Blueprint for a self-sustained European Centre for service provision in safe and sustainable innovation for nanotechnology.

The coming years are expected to bring rapid changes in the nanotechnology regulatory landscape, with the establishment of a new framework for nano-risk governance, in silico approaches for characterisation and risk assessment of nanomaterials, and novel procedures for the early identification and management of nanomaterial risks. In this context, Safe(r)-by-Design (SbD) emerges as a powerful preventive approach to support the development of safe and sustainable (SSbD) nanotechnology-based products and processes throughout the life cycle. This paper summarises the work undertaken to develop a blueprint for the deployment and operation of a permanent European Centre of collaborating laboratories and research organisations supporting safe innovation in nanotechnologies.

In-depth analysis of iodine in artificial biofilm model layers by variable excitation energy XPS and argon gas cluster ion sputtering XPS.

Here, we present a study on agarose thin-film samples that represent a model system for the exopolysaccharide matrix of biofilms. Povidone-iodide (PVP-I) was selected as an antibacterial agent to evaluate our x-ray photoelectron spectroscopy (XPS)-based methodology to trace specific marker elements, here iodine, commonly found in organic matrices of antibiotics. The in-depth distribution of iodine was determined by XPS analyses with variable excitation energies and in combination with argon gas cluster ion beam sputter cycles.

Comparative Study of NAP-XPS and Cryo-XPS for the Investigation of Surface Chemistry of the Bacterial Cell-Envelope.

Bacteria generally interact with the environment via processes involving their cell-envelope. Thus, techniques that may shed light on their surface chemistry are attractive tools for providing an understanding of bacterial interactions. One of these tools is Al Kα-excited photoelectron spectroscopy (XPS) with its estimated information depth of <10 nm.

Self-degrading graphene sheets for tumor therapy.

Low biodegradability of graphene derivatives and related health risks are the main limiting factors for their in vivo biomedical applications. Here, we present the synthesis of enzyme-functionalized graphene sheets with self-degrading properties under physiological conditions and their applications in tumor therapy. The synergistic enzyme cascade glucose oxidase and myeloperoxidase are covalently conjugated to the surface of graphene sheets and two-dimensional (2D) platforms are obtained that can produce sodium hypochlorite from glucose.

Metal-Assisted and Solvent-Mediated Synthesis of Two-Dimensional Triazine Structures on Gram Scale.

Covalent triazine frameworks are an emerging material class that have shown promising performance for a range of applications. In this work, we report on a metal-assisted and solvent-mediated reaction between calcium carbide and cyanuric chloride, as cheap and commercially available precursors, to synthesize two-dimensional triazine structures (2DTSs). The reaction between the solvent, dimethylformamide, and cyanuric chloride was promoted by calcium carbide and resulted in dimethylamino--triazine intermediates, which in turn undergo nucleophilic substitutions.

Boronic Acid-Functionalized Two-Dimensional MoS at Biointerfaces.

While noncovalent interactions at two-dimensional nanobiointerfaces are extensively investigated, less knowledge about covalent interactions at this interface is available. In this work, boronic acid-functionalized 2D MoS was synthesized and its covalent multivalent interactions with bacteria and nematodes were investigated. Polymerization of glycidol by freshly exfoliated MoS and condensation of 2,5-thiophenediylbisboronic acid on the produced platform resulted in boronic acid-functionalized 2D MoS.

Mussel-Inspired Multivalent Linear Polyglycerol Coatings Outperform Monovalent Polyethylene Glycol Coatings in Antifouling Surface Properties.

Biofouling constitutes a major challenge in the application of biosensors and biomedical implants, as well as for (food) packaging and marine equipment. In this work, an antifouling surface coating based on the combination of mussel-inspired dendritic polyglycerol (MI-dPG) and an amine-functionalized block copolymer of linear polyglycerol (lPG-b-OA, OA = oligo-amine) was developed. The coating was compared to a MI-dPG surface which was postfunctionalized with commercially available amine-terminated polyethylene glycol (HO-PEG-NH) of similar molecular weight.

Functionalized nanographene sheets with high antiviral activity through synergistic electrostatic and hydrophobic interactions.

