Scientific publications

Summary Lipophilic components are known to modulate the process of bioadhesion on the tooth surface. However, the presence of lipid droplets at the acquired pellicle under oral conditions has not been demonstrated, yet. The purpose of the present study was to establish a method for direct visualisation of lipids on the surface of hydrated, pellicle covered tooth samples by environmental scanning electron microscopy (ESEM), and to use this technique for studying the effects of rinsing with edible oils on the acquired pellicle under in vivo conditions. In situ pellicle formation was performed by 3 min exposure of enamel and dentin specimens in the oral cavity of volunteers. Subsequently, the volunteers rinsed in vivo with safflower oil or linseed oil for 30 s, and the specimens were further carried intraorally for periods from 0 min up to several hours. After intraoral exposure the specimens were treated by osmium tetroxide vapour, and were subsequently analysed by ESEM. This technique was capable to directly visualise the presence of lipid droplets at the pellicle's surface under hydrated conditions. ESEM analyses revealed that surface bound nano- and micro-sized lipid droplets were present at the acquired pellicle's surface even several hours after rinsing with edible oils indicating that these droplets had tightly adhered to the pellicle surface. Pellicle modification by edible oil rinsing as demonstrated in the present study might have the potential to be beneficial as an adjunct in dental prophylaxis.

HER2 is considered as one of the most important, predictive biomarkers in oncology. The diagnosis of HER2 positive cancer types such as breast- and gastric cancer is usually based on immunohistochemical HER2 staining of tumour tissue. However, the current immunohistochemical methods do not provide localized information about HER2’s functional state. In order to generate signals leading to cell growth and proliferation, the receptor spontaneously forms homodimers, a process that can differ between individual cancer cells.

Chemoselective deoxygenation by hydrogen is particularly challenging but crucial for an efficient late-stage modification of functionality-laden fine chemicals, natural products, or pharmaceuticals and the economic upgrading of biomass-derived molecules into fuels and chemicals. We report here on a reusable earth-abundant metal catalyst that permits highly chemoselective deoxygenation using inexpensive hydrogen gas. Primary, secondary, and tertiary alcohols as well as alkyl and aryl ketones and aldehydes can be selectively deoxygenated, even when part of complex natural products, pharmaceuticals, or biomass-derived platform molecules. The catalyst tolerates many functional groups including hydrogenation-sensitive examples. It is efficient, easy to handle, and conveniently synthesized from a specific bimetallic coordination compound and commercially available charcoal. Selective, sustainable, and cost-efficient deoxygenation under industrially viable conditions seems feasible.

The synthesis of important classes of chemical compounds from alcohols helps to conserve Earth’s fossil carbon resources, since alcohols can be obtained from indigestible and abundantly available biomass. The utilisation of visible light for the activation of alcohols permits alcohol-based C–N and C–C bond formation under mild conditions inaccessible with thermally operating hydrogen liberation catalysts. Herein, we report on a noble metal-free photocatalyst able to split alcohols into hydrogen and carbonyl compounds under inert gas atmosphere without the requirement of electron donors, additives, or aqueous reaction media. The reusable photocatalyst mediates C–N multiple bond formation using the oxidation of alcohols and subsequent coupling with amines. The photocatalyst consists of a CdS/TiO2 heterojunction decorated with co-catalytic Ni nanoparticles and is prepared on size-optimised colloidal metal–organic framework (MOF) crystallites.

New cryogenic characterization techniques for exploring the nanoscale structure and chemistry of intact solid–liquid interfaces have recently been developed. These techniques provide high-resolution information about buried interfaces from large samples or devices that cannot be obtained by other means. These advancements were enabled by the development of instrumentation for cryogenic focused ion beam liftout, which allows intact solid–liquid interfaces to be extracted from large samples and thinned to electron-transparent thicknesses for characterization by cryogenic scanning transmission electron microscopy or atom probe tomography. Future implementation of these techniques will complement current strides in imaging of materials in fluid environments by in situ liquid-phase electron microscopy, providing a more complete understanding of the morphology, surface chemistry, and dynamic processes that occur at solid–liquid interfaces.

