Titanium Dioxide as Food Additive

Titanium dioxide is a white metal oxide used in many food categories as food additives to provide a whitening effect. If its use complies with the five specifications including synthesis pathway, crystallographic phase, purity, amount and innocuousness, all other parameters are not defined and were hardly documented. However, in the last 3 years, two studies have deeply characterized food-grade TiO2 and converged to the fact that the size distribution of food-grade TiO2 spans over the nanoparticle range (<100 nm) and the surface is not pure TiO2 but covered by phosphate and eventually silicon species or aluminium species, which modify the surface chemistry of these particles. Until now, this material was considered as safe. However, the toxicological studies later to the last re-evaluation by the European Food Safety Agency reveal some concerns due to the ability of TiO2 particles to alter the intestinal barrier. This reinforces the idea to go on reinforcing the risk assessment about food-grade TiO2

Alpha localized radiolysis and corrosion mechanisms at the iron/water interface: Role of molecular species

This paper is devoted to the iron corrosion phenomena induced by the α (4He2+) water radiolysis species studied in conjunction with the production/consumption of H2 at the solid/solution interface. On one hand, the solid surface is characterized during the 4He2+ ions irradiation by in situ Raman spectroscopy; on another hand, the H2 gas produced by the water radiolysis is monitored by ex situ gas measurements. The 4He2+ ions irradiation experiments are provided either by the CEMHTI (E = 5.0 MeV) either by the ARRONAX (E = 64.7 MeV) cyclotron facilities. The iron corrosion occurs only under irradiation and can be slowed down by H2 reductive atmosphere. Pure iron and carbon steel solids are studied in order to show two distinct behaviors of these surfaces vs. the 4He2+ ions water irradiation: the corrosion products identified are the magnetite phase (Fe(II)Fe(III)2O4) correlated to an H2 consumption for pure iron and the lepidocrocite phase (γ-Fe(III)OOH) correlated to an H2 production for carbon steel sample. This paper underlined the correlation between the iron corrosion products formation onto the solid surface and the H2 production/consumption mechanisms. H2O2 species is considered as the single water radiolytic species involved into the corrosion reaction at the solid surface with an essential role in the oxidation reaction of the iron surface. We propose to bring some light to these mechanisms, in particular the H2 and H2O2 roles, by the in situ Raman spectroscopy during and after the 4He2+ ions beam irradiation. This in situ experiment avoids the evolution of the solid surface, in particular phases which are reactive to the oxidation processing

Radiolytic Corrosion of Uranium Dioxide: Role of Molecular Species

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Uranyl interaction with the hydrated (0001) basal face of gibbsite: A combined theoretical and spectroscopic study

International audienceThe sorption of uranyl cations and water molecules on the basal (001) face of gibbsite was studied by combining vibrational and fluorescence spectroscopies together with density functional theory ͑DFT͒ computations. Both the calculated and experimental values of O–H bond lengths for the gibbsite bulk are in good agreement. In the second part, water sorption with this surface was studied to take into account the influence of hydration with respect to the uranyl adsorption. The computed water configurations agreed with previously published molecular dynamics studies. The uranyl adsorption in acidic media was followed by time-resolved laser-induced fluorescence spectroscopy and Raman spectrometry measurements. The existence of only one kind of adsorption site for the uranyl cation was then indicated in good agreement with the DFT calculations. The computation of the uranyl adsorption has been performed by means of a bidentate interaction with two surface oxygen atoms. The optimized structures displayed strong hydrogen bonds between the surface and the-yl oxygen of uranyl. The uranium-surface bond strength depends on the protonation state of the surface oxygen atoms. The calculated U – O surface bond lengths range between 2.1–2.2 and 2.6– 2.7 Å for the nonprotonated and protonated surface O atoms, respectively

Know their Customers: An Empirical Study of Online Account Enumeration Attacks

Internet users possess accounts on dozens of online services where they are often identified by one of their e-mail addresses. They often use the same address on multiple services and for communicating with their contacts. In this paper, we investigate attacks that enable an adversary (e.g., company, friend) to determine (stealthily or not) whether an individual, identified by their e-mail address, has an account on certain services (i.e., an account enumeration attack). Such attacks on account privacy have serious implications as information about one’s accounts can be used to (1) profile them and (2) improve the effectiveness of phishing. We take a multifaceted approach and study these attacks through a combination of experiments (63 services), surveys (318 respondents), and focus groups (13 participants). We demonstrate the high vulnerability of popular services (93.7%) and the concerns of users about their account privacy, as well as their increased susceptibility to phishing e-mails that impersonate services on which they have an account. We also provide findings on the challenges in implementing countermeasures for service providers and on users’ ideas for enhancing their account privacy. Finally, our interaction with national data protection authorities led to the inclusion of recommendations in their developers’ guide

Pyrene coating transition metal disulfides as protection from photooxidation and environmental aging

