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.     

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.     

Spectroscopic analysis of Nd3+ doped (Lu x + Gd1−x )3Ga5O12 crystal

In this paper we report a complete optical investigation of Nd³⁺ doped (Lu _x  + Gd_1−x )₃Ga₅O₁₂ crystal including the absorption and emission spectroscopy at room temperature and 10 K, the excitation spectroscopy at 10 K clearly showing the multi-site feature, and the lifetime at temperatures from 10 K to 300 K. The Judd–Ofelt theory has been applied to calculate the spontaneous transition probabilities, the branching ratio, and the radiative lifetime of the ⁴F_3/2 multiplet; the calculated results are in good agreement with the experimental ones. Finally, we calculated the emission cross sections of the transitions concerned to evaluate the potential of the material in laser field application.     

Multi-wavelength diode-pumped Nd:LGGG picosecond laser

Laser operation near 1.06 μm by a diode-pumped Nd:(Lu _x Gd_1?x )₃Ga₅O₁₂ (Nd:LGGG) disordered crystal has been investigated. Cw oscillation, with a slope efficiency as high as 61% and 230 mW output power, was achieved with 400 mW absorbed power from a 1-W laser diode. Stable passive mode locking with single- or multi-banded spectrum was obtained with a semiconductor saturable absorber mirror (SAM) and a single-prism, dispersion-compensated cavity. Fourier limited pulses with duration ≈3–9 ps and output power ≈40 mW were generated at three well-defined laser transitions in the range 1062–1067 nm.     

Organic pollution in a Ramsar site (Piallassa Baiona, northern Adriatic Sea)

A core collected in the Piallassa Baiona lagoon, a salt-marsh area already studied for Hg contamination related to nearby industrial sites, was analysed for organic micropollutants. Surface sediments show high concentrations of total PCBs (1148 ng g-1), PCDD/Fs (64 ng g-1) and PAHs (4801 ng g-1). According to a sedimentation rate of 0.4 cm y-1, the high increases in total PAH, PCB and PCDD/F concentrations began in the 1960s and peaked in the 1970s, in parallel with the highest Hg concentrations. Instead, the recent contamination, which primarily involves PCBs and PCDD/Fs, has been observed to be unrelated to Hg concentrations. Organic micropollutant concentrations in the sample core were compared with the sediment quality criteria provided by international guidelines, and revealed high toxic potential. This heavy contamination was also confirmed by comparison with similar environments, particularly the Lagoon of Venice. Further investigations are needed to understand better the sources of the recent contamination and to explain the different transfer pathways involved during sedimentation of the "old" material, dumped 20-30 years ago.     

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.