Nuclear magnetic resonance in contemporary art: the case of “Moon Surface” by Turcato

Nuclear Magnetic Resonance (NMR) methodologies were applied to characterize the constitutive materials and the state of degradation of a contemporary painting. The investigation was mandatory to plan a suitable restoration. Noninvasive, portable NMR allowed the detection of degraded regions of the painting based on the measurement of longitudinal relaxation time. A few samples were investigated by high resolution solid state NMR and NMR in solution, which allowed us to identify the polyurethane constituting the artefact, to investigate the microstructure in detail, and to assess that the degradation process mostly affected the ethylene units used to cap the polypropylene oxide polymeric chain. As a matter of fact, a shortening of longitudinal relaxation time was accompanied by a degradation of ethylene units. The degradation of the inorganic loading was investigated by ²⁷Al MAS, which evidenced the absence of penta-coordinated aluminum in degraded samples.     

KAIUM at DAΦNE?

The possibility of producing and detecting at DAΦNE a new hydrogen isotope formed by a (K ^?+? e ^???) bound system (Kaium) is addressed, considering a dedicated, and relatively simple experiment of short duration. If Kaium will be detected, it could in perspective pave the way for a series of highly sophisticated experiments focused on the precision measurement of several observables, as the K ^?+????K ^??? mass difference, strictly related to CPT invariance.     

Chemoselective asymmetric synthesis of C-3a-(3-hydroxypropyl)tetrahydropyrrolo[2,3-b]indole and C-4a-(2-aminoethyl)-tetrahydropyrano[2,3-b]indole derivatives

The asymmetric synthesis of new tetrahydropyrrolo[2,3-b]indole 19 and tetrahydropyrano[2,3-b]indole 20 rings, substituted in position C-3a and C-4a with a hydroxy- and an amino functionalized chain, respectively, was performed starting from the racemic spiro[cyclohexane-1,3′-indoline]-2′,4-diones 7. The enantiopure spiro oxo-azepinoindolinone (+)-10, obtained from (±)-7 by the way of an asymmetric ring enlargement, and the amino acid (+)-14, obtained by the hydrolysis of 10, were prepared as key intermediates for the synthesis of enantiopure compounds (−)-19 and (−)-20. Since the amino acid 14 is the common intermediate for the chemoselective preparation of derivatives 19 and 20, experimental and computational studies were performed in order to selectively obtain these compounds and to provide a mechanistic rationalization for their formation.     

Halide anions driven self-assembly of haloperfluoroarenes: Formation of one-dimensional non-covalent copolymers

The supramolecular organization in six solid assemblies involving iodo- and bromoperfluoroarene derivatives is described. Single crystal X-ray analyses show that the formation of the supramolecular architectures is controlled by I⁻?Br–Ar_F, I⁻?I–Ar_F, Br⁻?I–Ar_F, and Cl⁻?I–Ar_F halogen bondings thus proving the X⁻?X′–Ar_F supramolecular synthon, where X can be the same as or different from X′, is particularly robust. In five of the described architectures halide anions form two halogen bondings and form infinite chains wherein dihaloperfluoroarenes, which function as bidentate electron acceptors, and halide anions, which function as bidentate electron donors, alternate. This behaviour shows halide anions have a fair tendency to work as bidentate halogen bonding acceptors.     

ARDESIA: A fast silicon drift detector X-ray spectrometer for synchrotron applications

ARDESIA, a four-channel X-ray spectrometer based on silicon drift detectors (SDDs), is presented. It has been developed for synchrotron applications targeting especially X-ray fluorescence (XRF) and X-ray absorption spectroscopy (XAS) with good energy resolution at high count rates (a few Mcps per second). The main target applications are XRF and XAFS techniques. The system features a 2 × 2 monolithic array of 5-mm-pitch SDDs cooled with a double Peltier scheme and coupled to a four-channel CUBE charge preamplifier. Different digital pulse processors allowing operation in Mcps per second count rates are employed. The results of preliminary characterization measurements performed at both the LNF DAΦNE-Light DXR1 beamline and the ESRF LISA BM-08 are reported, in particular, XRF measurements on low atomic number elements (down to the Carbon K-line, 270 eV) and extended X-ray absorption fine structure of trace materials in pyrite.     

