Photodissociation of leucine-enkephalin protonated peptide: an experimental and theoretical perspective.

Understanding the competing processes that govern far ultraviolet photodissociation (FUV-PD) of biopolymers such as proteins is a challenge. Here, we report a combined experimental and theoretical investigation of FUV-PD of protonated leucine-enkephalin pentapeptide ([YGGFL + H]) in the gas-phase. Time-dependent density functional theory (TD-DFT) calculations in combination with experiments and previous results for amino acids and shorter peptides help in rationalizing the evolution of the excited states.

Correction: UV and VUV-induced fragmentation of tin-oxo cage ions.

Correction for 'UV and VUV-induced fragmentation of tin-oxo cage ions' by Jarich Haitjema , , 2021, , 20909-20918, https://doi.org/10.1039/D1CP03148A.

Effect of Protonation on the Molecular Structure of Adenosine 5'-Triphosphate: A Combined Theoretical and Near Edge X-ray Absorption Fine Structure Study.

The present work combines the near edge X-ray absorption mass spectrometry of a protonated adenosine 5'-triphosphate (ATP) molecule isolated in an ion trap with (time-dependent) density functional theory calculations. Our study unravels the effect of protonation on the ATP structure and its spectral properties, providing structure-property relationships at atomistic resolution for protonated ATP (ATPH) isolated in the gas-phase conditions. On the other hand, the present C and N K-edge X-ray absorption spectra of isolated ATPH appear closely like those previously reported for solvated ATP at low pH.

Vacuum Ultraviolet Fingerprints as a New Way of Disentangling Tropylium/Benzylium Isomers.

The two inseparable companions, tropylium () and benzylium (), were interrogated by vacuum ultraviolet (VUV) radiation from 4.5 to 7.0 eV in an ion trap.

Peptide Bond Formation in the Protonated Serine Dimer Following Vacuum UV Photon-Induced Excitation.

Possible routes for intra-cluster bond formation (ICBF) in protonated serine dimers have been studied. We found no evidence of ICBF following low energy collision-induced dissociation (in correspondence with previous works), however, we do observe clear evidence for ICBF following photon absorption in the 4.6-14 eV range.

UV-VUV Photofragmentation Spectroscopy of Isolated Neutral Fragile Macromolecules: A Proof-of-Principle Based on a Deprotonated Vancomycin-Peptide Noncovalent Complex.

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.

UV and VUV-induced fragmentation of tin-oxo cage ions.

Photoresist materials are being optimized for the recently introduced Extreme Ultraviolet (EUV) photolithographic technology. Organometallic compounds are potential candidates for replacing the ubiquitous polymer-based chemically amplified resists. Tin (Sn) has a particularly large absorption cross section for EUV light (13.

Ultraviolet Photoactivation Using Synchrotron Radiation for Tandem Mass Spectrometry of Polysiloxanes.

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--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.

Mammal hyaluronidase activity on chondroitin sulfate and dermatan sulfate: Mass spectrometry analysis of oligosaccharide products.

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.

New exploration of the γ-gliadin structure through its partial hydrolysis.

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.

Oxygen K-shell spectroscopy of isolated progressively solvated peptide.

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 →π* 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.

Synchrotron UV photoactivation of trapped sodiated ions produced from poly(ethylene glycol) by electrospray ionization.

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).

Time resolved transient circular dichroism spectroscopy using synchrotron natural polarization.

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).

Role of protein conformation and weak interactions on γ-gliadin liquid-liquid phase separation.

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.

State-Dependent Fragmentation of Protonated Uracil and Uridine.

Action spectroscopy using photon excitation in the VUV range (photon energy 4.5-9 eV) was performed on protonated uracil (UraH) and uridine (UrdH). The precursor ions with m/ z 113 and m/ z 245, respectively, were produced by an electrospray ionization source and accumulated inside a quadrupole ion trap mass spectrometer.

Photoprocessing of large PAH cations.

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.

Vacuum-UV and Low-Energy Electron-Induced DNA Strand Breaks - Influence of the DNA Sequence and Substrate.

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.

Vacuum-UV induced DNA strand breaks - influence of the radiosensitizers 5-bromouracil and 8-bromoadenine.

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.

Spectroscopy and Photodissociation of the Perfluorooctanoate Anion.

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.

Radical Anions of Oxidized vs. Reduced Oxytocin: Influence of Disulfide Bridges on CID and Vacuum UV Photo-Fragmentation.

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.

Extreme Ultraviolet Radiation: A Means of Ion Activation for Tandem Mass Spectrometry.

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.

MS/MS-Guided Isolation of Clarinoside, a New Anti-Inflammatory Pentalogin Derivative.

Re-investigation of the chemical composition of the annual plant 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.

Carotenoids: Experimental Ionization Energies and Capacity at Inhibiting Lipid Peroxidation in a Chemical Model of Dietary Oxidative Stress.

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.

Investigation of secondary structure evolution of micellar casein powder upon aging by FTIR and SRCD: consequences on solubility.

Background: 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.

Structural proteomics: Topology and relative accessibility of plant lipid droplet associated proteins.

Unlabelled: 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.