This article belongs to the Section Nanocomposite Materials.Environmental degradation of transition metal disulfides (TMDs) is a key stumbling block in a range of applications. We show that a simple one-pot non-covalent pyrene coating process protects TMDs from both photoinduced oxidation and environmental aging. Pyrene is immobilized non-covalently on the basal plane of exfoliated MoS2 and WS2. The optical properties of TMD/pyrene are assessed via electronic absorption and fluorescence emission spectroscopy. High-resolution scanning transmission electron microscopy coupled with electron energy loss spectroscopy confirms extensive pyrene surface coverage, with density functional theory calculations suggesting a strongly bound stable parallel-stacked pyrene coverage of ~2–3 layers on the TMD surfaces. Raman spectroscopy of exfoliated TMDs while irradiating at 0.9 mW/4 μm2 under ambient conditions shows new and strong Raman bands due to oxidized states of Mo and W. Yet remarkably, under the same exposure conditions TMD/pyrene remain unperturbed. The current findings demonstrate that pyrene physisorbed on MoS2 and WS2 acts as an environmental barrier, preventing oxidative surface reactions in the TMDs catalyzed by moisture, air, and assisted by laser irradiation. Raman spectroscopy confirms that the hybrid materials stored under ambient conditions for two years remained structurally unaltered, corroborating the beneficial role of pyrene for not only hindering oxidation but also inhibiting aging.This research was funded by the European Union’s Horizon 2020 research and innovation programme under the Marie Sklodowska-Curie grant agreement No 642742, under the “Graphene Flagship” project grant agreement No 785219 and under the ESTEEM-3 project grant agreement No 823717. This research was also partially funded by the project “Advanced Materials and Devices” (MIS 5002409), which is implemented under the “Action for the Strategic Development on the Research and Technological Sector” funded by the Operational Program “Competitiveness, Entrepreneurship and Innovation” (NSRF 2014–2020) and co-financed by Greece and the European Union (European Regional Development Fund). This work was supported by the COST Action CA15107 MultiComp. This research was also supported by the Spanish Ministerio de Economia y Competitividad (MAT2016-79776-P), from the Government of Aragon and the European Social Fund under the project “Construyendo Europa desde Aragon” 2014–2020 (grant number E13_17R).Peer reviewe

Ripple edge engineering of graphene nanoribbons

It is now possible to produce graphene nanoribbons (GNRs) with atomically defined widths. GNRs offer many opportunities for electronic devices and composites, if it is possible to establish the link between edge structure and functionalisation, and resultant GNR properties. Switching hydrogen edge termination to larger more complex functional groups such as hydroxyls or thiols induces strain at the ribbon edge. However we show that this strain is then relieved via the formation of static out-of-plane ripples. The resultant ribbons have a significantly reduced Young's Modulus which varies as a function of ribbon width, modified band gaps, as well as heterogeneous chemical reactivity along the edge. Rather than being the exception, such static edge ripples are likely on the majority of functionalized graphene ribbon edges.Comment: Supplementary Materials availabl

Stable hydrogenated graphene edge types: Normal and reconstructed Klein edges

Hydrogenated graphene edges are assumed to be either armchair, zigzag or a combination of the two. We show that the zigzag is not the most stable fully hydrogenated structure along the direction. Instead hydrogenated Klein and reconstructed Klein based edges are found to be energetically more favourable, with stabilities approaching that of armchair edges. These new structures "unify" graphene edge topology, the most stable flat hydrogenated graphene edges always consisting of pairwise bonded C2H4 edge groups, irrespective the edge orientation. When edge rippling is included, CH3 edge groups are most stable. These new fundamental hydrogen terminated edges have important implications for graphene edge imaging and spectroscopy, as well as mechanisms for graphene growth, nanotube cutting, and nanoribbon formation and behaviour.Fundação para a Ciência e a Tecnologia (FCT

Regulation of ploidy and senescence by the AMPK-related kinase NUAK1.

Senescence is an irreversible cell-cycle arrest that is elicited by a wide range of factors, including replicative exhaustion. Emerging evidences suggest that cellular senescence contributes to ageing and acts as a tumour suppressor mechanism. To identify novel genes regulating senescence, we performed a loss-of-function screen on normal human diploid fibroblasts. We show that downregulation of the AMPK-related protein kinase 5 (ARK5 or NUAK1) results in extension of the cellular replicative lifespan. Interestingly, the levels of NUAK1 are upregulated during senescence whereas its ectopic expression triggers a premature senescence. Cells that constitutively express NUAK1 suffer gross aneuploidies and show diminished expression of the genomic stability regulator LATS1, whereas depletion of NUAK1 with shRNA exerts opposite effects. Interestingly, a dominant-negative form of LATS1 phenocopies NUAK1 effects. Moreover, we show that NUAK1 phosphorylates LATS1 at S464 and this has a role in controlling its stability. In summary, our work highlights a novel role for NUAK1 in the control of cellular senescence and cellular ploidy.We thank the members of the Laboratory for helpful discussions. We also thank Virginie Glippa and Julie Bertout for technical assistance. We thank H Esumi for the NUAK1 cDNA, E Hara and H Saya for the LATS1‐encoding vector. This work was carried out with the support of the ‘Association pour la Recherche sur le Cancer’, the ‘Fondation pour la Recherche Médicale Nord Pas de Calais’, the ‘Comité du Pas de Calais de la Ligue Nationale contre le Cancer’, the RTRS Fondation Synergie Lyon Cancer, and the Medical Research Council, UK.S