Impedance spectroscopy of reactive polymers. 2. Multifunctional epoxy/amine formulations

Dielectric measurements were utilized to follow the advancement of cure in a bifunctional and a tetrafunctional epoxy/amine formulation. In deferance to earlier dielectric studies of cure, complex impedance was measured and used to calculate ionic resistivity. By using complex impedance we were able to separate, according to their frequency dependence, the contributions to overall polarization from electrode blocking layers, mobile charge carriers, and dipole relaxations. At any stage of cure, there is a unique frequency at which ionic resistivity can be singularly measured. Our approach does not involve trial-and-error frequency search, it measures dielectric response in real time, and is conducive to the development of phenomenological models based on equivalent circuits. Values of ionic resistivity measured at different cure time and temperature were used to quantify the progress of cure. Excellent agreement was reported between the calculated values of normalized degree of cure obtained by dielectric and calorimetric measurements. It was suggested that apart from the extrinsic conductivity by ionic impurities, an intrinsic mechanism which involves the reactive molecules contributes to the overall ionic conductivity. © 1995 John Wiley & Sons, Inc.     

A study of the photochemically induced electron-transfer reactions between pyridinedicarbonitriles and primary and secondary aliphatic amines

A study on the photochemically induced electron-transfer from primary and secondary aliphatic amines as donors to pyridinedicarbonitriles as the acceptor is reported. A comparison between the substitution positions and the spin density distributions, obtained via theoretical calculations using the 6-31+G basis set, shows some discrepancies, and forms the basis of a hypothesis on the mechanism of the reaction.     

Entanglement and Properties of Composite Quantum Systems: A Conceptual and Mathematical Analysis

Various topics concerning the entanglement of composite quantum systems are considered with particular emphasis concerning the strict relations of such a problem with the one of attributing objective properties to the constituents. Most of the paper deals with composite systems in pure states. After a detailed discussion and a precise formal analysis of the case of systems of distinguishable particles, the problems of entanglement and the one of the properties of subsystems of systems of identical particles are thoroughly discussed. This part is the most interesting and new and it focuses in all details various subtle questions which have never been adequately discussed in the literature. Some inappropriate assertions which appeared in recent papers are analyzed. The relations of the main subject of the paper with the nonlocal aspects of quantum mechanics, as well as with the possibility of deriving Bell's inequality are also considered.     

Stereoselective synthesis of heterosubstituted aziridines and their functionalization

Lithiated (α-chloroalkyl)heterocycles, generated by deprotonation with LDA at −78 °C in THF, add to various enantiopure imines affording ‘one pot’ chiral heterosubstituted aziridines in a diastereoselective manner. Lithiated heterosubstituted aziridines, obtained by deprotonation of the corresponding aziridines with n-BuLi at −78 °C in THF, were trapped by electrophiles (D₂O or CH₃I) with high stereoselectivity.     

Engineering functional materials by halogen bonding

Engineering functional materials endowed with unprecedented properties require the exploitation of new intermolecular interactions, which can determine the characteristics of the bulk materials. The great potential of Halogen Bonding (XB), namely any noncovalent interaction involving halogens as electron acceptors, in the design of new and high‐value functional materials is now emerging clearly. This Highlight will give a detailed overview on the energetic and geometric features of XB, showing how some of them are quite constant in most of the formed supramolecular complexes (e.g., the angle formed by the covalent and the noncovalent bonds around the halogen atom), while some others depend strictly on the nature of the interacting partners. Then, several specific examples of halogen‐bonded supramolecular architectures, whose structural aspects as well as applications in fields as diverse as enantiomers' separation, crystal engineering, liquid crystals, natural, and synthetic receptors, will be fully described. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: PolymChem 45: 1–15, 2007