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N-heterocycles are suspected to play an important role in the chemical origin of life. Despite their detection in meteorites and in Titan’s atmosphere, their extra-terrestrial chemical formation networks remain elusive. Furthermore N-heterocyclics are undetected in the interstellar medium. This paper assesses the photostability of protonated N-hetero(poly)acenes after ultraviolet (UV) and vacuum ultraviolet (VUV) excitation. It provides information on their ability to retain the N atom into the cycle to generate larger N-containing species or functionalized N-heterocyles. Protonated N-hetero(poly)acenes were generated using electrospray ionization and injected into a linear ion trap where they were irradiated by radiation of 4.5 to 10 eV using the DESIRS beamline at the synchrotron SOLEIL. The photodissociation action spectra of protonated pyridine, quinoline, isoquinoline, and acridine were measured by recording the photofragment yields as a function of photon energy. The four systems exhibit dissociation channels associated with H2 and HCN/HNC loss but with different branching ratios. The results indicate that increasing the size of the N-hetero(poly)acenes increases the chance of retaining the N atom in the larger fragment ion after photodissociation but it remains that all the protonated N-hetero(poly)acenes studied lose their N atom at part of a small neutral photofragment, with high propensity. Therefore, protonated N-hetero(poly)acenes in interstellar space are unlikely precursors to form larger N-containing species. However, protonated pyridine, quinoline, isoquinoline, and acridine are most likely to retain their N atoms in planetary atmospheres where UV radiation at the planet’s surface is typically restricted to wavelengths greater than 200 nm – suggesting such environments are possible substrates for prebiotic chemistry.

The gas phase offers the possibility to analyze organic molecules by ultraviolet-vacuum ultraviolet (UV-VUV) spectroscopy without any solvent effect or limitation in terms of spectral range due to absorption by the solvent. Up to now, the size and chemical composition of neutral molecular systems under study have been limited by the use of vaporization methods based on thermal heating. Soft sources of gas-phase thermolabile molecular systems such as electrospray or matrix-assisted laser desorption ionization are appealing alternatives to heating-based techniques, but they lead to the production of ions. In such cases, UV-VUV action spectroscopy is then the method of choice to study the electronic structure and corresponding photodynamics of these gas-phase molecular ions. However, previous investigations have shown that the UV-VUV action spectrum of a given molecular ion depends on the charge state, which in many cases might be a caveat. Here, by means of synchrotron radiation coupled to mass spectrometry and through the test case of the glycopeptide antibiotic vancomycin noncovalently bound to a deprotonated small peptide, we show that the UV-VUV photofragmentation spectrum of neutral thermally fragile organic molecules can be obtained via charge-tagging action spectroscopy.

Mammalian hyaluronidases are endo-N-acetyl-D-hexosaminidases involved in the catabolism of hyaluronic acid (HA) but their role in the catabolism of chondroitin sulfate (CS) is also examined. HA and CS are glycosaminoglycans implicated in several physiological and pathological processes, and understanding their metabolism is of significant importance. Data have been previously reported on the degradation of CS under the action of hyaluronidase, yet a detailed structural investigation of CS depolymerization products remains necessary to improve our knowledge of the CS depolymerizing activity of hyaluronidase. For that purpose, the fine structural characterization of CS oligosaccharides formed upon the enzymatic depolymerization of various CS subtypes by hyaluronidase has been carried out by high-resolution Orbitrap mass spectrometry (MS) and extreme UV (XUV) photodissociation tandem MS. The exact mass measurements show the formation of wide size range of even oligosaccharides upon digestion of CS-A and CS-C comprising hexa- and octa-saccharides among the main digestion products, as well as formation of small quantities of odd-numbered oligosaccharides, while no hyaluronidase activity was detected on CS-B. In addition, slight differences have been observed in the distribution of oligosaccharides in the digestion mixture of CS-A and CS-C, the contribution of longer oligosaccharides being significantly higher for CS-C. The sequence of CS oligosaccharide products determined XUV photodissociation experiments verifies the selective β(1 → 4) glycosidic bond cleavage catalyzed by mammal hyaluronidase. The ability of the mammal hyaluronidase to produce hexa- and higher oligosaccharides supports its role in the catabolism of CS anchored to membrane proteoglycans and in extra-cellular matrix.

The investigation of the photoionization processes of a series of titanium oxo clusters evidenced that doping their organic shell with extended aromatic structures decreases their ionization energy and stabilises the resulting radical cations. Such tunability of their photochemistry arising from ligand exchange gives these hybrid compounds great potential as EUV photoresists.

International audience; The partial enzymatic hydrolysis of wheat gliadins constitutes an interesting tool to unravel their structural specificity. In this work, the structure and conformation of γ-gliadin were investigated through its limited chymotrypsic digestion. Using a combination of computational, biochemical and biophysical tools, we studied each of its N and C terminal domains. Our results reveal that γ-gliadin is a partially disordered protein with an unfolded N-terminal domain surprisingly resistant to chymotrypsin and a folded C-terminal domain. Using spectroscopic tools, we showed that structural transitions occured over the disordered N-terminal domain for decreasing ethanol/water ratios. Using SAXS measurements, low-resolution 3D structures of γ-gliadin were proposed. To relate the repeated motifs of the N-terminal domain of γ-gliadin to its structure, engineered peptide models PQQPY/F were also studied. Overall results demonstrated similarities between the N-terminal domain and its derived model peptides. Our findings support the use of these peptides as general templates for understanding the wheat protein assembly and dynamics.

