Printable Bioelectronics To Investigate Functional Biological Interfaces

Thin‐film transistors can be used as high‐performance bioelectronic devices to accomplish tasks such as sensing or controlling the release of biological species as well as transducing the electrical activity of cells or even organs, such as the brain. Organic, graphene, or zinc oxide are used as convenient printable semiconducting layers and can lead to high‐performance low‐cost bioelectronic sensing devices that are potentially very useful for point‐of‐care applications. Among others, electrolyte‐gated transistors are of interest as they can be operated as capacitance‐modulated devices, because of the high capacitance of their charge double layers. Specifically, it is the capacitance of the biolayer, being lowest in a series of capacitors, which controls the output current of the device. Such an occurrence allows for extremely high sensitivity towards very weak interactions. All the aspects governing these processes are reviewed here.     

Fingerprinting of egg and oil binders in painted artworks by matrix-assisted laser desorption ionization time-of-flight mass spectrometry analysis of lipid oxidation by-products

A matrix-assisted laser desorption ionization time-of-flight mass spectrometry-based approach was applied for the detection of various lipid classes, such as triacylglycerols (TAGs) and phospholipids (PLs), and their oxidation by-products in extracts of small (50–100 μg) samples obtained from painted artworks. Ageing of test specimens under various conditions, including the presence of different pigments, was preliminarily investigated. During ageing, the TAGs and PLs content decreased, whereas the amount of diglycerides, short-chain oxidative products arising from TAGs and PLs, and oxidized TAGs and PLs components increased. The examination of a series of model paint samples gave a clear indication that specific ions produced by oxidative cleavage of PLs and/or TAGs may be used as markers for egg and drying oil-based binders. Their elemental composition and hypothetical structure are also tentatively proposed. Moreover, the simultaneous presence of egg and oil binders can be easily and unambiguously ascertained through the simultaneous occurrence of the relevant specific markers. The potential of the proposed approach was demonstrated for the first time by the analysis of real samples from a polyptych of Bartolomeo Vivarini (fifteenth century) and a “French school” canvas painting (seventeenth century).     

Luminescence Properties of Eu3+ Complexes of Tripode and Tetrapode Ligands Containing 2,2′-Bipyridine Units

The Eu³⁺ complexes of the tripode and tetrapode ligands 1 and 2 , respectively, containing 2,2′-bipyridine coordinating units have been prepared. The UV absorption and luminescence spectra, lifetimes, and quantum yields have been measured under a variety of experimental conditions. The contributions of different paths to the decay of the luminescent excited state are evaluated, and the structures of the complexes are discussed on the basis of spectroscopic and photophysical data.     

An integrated spectroscopic approach to investigate pigments and engobes on pre‐Roman pottery

Painted Canosa ceramics were examined to identify the nature of the pigments employed and their manufacturing technology. A multi‐technique approach was used, comprising Raman microspectroscopy and laser ablation hyphenated to inductively coupled plasma‐mass spectrometry (LA‐ICP‐MS). The analysed samples were mainly produced for burial in tombs and were not intended for everyday use. They belong to the period between the end of the mid‐7th century and the first half of the 4th century BC, and were excavated from the Toppicelli archaeological district near the suburbs of Canosa (Puglia, Italy). Forty‐eight pottery fragments were available for this study. No handling of the samples was required for the Raman study, and it was possible to excise the pigmented layer in such a way that the lacunae were not distinguishable to the naked eye due to the micrometric size of the laser spot as far as LA‐ICP‐MS is concerned. Their combination turned out to be quite useful for the investigation of these archaeological materials: the chemical nature of the white, red, brown and black pigments employed in the pottery manufacture was investigated. Iron and manganese compounds were identified as the red and brown/black main colouring substances, respectively; on the other hand, whites and engobes (whitish slips) were based on kaolinite. This set of colouring substances is of importance, as it enabled the artisan to obtain in one oxidising firing cycle brown, black and red paints. Finally, the finding of manganese black in these Canosa potsherds confirms that Canosa was an important centre connecting the near East to central Italy and Europe since the pre‐Roman age. Copyright © 2010 John Wiley & Sons, Ltd.     

Molecular field analysis and 3D-quantitative structure-activity relationship study (MFA 3D-QSAR) unveil novel features of bile acid recognition at TGR5

Bile acids regulate nongenomic actions through the activation of TGR5, a membrane receptor that is G protein-coupled to the induction of adenylate cyclase. In this work, a training set of 43 bile acid derivatives is used to develop a molecular interaction field analysis (MFA) and a 3D-quantitative structure-activity relationship study (3D-QSAR) of TGR5 agonists. The predictive ability of the resulting model is evaluated using an external set of compounds with known TGR5 activity, and six bile acid derivatives whose unknown TGR5 activity is herein assessed with in vitro luciferase assay of cAMP formation. The results show a good predictive model and indicate a statistically relevant degree of correlation between the TGR5 activity and the molecular interaction fields produced by discrete positions of the bile acid scaffold. This information is instrumental to extend on a quantitative basis the current structure-activity relationships of bile acids as TGR5 modulators and will be fruitful to design new potent and selective agonists of the receptor.     

Correlation between CMC and chromatographic index: simple and effective evaluation of the hydrophobic/hydrophilic balance of bile acids

The discovery that bile acids are involved in the modulation of nuclear steroid receptors has prompted renewed interest in this field of research. Due to the nature of research in this field, a technique that enables simple and effective assessment of the hydrophobic/hydrophilic balance, thus improving and speeding up evaluations of the biological profiles of these compounds, is greatly needed. In this context, both CMC value determination and RP-HPLC mobility evaluation were explored as possible approaches. While the CMC was calculated using the noninvasive conductimetric method, the RP-HPLC mobility was assessed by measuring the retention factor at several mobile phase compositions and extrapolating back to the pure aqueous mobile phase. The correlation of the CMC with the derived chromatographic hydrophobic index ϕ ₀ was satisfactory. Figure Experimental versus predicted pCMC values     

Analytical investigations of poly(acrylic acid) coatings electrodeposited on titanium-based implants: a versatile approach to biocompatibility enhancement

A polyacrylic acid film was synthesized on titanium substrates from aqueous solutions via an electroreductive process for the first time. This work was done in order to develop a versatile coating for titanium-based orthopaedic implants that acts as both an effective bioactive surface and an effective anti-corrosion barrier. The chemical structure of the PAA coating was investigated by X-ray photoelectron spectroscopy (XPS). Scanning electron microscopy (SEM) was employed to evaluate the effect of annealing treatment on the morphology of the coatings in terms of their uniformity and porosity. Inductively coupled plasma mass spectrometry was used to measure ion concentrations in ion release tests performed on Ti-6Al-4V sheets modified with PAA coatings (annealed and unannealed). Results indicate that the annealing process produces coatings that possess considerable anti-corrosion performance. Moreover, the availability and the reactivity of the surface carboxylic groups were exploited in order to graft biological molecules onto the PAA-modified titanium implants. The feasibility of the grafting reaction was tested using a single aminoacid residue. A fluorinated aminoacid was selected, and the grafting reaction was monitored both by XPS, using fluorine as a marker element, and via quartz crystal microbalance (QCM) measurements. The success of the grafting reaction opens the door to the synthesis of a wide variety of PAA-based coatings that are functionalized with selected bioactive molecules and promote positive reactions with the biological system interfacing the implant while considerably reducing ion release into surrounding tissues. Figure Vanadium release from bare Ti-6Al-4V sheets compared with the release from sheets coated with annealed and unannealed electrosynthesised PAA Dedicated to Professor P.G. Zambonin on the occasion of his 72nd birthday.