Independent components analysis coupled with 3D-front-face fluorescence spectroscopy to study the interaction between plastic food packaging and olive oil

Olive oil is one of the most valued sources of fats in the Mediterranean diet. Its storage was generally done using glass or metallic packaging materials. Nowadays, plastic packaging has gained worldwide spread for the storage of olive oil. However, plastics are not inert and interaction phenomena may occur between packaging materials and olive oil. In this study, extra virgin olive oil samples were submitted to accelerated interaction conditions, in contact with polypropylene (PP) and polylactide (PLA) plastic packaging materials. 3D-front-face fluorescence spectroscopy, being a simple, fast and non destructive analytical technique, was used to study this interaction. Independent components analysis (ICA) was used to analyze raw 3D-front-face fluorescence spectra of olive oil. ICA was able to highlight a probable effect of a migration of substances with antioxidant activity. The signals extracted by ICA corresponded to natural olive oil fluorophores (tocopherols and polyphenols) as well as newly formed ones which were tentatively identified as fluorescent oxidation products. Based on the extracted fluorescent signals, olive oil in contact with plastics had slower aging rates in comparison with reference oils. Peroxide and free acidity values validated the results obtained by ICA, related to olive oil oxidation rates. Sorbed olive oil in plastic was also quantified given that this sorption could induce a swelling of the polymer thus promoting migration.     

Surfactant-free miniemulsion polymerization as a simple synthetic route to a successful encapsulation of magnetite nanoparticles

Due to the existing interest in new hybrid particles in the colloidal range based on both magnetic and polymeric materials for applications in biotechnological fields, this work is focused on the preparation of magnetic polymer nanoparticles (MPNPs) by a single-step miniemulsion process developed to achieve better control of the morphology of the magnetic nanocomposite particles. MPNPs are prepared by surfactant-free miniemulsion polymerization using styrene (St) as a monomer, hexadecane (HD) as a hydrophobe, and potassium persulfate (KPS) as an initiator in the presence of oleic acid (OA)-modified magnetite nanoparticles. The effect of the type of cross-linker used [divinylbenzene (DVB) and bis[2-(methacryloyloxy)ethyl] phosphate (BMEP)] together with the effect of the amount of an aid stabilizer (dextran) on size, particle size distribution (PSD), and morphology of the hybrid nanoparticles synthesized is analyzed in detail. The mixture of different surface modifiers produces hybrid nanocolloids with various morphologies: from a typical core-shell composed by a magnetite core surrounded by a polymer shell to a homogeneously distributed morphology where the magnetite is uniformly distributed throughout the entire nanocomposite.     

DOSY-NMR analysis of ring-closing metathesis (RCM) products from β-lactam precursors

The discrimination between cyclomonomers and various oligomers formed during a ring-closing metathesis (RCM) process is not an easy task. Their (1)H NMR patterns are often very similar, and the use of mass spectrometry techniques is usually recommended. Here, we show that the DOSY-NMR method is a reliable tool to help in the identification of cyclomonomers versus cyclodimers by comparing the translational diffusion coefficient of the compounds issued from RCM reactions with the diffusion coefficient of their respective precursors.     

Activity of SiDbCl in the Electrooxidation of Ascorbic Acid,Dopamine, and Uric Acid

Selective electroanalytical responses for ascorbic acid, dopamine and uric acid at a carbon modified electrode based on 3‐n‐propyl‐1‐azonia‐4‐azabicyclo[2.2.2]octane silsesquioxane chloride (SiDbCl) is reported. The overlapped peaks observed at an unmodified electrode are resolved into three well defined voltammetric peaks allowing the simultaneous determination of the three species. Detection limits of 37, 0.3 and 0.1 μmo L⁻¹ of ascorbic acid, dopamine and uric acid, respectively, were calculated from calibration curves based on differential pulse voltammetric experiments performed in Britton ‐ Robinson buffer solution at pH 7.04.     

Synthesis and characterization of diiron dithiolate complexes containing a quinoxaline bridge

