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In the realm of plasmonic catalytic systems, much attention has been devoted to the plasmon-derived mechanisms, yet the influence of nanoparticles' crystal facets in this type of processes has been sparsely investigated. In this work, we study the plasmon-assisted electrocatalytic CO2 reduction reaction using three different shapes of plasmonic Au nanoparticles - nanocube (NC), rhombic dodecahedron (RD) and octahedron (OC) - with three different exposed facets: {100}, {110} and {111}, respectively. These particles were synthesized with similar sizes and LSPR wavelengths to reveal the role of the facet more than other contributions to the plasmon-assisted reaction. Upon plasmon excitation, Au OCs exhibited nearly a doubling in the Faradaic efficiency of CO (FE(CO)) and a remarkable threefold enhancement in the partial current density of CO (j(CO)) compared to the non-illuminated response, NCs also demonstrated an improved performance under illumination. In contrast, Au RDs showed nearly the same performance in dark or light conditions. Temperature-dependent experiments ruled out heat as the main factor in the enhanced response of Au OCs and NCs. Large-scale atomistic simulations of the nanoparticles' electronic structure and electromagnetic modeling revealed higher hot carrier abundance and electric field enhancement on Au OCs and NCs compared to RDs. Abundant hot carriers on edges facilitate molecular activation, leading to enhanced selectivity and activity. Thus, OCs with the highest edge/facet ratio exhibited the strongest enhancement in FE(CO) and j(CO) upon illumination. This observation is further supported by plasmon-assisted H2 evolution reaction experiments. Our findings highlight the dominance of low coordinated sites over facets in plasmonic catalytic processes, providing valuable insights for designing more efficient catalysts for solar fuels production.

Heterovalent substitution of toxic lead is an increasingly popular design strategy to obtain environmentally sustainable variants of the exciting material class of halide perovskites. Perovskite nanocrystals (NCs) obtained through solution-based methods exhibit exceedingly high optical quality. Unfortunately, most of these synthesis routes still require reaction under inert gas and at very high temperatures. Herein we present a novel synthesis routine for lead-free double perovskite NCs. We combine hot injection and ligand-assisted reprecipitation (LARP) methods to achieve a low-temperature and ambient atmosphere-based synthesis for manganese-doped Cs_{2}NaBiCl_{6} NCs. Mn incorporation is critical for the otherwise non-emissive material, with a 9:1 Bi:Mn precursor ratio maximizing the bright orange photoluminescence (PL) and quantum yield (QY). Higher temperatures slightly increased the material's performance, yet NCs synthesized at room temperature were still emissive, highlighting the versatility of the synthetic approach. Furthermore, the NCs show excellent long-term stability in ambient conditions, facilitating additional investigations and energy-related applications.

The silicification of DNA origami structures increases their mechanical and thermal stability and provides chemical protection. So far, it is unclear how silicification affects the internal structure of the DNA origami and whether the whole DNA framework is embedded or if silica just forms an outer shell. By using in situ small-angle X-ray scattering (SAXS), we show that the net-cationic silica precursor TMAPS induces substantial condensation of the DNA origami, which is further enhanced by the addition of TEOS at early reaction times to an almost 10 % size reduction. We identify the SAXS Porod invariant as a reliable, model-free parameter for the evaluation of the amount of silica formation at a given time. Contrast matching of the DNA double helix Lorentzian peak reveals that silica growth also occurs on the inner surfaces of the origami. The less polar silica forming within the origami structure, replacing more than 40 % of the internal hydration water causes a hydrophobic effect: origami condensation. In the maximally condensed state, thermal stabilization of the origami up to 60 {\deg}C could be observed. If the reaction is driven beyond this point, the overall size of the silicified origami increases again due to more and more silica deposition on the DNA origami. DNA origami objects with flat surfaces show a strong tendency towards aggregation during silicification, presumably driven by the very same entropic forces causing condensation. Our studies provide novel insights into the silicification reaction and hints for the formulation of optimized reaction protocols.

