Michael reaction,VI. Effect of carbonyl compounds on the stereochemistry and mechanism of the reaction

Zusammenfassung Die Stereochemie einer zweistufigen Gleichgewichts-Michael-Reaktion zwischen Dialkylamiden der Phenylessigsäure und Methylestern oder Dialkylamiden der Zimtsäure wird von den neutralen Carbonylverbindungen stark beeinflußt. Dieser Effekt kann mit der Zerstörung einer intramolekularen Chelatstruktur des Addukts und der darauffolgenden Bildung einer offenen Metallform mit einem dem neutralen Addukt ähnlichenerythro-threo-Verhältnis erklärt werden. Die Zunahme der elektrischen Leitfähigkeit des Reaktionsgemisches stützt diese Vorstellung.Es wird ein über das Chelat verlaufender Mechanismus im nichtpolaren Medium postuliert. Dieser Mechanismus ist in guter Übereinstimmung sowohl mit der geringen Stereoselektivität (bei kinetischer Kontrolle) als auch mit dem Einfluß der Lösungsmittel auf die Stereochemie.

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Michael reaction, VI. Effect of carbonyl compounds on the stereochemistry and mechanism of the reaction

The equilibrium stereochemical result of the two-stepMichael reaction between phenylacetic acid dialkylamides and methyl cinnamate or cinnamic acid dialkylamides is affected by the neutral carbonyl compounds taking part in the synthesis. This effect is explained by breakdown of the intramolecular chelate structure of the reaction adduct and appearance of an open metal form with isomeric partitioning close to that of the neutral adduct. This is further supported by the increased electroconductivity of the reaction mixtures. A chelate mechanism for the reaction in nonpolar medium is postulated which is in good agreement with the low stereoselectivity under kinetic conditions as well as with the effect of the polarity of the solvent on the kinetic stereochemical result.

     

Antibacterial and antioxidant properties of mixed linkage beta-oligosaccharides from extracted β-glucan hydrolysed by Penicillium occitanis EGL lichenase

The aim of this study was first to ascertain the chemical composition and the physicochemical properties of cereal extracted β-glucan from barley flour. Secondly, to assess the antioxidant properties and the antibacterial properties of extracted β-glucan hydrolysates. The proximate composition, FT-IR and scanning electron microscopy of extracted β-Glucan were studied. Hydrolysates from extracted β-glucan, obtained by lichenase EG_L from Penicillium occitanis, were a mixed linkage beta-oligosaccharides (MLBO) of trisaccharides and tetrasaccharides. MLBO showed a DPPH radical scavenger with IC50 about 1.8 ± 0.01 mg/mL whereas the IC50 of extracted β-glucan was about 5 ± 0.01 mg/mL. MLBO showed a high antioxidative capacity (175 μmol/mL α-tocopherol equivalents) at 5 mg/mL. The antimicrobial activity was confirmed against all tested bacteria especially at 20 mg/mL of MLBO while no inhibition was observed for all the strains used after the addition of either EG_L or extracted β-glucan.     

Building‐Block Approach for the Straightforward Incorporation of a New FRET (Fluorescence‐Resonance‐Energy Transfer) System into Synthetic DNA

The synthesis of the two new phosphoramidites 5 and 8 bearing a carbostyril (=quinolin‐2(1H)‐one) chromophore used as donor entity in our recently developed new FRET (fluorescence‐resonance‐energy transfer) system is described (Schemes 1 and 2) The high stability of the chromophore to basic conditions enables the incorporation of the phosphoramidites directly into DNA during solid‐phase synthesis (Schemes 3 and 4). Since this is also possible for the (bathophenanthroline)ruthenium(II) complex used as acceptor (Scheme 4, Steps d and e), the whole labelling procedure to insert the FRET system into synthetic DNA is straightforward and represents a major improvement to our previous strategy.     

Microbial and enzymatic hydrolysis of tannic acid: influence of substrate chemical quality

Tannic acid is commonly employed as the main component in culture media for the selection of tannase-producing strains. In biotechnological processes it is the favorite substrate used to induce the tannase enzyme in both solid and submerged culture for microbial and/or enzymatic production of gallic acid. However, the results found in literature are inconsistent notwithstanding the strict control of all parameters that rule the bioprocesses. The present work, for the first time, reveals the importance of differences in the quality and chemical profile of tannic acid from different suppliers and their influence on the fungal and enzymatic hydrolytic pattern obtained when it is used as a substrate. A degree of hydrolysis between 64.7 % and 100 % has been determined in different tannic acid samples. The specific growth rate of 0.712 h^?1, 0.792 h^?1, 0.477 h^?1, 0.536 h^?1 for Jalmek®, Faga Lab®, Division Food®, and Riedel de Häen®, respectively, was obtained at the concentration of 80 g L^?1 of each of the tannic acids.     

Production of color centers in PMMA by ultrashort laser pulses

We report here the creation of color centers in commercial, transparent PMMA samples by ultrashort pulses from a Ti:Sapphire laser emitting at 800 nm, with spatial control. Although the 800 nm photon energy is not sufficient to ionize the polymer, the centers are created following a multiphotonic absorption that causes the ionization. We propose that the free electrons quivering motion on the pulse electric field displaces atoms from its equilibrium positions, creating free radicals and double bonds that coalesce into color centers. The absorption and emission spectra of the centers were measured, but a dose-like curve could not be built due to the presence of damages created along with the centers that scatter the excitation and emission lights due to the commercial sample's poor optical quality.     

