Determination of the acid dissociation constant of bromocresol green and cresol red in water/AOT/isooctane reverse micelles by multiple linear regression and extended principal component analysis

The pKa of 3',3",5',5"tetrabromo-m-cresolsulfonephtalein (Bromocresol Green) and o-cresolsulphonephtalein (Cresol Red) was spectrophotometrically measured in a water/AOT/isooctane microemulsion in the presence of a series of buffers carrying different charges at different water/surfactant ratios. Extended Principal Component Analysis was used for a precise determination of the apparent pKa and of the spectra of the acid and base forms of the dye. The apparent pKa of dyes in water-in-oil microemulsions depends on the charge of the acid and base forms of the buffers present in the water pool. Combination with multiple linear regression increases the precision. Results are discussed taking into account the profile of the electrostatic potential in the water pool and the possible partition of the indicator between the aqueous core and the surfactant. The pKa corrected for these effects are independent of w0 and are close to the value of the pKa in bulk water. On the basis of a tentative hypothesis it is possible to calculate the true pKa of the buffer in the pool.     

Role of additives in the water vapor transport through block co-poly(amide/ether) membranes: effects on surface and bulk polymer properties

In the last years there has been a growing industrial interest in modifying the performance of traditional polymers by using additives, working as modifiers for processing, rheological, transport, bonding, and pigmentation properties. This work was focused on the understanding of the relationships between chemical structure and water vapour transport through a polymer matrix modified by different additives regarding hydrophilicity and molecular structure. A screening of the changes in surface energies and bulk morphology, as a function of the chemical nature and weight percent modifier, allowed estimating the effects on the water vapour transport through polymer membranes. Static and dynamic contact angle measurements explained the difference in surface wettability and affinity to polar species such as water molecules. Modifiers having polar groups improved the surface hydrophilicity, enhancing the breathability of the membranes, while hydrophobic components such as aromatic structures led to a reduction of the water vapour mass uptake onto the membrane surface. On the other hand, thermal analyses showed a tendency of the polymer structure to reduce its own mobility with consequent slowdown of the diffusion through polymer matrix. Modification with large and bulky structures disrupted the polymer packing density, but simultaneously increased the stiffness of the polymer chains, inhibiting the penetrant migration. As a result, balancing the effects due to modifier polarity and bulky structure, it is possible to change the performance of a polymer in terms of transport, going from breathable membranes to barrier films.     

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.     

Water droplets as template for next-generation self-assembled poly-(etheretherketone) with cardo membranes

Next generation PEEK-WC membranes have been fabricated by using an innovative self-assembly technique. Patterned architectures have been achieved via a solvent-reduced and water-assisted process, resulting in honeycomb packed geometry. The membranes exhibit monodisperse pores with size and shape comparable to those left by templating water droplets. Influencing factors for the formation of self-assembled poly-(etheretherketone) with Cardo [PEEK-WC] membranes have been evaluated, identifying the critical parameters for nucleation, growth, and propagation of the droplet-mobile arrays through the overall films. Structure-transport relationships have been discussed according to the results achieved from the implementation of membrane distillation processes, yielding indication about the suitability of self-assembled PEEK-WC films to work as interfaces in contactor operations.     

Investigations by various analytical techniques to the correct classification of archaeological finds and delineation of technological features: Late Roman lamps from Egnatia: From imports to local production

Late Roman oil lamps from the archaeological site of Egnatia (Fasano, Brindisi, Italy) were characterized from physical–chemical, mineralogical and morphological points of view. Atomic Spectroscopy, Scanning Electron Microscopy and X-Ray Diffraction analyses were carried out on ceramic body and coatings with the aim of identifying the provenance of lamps, in order to arrive at a correct archaeological classification of finds and to outline their technological features.The analytical results show that the finds differ in raw materials and in production technology. The statistical multivariate treatment of compositional data of ceramic bodies groups the objects into two macro clusters and, according to a study of their different petrographic features and by a comparison with coeval pottery whose provenance is already known, suggests one group to have been imported from North Africa and the other to have been locally produced. Moreover, chemical results and in-depth archaeological analyses allow us to split the imported lamps into two subgroups, hypothesizing the first group to originate from central Tunisia and the second from the north of the same country.The analytical characterisation of finds, by different complementary techniques, has allowed us to identify the raw materials and the technological solutions used by the ancient potters from Egnatia to produce lamps. The potters made lamps which had an external appearance very similar to that of African prototypes, but which were nevertheless different as they employed the locally available materials.     

