS) and cryogenic transmission electron microscopy (cryo-TEM). SANS and SAXS revealed that at lower aescin contents vesicular structures are conserved and vesicles tend to aggregate already at aescin contents of around 1 mol%. Aggregation and vesicle deformation effects are found to be stronger when the phospholipids are in the L [Formula: see text] phase. With increasing aescin content, mixed structures, i.e. aggregated and deformed vesicles and solubilized bilayer fragments, are present. This was proven for a sample with 4 mol% aescin by cryo-TEM. An increasing aescin amount leads to membrane decomposition and free standing bilayers which tend to build stacks at high temperature. These stacks are characterized by SAXS using the modified Caillé theory. Analyses and model dependent fitting reveal formation of well-defined structures beginning at 7 mol% aescin.

Swelling behaviour of core-shell microgels in H2O, analysed by temperature-dependent FTIR spectroscopy.

Stimuli-responsive microgels are colloidal particles and promising candidates for applications such as targeted drug delivery, matrices for catalysts, nanoactuators and smart surface coatings. To tailor the response, the architecture of microgels is of paramount importance with respect to these applications. Statistical copolymer microgels based on N-isopropylmethacrylamide (NiPMAM) and N-n-propylacrylamide (NnPAM) show a cooperative phase transition leading to a collapse at a specific temperature. Interestingly, some core-shell microgel particles reveal a linear response of the hydrodynamic radius with temperature. Such observations were made by photon correlation spectroscopy (PCS), which is limited to the diffusion properties dominated by the particle shell. In this work we investigate the molecular hydration within the network of microgels in H2O by temperature-dependent FTIR spectroscopy. The phase transition temperature was determined by the shift in frequency of the NH bending vibration in homopolymer and statistical copolymer microgels and the results are in accordance with those from PCS. In contrast, experiments on core-shell particles show a broadening and shift of the respective phase transition temperatures of the core and shell indicating an interaction of the core and shell polymers on a molecular level that extends far into the core. In conclusion, temperature-dependent FTIR spectroscopy is a convenient approach to elucidate the internal architecture of complex microgel particles in H2O.

Volume phase transition kinetics of smart N-n-propylacrylamide microgels studied by time-resolved pressure jump small angle neutron scattering.

The use of smart colloidal microgels for advanced applications critically depends on their response kinetics. We use pressure jump small angle neutron scattering with supreme time resolution to study the rapid volume phase transition kinetics of such microgels. Utilizing the pressure induced microphase separation inside the microgels we were able to resolve their collapse and swelling kinetics. While the collapse occurs on a time scale of 10 ms, the particle swelling turned out to be much faster. Photon correlation spectroscopy and static small angle neutron scattering unambiguously show, that the much slower collapse can be associated with the complex particle architecture exhibiting a loosely-crosslinked outer region and a denser inner core region. These insights into the kinetics of stimuli-responsive materials are of high relevance for their applications as nano-actuators, sensors or drug carriers. Moreover, the used refined pressure jump small angle neutron scattering technique is of broad interest for soft matter studies.

Interaction of the Saponin Aescin with Ibuprofen in DMPC Model Membranes.

In the present work, we study the interaction of the saponin aescin with the nonsteroidal anti-inflammatory drug (NSAID) ibuprofen at concentrations of 1.2-2.5 mM. These amounts are higher than those usually used for medication (10-300 µM) to show possible structures and formulations for orally absorbed drug delivery systems. It is shown how the interaction of both substances, separately or together, alters the thermotropic phase behavior of the 1,2-dimyristoyl- sn-glycero-3-phosphocholine (DMPC) bilayer in the presence of different amounts of aescin, ranging from 20 µM to 1 mM. The methods of choice are differential scanning calorimetry (DSC), and additionally wide-angle (WAXS) and small-angle X-ray scattering (SAXS). We found that these two additives, aescin and ibuprofen, alter the temperature-dependent structural appearance of the DMPC membrane depending on the aescin and drug content. The presence of the saponin and the drug become visible on different length scales, i.e., ranging from a global structural change to inner-membrane interactions. DSC reveals that the drug and saponin alter the cooperativity of the DMPC phase transition in a concentration-dependent manner. Furthermore, there is a significant difference between the drug-containing compared to the drug-free systems. By WAXS, we could resolve that aescin reverses the strong impact of ibuprofen on the diffraction peak of DMPC. Both molecules interact strongly with the phospholipid headgroups. This becomes visible in a changing area per lipid and shifting phase transition to higher temperatures. SAXS experiments reveal that the addition of ibuprofen leads to major morphological changes in the phospholipid bilayer. SAXS experiments performed on representative samples do not only cover the drug-saponin interaction within the bilayer from the structural perspective but also confirm the visually observed macroscopic concentration and temperature-dependent phase behavior. Vesicular shape of extruded samples is conserved at low aescin contents. At intermediate aescin content, aggregation between vesicles occurs, whereby the strength of aggregation is reduced by ibuprofen. At high aescin contents, DMPC bilayers are solubilized. The kind of formed structures depends on temperature and drug content. At low temperature, separated bilayer sheets are formed. Their size increases with ibuprofen in a concentration-dependent manner. At high temperature, the drug-free system reorganizes into stacked sheets. Whereas sheets at 5 mol % ibuprofen close to vesicles, the ones with 10 mol % of the drug increase massively in size. Altogether, ibuprofen was found to rather enhance than inhibit structural and thermotropic membrane modifications induced by the aescin on the DMPC model membrane.

