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For the last four decades space exploration missions have searched for molecular life on planetary surfaces beyond Earth. Often pyrolysis gas chromatography mass spectrometry has been used as payload on such space exploration missions. These instruments have relatively low detection sensitivity and their measurements are often undermined by the presence of chloride salts and minerals. Currently, ocean worlds in the outer Solar System, such as the icy moons Europa and Enceladus, represent potentially habitable environments and are therefore prime targets for the search for biosignatures. For future space exploration missions, novel measurement concepts, capable of detecting low concentrations of biomolecules with significantly improved sensitivity and specificity are required. Here we report on a novel analytical technique for the detection of extremely low concentrations of amino acids using ORIGIN, a compact and lightweight laser desorption ionization – mass spectrometer designed and developed for in situ space exploration missions. The identified unique mass fragmentation patterns of amino acids coupled to a multi-position laser scan, allows for a robust identification and quantification of amino acids. With a detection limit of a few fmol mm−2, and the possibility for sub-fmol detection sensitivity, this measurement technique excels current space exploration systems by three orders of magnitude. Moreover, our detection method is not affected by chemical alterations through surface minerals and/or salts, such as NaCl that is expected to be present at the percent level on ocean worlds. Our results demonstrate that ORIGIN is a promising instrument for the detection of signatures of life and ready for upcoming space missions, such as the Europa Lander.

A new phase of carbon named Q-carbon is found to be over 40% harder than diamond. This phase is formed by nanosecond laser melting of amorphous carbon and rapid quenching from the super-undercooled state. Closely packed atoms in molten metallic carbon are quenched into Q-carbon with 80-85% sp3 and the rest sp2. The number density of atoms in Q-carbon can vary from 40% to 60% higher than diamond cubic lattice, as the tetrahedra packing efficiency increases from 70% to 80%. Using this semiempirical approach, the corresponding increase in Q-carbon hardness is estimated to vary from 48% to 70% compared to diamond.

Atomically thin graphene exhibits fascinating mechanical properties, although its hardness and transverse stiffness are inferior to those of diamond. To date, there hasn't been any practical demonstration of the transformation of multi-layer graphene into diamond-like ultra-hard structures. Here we show that at room temperature and after nano-indentation, two-layer graphene on SiC(0001) exhibits a transverse stiffness and hardness comparable to diamond, resisting to perforation with a diamond indenter, and showing a reversible drop in electrical conductivity upon indentation. Density functional theory calculations suggest that upon compression, the two-layer graphene film transforms into a diamond-like film, producing both elastic deformations and sp2-to-sp3 chemical changes. Experiments and calculations show that this reversible phase change is not observed for a single buffer layer on SiC or graphene films thicker than 3 to 5 layers. Indeed, calculations show that whereas in two-layer graphene layer-stacking configuration controls the conformation of the diamond-like film, in a multilayer film it hinders the phase transformation., Comment: Published online on Nature Nanotechnology on December 18, 2017

Nine black powders found in Pompeii houses in three different types of bronze vessels (cylindrical theca atramentaria, unguentaries, and aryballoi) were characterized in order to assess a correspondence between the composition and the type of vessel and, possibly, to verify if these powders were inks or not. For the compositional characterization, a multi-analytical approach was adopted, which involved the use of scanning electron microscopy-energy dispersive X-ray, Fourier-transformed infrared spectroscopy, Raman, X-ray diffraction, electron paramagnetic resonance spectroscopy, thermogravimetric analysis, gas chromatography coupled with mass spectrometry (GC/MS), and pyrolysis GC/MS. Powders contained in cylindrical theca atramentaria form a homogeneous group, and their organic and inorganic compositions suggest that they were writing inks, while powders contained in unguentaries and aryballoi could have had several different uses, including writing inks and cosmetics. Furthermore, the composition profile of the powders found in cylindrical cases shows that, at 79 AD: , in Pompeii, carbon-based inks were still used for writing, and iron gall inks had not been introduced yet.

The possibility of successfully applying a common GC–MS procedure for identification in one step of all types of dyes from plants of unknown origin and from historical objects is particularly attractive due to the high separation efficiency of the capillary columns, the MS detection sensitivity and the reproducibility of results. In this work, GC–MS analysis, previously and successfully used for the characterization of anthraquinones, flavonoids and tannins from plant extracts and historical samples, has been tested on indigoid dyestuffs. An analytical procedure based on the silylating agent N,O-bis-(trimethylsilyl)trifluoroacetamide (BSTFA) with 1 % trimethylchlorosilane (TMCS) was applied to pure molecules of indigotin and indirubin and to plant extracts of Indigofera tinctoria L. and Isatis tinctoria L. Preliminary tests have been done to establish the chromatographic conditions and the derivatization amounts most suitable for the simultaneous detection of indigoid molecules and of the other natural compounds, such as fatty acids, carboxylic acids and sugars, contained within the plant extracts. In order to assess the capacity and the sensitivity of the analytical procedure in typical archaeometric applications, wool samples dyed in the laboratory with indigo were analysed by mimicking the sample amounts typically available with historical objects. The electron ionization (EI) spectra of the main silylated derivatives of indigoid molecules obtained in this way constitute the necessary data set for the characterization of natural extracts and historical works of art. Subsequently, the procedure has been applied to historical samples for the detection of indigo and of other dyestuffs eventually contained in samples. Additional information, useful for restoration and preservation of works of art, could be also obtained on the nature of stains and smudges present on the sampled textile material. The GC–MS method turns out to be an efficient and fast analytical tool also for the identification of natural indigo in plants and textile artefacts, providing results complementary to those from high-performance liquid chromatography (HPLC).

