Standardisation of elemental analytical techniques applied to provenance studies of archaeological ceramics: an inter laboratory calibration study

Chemical analysis is a well-established procedure for the provenancing of archaeological ceramics. Various analytical techniques are routinely used and large amounts of data have been accumulated so far in data banks. However, in order to exchange results obtained by different laboratories, the respective analytical procedures need to be tested in terms of their inter-comparability. In this study, the schemes of analysis used in four laboratories that are involved in archaeological pottery studies on a routine basis were compared. The techniques investigated were neutron activation analysis (NAA), X-ray fluorescence analysis (XRF), inductively coupled plasma optical emission spectrometry (ICP-OES) and inductively coupled plasma mass spectrometry (ICP-MS). For this comparison series of measurements on different geological standard reference materials (SRM) were carried out and the results were statistically evaluated. An attempt was also made towards the establishment of calibration factors between pairs of analytical setups in order to smooth the systematic differences among the results.     

Microchemical and microstructural characterisation of medieval and post-medieval ceramic glaze coatings

A large number of ceramic samples (from the 10th to the 19th century), found during the excavation of Sicilian archaeological sites (Syracuse, Caltagirone, Sciacca and Piazza Armerina), have been studied by combining scanning electron microscopy, energy-dispersive X-ray spectrometry and optical microscopy. Attention has been focused on the microchemical and microstructural properties of the painted surfaces to investigate the nature of the enamels and pigments in the decorative layers. The general perspective has been the identification of consistent archeometric criteria, other than the standard stylistic considerations, which can be used for a reliable recognition of the production sites. The results collected for each ceramic typology were used to cluster the different ceramic reference groups in a wide database suitable for a reliable discrimination of the provenance of artefacts. Moreover, the same compositional and microstructural data allow the identification of the raw materials used for pigments. There is evidence of some differences with existing information found in the literature concerning the formulas used in ancient times. Finally, attention has also been devoted to identify the technological aspects of the manufacturing techniques and firing conditions adopted for each typology of glaze coating depending on different ceramic materials .PACS 81.05.Je; 82.80.-d; 68.37.Hk; 68.55.-a     

A Chemical Proteomic Strategy Reveals Inhibitors of Lipoate Salvage in Bacteria and Parasites

The development of novel anti-infectives requires unprecedented strategies targeting pathways which are solely present in pathogens but absent in humans. Following this principle, we developed inhibitors of lipoic acid ( LA ) salvage, a crucial pathway for the survival of LA auxotrophic bacteria and parasites but non-essential in human cells. An LA -based probe was selectively transferred onto substrate proteins via lipoate protein ligase (LPL) in intact cells, and their binding sites were determined by mass spectrometry. Probe labeling served as a proxy of LPL activity, enabling in situ screenings for cell-permeable LPL inhibitors. Profiling a focused compound library revealed two substrate analogs ( LAMe and C3 ) as inhibitors, which were further validated by binding studies and co-crystallography. Importantly, LAMe exhibited low toxicity in human cells and achieved killing of Plasmodium falciparum in erythrocytes with an EC₅₀ value of 15 μM, making it the most effective LPL inhibitor reported to date.     

Nanostructures and magnetic properties of cobalt ferrite (CoFe2O4) fabricated by electrospinning

This paper describes the fabrication of cobalt ferrite (CoFe₂O₄) nanostructures (in the form of nanofibers and nanoparticles) by the electrospinning method using a solution that contained poly(vinyl pyrrolidone) (PVP) and cheap Co and Fe nitrates as metal sources. The as-spun and calcined CoFe₂O₄/PVP composite samples were characterized by TG-DTA, X-ray diffraction, FT-IR, SEM and TEM, respectively. After calcination of the as-spun CoFe₂O₄/PVP composite nanofibers (fiber size of 320±48 nm in diameter) at 500, 600, and 800°C in air for 3 h with different heating rates of 5 or 20°C/min, either NiFe₂O₄ nanofibers of ∼10−200 nm in diameter or nanoparticles with particle sizes of ∼50−400 nm having a well-developed spinel structure were successfully obtained. The crystal structure and morphology of the nanofibers were influenced by the calcination temperature and heating rate. A faster heating rate allowed for a rapid removal of the PVP matrix and resulted in a complete change from fibrous structure to particle in the calcined CoFe₂O₄/PVP composite nanofibers. Room temperature magnetization results showed a ferromagnetic behavior of the calcined CoFe₂O₄/PVP composite nanofibers, having their hysteresis loops in the field range of ± 4500 and 3000 Oe for the samples calcined respectively with heating rates of 5 and 20°C/min. The values of the specific magnetization (M _s) at 10 kOe, remnant magnetization (M _r), M _r/M _s ratio, and coercive forces (H _c) are obtained from hysteresis loops. It was found that the values of M _s, M _r, M _r/M _s, and H _c depended strongly on morphology of the CoFe₂O₄ nanostructures.     