As a part of interstellar dust, polycyclic aromatic hydrocarbons (PAHs) are processed by the interaction with vacuum ultraviolet (VUV) photons that are emitted by hot young stars. This interaction leads to the emission of the well-known aromatic infrared bands but also of electrons, which can significantly contribute to the heating of the interstellar gas.Our aim is to investigate the impact of molecular size on the photoionization properties of cationic PAHs.Methods. Trapped PAH cations of sizes between 30 and 48 carbon atoms were submitted to VUV photons in the range of 9 to 20 eV from the DESIRS beamline at the synchrotron SOLEIL. All resulting photoproducts including dications and fragment cations were mass-analyzed and recorded as a function of photon energy.Photoionization is found to be predominant over dissociation at all energies, which differs from an earlier study on smaller PAHs. The photoionization branching ratio reaches 0.98 at 20 eV for the largest studied PAH. The photoionization threshold is observed to be between 9.1 and 10.2 eV, in agreement with the evolution of the ionization potential with size. Ionization cross sections were indirectly obtained and photoionization yields extracted from their ratio with theoretical photoabsorption cross sections, which were calculated using time-dependent density functional theory. An analytical function was derived to calculate this yield for a given molecular size.Large PAH cations could be efficiently ionized in H i regions and provide a contribution to the heating of the gas by photoelectric effect. Also, at the border of or in H ii regions, PAHs could be exposed to photons of energy higher than 13.6 eV. Our work provides recipes to be used in astronomical models to quantify these points., Comment: Astronomy and Astrophysics - A\&A, EDP Sciences, In press

International audience; To meet the requirements for EUV nanolithography, the semiconductor industry has drawn attention towards hybrid inorganic-organic based photoresists. However, the mechanisms responsible for the solubility switch in these materials are not well understood. In this work, UV/ VUV (4-14 eV) photon-induced fragmentations of Zn-based oxoclusters in the gas phase are investigated to study the fundamental reactivity of their cationic form. Irradiation of the parent cations results mainly in the ligand dissociation and fragmentation of the inorganic clusters at energies below the second ionization threshold (～12 eV). This ionization energy appears to be linked to the methacrylate ligand in the organic shell. We presume that this type of fragmentations can also occur when the oxoclusters are ionized in the thin film upon EUV irradiation.

Polycyclic aromatic hydrocarbons (PAHs) are key species in astrophysical environments in which vacuum ultraviolet (VUV) photons are present, such as star-forming regions. The interaction with these VUV photons governs the physical and chemical evolution of PAHs. Models show that only large species can survive. However, the actual molecular properties of large PAHs are poorly characterized and the ones included in models are only an extrapolation of the properties of small and medium-sized species. We discuss here experiments performed on trapped ions including some at the SOLEIL VUV beam line DESIRS. We focus on the case of the large dicoronylene cation, C 48 H 20 + , and compare its behavior under VUV processing with that of smaller species. We suggest that C2 H2 is not a relevant channel in the fragmentation of large PAHs. Ionization is found to largely dominate fragmentation. In addition, we report evidence for a hydrogen dissociation channel through excited electronic states. Although this channel is minor, it is already effective below 13.6 eV and can significantly influence the stability of astro-PAHs. We emphasize that the competition between ionization and dissociation in large PAHs should be further evaluated for their use in astrophysical models.

Ultraviolet (UV) synchrotron radiation circular dichroism (SRCD) spectroscopy has made an important contribution to the determination and understanding of the structure of bio-molecules. In this paper, we report an innovative approach that we term time-resolved SRCD (tr-SRCD), which overcomes the limitations of current broadband UV SRCD setups. This technique allows accessing ultrafast time scales (down to nanoseconds), previously measurable only by other methods, such as infrared (IR), nuclear magnetic resonance (NMR), fluorescence and absorbance spectroscopies and small angle X-ray scattering (SAXS). The tr-SRCD setup takes advantage of the natural polarisation of the synchrotron radiation emitted by a bending magnet to record broadband UV CD faster than any current SRCD setup, improving the acquisition speed from 10 mHz to 130 Hz and the accessible temporal resolution by several orders of magnitude. We illustrate the new approach by following the isomers concentration changes of an azopeptide after a photoisomerisation. This breakthrough in SRCD spectroscopy opens up a wide range of potential applications to the detailed characterisation of biological processes, such as protein folding, protein-ligand binding.