Structural Characterization of a High-Nuclearity Niobium(V) Carboxylate Cluster Based on Pivalic Acid

We report a novel Nb(V)−carboxylate cluster obtained from reaction of niobium(V) ethoxide and pivalic (trimethylacetic) acid. Single crystal X-ray diffraction data reveal a structure composed of 16 Nb(V) ions featuring oxo-, ethoxy- and pivalate moieties. The new cluster exhibits the highest nuclearity among structurally characterized niobium carboxylates reported to date.     

Versatile low-molecular-weight hydrogelators: achieving multiresponsiveness through a modular design

Multiresponsive low-molecular-weight hydrogelators (LMWHs) are ideal candidates for the development of smart, soft, nanotechnology materials. The synthesis is however very challenging. On the one hand, de novo design is hampered by our limited ability to predict the assembly of small molecules in water. On the other hand, modification of pre-existing LMWHs is limited by the number of different stimuli-sensitive chemical moieties that can be introduced into a small molecule without seriously disrupting the ability to gelate water. Herein we report the synthesis and characterization of multistimuli LMWHs, based on a modular design, composed of a hydrophobic, disulfide, aromatic moiety, a maleimide linker, and a hydrophilic section based on an amino acid, here N-acetyl-L-cysteine (NAC). As most LMWHs, these gelators experience reversible gel-to-sol transition following temperature changes. Additionally, the NAC moiety allows reversible control of the assembly of the gel by pH changes. The reduction of the aromatic disulfide triggers a gel-to-sol transition that, depending on the design of the particular LMWH, can be reverted by reoxidation of the resulting thiol. Finally, the hydrolysis of the cyclic imide moieties provides an additional trigger for the gel-to-sol transition with a timescale that is appropriate for use in drug-delivery applications. The efficient response to the multiple external stimuli, coupled to the modular design makes these LMWHs an excellent starting point for the development of smart nanomaterials with applications that include controlled drug release. These hydrogelators, which were discovered by serendipity rather than design, suggest nonetheless a general strategy for the introduction of multiple stimuli-sensitive chemical moieties, to offset the introduction of hydrophilic moieties with additional hydrophobic ones, in order to minimize the upsetting of the critical hydrophobic-hydrophilic balance of the LMWH.     

Application of Fluorescence to the Study of Crude Petroleum

Crude petroleum oils are complex mixtures of different compounds (mainly organic), which are obtained from an extensive range of different geological sources. The fluorescence of crude petroleum oils derives largely from the aromatic hydrocarbon fraction, and this fluorescence emission is strongly influenced by the chemical composition (e.g., fluorophore and quencher concentrations) and physical characteristics (e.g., viscosity and optical density) of the oil. The fluorescence spectroscopy (FS) is increasingly used in petroleum technology due the availability of better optical detection techniques, because FS offers high sensitivity, good diagnostic potential, and relatively simple instrumentation. In this work we analyzed crude petroleum at different dilution in Nujol, a transparent mineral oil. The main objective of this work was to verify the possibility to measure crude oil emission spectroscopic without use of volatile solvents. The mixtures of nujol with different -crude oil concentrations were measured with a 10 mm optical path cuvette thus simplifying the fluorescence spectroscopy signal detection. The emission spectra were obtained by exciting the samples with a 400 W Xenon lamp at 350 nm, 450 nm and 532 nm. The emissions of the samples were collected perpendicularly with the excitation axis.     

The synthesis of 4-benzylamino-6-methyl-1H-pyrrolo[3, 2-c]pyridine and 4-benzylamino-6-methyl-1H-pyrrolo[2, 3-b]pyridine

4-Benzylamino-6-methyl-1H-pyrrolo[3,2-c]pyridine ( 2 ) and 4-benzylamino-6-methyl-1H-pyrrolo[2,3-b]pyridine ( 3 ) were synthesized as deaza analogues of the anxiolytic agent 4-benzylamino-2-methyl-7H-pyrrolo[2,3-d]pyrimidine ( 1 ). The 1-deaza analogue (2) was prepared via a multi-step procedure from a pyrrole precursor, 1-benzyl-2-formylpyrrole ( 4 ) while the 3-deaza analogue 3 was synthesized from a pyridine precursor, 2-amino-3,6-dimethylpyridine ( 12 ).     

ACTION DES HYDRAZINES ET DE L'HYDROXYLAMINE SUR QUELQUES PHOSPHONATES β, β-BIFONCTIONNALISES: SYNTHESE DE PHOSPHONOAMINOPYRAZOLES ET ISOXAZOLES

Abstract

Reaction of hydrazines and hydroxylamine with β, β-bifunctionalized phosphonates 1 and 1′ leads to phosphoaminopyrazoles and isoxazoles 2 3, 4 and 5. The structure of all obtained products was confirmed by NMR and IR spectroscopy.