Samuel Grandthyll

Subsurface influence on the structure of protein adsorbates as revealed by in situ X-ray reflectivity.

The adsorption process of proteins to surfaces is governed by the mutual interactions among proteins, the solution, and the substrate. Interactions arising from the substrate are usually attributed to the uppermost atomic layer. This actual surface defines the surface chemistry and hence steric and electrostatic interactions. For a comprehensive understanding, however, the interactions arising from the bulk material also have to be considered. Our protein adsorption experiments with globular proteins (α-amylase, bovine serum albumin, and lysozyme) clearly reveal the influence of the subsurface material via van der Waals forces. Here, a set of functionalized silicon wafers enables a distinction between the effects of surface chemistry and the subsurface composition of the substrate. Whereas the surface chemistry controls whether the individual proteins are denatured, the strength of the van der Waals forces affects the final layer density and hence the adsorbed amount of proteins. The results imply that van der Waals forces mainly influence surface processes, which govern the structure formation of the protein adsorbates, such as surface diffusion and spreading.

Epitaxial growth of graphene on transition metal surfaces: chemical vapor deposition versus liquid phase deposition

The epitaxial growth of graphene on transition metal surfaces by ex situ deposition of liquid precursors (LPD, liquid phase deposition) is compared to the standard method of chemical vapor deposition (CVD). The performance of LPD strongly depends on the particular transition metal surface. For Pt(111), Ir(111) and Rh(111), the formation of a graphene monolayer is hardly affected by the way the precursor is provided. In the case of Ni(111), the growth of graphene strongly depends on the applied synthesis method. For CVD of propene on Ni(111), a 1 × 1 structure as expected from the vanishing lattice mismatch is observed. However, in spite of the nearly perfect lattice match, a multi-domain structure with 1 × 1 and two additional rotated domains is obtained when an oxygen-containing precursor (acetone) is provided ex situ.

Is adhesion superficial? Silicon wafers as a model system to study van der Waals interactions

Adhesion is a key issue for researchers of various fields, it is therefore of uppermost importance to understand the parameters that are involved. Commonly, only surface parameters are employed to determine the adhesive forces between materials. Yet, van der Waals forces act not only between atoms in the vicinity of the surface, but also between atoms in the bulk material. In this review, we describe the principles of van der Waals interactions and outline experimental and theoretical studies investigating the influence of the subsurface material on adhesion. In addition, we present a collection of data indicating that silicon wafers with native oxide layers are a good model substrate to study van der Waals interactions with coated materials.

Reduced Adhesion of Oral Bacteria on Hydroxyapatite by Fluoride Treatment

The mechanisms of action of fluoride have been discussed controversially for decades. The cavity-preventive effect for teeth is often traced back to effects on demineralization. However, an effect on bacterial adhesion was indicated by indirect macroscopic studies. To characterize adhesion on fluoridated samples on a single bacterial level, we used force spectroscopy with bacterial probes to measure adhesion forces directly. We tested the adhesion of Streptococcus mutans , Streptococcus oralis , and Staphylococcus carnosus on smooth, high-density hydroxyapatite surfaces, pristine and after treatment with fluoride solution. All bacteria species exhibit lower adhesion forces after fluoride treatment of the surfaces. These findings suggest that the decrease of adhesion properties is a further key factor for the cariostatic effect of fluoride besides the decrease of demineralization.

Role of aluminum as an oxygen-scavenger in zirconium based bulk metallic glasses

In order to investigate a way to diminish the impact of oxygen onto the critical cooling rate of Zr-based alloys, the bonding chemistry of the elements in Zr-Cu-Ni-Al-Nb-Si bulk metallic glasses with different oxygen contents is studied by x-ray photoelectron spectroscopy. Complementary undercooling experiments lead to continuous-cooling-transformation diagrams for the studied alloys. The experimental results demonstrate that Al not only acts as a scavenger for both absorbed and intrinsic oxygen but the dissolution of its oxide on atomic length scales refrains from heterogeneous nucleation. The combined effect is an enhancement of oxygen tolerance in the investigated alloy.

