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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.

Gas-phase near-edge X-ray-absorption fine structure (NEXAFS) action spectroscopy around the oxygen K-edge and mass spectrometry were employed to probe isolated substance P (SP) molecular ions, both bare and progressively solvated with 4 and 11 water molecules. Detailed mass spectra of bare and hydrated precursors are presented for the resonant photon energy of 532 eV that corresponds to O1s --> pi(amide)* core excitation, triggering resonant Auger decay and fragmentation from the ionized radical molecular system. The fragmentation pattern of doubly protonated SP hydrated with 4 water molecules clearly shows a series of abundant doubly charged backbone fragments, as well as triply charged precursor with small neutral losses, all preserving full water cluster. This is drastically different from the collisional induced dissociation of the hydrated peptide where the water loss is a dominant relaxation process. Moreover, the action NEXAFS obtained from several resolved small backbone fragments revealed increased fragmentation of hydrated SP relative to the bare one, due to a resonant O1s excitation of the attached water molecules. Such unexpected result inspires further experimental developments to investigate possible nonlocal energy transfer from the solvent to the biomolecules within the first solvation shell. The experiment is supported by molecular dynamics and DFT calculations to estimate the intensity of the resonant X-ray absorption of bare and hydrated SP around peptide and water O1s excitation region.

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.

Gas-phase decompositions of polymer ions play an important role in mass spectrometry to obtain accurate structural information. In this work, UV photoactivation experiments were performed from two poly(dimethylsiloxane)s bearing different end groups (two trimethylsilyl, or α-sec-butyl and ω- trimethylsilyl). Precursor ions, such as [Polysiloxane+Cation]+ produced by an electrospray source, were stored in a linear ion trap and then submitted to synchrotron UV irradiation during different activation times and over a range of wavelengths (52 to 248 nm) from extreme UV (XUV) to deep UV. Upon photoactivation of a precursor ion from poly(dimethylsiloxane) (PDMS; with two trimethylsilyl end groups, [PDMS25+Na]+), important fragmentations were observed, including the loss of a methyl radical followed by various heterolytic cleavages along the polymer backbone, for photon energies typically >9.5-10 eV (ionization threshold of the neutral oligomer). This report focuses on different aspects: (i) the identification of the UV photodissociation (UV-PD) products of PDMS, (ii) the influence of the irradiation time for two photon energies (10 or 20 eV), (iii) the influence of the energy of the photon for two activation times (100 or 5000 ms), (iv) the influence of the nature of the cation, and (v) the influence of the end groups of PDMS. Synchrotron UV irradiation with a tunable wavelength was a great opportunity to study the effect of the photon energy and to probe the original mechanisms of ion decomposition from poly(dimethylsiloxane).

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.

Synchrotron radiation circular dichroism (SRCD) and Fourier transform infrared (FTIR) spectroscopy were used to examine the conformation evolution of micellar casein (MC) powder during storage and to determine whether the spectral changes could be related to their solubility evolution.; Results: A loss in intensity of SRCD spectra as a function of storage time has been observed. Quantification of secondary structures revealed losses of α-helix content during storage. Moreover, a redshift of the amide I band in the FTIR spectrum was demonstrated during the storage and was interpreted as a rearrangement of the secondary structure of the protein, which is in line with the SRCD results. The qualitative results obtained by FTIR clearly support the quantitative evolution of the secondary structure obtained by the analysis of SRCD spectra. Principal component analysis (PCA) of FTIR spectra permits a good separation of samples according to the storage time. PCA shows that the evolution of secondary structures and solubility loss are closely linked.; Conclusion: With the quantitative data provided by SRCD spectra, it was established that, whatever the storage conditions, a unique curve exists between loss of α-helix content and loss in solubility, showing that loss of α-helix content is a marker of solubility loss for the MC powders studied. © 2017 Society of Chemical Industry.; © 2017 Society of Chemical Industry.

