Investigating the history of prehistoric glues by gas chromatography-mass spectrometry

Although organic materials are very sensitive to biochemical alteration processes, they may be preserved for millennia in various archaeological contexts. Remains of adhesives made during prehistory were discovered at different sites, in the form of residues adhering to flint tools and ceramic vessels or as free lumps in sediment. To characterise the natural substances exploited for adhesive production during late prehistory, we undertook GC and GC/MS analysis of 90 samples from 8 sites dating from the Neolithic to Iron Age periods. This paper discusses our approach to the study of organic adhesives preserved in archaeological contexts, with a particular focus on the presentation of the various categories of organic adhesives that we analysed and the choice of chromatographic conditions adapted to the specificity of such samples. The results obtained show that birch bark tar, a triterpenoid adhesive made by destructive distillation of white birch bark, was predominantly used during the neolithic period even though other materials such as various barks or organic fossil substance were also used. During the Bronze and Iron ages, which follow the Neolithic period, adhesive production is evolving through the expansion of the range of the natural substances used (identification of diterpenoid pine resin) and the addition of beeswax as a plasticiser to birch bark tar. By combining chromatographic analysis and archaeological data, it was thus possible to follow the evolution of adhesive making at the end of prehistory, testifying to the inventiveness of the craftsmen whatever the period considered.     

Comparison of the (17)O NMR spectra of zeolites LTA and LSX

¹⁷O NMR studies of various cation-exchanged LTA and LSX zeolites have shown similarities between the two systems. LSX samples containing divalent cations contain resonances with similar chemical shifts to those previously assigned to ‘bare’ framework oxygen atoms in Ca-LTA and Sr-LTA. The assignments are consistent with the trends seen in the spectra of monovalent cation-containing LSX and LTA zeolites, which show an increase in the average chemical shift with increasing cationic radius. The spectrum of Li-LSX, like Na-LSX, can be assigned based on the T–O–T bond angles. Gas sorption studies on Li-LSX are used to help identify the framework oxygen atoms that form the β-cages and demonstrate the sensitivity of the ¹⁷O shifts to gas loading.     

Numerical predictions and experiments on the free-plate edge mode

In this paper, te edge mode variation is studied with three different methods: the reciprocal work method, already used by Torvik [J. Acoust. Soc. Am. 41 (1967) 346] to model this phenomenon, the S-parameter method and a finite element model that are applied for the first time to the study of the edge resonance. Moreover, laser probe measurements of the edge mode have also been performed and compared to the numerical predictions. The good agreement between the numerical predictions and the experimental data allows full understanding of the resonant phenomenon. The edge resonance is linked to the strong increase in amplitude of two complex Lamb waves, and the edge mode is proved to radiate into the plate as the first symmetrical Lamb mode S(0). Displacements at the edge and away from the edge have been computed and measured to evaluate the spatial and temporal behaviour of the edge mode. The dependence of the edge resonance frequency and amplitude on the Poisson coefficient has also been studied.     

The structure of a self-assembled calixarene aqua-channel system

The crystal structure of the complex 12.calix-[4]-arene dihydroxyphosphonic acid, 12.propane diammonium, 12.ethanol and 40.water molecules is based on dimeric units of the calix, assembled via trigonal units into a hexameric tube of 15 A radius and 16 A depth, further assemby via spanning propane diammonium cations and ethanol molecules forms a channel (40 A), selectively containing all the water molecules.     

Some remarks on half-factorial orders

In questo articolo, si dimostra il legame fra la semi-fattorialità e la fattorialità debole nel contesto degli ordini algebrici. In particolare, si ottiene che un ordine semi-fattoriale ha il stesso numero di classi che su chiusura integrale.     

Optimization models for the single delay management problem in public transportation

Passengers travelling in public transportation networks often have to use different lines to cover the trip from their origin to the desired destination. As a consequence, the reliability of connections between vehicles is a key issue for the attractiveness of the intermodal transportation network and it is strongly affected by some unpredictable events like breakdowns or vehicle delays. In such cases, a decision is required to determine if the connected vehicles should wait for the delayed ones or keep their schedule. The delay management problem (DMP) consists in defining the wait/depart policy which minimizes the total delay on the network. In this work, we present two equivalent mixed integer linear programming models for the DMP with a single initial delay, able to reduce the number of variables with respect to the formulations proposed by the literature. The two models are solved by a branch and cut procedure and by a constraint generation approach respectively, and preliminary computational results are presented.     

Crystal Structure and Complexing Properties of p-tert-butylcalix[6]-1,4-2,5-bis(crown-4)

The X-ray structure of the alreadypublished p-tert-butylcalix[6]-1,4-2,5-bis(crown-4)1 is reported. Extraction of solid ammoniumpicrate in chloroform-d indicates thecation to be located outside of the calixcrown andforming a 1:2 (metal-ligand) complex.     

Transient rheological behaviour of poly-para-henylenetherephthalamide (PpPTA) in sulphuric acid

Nearly all the available information on the transient flow behaviour of liquid crystalline polymers has been obtained on model systems, especially on solutions of polybenzylglutamate (PBG) and hydroxypropylcellulose (HPC). The assessment of rheological models has been based almost entirely on these model systems. It is not clear how much of the available theoretical and experimental knowledge can be applied to systems of industrial relevance, which have quite different molecular structures. Here, an industrial lyotropic system, poly(p-phenylenetherephthalamide) (PpPTA) in sulphuric acid (TWARON from AKZO), is investigated. Various techniques to study transient behaviour are used, these include measurements of transient shear and normal stresses after sudden changes in shear rate, dynamic moduli and stress relaxation after cessation of flow and elastic recoil. At all shear rates studied the PpPTA solution is shear thinning, and the first normal stress difference remains positive. For the stress transients a strain scaling applies reasonably well as it did in model systems. The moduli increase with time upon cessation of flow, indicating that the molecules become less oriented in the previous flow direction. This particular behaviour is similar to that of HPC. Transients also resemble more closely those of HPC rather than those of PBG. This latter difference might be attributed to the higher flexibility of HPC and PpPTA chains as compared with PBG molecules.