Enolates de l'acetylacetate d'ethyle. Structure et reactivite du sel de potassium en presence d'ether couronne et de cryptand

It is shown that, through the addition of 18-crown-6 or cryptand (2.2.2) to potassium ethyl acetoacetate enolate solutions in tetrahydrofuran, 1:1 complexes are formed. A single crystal of the 1:1 potassium énolate-18-crown-6 complex has been obtained. Its structure has been determined by X-ray diffraction. The crystal includes entities formed from an enolate anion chelating a potassium cation externally complexed by the crown-ether. The vibrational spectrometry shows that the structure of the entity is kept in solution. In the species formed through the addition of cryptand (2.2.2), the enolate anion has a structure (IR spectroscopy) and a reactivity very close to that of the free anion, observed in a dissociating solvent (DMSO, HMPA). When crown ether is added, a contact ion pair is formed, in which the cation is externally solvated by the crown. On the other hand, the cation encapsulation by the cryptand leads to a released anion with an “ S-trans” or “W” structure. The reactivity and the orientation of the alkylation reactions of these entities have been measured in THF solutions. They are discussed in relation to the structure of the species present in the reaction medium.     

Gas-phase behaviour of negative ions produced from thiazidic diuretics under electrospray conditions

A systematic mass spectrometric study of 10 thiazidic diuretics and related compounds was undertaken by mass spectrometry (MS) with electrospray ionization in the negative ion mode. Collisional dissociation 'in-source' (CID-MS) and in a low-pressure collision cell (CID-MS/MS) were compared in both excitation regions. Spectra obtained by CID-MS and by CID-MS/MS were matched. Using the two methods, loss of HCl and consecutive dissociations from 2HCl losses were exhibited from compounds such as methyclothiazide and trichlormethiazide but not from other thiazidic diuretics that contain chlorine substituents in the aromatic moiety. However, deprotonated dichlorphenamide gave rise to loss of HCl by CID-MS and CID-MS/MS. For other diuretics such as hydroflumethiazide and hydrochlorothiazide, the loss of HCN and [HCN + SO(2)] was relevant. Reaction mechanisms were checked by means of deuterium-hydrogen exchange, which showed that deprotonation took place regioselectively on the heterocyclic moiety. The cleavage pathways require molecular isomerization forming ion-dipole complexes prior to decompositions, allowing long-distance proton transfer for neutral elimination. Identifications of the most specific fragmentations presented in this paper were applied to the screening and unambiguous identification of diuretics for horse doping control.     

Analysis of paramagnetic NMR spectra of triple-helical lanthanide complexes with 2,6-dipicolinic acid revisited: a new assignment of structural changes and crystal-field effects 25 years later

Variable-temperature (1)H and (13)C NMR measurements of the D(3)-symmetrical triple-helical complexes [Ln(L1-2H)(3)](3)(-) (L1 = pyridine-2,6-dicarboxylic acid; Ln = La-Lu) show evidence of dynamic intermolecular ligand-exchange processes whose activation energies depend on the size of the metal ion. At 298 K, the use of diastereotopic probes in [Ln(L3-2H)(3)](3)(-) (L3 = 4-ethyl-pyridine-2,6-dicarboxylic acid) shows that fast intramolecular P <==> M interconversion between the helical enantiomers occurs on the NMR time scale. Detailed analyses of the paramagnetic NMR hyperfine shifts according to crystal-field independent techniques demonstrate the existence of two different helical structures, one for large lanthanides (Ln = La-Eu) and one for small lanthanides (Ln = Tb-Lu), in complete contrast with the isostructurality proposed 25 years ago. A careful reconsideration of the original crystal-field-dependent analysis shows that an abrupt variation of the axial crystal-field parameter A(0)2 parallels the structural change leading to some accidental compensation effects that prevent the detection of structural variations according to the classical one-nucleus method. Crystal structures in the solid state and density functional theory calculations in the gas phase provide structural models that rationalize the paramagnetic NMR data. A regular triple-helical structure is found for small lanthanides (Ln = Tb-Lu) in which the terdentate chelating ligands are rigidly tricoordinated to the metals. A flexible and distorted structure is evidenced for Ln = La-Eu in which the central pyridine rings interact poorly with the metal ion. The origin of the simultaneous variation of structural parameters and crystal-field and hyperfine constants near the middle of the lanthanide series is discussed together with the use of crystal-field-independent techniques for the interpretation of paramagnetic NMR spectra in axial lanthanide complexes.     

