Raman spectroscopy of gallium ion irradiated graphene

The successful integration of graphene in future technologies, such as filtration and nanoelectronics, depends on the ability to introduce controlled nanostructured defects in graphene. In this work, Raman spectroscopy is used to investigate the induction of disorder in graphene via gallium ion beam bombardment. Two configurations of CVD-grown graphene samples are used: (i) graphene supported on a Si/SiO2 substrate, and (ii) graphene suspended on porous TEM grids. It is observed that the supported graphene experiences more damage in response to lower beam doses than suspended graphene. This phenomenon is attributed to the behaviour of the energetic ions impinging the sample. In suspended graphene, the ions pass through the graphene membrane once and disperse to the atmosphere, while in supported graphene, the ions embed themselves in the substrate causing swelling and backscattering events, hence increasing the induced disorder. In supported graphene, the ratio between the Gaussian D and G peaks attributed to amorphous carbon, and the Lorentzian D and G peaks attributed to graphene, (IDG/IDL) and (IGG/IGL), are suggested to be used to quantify the degree of amorphization. The results are relevant to the development of nanostructured graphene-based filtration or desalination membranes, as well as for graphene-based nanoelectronics.JRC.F.2-Consumer Products Safet

Physicochemical characterisation of gold, silica and silver nanoparticles in water and in serum-containing cell culture media

This report presents the results from a study organised under the coordination of JRC as part of a project aiming at the adaptation of the in vitro micronucleus test (Test Guideline 487) for the assessment of manufactured NMs. The aim of the first step of the project was to evaluate the physicochemical characterisation of selected representative nanomaterials (5 nm gold, 30 nm gold, 22 nm silica, 30 nm citrate and 30 nm PVP stabilised silver nanoparticles) in pure water and in different complete culture media. The results of the study show that using a combination of different characterisation techniques is important to providing reliable information about the agglomeration behaviour of the tested nanoparticles in complete cell culture media (CCM). Most of the materials exhibited mild agglomeration in serum containing CCM. Only the PVP functionalised silver nanoparticles showed a size distribution change in all of the culture media that is so small that it could be attributed to solely protein adsorption without notable agglomeration. Silica nanoparticles were found to be the most sensitive to interaction with serum containing CCM, showing massive concentration and time dependent agglomeration strongly affected by the CCM composition. Extensive agglomeration might lead also to the accelerated sedimentation of the particles changing drastically the true, effective dose that the cells will receive under in vitro conditions1, 2. Thus, it has to be investigated in more detail and taken in account when designing in vitro experiments in the next phase of the project.JRC.F.2-Consumer Products Safet

Dispersion Behaviour of Silica Nanoparticles in Biological Media and Its Influence on Cellular Uptake

Given the increasing variety of manufactured nanomaterials, suitable, robust, standardized in vitro screening methods are needed to study the mechanisms by which they can interact with biological systems. The in vitro evaluation of interactions of nanoparticles (NPs) with living cells is challenging due to the complex behaviour of NPs, which may involve dissolution, aggregation, sedimentation and formation of a protein corona. These variable parameters have an influence on the surface properties and the stability of NPs in the biological environment and therefore also on the interaction of NPs with cells. We present here a study using 30 nm and 80 nm fluorescently-labelled silicon dioxide NPs (Rubipy-SiO2 NPs) to evaluate the NPs dispersion behaviour up to 48 hours in two different cellular media either supplemented with 10% of serum or in serum-free conditions. Size-dependent differences in dispersion behaviour were observed and the influence of the living cells on NPs stability and deposition was determined. Using flow cytometry and fluorescence microscopy techniques we studied the kinetics of the cellular uptake of Rubipy-SiO2 NPs by A549 and CaCo-2 cells and we found a correlation between the NPs characteristics in cell media and the amount of cellular uptake. Our results emphasize how relevant and important it is to evaluate and to monitor the size and agglomeration state of nanoparticles in the biological medium, in order to interpret correctly the results of the in vitro toxicological assays.JRC.I.4-Nanobioscience

