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Nanoporous materials relying on supramolecular liquid crystals (LCs) are excellent candidates for size- and charge-selective membranes. However, whether they can be manufactured using printing technologies remained unexplored so far. In this work, we develop a new approach for the fabrication of ordered nanoporous microstructures based on supramolecular LCs using two-photon laser printing. In particular, we employ photo-cross-linkable hydrogen-bonded complexes, that self-assemble into columnar hexagonal (Col h ) mesophases, as the base of our printable photoresist. The presence of photopolymerizable groups in the periphery of the molecules enables the printability using a laser. We demonstrate the conservation of the Col h arrangement and of the adsorptive properties of the materials after laser microprinting, which highlights the potential of the approach for the fabrication of functional nanoporous structures with a defined geometry. This first example of printable Col h LC should open new opportunities for the fabrication of functional porous microdevices with potential application in catalysis, filtration, separation, or molecular recognition.

Using the magnetocaloric effect in nanoparticles holds great potential for efficient refrigeration and energy conversion. The most promising candidate materials for tailoring the Curie temperature to room temperature are rare-earth-based magnetic nanoalloys. However, only few high-nuclearity lanthanide/transition-metal nanoalloys have been produced so far. Here we report, for the first time, the observation of magnetic response in spark-produced LaFeSi nanoalloys. The results suggest that these nanoalloys can be used to exploit the magnetocaloric effect near room temperature; such a finding can lead to the creation of unique multicomponent materials for energy conversion, thus helping toward the realization of a sustainable energy economy.

Many food preparations, pharmaceuticals, and cosmetics use water-in-oil (W/O) emulsions stabilized by phospholipids. Moreover, recent technological developments try to produce liposomes or lipid coated capsules from W/O emulsions, but are faced with colloidal instabilities. To explore these instability mechanisms, emulsification by sonication was applied in three cycles, and the sample stability was studied for 3 h after each cycle. Clearly identifiable temporal structures of instability provide evidence about the emulsion morphology: an initial regime of about 10 min is shown to be governed by coalescence after which Ostwald ripening dominates. Transport via molecular diffusion in Ostwald ripening is commonly based on the mutual solubility of the two phases and is therefore prohibited in emulsions composed of immiscible phases. However, in the case of water in oil emulsified by phospholipids, these form water-loaded reverse micelles in oil, which enable Ostwald ripening despite the low solubility of water in oil, as is shown for squalene. As is proved for the phospholipid dipalmitoylphosphatidylcholine (DPPC), concentrations below the critical aggregation concentration (CAC) form monolayers at the interfaces and smaller droplet sizes. In contrast, phospholipid concentrations above the CAC create complex multilayers at the interface with larger droplet sizes. The key factors for stable W/O emulsions in classical or innovative applications are first, the minimization of the phospholipids' capacity to form reversed micelles, and second, the adaption of the initial phospholipid concentration to the water content to enable an optimized coverage of phospholipids at the interfaces for the intended drop size.

A major challenge in nanotechnology is that of determining how to introduce green and sustainable principles when assembling individual nanoscale elements to create working devices. For instance, textile nanofinishing is restricted by the many constraints of traditional pad-dry-cure processes, such as the use of costly chemical precursors to produce nanoparticles (NPs), the high liquid and energy consumption, the production of harmful liquid wastes, and multistep batch operations. By integrating low-cost, scalable, and environmentally benign aerosol processes of the type proposed here into textile nanofinishing, these constraints can be circumvented while leading to a new class of fabrics. The proposed one-step textile nanofinishing process relies on the diffusional deposition of aerosol NPs onto textile fibers. As proof of this concept, we deposit Ag NPs onto a range of textiles and assess their antimicrobial properties for two strains of bacteria (i.e., Staphylococcus aureus and Klebsiella pneumoniae). The measurements show that the logarithmic reduction in bacterial count can get as high as ca. 5.5 (corresponding to a reduction efficiency of 99.96%) when the Ag loading is 1 order of magnitude less (10 ppm; i.e., 10 mg Ag NPs per kg of textile) than that of textiles treated by traditional wet-routes. The antimicrobial activity does not increase in proportion to the Ag content above 10 ppm as a consequence of a "saturation" effect. Such low NP loadings on antimicrobial textiles minimizes the risk to human health (during textile use) and to the ecosystem (after textile disposal), as well as it reduces potential changes in color and texture of the resulting textile products. After three washes, the release of Ag is in the order of 1 wt %, which is comparable to textiles nanofinished with wet routes using binders. Interestingly, the washed textiles exhibit almost no reduction in antimicrobial activity, much as those of as-deposited samples. Considering that a realm of functional textiles can be nanofinished by aerosol NP deposition, our results demonstrate that the proposed approach, which is universal and sustainable, can potentially lead to a wide number of applications.