Electrochemical response of ascorbic and uric acids at organoclay film modified glassy carbon electrodes and sensing applications

A naturally occurring Cameroonian smectite clay has been grafted with trimethylpropylammonium groups and the resulting organoclay deposited as thin film onto a glassy carbon electrode (GCE) surface. It was then exploited as a suitable matrix for the accumulation and the electrochemical detection of ascorbic acid (AA) and uric acid (UA). Cyclic voltammetry revealed an increase in oxidation peak responses along with a negative shift of the corresponding anodic peak potential for both AA and UA species when using the organoclay coated GCE in comparison with the bare electrode. The electroanalytical response was improved by coating the electrode surface with a first layer of sublimed ferrocene (FC(s)), and then overcoating with the organoclay film to avoid the mediator leaching. The resulting bilayer film exhibited good characteristics such as extended linear range and high sensitivities for AA and UA, in cyclic voltammetry and amperometry. Interestingly, the redox mediator FC(s) was likely to lower overpotentials for AA oxidation (but not for UA), making possible the selective detection of these species in a mixture. The developed method could be used for the determination of AA in a pharmaceutical preparation and for UA in urine.     

Efficient Synthesis of New 2H‐Chromene Retinoids Hybrid Derivatives by Suzuki Cross‐coupling Reactions

In an attempt to improve anticancer activity, a series of retinoids–chromene hybrids was described. The novel heterocyclic chromene–retinoids hybrid including oxygen as a heteroatom in a six‐membered cyclic ring (2H‐chromene or 2H‐1‐benzopyran) was designed and synthesized by introducing different groups such as an aromatic or styrylphenyl ring in 6‐position of 2H‐chromene. These novel compounds were synthesized by using the efficient cascades one‐pot process involving Wittig–Horner–Emmons reaction and Suzuki–Miyaura cross‐coupling pallado‐catalyzed reactions with 60% to 90% overall yields. These new compounds were tested against glioblastoma multiforme brain cancer, medulloblastoma, neuroblastoma cell lines, and breast cancer MCF‐7 cell lines. Two of them exhibited an appreciable anti‐tumor activity in the low micromolar range, which opens new perspectives for therapeutic application on humans.     

Simple Derivatization–Gas Chromatography–Mass Spectrometry for Fatty Acids Profiling in Soil Dissolved Organic Matter

Dissolved organic matter is an important component of the global carbon cycle that allows the distribution of carbon and nutrients. Therefore, analysis of soil dissolved organic matter helps us to better understand climate change impacts as it is the most dynamic and reactive fraction in terrestrial ecosystems. Its characterization at the molecular level is still challenging due to complex mixtures of hundreds of compounds at low concentration levels in percolating water. This work presents simple methods, such as thermochemolysis– or derivatization–gas chromatography, as an alternative for the analysis of fatty acids in dissolved organic matter without any purification step. The variables of the protocols were examined to optimize the processing conditions for the C₉–C₁₈ range. As a proof of concept, fatty acid distributions of soil percolating water samples from a long-term field experiment were successfully assessed. The variability of dissolved organic acid distributions was pronounced through depth profile and soil treatment but no major change in composition was observed. However, although the optimization was done from C₉ to C₁₈, detection within the C₆-C₃₂ fatty acids range was performed for all samples.     

