Exploring conformational energy landscape of glassy disaccharides by CPMAS 13C NMR and DFT/GIAO simulations. I. Methodological aspects

The aim of this article is to assess the ability of chemical shift surfaces to provide structural information on conformational distributions of disaccharides in glassy solid state. The validity of the general method leading to a simulation of inhomogeneous 13C chemical shift distributions is discussed in detail. In particular, a proper consideration of extrema and saddle points of the chemical shift map correctly accounts for the observed discontinuities in the experimental CPMAS spectra. Provided that these basic requirements are met, DFT/GIAO chemical shift maps calculated on relaxed conformations lead to a very satisfactory description of the experimental lineshapes. On solid-state trehalose as a model of amorphous disaccharide, this simulation approach defines unambiguously the most populated sugar conformation in the glass, and can help in discriminating the validity of different models of intramolecular energy landscape. Application to other molecular systems with broad conformational populations is foreseen to produce a larger dependence of the calculated chemical shift distribution on the conformational map

Fat residue and use-wear found on Acheulian biface and scraper associated with butchered elephant remains at the site of Revadim, Israel

The archaeological record indicates that elephants must have played a significant role in early human diet and culture during Palaeolithic times in the Old World. However, the nature of interactions between early humans and elephants is still under discussion. Elephant remains are found in Palaeolithic sites, both open-air and cave sites, in Europe, Asia, the Levant, and Africa. In some cases elephant and mammoth remains indicate evidence for butchering and marrow extraction performed by humans. Revadim Quarry (Israel) is a Late Acheulian site where elephant remains were found in association with characteristic Lower Palaeolithic flint tools. In this paper we present results regarding the use of Palaeolithic tools in processing animal carcasses and rare identification of fat residue preserved on Lower Palaeolithic tools. Our results shed new light on the use of Palaeolithic stone tools and provide, for the first time, direct evidence (residue) of animal exploitation through the use of an Acheulian biface and a scraper. The association of an elephant rib bearing cut marks with these tools may reinforce the view suggesting the use of Palaeolithic stone tools in the consumption of large game

The fate of microplastics during the anaerobic digestion of thermally pretreated sludge

The presence of microplastics (MPs) in the water environment has raised as an issue of great concern, mainly due to their persistence and potential adverse effects on biota. Municipal wastewater treatment plants have been claimed among the most important point source of MPs. Nevertheless, they act as a barrier for the spread of MPs in water, since a significant amount of these pollutants concentrates in the sludge originating from wastewater treatment. This study focuses on the presence of MPs in sewage sludge, with the main aim of assessing their fate during the mesophilic anaerobic digestion of thermally pretreated sludge. MP abundance in the digestate as well as the anaerobic biodegradability of the pretreated substrates were assessed. Experimental results addressed preliminary considerations on the effects of high temperature on the MPs as well as on their influence on anaerobic degradation processes

Vibrational Spectrum of HMX at CO2 Laser Wavelengths: A Combined DRIFT and LPAS Study

The vibrational spectrum of solid standard HMX (octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine) was investigated. Two spectroscopic techniques were adopted for their different sensitivity and resolution. A preliminary survey of the absorption bands of the compound was performed in the 8000–400 cm−1 spectral range by employing the diffuse reflectance infrared Fourier transform (DRIFT) technique at room temperature. The high-resolution line spectrum of HMX was obtained in the 9.2–10.8 μm spectral range by laser photoacoustic spectroscopy (LPAS) method, using a line tuneable 10 W stabilised cw CO2 laser light source. By comparing the data collected with the two techniques in the common frequency range, a very good agreement was observed

Vibrational Spectrum of HMX at CO 2

The vibrational spectrum of solid standard HMX (octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine) was investigated. Two spectroscopic techniques were adopted for their different sensitivity and resolution. A preliminary survey of the absorption bands of the compound was performed in the 8000–400 cm−1 spectral range by employing the diffuse reflectance infrared Fourier transform (DRIFT) technique at room temperature. The high-resolution line spectrum of HMX was obtained in the 9.2–10.8 μm spectral range by laser photoacoustic spectroscopy (LPAS) method, using a line tuneable 10 W stabilised cw CO2 laser light source. By comparing the data collected with the two techniques in the common frequency range, a very good agreement was observed

The use of ash at Late Lower Paleolithic Qesem Cave, Israel—An integrated study of use-wear and residue analysis

Employing an integrated approach to investigate the use of Late Lower Paleolithic flint tools found at the site of Qesem Cave (Israel), we revealed a particular trace pattern related to the employment of ashes at the site. Using a designated collection of replica items and combining use-wear and residue (morphological analysis, FTIR, SEM-EDX) analyses, we revealed the intentional use of ashes in preserving foods for delayed consumption as well as hide for delayed processing. Our interpretation, we believe is the most plausible one since we were able to delineate the specific use-wear fingerprints of the intentional use of ashes for such purposes, suggesting that our approach might be useful for the recognition of other similar functional-behavioral patterns. Lastly, in support of previous findings at Qesem Cave, our current findings present evidence for the processing of organic matters intentionally mixed with ash, leading us to suggest that the inhabitants of Qesem Cave were proficient not only in the habitual use of fire but also of its main by-product, ash. Hence, we call for a reassessment of the timeline currently assigned to hominins’ utilization of ash for storing and processing vegetal foods and hide

Potentialities of Complex Network Theory Tools for Urban Drainage Networks Analysis

Urban drainage networks (UDNs) represent important infrastructures to protect and maintain community health and safety. For these reasons, technicians and researcher are focusing more and more on topics related to vulnerability, resilience and monitoring for controlling illicit intrusions, contaminant and pathogenic spread. In the last years the complex network theory (CNT) is attracting attention as a new, useful and structured approach to analyze urban systems. The aim of this work is to evaluate potentialities of CNT approaches for UDNs vulnerability assessment and monitoring system planning. Limits and potentialities of applicability of CNT tools to UDNs are first provided evaluating the performances of standard centrality metrics. Then, it is proposed the use of tailored metrics embedding prior information, as intrinsic relevance of each node and pipe flow direction, which derive from the Horton's hierarchy and geometric data (pipe slope), respectively, without performing hydraulic simulations. The analysis is applied on two schematic literature networks of different complexity and to a real case-study. The results suggest that vulnerability/resilience, monitoring design, contaminant and pathogenic spreads can be effectively analyzed using tailored metrics. Therefore, the proposed approach represents a complementary tool respect the more complex and computationally expensive methodologies and it is particular useful for large complex networks

Effective action in spherical domains

The effective action on an orbifolded sphere is computed for minimally coupled scalar fields. The results are presented in terms of derivatives of Barnes zeta-functions and it is shown how these may be evaluated. Numerical values are shown. An analytical, heat-kernel derivation of the Ces\`aro-Fedorov formula for the number of symmetry planes of a regular solid is also presented.Comment: 18 pages, Plain TeX (Mailer oddities possibly corrected.