Selective control of molecule charge state on graphene using tip-induced electric field and nitrogen doping

The combination of graphene with molecules offers promising opportunities to achieve new functionalities. In these hybrid structures, interfacial charge transfer plays a key role in the electronic properties and thus has to be understood and mastered. Using scanning tunneling microscopy and ab initio density functional theory calculations, we show that combining nitrogen doping of graphene with an electric field allows for a selective control of the charge state in a molecular layer on graphene. On pristine graphene, the local gating applied by the tip induces a shift of the molecular levels of adsorbed molecules and can be used to control their charge state. Ab initio calculations show that under the application of an electric field, the hybrid molecule/graphene system behaves like an electrostatic dipole with opposite charges in the molecule and graphene sub-units that are found to be proportional to the electric field amplitude, which thereby controls the charge transfer. When local gating is combined with nitrogen doping of graphene, the charging voltage of molecules on nitrogen is greatly lowered. Consequently, applying the proper electric field allows one to obtain a molecular layer with a mixed charge state, where a selective reduction is performed on single molecules at nitrogen sites. The local gating applied by a tip induces a shift of the energy levels of molecules adsorbed on graphene. A team led by Jerome Lagoute at Universite Paris Diderot investigated the interplay between the charge state of molecules on pristine and doped-graphene, and the tip-induced electric fields in scanning tunneling microscopy experiments. The tip-induced electric field was found to shift the molecular levels of tetracyanoquinodimethane molecules on graphene, leading to a change of charge state at negative bias. Ab initio calculations indicated that the molecule-on-graphene hybrid structure can be regarded as an electrostatic dipole, hence the charge transfer and associated electronic charge in the molecule and graphene could be tuned by the electric field. Furthermore, inserting nitrogen atom dopants allowed shifting the energy levels of single molecules absorbed directly on the electron-donating point defects

Molecular-scale dynamics of light-induced spin cross-over in a two-dimensional layer

Spin cross-over molecules show the unique ability to switch between two spin states when submitted to external stimuli such as temperature, light or voltage. If controlled at the molecular scale, such switches would be of great interest for the development of genuine molecular devices in spintronics, sensing and for nanomechanics. Unfortunately, up to now, little is known on the behaviour of spin cross-over molecules organized in two dimensions and their ability to show cooperative transformation. Here we demonstrate that a combination of scanning tunnelling microscopy measurements and ab initio calculations allows discriminating unambiguously between both states by local vibrational spectroscopy. We also show that a single layer of spin cross-over molecules in contact with a metallic surface displays light-induced collective processes between two ordered mixed spin-state phases with two distinct timescale dynamics. These results open a way to molecular scale control of two-dimensional spin cross-over layers

Impact of air pollution in industrial areas on the foliar accumulation and transfer of metals in plants