Rapid test by liquid chromatography/tandem mass spectrometry to evaluate equine urine reactivity towards 17beta-OH steroids

Bacteria frequently found in equine urine samples may cause degradation of 17beta-OH steroids. A simple liquid chromatography/tandem mass spectrometry (LC/MS/MS) method has been developed to evaluate the microbiological contamination of equine urine as a marker of poor storage conditions. Norethandrolone was used as the internal standard, and the linearity, sensitivity, precision and accuracy of the method were evaluated. 17beta-OH oxidation was demonstrated for testosterone, nandrolone, trenbolone and boldenone, but did not occur in alpha-epimers such as alpha-boldenone and epitestosterone, demonstrating the stereoselectivity of the reaction. A rapid test was performed by spiking one of the four 17beta-OH steroids in samples of diluted equine urine. The steroids were transformed into their respective ketones in the presence of bacterial activity. The test allows direct injection of diluted samples into the LC/MS system, without the need for prior extraction. Results show that the best method of storage is freezing at -18 degrees C. Urine specimens should be analyzed as soon as possible after thawing. This allows bacterial degradation of equine urine to be arrested temporarily, so that the urine can be used for qualitative or quantitative analysis of 17beta-OH steroids.     

Laboratory tests addressed to realize customized restoration procedures of underwater archaeological ceramic finds

The present contribution is part of a biennial research project funded by the Italian Ministry of Education, Universities and Research (MIUR). This study, currently in progress, deals with innovative experimental approaches applied to the chemical, mineralogical and physical transformations occurring during the prolonged permanence of archaeological ceramic finds in seawater environments as well as to restoration and conservation issues of the same underwater artifacts. The experimental approach used in this research consisted in the manufacture of ceramic test-pieces (briquettes) and their successive placing in underwater environment. This work aims at assessing how textural and compositional parameters along with firing temperatures of a ceramic paste could affect total porosity, pore size distribution and kinetics of capillary water absorption. A further purpose is concerned with the study of the potential modification of porosity and pore size distribution in the same ceramic bodies after immersion in seawater (3 and 6 months). The study was carried out using a multi-technique approach including investigations through polarized light microscopy (PLM), capillary water absorption test, mercury intrusion porosimetry (MIP) analyses and theoretical calculation of salt crystallization pressures. The obtained results show a different behavior of the six experimental pastes as a function of their compositional and textural features as well as pore size distribution and firing temperatures. These parameters, in various extents, have been found significantly influencing the kinetics of water absorption and the susceptibility of ceramic artifacts to salt crystallization processes, with important implications on conservation procedures needed before the musealization.     

Original synthesis of α-chloroketones in azaheterocyclic series using TDAE approach

We report herein an original and rapid synthesis of new α-chloroketones in azaheterocyclic series based on TDAE strategy from the reaction between 2-(trichloromethyl)quinoxaline and aromatic aldehydes. This reactivity has been generalized to a quinolinic trichloride.     

Original synthesis of oxiranes via TDAE methodology: reaction of 2,2-dibromomethylquinoxaline with aromatic aldehydes

We report herein the reaction of 2,2-dibromomethylquinoxaline 2 with aromatic aldehydes 3a-g in the presence of TDAE. These reactions lead to a mixture of cis/trans-isomers of corresponding oxiranes 4a-g in good yields. The stereoselectivity of the reaction was sensitive to steric hindrance.     

Quinoxaline Moiety: A Potential Scaffold against Mycobacterium tuberculosis

Background. The past decades have seen numerous efforts to develop new antitubercular agents. Currently, the available regimens are lengthy, only partially effective, and associated with high rates of adverse events. The challenge is therefore to develop new agents with faster and more efficient action. The versatile quinoxaline ring possesses a broad spectrum of pharmacological activities, ensuring considerable attention to it in the field of medicinal chemistry. Objectives. In continuation of our program on the pharmacological activity of quinoxaline derivatives, this review focuses on potential antimycobacterial activity of recent quinoxaline derivatives and discusses their structure—activity relationship for designing new analogs with improved activity. Methods. The review compiles recent studies published between January 2011 and April 2021. Results. The final total of 23 studies were examined. Conclusions. Data from studies of quinoxaline and quinoxaline 1,4-di-N-oxide derivatives highlight that specific derivatives show encouraging perspectives in the treatment of Mycobacterium tuberculosis and the recent growing interest for these scaffolds. These interesting results warrant further investigation, which may allow identification of novel antitubercular candidates based on this scaffold.