Sulfonium salts as prenyl, geranyl, and isolavandulyl transfer agents towards benzoylphloroglucinol derivatives

In search for new methods aiming biomimetic synthesis of polyprenylated acylphloroglucinols (PPAPs), we now report the results of an evaluation of sulfonium salts as prenyl, geranyl, and isolavandulyl transfer agents towards benzoylphloroglucinol derivatives, in neutral conditions. As a result, conditions were found for rather efficient C-prenylation of these compounds. The corresponding trimethyl ether gave the best results, but the reaction was accompanied by a deacylation process. Geranyl transfer was also observed, but in low yield, and, interestingly, an isolavandulyl group could be introduced with an appreciable yield.     

The status of strontium in biological apatites: an XANES/EXAFS investigation

Osteoporosis represents a major public health problem through its association with fragility fractures. The public health burden of osteoporotic fractures will rise in future generations, due in part to an increase in life expectancy. Strontium‐based drugs have been shown to increase bone mass in postmenopausal osteoporosis patients and to reduce fracture risk but the molecular mechanisms of the action of these Sr‐based drugs are not totally elucidated. The local environment of Sr²⁺ cations in biological apatites present in pathological and physiological calcifications in patients without such Sr‐based drugs has been assessed. In this investigation, X‐ray absorption spectra have been collected for 17 pathological and physiological calcifications. These experimental data have been combined with a set of numerical simulations using the ab initioFEFF9 X‐ray spectroscopy program which takes into account possible distortion and Ca/Sr substitution in the environment of the Sr²⁺ cations. For selected samples, Fourier transforms of the EXAFS modulations have been performed. The complete set of experimental data collected on 17 samples indicates that there is no relationship between the nature of the calcification (physiological and pathological) and the adsorption mode of Sr²⁺ cations (simple adsorption or insertion). Such structural considerations have medical implications. Pathological and physiological calcifications correspond to two very different preparation procedures but are associated with the same localization of Sr²⁺versus apatite crystals. Based on this study, it seems that for supplementation of Sr at low concentration, Sr²⁺ cations will be localized into the apatite network.     

Calcifications in human osteoarthritic articular cartilage: ex vivo assessment of calcium compounds using XANES spectroscopy

Calcium (Ca²⁺)‐containing crystals (CCs), including basic Ca²⁺ phosphate (BCP) and Ca²⁺ pyrophosphate dihydrate (CPPD) crystals, are associated with severe forms of osteoarthritis (OA). Growing evidence supports a role for abnormal articular cartilage mineralization in the pathogenesis of OA. However, the role of Ca²⁺ compounds in this mineralization process remains poorly understood. Six patients, who underwent total knee joint replacement for primary OA, have been considered in this study. Cartilage from femoral condyles and tibial plateaus in the medial and lateral compartments was collected as 1 mm‐thick slices cut tangentially to the articular surface. First, CCs presence and biochemical composition were assessed using Fourier transform infrared spectroscopy (FT‐IR). Next, Ca²⁺ compound biochemical form was further assessed using X‐ray absorption spectroscopy (XAS) performed at the Ca²⁺K‐absorption edge. Overall, 12 cartilage samples were assessed. Using FT‐IR, BCP and CPPD crystals were detected in four and three out of 12 samples, respectively. Ca²⁺ compound biochemical forms differed between areas with versus without CCs, when compared using XAS. The complete set of data shows that XANES spectroscopy can be used to accurately characterize sparse CCs in human OA cartilage. It is found that Ca²⁺ compounds differ between calcified and non‐calcified cartilage areas. In calcified areas they appear to be mainly involved in calcifications, namely Ca²⁺ crystals.     

Investigation of Cl corrosion products of iron archaeological artefacts using micro-focused synchrotron X-ray absorption spectroscopy

Synchrotron-based micro-X-ray absorption spectroscopy is used in the present study to obtain chemical information at the microscopic scale such as coordination and oxidation state of Fe atoms in phases constituting corrosion products within archaeological iron artefacts buried in soil. This technique is required in order to answer questions about the iron corrosion process related to the presence of chloride, particularly for restoration and conservation of metallic artefacts of the cultural heritage. The samples available for X-ray microprobe analyses are cross sections from corroded iron archaeological objects. Previously, complementary techniques have been used such as μXRD and μRaman. This specific study applies micro-X-ray absorption spectroscopy to determine the spatial variation of the predominant Fe oxidation state and to identify the corresponding crystallographic phase. The analyses performed at Fe and Cl K-edges (μXANES) reveal the correlation between the valence distribution in the corrosion products and the evolution of the chloride concentration. In addition to the presence of the well-known iron oxyhydroxide β-FeOOH: akaganeite, we highlight the presence of another important phase, the β-Fe₂(OH)₃Clhydroxychloride. These important findings help to gain new insights concerning the influence of such phases in the iron corrosion mechanism within their precise characterization. PACS 61.10.Ht; 61.10.-i; 68.49.Uv     

Very first tests on SOLEIL regarding the Zn environment in pathological calcifications made of apatite determined by X‐ray absorption spectroscopy

This very first report of an X‐ray absorption spectroscopy experiment at Synchrotron SOLEIL is part of a long‐term study dedicated to pathological calcifications. Such biological entities composed of various inorganic and/or organic compounds also contain trace elements. In the case of urinary calculi, different papers already published have pointed out that these oligo‐elements may promote or inhibit crystal nucleation as well as growth of mineral. Use of this analytical tool specific to synchrotron radiation, allowing the determination of the local environment of oligo‐elements and thus their occupation site, contributes to the understanding of the role of trace elements in pathological calcifications.     

A complementary set of electrochemical and X-ray synchrotron techniques to determine the passivation mechanism of iron treated in a new corrosion inhibitor solution specifically developed for the preservation of metallic artefacts

Metallic artefacts of the cultural heritage are often stored in uncontrolled environmental conditions. They are very sensitive to atmospheric corrosion caused by a succession of wet and dry periods due to variations of relative humidity and temperature. To avoid the complete degradation of the metallic artefacts, new preventive strategies must be developed. In this context, we have studied new compounds based on sodium carboxylates solutions CH₃(CH₂) _n−2COO⁻, Na⁺ hereafter called NaC _n . They allow the formation of a passive layer at the metallic surface composed of a metal–carboxylate complex. To understand the action of those inhibitors in the passivation process of iron we have performed electrochemical measurements and surface characterisation. Moreover, to monitor in real time the growth of the coating, in situ X-ray absorption spectroscopy (XAS) experiments at iron K-edge were carried out in an electrochemical cell. These analyses have shown that in the case of NaC₁₀ solution, the protection of iron surface is correlated to the precipitation of a well-organised layer of FeC₁₀. These experiments confirmed that this compound is a fully oxidised trinuclear Fe(III) complex containing decanoate anions as ligands. Such information concerning the passive layer is a key factor to evaluate its stability and finally the long-term efficiency of the protection treatment.