Ancient wood of the Acqualadrone rostrum: Materials history through gas chromatography/mass spectrometry and sulfur X-ray absorption spectroscopy

In 2008 the rostrum from an ancient warship was recovered from the Mediterranean near Acqualadrone, Sicily. To establish its provenance and condition, samples of black and brown rostrum wood were examined using sulfur K-edge X-ray absorption spectroscopy (XAS) and gas chromatography/mass spectrometry (GC/MS). GC/MS of pyrolytic volatiles yielded only guaiacyl derivatives, indicating construction from pinewood. A derivatized extract of black wood yielded forms of abietic acid and sandaracopimaric acid consistent with pine pitch waterproofing. Numerical fits to the sulfur K-edge XAS spectra showed that about 65% of the endogenous sulfur consisted of thiols and disulfides. Elemental sulfur was about 2% and 7% in black and brown wood, respectively, while pyritic sulfur was about 12% and 6%. About 2% of the sulfur in both wood types was modeled as trimethylsulfonium, possibly reflecting biogenic (dimethylsulfonio)propionate. High-valent sulfur was exclusively represented by sulfate esters, consistent with bacterial sulfotransferase activity. Traces of chloride were detected, but no free sulfate ion. In summary, the rostrum was manufactured of pine wood and subsequently waterproofed with pine pitch. The subsequent 2300 years included battle, foundering, and marine burial followed by anoxia, bacterial colonization, sulfate reduction, and mobilization of transition metals, which produced pyrite and copious appended sulfur functionality

Improvement of interation in and properties of PMMA-MWNT nanocomposites through microwave assisted acid treatment of MWNT

Soluble derivatives of multi-walled carbon nanotubes (MWNT) embedded in a poly(methylmethacrylate) (PMMA) matrix forming thick, homogeneous and transparent nanocomposites, were prepared and characterized. A new photo-assisted method using microwaves, to purify the MWNTs from amorphous carbon and synthesis catalyst clusters, was tested in a sulphonitric mix. This method shortened the processing time compared to other methods. Pristine and functionalized MWNTs were introduced into the MMA, then in situ photo-polymerized. Transmission electron microscopy (TEM) and X-ray diffractometry (XRD), as well as Fourier-transform infrared (FTIR), Raman and nuclear magnetic resonance (NMR) spectroscopy were used to monitor the effects of the treatment on the different components. The thermal properties of the composites were determined through differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). The short, microwave treated and polyethylene glycol (PEG) functionalized MWNTs showed the best dispersion in and interaction with PMMA, and had the most significant influence on the thermal properties of this polymer

Microstructure and phase composition of bronze Montefortino helmets discovered Mediterranean seabed to explain an unusual corrosion

Two Monterfortino helmets, recovered in the Mediterranean seabed, show unusual features with respect to the more common helmets of the same period and found in underwater environments. Hence, they were investigated by a multi-analytical approach, which allowed us to identify the compounds constituting the helmets and to make some considerations about their metallurgy, although all the metal was converted to degradation products. The helmets, originally made in bronze, have maintained their original shape because of copper sulphides formation. The observed differences in composition between the two helmets were attributed to the position modification, of one of them, into the seabed along centuries. For the first time, a microstructural investigation permits to reconstruct the history of the aging processes involved in the total oxidation of roman bronze helmet metal

Scienza e Arti Perdute: i Segreti degli Antichi Maestri Liutai

Lo scopo di questo lavoro è illustrare agli insegnanti la connessione tra due settori di attività apparentemente lontani: la scelta dei materiali utilizzati nella liuteria artigianale e la chimica. Il ruolo, la composizione e la classificazione delle principali vernici per liuteria sono qui descritte assieme ad una breve sintesi dello stato dell’arte. Nel lavoro, vengono presentati i principali concetti di una tecnica analitica non distruttiva abbastanza semplice (la spettroscopia di fluorescenza da raggi X) ma, probabilmente, non abbastanza nota ai non addetti ai lavori. Un caso di studio a essa correlato è inoltre presentato per evidenziare uno dei possibili contributi del chimico nello studio dei beni culturali.The aim of this paper is showing teachers the connection between two apparently distant working fields: the choice of materials used in artisanal lute making and chemistry. The role, the composition and the classification of the main varnishes for classical lute making are here described with a brief review of the state of the art. Furthermore, the main theoretical basis of a relatively simple non-destructive analytical technique (X-Ray Fluorescence Spectroscopy), probably not very well known by non-specialists, is here illustrated. A case study is also presented to highlight one of the possible roles of the chemist in the study of cultural heritage

