Nickel-catalyzed Asymmetric Alkylation of Some Chiral and Achiral Allylic Alcohols. Preliminary communication

[(?) (R)-1,2-bis (Diphenylphosphino)-1-phenylethane]nickel (II) chloride was found to catalyze the asymmetric alkylation of some chiral and achiral allylic alcohols with Grignard reagents, leading to the formation of optically active olefins. Enantiomer discrimination of the substrate takes place in the alkylation of chiral allylic alcohols.     

Order from Chaos: Self‐Assembly of Nanoprism from a Mixture of Tetratopic Terpyridine‐Porphyrin Conformers

Porphyrins have been widely used in the self‐assembly of metallo‐supramolecules. In this study, we introduced 2,2':6,2"‐terpyridine (tpy) into a porphyrin core to synthesize a tetratopic building block with multiple conformers. During the self‐assembly with Zn(II), such a mixture of conformers was able to form a discrete nanoprism with all building blocks in one conformation. Detailed characterizations, including NMR, ESI‐MS and traveling‐wave ion mobility‐mass spectrometry (TWIM‐MS), all supported the formation of the desired assemblies. AFM and TEM further confirmed the dimensions of assembled nanoprisms. Moreover, the photophysical properties of the ligands and complexes were noticeably different depending upon size and metal ion center.     

Studies on simulated ageing of paper by photochemical degradation

The study of the ageing of two paper types was performed on monitoring it during a simulated process by means of the measure of the photocatalytic degradation of the paper cellulose. Such evaluation was possible due to the combined responses of a photosensor based on titanium dioxide in suspension, of an enzymatic biosensor based on superoxide dismutase (SOD), of a specific conductivity sensor and of an enzymatic biosensor based on glucose oxidase.     

Determination of hydroxycarbamates in aqueous matrices by direct derivatization and GC-MS analysis in chemical ionization mode

A rapid and effective procedure, developed for the determination of polar compounds in water, has been applied to hydroxycarbamates. In few minutes, it is possible to perform a catalyzed derivatization of such compounds directly in the aqueous medium, using n-hexyl chloroformate. Extraction with n-hexane and injection into a benchtop GC-MS system are the only two further steps to complete the analysis. Chemical ionization proved to be more effective than electron impact to produce valuable mass spectra in terms of selectivity and sensitivity. Linear quantitative responses were demonstrated over a two-order-of-magnitude range. The minimum detectable concentration was 3 ppb for acetohydroxamic acid and 10 ppb for hydroxyurethane, obtained from Po river water samples spiked with the two hydroxycarbamate standards.     

Molecular evaluation of soil organic matter characteristics in three agricultural soils by improved off-line thermochemolysis: The effect of hydrofluoric acid demineralisation treatment

The molecular composition of soil organic matter (SOM) in three agricultural fields under different managements, was evaluated by off-line thermochemolysis followed by gas chromatography mass spectrometry analysis (THM-GC-MS). While this technique enabled the characterization of SOM components in coarse textured soil, its efficiency in heavy textured soils was seriously affected by the interference of clay minerals, which catalyzed the formation of secondary artifacts in pyrolysates. Soil demineralization with hydrofluoric acid (HF) solutions effectively improved the reliable characterization of organic compounds in clayey soils by thermochemolysis, while did not alter significantly the results of coarse textured soil. A wide range of lignin monomers and lipids molecules, of plant and microbial origin, were identified in the pyrograms of HF treated soils, thereby revealing interesting molecular differences between SOM management practices. Our results indicated that clay removal provided by HF pretreatment enhanced the capacity of thermochemolysis to be a valuable and accurate technique to study the SOM dynamics also in heavy-textured and OC-depleted cultivated soils.     

Molecular Fluorescence Imaging Spectroscopy for Mapping Low Concentrations of Red Lake Pigments: Van Gogh's Painting The Olive Orchard

Vincent van Gogh used fugitive red lake pigments that have faded in some paintings. Mapping their distribution is key to understanding how his paintings have changed with time. While red lake pigments can be identified from microsamples, in situ identification and mapping remain challenging. This paper explores the ability of molecular fluorescence imaging spectroscopy to identify and, more importantly, map residual non‐degraded red lakes. The high sensitivity of this method enabled identification of the emission spectra of eosin (tetrabromine fluorescein) lake mixed with lead or zinc white at lower concentrations than elemental X‐ray fluorescence (XRF) spectroscopy used on account of bromine. The molecular fluorescence mapping of residual eosin and two carmine red lakes in van Gogh's The Olive Orchard is demonstrated and compared with XRF imaging spectroscopy. The red lakes are consistent with the composition of paint tubes known to have been used by van Gogh.