A potential model complex for the hydrogenase active site, [Fe(2){(μ-CH(2)S)(2)R}(CO)(6)] (1) (R = quinoxaline), was synthesized by condensation of [(μ-LiS)(2)Fe(2)(CO)(6)] with 2,3-bis(bromomethyl)quinoxaline. Reactions of 1 with bis(diphenylphosphino)methane (dppm) under a range of conditions yielded substituted complexes [Fe(2){(μ-CH(2)S)(2)R}(CO)(5)(dppm)] (2), [Fe(2){(μ-CH(2)S)(2)R}(CO)(4)(k(2)-dppm)] (3) and [Fe(2){(μ-CH(2)S)(2)R}(CO)(4)(μ-dppm)] (4). X-ray crystallography confirms that in 2, the dppm is terminally bonded to an iron atom via one phosphorus atom, whereas in 3, it acts as a chelating ligand to coordinate to an iron center in a dibasal-substituted manner. In 4, the dppm bridges the two iron atoms in a cis basal/basal fashion with one phosphorus bonded to each iron atom. Treatment of 1 with various tertiary phosphines at room temperature in acetonitrile (MeCN) generates a range of mono-substituted products [Fe(2){(μ-CH(2)S)(2)R}(CO)(5)L] (5, L = PEt(3); 6, PMe(3); 7, PPh(3); 8, Me(2)PPh). With Bu(t)NC, mono- and di-substituted [Fe(2){(μ-CH(2)S)(2)R}(CO)(5)(Bu(t)NC)] (9) and [Fe(2){(μ-CH(2)S)(2)R}(CO)(4)(Bu(t)NC)(2)] (10) complexes are generated. All the complexes were characterized by elemental analysis, IR, MS and NMR spectroscopy. IR and NMR spectroscopic studies suggest that addition of excess HBF(4)·OEt(2) acid to 1-4 led to the protonation of quinoxaline nitrogen atoms. In contrast, 5-10 were not stable in acidic media. Electrochemistry of 1-4 was investigated in the acetonitrile medium (0.1 M Bu(4)NPF(6)). The electrochemical instability of the reduced ligand, quinoxaline, and the reduced forms of these complexes revealed from the electrochemical studies suggests that they do not provide ideal models of the hydrogenase active site.     

Circadian variations in biologically closed electrochemical circuits in Aloe vera and Mimosa pudica

The circadian clock regulates a wide range of electrophysiological and developmental processes in plants. This paper presents, for the first time, the direct influence of a circadian clock on biologically closed electrochemical circuits in vivo. Here we show circadian variation of the plant responses to electrical stimulation. The biologically closed electrochemical circuits in the leaves of Aloe vera and Mimosa pudica, which regulate their physiology, were analyzed using the charge stimulation method. The electrostimulation was provided with different timing and different voltages. Resistance between Ag/AgCl electrodes in the leaf of Aloe vera was higher during the day than at night. Discharge of the capacitor in Aloe vera at night was faster than during the day. Discharge of the capacitor in a pulvinus of Mimosa pudica was faster during the day. The biologically closed electrical circuits with voltage gated ion channels in Mimosa pudica are also activated the next day, even in the darkness. These results show that the circadian clock can be maintained endogenously and has electrochemical oscillators, which can activate ion channels in biologically closed electrochemical circuits. We present the equivalent electrical circuits in both plants and their circadian variation to explain the experimental data.     

Synthesis and anion-exchange reactions of a new anionic clay, α-magnesium hydroxide

A new anionic clay, α-magnesium hydroxide, was synthesized by hydrolysis of magnesium acetate in propylene glycol. The structure of this α-hydroxide is similar to that of hydrotalcites. It consists of positively charged magnesium hydroxide layers arising out of partial protonation of the hydroxyl groups of the [Mg(OH)(2)] layers and loosely held anions in the interlayer region. As expected it ages readily in water to give β-magnesium hydroxide, brucite. While anion-exchange reactions of α-magnesium hydroxide could not be carried out in aqueous medium a number of anion-exchange reactions could be carried out successfully in ethanol medium.     

Ce(IV) complexes with donor-functionalized alkoxide ligands: improved precursors for chemical vapor deposition of CeO2

Thin films of ceria (CeO(2)) have many applications, and their synthesis by liquid-injection MOCVD (metal-organic chemical vapor deposition) or ALD (atomic layer deposition) requires volatile precursor compounds. Here we report the synthesis of a series of homoleptic and heteroleptic Ce(IV) complexes with donor-functionalized alkoxide ligands mmp (1-methoxy-2-methylpropan-2-olate), dmap (1-(dimethylamino)propan-2-olate), and dmop (2-(4,4-dimethyl-4,5-dihydrooxazol-2-yl)propan-2-olate) and their potential as precursors for MOCVD and ALD of CeO(2). New complexes were synthesized by alcohol exchange reactions with [Ce(OBu(t))(4)]. [Ce(mmp)(4)] and [Ce(dmap)(4)] were both found to be excellent precursors for liquid-injection MOCVD of CeO(2), depositing high purity thin films with very low carbon contamination, and both have a large temperature window for diffusion controlled growth (350-600 °C for [Ce(mmp)(4)]; 300-600 °C for [Ce(dmap)(4)]). [Ce(mmp)(4)] is also an excellent precursor for liquid-injection ALD of CeO(2) using H(2)O as oxygen source and demonstrates self-limiting growth from 150 to 350 °C. [Ce(dmap)(4)] has lower thermal stability than [Ce(mmp)(4)] and does not show self-limiting growth in ALD. Heteroleptic complexes show a tendency to undergo ligand redistribution reactions to form mixtures in solution and are unsuitable as precursors for liquid-injection CVD.     

Chiral properties of tetrathiatriarylmethyl spin probes

We report that tetrathiatriarylmethyl (trityl) EPR probes are chiral molecules at room temperature, the two stereoisomers that differ in their helicity being configurationally stable enough to be separated and stored independently.