Aero-TiO2 Prepared on the Basis of Networks of ZnO Tetrapods

In this paper, new aeromaterials are proposed on the basis of titania thin films deposited using atomic layer deposition (ALD) on a sacrificial network of ZnO microtetrapods. The technology consists of two technological steps applied after ALD, namely, thermal treatment at different temperatures and etching of the sacrificial template. Two procedures are applied for etching, one of which is wet etching in a citric acid aqua solution, while the other one is etching in a hydride vapor phase epitaxy (HVPE) system with HCl and hydrogen chemicals. The morphology, composition, and crystal structure of the produced aeromaterials are investigated depending on the temperature of annealing and the sequence of the technological steps. The performed photoluminescence analysis suggests that the developed aeromaterials are potential candidates for photocatalytic applications

A tribocorrosion appraisal of a dual layer PVD coated CoCrMo alloy tribopair

A dual layer PVD coating consisting of a CrN layer on top of a CoCrMo(C) S-phase underlayer (CrN/S) was deposited on low-carbon wrought CoCrMo alloy discs and CoCrMo Stellite® 21 spheres. The tribocorrosion response of the uncoated CoCrMo tribopairs and coated CrN/S tribopairs was studied under reciprocating sliding conditions in Ringer's and diluted foetal bovine serum (FBS) solutions under anodic potential and elastic contact for a sliding time of 2 h. Compared to the uncoated tribopair, CrN/S successfully mitigated both oxidation and mechanical material losses and resulted in a low dynamic coefficient of friction and smoother scar morphologies in both test solutions. For the uncoated tribopair, the presence of proteins acted as a barrier to charge transfer and lowered the friction during tribocorrosion testing contributing to a marked reduction in material loss, primarily by a reduction in oxidative losses, but resulted in a rougher scar morphology. Tribocorrosion tests of the coated tribopair were also carried out for a duration of 24 h and revealed minimal material losses in diluted FBS and no evidence of other damage. It, however, resulted in substantial thinning of the outer CrN layer, transverse microcracking and delamination when testing in Ringer's solution. This coating loss produced a source for coating debris which led to three-body micro-abrasion damage. FIB investigation revealed that the observed transverse microcracks were limited to the outer layer and hence have not provided electrolytic pathways to the substrate interface. The excellent tribocorrosion response of dual layer CrN/S on CoCrMo metal tribopairs in diluted FBS renders them good candidates for further investigation to mitigate tribocorrosion damage of biomedical CoCrMo alloys.peer-reviewe

Rationally modified estrogen receptor protein as a bio-recognition element for the detection of EDC pollutants: strategies and opportunities

The estrogen receptor protein (ER) can bind a vast number of organic pollutants widely spread in the environment and collectively known as Endocrine Disrupting Chemicals, EDCs. Its broad selectivity makes it an ideal bio-recognition element for the detection of EDCs. Here we describe the strategy and rationale for the design of ER based biosensors and assays that generate a signal in the presence of EDCs. The opportunity to use either natural or rationally modified ER molecules is discussed. The latter approach was successfully applied in the EU-FP7 project RADAR, with the aim to develop a novel biosensor for the detection of organic pollutants both in the environment and in commercial water products

Modulation of surface bio-functionality by using gold nanostructures on protein repellent surfaces

The integration of gold nanoparticles (Au NPs) or nanostructures with special optical properties on solid surfaces has become a major research topic in the field of nanobiotechnology in particular for the development of new generation of multifunctional bioanalytical platforms. This has led to considerable research efforts for developing quick and direct nanofabrication methods capable of producing well-ordered 2D nanostructured arrays with tunable morphological, chemical and optical properties. In this paper, we propose a simple and fast nanofabrication method enabling the creation of Au NPs patterns on a non-adhesive and cell repellent plasma-deposited poly(ethyleneoxide) (PEO-like) coating. The immobilization of Au NPs on PEO-like coatings does not require any prior chemical modifications and is achieved by a straightforward and stable self-assembly technique. By varying the size and the concentration of the Au NPs it is possible to control the Au NPs density and spatial distribution on the PEO-like coated surface with direct effects on the bio-functionality of the surface. These nanostructured surfaces have been tested for protein bio-recognition analysis and as a cell culture platform. The developed nanostructured platform has many potential applications in the field of protein-nanoparticle and cell-nanoparticle interaction studies, nanotoxicology and bioengineering.JRC.I.4-Nanobioscience