The rhombic dodecahedral nanocluster [Ag14(C≡CtBu)12Cl]+, which has been structurally characterized using X-ray crystallography, was transferred to the gas phase using electrospray ionization, where it was characterized by ion mobility (IM), vacuum ultraviolet (VUV), and ultraviolet (UV) spectroscopies in conjunction with DFT calculations. IM reveals a single peak, and modeling of the collision cross-section with the X-ray structure suggests that the cluster maintains its condensed phase structure upon transfer to the gas phase. The VUV spectra exhibit rich fragmentation, including: photoionization to give [Ag14(C≡CtBu)12Cl]2+• with an onset of 8.84 ± 0.08 eV; cluster fission fragmentation via losses of (AgC≡CtBu)n and (AgC≡CtBu)n−1(AgCl); and via reductive elimination of (tBuC≡C)2. Apart from channels associated with photoionization, similar fragment ions are observed in the UVPD spectra, although their relative intensities differ. The TDDFT absorption spectra are symmetry-allowed transitions including A...

Rationale By taking advantage of the gas-phase decompositions of polymer ions, tandem mass spectrometry of polymers allows us to obtain more accurate structural information than from a simple mass measurement. Applied to a model polymer, the goal of this work was to evaluate the performances of an activation technique based on ultraviolet (UV) irradiation, as an alternative to conventional collisional activation. Methods Sodiated poly(ethylene glycol) produced by electrospray ionization was isolated in a linear ion trap, then submitted to synchrotron UV irradiation over a range of wavelengths (52 to 248 nm). Fragmentation pathways resulting from UV photoactivation were investigated. The proposed mechanisms take into account: (i) the comparison with collision-induced dissociation (CID) product ions, (ii) the effect of wavelength-tunable UV activation, and (iii) deuterium-labeling and various other complementary experiments. For the highest molecular weight compounds, ion mobility spectrometry was used before UV photoactivation. Results Synchrotron UV irradiation can induce dissociation of poly(ethylene glycol) sodiated ions without the requirement of the presence of a specific chromophore, if the photon energy is above 10 eV. UV photoactivation of poly(ethylene glycol) ions can yield fragmentations that differ from those in classical low-energy CID, especially from higher masses (>4000 g mol-1 ). A successful coupling of UV photoactivation with ion mobility pre-filtering was presented. Conclusions UV activation combined or not with pre-filtering ion mobility is a promising alternative approach for the structural characterization of polymers. UV synchrotron radiation with a tunable wavelength was a great opportunity to study the effect of the photon energy, and to probe the mechanisms of ion decomposition from poly(ethylene glycol).

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.

International audience; Radiation therapy is a basic part of cancer treatment. To increase the DNA damage in carcinogenic cells and preserve healthy tissue at the same time, radiosensitizing molecules such as halogenated nucleobase analogs can be incorporated into the DNA during the cell reproduction cycle. In the present study 8.44 eV photon irradiation induced single strand breaks (SSB) in DNA sequences modified with the radiosensitizer 5-bromouracil (U-5Br) and 8-bromoadenine ((8Br)A) are investigated. U-5Br was incorporated in the 13mer oligonucleotide flanked by different nucleobases. It was demonstrated that the highest SSB cross sections were reached, when cytosine and thymine were adjacent to U-5Br, whereas guanine as a neighboring nucleobase decreases the activity of U-5Br indicating that competing reaction mechanisms are active. This was further investigated with respect to the distance of guanine to U-5Br separated by an increasing number of adenine nucleotides. It was observed that the SSB cross sections were decreasing with an increasing number of adenine spacers between guanine and U-5Br until the SSB cross sections almost reached the level of a non-modified DNA sequence, which demonstrates the high sequence dependence of the sensitizing effect of U-5Br. (8Br)A was incorporated in a 13mer oligonucleotide as well and the strand breaks were quantified upon 8.44 eV photon irradiation in direct comparison to a non-modified DNA sequence of the same composition. No clear enhancement of the SSB yield of the modified in comparison to the non-modified DNA sequence could be observed. Additionally, secondary electrons with a maximum energy of 3.6 eV were generated when using Si as a substrate giving rise to further DNA damage. A clear enhancement in the SSB yield can be ascertained, but to the same degree for both the non-modified DNA sequence and the DNA sequence modified with (8Br)A.

