Archaeo-metallurgical studies of tuyeres and smelting slags found at Tharros (north-western Sardinia, Italy)

A large number of pyrometallurgical materials such as tuyeres, slags and refractory tools likely associated with metal extraction processes have been found at Tharros (north-western Sardinia, Italy) during archaeological excavations stratigraphically related to the Phoenician–Punic period (VI–III centuries BC). Micro-chemical, micro-structural and mineralogical studies have been carried out by means of the combined use of X-ray diffraction (XRD), selected-area X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM) combined with energy-dispersive X-ray analysis (EDS) in order to identify pyrometallurgical processes and main relevant technological parameters. The results reveal that tuyeres, slags and refractory tools can be associated with an iron ore smelting process to extract the metal by slagging the unwanted by-products. Moreover, temperature and duration of the smelting process have been estimated through mineralogical studies and by a comparative analysis between the micro-chemical and structural features of thermally treated refractory materials and tuyeres. The results disclose the high level of technological competence of the ancient metallurgists able to carry out complex high-temperature processes to extract iron from ores by separating the metal from unwanted siliceous species.     

Statistical Entropy of a Lattice-Gas Model: Multiparticle Correlation Expansion

A formula expressing the statistical entropy of a lattice-gas model as a multiparticle correlation expansion is derived in the grand-canonical and in the canonical ensembles. The differences from the analogous expansion in the continuum case are elucidated. The Ising model in one dimension is discussed as a case study.     

New insights into the seleniranium ion promoted cyclization of prenyl and propenylbenzene aryl ethers

The chromane core is widely represented in nature being part of a wide array of secondary metabolites of plant, fungal, and bacterial origin. In this paper an improved method for the chemical synthesis of differently substituted chromanes is described. Substituted 2H-1-benzopyrans have been synthesized in good to excellent yields (52–81%) by treatment of 3,3-dimethylallyl and propenylbenzene ethers of differently substituted phenols with phenylselenyl chloride.     

Characterization of the volatile organic compounds of Italian 'Fossa' cheese by solid-phase microextraction gas chromatography/mass spectrometry

Fossa cheese is an Italian hard cheese, ripened for up to 3 months in underground pits dug into tuffaceous rock. During this period, the cheese develops a unique flavour and intense and somewhat piquant aroma. Solid-phase microextraction gas chromatography/mass spectrometry (SPME-GC/MS) was utilized to characterize the volatile organic compounds (VOCs) of Fossa cheese. A total of 75 VOCs were separated and identified; in particular, the major class of compounds found in the cheeses ripened in the pits were the esters of fatty acids. Discriminant analysis of volatile profiles allowed us to distinguish between cheeses in different stages of seasoning (60-day-old cheese and cheese ripened an additional 90 days in and out of the pits).     

Quantification of Photosensitized Singlet Oxygen Production by a Fluorescent Protein

Fluorescent proteins are increasingly becoming actuators in a range of cell biology techniques. One of those techniques is chromophore‐assisted laser inactivation (CALI), which is employed to specifically inactivate the function of target proteins or organelles by producing photochemical damage. CALI is achieved by the irradiation of dyes that are able to produce reactive oxygen species (ROS). The combination of CALI and the labelling specificity that fluorescent proteins provide is useful to avoid uncontrolled photodamage, although the inactivation mechanisms by ROS are dependent on the fluorescent protein and are not fully understood. Herein, we present a quantitative study of the ability of the red fluorescent protein TagRFP to produce ROS, in particular singlet oxygen (¹O₂). TagRFP is able to photosensitize ¹O₂ with an estimated quantum yield of 0.004. This is the first estimation of a quantum yield of ¹O₂ production value for a GFP‐like protein. We also find that TagRFP has a short triplet lifetime compared to EGFP, which reflects relatively high oxygen accessibility to the chromophore. The insight into the structural and photophysical properties of TagRFP has implications in improving fluorescent proteins for fluorescence microscopy and CALI.     