As resistance to traditional drugs emerges for treatment of virus infections, the need for new methods for virus inhibition increases. Graphene derivatives with large surface areas have shown strong activity against different viruses. However, the inability of current synthetic protocols to accurately manipulate the structure of graphene sheets in order to control their antiviral activity remains a major challenge.

Scalable Production of Nanographene and Doping via Nondestructive Covalent Functionalization.

A new method for top-down, one-pot, gram-scale production of high quality nanographene by incubating graphite in a dilute sodium hypochlorite solution at only 40 °C is reported here. The produced sheets have only 4 at% oxygen content, comparable with nanographene grown by chemical vapor deposition. The nanographene sheets are covalently functionalized using a nondestructive nitrene [2+1] cycloaddition reaction that preserves their π-conjugated system.

Functionalized 2D nanomaterials with switchable binding to investigate graphene-bacteria interactions.

Graphene and its derivatives have recently attracted much attention for sensing and deactivating pathogens. However, the mechanism of multivalent interactions at the graphene-pathogen interface is not fully understood. Since different physicochemical parameters of graphene play a role at this interface, control over graphene's structure is necessary to study the mechanism of these interactions.

Transfer of functional thermoresponsive poly(glycidyl ether) coatings for cell sheet fabrication from gold to glass surfaces.

Thermoresponsive polymer coatings can facilitate cell sheet fabrication under mild conditions by promoting cell adhesion and proliferation at 37 °C. At lower temperatures the detachment of confluent cell sheets is triggered without enzymatic treatment. Thus, confluent cell sheets with intact extracellular matrix for regenerative medicine or tissue engineering applications become available.

Detection of suspended nanoparticles with near-ambient pressure x-ray photoelectron spectroscopy.

Two systems of suspended nanoparticles have been studied with near-ambient pressure x-ray photoelectron spectroscopy: silver nanoparticles in water and strontium fluoride-calcium fluoride core-shell nanoparticles in ethylene glycol. The corresponding dry samples were measured under ultra high vacuum for comparison. The results obtained under near-ambient pressure were overall comparable to those obtained under ultra high vacuum, although measuring silver nanoparticles in water requires a high pass energy and a long acquisition time.

Controlled Covalent Functionalization of Thermally Reduced Graphene Oxide To Generate Defined Bifunctional 2D Nanomaterials.

A controlled, reproducible, gram-scale method is reported for the covalent functionalization of graphene sheets by a one-pot nitrene [2+1] cycloaddition reaction under mild conditions. The reaction between commercially available 2,4,6-trichloro-1,3,5-triazine and sodium azide with thermally reduced graphene oxide (TRGO) results in defined dichlorotriazine-functionalized sheets. The different reactivities of the chlorine substituents on the functionalized graphene allow stepwise post-modification by manipulating the temperature.

A photoswitchable rotaxane operating in monolayers on solid support.

A novel photoswitchable rotaxane was synthesised and its switching behaviour in solution was analysed with NMR and UV-Vis. A monolayer of rotaxanes was deposited on glass surfaces and the on-surface photoswitching was investigated. Angle-resolved NEXAFS spectra revealed a preferential orientation that reversibly changes upon switching.

X-ray spectromicroscopy of nanoparticulate iron oxide phases.

Soft x-ray spectromicroscopy techniques have seen great amount of development in the recent years, and with the development of new diffraction limited synchrotron source, many new nanoscale and mesoscale characterization opportunities of applied materials are foreseen. In this perspective, the authors present some examples that illustrate the capabilities of spectromicroscopy techniques, namely, 2D and 3D spatially resolved chemical quantification, surface and bulk sensitive measurements, and polarization dependent measurements as applied to iron oxide nanoparticulate materials of biological, geological, and other origins.

Photocontrolled On-Surface Pseudorotaxane Formation with Well-Ordered Macrocycle Multilayers.

