Selective Transesterification to Control Copolymer Microstructure in the Ring-Opening Copolymerization of Lactide and ε-Caprolactone by Lanthanum Complexes.

A series of novel lanthanum amido complexes, supported by ligands designed around the salan framework (salan = ,'-(-hydroxy, -di--butylbenzyl)-1,2-diaminoethane) were synthesized and fully characterized in the solid and solution states. The ligands incorporate benzyl or 2-pyridyl substituents at each tertiary amine center. The complexes were investigated as catalysts in the ring-opening homopolymerization of lactide (LA) and ε-caprolactone (ε-CL) and copolymerization of equimolar amounts of LA and ε-CL at ambient temperature.

Deciphering immune responses primed by a bacterial lipopeptide in wheat towards .

Plant immunity induction with natural biocontrol compounds is a valuable and promising ecofriendly tool that fits with sustainable agriculture and healthy food. Despite the agroeconomic significance of wheat, the mechanisms underlying its induced defense responses remain obscure. We reveal here, using combined transcriptomic, metabolomic and cytologic approach, that the lipopeptide mycosubtilin from the beneficial bacterium , protects wheat against through a dual mode of action (direct and indirect) and that the indirect one relies mainly on the priming rather than on the elicitation of plant defense-related mechanisms.

Bioinspired Rhamnolipid Protects Wheat Against Through Mainly Direct Antifungal Activity and Without Major Impact on Leaf Physiology.

Rhamnolipids (RLs), glycolipids biosynthesized by the and genera, are known to display various activities against a wide range of pathogens. Most previous studies on RLs focused on their direct antimicrobial activity, while only a few reports described the mechanisms by which RLs induce resistance against phytopathogens and the related fitness cost on plant physiology. Here, we combined transcriptomic and metabolomic approaches to unravel the mechanisms underlying RL-induced resistance in wheat against the hemibiotrophic fungus , a major pathogen of this crop.

Importance of the C Carbon Chain in the Biological Activity of Rhamnolipids Conferring Protection in Wheat against .

The hemibiotrophic fungus , responsible for Septoria tritici blotch, is currently the most devastating foliar disease on wheat crops worldwide. Here, we explored, for the first time, the ability of rhamnolipids (RLs) to control this pathogen, using a total of 19 RLs, including a natural RL mixture produced by and 18 bioinspired RLs synthesized using green chemistry, as well as two related compounds (lauric acid and dodecanol). These compounds were assessed for in vitro antifungal effect defence elicitation (peroxidase and catalase enzyme activities), and protection efficacy on the wheat- pathosystem.

Synthesis of hybrid colloidal nanoparticles for a generic approach to 3D electrostatic directed assembly: Application to anti-counterfeiting.

Hypothesis: The capability of making 3D directed assembly of colloidal nanoparticles on surfaces, instead of 2D one, is of major interest to generate, tailor, and enhance their original functionalities. The nanoxerography technique, i.e.

Reducing zirconium(IV) phthalocyanines and the structure of a Pc(4-)Zr complex.

The synthesis and characterization of the ring-unsubstituted zirconium phthalocyanine PcZrCl2 (; Pc(x-) = phthalocyaninato(x-)) and its reduction products are described. X-ray analysis of (crystallized from hot 1-chloronaphthalene) reveals that is a chloride-bridged dimer [PcZrCl]2(μ-Cl)2 in the solid-state; was also characterized by UV-vis/MCD spectroscopy and cyclic voltammetry, which indicated reduction potentials at -0.55, -0.

Stereoelectronic control of photophysics: red and yellow axial and equatorial anomers of a rhenium-quinoline complex.

A novel quinoline-substituted pyrimidine ligand forms two different coloured complexes upon reaction with Re(CO)5Br. These compounds display distinct photophysical properties that are dictated by their stereochemistry.

Metallophthalocyanin-ocenes: scandium phthalocyanines with an η(5)-bound Cp ring.

A series of new scandium complexes supported by the phthalocyanine (Pc) ligand have been prepared and structurally characterized. Reaction of ScCl3 with phthalonitrile affords a mixture of PcScCl (1) and unreacted ScCl3, which upon addition of LiCH(SiMe3)2 yields THF-soluble PcSc(μ-Cl2)Li(THF)2 (2). Metathesis with NaCp or LiCp* generates PcSc(η(5)-C5H5) and PcSc(η(5)-C5Me5), respectively, which represent the first examples of η(5)-Cp metal phthalocyanines where the Cp fragment sandwiches the metal centre.

Zirconium catalyzed alkyne dimerization for selective Z-enyne synthesis.

The regioselective head-to-head dimerization of alkynes is catalyzed by a dibenzyl tethered bis(ureate) zirconium precatalyst with aniline as an additive. This system also gives outstanding stereoselectivity to furnish Z-enynes in high yields. A dinuclear reactive intermediate has been characterized, which provides a potential mechanistic rationale for the unexpected regio- and stereoselectivity in this catalytic system.

Mechanistic elucidation of intramolecular aminoalkene hydroamination catalyzed by a tethered bis(ureate) complex: evidence for proton-assisted C-N bond formation at zirconium.

A broad mechanistic investigation regarding hydroamination reactions catalyzed by a tethered bis(ureate) zirconium species, [ureate(2-)]Zr(NMe(2))(2)(HNMe(2)), is described. The cyclization of both primary and secondary aminoalkene substrates gives similar kinetic profiles, with zero-order dependence on substrate concentration up to ∼60-75% conversion, followed by first-order dependence for the remainder of the reaction. The addition of 2-methylpiperidine changes the observed substrate dependence to first order throughout the reaction, but does not act as a competitive inhibitor.

