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The ion-induced fragmentation of C H 4 2 + into H+ and C H 3 + is studied using a cold target recoil ion momentum spectroscopy in coincidence with the charge state of the post-collision projectile. Using constant velocity Ar9+ and N3+, results from four different datasets are presented, with a selection on the final charge state of the projectile (Ar8+ or Ar7+ and N2+ or N+). Three distinct dissociation pathways (I, II, and III) are observed for each dataset, with the mean kinetic energy release values of around 4.7, 5.8, and 7.9 eV, respectively. The electronic states that are populated correspond to electronic configurations (1 t 2 ) − 2 and (2 a 1 ) − 1 (1 t 2 ) − 1 of the methane dication, C H 4 2 + . The relative branching ratios between the three pathways are discussed as a function of the charge state of the post-collision projectile, and a strong correlation with the specific nature of the ion–molecule interaction is found. The existing ab initio calculations have provided an explanation only for pathway II. In this article, we propose an explanation for pathway III, but pathway I still remains unexplained and requires further theoretical efforts. A discussion of the dependence of dissociation on the mode of excitation is presented. [ABSTRACT FROM AUTHOR]

Most common methods of cellular analysis employ the top-down approach (investigating proteomics or genomics directly), thereby destroying the cell, which does not allow the possibility of using the same cell to correlate genomics with functional assays. Herein we describe an approach for single-cell tools that serve as a bottom-up approach. Our technology allows functional phenotyping to be conducted by observing the cytotoxicity of cells and then probe the underlying biology. We have developed a droplet microfluidic device capable of trapping droplets in the array and releasing the droplet of interest selectively using microvalves. Each droplet in the array encapsulates natural killer cells (NK cells) and tumour cells for real-time monitoring of burst kinetics and spatial coordination during killing by single NK cells. Finally, we use the microvalve actuation to selectively release droplets with the desired functional phenotype such as for fast and serial killing of target tumour cells by NK cells. From this perspective, our device allows for investigating first interactions and real-time monitoring of kinetics and later cell recovery on demand for single-cell omic analysis such as single-cell RNA sequencing (scRNA), which to date, is primarily based on in-depth analyses of the entire transcriptome of a relatively low number of cells. [ABSTRACT FROM AUTHOR]

In this paper, we demonstrate a selective multisite splitting and merging system to perform the type of permutations of reactions required for high-throughput screening. Our approach uses multiple single-layer microfluidic valves as they offer simplicity, biocompatibility, and high-speed operation. These valves are used both to control the generation of droplets and the location of splitting. In the former, the valves are used to completely block some microchannels; in the latter, they create a more modest local geometry variation. The generated droplets act as a vessel that transports different samples around the chip; these vessels can then be subdivided at splitting locations, just as a pipette can be used to dispense a fraction of its total volume. The split droplets enter a merging channel, in which daughter droplets of different types can be merged. We demonstrate the merging of different droplet types in different concentrations at four merging locations. [ABSTRACT FROM AUTHOR]

The fallopian tube is lined with a highly complex folded epithelium surrounding a lumen that progressively narrows. To study the influence of this labyrinthine complexity on sperm behavior, we use droplet microfluidics to create soft curved interfaces over a range of curvatures corresponding to the in vivo environment. We reveal a dynamic response mechanism in sperm, switching from a progressive surface-aligned motility mode at low curvatures (larger droplets), to an aggressive surface-attacking mode at high curvatures (smaller droplets of <50 µm-radius). We show that sperm in the attacking mode swim ~33% slower, spend 1.66-fold longer at the interface and have a 66% lower beating amplitude than in the progressive mode. These findings demonstrate that surface curvature within the fallopian tube alters sperm motion from a faster surface aligned locomotion in distal regions to a prolonged physical contact with the epithelium near the site of fertilization, the latter being known to promote capacitation and fertilization competence. The effect of fallopian tube's curvature on sperm motion has not been studied in detail. Here, the authors use droplet microfluidics to create soft curved interfaces, revealing a dynamic switch in sperm motility from a progressive surface-aligned mode at low curvatures, to an aggressive surface-attacking mode at high curvatures. [ABSTRACT FROM AUTHOR]

