HPLC/DAD/MS and antioxidant activity of isoflavone-based food supplements

Isoflavones are polyphenolic compounds found mainly in legumes the benefits of which have been widely studied and attributed in particular to their phytoestrogenic activity. The aim of this study was to evaluate the quali-quantitative composition of food supplements based on soy isoflavones (Glycine max L.) and red clover (Trifolium pratense). Six commercial food supplements (five soy-based and one red clover-based) were analyzed by HPLC/DAD/MS. Genistein, daidzein, glycitein, biochanin A and formononetin derivatives (glycosides and acylglycosides) were identified in the analyzed samples. Also the antiradical activities (towards the DPPH* radical) and Fe2+ chelating abilities were compared.     

Synthesis of Fluoroolefins via Julia-Kocienski Olefination

The Julia-Kocienski olefination provides a versatile platform for the synthesis of fluorovinyl compounds. This review describes our efforts as well as those of others in the synthesis of various fluorinated aryl and heteroaryl sulfones and their utility as olefination reagents for the modular assembly of fluoroalkenes. Where data is available, the influence of the fluorine atom on the reactivity of the olefination reagents and the stereochemical outcome of the olefination are described.     

Probing ore deposits formation: New insights and challenges from synchrotron and neutron studies

The understanding of the physico-chemical processes leading to the formation and weathering of ore deposits plays an increasingly important role in mineral exploration. Synchrotron, neutron, and nuclear radiation are contributing to this endeavour in many ways, including (i) support the modelling of ore transport and deposition, by providing molecular-level understanding of solvent–solute interaction and thermodynamic properties for the important metal complexes in brines, vapours, and supercritical fluids over the range of conditions relevant for the formation of ore deposits (i.e., temperature 25–600 °C; pressure 1–10⁹ Pa; and fluid compositions varying from hypersaline (e.g., >50 wt% NaCl) to volatile-rich (e.g., CO₂, CH₄, and H₂S)); (ii) track the fluids that travelled through rocks and predict their ore-forming potential by analysing hydrothermal minerals and remnants of those fluids trapped in these minerals as ‘fluid inclusions’; (iii) characterize the biochemical controls on metal mobility in soils to predict the geochemical footprint of a buried mineral deposit.X-ray fluorescence (XRF), particle-induced X-ray emission (PIXE), and X-ray absorption spectroscopy (XAS) are the most common techniques used in support of mineral exploration. Analytical challenges are related to (i) the complexity of heterogeneous natural samples, which often contain only low concentrations of the elements of interest; (ii) beam sensitivity, especially for redox-sensitive elements in aqueous fluids or biological samples; (iii) extreme sample environments, e.g., in-situ study of fluids at high pressure and temperature. Thus, critical improvements need to be made on a number of fronts to: (i) develop more efficient detectors, able to map large areas in heterogeneous samples (e.g., 10⁶–10⁸ pixels per map), and also to collect a maximum number of photons to limit sample exposure and beam damage; (ii) integrate techniques (e.g., XRF, XAS, and X-ray diffraction (XRD)) on a single beamline, and promote synergy between neutron-, synchrotron-, and nuclear microprobe-based methods; (iii) advance the theory (e.g., quantitative XANES interpretation; X-ray extended range technique (XERT) measurements) to gain maximum information from the hard-won datasets.     

First steps towards dissolution of NaSO4- by water

NaSO(4)(-)(H(2)O)(n) (n = 0-4) clusters have been generated in the gas phase as model systems to simulate the first dissolution steps of sulfate salts in water; photoelectron spectroscopy and theoretical calculations indicate that the first three water molecules strongly interact with both Na(+) and SO(4)(2-), forming a three-water solvation ring to start to pry apart the Na(+)SO(4)(2-) contact ion pair.     