Wheat storage proteins, gliadins, were found to form in vitro condensates in 55% ethanol/water mixture by decreasing temperature. The possible role of this liquid-liquid phase separation (LLPS) process on the in vivo gliadins storage is elusive and remains to be explored. Here we use γ-gliadin as a model of wheat proteins to probe gliadins behavior in conditions near physiological conditions. Bioinformatic analyses suggest that γ-gliadin is a hybrid protein with N-terminal domain predicted to be disordered and C-terminal domain predicted to be ordered. Spectroscopic data highlight the disordered nature of γ-gliadin. We developed an in vitro approach consisting to first solubilize γ-gliadin in 55% ethanol (v/v) and to progressively decrease ethanol ratio in favor of increased aqueous solution. Our results show the ability of γ-gliadin to self-assemble into dynamic droplets through LLPS, with saturation concentrations ranging from 25.9 µM ± 0.85 µM (35% ethanol (v/v)) to 3.8 µM ± 0.1 µM (0% ethanol (v/v)). We demonstrate the importance of the predicted ordered C-terminal domain of γ-gliadin in the LLPS by highlighting the protein condensates transition from a liquid to a solid state under reducing conditions. We demonstrate by increasing ionic strength the role displayed by electrostatic interactions in the phase separation. We also show the importance of hydrogen bonds in this process. Finally, we discuss the importance of gliadins condensates in their accumulation and storage in the wheat seed.

International audience; Ultraviolet (UV) synchrotron radiation circular dichroism (SRCD) spectroscopy has made an important contribution to the determination and understanding of the structure of bio-molecules. In this paper, we report an innovative approach that we term time-resolved SRCD (tr-SRCD), which overcomes the limitations of current broadband UV SRCD setups. This technique allows accessing ultrafast time scales (down to nanoseconds), previously measurable only by other methods, such as infrared (IR), nuclear magnetic resonance (NMR), fluorescence and absorbance spectroscopies and small angle X-ray scattering (SAXS). The tr-SRCD setup takes advantage of the natural polarisation of the synchrotron radiation emitted by a bending magnet to record broadband UV CD faster than any current SRCD setup, improving the acquisition speed from 10 mHz to 130 Hz and the accessible temporal resolution by several orders of magnitude. We illustrate the new approach by following the isomers concentration changes of an azopeptide after a photoisomerisation. This breakthrough in SRCD spectroscopy opens up a wide range of potential applications to the detailed characterisation of biological processes, such as protein folding, protein-ligand binding.

In cosmic environments, polycyclic aromatic hydrocarbons (PAHs) strongly interact with vacuum ultraviolet (VUV) photons emitted by young stars. Trapped PAH cations ranging in size from 30 to 48 carbon atoms were irradiated by tunable synchrotron light (DESIRS beamline at SOLEIL). Their ionization and dissociation cross sections were determined and compared with TD-DFT computed photoabsorption cross sections. Evidence for radiative cooling is reported.

Tandem mass spectroscopy ($\textrm{MS}^2$) combined with single photon excitation in the VUV range (photon energy 4.5-9 eV) was performed on protonated uracil ($\textrm{UraH}^{+}$) and uridine ($\textrm{UrdH}^{+}$). The precursor ions with $m/z\;113$ and $m/z\;245$ respectively were produced by an Electrospray Ionization source (ESI) and accumulated inside a quadrupole ion trap mass spectrometer. After irradiation with tunable synchrotron radiation, product ion mass spectra were obtained. Fragment yields as a function of exciting energy show several maxima that can be attributed to the photo-excitation into different electronic states. For uracil, vertically excited states were calculated using the equation-of-motion coupled cluster approach (EOM-CCSD) and compared to the observed maxima. This allows to establish correlations between electronic states and resulting fragment masses and can thus help to disentangle the complex deexcitation and fragmentation pathways of nucleic acid building blocks above the first electronically excited state. Photofragmentation of the nucleoside uridine shows a significantly lower variety of fragments, indicating stabilization of the nucleobase by the attached sugar., author version

International audience; Perfluorocarbons, a class of fully fluorinated compounds, are highly persistent and toxic pollutants that are receiving increasing attention due to their widespread environmental distribution. In this study, attention was focused on one compound in particular, namely, perfluorooctanoic acid (PFOA). The first investigation of the UV/VUV photochemistry of the PFOA anion in the gas phase by action spectroscopy of selected ions is reported. Two main relaxation channels were identified: photodissociation and photodetachment. Absolute cross sections for the individual observed processes were measured. DFT calculations and natural transition orbital analysis were carried out to help in the interpretation of the experimental results.

International audience; The nonapeptide oxytocin (OT) is used as a model sulfur-containing peptide to study the damage induced by vacuum UV (VUV) radiations. In particular, the effect of the presence (or absence in reduced OT) of oxytocin's internal disulfide bridge is evaluated in terms of photo-fragmentation yield and nature of the photo-fragments. Intact, as well as reduced, OT is studied as dianions and radical anions. Radical anions are prepared and photo-fragmented in two-color experiments (UV + VUV) in a linear ion trap. VUV photo-fragmentation patterns are analyzed and compared, and radical-induced mechanisms are proposed. The effect of VUV is principally to ionize but secondary fragmentation is also observed. This secondary fragmentation seems to be considerably enabled by the initial position of the radical on the molecule. In particular, the possibility to form a radical on free cysteines seems to increase the susceptibility to VUV fragmentation. Interestingly, disulfide bridges, which are fundamental for protein structure, could also be responsible for an increased resistance to ionizing radiations.