We irradiated the complex organic molecule pyridine and mixtures of pyridine and water in the solid phase (thin icy films) at 12 K at different beam lines of the GANIL facility (ARIBE: 90 keV O 6 + , SME: 650 MeV Zn 26 + ) . The destruction of the initial molecule and the appearance of radiolytic products were followed by in-situ infrared absorption spectroscopy as a function of the projectile fluence with the CASIMIR experimental set-up of CIMAP. We measured the destruction cross section as a function of pyridine concentration. A clear dependence on the percentage of pyridine in H 2 O was found: the destruction cross sections are significantly higher for small concentration, i.e. pure pyridine is more radioresistant than pyridine diluted in water ice at 12 K. Thus, the presence of water environment significantly modifies the radiation resistance of the initial complex organic molecules: it enhances radiosensitivity and destruction of pyridine, with implications for radiobiology and astrochemistry. [ABSTRACT FROM AUTHOR]

Context. Micrometeorites represent, at timescales shorter than a few million years, the dominant source of extraterrestrial matter at the surface of the Earth. Analyses of ultracarbonaceous micrometeorites recovered from Antarctica, known as UCAMMs reveal an exceptionally N-rich organic matter associated with spatially extended high D enrichments. Experiments show that this specific organic matter might have been formed in the outer solar system by energetic irradiation of N-rich icy surfaces. Aims. We experimentally investigate the hydrogen isotopic fractionation resulting from irradiation of normal and D-rich N2-CH4 ices by high energy ions, simulating the exposition to Galactic cosmic rays of icy bodies surfaces orbiting at large heliocentric distances. Methods. Films of N2-CH4 ices and a N2-CH4/CD4/N2-CH4 "sandwich" ice were exposed to 129Xe13+ ion beams at 92 and 88 MeV. The chemical evolution of the samples was monitored using in situ Fourier transform infrared spectroscopy. After irradiation, targets were annealed to room temperature. The solid residues of the whole process left after ice sublimation were characterized in situ by infrared spectroscopy, and the hydrogen isotopic composition measured ex situ by imaging secondary ion mass spectrometry at the sub-micron scale (NanoSIMS). Results. Irradiation leads to the formation of new molecules and radicals. After annealing, the resulting poly-HCN-like macro-molecular residue exhibits an infrared spectrum close to that of UCAMMs. The residue resulting from irradiation of N2-CH4 ices does not exhibit a significant deuterium enrichment comparable to that found in extraterrestrial organic matter. The residue formed by irradiation of D-rich ices shows the formation of isotopic heterogeneities with localised hotspots and an extended contribution likely due to the diffusion of the radiolytic products from the D-rich layer. Conclusions. These results show that high-energy cosmic ray irradiation does not induce the large hydrogen isotopic fractionation observed at small spatial scale in interplanetary organics. By contrast, large D/H ratio heterogeneities at the sub-micron spatial scale in extraterrestrial organic matter can result from isotopically heterogeneous ices mixtures (i.e. condensed with different D/H ratios), which were transformed into refractory organic matter upon irradiation. [ABSTRACT FROM AUTHOR]

Context. The occurrence of complex organic molecules (COMs) in the gas phase at low temperature in the dense phases of the interstellar medium suggests that a non-thermal desorption mechanism is at work because otherwise, COMs should condense within a short timescale onto dust grains. Vacuum ultraviolet (VUV) photodesorption has been shown to be much less efficient for complex organic molecules, such as methanol, because mostly photoproducts are ejected. The induced photolysis competes with photodesorption for large COMs, which considerably lowers the efficiency to desorb intact molecules. Aims. We pursue an experimental work that has already shown that water molecules, the dominant ice mantle species, can be efficiently sputtered by cosmic rays. We investigate the sputtering efficiency of complex organic molecules that are observed either in the ice mantles of interstellar dense clouds directly by infrared spectroscopy (CH3OH), or that are observed in the gas phase by millimeter telescopes (CH3COOCH3) and that could be released from interstellar grain surfaces. Methods. We irradiated ice films containing complex organic molecules (methanol and methyl acetate) and water with swift heavy ions in the electronic sputtering regime. We monitored the infrared spectra of the film as well as the species released to the gas phase with a mass spectrometer. Results. We demonstrate that when methanol or methyl acetate is embedded in a water-ice mantle exposed to cosmic rays, a large portion is sputtered as an intact molecule, with a sputtering yield close to that of the main water-ice matrix. This must be even more true for the case of more volatile ice matrices, such as those that are embedded in carbon monoxide. Conclusions. Cosmic rays penetrating deep into dense clouds provide an efficient mechanism to desorb complex organic molecules. Compared to the VUV photons, which are induced by the interaction of cosmic rays, a large portion desorb as intact molecules with a proportion corresponding to the time-dependent bulk composition of the ice mantle, the latter evolving with time as a function of fluence due to the radiolysis of the bulk. [ABSTRACT FROM AUTHOR]

