Separated nano jetting and micro jetting regimes by double-pulse irradiation of a metal film: towards multiscale printing.

The Double-Pulse (DP) version of the Laser-Induced Forward Transfer (LIFT) technique holds great potential to improve the resolution and flexibility of printing applications. In this study, we investigate the transfer of copper. A long laser pulse is first applied to melt thin copper films deposited on a transparent substrate, followed by an ultrashort laser pulse to initiate the transfer of the liquid material towards a receiver substrate. Time-resolved imaging experiments reveal that ejections from nanodrops to liquid jets with controllable diameters, from few micrometers down to the nanometers scale can be obtained with the control parameters of DP-LIFT. Comparing simulation and experiments we discuss how the ejection characteristics are governed by various factors including the shape, diameter and temperature of the melted pool created with the first long pulse. While the formation of microjets is due to the dynamical deformation of the melted film, as for the conventional LIFT process applied with liquid donors, the results indicate a different and distinct process for the formation of nanojets. We extrapolate from the observations a feature caused by the interaction of the shockwave, generated by the femtosecond laser irradiation, with the deformed surface of the pool. Ultimately, we establish the range of irradiation parameters leading to the observation of single separated microjets and nanojets. The latter are accompanied by nano printing demonstrations. Considering all accessible regimes together, a unique technological perspective is the possibility to achieve multi-scale printing from the same donor.

Timing of spring departure of long distance migrants correlates with previous year's conditions at their breeding site.

Precise timing of migration is crucial for animals targeting seasonal resources at locations encountered across their annual cycle. Upon departure, long-distance migrants need to anticipate unknown environmental conditions at their arrival site, and they do so with their internal annual clock. Here, we tested the hypothesis that long-distance migrants synchronize their circannual clock according to the phenology of their environment during the breeding season and therefore adjust their spring departure date according to the conditions encountered at their breeding site the year before. To this end, we used tracking data of Eurasian curlews from different locations and combined movement data with satellite-extracted green-up dates at their breeding site. The spring departure date was better explained by green-up date of the previous year, while arrival date at the breeding site was better explained by latitude and longitude of the breeding site, suggesting that other factors impacted migration timing en route. On a broader temporal scale, our results suggest that long-distance migrants may be able to adjust their migration timing to advancing spring dates in the context of climate change.

Short-Pulse Lasers: A Versatile Tool in Creating Novel Nano-/Micro-Structures and Compositional Analysis for Healthcare and Wellbeing Challenges.

Driven by flexibility, precision, repeatability and eco-friendliness, laser-based technologies have attracted great interest to engineer or to analyze materials in various fields including energy, environment, biology and medicine. A major advantage of laser processing relies on the ability to directly structure matter at different scales and to prepare novel materials with unique physical and chemical properties. It is also a contact-free approach that makes it possible to work in inert or reactive liquid or gaseous environment. This leads today to a unique opportunity for designing, fabricating and even analyzing novel complex bio-systems. To illustrate this potential, in this paper, we gather our recent research on four types of laser-based methods relevant for nano-/micro-scale applications. First, we present and discuss pulsed laser ablation in liquid, exploited today for synthetizing ultraclean "bare" nanoparticles attractive for medicine and tissue engineering applications. Second, we discuss robust methods for rapid surface and bulk machining (subtractive manufacturing) at different scales by laser ablation. Among them, the microsphere-assisted laser surface engineering is detailed for its appropriateness to design structured substrates with hierarchically periodic patterns at nano-/micro-scale without chemical treatments. Third, we address the laser-induced forward transfer, a technology based on direct laser printing, to transfer and assemble a multitude of materials (additive structuring), including biological moiety without alteration of functionality. Finally, the fourth method is about chemical analysis: we present the potential of laser-induced breakdown spectroscopy, providing a unique tool for contact-free and space-resolved elemental analysis of organic materials. Overall, we present and discuss the prospect and complementarity of emerging reliable laser technologies, to address challenges in materials' preparation relevant for the development of innovative multi-scale and multi-material platforms for bio-applications.