Les sites industriels de production et de recyclage de métaux ferreux et non-ferreux sont à l’origine d’émissions locales dans l’atmosphère de particules riches en métaux et métalloïdes (As, Cd, Fe, Pb, Sb, Zn …) qui peuvent avoir un impact sur l’environnement et la santé humaine. En particulier, lorsque ces industries sont situées près de zones urbaines, ces particules peuvent contaminer les sols et les végétaux lors de leur retombée, induisant ainsi un risque sanitaire pour les populations. La contamination des plantes potagères par les métaux est un sujet de préoccupation des pouvoirs publics et de la communauté scientifique. L’étude de l’accumulation et du transfert des métaux, dans les réseaux trophiques, est donc d’importance majeure pour évaluer les risques sanitaires. Si la contamination des végétaux par le transfert sol-plantes a donné lieu à de nombreuses études, la contamination des plantes potagères par la voie foliaire n’est plus à ignorer, comme le montrent des travaux récents. L’étude de l’accumulation et du transfert des métaux a été effectuée in situ et en conditions contrôlées pour différents végétaux consommables aux caractéristiques morphologiques différentes (laitue, ray-grass, chou commun). L’accumulation des métaux, leur transfert dans les végétaux et l’évaluation des impacts phytotoxiques, caractérisés par des techniques de microscopie et de spectrométrie (MEB-EDX, Raman, EXAFS/XANES, LA-ICP-MS, RPE…) ainsi que par des tests biologiques (activité photosynthétique, génotoxicité, expression génique), ont été discutés en fonction de la concentration en métaux, de leur spéciation et de leur localisation sur/dans les feuilles et du temps d’exposition.Industrial activities such as production and recycling of ferrous and non-ferrous metals can emit in the atmosphere large quantities of metal(loid)s-rich particles (As, Cd, Fe, Pb, Sb, Zn …) which may have an impact on the environment and human health. Especially when these industries are located near urban areas, particles can contaminate soils and plants when they fallout, thus inducing a health risk for the population. Contamination of vegetables by metals is a topic of concern for public authorities and the scientific community. Studying the accumulation and transfer of metal(loid)s in food webs is therefore of major importance to assess health risks. The plant contamination by the soil-plant transfer has led to numerous studies and the contamination of vegetables by foliar pathway can't be ignored, as shown by recent work. The study of accumulation and transfer of metals (metalloids) has been carried out in situ and under controlled conditions for various consumable plants with different morphological characteristics (lettuce, ryegrass and cabbage). The accumulation and transfer of metals and their phytotoxicity, characterized by microscopy and spectrometric techniques (SEM-EDX, Raman, EXAFS/XANES, LA-ICP-MS, EPR…) and biological tests (photosynthetic activity, genotoxicity, gene expression), have been discussed in terms of metals concentration, metals location and speciation on/into leaves and exposure time

Foliar or root exposures to smelter particles: Consequences for lead compartmentalization and speciation in plant leaves

International audienceIn urban areaswith high fallout of airborne particles,metal uptake by plantsmainly occurs by foliar pathways and can strongly impact crop quality. However, there is a lack of knowledge on metal localization and speciation in plants after pollution exposure, especially in the case of foliar uptake. In this study, two contrasting crops, lettuce (Lactuca sativa L.) and rye-grass (Lolium perenne L.), were exposed to Pb-rich particles emitted by a Pb-recycling factory via either atmospheric or soil application. Pb accumulation in plant leaves was observed for both ways of exposure. The mechanisms involved in Pb uptake were investigated using a combination of microscopic and spectroscopic techniques (electron microscopy, laser ablation, Raman microspectroscopy, and X-ray absorption spectroscopy). The results showthat Pb localization and speciation are strongly influenced by the type of exposure (root or shoot pathway) and the plant species. Foliar exposure is the main pathway of uptake, involving the highest concentrations in plant tissues. Under atmospheric fallouts, Pb-rich particles were strongly adsorbed on the leaf surface of both plant species. In lettuce, stomata contained Pb-rich particles in their apertures, with some deformations of guard cells. In addition to PbO and PbSO4, chemical forms that were also observed in pristine particles, newspecies were identified: organic compounds (minimum 20%) and hexagonal platy crystals of PbCO3. In rye-grass, the changes in Pb speciation were even more egregious: Pb–cell wall and Pb–organic acid complexes were the major species observed. For root exposure, identified here as a minor pathway of Pb transfer compared to foliar uptake, another secondary species, pyromorphite, was identified in rye-grass leaves. Finally, combining bulk and spatially resolved spectroscopic techniques permitted both the overall speciation and the minor but possibly highly reactive lead species to be determined in order to better assess the health risks involved

Foliar or root exposures to smelter particles: Consequences for lead compartmentalization and speciation in plant leaves

