AbstractThe control of heat conduction through the manipulation of phonons in solids is of fundamental interest and can be exploited in applications for thermoelectric conversion. In this context, the advent of novel semiconductor nanomaterials with high surface‐to‐volume ratio, e.g. nanowires, offer exciting perspectives, leading to significant leaps forwarding the efficiency of solid‐state thermoelectric converters after decades of stagnation. Beyond the high aspect ratio, the nanowire geometry offers unprecedented possibilities of materials combination and crystal phase engineering not achievable with 2D counterparts. In this work, the growth of long (up to 100 repetitions) wurtzite InAs/InP superlattice nanowires with homogeneous segment thicknesses is reported, with control down to the single digit of nanometer. By means of Raman scattering experiments, clear modifications of the phonon dispersion in superlattice nanowires are found, where both InAs‐like and InP‐like modes are present. The experimentally measured modes are well reproduced by density functional perturbation theory calculations. Remarkably, it is found that the phonon frequencies can be tuned by the superlattice periodicity, opening exciting perspectives for phonon engineering and thermoelectric applications.

We report a method of enzyme stabilisation exploiting the artificial protein chaperone properties of β-cyclodextrin (β-CD) covalently embedded in an ultrathin organosilica layer. Putative interaction points of this artificial chaperone system with the surface of the selected enzyme were studied in silico using a protein energy landscape exploration simulation algorithm. We show that this enzyme shielding method allows for drastic enhancement of enzyme stability under thermal and chemical stress conditions, along with broadening the optimal temperature range of the biocatalyst. The presence of the β-CD macrocycle within the protective layer supports protein refolding after treatment with a surfactant.

Basement membranes are among the most widespread, non-cellular functional materials in metazoan organisms. Despite this ubiquity, the links between their compositional and biophysical properties are often difficult to establish due to their thin and delicate nature. In this article, we examine these features on a molecular level by combining results from proteomics, elastic, and nanomechanical analyses across a selection of human basement membranes. Comparing results between these different membranes connects certain compositional attributes to distinct nanomechanical signatures and further demonstrates to what extent water defines these properties. In all, these data underline BMs as stiff yet highly elastic connective tissue layers and highlight how the interplay between composition, mechanics and hydration yields such exceptionally adaptable materials.

High-impedance resonators are a promising contender for realizing long-distance entangling gates between spin qubits. Often, the fabrication of spin qubits relies on the use of gate dielectrics which are detrimental to the quality of the resonator. Here, we investigate loss mechanisms of high-impedance NbTiN resonators in the vicinity of thermally grown SiO2 and Al2O3 fabricated by atomic layer deposition. We benchmark the resonator performance in elevated magnetic fields and at elevated temperatures and find that the internal quality factors are limited by the coupling between the resonator and two-level systems of the employed oxides. Nonetheless, the internal quality factors of high-impedance resonators exceed 103 in all investigated oxide configurations which implies that the dielectric configuration would not limit the performance of resonators integrated in a spin-qubit device. Because these oxides are commonly used for spin qubit device fabrication, our results allow for straightforward integration of high-impedance resonators into spin-based quantum processors. Hence, these experiments pave the way for large-scale, spin-based quantum computers.

By their role in biochemistry, porphyrins have played a central role for “Chemistry beyond the molecule”, long before the term ‘supramolecular chemistry’ has been coined. It is interesting that the bio-chemical functions of porphyrins predominantly derive from the center metal atom, its coordination shell and the coordination-site specific properties. The integration of porphyrins into bio-molecules is safeguarded by covalent chemistry and not ‘supra-molecular’ as such. Nevertheless, square planar porphyrins and pthalocyanines take a decisive role in the development of on-surface supra molecular chemistry: This for their excellent stability and for the many ways they can be functionalized with ligands. Thereby, porphyrin and phthalocyanine chemistry paved the way towards the systematic investigation of many different functional groups known to direct self-assembly and their influence on the formation of on-surface supramolecular layers and chains. I will review the results of on-surface supramolecular assembly experiments performed at the solid-vacuum interface with CN-[1], CN-phenyl, alkoxy [1], fluoro [2] and fluorophenyl [3] and di-methylene-aniline derived functional groups and discuss the supramolecular ordering in terms of estimated binding energies and formation kinetics. It is also interesting to compare the supramolecular ordering in fluids with the constrained ordering of molecules confined to surface substrates. Further insight into the directing power of the individual functional groups derives from a fresh look at the three-fold symmetric pyramidal sub-Phthalocyanines.Fig. 1) Supramolecular ordering of substituted porphyrins in networks fromed by CN-phenyl interaction: a) and b) show higher magnification micrographs of c) and d) in two different imaging modes emphasizing the pi orbitals (HOMO) and the alkyl substituants, respectively. e) shows the dynamicity of a network from sterically more demanding alkyl-phenyl substituents. (for further details see [1] and references therein)[1] N. Wintjes et al. J. Am. Chem. Soc. 2010, 132, 7306–7311[2] J. Girovsky et al. Nature Communications 2017 8:15388[3] S. Nowakowska et al. ACS Nano 2018, 12, 768−778. Figure 1

