Catalytic Nitrene Transfer by an FeIV-Imido Complex Generated by a Comproportionation Process

Nitrene transfer reactions have emerged as one of the most powerful and versatile ways to insert an amine function to various kinds of hydrocarbon substrates. However, the mechanisms of nitrene generation have not been studied in depth albeit their formation is taken for granted in most cases without definitive evidence of their occurrence. In the present work, we compare the generation of tosylimido iron species and NTs transfer from Fe^II and Fe^III precursors where the metal is embedded in a tetracarbene macrocycle. Catalytic nitrene transfer to reference substrates (thioanisole, styrene, ethylbenzene and cyclohexane) revealed that the same active species was at play, irrespective of the ferrous versus ferric nature of the precursor. Through combination of spectroscopic (UV-visible, Mössbauer), ESI-MS and DFT studies, an Fe^IV tosylimido species was identified as the catalytically active species and was characterized spectroscopically and computationally. Whereas its formation from the Fe^II precursor was expected by a two-electron oxidative addition, its formation from an Fe^III precursor was unprecedented. Thanks to a combination of spectroscopic (UV-visible, EPR, Hyscore and Mössbauer), ESI-MS and DFT studies, we found that, when starting from the Fe^III precursor, an Fe^III tosyliodinane adduct was formed and decomposed into an Fe^V tosylimido species which generated the catalytically active Fe^IV tosylimide through a comproportionation process with the Fe^III precursor.     

Complexes acetyleniques de titane(II). Reactivite vis-a-vis de l'hydrogene moleculaire: Une nouvelle approche du titanocene

¹³C NMR measurements were performed on [Re₃(μ-H)₃(CO)₁₀]^2? at various temperatures and field strengths. Selective decoupling allowed assignments of the carbonyl resonances. Spin-lattice relaxation time measurements indicated that two mechanisms, scalar coupling and chemical shielding anisotropy, contribute to the relaxation of carbon-13. Variable temperature experiments revealed that more than one mechanism is responsible for the fluxional behaviour.     

Synthesis and preliminary biological evaluation of a new pyridocarbazole derivative covalently linked to a thymidine nucleoside as a potential targeted antitumoral agent. I

The therapy of human cancer is one of the more pursued goals by medicinal chemistry research. Most of the compounds clinically used as a treatment owe their efficacy to their cytotoxic interaction (direct or indirect) with nuclear DNA. This interaction results in the inhibition of DNA synthesis and the degradation of nucleic strands. Ellipticine is a naturally occurring 6H-pyrido[4,3-b]carbazole alkaloid endowed with antitumor activity, and several ellipticine derivatives have been used in clinical trials. We previously reported some 1,4-dimethyl-9H-carbazole derivatives structurally related to ellipticine. The purpose of our research was to transform the pyridocarbazole in a prodrug so that it would have more penetration in the tumor cells and block their replication. Our prodrug is slowly hydrolyzed in human plasma in the corresponding acid. From these preliminary results, we deduce that our compound can block cellular replication. Our hypothesis is that the antitumoral activity is probably related to the induction of damage to DNA, without cellular lysis in the short term.     

Fast and easy multiresidue method employing acetonitrile extraction/partitioning and "dispersive solid-phase extraction" for the determination of pesticide residues in produce

A simple, fast, and inexpensive method for the determination of pesticide residues in fruits and vegetables is introduced. The procedure involves initial single-phase extraction of 10 g sample with 10 mL acetonitrile, followed by liquid-liquid partitioning formed by addition of 4 g anhydrous MgSO4 plus 1 g NaCl. Removal of residual water and cleanup are performed simultaneously by using a rapid procedure called dispersive solid-phase extraction (dispersive-SPE), in which 150 mg anhydrous MgSO4 and 25 mg primary secondary amine (PSA) sorbent are simply mixed with 1 mL acetonitrile extract. The dispersive-SPE with PSA effectively removes many polar matrix components, such as organic acids, certain polar pigments, and sugars, to some extent from the food extracts. Gas chromatography/mass spectrometry (GC/MS) is then used for quantitative and confirmatory analysis of GC-amenable pesticides. Recoveries between 85 and 101% (mostly > 95%) and repeatabilities typically < 5% have been achieved for a wide range of fortified pesticides, including very polar and basic compounds such as methamidophos, acephate, omethoate, imazalil, and thiabendazole. Using this method, a single chemist can prepare a batch of 6 previously chopped samples in < 30 min with approximately 1 dollar (U.S.) of materials per sample.     

The design, synthesis and photochemical study of a biomimetic cyclodextrin model of photoactive yellow protein (PYP)

The design, synthesis and study of the photophysical and photochemical properties of the first biomimetic cyclodextrin (CD) model of photoactive yellow protein (PYP) are described. This model bears a deprotonated trans-p-coumaric acid chromophore, covalently linked via a cysteine moiety to a permethylated 6-monoamino β-CD. NMR and UV/Visible spectroscopy studies showed the formation of strong self-inclusion complexes in water at basic pH. Steady-state photolysis demonstrated that, unlike the free chromophore in solution, excitation of the model molecule leads to the formation of a photoproduct identified as the cis isomer by NMR spectroscopy. These observations provide evidence that the restricted CD cavity offers a promising framework for the design of biomimetic models of the PYP hydrophobic pocket.     

Isolation of C-glycosyl xanthones from Coffea pseudozanguebariae and their location

The biochemical composition of leaves from Coffea pseudozanguebariae, a wild caffeine-free coffee species, was determined. Two phenolic compounds were extracted from leaves, separated and characterized. Their structures were elucidated by mass spectrometry, and 1D and 2D NMR spectroscopy and were shown to be mangiferin (1) and isomangiferin (2), which were the main polyphenol products. Multiphoton fluorescence imaging was performed to visualize polyphenol distribution in leaf cross sections. Consistent biochemical analysis cell imaging techniques on leaves revealed yellow fluorescence in the epidermis and parenchyma cells corresponding to xanthone compounds.     

Study of the acidity of H3PW12O40 supported on activated carbon by microcalorimetry and methanol dehydration reaction

H₃PW₁₂O₄₀/activated carbon catalysts have been studied by microcalorimetry and by the dehydration of methanol to dimethyl ether. It has been shown that the acidity of the polyacid is greatly reduced upon grafting on activated carbon. The decrease is so high that, at low polyanion loadings, the catalysts are relatively inactive in the dehydration of methanol to dimethyl ether.     

Introduction of Primary Amino Groups on Poly(ethylene terephthalate) Surfaces by Ammonia and a Mix of Nitrogen and Hydrogen Plasma

With the aim of introducing primary amino groups on the surface of poly(ethylene terephthalate) (PET), two methods were compared—the use of ammonia or a combination of nitrogen and hydrogen low-pressure microwave plasma. Several plasma parameters were optimized on the reactor to increase the –NH₂ surface density, which was estimated by colorimetric titration and X-ray photoelectron spectroscopy (XPS). These techniques show that whatever the plasma treatment, almost 2 –NH₂/nm2 are incorporated on PET films. Emission spectroscopy highlighted a correlation between the density of primary amino groups and the ratio between an NH peak intensity and an Ar peak intensity (I_NH/I_Ar). Variation in surface hydrophilicity with aging in air after plasma treatment was monitored with contact angle measurements and showed a hydrophobic recovery. This was confirmed by XPS, which suggests also that surfaces treated by NH₃ plasma are more stable than surfaces treated by N₂/H₂.