International audience; Graphene oxide has multiple potential applications. The chemistry of graphene oxide and its response to external stimuli such as temperature and light are not well understood and only approximately controlled. This under- standing is crucial to enable future applications of this material. Here, a com- bined experimental and density functional theory study shows that multilayer graphene oxide produced by oxidizing epitaxial graphene via the Hummers method is a metastable material whose structure and chemistry evolve at room temperature with a characteristic relaxation time of about one month. At the quasi-equilibrium, graphene oxide reaches a nearly-stable reduced O/C ratio, and exhibits a structure intensively deprived of epoxide groups and enriched of hydroxyl groups. Our calculations show that the structural and chemical changes are driven by the availability of hydrogen in the oxidized graphitic sheets, which favors the reduction of epoxide groups and the formation of water molecules.

Graphene oxide holds great promise for future applications in nano-technology. The chemistry of this material is not well understood. This understanding is crucial to enable future applications of graphene oxide. In this study, experiments and density functional theory calculations are combined to elucidate the chemical properties of multilayer graphene oxide obtained by oxidizing epitaxial graphene grown on silicon carbide via the Hummers method. This study shows that at room temperature as prepared graphene oxide films exhibit a uniform and homogeneous structure, include a minimal amount of edges and holes, and have an oxidation ratio of about 0.44. The comparison with density-functional calculations shows that graphene oxide includes a minimal amount of intercalated water molecules and well-defined fractions of epoxide and hydroxyl groups.

In contrast to the ultralow friction that exists between carbon layers in multiwalled carbon nanotubes, multiwalled boron nitride nanotubes are found to exhibit ultrahigh interlayer friction as a result of their ionic character.

What exactly Wolf von Niebelschutz did as a soldier in a propaganda unit during the wartime years of 1940–1945, and whether the Wehrmacht newspapers he took care of still exist, was not clear until recently. This article brings together all the currently available information on the German writer’s period of service in France and Germany and analyses the articles from the newspapers that were found. Whilst it is clear that the articles written by Niebelschutz are German wartime propaganda, it also becomes clear that the writer’s articles were not nearly as defaming as those of his propaganda unit colleagues. Moreover there were several attempts by Niebelschutz to stop working for the military, as well as clear remarks in letters to his relatives about his aversion to the kind of work he was doing. After his efforts to leave the military failed, he continued to work for the propaganda unit, apparently because he believed that this would be the easiest way to increase his probability of surviving the war.

In the version of this Article originally published, the second affiliation for Walter A. de Heer had not been included; it should be 'TICNN, Tianjin University, Tianjin, China'. This has now been added and the numbering of subsequent affiliations amended accordingly in all versions of the Article.

Poly(vinylacohol) (PVA) is a versatile polymer capable of forming hydrogels useful in a wide range of applications. Hydrogels based on cross-linking of PVA with borax, and able to incorporate organic solvents, have been used in the field of cultural heritage as tool for cleaning the surfaces. Poly(ethylenoxide) (PEO) has been introduced in the formulations of PVA-borax, with the aim of increasing the gel compatibility with organic solvents and of improving the mechanical properties of the materials. The formulations were investigated with rheological characterization, solvent loss measurements and study of the free water through the determination of the Free Water Index. The PEO molecules do not participate in the formation of the network but have been found to be responsible for a decrement of the storage moduli, explained by a spacing between crosslinks and the partial disentanglement of the PVA chains. At the same time PEO produces in the gel an increase of the apparent relaxation time, thus stabilizing the dispersions and enhancing their ability to maintain the shape. Cleaning tests for removal of an acrylic coating on limestone have been also successfully performed.

