Synthesis and anion binding properties of 2,5-diamidothiophene polypyrrole Schiff base macrocycles

[reaction: see text] Two easy-to-synthesize polypyrrolic 2,5-diamidothiophene Schiff base macrocycles are reported, along with their anion binding properties as determined via UV-vis spectroscopic titrations carried out in dichloroethane. There is a striking difference between the interactions with anions of the two macrocycles, a finding ascribed to differences in their rigidity. For example, the more flexible dipyrromethane-derived macrocycle displays a 1.2:1 hydrogen sulfate versus nitrate selectivity, while its more rigid bipyrrole-derived congener shows a 7.4:1 selectivity in favor to hydrogen sulfate.     

Photoemission of solid argon

Photoemission yield spectra of solid argon using synchrotron radiation for excitation in the photon energy range 11.7–16 eV show peaks closely following the known excitonic transitions, further peaks at 11.96 and 13.1 eV and also give an indication for band-gap photoconductivity.     

Growth and aging phenomena in silica gels

Growth and aging of silica aggregates are influenced both by temperature and by catalyzing fluorine ions as shown by SAXS and BET. It was found that both fluorine and increased temperature slightly increased the fractal dimension Df during aging, but the fluorine catalyzed system showed a lower BET surface area.To understand the effect of fluorine and increased temperature on the aggregates, 2D aggregations and SAXS simulations were carried out using two new programs GRASP and DALAI. In agreement with experiments it was found that binary RLCCA aggregates have a slightly higher Df value compared to DLCCA aggregates and that branch-flexibility during aging increases Df even further.     

The use of combined synchrotron radiation micro FT-IR and XRD for the characterization of Romanesque wall paintings

The high analytical sensitivity and high spatial resolution of synchrotron radiation-based techniques, in particular SR-XRD and SR-FT-IR, allows the identification of complex micrometric mixtures of compounds that constitute the different layers of ancient paintings. The reliability of the measurements even with an extremely small amount of sampled material is very high, and this is particularly important when analyzing art works. Furthermore, the micro size (10×10μm for FT-IR and 30 to 50 μm squared spot size for XRD) of the beam enables one to obtain detailed compositional profiles from the different chromatic and preparation layers. The sensitivity of the techniques is high enough for the determination of minor and trace compounds, such as reaction and weathering compounds. We report here the identification of pigments in the Romanesque wall paintings found in situ in the church of Saint Eulàlia of Unha place in the Aran valley (central Pyrenees). During the first centuries of the second millennium numerous religious buildings were built in Western Europe in the Romanesque style. In particular, a great number of churches were built in the Pyrenees, most of which were decorated with wall paintings. Although only a few of these paintings have survived, they represent one of the most important collections of Romanesque art, both for their quantity and quality. A full identification of the pigments, binder, supports, and reaction and weathering compounds has been obtained. The results obtained, in particular aerinite as a pigment, indicate a clear connection between the paintings found in this Occitanian church and the Catalan Romanesque paintings from the south bound of the Pyrenees. PACS 61.10.Nz; 07.85.Qe; 82.80.Gk     

Temperature resolved reproduction of medieval luster

Luster is a golden metallic-like decoration produced on glazed ceramics since early Islamic times (Iraq, 9th AD). Luster is obtained by the reaction of a luster paint and the glaze surface over which it is applied. A temperature-resolved XRD experiment was designed to study the high temperature reactions in the luster paint while the luster layer is formed. The luster paint composition has been made based on the original luster paints found during the excavation of the 13th AD workshop site at Paterna (Valencia). The sulfo-reducing atmosphere created during the decomposition of cinnabar promotes the reduction of Cu²⁺ containing compounds to Cu⁺ and the presence of Hg vapours delays the precipitation of metal silver. Moreover, evidence of the formation of a melt in which the copper and silver-containing compounds dissolve has also been obtained. The thickness of the luster paint applied results in the formation of luster layers of different hues and colours. The use of a mixture of copper and silver paint results in the formation of dark-brown luster layer similar to the ones produced in early Islamic times in Iraq and showed also the characteristic blue iridescences. PACS 81.05.Pj; 81.07.-b; 78.67.-n; 82.39.Wj     

Efficient and mild microwave-assisted stepwise functionalization of naphthalenediimide with alpha-amino acids

Microwave dielectric heating proved to be an efficient method for the one-pot and stepwise syntheses of symmetrical and unsymmetrical naphthalenediimide derivatives of alpha-amino acids. Acid-labile side chain protecting groups are stable under the reaction conditions; protection of the alpha-carboxylic group is not required. The stepwise condensation of different amino acids resulted in high yields of unsymmetrical naphthalenediimides. The reaction proceeds without racemization and is essentially quantitative.     

The 1B1u ← 1A1g 0—0 transition in crystal benzene

The transition linewidth ΔE in crystal C₆H₆, C₆D₆ and sym-C₆H₃D₃ has been measured as a function of temperature T from 4.2 to 135°K, and it extrapolates to a common value of ΔE_o = 50 cm^? at O°K. In C₆H₆ ΔE = (50 + 7T^{$\text{1}\text{2}$}) cm^?1, indicative of strong exciton—phonon coupling, and there is a line shift of +40 cm^?1 per substituent deuteron. Fluorescence excitation spectral data are used to separate the ¹B_1u(= S₂) decay rate k_H = 9.4 × 10¹² sec^?1, derived from ΔE₀, into S₂S₁ internal conversion (rate ≈ 6.6 × 10¹² sec^?1) and S₂S_x (channel 3) internal conversion (rate ≈ 2.8 × 10¹² sec^?1. A similar value of k_H = 9.9 × 10¹² sec^?1 is obtained from the S₂S_o fluorescence quantum yield of liquid benzene.     

Combined technique analysis of the composition of Punic make-up materials

Ten archaeological Punic make-up samples from Tunisia dating from the 4th to the 1st centuries BC were analysed by several techniques including Raman microscopy and synchrotron X-ray diffraction in order to determine their compositions. Eight samples were red and found to contain either quartz and cinnabar or quartz and haematite. The remaining two samples were pink, the main diffracting phase in them being quartz. Examination of these two samples by optical microscopy and by illumination under a UV lamp suggest that the pink dye is madder. These findings reveal the identities of the materials used by Carthaginians for cosmetic and/or ritual make-up purposes. PACS 82.80.Gk; 61.10.Nz; 41.60Ap     

XAFS study of copper and silver nanoparticles in glazes of medieval middle-east lustreware (10th–13th century)

It has recently been shown that lustre decoration of medieval and Renaissance pottery consists of silver and copper nanoparticles dispersed in the glassy matrix of the ceramic glaze. Here the findings of an X-ray absorption fine structure (XAFS) study on lustred glazes of shards belonging to 10th and 13rd century pottery from the National Museum of Iran are reported. Absorption spectra in the visible range have been also measured in order to investigate the relations between colour and glaze composition. Gold colour is mainly due to Ag nanoparticles, though Ag⁺, Cu⁺ and Cu²⁺ ions can be also dispersed within the glassy matrix, with different ratios. Red colour is mainly due to Cu nanoparticles, although some Ag nanoparticles, Ag⁺ and Cu⁺ ions can be present. The achievement of metallic Cu and the absence of Cu²⁺ indicate a higher reduction of copper in red lustre. These findings are in substantial agreement with previous results on Italian Renaissance pottery. In spite of the large heterogeneity of cases, the presence of copper and silver ions in the glaze confirms that lustre formation is mediated by a copper- and silver-alkali ion exchange, followed by nucleation and growth of metal nanoparticles.