Structured Biotinylated Poly(3,4-Ethylenedioxypyrrole) Electrodes for Biochemical Applications

The immobilization of biotin on transducer surfaces is a very important step for the fabrication of biosensors for many applications (immunoassay, DNA-hybridization assays, targeted imaging). Biotinylated polypyrroles have been studied and tested but gave rise to problems of polymerization and stability due to the intrinsic properties of pyrrole. As an alternative, biotinylated pyrroles were often used in a copolymerization with pyrrole or with an amphiphilic pyrrole derivative in a copolymerization to reduce the problems due to the pyrrole substitution. To find a new strategy, this paper presents the homopolymerization, instead of the use of a copolymerization, by replacing pyrrole by 3,4-ethylenedioxypyrrole bearing biotinylated substituent. We report the synthesis, characterization and electrochemical properties of two biotinylated 3,4-ethylenedioxypyrroles differing by the length of the alkyl spacer (ethyl or dodecyl) as well as the characterization of the corresponding polymer films. We successfully show, by cyclic voltammetry, that these monomers polymerize perfectly and give relatively stable polymer films. The increase of the alkyl spacer improves the polymerization and increases the polymer stability. For the first time, we also studied the surface morphology of an electrodeposited biotinylated polymer. The electrodeposition of these biotinylated derivatives gave rise to the ability to modulate the surface microstructuration, which consists of microspheres or cauliflower-like microstructures according to the length of the alkyl spacer.JRC.I.4-Nanobioscience

Aero-Ga2O3 Nanomaterial Electromagnetically Transparent from Microwaves to Terahertz for Internet of Things Applications

In this paper, fabrication of a new material is reported, the so-called Aero-Ga2O3 or Aerogallox, which represents an ultra-porous and ultra-lightweight three-dimensional architecture made from interconnected microtubes of gallium oxide with nanometer thin walls. The material is fabricated using epitaxial growth of an ultrathin layer of gallium nitride on zinc oxide microtetrapods followed by decomposition of sacrificial ZnO and oxidation of GaN which according to the results of X-ray diffraction (XRD) and X-ray photoemission spectroscopy (XPS) characterizations, is transformed gradually in β-Ga2O3 with almost stoichiometric composition. The investigations show that the developed ultra-porous Aerogallox exhibits extremely low reflectivity and high transmissivity in an ultrabroadband electromagnetic spectrum ranging from X-band (8-12 GHz) to several terahertz which opens possibilities for quite new applications of gallium oxide, previously not anticipated

Label-free biosensor detection of endocrine disrupting compounds using engineered estrogen receptors

Endocrine Disrupting Compounds (EDCs) are chemical substances shown to interfere with endogenous hormones affecting the endocrine, immune and nervous systems of mammals. EDCs are the causative agents of diseases including reproductive disorders and cancers. This highlights the urgency to develop fast and sensitive methods to detect EDCs, which are detrimental even at very low concentrations. In this work, we propose a label-free surface plasmon resonance (SPR) biosensor method to detect specific EDCs (17 β-estradiol (E2), ethinyl-estradiol, 4-nonylphenol, tamoxifen) through their binding to estrogen receptor alpha (ERα). We show that the use of rationally designed ERα (as bio-recognition element) in combination with conformation-sensitive peptides (as amplification agent, resulting in increased responses) enables the detection of low parts per billion (ppb) levels of E2. As a proof of concept, this bioassay was used to detect E2 in (spiked) real water samples from fish farms, rivers and the sea at low ppb levels after concentration by solid phase extraction. In addition, the present SPR assay that combines a conformation-sensitive peptide with an array of ERα mutants is very promising for the assessment of the risk of potential estrogenic activity for chemical substances