Graphene from fingerprints: exhausting the performance of liquid precursor deposition.

Epitaxial graphene is expected to be the only way to obtain large-area sheets of this two-dimensional material for applications on an industrial scale. So far, there are different recipes for epitaxial growth of graphene, using either intrinsic carbon, such as the selective desorption of silicon from a SiC surface, or extrinsic carbon, as via the chemical vapor deposition (CVD) of simple hydrocarbons on transition metal surfaces. In addition, even liquid precursor deposition (LPD) provides well-ordered graphene monolayers. It will be shown that graphene formation on transition metal surfaces by LPD synthesis is a very robust mechanism that even works if carbon is provided in a quite undefined way, namely by using a human fingerprint as a liquid precursor. Graphene growth from fingerprints provides well-ordered monolayers with the same quality as LPD grown graphene using ultrapure synthetic single precursors. The reliability of the self-assembly process of graphene growth on transition metals by LPD therefore offers a simple and extremely robust synthesis route for epitaxial graphene and may give access to production pathways for substrates for which the CVD method fails.

Increasing the wear resistance by interstitial alloying with boron via chemical vapor deposition.

The wear resistance of a Rh(111) surface can be strongly increased by interstitial alloying with boron atoms via chemical vapor deposition of trimethylborate [B(OCH3)3] at moderate temperatures of about 800 K. The fragmentation of the precursor results in single boron atoms that are incorporated in the fcc lattice of the substrate, as displayed by X-ray photoelectron diffraction. The penetration depth of the boron atoms is in the range of at least 100 nm with the boron distribution displaying a nearly homogeneous depth profile, as examined by combined X-ray photoelectron spectroscopy and Ar ion etching experiments. Compared to the bare Rh(111) surface, the wear resistance of the boron-doped Rh surface is increased to about 400%, as probed by the scratching experiments with atomic force microscopy. The presented synthesis route provides an easy method for case hardening of micro- or nanoelectromechanical devices (MEMS and NEMS, respectively) at moderate temperatures.

Single-Molecule Force Spectroscopy Study on Modular Resilin Fusion Protein

The adhesive and mechanical properties of a modular fusion protein consisting of two different types of binding units linked together via a flexible resilin-like-polypeptide domain are quantified. The adhesive domains have been constructed from fungal cellulose-binding modules (CBMs) and an amphiphilic hydrophobin HFBI. This study is carried out by single-molecule force spectroscopy, which enables stretching of single molecules. The fusion proteins are designed to self-assemble on the cellulose surface, leading into the submonolayer of proteins having the HFBI pointing away from the surface. A hydrophobic atomic force microscopy (AFM) tip can be employed for contacting and lifting the single fusion protein from the HFBI-functionalized terminus by the hydrophobic interaction between the tip surface and the hydrophobic patch of the HFBI. The work of rupture, contour length at rupture and the adhesion forces of the amphiphilic end domains are evaluated under aqueous environment at different pHs.

Reduced graphene oxide biosensor platform for the detection of NT-proBNP biomarker in its clinical range

Reduced graphene oxide (rGO) thin films can be exploited as highly sensitive transducer layers and integrated in interdigital micro-electrode systems for biosensing processes. The distinctive bipolar characterisitics of rGO thin films can be modulated by a very low external electric field due to the electrostatic charges of biomolecules. These charges lead to a fast response in the readout signals of rGO based ion sensitive field-effect transistors (ISFETs). The characterisitc changes of rGO ISFETs enable a fast, accurate and reproducible detection of biomolecules. The biosensing mechanism offers a fast and label-free approach for analyte detection in contrast to the classical ELISA method. In this contribution, we introduce a reproducible fabrication process of rGO based field-effect transistors on wafer level. The sensors are functionalized as biosensors to measure N-terminal pro-brain natriuretic peptide (NT-proBNP) in human serum within its clinical range. Our optimized rGO sensor shows very promising electrical properties and can be considered as a proof of concept study for the detection of various analytes. The easy and cost-effective fabrication as well as the versatile usability make this new technological platform an auspicious tool for different sensing applications in future.