Multimodal Control of Liquid Crystalline Mesophases from Surfactants with Photoswitchable Tails

Non-invasive manipulation of the hierarchical structure of functional materials is a key challenge in the advancement of optoelectronics, energy conversion and storage devices and drug delivery systems. Here, using a combination of small-angle X-ray scattering and polarised optical microscopy, we decipher the various structure/self- assembly relationships of neutral surfactants bearing photoswitchable tails, which self-organise into a rich variety of lyotropic liquid crystalline mesophases. Facile, multimodal control of the nanoscale morphology of these single-component systems is achieved through: i) molecular structure, via careful selection of the alkyl tail/ethylene oxide headgroup lengths; ii) concentration; iii) temperature; and iv) photoisomerisation. The nanoscale architectures range from the weakly concentrated hyperswollen lamellar phases, the more common lyotropic lamellar and hexagonal phases, to pure thermotropic liquid crystals; all of which are accessible at room temperature. Photoisomerisation with UV light leads to the reversible destruction of the liquid crystalline phase, which can be spatially controlled through the use of a mask. This extensive study demonstrates the versatility of neutral photosurfactants and paves the way for them to be investigated for new applications, such as photoresponsive templates or drug delivery systems.Isaac Newton Trust/University of Cambridge Early Career Support Scheme grant. Irish Research Council EU COST action MP120

Magnetic measurement methods to probe nanoparticle–matrix interactions

Magnetic nanoparticles (MNPs) are key elements in several biomedical applications, e.g., in cancer therapy. Here, the MNPs are remotely manipulated by magnetic fields from outside the body to deliver drugs or generate heat in tumor tissue. The efficiency and success of these approaches strongly depend on the spatial distribution and quantity of MNPs inside a body and interactions of the particles with the biological matrix. These include dynamic processes of the MNPs in the organism such as binding kinetics, cellular uptake, passage through cell barriers, heat induction and flow. While magnetic measurement methods have been applied so far to resolve the location and quantity of MNPs for therapy monitoring, these methods can be advanced to additionally access these particle–matrix interactions. By this, the MNPs can further be utilized as probes for the physical properties of their molecular environment. In this review, we first investigate the impact of nanoparticle–matrix interactions on magnetic measurements in selected experiments. With these results, we then advanced the imaging modalities magnetorelaxometry imaging and magnetic microsphere tracking to spatially resolve particle–matrix interactions

Magnetic measurement methods to probe nanoparticle–matrix interactions

Magnetic nanoparticles (MNPs) are key elements in several biomedical applications, e.g., in cancer therapy. Here, the MNPs are remotely manipulated by magnetic fields from outside the body to deliver drugs or generate heat in tumor tissue. The efficiency and success of these approaches strongly depend on the spatial distribution and quantity of MNPs inside a body and interactions of the particles with the biological matrix. These include dynamic processes of the MNPs in the organism such as binding kinetics, cellular uptake, passage through cell barriers, heat induction and flow. While magnetic measurement methods have been applied so far to resolve the location and quantity of MNPs for therapy monitoring, these methods can be advanced to additionally access these particle–matrix interactions. By this, the MNPs can further be utilized as probes for the physical properties of their molecular environment. In this review, we first investigate the impact of nanoparticle–matrix interactions on magnetic measurements in selected experiments. With these results, we then advanced the imaging modalities magnetorelaxometry imaging and magnetic microsphere tracking to spatially resolve particle–matrix interactions

Inner structure and dynamics of microgels with low and medium crosslinker content prepared via surfactant-free precipitation polymerization and continuous monomer feeding approach

The preparation of poly(N-isopropylacrylamide) microgels via classical precipitation polymerization (batch method) and a continuous monomer feeding approach (feeding method) leads to different internal crosslinker distributions, i.e., from core–shell-like to a more homogeneous one. The internal structure and dynamics of these microgels with low and medium crosslinker concentrations are studied with dynamic light scattering and small-angle neutron scattering in a wide q-range below and above the volume phase transition temperature. The influence of the preparation method, and crosslinker and initiator concentration on the internal structure of the microgels is investigated. In contrast to the classical conception where polymer microgels possess a core–shell structure with the averaged internal polymer density distribution within the core part, a detailed view of the internal inhomogeneities of the PNIPAM microgels and the presence of internal domains even above the volume phase transition temperature, when polymer microgels are in the deswollen state, are presented. The correlation between initiator concentration and the size of internal domains that appear inside the microgel with temperature increase is demonstrated. Moreover, the influence of internal inhomogeneities on the dynamics of the batch- and feeding-microgels studied with neutron spin-echo spectroscopy is reported.TU Berlin, Open-Access-Mittel - 201

Towards the polymer nanocomposites based on hairy nanoparticles

Polymer nanocomposites exhibit versatility in their mechanical and structuralfeatures predominantly due to the huge surface area provided by nanoparticles.Interaction of the nanoparticles with polymer matrix selectively dictates theapplications suitable for a particular polymer nanocomposite system. Novelhybrid polymer-derived materials based on polymer grafted nanoparticles (NPs)can either be mixed with the polymer matrix or self-suspended without matrixpolymer. In both cases superior properties are demonstrated compared to thetraditional polymer nanocomposites, most notably by 1) incorporation of NPsinto polymers without “mixing problems” and 2) a wide range of the transportphenomena (from solids to viscous fluids). Hence, hairy nanoparticle-basednanocomposites are equipped to handle specific and unique challenges inmanufacturing and processing methods. It is known that the transportproperties can be tuned by altering the molecular design of hairynanoparticles (i.e., grafted polymer chemistry, NP concentrations, graftingdensity, and polymer molecular weight) and matrix polymer (e.g., molecularweight). In this article, we review the 1) most common methods of synthesizinghairy nanoparticle, 2) their microscopic dynamics and structural features and 3)some interesting applications of nanocomposite based on hairy nanoparticles.We discuss the effect of various parameters like nanoparticle size, molecularweight of the polymer etc. on the features of nanocomposites and itsimplications on the properties

Polymer dynamics under confinement

We review recent neutron scattering work and related results from simulation and complementary techniques focusing on the microscopic dynamics of polymers under confinement. Confinement is either realized in model porous materials or in polymer nanocomposites (PNC). The dynamics of such confined polymers is affected on the local segmental level, the level of entanglements as well as on global levels: (i) at the segmental level the interaction with the surface is of key importance. At locally repulsive surfaces compared to the bulk the segmental dynamics is not altered. Attractive surfaces slow down the segmental dynamics in their neighborhood but do not give rise to dead, glassy layers. (ii) Confinement generally has little effect on the inter-chain entanglements: both for weakly as well as for marginally confined polymers the reptation tube size is not changed. Only for strongly confined polymers disentanglement takes place. Similarly, in PNC at higher NP loading disentanglement phenomena are observed; in addition, at very high loading a transition from polymer caused topological constraints to purely geometrical constraints is observed. (iii) On the more global scale NSE experiments revealed important information on the nature of the interphase between adsorbed layer and bulk polymer. (iv) Polymer grafts at NP mutually confine each other, an effect that is most pronounced for one component NP. (v) Global diffusion of entangled polymers both in weakly and strongly attractive PNC is governed by the ratio of bottle-neck to chain size that characterizes the ‘entropic barrier’ for global diffusion