Lipid oxidation plays a major role in biochemical processes and nutrition. Structural changes during oxidation can lead to alterations of lipid functions. Rancidification and production of secondary lipid messengers are well-known examples for the impact of oxidation on lipid function. Especially lipids with a high degree of unsaturation are prone to oxidize. In order to investigate structural changes of lipids upon oxidation, we here introduce a photochemical Paternò-Büchi functionalization workflow and subsequent mass spectrometric analysis for analysis of unsaturated, oxidized lipids. Results for hydroxylated fatty acids and triglycerides containing isolated and conjugated C[double bond, length as m-dash]C bonds will be presented making use of 3-acetylpyridine as a photochemically active compound. Photochemical derivatization is performed in nano-electrospray emitter tips in 30 s resulting in the formation of oxetanes without inducing light-triggered oxidation of analytes. Collisional-activation of photoproducts facilitates selective cleavage of oxetane moieties. Resulting fragment ions not only allow the determination of C[double bond, length as m-dash]C bond locations for isolated and conjugated C[double bond, length as m-dash]C bonds but also restrict the site of oxidation. By registering the mass shift in some fragment ions of +15.99 Da due to hydroxylation, the oxidized sections of lipids can be identified. In order to demonstrate its analytical robustness, the method is applied to determine the structural impact of non-selective ambient oxidation on fatty acids, triglycerides and complex triglyceride mixtures obtained from Sacha inchi oil.

CeO2 is a promising material in the catalytic recovery of Cl-2 from HCl by oxidation with O-2 due to its beneficial redox properties (Ce3+/Ce4+) and accompanied oxygen storage capacity (OSC). Two options to tailor the OSC are the usage of dopants and nanostructuring. In this work, we report the synthesis of mesoporous doped Ce0.9M0.1O2 (M = Zr, Gd, Pr, and Tb) powders with identical mesopore size, shape, and specific surface area (approximate to 90 m(2) g(-1)) to investigate the impact of aliovalent (Gd), isovalent (Zr), and aliovalent/isovalent (Pr and Tb) dopants on the OSC as well as on the catalytic activity/stability. The cubic arrangement of spherical 12 nm mesopores surrounded by a crystalline framework is obtained by using a diblock copolymer as structure directing agent in the sol-gel-based preparation approach, indicated by small angle X-ray scattering (SAXS) and scanning electron microscopy (SEM). Pr-doped CeO2 revealed the highest oxygen storage capacity but the lowest catalytic activity/stability in the HCl oxidation together with the Tb- and Gd-doped samples. By contrast, the Zr-doped mesoporous CeO2 powders showed the highest catalytic performance and stability in the CO and HCl oxidation of all samples but a lower OSC. These findings suggest that the OSC should therefore be treated with caution when relating to the catalytic performance in oxidation reactions. The differences in the stability are in agreement with recent studies of the HCl oxidation on model cerium oxide films with defined stoichiometry: the low stability of the aliovalent doped CeO2 materials in the HCl oxidation reaction can be attributed to a large number of oxygen vacancies.

This contribution is part of our ongoing efforts to develop innovative cross-linking (XL) reagents and protocols for facilitated peptide mixture analysis and efficient assignment of cross-linked peptide products. In this report, we combine in-source Paternò-Büchi (PB) photo-chemistry with a tandem mass spectrometry approach to selectively address the fragmentation of a tailor-made cross-linking reagent. The PB photochemistry, so far exclusively used for the identification of unsaturation sites in lipids and in lipidomics, is now introduced to the field of chemical cross-linking. Based on trans-3-hexenedioic acid, an olefinic homo bifunctional amine reactive XL reagent was designed and synthesized for this proof-of-principle study. Condensation products of the olefinic reagent with a set of exemplary peptides are used to test the feasibility of the concept. Benzophenone is photochemically reacted in the nano-electrospray ion source and forms oxetane PB reaction products. Subsequent CID-MS triggered retro-PB reaction of the respective isobaric oxetane molecular ions and delivers reliably and predictably two sets of characteristic fragment ions of the cross-linker. Based on these signature ion sets, a straightforward identification of covalently interconnected peptides in complex digests is proposed. Furthermore, CID-MSn experiments of the retro-PB reaction products deliver peptide backbone characteristic fragment ions. Additionally, the olefinic XL reagents exhibit a pronounced robustness upon CID-activation, without previous UV-excitation. These experiments document that a complete backbone fragmentation is possible, while the linker-moiety remains intact. This feature renders the new olefinic linkers switchable between a stable, noncleavable cross-linking mode and an in-source PB cleavable mode.