Fluorescence spectroscopy for monitoring deterioration of extra virgin olive oil during heating

The potential of fluorescence spectroscopy for characterizing the deterioration of extra virgin olive oil (EVOO) during heating was investigated. Two commercial EVOO were analysed by HPLC to determine changes in EVOO vitamin E and polyphenols as a result of heating at 170°C for 3 h. This thermal oxidation of EVOO caused an exponential decrease in hydroxytyrosol and vitamin E (R²=0.90 and 0.93, respectively) whereas the tyrosol content was relatively stable. At the same time, amounts of preformed hydroperoxides (ROOH), analysed by an indirect colorimetric method, decreased exponentially during the heating process (R²=0.94), as a result of their degradation into secondary peroxidation products. Fluorescence excitation spectra with emission at 330 and 450 nm were recorded to monitor polyphenols and vitamin E evolution and ROOH degradation, respectively. Partial least-squares calibration models were built to predict these indicators of EVOO quality from oil fluorescence spectra. A global approach was then proposed to monitor the heat charge from the overall fluorescence fingerprint. Different data pretreatment methods were tested. This study indicates that fluorescence spectroscopy is a promising, rapid, and cost-effective approach for evaluating the quality of heat-treated EVOO, and is an alternative to time-consuming conventional analyses. In future work, calibration models will be developed using a wide range of EVOO samples.     

Analytical and Preparative Chiral Separation of β-Carboline Derivatives, LDL Oxidation Inhibitors, Using HPLC and CE Methodologies: Determination of Enantiomeric Purity

In the present study, baseline separation of the enantiomers of 16 β-carboline derivatives was successfully achieved using both capillary electrophoresis (CE) and high-performance liquid chromatography (HPLC) techniques in short run times (<15?min) and thus permit the determination of enantiomeric excess. In HPLC methodology, cellulose chiral stationary phase (Chiralcel OD-H) was used with a binary mobile phase constituted of n-hexane/ethanol 85/15 leading to a resolution factor of 12.6 in 15?min. Preparative HPLC allowed to obtain pure enantiomers of two compounds. In CE, chiral selectivity was developed with an in-capillary stacking strategy using anionic (highly sulfated-γ) cyclodextrins 5% (w/v) as chiral selectors and a 60?mM phosphate buffer (pH 2.5) resulting in a resolution of 10.26 in 14?min of analysis. The analytical characteristics of the two developed methods were studied in terms of repeatability, limits of detection and limits of quantification showing their suitability to be extended to all the other molecules.     

Electronic structure of Li-intercalated oligopyridines: a comparative study by photoelectron spectroscopy

The role of nitrogen in the charge transfer and storage capacity of lithium-intercalated heterocyclic oligophenylenes was investigated using photoelectron spectroscopy. The development of new occupied states at low binding energies in the valence band region, as well as core level chemical shifts at both carbon and nitrogen sites, demonstrates partial charge transfer from lithium atoms to the organic component during formation of the intercalated compound. In small compounds, i.e., biphenyl and bipyridine derivatives, the position of the nitrogen heteroatom significantly affects the spacing between gap states in the Li-intercalated film; yet it has minimal effects on the charge storage capacity. In larger, branched systems, the presence of nitrogen in the aromatic system significantly enhances the charge storage capacity while the Li-N bond strength at high intercalation levels is significantly weakened relative to the nitrogen-free derivative. These observations have strong implications towards improved deintercalation processes in organic electrodes in lithium-ion batteries.     

A canted antiferromagnetic ordered phase of cyanido-bridged Mn(III)(2)Re(IV) single-chain magnets

A new cyanido-bridged Re(IV)-Mn(III) heterometallic 1D system, [Mn(III)(5-Me-saltmen)](2)[Re(IV)Cl(4)(CN)(2)]·3CH(3)CN (), was designed and structurally characterized. Interchain interactions stabilize a canted antiferromagnetic ordered state below 6.2 K that does not prevent slow relaxation of the magnetization reminiscent of the single-chain magnet properties of the individual chains.