Halide perovskite nanocrystals (NCs) have emerged as a promising material for applications ranging from light-emitting diodes (LEDs) to solar cells and photodetectors. Still, several issues impede the realization of the nanocrystals' full potential, most notably their susceptibility to degradation from environmental stress. This work demonstrates highly stable perovskite nanocrystals (NCs) with quantum yields as high as 95 % by exploiting a ligand-assisted copolymer nanoreactor-based synthesis. The organic ligands thereby serve a dual function by enhancing the uptake of precursors and passivating the NCs. The polymer micelles and ligands thus form a double protection system, shielding the encapsulated NCs from water-, heat- and UV-light-induced degradation. We demonstrate the optoelectronic integrability by incorporating the perovskite NCs as spectrally pure downconverters on top of a deep-blue-emitting organic LED. These results establish a way of stabilizing perovskite NCs for optoelectronics while retaining their excellent optical properties.

Photoresponsive materials feature properties that can be adjusted near- instantaneously, reversibly, and with high spatiotemporal precision, by light. There is considerable interest in maximising the degree of switching, and in measuring this degree during illumination in complex environments. We study the switching of photoresponsive lipid membranes that allow precise and reversible manipulation of membrane shape, permeability, and fluidity. Though these macroscopic photoresponses are clear, it is unclear how large the changes of trans/cis ratio are, and whether they can be improved. Here, we used small-angle X-ray scattering to measure the thickness of photoswitchable lipid membranes, and correlate thickness to trans/cis ratios. This revealed an unexpected dependency of photoswitching upon aqueous phase composition, highlighting smaller-than-expected photoswitching with deionized water, and showed thickness variations twice as large as previously observed. Soft X-rays can quantitatively isomerise photolipid membranes to the all- trans state: both enabling more powerful X-ray-based membrane control and underlining the role of high energy X-rays for observation-only soft matter experiments.

Halide perovskite nanocrystals (NCs) have shown impressive advances, exhibiting optical properties that outpace conventional semiconductor NCs, such as near-unity quantum yields and ultrafast radiative decay rates. Nevertheless, the NCs suffer even more from stability problems at ambient conditions and due to moisture than their bulk counterparts. Herein, we report a strategy of employing polymer micelles as nanoreactors for the synthesis of methylammonium lead trihalide perovskite NCs. Encapsulated by this polymer shell, the NCs display strong stability against water degradation and halide ion migration. Thin films comprising these NCs exhibit a more than 15-fold increase in lifespan in comparison to unprotected NCs in ambient conditions and even survive over 75 days of complete immersion in water. Furthermore, the NCs, which exhibit quantum yields of up to 63% and tunability of the emission wavelength throughout the visible range, show no signs of halide ion exchange. Additionally, heterostructures of MAPI and MAPBr NC layers exhibit efficient F\"orster resonance energy transfer (FRET), revealing a strategy for optoelectronic integration., Comment: This document is the unedited Author version of a Submitted Work that was subsequently accepted for publication in Nano Letters, copyright American Chemical Society after peer review. To access the final edited and published work see http://pubs.acs.org/articlesonrequest/AOR-W59yZfkIX7sG6Xuvp8NE

Engineering shape and interactions of nanoscopic building blocks allows for the assembly of rationally designed macroscopic three-dimensional (3D) materials with spatial accuracy inaccessible to top-down fabrication methods. Owing to its sequence-specific interaction, DNA is often used as selective binder to connect metallic nanoparticles into highly ordered lattices. Moreover, 3D crystals assembled entirely from DNA have been proposed and implemented with the declared goal to arrange guest molecules in predefined lattices. This requires design schemes that provide high rigidity and sufficiently large open guest space. We here present a DNA origami-based tensegrity triangle structure that assembles into a 3D rhombohedral crystalline lattice. We site-specifically place 10 nm and 20 nm gold particles within the lattice, demonstrating that our crystals are spacious enough to host e.g. ribosome-sized macromolecules. We validate the accurate assembly of the DNA origami lattice itself as well as the precise incorporation of gold particles by electron microscopy and small angle X-ray scattering (SAXS) experiments. Our results show that it is possible to create DNA building blocks that assemble into lattices with customized geometry. Site-specific hosting of nano objects in the transparent DNA lattice sets the stage for metamaterial and structural biology applications., Comment: 21 pages; 4 figures; supplementary information is included