Nanosecond Laser-Fabricated Monolayer of Gold Nanoparticles on ITO for Bioelectrocatalysis.

Redox enzymes can be envisioned as biocatalysts in various electrocatalytic-based devices. Among factors that play roles in bioelectrochemistry limitations, the effect of enzyme-enzyme neighboring interaction on electrocatalysis has rarely been investigated, although critical in vivo. We report in this work an in-depth study of gold nanoparticles prepared by laser ablation in the ultimate goal of determining the relationship between activity and enzyme density on electrodes. Nanosecond laser interaction with nanometric gold films deposited on indium tin oxide support was used to generate in situ gold nanoparticles (AuNPs) free from any stabilizers. A comprehensive analysis of AuNP size and coverage, as well as total geometric surface vs. electroactive surface is provided as a function of the thickness of the treated gold layer. Using microscopy and electrochemistry, the long-term stability of AuNP-based electrodes in the atmosphere and in the electrolyte is demonstrated. AuNPs formed by laser treatment are then modified by thiol chemistry and their electrochemical behavior is tested with a redox probe. Finally, enzyme adsorption and bioelectrocatalysis are evaluated in the case of two enzymes, i.e., the Myrothecium verrucaria bilirubin oxidase and the Thermus thermophilus laccase. Behaving differently on charged surfaces, they allow demonstrating the validity of laser treated AuNPs for bioelectrocatalysis.

In Vitro Analysis of the Effects of ITER-Like Tungsten Nanoparticles: Cytotoxicity and Epigenotoxicity in BEAS-2B Cells.

Tungsten was chosen as a wall component to interact with the plasma generated by the International Thermonuclear Experimental fusion Reactor (ITER). Nevertheless, during plasma operation tritiated tungsten nanoparticles (W-NPs) will be formed and potentially released into the environment following a Loss-Of-Vacuum-Accident, causing occupational or accidental exposure. We therefore investigated, in the bronchial human-derived BEAS-2B cell line, the cytotoxic and epigenotoxic effects of two types of ITER-like W-NPs (plasma sputtering or laser ablation), in their pristine, hydrogenated, and tritiated forms. Long exposures (24 h) induced significant cytotoxicity, especially for the hydrogenated ones. Plasma W-NPs impaired cytostasis more severely than the laser ones and both types and forms of W-NPs induced significant micronuclei formation, as shown by cytokinesis-block micronucleus assay. Single DNA strand breaks, potentially triggered by oxidative stress, occurred upon exposure to W-NPs and independently of their form, as observed by alkaline comet assay. After 24 h it was shown that more than 50% of W was dissolved via oxidative dissolution. Overall, our results indicate that W-NPs can affect the in vitro viability of BEAS-2B cells and induce epigenotoxic alterations. We could not observe significant differences between plasma and laser W-NPs so their toxicity might not be triggered by the synthesis method.

Tracing changes in the diet and habitat use of black-tailed godwits in Western France, using a stable isotope approach.

Western France is at the crossroads of the migratory routes of two subspecies of black-tailed godwit, Limosa limosa. After leaving Iceland, the godwit L.l. islandica Icelandic black-tailed godwit (IBTG) winters on the coast of western Europe, while the continental black-tailed godwit (CBTG) L.l. limosa can stop in France when migrating between Iberia or Africa and their main breeding grounds in the Netherlands. In this study, we analysed δ15N and δ13C from flight feathers and whole blood throughout the non-breeding period to trace variations in habitat use for both subspecies on the western French coast. Adults and juveniles of IBTG adopt the same feeding habitats as soon as they arrive in the study area, progressively losing the Icelandic freshwater habitat signal, and becoming clearly restricted to marine habitats in winter. Some individuals begin to move locally to freshwater habitats, joining CBTG in a stopover at the end of the wintering period in preparation for northward migration.

Generating liquid nanojets from copper by dual laser irradiation for ultra-high resolution printing.

