The role of the mobile proton in fucose migration

Fucose migration reactions represent a substantial challenge in the analysis of fucosylated glycan structures by mass spectrometry. In addition to the well-established observation of transposed fucose residues in glycan-dissociation product ions, recent experiments show that the rearrangement can also occur in intact glycan ions. These results suggest a low-energy barrier for migration of the fucose residue and broaden the relevance of fucose migration to include other types of mass spectrometry experiments, including ion mobility-mass spectrometry and ion spectroscopy. In this work, we utilize cold-ion infrared spectroscopy to provide further insight into glycan scrambling in intact glycan ions. Our results show that the mobility of the proton is a prerequisite for the migration reaction. For the prototypical fucosylated glycans Lewis x and blood group antigen H-2, the formation of adduct ions or the addition of functional groups with variable proton affinity yields significant differences in the infrared spectra. These changes correlate well with the promotion or inhibition of fucose migration through the presence or absence of a mobile proton

Cavity ring down spectroscopy on solid C₆₀

The light absorption of a solid sample in the 8.5 μm region is measured via cavity ring down (CRD) absorption spectroscopy, using a free electron laser (FEL) as a source of widely tunable infrared (IR) radiation. A 3 mm thick zinc-selenide (ZnSe) window is used as a substrate for a 20–30 nm thick C60 film. On top of the structureless absorption due to ZnSe (60 is measured with monolayer sensitivity

Atomic clusters of magnetic oxides: Structure and phonons

This work represents a combined experimental and theoretical study of structural and magnetic properties of clusters made of cobalt, chromium, and manganese oxides. The clusters were prepared in a molecular cluster source by oxidation of laser-vaporized metal and studied in a time-of-flight spectrometer. Infrared laser-induced cluster dissociation experiments revealed the spectrum of cluster vibrational states. We also performed ab initio local spin density approximation calculations of the equilibrium geometry, electronic structure, and magnetic properties of these clusters

Downregulation of Fzd6 and Cthrc1 and upregulation of olfactory receptors and protocadherins by dietary beta-carotene in lungs of Bcmo1-/- mice.

An ongoing controversy exists on beneficial versus harmful effects of high beta-carotene (BC) intake, especially for the lung. To elucidate potential mechanisms, we studied effects of BC on lung gene expression. We used a beta-carotene 15,15'-monooxygenase 1 (Bcmo1) knockout mouse (Bcmo1-/-) model, unable to convert BC to retinoids, and wild-type mice (Bcmo1+/+) mice to dissect the effects of intact BC from effects of BC metabolites. As expected, BC supplementation resulted in a higher BC accumulation in lungs of Bcmo1-/- mice than in lungs of Bcmo1+/+ mice. Whole mouse genome transcriptome analysis on lung tissue revealed that more genes were regulated in Bcmo1-/- mice than Bcmo1+/+ mice upon BC supplementation. Frizzled homolog 6 (Fzd6) and collagen triple helix repeat containing 1 (Cthrc1) were significantly downregulated (fold changes -2.99 and -2.60, respectively, false discovery rate <0.05) by BC in Bcmo1-/-. Moreover, many olfactory receptors and many members of the protocadherin family were upregulated. Since both olfactory receptors and protocadherins have an important function in sensory nerves and Fzd6 and Cthrc1 are important in stem cell development, we hypothesize that BC might have an effect on the highly innervated pulmonary neuroendocrine cell (PNEC) cluster. PNECs are highly associated with sensory nerves and are important cells in the control of stem cells. A role for BC in the innervated PNEC cluster might be of particular importance in smoke-induced carcinogenesis since PNEC-derived lung cancer is highly associated with tobacco smoke

Downregulation of Fzd6 and Cthrc1 and upregulation of olfactory receptors and protocadherins by dietary beta-carotene in lungs of Bcmo1-/- mice.