Liquid cell electron microscopy possesses a combination of spatial and temporal resolution that provides a unique view of static structures and dynamic processes in liquids. Optimizing the resolution in liquids requires consideration of both the microscope performance and the properties of the sample. In this Review, we survey the competing factors that determine spatial and temporal resolution for transmission electron microscopy and scanning transmission electron microscopy of liquids. We discuss the effects of sample thickness, stability and dose sensitivity on spatial and temporal resolution. We show that for some liquid samples, spatial resolution can be improved by spherical and chromatic aberration correction. However, other benefits offered by aberration correction may be even more useful for liquid samples. We consider the greater image interpretability offered by spherical aberration correction and the improved dose efficiency for thicker samples offered by chromatic aberration correction. Finally, we discuss the importance of detector and sample parameters for higher resolution in future experiments.

Molecular mechanisms of adhesion and friction include the rupture of single and multiple bonds. The strength of adhesion and friction thus depends on the molecular kinetics and cooperative effects in the lifetime of bonds under stress. We measured the rate dependence of friction and adhesion mediated by supramolecular guest–host bonds using atomic force microscopy (AFM). The tip of the AFM and the surface were functionalized with cyclodextrin hosts. The influence of molecular kinetics on adhesion and friction was studied using three different ditopic guest molecules that connected the AFM tip and the surface. Adamantane, ferrocene, and azobenzene were the guest end groups of the connector molecules that formed inclusion complexes with the cyclodextrin hosts. The results confirm the importance of the molecular off-rate and of cooperative effects for the strength of adhesion and friction. Positive cooperativity also shapes the dependence of friction on the concentration of connector molecules, which follows the Hill–Langmuir model. Based on the Hill coefficient of 3.6, reflecting a characteristic rupture of at least 3–4 parallel bonds, a rescaling of the pulling rate is suggested that shifts the rate dependence of adhesion and friction for the three different molecules towards one master curve.

Molecular mechanisms in the shear of an ionic liquid in nanometer-scale confinement were investigated by atomic force microscopy with a laterally oscillating tip. On a single-crystal gold electrode, the ionic liquid 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([EMIM][NTf2]) exhibits molecular ordering in a simple cubic structure upon confinement by the nanometer-sized asperity. The strength of shear resistance decreases exponentially with increasing number of confined molecular layers. The dependence of lateral forces and of dissipation on the applied electrochemical potential confirms a mechanism in the electrolubrication by ionic liquids, namely, the change of the slippage plane from the interface with the electrode into the ionic liquid for increasing surface potential.

The influence of a single layer graphene on the interface between a polished steel surface and the model lubricant hexadecane is explored by high-resolution force microscopy. Nanometer-scale friction is reduced by a factor of three on graphene compared to the steel substrate, with an ordered layer of hexadecane adsorbed on the graphene. Graphene furthermore induces a molecular ordering in the confined lubricant with an average range of 4–5 layers and with a strongly increased load-bearing capacity compared to the lubricant on the bare steel substrate.

Wear mechanisms of three Ag–Cu eutectic alloy samples cooled at different rates from the melt have been investigated by friction force microscopy. The eutectic phase exhibits a lamellar structure where the interlamellar thickness decreases with increasing cooling rate. The hardness of the samples decreases with decreasing thickness of the lamellae. In the low normal force regime (Fn ≤ 1000 nN) friction is governed by shearing and the relevant contact area can be well described by the Johnson–Kendal–Roberts model. At higher normal force values, the surface is worn, and friction can be described by the ploughing friction coefficient. A ploughing friction coefficient is determined, which is positively correlated with the hardness of the Ag–Cu eutectic alloy samples cooled at different rates, while the wear volume negatively correlates with the hardness.