Fermentation broths of Ashbya gossypii from the industrial production of riboflavin emit an intense floral, fruity, and nutty smell. Typical Ehrlich pathway products, such as 2-phenylethan-l-ol and 2-/3-methylbutan-l-ol, were detected in large amounts as well as some intensely smelling saturated and unsaturated lactones, e.g., gamma-decalactone and gamma-(Z)-dodec-6-enlactone. An aroma extract dilution analysis identified 2-phenylethan-l-ol and gamma-(Z)-dodec-6-enlactone as the main contributors to the overall aroma, with flavor dilution factors of 32 768. The position of the double bonds of unsaturated lactones was determined by the Paterno-Buchi reaction, and reference compounds that were not available commercially were synthesized to elucidate the structures of the uncommon lactones. The absolute configuration and enantiomeric excess values of the lactones were determined by converting the lactones to their corresponding Mosher's esters. In addition, the odor impressions and odor thresholds in air were determined.

Phosphatidylcholines are the major phospholipid component of most eukaryotic cell membranes. Phosphatidylcholines have been shown to actively participate in regulatory and metabolic processes. Dysfunctional metabolic processes have been linked to human disease and can result in altered phosphatidylcholine structural features, such as permutation of fatty acid connectivity. Assignment and relative quantitation of structural isomers that arise from fatty acid permutation on the phosphatidylcholine backbone, so-called sn-isomers, is difficult with routine tandem mass spectrometry or with liquid chromatography without authentic standards. In this work, we report on the observation that phosphatidylcholines form abundant doubly charged metal ion complexes during electrospray ionization (ESI) and show that these complexes can be used to assign fatty acid moieties, relatively quantify sn-isomers in MS2 experiments, and mass spectrometrically separate phosphatidylcholines from other phospholipid classes in positive ion mode. Addition of Fe2+ salts (20 mol %) to ESI spray solutions affords highly abundant doubly charged metal ion phosphatidylcholine complexes (∼110% of protonated compounds) and allows sensitive fragment ion detection (limit of detection = 100 pM). Higher energy collisional dissociation, collision-induced dissociation, and ultraviolet photodissociation of doubly charged complexes yield two fragment ions for every fatty acid moiety. The latter two tandem MS methods preferentially yield sn-2 associated product ions enabling relative sn-isomer quantification. The analytical utility of doubly charged phosphatidylcholine-metal ion complexes is demonstrated for polar lipid extracts, including extracts from diabetes type 1 and type 2 mouse models, and sn-isomer abundances are derived.

The ability to control the charge state and ionization efficiency of lipids and hydrocarbons by means of in-source Paternò-Büchi functionalization in nano-electrospray ionization mass spectrometry experiments is investigated. Ultraviolet light irradiation of acetylpyridine filled nano-electrospray emitter tips, containing unsaturated analytes, generates protonated lipid and hydrocarbon ions. Comparison of reaction yields and fragment ion abundances of functionalized unsaturated fatty acids indicate that acetylpyridine Paternò-Büchi functionalization allows to readily detect fatty acids and determine double bond positions, but fragmentation efficiency and reactivity depend on double bond position and varies between different acetylpyridine isomers. Results for methyl oleate and olefins suggest that fragment ion abundances of unsaturated compounds depend on interactions between acetylpyridine and nearby functional groups. Paternò-Büchi functionalization with acetylpyridine was used to detect and assign double bond positions of mono- and polyunsaturated fatty acid, cholesterol ester, triglyceride, and hydrocarbon standards with ion abundances that are up to 631 times higher than abundances of the same compounds prior Paternò-Büchi reaction. To demonstrate the scope and analytical robustness of the newly developed method, free fatty acids in mouse brain as well as male Schistosoma mansoni extracts and hydrocarbons in an olefin mixture are investigated. For this complex set of analytes, charging and charge switching using acetylpyridine Paternò-Büchi functionalization enable double bond position assignment and relative quantification in positive ion mode. Graphical Abstract.