Influence of temperature on calcium hydroxyapatite nanopowders

The aim of this work is to investigate the effects of thermal treatment, in the range of temperature between 80°C - 900°C, on crystallinity, morphology and particles size of calcium hydroxylapatite nanopowders (HAp). A complete study was carried out applying 31P Magic Angle Spinning NMR, X-ray diffraction, nitrogen porosimetry and Transmis- sion Electron Microscopy techniques. HAp specimens were prepared by chemical precipitation in an aqueous solution of calcium nitrate and ammonium hydrogen phosphate. The thermal treatment performed, showed the formation of crystals whose appearance has three main morphologies and different particles size. HAp treated up to 500°C showed a set of needle-like shape crystals with a low surface area value. These crystals turned into rod-like crystals with tem- perature increase, along with an increase in crystallite size. At 900°C was detected a hexagonal hydroxylapatite phase. Furthermore, Dynamic Light Scattering explored a stable HAp dispersion. The isopropyl alcohol dispersion resulted stable for at least two weeks, useful to create layers of determined morphology nanoparticles

Geopolymers for hazardous cations and anions inertization

Several waste liquors are classified as toxic or hazardous waste and represent a real burden for companies in terms of costs and treatment time. One of the most difficult to treat is the tannery waste water that represent a high pollution risk if not treated and collected properly. Geopolymeric matrix based on metakaolin has been used to treat tannery waste water without any post use treatment. The as received waste water containing tannins, chromium soluble salts, phenols, bicarbonates, and a mixture of organic compounds have been added to a geopolymeric formulation which was optimized for Cr+3 liquor [1]. Please click Additional Files below to see the full abstract

Micro-X-Ray Fluorescence and the Old Masters: Non-destructive in situ characterisation of the varnish of historical Low Countries stringed musical instruments

In recent years, a growing attention has been addressed to the study of the varnish from early musical instruments. The surfaces of nine historical Low Countries stringed musical instruments from the collection of the "Musical Instruments Museum” in Brussels were non-destructively analysed by in situ micro-X-Ray Fluorescence spectroscopy in dispersive mode. It was found that the main pigments dispersed in the varnish were iron- and manganese-based earths. The presence of a chromium-based pigment in one of the analysed instruments makes it appreciably different from the others. Other findings were discussed and compared with previously published results. The collection of such information plays a relevant role in the recovery of the applied formulations that is an interesting issue for conservators, luthiers and art historian

Pt(II) complex @mesoporous silica: preparation, characterization and study of release

Cisplatin analogs, having cytotoxic activity higher than that exerted by cisplatin, have recently triggered considerable interest by the community. The cis-[PtCl2(DMSO)HL]·2DMSO, where HL = 7-amino-2-(methylthio)[1,2,4]triazolo[1,5-a]pyrimidine-6-carboxylic acid, has shown a potent cytotoxic activity on HepG2 hepatocarcinoma cells, while under identical conditions, it did not affect normal immortalized human liver cells (Chang). In this work, the above complex has been incorporated into MCM41 mesoporous silica, pure and functionalized with amino group, which is considered one of the best host for a drug delivery system for carrying high dosages of a variety of drugs in their mesopores. Since the controlled release of an anticancer drug helps to maintain its therapeutic level for an extended time period while minimizing undesirable high peaks immediately following administration, the in vitro tests have been performed in order to obtain the corresponding drug release profile. The investigated system demonstrated to be an efficient system for pharmaceutic controlled release. A deepened characterization of the systems has been performed in order to known their structure and features and to speculate the mechanisms involved in the release

Effect of the cerium loading on the HMS structure. Preparation, characterization and catalytic properties

Ce–HMS mesoporous materials were prepared by incipient wetness method starting from HMS synthesized in acid condition. The effect of ceriumquantity, in the range of Ce/Si atomic ratio 0.02–0.3, on its structure and properties was investigated. Results showed that the HMS hexagonal structure was maintained after the cerium adding. Furthermore, the surface area and the pore volume were reduced. The presence of the cerianite nanoparticles located within the HMS channels up to 0.05, thus covering the HMS surface at higher Ce/Si atomic ratio,was observed. The catalytic performances of the materials were tested in ethanol partial oxidation reactio