The possibility to detect and analyze single or few biological molecules is very important for understanding interactions and reaction mechanisms. Ideally, the molecules should be confined to a nanoscale volume so that the observation time by optical methods can be extended. However, it has proven difficult to develop reliable, non-invasive trapping techniques for biomolecules under physiological conditions. Here we present a platform for long-term tether-free (solution phase) trapping of proteins without exposing them to any field gradient forces. We show that a responsive polymer brush can make solid state nanopores switch between a fully open and a fully closed state with respect to proteins, while always allowing the passage of solvent, ions and small molecules. This makes it possible to trap a very high number of proteins (500-1000) inside nanoscale chambers as small as one attoliter, reaching concentrations up to 60 gL−1. Our method is fully compatible with parallelization by imaging arrays of nanochambers. Additionally, we show that enzymatic cascade reactions can be performed with multiple native enzymes under full nanoscale confinement and steady supply of reactants. This platform will greatly extend the possibilities to optically analyze interactions involving multiple proteins, such as the dynamics of oligomerization events.

Graphene nanoribbons synthesized using bottom-up approaches can be structured with atomic precision, allowing their physical properties to be precisely controlled. For applications in quantum technology, the manipulation of single charges, spins or photons is required. However, achieving this at the level of single graphene nanoribbons is experimentally challenging due to the difficulty of contacting individual nanoribbons, particularly on-surface synthesized ones. Here we report the contacting and electrical characterization of on-surface synthesized graphene nanoribbons in a multigate device architecture using single-walled carbon nanotubes as the electrodes. The approach relies on the self-aligned nature of both nanotubes, which have diameters as small as 1 nm, and the nanoribbon growth on their respective growth substrates. The resulting nanoribbon-nanotube devices exhibit quantum transport phenomena-including Coulomb blockade, excited states of vibrational origin and Franck-Condon blockade-that indicate the contacting of individual graphene nanoribbons.

Hybridization is one of the most fundamental quantum mechanical phenomena, with the text book example of binding two hydrogen atoms in a hydrogen molecule. Here we report tunnel spectroscopy experiments illustrating the hybridization of another type of discrete quantum states, namely of superconducting subgap states that form in segments of a semiconducting nanowire in contact with superconducting reservoirs. We discuss a collection of intermediate states with unique (tunnel) spectroscopic fingerprints in the process of merging well-known individual bound states, hybridized by a central quantum dot and eventually coherently linking the reservoirs, carrying a Josephson current. These coupled and fused Andreev bound states can be seen as superconducting analogues to atomic and molecular single electron states in nature, and explain a variety of recent bound state spectra, with specific fingerprints that will have to be winnowed in future Majorana fusion experiments.

The control of elastic and inelastic electron tunnelling relies on materials with well-defined interfaces. Two-dimensional van der Waals materials are an excellent platform for such studies. Signatures of acoustic phonons and defect states have been observed in current-to-voltage measurements. These features can be explained by direct electron-phonon or electron-defect interactions. Here we use a tunnelling process that involves excitons in transition metal dichalcogenides (TMDs). We study tunnel junctions consisting of graphene and gold electrodes separated by hexagonal boron nitride with an adjacent TMD monolayer and observe prominent resonant features in current-to-voltage measurements appearing at bias voltages that correspond to TMD exciton energies. By placing the TMD outside of the tunnelling pathway, we demonstrate that this tunnelling process does not require any charge injection into the TMD. The appearance of such optical modes in electrical transport introduces additional functionality towards van der Waals material-based optoelectronic devices.

Polymeric nano- and microscale materials bear significant potential in manifold applications related to biomedicine. This is owed not only to the large chemical diversity of the constituent polymers, but also to the various morphologies these materials can achieve, ranging from simple particles to intricate self-assembled structures. Modern synthetic polymer chemistry permits the tuning of many physicochemical parameters affecting the behavior of polymeric nano- and microscale materials in the biological context. In this Perspective, an overview of the synthetic principles underlying the modern preparation of these materials is provided, aiming to demonstrate how advances in and ingenious implementations of polymer chemistry fuel a range of applications, both present and prospective.