An ongoing controversy exists on beneficial versus harmful effects of high beta-carotene (BC) intake, especially for the lung. To elucidate potential mechanisms, we studied effects of BC on lung gene expression. We used a beta-carotene 15,15'-monooxygenase 1 (Bcmo1) knockout mouse (Bcmo1-/-) model, unable to convert BC to retinoids, and wild-type mice (Bcmo1+/+) mice to dissect the effects of intact BC from effects of BC metabolites. As expected, BC supplementation resulted in a higher BC accumulation in lungs of Bcmo1-/- mice than in lungs of Bcmo1+/+ mice. Whole mouse genome transcriptome analysis on lung tissue revealed that more genes were regulated in Bcmo1-/- mice than Bcmo1+/+ mice upon BC supplementation. Frizzled homolog 6 (Fzd6) and collagen triple helix repeat containing 1 (Cthrc1) were significantly downregulated (fold changes -2.99 and -2.60, respectively, false discovery rate <0.05) by BC in Bcmo1-/-. Moreover, many olfactory receptors and many members of the protocadherin family were upregulated. Since both olfactory receptors and protocadherins have an important function in sensory nerves and Fzd6 and Cthrc1 are important in stem cell development, we hypothesize that BC might have an effect on the highly innervated pulmonary neuroendocrine cell (PNEC) cluster. PNECs are highly associated with sensory nerves and are important cells in the control of stem cells. A role for BC in the innervated PNEC cluster might be of particular importance in smoke-induced carcinogenesis since PNEC-derived lung cancer is highly associated with tobacco smoke

IR action spectroscopy of glycosaminoglycan oligosaccharides

Glycosaminoglycans (GAGs) are a physio- and pharmacologically highly relevant class of complex saccharides, possessing a linear sequence and strongly acidic character. Their repetitive linear core makes them seem structurally simple at first glance, yet differences in sulfation and epimerization lead to an enormous structural diversity with only a few GAGs having been successfully characterized to date. Recent infrared action spectroscopic experiments on sulfated mono- and disaccharide ions show great promise. Here, we assess the potential of two types of gas-phase action spectroscopy approaches in the range from 1000 to 1800 cm−1 for the structural analysis of complex GAG oligosaccharides. Synthetic tetra- and pentasaccharides were chosen as model compounds for this benchmark study. Utilizing infrared multiple photon dissociation action spectroscopy at room temperature, diagnostic bands are largely unresolved. In contrast, cryogenic infrared action spectroscopy of ions trapped in helium nanodroplets yields resolved infrared spectra with diagnostic features for monosaccharide composition and sulfation pattern. The analysis of GAGs could therefore significantly benefit from expanding the conventional MS-based toolkit with gas-phase cryogenic IR spectroscopy

Infrared Resonance Enhanced Multiphoton Ionization of Fullerenes

Gas-phase fullerenes are resonantly heated by a train of high power subpicosecond pulses from a free electron laser (FEL) to internal energies at which they efficiently undergo delayed ionization. When the laser is tuned from 6–20μm while the amount of laser produced parent ions is recorded, resonant absorption of 200–600 IR photons, resulting in almost fragmentation-free ion spectra, is observed. Infrared resonance enhanced multiphoton ionization with a FEL is shown to enable extremely sensitive IR spectroscopy with mass selective detection of gas-phase fullerenes

Unraveling the internal dynamics of the benzene dimer: a combined theoretical and microwave spectroscopy study

Contains fulltext : 111457.pdf (publisher's version ) (Open Access

'Mine's a Pint of Bitter': Performativity, gender, class and representations of authenticity in real-ale tourism

Leisure choices are expressive of individual agency around the maintenance of taste, boundaries, identity and community. This research paper is part of a wider project designed to assess the social and cultural value of real ale to tourism in the north of England. This paper explores the performativity of real-ale tourism and debates about belonging in northern English real-ale communities. The research combines an ethnographic case study of a real-ale festival with semi-structured interviews with organisers and volunteers, northern English real-ale brewers and real-ale tourists visiting the festival. It is argued that real-ale tourism, despite its origins in the logic of capitalism, becomes a space where people can perform Habermasian, communicative leisure, and despite the contradictions of preferring some capitalist industries over others on the basis of their perceived smaller size and older age, real-ale fans demonstrate agency in their performativity

Nazi Punks Folk Off: Leisure, Nationalism, Cultural Identity and the Consumption of Metal and Folk Music

Far-right activists have attempted to infiltrate and use popular music scenes to propagate their racialised ideologies. This paper explores attempts by the far right to co-opt two particular music scenes: black metal and English folk. Discourse tracing is used to explore online debates about boundaries, belonging and exclusion in the two scenes, and to compare such online debates with ethnographic work and previous research. It is argued that both scenes have differently resisted the far right through the policing of boundaries and communicative choices, but both scenes are compromised by their relationship to myths of whiteness and the instrumentality of the pop music industry