Investigation of IR and Raman spectra of species present in formaldehyde-water-methanol systems

Formaldehyde forms a variety of hydrated and methoxylated species when reacted with water and methanol. Vibrational spectroscopy has been deployed for both remote and in situ sensing of formaldehyde species and it can be a useful tool for process development, monitoring and control at both laboratory and industrial scale, as well as for environmental, atmospheric and space monitoring. While IR and Raman spectroscopic studies of formaldehyde species in solid, liquid or gas phases have been reported, assignments of vibrational frequencies of relevant species in previous literature have been contradictory and incomplete. In this work we report IR and Raman spectra for formaldehyde-water-methanol solutions across a wide range of formaldehyde concentrations and solvent compositions. We present an analysis of vibrational spectra of formaldehyde-water-methanol systems using a combination of experimental measurements and gas phase quantum mechanical density functional theory simulations. For the first time, we explicitly consider spectra of oligomeric mixtures of formaldehyde species in relation to spectra of specific representative hydrated and methoxylated species and we resolve some previously reported contradictions in assignments of vibrational frequencies for formaldehyde systems

Measurements, Models, Systems and Design

531 s.

Rapid detection of peptide markers for authentication purposes in raw and cooked meat using ambient liquid extraction surface analysis mass spectrometry

In this paper, our previously developed ambient LESA-MS methodology is implemented to analyze five types of thermally treated meat species, namely beef, pork, horse, chicken, and turkey meat, in order to select and identify heat-stable and species-specific peptide markers. In-solution tryptic digests of cooked meats were deposited onto a polymer surface, followed by LESA-MS analysis and evaluation using multivariate data analysis and tandem electrospray MS. The five types of cooked meat were clearly discriminated using principal component analysis and orthogonal partial least squares discriminant analysis. A number of 23 heat stable peptide markers unique to species and muscle protein were identified following data-dependent tandem LESA-MS analysis. Surface extraction and direct ambient MS analysis of mixtures of cooked meat species was performed for the first time and enabled detection of 10% (w/w) of pork, horse, and turkey meat, and 5% (w/w) of chicken meat in beef, using the developed LESA-MS/MS analysis. The study shows, for the first time, that ambient LESA-MS methodology displays specificity sufficient to be implemented effectively for the analysis of processed and complex peptide digests. The proposed approach is much faster and simpler than other measurement tools for meat speciation; it has potential for application in other areas of meat science or food production

Evolution and environment of the eastern linear pottery culture: A case study in the site of Polgár-Piócási-Dűlő

A salvage excavation preceding a major investment project was conducted in 2006–2007, during which associated settlement features of a Middle Neolithic, Eastern Linear Pottery Culture (Alföld Linearbandkeramik – ALBK) were uncovered in an area called Piócási-dűlő on the eastern outskirts of Polgár. The features of the ALBK settlement date from two periods. The cluster of multi-functional pits yielding a rich assortment of finds, the handful of post-holes and an unusual ritual well found in the southern part of the investigated area formed one unit from the earliest phase of the Middle Neolithic (ALBK I). The settlement’s other occupation can be assigned to the late phase of the Middle Neolithic (ALBK IV). Five houseplans representing the remains of timber-framed buildings outlined a distinct area with three multi-functional pits. Associated with the above features were 8 burials. The preliminary archaeobotanical results from Polgár–Piócási-dűlő are based on the plant material found within the sediments of 11 archaeological structures, which mainly represent pits and a welI. It can be stated that the natural environment offered habitats in which oak trees dominated in the local vegetation, forming floodplain forests and wooded steppes. They also provided food in the form of fruits and formed an optimal habitat for domestic animals. Arable fields were probably also established in the vicinity of the settlements, suggested by findings of macroscopic plant remains that represented cultivated species. In both settlement phases lithic production activities are manifested both by the local on-site lithic production and – most importantly – by the presence of imported, mainly mesolocal, raw materials that point to contacts with deposit areas, or off-site preliminary working of obsidian and limnoquartzites. The kit of harvesting tools and a large number of grinding stones – especially in the younger phase – for the preparation of plant food suggest a major role of plant cultivation

Measurement of the diffractive structure function in deep inelastic scattering at HERA

This paper presents an analysis of the inclusive properties of diffractive deep inelastic scattering events produced in $ep$ interactions at HERA. The events are characterised by a rapidity gap between the outgoing proton system and the remaining hadronic system. Inclusive distributions are presented and compared with Monte Carlo models for diffractive processes. The data are consistent with models where the pomeron structure function has a hard and a soft contribution. The diffractive structure function is measured as a function of \xpom, the momentum fraction lost by the proton, of $\beta$, the momentum fraction of the struck quark with respect to \xpom, and of $Q^2$. The \xpom dependence is consistent with the form \xpoma where $a~=~1.30~\pm~0.08~(stat)~^{+~0.08}_{-~0.14}~(sys)$ in all bins of $\beta$ and $Q^2$. In the measured $Q^2$ range, the diffractive structure function approximately scales with $Q^2$ at fixed $\beta$. In an Ingelman-Schlein type model, where commonly used pomeron flux factor normalisations are assumed, it is found that the quarks within the pomeron do not saturate the momentum sum rule.Comment: 36 pages, latex, 11 figures appended as uuencoded fil

On the influence of Si:Al ratio and hierarchical porosity of FAU zeolites in solid acid catalysed esterification pretreatment of bio-oil

A family of faujasite (FAU) zeolites with different Si:Al ratio, and/or hierarchical porosity introduced via post-synthetic alkaline desilication treatment, have been evaluated as solid acid catalysts for esterification pretreatments of pyrolysis bio-oil components. Acetic acid esterification with aliphatic and aromatic alcohols including methanol, anisyl alcohol, benzyl alcohol, p-cresol and n-butanol was first selected as a model reaction to identify the optimum zeolite properties. Materials were fully characterised using N2 porosimetry, ICP, XRD, XPS, FT-IR, pyridine adsorption, NH3 TPD, In-situ ATR and inverse gas chromatography (IGC). IGC demonstrates that the surface polarity and hence hydrophobicity of FAU decreases with increased Si:Al ratio. Despite possessing a higher acid site loading and acetic acid adsorption capacity, high Al-content FAU possess weaker acidity than more siliceous catalysts. Esterification activity increases with acid strength and decreasing surface polarity following the order FAU30>FAU6>FAU2.6. The introduction of mesoporosity through synthesis of a hierarchical HFAU30 material further enhances esterification activity through improved acid site accessibility and hydrophobicity. Methanol was the most reactive alcohol for esterification, and evaluated with HFAU30 for the pretreatment of a real pyrolysis bio-oil, reducing the acid content by 76% under mild conditions