A new look at XRD patterns of archaeological ceramic bodies

In this paper, the general rules of phase transformations in calcareous clay bodies during firing were used to estimate the equivalent firing temperature (EFT) of seventeenth century polychrome Persian haft rang tiles based on their X-ray diffraction (XRD) patterns. The novelty of this work is, however, that it handles the XRD patterns of archaeological clay bodies with principal component analysis (PCA) in order to have a new look at their firing and thermal behaviour. Statistically handling the XRD patterns, different clusters were discriminated in the clay bodies whose mineralogical composition showed various proportions of amorphous and quartz contents. The results showed interesting trends in the different clusters in terms of the EFT, quartz content and the density of the bodies. The present work uses PCA to have a new look at XRD patterns of archaeological clay bodies and, moreover, to interpret the PCA results in order to estimate the EFT of a large number of archaeological clay bodies.     

Magneto-responsive nanocomposites: Preparation and integration of magnetic nanoparticles into films,capsules, and gels

This review reports on the latest developments in the field of magnetic nanocomposites, with a special focus on the potentials introduced by the incorporation of magnetic nanoparticles into polymer and supramolecular matrices. The general notions and the state of the art of nanocomposite materials are summarized and the results reported in the literature over the last decade on magnetically responsive films, capsules and gels are reviewed. The most promising concepts that have inspired the design of magneto-responsive nanocomposites are illustrated through remarkable examples where the integration of magnetic nanoparticles into organic architectures has successfully taken to the development of responsive multifunctional materials.     

Electrochemical Approach for the Production of Layered Double Hydroxides with a Well-Defined Co/MeIII Ratio

Layered double hydroxides (LDHs) have been widely studied for their plethora of fascinating features and applications. The potentiostatic electrodeposition of LDHs has been extensively applied in the literature as a fast and direct method to substitute classical chemical routes. However, the electrochemical approach does not usually allow for a fine control of the M^II/M^III ratio in the synthesized material. By employing a recently proposed potentiodynamic method, LDH films of controlled composition are herein prepared with good reproducibility, using different ratios of the trivalent (Fe or Al) to bivalent (Co) cations in the electrolytic solution. All the obtained materials are shown to be effective oxygen evolution reaction (OER) catalysts, and are thoroughly characterized by a multi-technique approach, including FE-SEM, XRD, Raman, AES and a wide range of electrochemical procedures.     

Analysis of Organic Compounds in Antarctic Snow and Their Origin

Abstract

Organic compounds extractable with n-hexane were identified and quantitatively determined in pack, surface and deep snow samples taken at different depths and collected at several altitudes above sea level from Antarctica during the 1993/94 Italian expedition. The comparison between the composition of organic compounds in snow and the ones in pack and sea-water samples pointed out that the three matrices substantially contain the same biogenic and anthropogenic organic compounds. The contribution of marine aerosol to organic content in the snow is confirmed by the enrichment ratios calculated for the more representative classes of identified compounds (n-alkanes, phthalates and low molecular weight alkylbenzenes). The changes in the composition of organic compounds in snow as the altitude increases seem to depend on the dimensional spectrum of the aerosol. Thus, smallest particles, richest in surfactant material, reach the highest altitudes.     

Phosphinine-Based Ligands in Gold-Catalyzed Reactions

A series of substituted phosphinines, 1-phosphabarrelenes and 5-phosphasemibullvalenes were synthesized and evaluated for their potential application as ligands in homogeneous catalytic reactions. While their buried volume (%V_bur) was calculated to get insight into the steric properties, [LNi(CO)₃] complexes were prepared in order to determine the corresponding Tolman electronic parameter. ETS-NOCV (extended-transition-state natural orbital for chemical valence) calculations on [LAuCl] complexes further allowed an estimation of the σ- and π-contributions to the L− M interaction. Au^I coordination compounds of selected examples were prepared and characterized by single crystal X-ray diffraction. Finally, the three classes of P^III compounds were successfully used in the Au^I-catalyzed cycloisomerization of N-2-propyn-1-ylbenzamide, showing very good activities and selectivities, which are comparable with the reported data of cationic phosphorus-based gold catalysts.     

Certification of nitrate in spinach powder reference material SPIN-1 by high-precision isotope dilution GC–MS

A high-precision exact-matching quadruple isotope dilution method (ID⁴MS) was employed for the quantitation of nitrate in an air-dried spinach powder Certified Reference Material (CRM). The analyte was extracted in hot water following addition of ¹⁵NO\({}_{3}^{-}\) internal standard. The blend was then treated with sulfamic acid to remove nitrite and with triethyloxonium tetrafluoroborate to promote aqueous conversion of nitrate into volatile EtONO₂. The derivative was analyzed by headspace GC–MS with 3-min elution time. The method performance was validated with a series of tests which demonstrated adequate selectivity and ruggedness. This method supported the development of novel SPIN-1 CRM giving a modest contribution to its uncertainty (u_char = 0.85%). With respect to previous attempts, the SPIN-1 was proven stable, homogeneous (u_hom = 0.44%), and suitable for spinach monitoring under EU regulations. On dried basis, the nitrate content of SPIN-1 was found to be 22.53 ± 0.43 mg/g (U_c = 1.9%, k = 2). The material was also used in an inter-laboratory study where four laboratories employed a total of ten measurement methods.

SPIN-1 Certified Reference Material for nitrate in spinach powder

     

Direct meta-C−H Perfluoroalkenylation of Arenes Enabled by a Cleavable Pyrimidine-Based Template

The development of efficient and mild methods for the synthesis of organofluorine compounds is of foremost interest in various fields of chemistry. A direct pyrimidine-based selective meta-C−H perfluoroalkenylation of arenes involving several commercially available perfluoroolefins is described. The synthetic versatility of the protocol is demonstrated by an extensive substrate scope including different benzylsulfonyl, alkylarene and phenylacetic acid scaffolds. The generality of this methodology including the meta-C−H perfluoroalkenylation of Ibuprofen, the facile cleavage of the directing group and gram-scale reactions are presented.