We report the result of the search for neutrinoless double beta decay of Se82 obtained with CUPID-0, the first large array of scintillating ZnSe82 cryogenic calorimeters implementing particle identification. We observe no signal in a 1.83 kg yr Se82 exposure, and we set the most stringent lower limit on the 0νββ Se82 half-life T1/20ν>2.4×1024 yr (90% credible interval), which corresponds to an effective Majorana neutrino mass mββ

International audience; Re-investigation of the chemical composition of the annual plant Mitracarpus scaber Zucc. led to the identification of clarinoside, a new pentalogin derivative containing a rare quinovose moiety, and the known compound harounoside. While the planar structure was fully determined using tandem mass spectrometry (MS) and quantum mechanics (QM) calculations, the tridimensional structure was unravelled after isolation and NMR analysis. The absolute configuration was assigned by comparison of experimental and theoretical synchrotron radiation circular dichroism spectra. Both compounds were tested for anti-inflammatory activity, and compound 1 showed the ability to inhibit the production of interleukin-8 (Il-8) with an IC50 value of 9.17 mu M.

International audience; Carotenoids are important natural pigments and micronutrients contributing to health prevention by several mechanisms, including their electron-donating (antioxidant) activity. In this work, a large series of carotenoids, including 11 carotenes and 14 xanthophylls, have been investigated by wavelength-resolved atmospheric pressure photoionization mass spectrometry (DISCO line of SOLEIL synchrotron), thus allowing the experimental determination of their ionization energy (IE) for the first time. On the other hand, the carotenoids have been also investigated for their ability to inhibit the heme iron-induced peroxidation of linoleic acid in mildly acidic micelles, a simple but relevant chemical model of oxidative stress in the gastric compartment. Thus, the carotenoids can be easily classified from IC50 concentrations deduced from the time dependence of the lipid hydroperoxide concentration. With a selection of two carotenes and three xanthophylls a quantitative analysis is also provided to extract stoichio-kinetic parameters. The influence of the carotenoid structure (number of conjugated carbon−carbon double bonds, presence of terminal six-membered rings, hydroxyl, keto, and/or epoxy groups) on the IE, IC50, and stoichio-kinetic parameters is discussed in details. The data show that the antioxidant activity of carotenes is well correlated to their electron-donating capacity, which itself largely depends on the length of the conjugated polyene chain. By contrast, the IE of xanthophylls is poorly correlated to the polyene chain length because of the strong, and sometimes unexpected, electronic effects of the O-atoms. Although IE remains an approximate predictor of the antioxidant activity of xanthophylls, other factors (interaction with the aqueous phase, competing radical-scavenging mechanisms, the residual activity of the antioxidant’s oxidation products) probably play a significant role.

Re-investigation of the chemical composition of the annual plant Mitracarpus scaber Zucc. led to the identification of clarinoside, a new pentalogin derivative containing a rare quinovose moiety, and the known compound harounoside. While the planar structure was fully determined using tandem mass spectrometry (MS) and quantum mechanics (QM) calculations, the tridimensional structure was unravelled after isolation and NMR analysis. The absolute configuration was assigned by comparison of experimental and theoretical synchrotron radiation circular dichroism spectra. Both compounds were tested for anti-inflammatory activity, and compound 1 showed the ability to inhibit the production of interleukin-8 (Il-8) with an IC 50 value of 9.17 μ M.

Tin-oxo cage materials are of interest for use as photoresists for EUV (Extreme­ Ultraviolet) lithography (13.5 run, 92 eV), owing to their large absorption cross section for EUV light. In this work we exposed an n-butyl tin-oxo cage dication in the gas phase to photons in the energy range 4-14 eV to explore its fundamental photoreactivity. At all energies above the onset of electronic absorption at 5 eV (250 run) cleavage of tin-carbon bonds was observed. With photon energies >12 eV (

Understanding the correlation between proteins' tertiary and electronic structures is a great challenge, which could possibly lead to a more efficient prediction of protein functions in living organisms. Here, we report an experimental study of the interplay between electronic and tertiary protein structure, by probing resonant core excitation and ionization over a number of charge-state selected precursors of electrically charged proteins. The dependence of the core ionization energies on the protein charge state shows that the ionization of a protonated protein is strongly correlated to its tertiary structure, which influences its effective Coulomb field. On the other hand, the electronic core-to-valence shell transition energies are not markedly affected by the unfolding of the protein, from compact to totally elongated structures, suggesting that frontier protein orbitals remain strongly localized. Nevertheless, the unfolding of a protein seems to influence the cross section ratio between different resonant electronic transitions.