International audienceIn urban areaswith high fallout of airborne particles,metal uptake by plantsmainly occurs by foliar pathways and can strongly impact crop quality. However, there is a lack of knowledge on metal localization and speciation in plants after pollution exposure, especially in the case of foliar uptake. In this study, two contrasting crops, lettuce (Lactuca sativa L.) and rye-grass (Lolium perenne L.), were exposed to Pb-rich particles emitted by a Pb-recycling factory via either atmospheric or soil application. Pb accumulation in plant leaves was observed for both ways of exposure. The mechanisms involved in Pb uptake were investigated using a combination of microscopic and spectroscopic techniques (electron microscopy, laser ablation, Raman microspectroscopy, and X-ray absorption spectroscopy). The results showthat Pb localization and speciation are strongly influenced by the type of exposure (root or shoot pathway) and the plant species. Foliar exposure is the main pathway of uptake, involving the highest concentrations in plant tissues. Under atmospheric fallouts, Pb-rich particles were strongly adsorbed on the leaf surface of both plant species. In lettuce, stomata contained Pb-rich particles in their apertures, with some deformations of guard cells. In addition to PbO and PbSO4, chemical forms that were also observed in pristine particles, newspecies were identified: organic compounds (minimum 20%) and hexagonal platy crystals of PbCO3. In rye-grass, the changes in Pb speciation were even more egregious: Pb–cell wall and Pb–organic acid complexes were the major species observed. For root exposure, identified here as a minor pathway of Pb transfer compared to foliar uptake, another secondary species, pyromorphite, was identified in rye-grass leaves. Finally, combining bulk and spatially resolved spectroscopic techniques permitted both the overall speciation and the minor but possibly highly reactive lead species to be determined in order to better assess the health risks involved

Copper oxide nanoparticle foliar uptake, phytotoxicity, and consequences for sustainable urban agriculture

International audienceThroughout the world, urban agriculture supplies fresh local vegetables to city populations. However, the increasing anthropogenic uses of metal-containing nanoparticles (NPs) such as CuO-NPs in urban areas may contaminate vegetables through foliar uptake. This study focused on the CuO-NP transfer processes in leafy edible vegetables (i.e., lettuce and cabbage) to assess their potential phytotoxicity. Vegetables were exposed via leaves for 5, 10, or 15 days to various concentrations of CuO-NPs (0, 10, or 250 mg per plant). Biomass and gas exchange values were determined in relation to the Cu uptake rate, localization, and Cu speciation within the plant tissues. High foliar Cu uptake occurred after exposure for 15 days for lettuce [3773 mg (kg of dry weight)-1] and cabbage [4448 mg (kg of dry weight)-1], along with (i) decreased plant weight, net photosynthesis level, and water content and (ii) necrotic Cu-rich areas near deformed stomata containing CuO-NPs observed by scanning electron microscopy and energy dispersive X-ray microanalysis. Analysis of the CuO-NP transfer rate (7.8-242 μg day-1), translocation of Cu from leaves to roots and Cu speciation biotransformation in leaf tissues using electron paramagnetic resonance, suggests the involvement of plant Cu regulation processes. Finally, a potential health risk associated with consumption of vegetables contaminated with CuO-NPs was highlighted

Chroniques du GDR NEMO N°3

Chronique scientifique du Groupe de Recherche CNRS : NEw MOlecular Electronic

Control of Molecule–Metal Interaction by Hydrogen Manipulation in an Organic Molecule

International audienceFree-base porphyrin molecules offer appealing options to tune theinteraction with their environment via the manipulation of their inner hydrogen atomsand molecular conformation. Using scanning tunneling microscopy we show, through asystematic study, that the molecular conformation, electronic gap, wave function, andmolecule−substrate interaction are modified by hydrogen switch or removal.Experimental results in combination with ab initio calculations provide an understandingof the underlying physical process

Chroniques du GDR NEMO N°3

Chronique scientifique du Groupe de Recherche CNRS : NEw MOlecular Electronic

Black Phosphorus for Directed Molecular Assembly with Weak Electronic Coupling

International audienceThe combination of two-dimensional materials with organic molecules offers the possibility to obtain low dimensional hybrid materials with tailored properties. Black phosphorus is a monoelemental semiconducting material with a non-planar puckered atomic structure. Here, we study porphyrin molecules on black phosphorus and show that they self-assemble with an epitaxial relationship indicating that the molecule-surface interaction largely dominates the molecule-molecule interaction. The atomic structure of black phosphorus is found to be at the origin of the substrate driven self-assembly. Despite this strong interaction with molecules, the electronic coupling is found to be weak allowing the molecules to maintain the properties of their gas phase, which is the usual behaviour for van der Waals materials. Therefore, the combination of the peculiar puckered structure with the van der Waals nature of black phosphorus provides this material with the ability to interact strongly enough with adsorbed molecules to drive their assembly but weakly enough to keep their electronic properties intact