Selected Reactions of Diethyl (E)‐1‐(bromomethyl)‐2‐cyanovinylphosphonate with Secondary and Tertiary Amines

An easy regio‐ and stereoselective synthesis of new nitrogenous molecules 2a–e was successfully realized via an effective coupling reaction of diethyl (E)‐1‐(bromomethyl)‐2‐cyanovinylphosphonate 1 with various secondary amines in methanol. Hence, the use of less and more bulky secondary amines gives rise, respectively, to the successive (S_N2′) substitution–isomerization and (S_N2) substitution derivatives 2a–c and 2d–e . Moreover, the addition of tertiary amines to 1 in the same reaction conditions, leads exclusively to the rearranged vinyl ether 3 in good yields.     

Electroconvection between coaxial cylinders of arbitrary ratio subjected to strong unipolar injection

This study deals with the electroconvection phenomenon that takes place in a dielectric liquid layer placed between two annular electrodes and subjected to the action of an electric field.The full set of governing equations describing the combined Electro-Hydro-Dynamic (EHD) flow is directly solved with the finite volume method.The development of electroconvective motion is investigated in details in the case of strong injection when the emitter electrode is the inner cylinder.We first examine the stability of such flow. As in the plane–plane configuration we have highlighted the existence of a linear and non-linear critical electric Rayleigh numbers giving rise to a hysteresis loop. The flow structure under the effect of the electric field is analyzed and the distribution of electric charge density is presented. In particular we investigate the effect of various parameters involved in this configuration, such as the radius ratio, injection strength and electric Rayleigh number.A multicellular convective pattern is particularly observed and it is shown that the number of cells is increased when the annular gap is narrower. Finally a significant increase of the rotational speed of the vortex with the electric Rayleigh number is recorded.     

Raman study of cation effect on sulfate vibration modes in solid state and in aqueous solutions

Raman spectra of potassium, sodium, and ammonium sulfates (K₂SO₄, Na₂SO₄, and (NH₄)₂SO₄) are reported and analyzed. These sulfates have been investigated under two states: solid (anhydrous and hydrated) salts and aqueous solutions. The effects of monovalent ions (K⁺, Na⁺, and NH₄⁺) and hydration on the position of Raman lines assigned to internal vibrations of sulfate anion SO₄²⁻ are discussed. In solid salts, the line position of each Raman peak is shown to decrease with increasing radius of the cation. The main ν₁ mode of sulfate molecule is particularly affected. It is emphasized that this sensitivity in solid sulfates vanishes in aqueous solutions. As a consequence, this mode can be probed by Raman spectroscopy as the main signature of SO₄²⁻ to determine its concentration within a single calibration. Copyright © 2013 John Wiley & Sons, Ltd.     

Impact of rough silicon buffer layer on electronic quality of GaAs grown on Si substrate

The electronic and the structural properties of n-GaAs layers grown on rough surface of silicon substrate by molecular beam epitaxy (MBE) has been investigated by photoluminescence (PL), time resolved photoluminescence (TRPL) and high resolution X-ray diffraction (HRXRD). The relationship between electronic and structural properties of the n-GaAs layer was checked, showing that the defect density is a strong cause for trapping the minority carriers. The impact of introducing intermediate rough silicon layer between silicon substrate and n-GaAs layer on the electronic properties was observed, showing that the structure grown on rough Si involves higher lifetime than those developed on flat silicon substrate. Such structure could be used for economic solar cells fabrication.     

Cleavage of the N-PChd group from protected amino acids and peptides by cathodic reduction

Amino acid and peptide esters protected by the PChd group can be deprotected cathodically under mild conditions.     

Action des hydrazines fluoroalkylées sur les phosphoallènes: synthèse d’hydrazones N-fluoroalkylées β-phosphonatées

Ten phosphorylated β-hydrazones of structure R₂P(O)C(NNHR_F)CHR₂′ were prepared in 54-91% yield by heating the allenes R₂P(O)CHCCR₂′ with fluorinated hydrazines H₂NNHR_F in chloroform or methanol [R=Ph, OCH₂C(Me)₂CH₂O or OCH₂C(Me)(Pr)CH₂O, R′=H or Me and R_F=CH₂CF₃ or C₆F₅]. Two cyclohexyl derivatives were prepared similarly from R₂P(O)CHCCy. The triphenyl derivatives Ph₂P(O)CH₂C(NNHCH₂CF₃)Ph and Ph₂P(O)CH₂C(NNHC₆F₅)Ph were made in 91 and 68% yield by heating the ketones Ph₂P(O)CH₂C(O)Ph with an ethanol solution of the corresponding hydrazines. The stereochemistry of the hydrazones was determined by multinuclear NMR experiments. Compounds with C(NNHR_F)Me groups exist as a mixture of Z and E isomers, with the Z form predominating (fluorinated group syn to phosphorus). Those with C(NNHR_F)CHMe₂, C(NNHR_F)Cy or C(NNHR_F)Ph groups were formed selectively, the Z isomers being the only products. The results are explained by steric hindrance, the bulkier isopropyl, cyclohexyl or phenyl group disfavouring the E configuration. , , , NMR data, coupling constants and IR data are reported.     

A conductometric biosensor for the estimation of the number of cleaving sites in peptides and proteins

A conductometric enzyme biosensor using proteinase K was developed and then tested to relate its electrical signal to the number of proteinase K hydrolysis sites in bovine serum albumin (BSA) and angiotensin, a ten amino acid peptide, with one cleaving site.The conductometric sensor presents a large linear range of response for BSA and angiotensin ranging from 0.5 to 8 mg/l and from 4 to 8 mg/l, respectively. For a same tested concentration (mg/l), the response for native BSA is 12 times higher than for angiotensin. Aspartam was used as negative test and no response was obtained with the proteinase K biosensor. The conductometric sensor permitted also to detect difference on enzyme activity on native and non-native BSA, a response three times higher was obtained for non-native BSA.     

Two‐Step Synthesis of Multifunctional γ‐Lactams from γ‐Lactone

We present herein an efficient and rapid method for the synthesis of N,1‐dialkyl‐4‐(2‐hydroxyethyl)‐5‐oxopyrrolidine‐3‐carboxamides based on the conversion of γ‐lactone to γ‐lactam via the conjugate addition of primary amines to an ethyl α‐functionalized acrylate followed by intramolecular cyclization.     

Development and validation of a turbidimetry method for hydrogen sulphide evaluation in effluents of phosphoric acid production unit

The aim of this study was to develop and validate a simple, new and efficient method for the analysis of hydrogen sulphide (H₂S) released from the effluents of phosphoric acid production units. H₂S sampling was performed by absorption of the industrial gas into a cadmium acetate absorbing solution. The formed cadmium sulphide (CdS), as a result of a chemical reaction, was analysed by turbidimetry. A methodical validation study of the proposed method was performed according to the requirements of ISO 17025 standards. The proposed method was demonstrated to be precise, linear and accurate over a concentration range of 6.91–92.16 mg/l. Detection and quantification limits were equal to 5.09 mg/l and 6.91 mg/l, respectively. Sample analysis had to be performed within 48 h of the sampling step. The turbidimetry method was applied successfully to the industrial gaseous effluents and can be considered as an economical alternative to the iodometric method.