The achievement of deep ultraviolet (UV) focal plane arrays (FPA) is required for both solar physics [1] and micro electronics industry. The success of solar mission (SOHO, STEREO [2], SDO [3]…), has shown the accuracy of imaging at wavelengths from 10 nm to 140 nm to reveal effects occurring in the sun corona. Deep UV steppers at 13 nm are another demanding imaging technology for the microelectronic industry in terms of uniformity and stability. A third application concerns beam shaping of Synchrotron lines [4]. Consequently, such wavelengths are of prime importance whereas the vacuum UV wavelengths are very difficult to detect due to the dramatic interaction of light with materials. The fast development of nitrides has given the opportunity to investigate AlGaN as a material for UV detection. Camera based on AlGaN present an intrinsic spectral selectivity and an extremely low dark current at room temperature. We have previously presented several FPA dedicated to deep UV based on 320 x 256 pixels of Schottky photodiodes with a pitch of 30 μm [4, 5]. AlGaN is grown on a silicon substrate instead of sapphire substrate only transparent down to 200 nm. After a flip-chip hybridization, silicon substrate and AlGaN basal layer was removed by dry etching. Then, the spectral responsivity of the FPA presented a quantum efficiency (QE) from 5p to 20p from 50 nm to 290 nm when removing the highly doped contact layer via a selective wet etching. This FPA suffered from a low uniformity incompatible with imaging, and a long time response due to variations of conductivity in the honeycomb. We also observed a low rejection of visible. It is probably due to the same honeycomb conductivity enhancement for wavelength shorter than 360 nm, i.e., the band gap of GaN. We will show hereafter an improved uniformity due to the use of a precisely ICP (Inductively Coupled Plasma) controlled process. The final membrane thickness is limited to the desertion layer. Neither access resistance limitation nor long response time are observed. QE varies from 5p at 50 nm to 15p at 6 nm (85p more when taking into account the filling factor). Consequently, we can propose prototypes concerning not only “solar blind” camera optimized for narrow band in the near UV range (between 280 nm and 260 nm), but also devices with spectral range extended in the deep UV (290 nm to 10 nm). Both detectors are available for an optical budget evaluation.

A multiwavelength study of laboratory carbons with varying degrees of hydrogenation and sp$^2$ hybridization is required to characterize the structure of the carbonaceous carriers of interstellar and circumstellar extinction. Analogs to carbonaceous interstellar dust encountered in various phases of the interstellar medium have been prepared in the laboratory. Thin films have been measured in transmission in the vacuum ultraviolet (VUV; 120 - 210 nm) within the atmospheric pressure experiment (APEX) chamber of the DISCO beam line at the SOLEIL synchrotron radiation facility. Spectra of these films were further measured through the UV-Vis (210 nm - 1 $\mu$m) and in the mid-infrared (3 - 15 $\mu$m). Tauc optical gaps, E$_g$, are derived from the visible spectra. The major spectral features are fitted through the VUV to the mid infrared to obtain positions, full-widths at half maximum (FWHM), and integrated intensities. These are plotted against the position of the $\pi$-$\pi^*$ electronic transitions peak. Unidentified or overlapping features in the UV are identified by correlations with complementary infrared data. A correlation between the optical gap and position of the $\pi$-$\pi^*$ electronic transitions peak is found. The latter is also correlated to the position of the sp$^3$ carbon defect band at ~8 $\mu$m, the aromatic C=C stretching mode position at ~6 $\mu$m, and the H/C ratio. Our study suggests that carriers of the interstellar UV bump should exhibit infrared bands akin to the A/B classes of the aromatic infrared bands, while the circumstellar bump carriers should exhibit bands corresponding to the B/C classes., Comment: 20 pages, 101 figures. Accepted for publication in Astronomy & Astrophysics (24 July 2017)

International audience; A method for spectroscopic characterization of free ionic clusters and nanoparticles utilizing X-ray synchrotron radiation is presented. We demonstrate that size-selected ammonium bisulphate cluster ions, NH4+(NH4HSO4)(n), captured in a linear ion trap, exhibit well-defined core-level absorption edges in the reconstructed fragment-ion abundance spectra. In addition to the specific photo-fragmentation pathways observed at the N1s-, O1s- and S2p-edges, dissociation also occurs as a consequence of clusters colliding with helium present as buffer gas in the ion trap. Separate off-beam experiments were conducted to establish the activation kinetics of these collision induced dissociation processes. Furthermore, it is demonstrated that the electrons released upon photoionization of background helium are too few in number to produce multiply charged cluster ions, and thereby induce fragmentation of the salt clusters, to any significant degree. The mechanisms for photon absorption and subsequent cluster fragmentation are analysed and discussed. In addition to its inherent element specificity, the method holds promise for cluster structure elucidation resulting from the sensitivity of the near edge absorption structure to the local chemical environment of the excited atom.

A new reactor, named APSIS for Atmospheric Photochemistry SImulated by Synchrotron, is designed for simulating the reactivity occurring in planetary upper atmospheres. In this reactor, a gas mixture roughly reproducing the main Titan's atmosphere composition (N2/CH4 = 90/10) is irradiated by a continuous-spectrum in the 60−350 nm range, provided by the DISCO beamline at SOLEIL synchrotron radiation facility. This spectral range enables the dissociation and ionization of N2 and CH4, as observed in plasma reactors and Titan's ionosphere. The neutral products are detected in situ by quadrupole mass spectrometry, and collected with a cryogenic trap for ex-situ analysis by gas chromatography-mass spectrometry. The detected reaction products include C2, C3, C4 and probably C5 organic compounds, with important amounts of nitrogen-bearing species: HCN, CH3CN and C2N2. Neutral mass spectra obtained with APSIS are compared with INMS experiments of the Cassini space probe in the upper Titan atmosphere and with other results of current Titan atmosphere chemistry laboratory simulations.