When the energy of a short laser pulse is localized in a fluid material, a flow motion is induced that can lead to the generation of free-surface jets. This nozzle-free jetting process is exploited to print conductive materials, typically metal nanoparticle inks, but this approach remains limited to the transfer of low viscosity fluids with a minimum feature size of few micrometers. We introduce a dual-laser method to achieve reproducible high-aspect-ratio jets from thin solid films. A first laser irradiation induces the melting of copper thin films and a second synchronized short pulse irradiation initiates the jetting process. Using time-resolved microscopy, we investigate the influence of the film thickness on the flow motion mechanisms and the ejection dynamics. For a wide range of laser fluences, we present observations similar to those obtained when the jets are generated by a single laser pulse from liquid donor films. The use of a solid film allows reducing the film thickness and then the volume of transferred material. Finally, we analyze these results in the perspective of using this double pulse LIFT technique for additive manufacturing of nano-micro-structures. Stable jets are formed from the copper films over distances exceeding 50-µm and are exploited to demonstrate periodic printing of 1.5-µm diameter droplets.

Building a database for long-term monitoring of benthic macrofauna in the Pertuis-Charentais (2004-2014).

BACKGROUND: Long-term benthic monitoring is rewarding in terms of science, but labour-intensive, whether in the field, the laboratory, or behind the computer. Building and managing databases require multiple skills, including consistency over time as well as organisation via a systematic approach. Here, we introduce and share our spatially explicit benthic database, comprising 11 years of benthic data. It is the result of intensive benthic sampling that has been conducted on a regular grid (259 stations) covering the intertidal mudflats of the Pertuis-Charentais (Marennes-Oléron Bay and Aiguillon Bay). Samples were taken by foot or by boats during winter depending on tidal height, from December 2003 to February 2014. The present dataset includes abundances and biomass densities of all mollusc species of the study regions and principal polychaetes as well as their length, accessibility to shorebirds, energy content and shell mass when appropriate and available. This database has supported many studies dealing with the spatial distribution of benthic invertebrates and temporal variations in food resources for shorebird species as well as latitudinal comparisons with other databases. In this paper, we introduce our benthos monitoring, share our data, and present a "guide of good practices" for building, cleaning and using it efficiently, providing examples of results with associated R code. NEW INFORMATION: The dataset has been formatted into a geo-referenced relational database, using PostgreSQL open-source DBMS. We provide density information, measurements, energy content and accessibility of thirteen bivalve, nine gastropod and two polychaete taxa (a total of 66,620 individuals)​ for 11 consecutive winters. Figures and maps are provided to describe how the dataset was built, cleaned, and how it can be used. This dataset can again support studies concerning spatial and temporal variations in species abundance, interspecific interactions as well as evaluations of the availability of food resources for small- and medium size shorebirds and, potentially, conservation and impact assessment studies.

High-speed multi-jets printing using laser forward transfer: time-resolved study of the ejection dynamics.

This paper extends the current understanding of the laser-induced forward transfer (LIFT) process to the multi-jets ejection problem. LIFT has already been used to print micrometer-sized droplets from a liquid donor substrate with single pulse experiments. Here we study the dynamics of the high-speed multi-jets formation from silver nanoparticles ink films with a time-resolved imaging technique. A galvanometric mirrors head controls the spacing between adjacent pulses by scanning the focused beam of a high repetition rate UV picosecond laser along an ink-coated donor substrate. The laser pulses interact with the liquid film and generate cavitation bubbles that propel the ink away from the substrate and form the jets. When the spacing between consecutive pulses is substantially higher than the maximum diameter of the bubbles, there is no interaction between adjacent jets, and these remain unperturbed. However, when the pulses are brought closer significant jet-jet interaction takes place, which results in a clear deviation from the single jet dynamics. Thus, the cavitation bubbles acquire different shapes, the ink is ejected faster and along different directions depending on the spacing between the pulses, and each bubble alters the evolution of the previous one and shifts away from it.

Influence of pyrene grafting on PMMA nanosecond laser ablation at 248 nm.