The process-based Pasture Simulation Model (PaSim 2.5) has been extended to simulate N2O production and emission from grassland caused by nitrogen inputs from different sources. The model was used to assess the influence of management on N2O emissions, such as the effect of shifts in the amount and timing of fertilizer application. Model performance has been tested against season-long field measurements at two different field sites. Simulation results agreed favourably with measured N2O emission and soil air concentrations, except during an extremely wet period at one site when grass growth was very poor. The results of short-term and long-term simulation runs demonstrated the potential of the model to estimate N2O emission factors under various conditions. During the first growing season, simulated emissions from organic fertilizers were lower than from synthetic fertilizers because more of the nitrogen was used to build up soil organic matter. The relative difference between the fertilizer types became larger with increasing application rate. The difference between fertilizer types was smaller at steady-state when higher soil organic matter content from repeated application of organic fertilizer over time led to enhanced mineralization and N2O emissions. The dependence of simulated N2O emissions on N input was close to linear at low, but non-linear at high fertilization rates. Emission factors calculated from the linear part of the curve suggested that the factors used in the current IPCC method underestimate the long-term effects of changes in fertilizer management. Furthermore the simulations show that N2O emissions caused by nitrogen inputs from the decomposition of harvest losses and from biological fixation in grassland can be considerable and should not be neglected in national emission inventories.

A new study to address the biosphere-atmosphere exchange of ammonia (NH3) with grasslands is applying a European transect to interpret NH3 fluxes in relation to atmospheric conditions, grassland management and soil chemistry. Micrometeorological measurements using the aerodynamic gradient method (AGM) with continuous NH3 detectors are supported by bioassays of the NH3 `stomatal compensation point' (χs). Relaxed eddy accumulation (REA) is also applied to enable flux measurements at one height; this is relevant to help address flux divergence due to gas-particle inter-conversion or the presence of local sources in a landscape.

The surface flux of nitric oxide from a wheat field was investigated from 23 March to 29 May 1997 in the Kerzersmoos, Switzerland. A plot fertilised with 19 kg N ha-1 in cattle slurry and 40 kg N ha-1 in mineral NH4NO3 fertiliser and a plot receiving no nitrogen containing fertiliser were compared. The flux was calculated based on hourly measurements of the NO soil–atmosphere concentration gradient using the one-dimensional soil diffusion model of Galbally and Johansson (1989). The soil bulk diffusion coefficient was determined from measurements of the 222Rn surface flux and the activity gradient between 10 cm depth and the surface. It ranged between 79% and 0.3% of the NO diffusion coefficient in air and was parameterised by air filled soil pore space. The indirectly determined NO flux agreed well with standard flux measurements using dynamic chambers. The largest NO emission was found following fertiliser application and irrigation. The emission occurred in pulses, which lasted for 4 days up to 3 weeks coinciding with elevated soil ammonium concentrations. Nitric oxide emission in 5 days following application of cattle slurry were 31 g NO-N ha-1 and 5 g NO-N ha-1 from the non-fertilised plot, respectively. Nitric oxide emission in 15 days following application of NH4NO3 was 95 g NO-N ha-1 and 10 g NO-N ha-1 from the non-fertilised plot, respectively. NO emission in 4 days following irrigation on 21 April were 36 g N ha-1 from the fertilised and 39 g N ha-1 from the non-fertilised plot. The daily NO emission before and after fertiliser and irrigation pulses was between 0.3 and 0.7 g NO-N ha-1 d-1. NO production and NO uptake of the soil was measured regularly. No systematic influence of management or climate on NO uptake was found. NO production was strongly stimulated by fertiliser input and soil moisture content. The simulation of NO production could be reproduced using a nitrification algorithm (Riedo et al., 1998) driven by soil temperature, moisture and ammonium concentration. A NO production rate constant of 1.1ċ10-3 h-1 at 15 °C was derived from a linear regression between nitrification and NO production. Introducing the parameterisation of NO production into the model of Galbally and Johansson (1989) the duration and the strength of the NO emission pulses could be reproduced and the total NO emission during the experiment was approximated within a factor of two.

Nanoscience can play an important role in addressing a number of societal challenges, but, as Rein V. Ulijn and Elisa Riedo explain, research training needs to evolve.

Recently, the development of a versatile thermochemical nanolithography (TCNL) technique has been reported. It allows simultaneous control of the local chemistry and topography of thin polymer films. This technique can pattern sub 15 nm chemical and topographical features at the rate of 1.4 mm per second by inducing thermally-activated chemical reactions by means of a heated atomic force microscope (AFM) tip. TCNL is achievable in different environments and can easily be adapted to a variety of substrates and chemical functionalities. Here, we demonstrate that a thin polymer film can be chemically modified twice using TCNL to tune its wettability. We are able to write hydrophilic nanopatterns over a hydrophobic polymer surface upon a first step heating and then revert back to hydrophobic surface by a second step heating. This write-read-overwrite capability is particularly useful in data storage application and complex nanofluidic device design.

High resistivity CdTe:In and CdZnTe samples were studied by means of continuos and picosecond time-resolved photoluminescence (PL). Detected PL signal is affected by non-radiative trapping into defects, while radiative recombination has an excitonic character. Time-resolved PL can be described by two lifetimes: the first (30-60 ps) takes into account fast non radiative recombination, the second in the range 200-300 ps can be related to exciton decay.