Super-resolution optical microscopy resolves network morphology of smart colloidal microgels.

We present a new method to resolve the network morphology of colloidal particles in an aqueous environment via super-resolution microscopy. By localization of freely diffusing fluorophores inside the particle network we can resolve the three dimensional structure of one species of colloidal particles (thermoresponsive microgels) without altering their chemical composition through copolymerization with fluorescent monomers. Our approach utilizes the interaction of the fluorescent dye rhodamine 6G with the polymer network to achieve an indirect labeling. We calculate the 3D structure from the 2D images and compare the structure to previously published models for the microgel morphology, e.g. the fuzzy sphere model. To describe the differences in the data an extension of this model is suggested. Our method enables the tailor-made fabrication of colloidal particles which are used in various applications, such as paints or cosmetics, and are promising candidates for drug delivery, smart surface coatings, and nanocatalysis. With the precise knowledge of the particle morphology an understanding of the underlying structure-property relationships for various colloidal systems is possible.

Core-Shell Microgel-Based Surface Coatings with Linear Thermoresponse.

We study the swelling and shrinking behavior of core-shell microgels adsorbed on silicon wafers. In these systems, the core is made of cross-linked poly(N-isopropylmethacrylamide) and the shell consists of cross-linked poly(N-n-propylacrylamide). In suspension, these particles exhibit an extended linear swelling behavior in the temperature interval between the lower critical solution temperatures of the two polymers. Using ellipsometry and atomic force microscopy, we show that this linear response is also observed in the adsorbed state.

Smart Homopolymer Microgels: Influence of the Monomer Structure on the Particle Properties.

In this work, we compare the properties of smart homopolymer microgels based on N-n-propylacrylamide (NNPAM), N-isopropylacrylamide (NIPAM) and N-isopropylmethacrylamide (NIPMAM) synthesized under identical conditions. The particles are studied with respect to size, morphology, and swelling behavior using scanning electron and scanning force microscopy. In addition, light scattering techniques and fluorescent probes are employed to follow the swelling/de-swelling of the particles. Significant differences are found and discussed. Poly(N-n-propylacrylamide) (PNNPAM) microgels stand out due to their very sharp volume phase transition, whereas Poly(N-isopropylmethacrylamide) (PNIPMAM) particles are found to exhibit a more homogeneous network structure compared to the other two systems.

Phosphine-stabilised Au9 clusters interacting with titania and silica surfaces: the first evidence for the density of states signature of the support-immobilised cluster.

Chemically made, atomically precise phosphine-stabilized clusters Au9(PPh3)8(NO3)3 were deposited on titania and silica from solutions at various concentrations and the samples heated under vacuum to remove the ligands. Metastable induced electron spectroscopy was used to determine the density of states at the surface, and X-ray photoelectron spectroscopy for analysing the composition of the surface. It was found for the Au9 cluster deposited on titania that the ligands react with the titania substrate. Based on analysis using the singular value decomposition algorithm, the series of MIE spectra can be described as a linear combination of 3 base spectra that are assigned to the spectra of the substrate, the phosphine ligands on the substrate, and the Au clusters anchored to titania after removal of the ligands. On silica, the Au clusters show significant agglomeration after heat treatment and no interaction of the ligands with the substrate can be identified.