Morphology, physiology, and biochemistry of zinc-stressed caraway plants.

A greenhouse pot experiment was conducted to evaluate the impact of zinc supply (0, 1, and 2 mM Zn as ZnSO4) on morpho-physiological and biochemical parameters of caraway (Carum carvi L.). Exposure to different Zn concentrations for 12 weeks compromised severely all growth parameters (plant height, number of secondary branches, diameter of primary and secondary branches, fresh and dry weight of aerial parts and roots) yield and its components (number of umbels per primary branches and secondary branches; number of umbel per plant; number of seeds per plant; and the weight of 1000 seeds). These manifestations were intimately linked with excessive accumulation of Zn in roots and leaves, alteration of the content of photosynthetic pigments, and extended lipid peroxidation. A manifest increment of proline and soluble sugar content was also observed in response to Zn application. Lipid content in seeds was dropped in Zn-treated plants and the fatty acid profiles were profoundly affected as they were enriched with saturated fatty acids at the expense of unsaturated ones. While improving their oxidative stability as revealed by the reduced values calculated oxidizability and oxidative susceptibility, Zn treatment reduced the lipid nutritional quality of caraway seeds. Moreover, Zn treatment reduced the essential oil yield and its main component carvone while it enhanced the content of its precursor limonene. It also induced alteration of terpene metabolism as revealed in the redirection of the carbon flux to the shikimate/phenylpropanoid pathway resulting in the stimulation of the production of phenolic compounds and their subsequent antioxidant activities.

New poly(ether-phosphoramide)s sulfides based on green resources as sensitive films for the specific impedimetric detection of nickel ions.

For the development of selective and sensitive chemical sensors, we have developed a new family of poly(ether-phosphoramide) polymers. These polymers were obtained with satisfactory yields by nucleophilic aromatic polycondensation using isosorbide as green resources, and bisphenol A with two novel difluoro phosphinothioic amide monomers. Unprecedented, the thiophosphorylated aminoheterocycles monomers, functionalized with two heterocyclic amine, N-methylpiperazine and morpholine were successfully obtained by nucleophilic substitution reaction of P(S)-Cl compound. The resulting polymers were characterized by different analytical techniques (NMR, MALDI-ToF MS, GPC, DSC, and ATG). The resulting partially green polymers, having tertiary phosphine sulfide with P-N side chain functionalities along the main chain of polymers are the sensitive film at the surface of a gold electrode for the impedimetric detection of Cd, Ni, Pb and Hg. The bio-based poly(ether-phosphoramide) functionalized with N-methylpiperazine modified sensor showed better analytical performance than petrochemical based polymers for the detection of Ni2+. A detection limit of 50 pM was obtained which is very low compared to the previously published electrochemical sensors for nickel detection.

About the transformation of low T m into high T m poly(l-lactide)s by annealing under the influence of transesterification catalysts.

Cyclic polylactides were prepared in bulk at 170 °C, crystallized at 120 °C and then annealed at temperatures between 130 and 170 °C with variation of catalyst, catalyst concentration and annealing time. The transformation of the initially formed low melting (LT m) crystallites, having melting temperatures (T m) < 180 °C into high melting (HT m) crystallites having T m values > 189 °C was monitored by means of DSC measurements and characterized in selected cases by SAXS measurements. It was confirmed that the formation of HT m crystallites involves a significant growth of the thickness of the lamellar crystallites along with smoothing of their surface. Annealing at 170 °C for 1 d or longer causes thermal degradation with lowering of the molecular weights, a gradual transition of cyclic into linear chains and a moderate decrease of lamellar thickness. An unexpected result revealed by MALDI TOF mass spectrometry is a partial reorganization of the molecular weight distribution driven by a gain of crystallization enthalpy.

New biosourced AA and AB monomers from 1,4:3,6-dianhydrohexitols, Isosorbide, Isomannide, and Isoidide.

In the present work, we propose the synthesis of a new family of sugar derived 1,4:3,6-dianhydrohexitol based AA/AB-type monomers. Unprecedented diacids based on Isomannide and Isoidide were elaborated with high yields and showed interestingly high melting point ranges (240-375 °C). Optimization of reaction conditions (temperature, time of reaction, and reactant ratios) has been investigated to synthesize the key intermediate of a set of AB monomers with acid, ester, and acid chloride functionalities. Isosorbide based ether benzoic acid AB monomer was polymerized and characterized by NMR and DSC techniques. The results show a semicrystalline behavior of the obtained polymer thanks to the controlled stereoregular arrangement of the AB starting monomer.

New biosourced chiral molecularly imprinted polymer: Synthesis, characterization, and evaluation of the recognition capacity of methyltestosterone.

New biosourced chiral cross-linkers were reported for the first time in the synthesis of methyltestosterone (MT) chiral molecularly imprinted polymers (cMIPs). Isosorbide and isomannide, known as 1,4:3,6-dianhydrohexitols, were selected as starting diols. The cMIPs were synthesized following a noncovalent approach via thermal radical polymerization and monitored by Raman spectroscopy. These cross-linkers were fully characterized by 1 H and 13 C nuclear magnetic resonance (NMR) spectroscopy and high-resolution mass spectrometry. The cross-polarization magic angle spinning 13 C NMR, Fourier transform infrared spectroscopy, scanning electron microscopy, and specific surface areas following the Brunauer-Emmett-Teller (BET) method were used to characterize the cMIPs. The effect of stereochemistry of cross-linkers on the reactivity of polymerization, morphology, and adsorption-recognition properties of the MIP was evaluated. The results showed that the cMIP exhibited an obvious improvement in terms of rebinding capacity for MT as compared with the nonimprinted polymer (NIP). The highest binding capacity was observed for cMIP-Is (27.298 mg g-1 ) for high concentrations (500 mg L-1 ). However, the isomannide homologue cMIP-Im showed higher recovery-up to 65% and capacity for low concentrations (15 mg L-1 ). The experimental data were properly fitted by the Freundlich adsorption isothermal model.

A facile preparation of trisubstituted amino-furan and -thiophene derivatives.

ß-Alkylation of amino-furan and -thiophene heterocycles is described through metal-, acid- and base-free carbon-carbon bond formation. The ability of both heterocycles to undergo selective ß-alkylation is compared by mean of experimental and theoretical data. The presence of chiral amine substituents induced the diastereoselective generation of the newly formed additional stereocenter.

Concise synthesis of tricyclic isoindolinones via one-pot cascade multicomponent sequences.

A series of enantiopure tricyclic isoindolinones has been successfully synthesized through a one-pot selective cascade process from furan derivatives. The synthesis is straightforward and gave good overall yields taking into account the concomitant formation of five C-C, C-O, and C-N bonds. The strategy was extended to the preparation of a thiazolidine analogue.

From furans to anilines: toward one-pot two-step amination/diels-alder sequences.

Selective metal-free amination and Diels-Alder reactions are described in the furan series, leading to polysubstituted anilines or to stable oxabicyclic adducts in high yield. Interestingly, anilines are conveniently prepared through a novel one-pot, two-step amination/Diels-Alder procedure from commercially available 5-bromo-2-furaldehyde.