The photoinduced pseudorotaxane formation between a photoresponsive axle and a tetralactam macrocycle was investigated in solution and on glass surfaces with immobilized multilayers of macrocycles. In the course of this reaction, a novel photoswitchable binding station with azobenzene as the photoswitchable unit and diketopiperazine as the binding station was synthesized and studied by NMR and UV/Vis spectroscopy. Glass surfaces have been functionalized with pyridine-terminated SAMs and subsequently with multilayers of macrocycles through layer-by-layer self assembly.

Ionic Liquids as a Reference Material Candidate for the Quick Performance Check of Energy Dispersive X-ray Spectrometers for the Low Energy Range below 1 keV.

Ionic liquids (ILs) are proposed as simple and efficient test materials to evaluate the performance of energy dispersive X-ray spectrometers (EDS) in the low energy range below 1 keV. By only one measurement, C Kα, N Kα, O Kα, and F Kα X-ray lines can be excited. Additionally, the S Kα line at 2.

XPS depth profiling of an ultrathin bioorganic film with an argon gas cluster ion beam.

The growing interest in artificial bioorganic interfaces as a platform for applications in emerging areas as personalized medicine, clinical diagnostics, biosensing, biofilms, prevention of biofouling, and other fields of bioengineering is the origin of a need for in detail multitechnique characterizations of such layers and interfaces. The in-depth analysis of biointerfaces is of special interest as the properties of functional bioorganic coatings can be dramatically affected by in-depth variations of composition. In worst cases, the functionality of a device produced using such coatings can be substantially reduced or even fully lost.

A detailed assignment of NEXAFS resonances of imidazolium based ionic liquids.

In Near Edge X-Ray Absorption Fine Structure (NEXAFS) spectroscopy X-Ray photons are used to excite tightly bound core electrons to low-lying unoccupied orbitals of the system. This technique offers insight into the electronic structure of the system as well as useful structural information. In this work, we apply NEXAFS to two kinds of imidazolium based ionic liquids ([C(n)C1im](+)[NTf2](-) and [C4C1im](+)[I](-)).

Real Time Imaging of Deuterium in a Duplex Stainless Steel Microstructure by Time-of-Flight SIMS.

For more than one century, hydrogen assisted degradation of metallic microstructures has been identified as origin for severe technical component failures but the mechanisms behind have not yet been completely understood so far. Any in-situ observation of hydrogen transport phenomena in microstructures will provide more details for further elucidation of these degradation mechanisms. A novel experiment is presented which is designed to elucidate the permeation behaviour of deuterium in a microstructure of duplex stainless steel (DSS).

Multimode Surface Functional Group Determination: Combining Steady-State and Time-Resolved Fluorescence with X-ray Photoelectron Spectroscopy and Absorption Measurements for Absolute Quantification.

The quantitative determination of surface functional groups is approached in a straightforward laboratory-based method with high reliability. The application of a multimode BODIPY-type fluorescence, photometry, and X-ray photoelectron spectroscopy (XPS) label allows estimation of the labeling ratio, i.e.

Quantification of silane molecules on oxidized silicon: are there options for a traceable and absolute determination?

Organosilanes are used routinely to functionalize various support materials for further modifications. Nevertheless, reliable quantitative information about surface functional group densities after layer formation is rarely available. Here, we present the analysis of thin organic nanolayers made from nitrogen containing silane molecules on naturally oxidized silicon wafers with reference-free total reflection X-ray fluorescence (TXRF) and X-ray photoelectron spectroscopy (XPS).

Dual beam organic depth profiling using large argon cluster ion beams.

Argon cluster sputtering of an organic multilayer reference material consisting of two organic components, 4,4'-bis[N-(1-naphthyl-1-)-N-phenyl- amino]-biphenyl (NPB) and aluminium tris-(8-hydroxyquinolate) (Alq), materials commonly used in organic light-emitting diodes industry, was carried out using time-of-flight SIMS in dual beam mode. The sample used in this study consists of a ∽400-nm-thick NPB matrix with 3-nm marker layers of Alq at depth of ∽50, 100, 200 and 300 nm. Argon cluster sputtering provides a constant sputter yield throughout the depth profiles, and the sputter yield volumes and depth resolution are presented for Ar-cluster sizes of 630, 820, 1000, 1250 and 1660 atoms at a kinetic energy of 2.