A Cross-Entropy Approach to the Estimation of Generalized Linear Multilevel Models

In this article, we use the cross-entropy method for noisy optimization for fitting generalized linear multilevel models through maximum likelihood. We propose specifications of the instrumental distributions for positive and bounded parameters that improve the computational performance. We also introduce a new stopping criterion, which has the advantage of being problem-independent. In a second step we find, by means of extensive Monte Carlo experiments, the most suitable values of the input parameters of the algorithm. Finally, we compare the method to the benchmark estimation technique based on numerical integration. The cross-entropy approach turns out to be preferable from both the statistical and the computational point of view. In the last part of the article, the method is used to model the probability of firm exits in the healthcare industry in Italy. Supplemental materials are available online.     

Shakedown analysis of limited-ductility structures

Summary The paper deals with the shakedown analysis problem of discrete elastoplastic structures, subjected to variable and repeated quasi-static loads, account being given to the limited structural ductility by imposing a-priori limit values to some relevant parameters of plastic deformation. The key-concept of limited-ductility load amplifier is assessed and the problem is given a unified formulation as a nonlinear mathematical programming problem, where ductility constraints — of generalized character — are obtained by using a so-called perturbation method which leads to a-priori upper bounds of the relevant plastic deformation measures. Lower bounds to the load amplifier are so obtained and three different computationals stratagies are herein outlined: the linear parametric programming one is applied to three case-study structures.

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Sommario La memoria affronta lo studio del problema di adattamento elastoplastico di strutture discrete, sottoposte a carichi comunque variabili in modo quasi-statico, tenendo conto di un comportamento a limitata duttilità della struttura, il quale richiede che uno o più parametri della deformazione plastica risultino non superiori di assegnati valori. Del problema di analisi posto, utilizzando il concetto di moltiplicatore dei carichi per l'adattamento con limitata duttilità, viene data una formulazione unitaria come problema di programmazione matematica non lineare, i cui vincoli di duttilità sono ottenuti con tecniche perturbative di maggiorazione a-priori delle deformazioni plastiche. Il metodo conduce a limiti inferiori del moltiplicatore dei carichi dipendenti dal livello assegnato alla deformazione plastica. Tre differenti strategie computazionali vengono delineate per la soluzione del problema, una delle quali di tipo programmazione lineare parametrica viene applicata a tre esempi.

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Ricerca finanziata dal CNR e dal MPI.     

Charge mapping in 3(10)-helical peptide chains by oxidation of the terminal ferrocenyl group

Two series of 3(10)-helical peptides of different lengths and rigidity, based on the strongly foldameric α-aminoisobutyric acid and containing a terminal ferrocenyl unit, have been synthesized. Oxidation-state sensitive spectroscopic tags of helical peptides, the N-H groups, allowed mapping of the charge delocalization triggered by oxidation of the terminal ferrocenyl moiety and were monitored by IR spectroelectrochemistry.     

Bronze Age pottery from the Aeolian Islands: definition of Temper Compositional Reference Units by an integrated mineralogical and microchemical approach

An integrated microchemical–petrographic approach is here proposed to discriminate the provenance of archaeological pottery artefacts from distinct production centres. Our study focuses on a statistically significant sampling (n=186) of volcanic temper-bearing potteries representative of the manufacturing and dispersion among the islands of the Aeolian Archipelago during the Bronze Age. The widespread establishment of new settlements and the abundant recovery of Aeolian-made ceramic in southern Italy attest for the increased vitality of the Archipelago during the Capo Graziano culture (Early Bronze Age–Middle Bronze Age 2; 2300–1430 BC). Potteries from three of the main known ancient communities (Lipari, Filicudi and Stromboli) have been studied integrating old collections and newly excavated material. Volcanic tempers have been first investigated through multivariate analyses of relative abundances of mineral and rock clasts along with petrographic characters. In addition, we performed in-situ mineral chemistry microanalyses by Electron Microprobe and Laser Ablation—Inductively Coupled Plasma Mass Spectrometry to assess major and trace element composition of the most common mineral phases. Four Temper Compositional Reference Units have been recognised based on compositional trends. Two units (AI and AX) are unequivocally distinct by their peculiar trace element enrichment and petrographic composition; they mostly contain samples from the sites of Lipari and Stromboli, respectively. Units AIV and AVIII, restricted to the sites of Filicudi and Stromboli, show distinct petrographic characters but overlapped geochemical fingerprints.