On-line database of voltammetric data of immobilized particles for identifying pigments and minerals in archaeometry, conservation and restoration (ELCHER database).

A web-based database of voltammograms is presented for characterizing artists' pigments and corrosion products of ceramic, stone and metal objects by means of the voltammetry of immobilized particles methodology. Description of the website and the database is provided. Voltammograms are, in most cases, accompanied by scanning electron microphotographs, X-ray spectra, infrared spectra acquired in attenuated total reflectance Fourier transform infrared spectroscopy mode (ATR-FTIR) and diffuse reflectance spectra in the UV-Vis-region. For illustrating the usefulness of the database two case studies involving identification of pigments and a case study describing deterioration of an archaeological metallic object are presented.

Screening and mapping of pigments in paintings using scanning electrochemical microscopy (SECM).

The use of the scanning electrochemical microscopy (SECM) technique for identifying and mapping of both organic and inorganic pigments in sub-microsamples from pictorial specimens is described. This methodology, inspired by the voltammetry of immobilized particles technique, permits the study of textural properties of paint layers and mapping the distribution of pigment grains upon application of different potentials to the substrate. A combination of the redox competition SECM strategy with voltammetry yields a local identification methodology for different organic and inorganic pigments in paint samples.

Determination of the depth profile distribution of guest species in microporous materials using the voltammetry of immobilized particles methodology: application to lapachol attachment to palygorskite and kaolinite.

A model for determining the in-depth profile distribution of electroactive species hosted in inorganic microporous matrixes using the voltammetry of immobilized particles methodology is described. The method, based on the analysis of cyclic voltammetric data at different potential scan rates, allows us to determine the in-depth profile variation of the concentration of electroactive guest species as well as the evaluation of the (oxidized form)/(reduced form) concentration ratio in cases where two oxidation states of the electroactive species coexist. The application to Maya blue-type materials prepared from lapachol, a naphtoquinonic dye, and palygorskite and kaolinite clays is reported. The determination of the in-depth distribution of guest molecules is not easy due to the heterogeneity of the clay particle size distribution and the appearance of cyclization and redox tuning reactions. Electrochemical data revealed differences in the in-depth distribution of the dye molecules in the grains of the channelled (palygorskite) and the laminar (kaolinite) clays that suggest that lapachol compounds can ingress into the channels of the palygorskite framework whereas remain externally adsorbed onto the kaolinite crystals.

Redox tuning and species distribution in Maya Blue-type materials: a reassessment.

Maya Blue-type specimens prepared from indigo (1 wt %) plus kaolinite, montmorillonite, palygorskite, sepiolite, and silicalite are studied. Liquid chromatography with diode array detection, ultra-performance liquid chromatography coupled with mass spectrometry, and pyrolysis-silylation gas chromatography-mass spectrometry analyses of the extracts from these specimens combined with spectral and solid-state voltammetry, electrochemical impedance spectroscopy, and scanning electrochemical microscopy techniques provide evidence for the presence of a significant amount of dehydroindigo and isatin accompanying indigo and other minority organic compounds in all samples. Solid-state electrochemistry data permits the estimatation of indigo loading in archeological Maya Blue, which is in the range of 0.2 to 1.5 wt %. These results support a view of 'genuine' Maya Blue-type materials as complex polyfunctional organic-inorganic hybrids.

Study of Spanish grape mycobiota and ochratoxin A production by Isolates of Aspergillus tubingensis and other members of Aspergillus section Nigri.

The native mycobiota of five grape varieties grown in Spain has been studied. Four (Bobal, Tempranillo, Garnacha, and Monastrell) were red varieties and one (Moscatel) was white. The main fungal genera isolated were Alternaria, Cladosporium, and Aspergillus. The isolation frequency of Aspergillus spp. section Nigri in contaminated samples was 82%. Ochratoxin A (OTA) production was assessed using yeast extract-sucrose broth supplemented with 5% bee pollen. Cultures of 205 isolates from this section showed that 74.2% of Aspergillus carbonarius and 14.3% of Aspergillus tubingensis isolates produced OTA at levels ranging from 1.2 to 3,530 ng/ml and from 46.4 to 111.5 ng/ml, respectively. No Aspergillus niger isolate had the ability to produce this toxin under the conditions assayed. Identification of the A. niger aggregate isolates was based on PCR amplification of 5.8S rRNA genes and its two intergenic spacers, internal transcribed spacer 1 (ITS1) and ITS2, followed by digestion with restriction endonuclease RsaI of the PCR products. The restriction patterns were compared with those from strains of A. niger CECT 2807 and A. tubingensis CECT 20393, held at the Spanish Collection of Type Cultures. DNA sequencing of the ITS1-5.8S rRNA gene-ITS2 region of the OTA-producing isolates of A. tubingensis matched 99 to 100% with the nucleotide sequence of strain A. tubingensis CBS 643.92. OTA determination was accomplished by liquid chromatography with fluorescence detection. OTA confirmation was carried out by liquid chromatography coupled to ion trap mass spectrometry. The results showed that there are significant differences with regard to the isolation frequency of ochratoxinogenic fungi in the different grape varieties. These differences were uncorrelated to berry color. The ability of A. tubingensis to produce OTA and the influence of grape variety on the occurrence of OTA-producing fungi in grapes are described in this report for the first time.