The adsorption of phosphatidylcholines (PCs), dissolved in squalene or squalane as an organic phase, was studied at the interface with water. Using profile analysis tensiometry, the equilibrium adsorption isotherms, minimum molecular interfacial areas, and solubility limits were derived. For squalene, differences in PC solubility and interfacial adsorption were found, depending on PC saturation. Compared to saturated PCs, unsaturated PCs showed a 3-fold-lower interfacial density but up to a 28-fold-higher critical aggregation concentration (CAC). In addition, the solubility limit of unsaturated PC in squalene and in its saturated form squalane diverged by a factor of 739. These findings provided evidence for steric repulsion or π-π interactions of π bonds in both solvent and solute or both effects acting complementarily. In squalane, low solubilities but high interfacial densities were found for all investigated PCs. Changes in fatty acid chain lengths showed that the influence of the increases in entropy and enthalpy on solubility is much smaller than solvent/solute interactions. Oxidation products of squalene lowered the interfacial tension, but increasing concentrations of PC expelled them from the interface. The CAC of saturated PC was increased by oxidation products of squalene whereas that of unsaturated PCs was not. Our findings indicate that the oxidation of triglycerides in lipoprotein cores can lead to increased solubility of saturated phospholipids covering the lipoproteins, contributing to destabilization, coalescence, and terminally the formation of atherosclerotic plaques. The consideration of solvent/solute interactions in molecular modeling may contribute to the interfacial tension and the corresponding kinetic or thermodynamic stability of lipoproteins. Measured areas per molecule prove that PCs form monolayers of different interfacial densities at the squalene/water interface but multilayers at the squalane/water interface. These findings showed that combinations of solvent or solute saturation affect the outcome for nanoemulsions forming either expanded or condensed monolayers or multilayers.

We studied the effect of poly(ethylene glycol) (PEG) on the extrusion of large, multilamellar nanocapsules (also called liposomes or vesicles) through nanochannels with a length of 6 microm. For the generation of the nanocapsules, we used a lipid mixture with lecithin consisting of saturated and unsaturated fatty acids (dipalmitoylphosphatidylcholine (DPPC) and dioleoylphosphatidylcholine (DOPC)), cholesterol, and 2-8 mol % PEG linked to a lipid anchor (distearoylphosphatidylethanolamine (DSPE)) or the plain lipid anchor without PEG. An increase in PEG leads to a decrease of the critical tension for nanocapsule rupture (lysis tension) between 20-30%, whereas the pure lipid anchor does not produce any differences. We interpret these findings to be produced by a partial intrusion of the polymeric chain into the phospholipid bilayer of the nanocapsule which weakens its tensile strength. We evaluate statistically the discrepancies of lysis tensions found for different channels widths (50-100 nm) and two or four channels in series. Comparing our results on the flow resistance of either nanocapsules or pure water with lubrication theory, we find that the calculated viscous forces are not sufficient to account for the measured friction of nanocapsules. This shows that the nanocapsules are decelerated in the nanochannels by van der Waals interactions between channel and capsule walls and the intermediate water layer. The strength of these forces is 24 times higher for PEG and 94 times higher for the pure lipid anchor than the respective calculated viscous forces alone, showing that nanocapsule flow in nanochannels cannot be considered under the classical continuum assumption of the intermediate water layer.

Typical characterization of nanoparticle dispersion and compounding processes by dynamic light scattering (DLS) and TEM lack quantitative information on fractal structure, aggregation number, and specific surface area. In this work a synchrotron ultra-small-angle X-ray scattering (USAXS) investigation on diffusion flame and 'Aerosil' silica powders, as well as on their desagglomeration by high-pressure liquid dispersion (200-1400 bar) is presented. Primary particle size, polydispersity, and specific surface area are measured for powders, stirred-in dispersions, and after high-pressure processing with identical results, showing the in-situ applicability of USAXS. These parameters, as well as the hard aggregate mass fractal dimension, with typically Df = 2.15 representing reaction-limited cluster aggregation, are determined by synthesis process conditions. They are unchanged even at the highest hydrodynamic stresses; thus, neither comminution nor agglomerate restructuring nor re-agglomeration occurs. Fragmentation reflects in decreasing radii of gyration, which are compared to mobility equivalent radii from DLS in agreement with theory.

The influence of primary particle diameter and the degree of agglomeration of flame-made silica agglomerate suspensions in aqueous solutions is studied by high-pressure dispersion (up to 1500 bar) through a nozzle with a 125 microm inner diameter. These particles were produced (4-15 g/h) by oxidation of hexamethyldisiloxane (HMDSO) in a coflow diffusion flame reactor. Their average primary particle size (10-50 nm) and degree of agglomeration were controlled by varying the oxygen and precursor flow rates. The particles were characterized by nitrogen adsorption, electron microscopy, and small-angle X-ray scattering. Hydrodynamic stresses break up soft agglomerates and yield hard agglomerate sizes in the range of 100-180 nm, as characterized by dynamic light scattering. Soft agglomerates exhibited decreasing light scattering diameters with increasing dispersion pressure, while hard agglomerates were insensitive.