The feasibility of using highly pixelated light sensors as neutron detectors is the subject of a collaboration between ILL and ESS Bilbao. The fast paced development of camera sensors can meet the future challenges of neutron detection if an optical coupling able to increase the signal to noise ratio and enlarge the detection area is identified. Fiber optics tapers seem the best candidates, but issues about their radiation resistance and price make photographic objectives a more sensible choice. The performances of photographic optics have been tested as well as the light output of several thermal neutron scintillators. Thanks to the use of a highly transmissive optics, single neutrons could be observed in 6 LiF/ZnS(Ag) for the first time.

It is possible to detect individual flashes from thermal neutron impacts in a ZnS scintillator using a CMOS camera looking at the scintillator screen, and off line image processing. Some preliminary results indicated that the efficiency of recognition could be improved by optimizing the light collection and the image processing. We will report on this ongoing work which is a result from the collaboration between ESS Bilbao and the ILL. The main progress to be reported is situated on the level of the on-line treatment of the imaging data. If this technology is to work on a genuine scientific instrument, it is necessary that all the processing happens on line, to avoid the accumulation of large amounts of image data to be analyzed off line. An FPGA-based real-time full-deca mode VME-compatible CameraLink board has been developed at the SCI of the ILL, which is able to manage the data flow from the camera and convert it in a reasonable “neutron impact” data flow like from a usual neutron counting detector. The main challenge of the endeavor is the optical light collection from the scintillator. While the light yield of a ZnS scintillator is a priori rather important, the amount of light collected with a photographic objective is small. Different scintillators and different light collection techniques have been experimented with and results will be shown for different setups improving upon the light recuperation on the camera sensor. Improvements on the algorithm side will also be presented. The algorithms have to be at the same time efficient in their recognition of neutron signals, in their rejection of noise signals (internal and external to the camera) but also have to be simple enough to be easily implemented in the FPGA. The path from the idea of detecting individual neutron impacts with a CMOS camera to a practical working instrument detector is challenging, and in this paper we will give an overview of the part of the road that has already been walked.

A new mass spectrometric method is described that allows to selectively probe double bond positions by ultraviolet photodissociation of phosphatidylcholines from complex lipid mixtures.

1D or 2D neutron imaging detectors with individual wire or strip readout using discriminators have the advantage of being able to treat several neutron impacts partially overlapping in time, hence reducing global dead time. A single neutron impact usually gives rise to several discriminator signals. In this paper, we introduce an information-theoretical definition of image resolution. Two point-like spots of neutron impacts with a given distance between them act as a source of information (each neutron hit belongs to one spot or the other), and the detector plus signal treatment is regarded as an imperfect communication channel that transmits this information. The maximal mutual information obtained from this channel as a function of the distance between the spots allows to define a calibration-independent measure of resolution. We then apply this measure to quantify the power of resolution of different algorithms treating these individual discriminator signals which can be implemented in firmware. The method is then applied to different detectors existing at the ILL. Center-of-gravity methods usually improve the resolution over best-wire algorithms which are the standard way of treating these signals.

The present supply of 3He can no longer meet the detector demands of the upcoming ESS facility and continued detector upgrades at current neutron sources. Therefore viable alternative technologies are required to support the development of cutting-edge instrumentation for neutron scattering science. In this context, 10B-based detectors are being developed by collaboration between the ESS, ILL, and Linköping University. This paper reports on progress of this technology and the prospects applying it in modern neutron scattering experiments. The detector is made-up of multiple rectangular gas counter tubes coated with B4C, enriched in 10B. An anode wire reads out each tube, thereby giving position of conversion in one of the lateral co-ordinates as well as in depth of the detector. Position resolution in the remaining co-ordinate is obtained by segmenting the cathode tube itself. Boron carbide films have been produced at Linköping University and a detector built at ILL. The characterization study is presented in this paper, including measurement of efficiency, effects of the fill gas species and pressure, coating thickness variation on efficiency and sensitivity to gamma-rays.