Addition of 2-silylazoles to heteroaryl cations. Synthesis of unsymmetrical azadiaryls

Thiazole, pyridine and some of their benzoderivatives react $\text{via}$ their N-ethoxycarbonyl chlorides with 2-trimethylsilylthiazole (1a) and 4-methyl-2-trimethylsilyloxazole (1b) to give the corresponding adducts at C_α which by oxidative deacylation afford azadiaryls.     

PVDF and HYFLON AD membranes: Ideal interfaces for contactor applications

Super-hydrophobic fluorinated membranes were tailored by combining traditional dry-wet phase inversion and wet chemical treatment techniques. PVDF and HYFLON AD 60X were selected as raw polymers for their chemical and mechanical resistance as well as hydrophobic and solvophobic properties. Membranes with modulated pore size, narrow distribution and high overall porosity were manufactured without using additional additives or modifiers. High resistance to liquid water entry pressure (LEPw), high mass transfer and low surface free energy of the membrane surfaces were fully achieved. The combination of these two fluorinated polymers improved dramatically the mechanical resistance and the water repellence of the PVDF membranes. Well-controlled structure combined with aimed supra-molecular chemistry makes these porous layers ideal interfaces to be processed in membrane contactor devices.     

A dynamical model of apoptosis and its role in tumor progression

Apoptosis is a biological process crucial for the development and maintenance of healthy living organism. A deregulated apoptosis underlies many diseases, including cancer. Under hypoxic conditions, p53 starts to accumulate and competes with HIF-1 for their common binding target p300. This can lead to the repression of HIF-1, and trigger the apoptotic derive. In addition apoptosis is accompanied by an enhancement of potassium (K⁺) fluxes, which in turn create a low-potassium intracellular micro-environment, which cooperates to the activation of caspases, the final actors of the apoptotic cascade. Based on this scenario, we elaborate a dynamical model aimed at resolving the complex dynamical interplay between the aforementioned processes. In the ideal continuum limit, the model reduces to a system of coupled differential equations, whose dynamics is analytically inspected.     

A nonlinear principal component analysis to study archeometric data

Statistical techniques, when applied to data obtained by chemical investigations on ancient artworks, are usually expected to recognize groups of objects to classify the archeological finds, to attribute the provenance of items compared with earlier investigated ones, or to determine whether an archaelogical attribution is possible or not. The statistical technique most frequently used in archeometry is the principal component analysis (PCA), because of its simplicity in theory and implementation. However, the application of PCA to archeometric data showed severe limitations because of its linear feature. Indeed, PCA is inadequate to classify data whose behavior describe a curve or a curved subspace of the original data space. As a consequence of it, an amount of information is lost because the multi‐dimensional data space is compressed into a lower‐dimensional subspace including principal components. The aim of this work is then to test a novel statistical technique for archeometry. We propose a nonlinear PCA method to extract maximum chemical information by plotting data on the smallest number of principal components and to answer archeological questions. The higher accuracy and effectiveness of nonlinear PCA approach with respect to standard PCA for the analysis of archeometric data are shown through the study of Apulian red figured pottery (fifth–fourth century BC) coming from some of the most relevant archeological sites of ancient Apulia (Monte Sannace (Gioia del Colle), Egnatia (Fasano), Canosa, Altamura, Conversano, and Arpi(Foggia)). Copyright © 2016 John Wiley & Sons, Ltd.