Ices are omnipresent in cold regions in space on, e.g., comets, dust grains, transneptunian objects, surfaces of planets and their satellites. The dominant molecule in such ices is water, but also other small molecules or even complex organic molecules (COMs) may be present. Ionizing radiation (UV photons, electrons, ions from cosmic rays or solar wind) induces several physico-chemical processes such as radiolysis. The fragmentation of initial molecules followed by chemical reactions between radicals may lead to formation of new molecules. Furthermore, also implanted projectiles can contribute to chemistry by forming new molecular species. Other observed effects include structural changes (compaction, amorphization) and desorption (sputtering) of particles from the surface. At CIMAP (Caen, France), using the different beam lines of the GANIL facility, and at GSI (Darmstadt, Germany), the interaction of swift highly charged heavy ions with astrophysical ices has been studied in a wide projectile energy range from keV to GeV. Here, two examples of our studies on astrophysical and astrochemical applications will be discussed in detail: 1) the synthesis of COMs under irradiation of ices made of small molecules, and 2) radiosensitivity of COMs such as pyridine, glycine and adenine, both for isolated molecules in the gas phase and in condensed phase. Special emphasis is given on pyridine and pyridine in water matrix. [ABSTRACT FROM AUTHOR]

Ionization and fragmentation of uracil molecules (C4H4N2O2, m = 112 amu) in collisions with fast highly charged C, O and F ions have been investigated using a time-of-flight mass spectrometer. The measurement of total ionization cross sections (TCS) is reported for different charge states (q), such as Fq+ with q = 5-8; Oq+ with q = 5,7; Cq+ with q = 5 and 6. These studies reveal a (q/v)~1.5 dependence of TCS, in contrast, to the well-known q2-dependence in ion-atom collisions. Scaling properties of the TCS with projectile energy and charge states are obtained. The experimental results for TCS measurements are compared with the theoretical calculations performed within classical and quantum mechanical frameworks. The trends in energy dependence of the TCSs is qualitatively well reproduced by the different models and more specifically by the classical description, which provides the best agreement with measurements. [ABSTRACT FROM AUTHOR]

The L x-ray intensities of 79Au, 82Pb and 83Bi have been measured in collisions with 18-60 MeV fluorine ions in an angular range 20°-75°. The Ll x-ray intensity, normalized to the intensity of other L x-ray lines in the same spectrum, shows an anisotropic emission pattern and the degree of anisotropy depends on the impact energy of the projectile. The alignment parameter values for the L₃ subshell, deduced from the measured anisotropy parameter for the Ll line, have been compared with the theoretical ones. [ABSTRACT FROM AUTHOR]

We have measured the double differential cross sections (DDCSs) for low energy electron emission from O₂ under the impact of 51 MeV bare carbon ions. This study is aimed at investigating the Young-type interference in electron emission from a multi-electronic diatomic molecule. The DDCS spectra, differential in emission energy and angle, are compared with state-of-the-art continuum distorted wave-eikonal initial state (CDW-EIS) calculations. The DDCS ratios (i.e. O₂/2O) do not produce any oscillatory behaviour due to the interference effect unlike that observed in the case of H2. The forward-backward angular asymmetry parameter, deduced from the measured DDCS values, is found to be a monotonically increasing function of electron velocity and does not show any oscillation. These observations are in qualitative agreement with the prediction of the molecular CDW-EIS model which uses a linear combination of atomic orbitals. The apparent absence of the oscillation in the spectra is qualitatively explained in terms of cancellation of contributions arising from different molecular orbitals. [ABSTRACT FROM AUTHOR]

The x-ray bremsstrahlung spectrum emitted by the electron population in a 14.5 GHz ECR plasma source has been measured using a NaI(Tl) detector, and hence the electron temperature of the higher energy electron population in the plasma has been determined. The x-ray spectra for Ne and Ar gases have been systematically studied as a function of inlet gas pressure from 7 × 10-7 mbar to 7 × 10-5 mbar and for input microwave power ∼1 W to ∼300 W. At the highest input power and optimum pressure conditions, the end point bremsstrahlung energies are seen to reach ∼700 keV. The estimated electron temperatures (Te) were found to be in the range 20 keV-80 keV. The Te is found to be peaking at a pressure of 1 × 10-5 mbar for both gases. The Te is seen to increase with increasing input power in the intermediate power region, i.e., between 100 and 200 W, but shows different behaviour for different gases in the low and high power regions. Both gases show very weak dependence of electron temperature on inlet gas pressure, but the trends in each gas are different. [ABSTRACT FROM AUTHOR]