Controlling size and shape of semiconducting nanocrystals advances nanoelectronics and photonics. Quantum confined, inexpensive, solution derived metal halide perovskites offer narrow band, color-pure emitters as integral parts of next-generation displays and optoelectronic devices. We use nanoporous silicon and alumina thin films as templates for the growth of perovskite nanocrystallites directly within device-relevant architectures without the use of colloidal stabilization. We find significantly blue shifted photoluminescence emission by reducing the pore size; normally infrared-emitting materials become visibly red, green-emitting materials cyan and blue. Confining perovskite nanocrystals within porous oxide thin films drastically increases photoluminescence stability as the templates auspiciously serve as encapsulation. We quantify the template-induced size of the perovskite crystals in nanoporous silicon with microfocus high-energy X-ray depth profiling in transmission geometry, verifying the growth of perovskite nanocrystals throughout the entire thickness of the nanoporous films. Low-voltage electroluminescent diodes with narrow, blue-shifted emission fabricated from nanocrystalline perovskites grown in embedded nanoporous alumina thin films substantiate our general concept for next generation photonic devices.

Basic understanding of biological membranes is of paramount importance as these membranes comprise the very building blocks of life itself. Cells depend in their function on a range of properties of the membrane, which are important for the stability and function of the cell, information and nutrient transport, waste disposal and finally the admission of drugs into the cell and also the deflection of bacteria and viruses. We have investigated the influence of ibuprofen on the structure and dynamics of L-alpha-phosphatidylcholine (SoyPC) membranes by means of grazing incidence small-angle neutron scattering (GISANS), neutron reflectometry and grazing incidence neutron spin echo spectroscopy (GINSES). From the results of these experiments we were able to determine that ibuprofen induces a two-step structuring behavior in the SoyPC films, where the structure evolves from the purely lamellar phase for pure SoyPC over a superposition of two hexagonal phases to a purely hexago- nal phase at high concentrations. Additionally, introduction of ibuprofen stiffens the membranes. This behavior may be instrumental in explaining the toxic behavior of ibuprofen in long-term application., Comment: -Improved indexing in Fig. 4e) -changed concentrations to mol% -improved arguments, however conclusions stay unchanged

Annexins are a family of proteins that bind to anionic phospholipid membranes in a Ca2+-dependent manner. Annexin A2 forms heterotetramers (Anx A2t) with the S100A10 (p11) protein dimer. The tetramer is capable of bridging phospholipid membranes and it has been suggested to play a role in Ca2+-dependent exocytosis and cell-cell adhesion of metastatic cells. Here, we employ x-ray reflectivity measurements to resolve the conformation of Anx A2t upon Ca2+-dependent binding to single supported lipid bilayers (SLBs) composed of different mixtures of anionic (POPS) and neutral (POPC) phospholipids. Based on our results we propose that Anx A2t binds in a side-by-side configuration, i.e., both Anx A2 monomers bind to the bilayer with the p11 dimer positioned on top. Furthermore, we observe a strong decrease of lipid mobility upon binding of Anx A2t to SLBs with varying POPS content. X-ray reflectivity measurements indicate that binding of Anx A2t also increases the density of the SLB. Interestingly, in the protein-facing leaflet of the SLB the lipid density is higher than in the substrate-facing leaflet. This asymmetric densification of the lipid bilayer by Anx A2t and Ca2+ might have important implications for the biochemical mechanism of Anx A2t-induced endo- and exocytosis., Comment: 27 pages, 7 figures; supplementary material available upon request from the authors

The build up of polyelectrolyte multilayers (PEMs) was observed by a silicon-on-insulator (SOI) based thin film resistor. Differently charged polyelectrolytes adsorbing to the sensor surface result in defined potential shifts, which decrease with the number of layers deposited. We model the response of the device assuming electrostatic screening of polyelectrolyte charges by mobile ions within the PEMs. The Debye screening length inside the PEMs was found to be increased compared to the value corresponding to the bulk solution. Furthermore the partitioning of mobile ions between the bulk phase and the polyelectrolyte film was employed to calculate the dielectric constant of the PEMs and the concentration of mobile charges., Comment: 18 pages, 5 figures