In this work, we investigate the effects of KrF nanosecond laser ablation on poly(methyl methacrylate) (PMMA) in combination with pyrene. Three materials containing PMMA were studied: (1) one doped with pure pyrene, (2) one doped with methyl 3-(1-pyrenyl)propanoate (so called alkylpyrene derivative thereafter), and (3) one grafted with pyrene. This last new material was developed by covalently bonding pyrene molecules to PMMA side-chains. A comparative study was undertaken to determine and compare the respective properties of the PMMA dye containing pyrene during nanosecond laser ablation at 248 nm. Cavities were etched for each material with up to 20 pulses for fluences between 0.03 and 1.7 J/cm(2) in samples containing 1, 2, and 4 mol % chromophore. The threshold fluences and the effective absorption coefficients were obtained. It was observed that effective absorption coefficients increased and threshold fluences decreased with the chromophore percentages in each kind of sample. Ablation parameters were not significantly modified when the dopant was changed from pyrene to the alkylpyrene derivative. On the other hand, when pyrene molecules were grafted on the polymer, the threshold fluences decreased, whereas the effective absorption coefficients became similar at fluences above 0.6 J/cm(2).

Pulsed-laser printing of silver nanoparticles ink: control of morphological properties.

Fine electrically-conductive patterns of silver nanoparticles ink have been laser printed using the laser-induced forward transfer (LIFT) technique. LIFT is a technique that offers the possibility of printing patterns with high spatial resolution from a wide range of materials in solid or liquid state. Influence of drying the ink film, previous to its transfer, on the printed droplet morphology is discussed. The laser pulse energy and donor-receiver substrate separation were systematically varied and their effects on the transferred droplets were analyzed. The use of an intermediate titanium dynamic release layer was also investigated and demonstrated the possibility of a better control of both the size and shape of the printed patterns. Conditions have been determined for printing flat-top droplets with sharp edges. 21 µm width silver lines with 80 nm thickness have been printed with a smooth convex profile. Electrical resistivities of the transferred patterns are only 5 times higher than the bulk silver.

Laser-induced breakdown spectroscopy and chemometrics: a novel potential method to analyze wheat grains.

Laser-induced breakdown spectroscopy (LIBS) has been widely used to evaluate the elemental composition (e.g., minerals or metal accumulation) on vegetal tissues. The main objective of this work was to differentiate wheat outer tissues during the grain ablation using LIBS and univariate/multivariate analysis. A high resolution spectrometer and a Nd:YAG laser (532 nm, 5 ns) was first used in order to easily identify atomic wheat emission lines. Then a pulsed excimer laser ArF (193 nm, 15 ns) and a compact fiber optic spectrometer was used to acquire LIBS spectral data from each pulse. Univariate and multivariate analyses (MW2D, PLS-DA) were carried out to provide more in depth information from the LIBS experiment. The number of pulses needed to ablate wheat tissues was successfully predicted by the supervised pattern recognition procedure. LIBS used in conjunction with multivariate analysis could be an interesting technique for rapid structural analysis of vegetal material.

Laser-generated plasma plume expansion: combined continuous-microscopic modeling.

The physical phenomena involved in the interaction of a laser-generated plasma plume with a background gas are studied numerically. A three-dimensional combined model is developed to describe the plasma plume formation and its expansion in vacuum or into a background gas. The proposed approach takes advantages of both continuous and microscopic descriptions. The simulation technique is suitable for the simulation of high-rate laser ablation for a wide range of background pressure. The model takes into account the mass diffusion and the energy exchange between the ablated and background species, as well as the collective motion of the ablated species and the background-gas particles. The developed approach is used to investigate the influence of the background gas on the expansion dynamics of the plume obtained during the laser ablation of aluminum. At moderate pressures, both plume and gas compressions are weak and the process is mainly governed by the diffusive mixing. At higher pressures, the interaction is determined by the plume-gas pressure interplay, the plume front is strongly compressed, and its center exhibits oscillations. In this case, the snowplough effect takes place, leading to the formation of a compressed gas layer in front of the plume. The background pressure needed for the beginning of the snowplough effect is determined from the plume and gas density profiles obtained at various pressures. Simulation results are compared with experimentally measured density distributions. It is shown that the calculations suggest localized formation of molecules during reactive laser ablation.