Due to the very limited availability of 3He, new kinds of neutron detectors, not based on 3He, are urgently needed. Here, we present a method to produce thin films of 10B4C, with maximized detection efficiency, intended to be part of a new generation of large area neutron detectors. B4C thin films have been deposited onto Al-blade and Si wafer substrates by dc magnetron sputtering from natB4C and 10B4C targets in an Ar discharge, using an industrial deposition system. The films were characterized with scanning electron microscopy, elastic recoil detection analysis, x-ray reflectivity, and neutron radiography. We show that the film-substrate adhesion and film purity are improved by increased substrate temperature and deposition rate. A deposition rate of 3.8 Å/s and substrate temperature of 400 °C result in films with a density close to bulk values and good adhesion to film thickness above 3 μm. Boron-10 contents of almost 80 at. % are obtained in 6.3 m2 of 1 μm thick 10B4C thin films coated on Al-blades. Initial neutron absorption measurements agree with Monte Carlo simulations and show that the layer thickness, number of layers, neutron wavelength, and amount of impurities are determining factors. The study also shows the importance of having uniform layer thicknesses over large areas, which for a full-scale detector could be in total ∼1000 m2 of two-side coated Al-blades with ∼1 μm thick 10B4C films.

We propose an analysis of the dead time losses in counting imaging detectors such as MWPC which can resolve k simultaneous hits, and analyze in more detail an X−Y detector which has a third wire set which allows for the recognition of simultaneous impacts.

An approximate analytical expression for " capacitance " of MWPC configurations circulates in the literature since decades and is copied over and over again. In this paper we will try to show that this formula corresponds to a physical quantity that is different from what it is usually thought to stand for.

Time-over-threshold measurements of the output of a first order integration amplifier can be used as a cheap way to estimate the charge deposited on a wire in an MWPC. Even if the time scale of the first order system is seemingly much larger than the signal development time, we noticed experimentally a significant deviation from the relationship of time-over-threshold and the charge, as would be naively expected from the exponential response of the amplifier. We strongly suspect the current induced by the residual ion movement to be at least partially responsible for this observation. It is of course well-known that the ion movement is responsible for the bulk of the signal generation in a wire chamber, this is not the point ; however, the surprise is rather that this movement has influences on time scales which are so long that the finite ion movement could be thought negligible. In this paper we will treat theoretically the influence of ion movement and of AC coupling on the expected time-overthreshold relationship and confront this to the measurements on a small test MWPC in thermal neutron detection.

Hossenfelder proposes in [S. Hossenfelder, Phys. Lett. B 636 (2006) 119] and [S. Hossenfelder, gr-qc/0605083] a symmetry between gravitating and anti-gravitating particles by superposing a negative charge to classical relativity. This Letter explicitly shows that the latter proposal does not address any of the difficulties that arise in such context. On the contrary, the “world-lines” of the anti-gravitating particles are defined as observer-dependent entities and no attempt whatsoever to dynamically restore local boost invariance is made. Both papers simply focus on the erroneous construction of a new bundle attached to a preferred timelike vector field, although the author gives the impression that no such preference is needed.

Proponents of the Everett interpretation of Quantum Theory have made efforts to show that to an observer in a branch, everything happens as if the projection postulate were true without postulating it. In this paper, we will indicate that it is only possible to deduce this rule if one introduces another postulate that is logically equivalent to introducing the projection postulate as an extra assumption. We do this by examining the consequences of changing the projection postulate into an alternative one, while keeping the unitary part of quantum theory, and indicate that this is a consistent (although strange) physical theory.

An amplifier has been designed for optimal use of position-sensitive thermal neutron detectors based upon the principle of resistive charge division. The important points in this optimization are: high counting rates and good spatial resolution (low noise). In this paper, we present a short theoretical analysis of the problem that led us to our design. We make an analysis of unwanted, secondary effects caused by extra resistance, the blocking capacitor and the finite input impedance of the amplifier which often occur in a practical measurement setup of this kind.