International audience; DNA is effectively damaged by radiation, which can on the one hand lead to cancer and is on the other hand directly exploited in the treatment of tumor tissue. DNA strand breaks are already induced by photons having an energy below the ionization energy of DNA. At high photon energies, most of the DNA strand breaks are induced by low-energy secondary electrons. In the present study we quantified photon and electron induced DNA strand breaks in four different 12mer oligonucleotides. They are irradiated directly with 8.44 eV vacuum ultraviolet (VUV) photons and 8.8 eV low energy electrons (LEE). By using Si instead of VUV transparent CaF2 as a substrate the VUV exposure leads to an additional release of LEEs, which have a maximum energy of 3.6 eV and can significantly enhance strand break cross sections. Atomic force microscopy is used to visualize strand breaks on DNA origami platforms and to determine absolute values for the strand break cross sections. Upon irradiation with 8.44 eV photons all the investigated sequences show very similar strand break cross sections in the range of 1.7-2.3x10(-16) cm(2). The strand break cross sections for LEE irradiation at 8.8 eV are one to two orders of magnitude larger than the ones for VUV photons, and a slight sequence dependence is observed. The sequence dependence is even more pronounced for LEEs with energies

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; Tandem mass spectrometry has long been established as a corner stone of analytical and structural chemistry. Fast radical-directed dissociation, produced by electron-transfer and electron-capture dissociation (ETD and ECD) has been shown to provide important complementary information to collision-induced dissociation (CID). We report the first application of extreme-ultraviolet (XUV) lamps to tandem mass spectrometry. These discharge lamps are versatile, robust, and low-cost sources of energetic photons (40-80 nm). The coupling of the discharge lamp with a Waters Synapt G2-Si Q-ToF mass spectrometer is achieved through a specific trapping scheme in the TriWave region of the instrument, allowing efficient irradiation of the precursor ions. Rich radical-directed dissociation was produced for a number of model compounds, providing unique, complementary information to existing dissociation techniques.

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 (

International audience; BACKGROUNDSynchrotron radiation circular dichroism (SRCD) and Fourier transform infrared (FTIR) spectroscopy were used to examine the conformation evolution of micellar casein (MC) powder during storage and to determine whether the spectral changes could be related to their solubility evolution. RESULTSA loss in intensity of SRCD spectra as a function of storage time has been observed. Quantification of secondary structures revealed losses of -helix content during storage. Moreover, a redshift of the amide I band in the FTIR spectrum was demonstrated during the storage and was interpreted as a rearrangement of the secondary structure of the protein, which is in line with the SRCD results. The qualitative results obtained by FTIR clearly support the quantitative evolution of the secondary structure obtained by the analysis of SRCD spectra. Principal component analysis (PCA) of FTIR spectra permits a good separation of samples according to the storage time. PCA shows that the evolution of secondary structures and solubility loss are closely linked. CONCLUSIONWith the quantitative data provided by SRCD spectra, it was established that, whatever the storage conditions, a unique curve exists between loss of -helix content and loss in solubility, showing that loss of -helix content is a marker of solubility loss for the MC powders studied. (c) 2017 Society of Chemical Industry

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.

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.

Photoionization of a buckminsterfullerene ion is investigated using an ion trap and a merged beam setup coupled to synchrotron radiation beamlines and compared to theoretical calculations. Absolute measurements derived from the ion trap experiment allow discrepancies concerning the photoionization cross section of C-60(+) to be solved.