International audience; Single-photon, two-electron photodetachment from nickel phthalocyanine tetrasulfonic acid tetra anions, [NiPc](4-), was examined in the gas-phase using a linear ion trap coupled to the DESIRS VUV beamline of the SOLEIL Synchrotron. This system was chosen since it has a low detachment energy, known charge localization, and well-defined geometrical and electronic structures. A threshold for two-electron loss is observed at 10.2 eV, around 1 eV lower than previously observed double detachment thresholds on multiple charged protein anions. The photodetachment energy of [NiPc](4-) has been previously determined to be 3.5 eV and the photodetachment energy of [NiPc](3-center dot) is determined in this work to be 4.3 eV. The observed single photon double electron detachment threshold is hence 5.9 eV higher than the energy required for sequential single electron loss. Possible mechanisms are for double photodetachment are discussed. These observations pave the way toward new, exciting experiments for probing double photodetachment at relatively low energies, including correlation measurements on emitted photoelectrons.

International audience; The control protein Factor H (FH) is a crucial regulator of the innate immune complement system, where it is active on host cell membranes and in the fluid phase. Mutations impairing the binding capacity of FH lead to severe autoimmune diseases. Here, we studied the solution structure of full-length FH, in its free state and bound to the C3b complement protein. To do so, we used two powerful techniques, hydroxyl radical protein footprinting (HRPF) and chemical cross-linking coupled with mass spectrometry (MS), to probe the structural rearrangements and to identify protein interfaces. The footprint of C3b on the FH surface matches existing crystal structures of C3b complexed with the N- and C-terminal fragments of FH. In addition, we revealed the position of the central portion of FH in the protein complex. Moreover, cross-linking studies confirmed the involvement of the C-terminus in the dimerization of FH.

A full spectral characterization of carbonaceous dust analogs is necessary to understand their potential as carriers of observed astronomical spectral signatures such as the ubiquitous UV bump at 217.5 nm and the far-ultraviolet (FUV) rise common to interstellar extinction curves. Our goal is to study the spectral properties of carbonaceous dust analogs from the FUV to the mid-infrared (MIR) domain. We seek in particular to understand the spectra of these materials in the FUV range, for which laboratory studies are scarce. We produced analogs to carbonaceous interstellar dust encountered in various phases of the interstellar medium: amorphous hydrogenated carbons (a-C:H), for carbonaceous dust observed in the diffuse interstellar medium, and soot particles, for the polyaromatic component. Analogs to a-C:H dust were produced using a radio-frequency plasma reactor at low pressures, and soot nanoparticles films were produced in an ethylene (C$_2$H$_4$) flame. We measured transmission spectra of these thin films (thickness < 100 nm) in the far-ultraviolet (190 - 250 nm) and in the vacuum-ultraviolet (VUV; 50 - 190 nm) regions using the APEX chamber at the DISCO beam line of the SOLEIL synchrotron radiation facility. These were also characterized through infrared microscopy at the SMIS beam line. We successfully measured the transmission spectra of these analogs from {\lambda} = 1 {\mu}m to 50 nm. From these, we extracted the laboratory optical constants via Kramers-Kronig inversion. We used these constants for comparison to existing interstellar extinction curves. We extend the spectral measurements of these types of carbonaceous analogs into the VUV and link the spectral features in this range to the 3.4 {\mu}m band. We suggest that these two materials might contribute to different classes of interstellar extinction curves., Comment: 10 pages, 10 figures, accepted to Astronomy & Astrophysics on 13/11/2015

International audience; We have studied the photodissociation of gas-phase deprotonated caerulein anions by vacuum ultraviolet (VUV) photons in the 4.5 to 20 eV range, as provided by the DESIRS beamline at the synchrotron radiation facility SOLEIL (France). Caerulein is a sulphated peptide with three aromatic residues and nine amide bonds. Electron loss is found to be the major relaxation channel at every photon energy. However, an increase in the fragmentation efficiency (neutral losses and peptide backbone cleavages) as a function of the energy is also observed. The oxidized ions, generated by electron photodetachment were further isolated and activated by collision (CID) in a MS3 scheme. The branching ratios of the different fragments observed by CID as a function of the initial VUV photon energy are found to be independent of the initial photon energy. Thus, there is no memory effect of the initial excitation energy on the fragmentation channels of the oxidized species on the time scale of our tandem MS experiment. We also report photofragment yields as a function of photon energy for doubly deprotonated caerulein ions, for both closed-shell ([M - 2H](2-)) non-radical ions and open-shell ([M - 3H](2-center dot)) radical ions. These latter ions are generated by electron photodetachment from[M - 3H](3-) precursor ions. The detachment yield increases monotonically with the energy with the appearance of several absorption bands. Spectra for radical and non-radical ions are quite similar in terms of observed bands; however, the VUV fragmentation yield is enhanced by the presence of a radical in caerulein peptides.

International audience; Intensive fragmentations into b/y- and c-sequence ions have been reported for Substance P ionized under dopant-assisted atmospheric pressure photoionization (APPI) conditions. It was postulated that the fragmentation comes from the reaction of the doubly charged peptide with photoelectrons, released upon photoionization of the dopant, through an electron capture or transfer dissociation-type mechanism. In order to investigate further the origin of each fragment ion type, a tunable VUV synchrotron radiation source coupled to a modified APPI source has been used. Using this set-up, the photon energy can be scanned continuously below and above the photoionization threshold of the dopant, i.e. toluene, probing the ionization/fragmentation processes occurring on Substance P peptide at the atmospheric pressure interface of the mass spectrometer.

