Determination of microtacticity of poly(vinylketones) and their derivatives by NMR spectroscopies of carbon-13 and proton

Sequence distribution of atactic poly(phenylvinylketone) (PPVK) has been determined by [¹³C]-[¹H]NMR spectroscopy. Quantitative analysis of the carbonyl pattern allows resolution into pentads with intensities fitting a first order Markov process. The carbonyl pattern of highly isotactic PPVK, initiated by diethylzinc, deviates strongly from Bernoullian statistics, as in the case of highly isotactic polymethylvinylketone (PMVK). For n-butyl-lithium initiated poly(isopropenylphenylvinylketone) (PIPK), the carbonyl pattern practically agrees with a Bernoullian distribution. Atactic PMVK, analyzed from the methylene and the carbonyl pattern in [¹³C] or [¹H]NMR, shows that the polymerization process is purely Bernoullian and quite different from that for poly(isopropenylmethylketone). Except for poly(methylallylalcohol) for which the tacticity can be determined, the resolution is too poor to allow a quantitative sequence distribution of poly(allylalcohols) or poly(allyltrifluoroacetates). [¹H] and [¹⁹F]NMR spectroscopies of these compounds do not give better results.     

A Stereoselective Approach to the Spiro [4, 5]decane System via Intramolecular Photocycloaddition and Reductive Fragmentation. Preliminary communication

The photoaddition 6 → 7 , followed by a reductive cleavage of the →-chlorocyclobutylketone 7 , gave the stereochemically pure spiro [4,5]decane 8 .     

Réaction de l'azaallyllithium en série acétylénique: Une méthode directe de préparation de phényléthynyl pyrrolidines, -pyrrolines et -pyrroles N-non substitués et N-alkylés

Cycloaddition of 1,3-diphenyl-2-azaallyllithium to tolane, diphenylbutadiyne and 1,4-diphenylbutenyne E produces quantitatively 2,3,4,5-tetraphenylpyrrole, 3-phenylethynyl-2,4,5-triphenyl-3-pyrroline and 3-phenylethynyl-2,4,5-triphenylpyrrolidine, respectively. Treatment before hydrolysis with benzyl bromide or dimethl sulfide gives N-alkyl-substituted derivatives. The structure of 3-pyrrolines was established by spectral data and chemical correlations. Stereochemical courses of this new synthetic method for 3-pyrrolines are discussed.     

Channel-Type Molecular Structures. Part 2. Synthesis of Bouquet-Shaped Molecules Based on a β-Cyclodextrin Core

A new series of channel-type molecules presenting the features of potential transmembrane structures is described. They result from the grafting of amphiphilic side chains on a β-cyclodextrin derivative 3 that constitutes the organizing core. They belong to the ‘bouquet’ family (B). Compounds bearing poly(oxyethylene) side chains, B 16 and 17 , and their polymethylene analogues B 18 and 19 , were synthesized. The properties investigated emphasize the suitability of such molecules to be incorporated into lipid bilayer membranes.     

Reactive Bis(cyclopentadienyl)niobium Moiety: Synthesis of the First Niobium Phosphorus Ylid Complexes

Abstract

Phosphorus ylides are known to form σ-metal-carbon bonds of unusual stability. Bis(cyclopentadienyl)niobium derivatives offer a general synthetic approach to niobium phosphorus ylide complexes, the first to be reported.     

N-(Benzyloxycarbonyl)-L-vinylglycike Methyl Ester from L-Methionine Methyl Ester Hydrochloride

A reproducible, large scale and practical synthesis of N-(benzyloxycarbonyl)-L-vinylglycine methyl ester starting from L-methionine methyl ester hydrochloride is described.     

Organ Repair,Hemostasis, and In Vivo Bonding of Medical Devices by Aqueous Solutions of Nanoparticles

Sutures are traumatic to soft connective tissues, such as liver or lungs. Polymer tissue adhesives require complex in vivo control of polymerization or cross‐linking reactions and currently suffer from being toxic, weak, or inefficient within the wet conditions of the body. Herein, we demonstrate using Stöber silica or iron oxide nanoparticles that nanobridging, that is, adhesion by aqueous nanoparticle solutions, can be used in vivo in rats to achieve rapid and strong closure and healing of deep wounds in skin and liver. Nanoparticles were also used to fix polymer membranes to tissues even in the presence of blood flow, such as occurring after liver resection, yielding permanent hemostasis within a minute. Furthermore, medical devices and tissue engineering constructs were fixed to organs such as a beating heart. The simplicity, rapidity, and robustness of nanobridging bode well for clinical applications, surgery, and regenerative medicine.     

The Effects of Formulation on Imidacloprid Dissipation in Grapes and Vine Leaves and on Required Pre-Harvest Intervals under Lebanese Climatic Conditions

In this study, imidacloprid, a systemic insecticide, currently having a specified European Commission MRL value for vine leaves (2 mg kg⁻¹), was applied on a Lebanese vineyard under different commercial formulations: as a soluble liquid (SL) and water dispersible granules (WDG). In Lebanon, many commercial formulations of imidacloprid are subject to the same critical good agricultural practice (cGAP). It was, therefore, important to verify the variability in dissipation patterns according to matrix nature and formulation type. Random samplings of grapes and vine leaves were performed starting at 2 days until 18 days after treatment. Residue extractions were performed according to the QuEChERS method and the analytical determination using liquid chromatography coupled to tandem mass spectrometry (LC-MS-MS). The SL formulation yielded significantly higher initial deposit than the WDG formulation on grapes and vine leaves. The formulation type did not significantly affect the dissipation rates; the estimated half-lives in grapes and vine leaves were 0.5 days for all imidacloprid formulations. No pre-harvest intervals were necessary on grapes. PHIs of 3.7 days for the SL formulation and 2.8 days for the WDG formulation were estimated on vine leaves. The results showed that the type of formulation and the morphological and physiological characteristics of the matrix had an effect on the initial deposits, and thus residue levels, but not on the dissipation patterns.     

Stereoselective access to the versatile 4-aminohex-5-ene-1,2,3-triol pattern

We developed a stereocontrolled route allowing potential access to the eight isomers of 4-benzylaminohex-5-ene-1,2,3-triol in two or four steps and ca. 50% yield from readily available chiral nonracemic cis- or trans-alpha,beta-epoxyimine precursors. A new (NH(4))(2)CO(3)-based carboxylation/intramolecular cyclization sequence allowed regio- and stereocontrolled C-3 epoxide opening while neat C-2 hydrolysis was ensured by simple aqueous acidic treatment.