International audience; Lipid droplets are the major stock of lipids in oleaginous plant seeds. Despite their economic importance for oil production and biotechnological issues (biofuels, lubricants and plasticizers), numerous questions about their formation, structure and regulation are still unresolved. To determine water accessible domains of protein coating at lipid droplets surface, a structural proteomic approach has been performed. This technique relies on the millisecond timescale production of hydroxyl radicals by the radiolysis of water using Synchrotron X-ray white beam. Thanks to the evolution of mass spectrometry analysis techniques this approach allows the creation of a map of the solvent accessibility for proteins difficult to study by other means. Using these results, a S3 oleosin water accessibility map is proposed. This is the first time that such a map on an oleosin co-purified with plant lipid droplets and other associated protein is presented. Biological significance: Lipid droplet associated proteins function is linked to stability, structure and probably formation and lipid mobilization of droplets. Structure of these proteins in their native environment, at the interface between bulk water and the lipidic core of these organelles is only based on hydrophobicity plot. Using hydroxyl radical footprinting and proteomics approaches we studied water accessibility of one major protein in these droplets: S3 oleosin of Arabidopsis thaliana seeds.

Collisions of 375 keV Xe25+ ions with trapped mass/charge selected poly-anions of the cytochrome C protein (similar to 12.5 kDa) were studied by coupling a linear quadrupole ion trap with low-energy ion beam facility. Tandem mass spectra were recorded for the protein precursor charge states ranging from -9 to -17. The present work reports the first study of slow highly charged ion collisions with poly-anions. A high signal to noise ratio allowed the study of the intensity of single and multiple electron removal by a projectile, as well as associated neutral losses, as a function of the target charge state. Relative single and double electron detachment cross sections were found to increase with increasing charge state of the precursor anion. The experimental findings are supported by the calculations of the total electron capture cross sections, based on the classical over-the-barrier model, restricted to a simple uniformly charged linear protein structure and a near-end electron capture.

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; The activation of ions by extreme-energy photons (XUV) produced by a synchrotron radiation beamline is a powerful method for characterizing complex glycans using tandem mass spectrometry (MS). As previously described, this activation method leads to rich fragmentation spectra with many structurally valuable cross-ring cleavages while maintaining labile modifications on the glycan structures. However, until now, the tandem MS event was too long to be compatible with liquid chromatography elution times. In this work, the duty cycle of the activation and detection of fragments was shortened, and the background signal on the spectra was drastically reduced. Both improvements allowed, for the first time, the successful coupling of a UHPLC system to XUV-activated tandem MS. The approach was used to characterize a complex mixture of oligo-porphyrans, which are a class of highly sulfated oligosaccharides, in a fully automated way. Due to an enhanced dynamic range and an increased sensitivity, some hypothetical structures of low abundance have been unequivocally confirmed in this study and others have been revised. Some previously undescribed species of oligo-porphyrans that exhibit lateral branching have been fully resolved. This work contributes to the scarce knowledge of the structure of porphyrans in red algae and pushes the current capacities of XUV-activation tandem MS by demonstrating the possibility of a direct coupling with UHPLC. This study will considerably broaden the applicability and practicality of this method in many fields of analytical biology.

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.

Near-edge X-ray absorption fine structure (NEXAFS) spectroscopy probes directly or indirectly the photoabsorption cross section of a system under study as a function of the photon energy around the core–shell ionization thresholds. When the photon energy matches the difference between the core level and an unoccupied valence level, the photoabsorption cross section increases. The core levels are associated with particular atoms within the system under the study; therefore, NEXAFS spectroscopy appears to be a very sensitive probe of physicochemical and structural properties of molecules and materials. It has been intensively applied to investigate gaseous, liquid, and solid species. In this chapter, we describe methods to perform gas-phase NEXAFS spectroscopy of large systems, such as nanoparticles, clusters, and biopolymers, as well as of ionic species. We also review recent research findings.

A new apparatus was designed, coupling an electron gun with a linear quadrupole ion trap mass spectrometer, to perform m/z (mass over charge) selected ion activation by electron impact for tandem mass spectrometry and action spectroscopy. We present in detail electron tracing simulations of a 300 eV electron beam inside the ion trap, design of the mechanical parts, electron optics and electronic circuits used in the experiment. We also report examples of electron impact activation tandem mass spectra for Ubiquitin protein, Substance P and Melittin peptides, at incident electron energies in the range from 280 eV to 300 eV.