International audience; The bis(diphenylphosphino)methane (L = Ph2PCH2PPh2) ligated silver deuteride nanocluster dication, [Ag10D8L6](2+), has been synthesised in the condensed phase via the reaction of bis(diphenylphosphino)methane, silver nitrate and sodium borodeuteride in the methanol : chloroform (1 : 1)mixed solvent system. The photoionisation and photofragmentation of this mass-selected cluster were studied using a linear ion trap coupled to the DESIRS VUV beamline of the SOLEIL Synchrotron. At 15.5 eV the main ionic products observed are [Ag10D8L5](2+), [Ag10D8L4](2+), [Ag10D8L6](3+center dot), [Ag9D8L4](2+center dot), and [AgL2](+). The later two products arise from fragmentation of [Ag10D8L6](3+center dot). An analysis of the yields of these product ions as a function of the photon energy reveals the onset for the formation of [AgL2](+) and [Ag9D8L4](2+center dot) is around 2 eV higher than that for ionisation to produce [Ag10D8L5](3+center dot). The onset of ionisation energy of [Ag10D8L6](2+) was determined to be 9.3 +/- 0.3 eV from a fit of the yield of the product ion, [Ag10D8L6](3+)center dot, as a function of the VUV photon energy. DFT calculations at the RI-PBE/RECP-def2-SVP level of theory were carried out to search for a possible structure of the cluster and to estimate its vertical and adiabatic ionisation energies. The calculated lowest energy structure of the [Ag10D8L6](2+) nanocluster contains a symmetrical bicapped square antiprism as a silver core in which hydrides are located as a mix of triangular faces and edges. Four of the bisphosphines bind to the edges of the cluster core as bidentate ligands, the remaining two bisphosphines bind via a single phosphorus donor atom to each of the apical silver atoms. The DFT calculated adiabatic ionisation energy for this structure is 8.54 eV, in satisfactory agreement with experiment.

International audience; In this article we report new results for action spectroscopy of protonated peptide Leucine enkephalin (YGGFL). By coupling a linear ion trap mass spectrometer with a vacuum ultraviolet (VUV) synchrotron radiation beamline, we investigate photofragmentation pattern of this peptide, through the analysis of tandem mass spectra recorded over a range of VUV photon energies, below and above the ionization energy. The obtained fragmentation patterns are discussed and compared to previous results.

International audience; Upon X-ray irradiation, lanthanide transfers visible energy to a photosensitizer, leading to local reactive oxygen species (ROS) production and triggering photodynamic therapy (PDT), even in deep tumors. The proposed nanolipoparticles, which contain both lanthanides and photosensitizer molecules, offer new opportunities in therapy and diagnosis.

Infrared and vibrational Raman spectra have been recorded in the liquid phase and interpreted using semiempirical calculations (PM3, AM1 and MNDO). Molecular properties and relative conformational energies have been calculated and compared with literature data, when available. The trans conformer of the molecule seems to be the conformation of lowest energy and its computed structural parameters are reported. Infrared and vibrational Raman spectra have been recorded in the liquid phase and interpreted using semiempirical calculations (PM3, AM1 and MNDO). Molecular properties and relative conformational energies have been calculated and compared with literature data, when available. The trans conformer of the molecule seems to be the conformation of lowest energy and its computed structural parameters are reported.

The photo-absorption cross section of trifluoromethyl sulphur pentafluoride, SF5CF3 has been measured using synchrotron radiation in the range of 4–11 eV (310 nm > l > 110 nm) and comparison made with electron energy loss spectroscopy (EELS). The measured VUV cross sections are used to derive the photolysis rate of SF5CF3 in the terrestrial atmosphere. It is estimated that the lifetime for this molecule is the order of a 1000 years and the calculated global warming potential (GWP) is found to be between 17000 and 18100, making it one of the most potent global warming gases in the terrestrial atmosphere.

International audience; One-photon multiple ionization is a signature of dynamical electron correlations in atoms and small molecules, as observed in the Auger process when Auger electron emission follows core-shell ionization. In such a process, the high energy needed to remove several electrons is due to the strong Coulombic attraction between the last departing electron(s) and the ionic core. Multiply negatively charged molecules offer the possibility to overcome the Coulombic attraction, opening the way for multielectron photodetachment following valence shell excitation. Here photodetachment studies have been performed on electrosprayed protein polyanions using vacuum ultraviolet synchrotron radiation coupled to a radiofrequency ion trap. Double, triple, and quadruple electron emissions from protein polyanions resulting from single-photon excitation in the valence shell were observed with ionization thresholds below 20 eV photon energy. This suggests the existence of large electronic correlations in proteins between weakly bound electrons standing on distant sites. Besides, the resulting multiradical polyanions appear to be remarkably stable, an important issue in racliobiology.