Bis(phosphinic)diamido yttrium amide, alkoxide, and aryloxide complexes: an evaluation of lactide ring-opening polymerization initiator efficiency.

The synthesis and characterization of a series of bis(phosphinic)diamido yttrium alkoxide, amide, and aryloxide initiators are reported. The new complexes are characterized using multinuclear nuclear magnetic resonance (NMR) spectroscopy, elemental analysis, and, in some cases, X-ray crystallography. The alkoxide complexes are all dimeric in both the solid state and in solution, as are the amide complexes substituted with iso-propyl or phenyl groups on the phosphorus atoms.

First neodymium(III) alkyl-carbene complex based on bis(iminophosphoranyl) ligands.

Serendipitous deprotonation of bis(iminophosphoranyl)methanide Nd(III) complexes afforded the first alkyl-carbene neodymium complex. Due to the presence of structurally similar methanide and methandiide fragments, this complex features, as evidenced by X-ray crystallographic analysis, Nd-C single and multiple bonds.

Stereocontrolled lactide polymerisation determined by the nuclearity of the yttrium initiator.

Two very rapid yttrium initiators for lactide polymerisation are reported; the nuclearity (monomer vs. dimer) of the initiator controls the stereochemistry of the polylactide produced.

Blood content of asymmetric dimethylarginine: new insights into its dysregulation in renal disease.

Background: Plasma asymmetric dimethylarginine (ADMA), an endogenous inhibitor of nitric oxide synthase, is significantly elevated in patients with kidney disease and is a potential risk factor for cardiovascular disease. Here, we tested whether human whole blood (WB), as in rodent blood, can accumulate free ADMA and whether this accumulation is a function of disease burden.

Methods: In 16 healthy control subjects (CO), 18 patients with ESRD and 18 matched hypertensive patients with normal renal function (HTN), we compared using high-pressure liquid chromatography baseline plasma and WB supernatant (WBSUP) ADMA and symmetrical dimethylarginine (SDMA) concentrations and accumulation during a 5-h incubation.

A series of bis(phosphinic)diamido yttrium complexes as initiators for lactide polymerization.

A series of new bis(phosphinic)diamido yttrium complexes have been synthesized and fully characterized. The complexes adopt dimeric structures, both in solution and in the solid state, where one phosphinic group bonds to one yttrium center and the other bonds to two yttrium centers. The complexes have all been tested as initiators for the ring-opening polymerization of lactide; they are all highly active.

[Anatomy of the brain of the New Zealand Gray Sphenodon punctatus (sphenodontidae). A quantitative study of the principle subdivisions of the brain].

This study has been carried out on two adults of the species Sphenodon punctatus (Sphenodontidae). The results allowed us to establish the numerical features of the brain organization in this species. Comparisons were done with regard to a sample of forty various species of lizards, in which six species of Lacertids were taken as a mean reference level (Platel, 1975).

[Comparative studies of the anatomy of the brain in three species of Agnatha: Petromyzon marinus, Lampetra fluviatilis and Lampetra planeri].

This study has been carried out upon 3 species of Petromyzonts: Petromyzon marinus, Lampetra fluviatilis and Lampetra planeri. According to the values of the index of encephalization (whole brain) and to these of the structures indices (brain subdivisions), similarities as well as differences have been pointed out. Other detail are brought by the relative volume of these subdivisions expressed by a per cent value of the entire brain volume (the ventricular volumes being removed).

[Encephalization of the marine lamprey, Petromyzon marinus (L.). Quantitative analysis of the principle brain subdivisions].

The measure of both the somatic weight (S) and the brain weight (E) on a sample of 13 adult individuals of Petromyzon marinus (L.) leads for this species to the determination of its brain-body weight coefficient of allometry and to the knowledge of its index of encephalization. The value of the first one is 0.

[Comparative volumetric analysis of the principal subdivisions of the telencephalon in saurian reptiles].

The volumetric measure of the main subdivisions of the telencephalon has been carried on 24 species of Lizards and 2 species of Snakes. The studied structures are termed as follows: main and accessory olfactory bulbs, medial cortex (M 1 and M 2), dorsal cortex (D 1, D 2 and D 3), lateral cortex (L), Septum, Tuberculum olfactorium, dorsal and ventral striatum, amygdala and nucleus sphaericus. The analysis of the datas makes use of the SNEL L's formula which relates the volume of the various telencephalic subdivisions (V) to the somatic weight (S): V = k x S alpha.

[Brain organization of Amia, Lepisosteus and Polypterus: comparative morphology and quantitative analysys].

The quantitative study of the brain of Amia, Lepisosteus and Polypterus leads to results which are compared to those previously got on the Sturgeon and three species of Tleosts (the Rainbow Trout, the Carp and the Ballan wrasse). The volumetric analysis has been applied at first to the whole brain (encephalization indices) and later to the main subdivision of the brain: telencephalon, diencepahlon..

Comparative volumetric analysis of the main subdivisions of the brain in saurian reptiles.

The volumetric measure of the main subdivisions of the brain has been carried out on 32 species of Lizards and 3 species of Snakes. The analysis of the allometrical relations between the volume (the weight) of these subdivisions and the body weight shows firstly that the evolutionary or/and adaptative processes are only located at the mesencephalic and metencephalic levels. A more elaborate study leads meanwhile to the conclusion that anothers brain structures - pallium, basal areas, dorsal thalamus - are also implicated, according to the possibility to group the various species into taxomic units (such as family) or in another way; thus it has been possible to corroborate with quantitative datas the NORTHCUTT'S definition (1972) of the Type I (Lacertomorpha) and Type II (Dracomorpha) lizards; the Dracomorpha show "dynamical" structures - pallium and dorsal thalamus - and remind, in some degree the mammal organization.