Enhanced photolysis in aerosols: evidence for important surface effects

While there is increasing evidence for unique chemical reactions at interfaces, there are fewer data on photochemistry at liquid-vapor junctions. This paper reports a comparison of the photolysis of molybdenum hexacarbonyl, Mo(CO)(6), in 1-decene either as liquid droplets or in bulk-liquid solutions. Mo(CO)(6) photolysis is faster by at least three orders of magnitude in the aerosols than in bulk-liquids. Two possible sources of this enhancement are considered: (1) increased light intensity due to either Morphology-Dependent Resonances (MDRs) in the spherical aerosol particles and/or to increased pathlengths for light inside the droplet due to refraction, which are termed physical effects in this paper; and (2) interface effects such as an incomplete solvent-cage at the gas-liquid boundary and/or enhanced interfacial concentrations of Mo(CO)(6), which are termed chemical effects. Quantitative calculations of the first possibility were carried out in which the light intensity distribution in the droplets averaged over 215-360 nm was obtained for 1-decene droplets. Calculations show that the average increase in light intensity over the entire droplet is 106%, with an average increase of 51% at the interface. These increases are much smaller than the observed increase in the apparent photolysis rate of droplets compared to the bulk. Thus, chemical effects, i.e., a decreased solvent-cage effect at the interface and/or enhancement in the surface concentration of Mo(CO)(6), are most likely responsible for the dramatic increase in the photolysis rate. Similar calculations were also carried out for broadband (290-600 nm) solar irradiation of water droplets, relevant to atmospheric conditions. These calculations show that, in agreement with previous calculations by Mayer and Madronich [B. Mayer and S. Madronich, Atmos. Chem. Phys., 2004, 4, 2241] MDRs produce only a moderate average intensity enhancement relative to the corresponding bulk-liquid slabs when averaged over a range of wavelengths characteristic of solar radiation at the Earth's surface. However, as in the case of Mo(CO)(6) in 1-decene, chemical effects may play a role in enhanced photochemistry at the aerosol-air interface for airborne particles.     

Asymmetric synthesis, stereochemistry and rearrangement reactions of naturally occurring 7'-hydroxylignano-9,9'-lactones

The asymmetric synthesis of a series of (7'S,8R,8'R)-7'-hydroxylignano-9,9'-lactones is presented, among them the mammalian lignan (7'S)-hydroxyenterolactone and (7'S)-parabenzlactone, allowing the stereochemistry of natural occurring (-)-parabenzlactone to be re-assigned. A hydroxylactone rearrangement and its possible mechanisms are discussed. Finally a brief survey of the current naming and numbering variants of 7'-hydroxylignano-9,9'-lactones is presented, along with a suggestion for harmonization of the nomenclature.     

Encapsulation of metal cations and anions within the cavity of bis(1,4,7-triazacyclononane) receptors

The synthesis and characterisation of a new bis([9]aneN3) ligand (L4) containing two [9]aneN3 macrocyclic moieties separated by a 2,6-dimethylenepyridine unit is reported. A potentiometric and 1H NMR study in aqueous solution reveals that ligand protonation occurs on the secondary amine groups and does not involve the pyridine nitrogen. The coordination properties toward Cu(II), Zn(II), Cd(II) and Pb(II) were studied by means of potentiometric and UV spectrophotometric measurements. The ligand can form mono- and binuclear complexes in aqueous solution. In the 1 : 1 complexes, the metal is sandwiched between the two [9]aneN3 moieties and the pyridine N-donor is coordinated to the metal, as actually shown by the crystal structure of the compound [ZnL4](NO3)2.CH3NO2. L4 shows a higher binding ability for Cd(II) with respect to Zn(II), probably due to a better fitting of Cd(II) ion inside the cavity generated by the two facing [9]aneN3 units. The formation of binuclear complexes is accompanied by the assembly of OH-bridged M2(OH)x (x = 1-3) clusters inside the cavity defined by the two facing [9]aneN3 units, and pyridine is not involved in metal coordination. A potentiometric and (1)H NMR study on the coordination of halogenide anions by L4 and its structural analogous L3 in which the two [9]aneN3 units are separated by a shorter quinoxaline linkage, shows that bromide is selectively recognised by L4, while chloride is selectively bound by L3. Such a behaviour is discussed in terms of dimensional matching between the spherical anions and the cavities generated by the two [9]aneN3 units of the receptors.     

Insights into the making of a stable silylene

Reduction of Cl2Si[(NR)2C6H4-1,2] (R = CH2Bu(t)) with potassium is known to lead to the stable silylene Si[(NR)2C6H4-1,2] (1). However, silylene is now shown to react further with an alkali metal (Na or K) to yield the (1)(2)2-, c-(1)(3)-*, c-(1)(3)2- or c-(1)(4)2- derivatives. Reduction of Cl2Si[(NR)2C6H4-1,2] (R = CH2CH3 or CH2CHMe2) with potassium does not lead to an isolable silylene, but such a silylene is proposed to be an intermediate and, as for 1, reacts further to afford the potassium salts of c-[Si{(NR)2C6H4-1,2}]4-* and c-[Si{(NR)2C6H4-1,2}](4)2-. The pathways leading to the anionic cyclotri- and cyclotetrasilanes are discussed and supported experimentally; including by X-ray structures of relevant intermediates.