International audience; The characterization of membrane proteins is still challenging. The major issue is the high hydrophobicity of membrane proteins that necessitates the use of detergents for their extraction and solubilization. The very poor compatibility of mass spectrometry with detergents remains a tremendous obstacle in studies of membrane proteins. Here, we investigated the potential of atmospheric pressure photoionization (APPI) for mass spectrometry study of membrane proteins. This work was focused on the tetraspanin CD9 and the multidrug transporter BmrA. A set of peptides from CD9, exhibiting a broad range of hydropathicity, was investigated using APPI as compared to electrospray ionization (ESI). Mass spectrometry experiments revealed that the most hydrophobic peptides were hardly ionized by ESI whereas all peptides, including the highly hydrophobic one that corresponds to the full sequence of the first transmembrane domain of CD9, were easily ionized by APPI. The native protein BmrA purified in the presence of the non-ionic detergent beta-D-dodecyl maltoside (DDM) was digested in-solution using trypsin. The resulting peptides were investigated by flow injection analysis of the mixture followed by mass spectrometry. Upon ESI, only detergent ions were detected and the ionic signals from the peptides were totally suppressed. In contrast, APPI allowed many peptides distributed along the sequence of the protein to be detected. Furthermore, the parent ion corresponding to the first transmembrane domain of the protein BmrA was detected under APPI conditions. Careful examination of the APPI mass spectrum revealed a-, b-, c- and y- fragment ions generated by in-source fragmentation. Those fragment ions allowed unambiguous structural characterization of the transmembrane domain. In conclusion, APPI-MS appears as a versatile method allowing the ionization and fragmentation of hydrophobic peptides in the presence of detergent.

Funding Agency: Agence Nationale de la Recherche Scientifique, France = 08-BLAN-0065 + GENCI-CINES = 2012-088620; International audience; A valence shell study of electrosprayed insulin protein polyanion photodetachment was carried out on a vacuum ultra-violet synchrotron radiation beamline coupled to a radiofrequency ion trap, for both close- and open-shell species. A two-electron photodetachment is observed, which arises from two different mechanisms that are disentangled: a sequential multi-photon absorption and a direct one-photon two-electron process. The threshold for the direct double-electron ejection is measured at 11.4 eV and corresponds to electronic excitation in the valence shell, which makes it the first observation of direct double photodetachment in the valence shell. The results are discussed in the light of previous knowledge from multiple photoionization and ab initio calculations on model polyanions. Double photodetachment appears to be a relaxation mechanism that leads to oxidized anions of striking stability, a feature of high relevance in radiobiology.

International audience; The coupling of a gas reactor, named APSIS, with a vacuum-ultraviolet (VUV) beamline at the SOLEIL synchrotron radiation facility, for a photochemistry study of gas mixtures, is reported. The reactor may be irradiated windowless with gas pressures up to hundreds of millibar, and thus allows the effect of energetic photons below 100 nm wavelength to be studied on possibly dense media. This set-up is perfectly suited to atmospheric photochemistry investigations, as illustrated by a preliminary report of a simulation of the upper atmospheric photochemistry of Titan, the largest satellite of Saturn. Titan's atmosphere is mainly composed of molecular nitrogen and methane. Solar VUV irradiation with wavelengths no longer than 100 nm on the top of the atmosphere enables the dissociation and ionization of nitrogen, involving a nitrogen chemistry specific to nitrogen-rich upper atmospheres.

We have performed inner-shell electron impact action spectroscopy of mass and charge selected macromolecular ions. For this purpose, we have coupled a focusing electron gun with a linear quadrupole ion trap mass spectrometer. This experiment represents a proof of principle that an energy-tunable electron beam can be used in combination with radio frequency traps as an activation method in tandem mass spectrometry (MS2) and allows performing action spectroscopy. Electron impact MS2 spectra of multiply protonated ubiquitin protein ion have been recorded at incident electron energies around the carbon 1 s excitation. Both MS2 and single ionization energy dependence spectra are compared with literature data obtained using the soft X-ray activation conditions.

International audience; Atmospheric pressure photoionization (APPI) source coupled to a krypton discharge lamp permits to specifically generate either radical cation or protonated species for guanine depending on the dopant molecule. In order to scrutinize the consecutive or competitive chemical reactions occurring in the gas phase, a tunable synchrotron VUV radiation source was coupled for the first time to the APPI source of a hybrid quadrupole time-of-flight mass spectrometer. Experiments were achieved at different photon energies close to the ionization energy of the different reagents. This unique set-up allowed the confirmation of theoretical models developed by several groups over the last ten years concerning ionization processes underlying APPI, such as proton or charge transfer reactions. (C) 2012 Elsevier B.V. All rights reserved.

International audience; In this work, atmospheric pressure photoionization was investigated for use in characterizing protein palmitoylation, which is a major post-translational modification of membrane proteins. The study focused on native and palmitoylated peptides originating from plasma membrane proteolipids, such as tetraspanins CD9 and CD151. Mass spectrometry experiments were performed using synchrotron radiation as a tunable UV source that provides optimal energy for photoionization (SR-APPI). In the positive ion mode, intense fragment ions corresponding to a. 6, candy ions were observed. Interestingly, these fragment ions conserved the palmitoyl modification, thus allowing for unambiguous structural characterization of the palmitoylated peptides. In-source fragmentation under APPI conditions offers a unique complement to conventional methods such as MS/MS, and the results demonstrate that APPI is a versatile and promising technique for the in-source characterization of post-translational modifications and top-down proteomics of membrane proteins. (C) 2012 Elsevier B.V. All rights reserved.