Preparation of 1,3-dienyl organotrifluoroborates and their Diels-Alder/cross-coupling reactions

2-BF₃-substituted 1,3-butadienes with potassium and tetrabutyl ammonium counterions have been prepared in gram quantities from chloroprene via a simple synthetic procedure. The potassium salt of this new main group element substituted diene has been characterized by ¹H, ¹³C, ¹¹B, and ¹⁹F NMR and the tetra n-butyl ammonium salt was also characterized by X-ray crystallography. Diels-Alder reactions of these dienes with dienophiles such as ethyl acrylate, methyl vinyl ketone, and N-phenylmaleimide are reported as well as subsequent Pd-catalyzed cross-coupling reactions of those Diels-Alder adducts. 4-Phenyl-2-BF₃-substituted 1,3-diene was prepared by magnesium-halogen exchange from the corresponding 2-bromo and iodo dienes. The 4-phenyl-2-bromo-1,3-butadiene was also characterized by X-ray crystallography. 4-Phenyl-2-BF₃-1,3-butadiene was used in Diels-Alder/cross-coupling reactions and the product of a Diels-Alder reaction with N-phenylmaleimide followed by cross-coupling with 4-bromo-benzonitrile was also characterized by X-ray crystallography.     

Chemoselective and stereoselective synthesis of gem-difluoro-β-aminoesters or gem-difluoro-β-lactams from ethylbromodifluoroacetate and imines during Reformatsky reaction

The chemoselective and stereoselective synthesis of gem-difluoro-β-aminoesters or gem-difluoro-β-lactams was investigated from ethylbromodifluoroacetate and imines during Reformatsky reaction. Influence of various reaction parameters, such as nature of the amine part, nature of the chiral auxiliary, was evaluated. High levels of stereoselectivity (up to 98%) were obtained for gem-difluoro-β-aminoesters and gem-difluoro-β-lactams using either (R)-phenylglycinol or (R)-methoxyphenylglycinol.     

Synthesis of beta‐proline like derivatives and their evaluation as sodium channel blockers

A simple and convenient procedure for the preparation of beta‐proline like derivatives in their racemic and optically active forms has been reported. The compounds have been screened for their potential activity as sodium channel blockers.     

Crystallization of binary carboxylic acids characterized with streaming potential measurement

The streaming potential of supersaturated solution of binary carboxylic acids, which have even carbon atoms, was determined to characterize crystallization under different temperatures. The value of the streaming potential was related to the type and solubility of the acids and the starting temperature of crystallization, and was easily influenced by the pressure difference of the liquid or the rate of temperature decline. When the temperature was declined to the point where a crystal nucleus appeared, the streaming potential reached the minimum. Thereafter, as the temperature was sequentially lowered, some minicrystals grew, and the streaming potential presented an ascendant tendency. The higher the starting temperature of the acids saturated solution, the higher is the temperature corresponding to the streaming potential minimum. The less the carbon atoms in the acids and the greater the solubility of the acids are, the higher is the temperature of the streaming potential minimum. Copyright © 2007 John Wiley & Sons, Ltd.     

Oxytetracycline as environmental contaminant in arable lands

Oxytetracycline (OXY) is a broad-range antimicrobial routinely used in pig production, at doses in the range of few g/kg of medicated feed, during the weaning period. It could persist at ppm level in pig liquid manure that routinely is used for organic fertilisation. In the present work we describe a methodology to study OXY environmental fate in arable land where crops are cultivated for animal feeding purposes. A liquid-liquid extraction followed by metal chelate affinity chromatography was applied to environmental samples of manures and soils drawn within a case-control study. Extracts were then analysed by high performance liquid chromatography with UV/DAD detection, using a reverse phase column, and expressing the results as 4-epioxytetracycline epimer. Results indicate OXY is well retained at mg kg(-1) levels in soil exposed to contaminated pig manure fertilisation. Such compartment could constitute an abiotic reservoir for the systemic and/or for the external contamination of corn.     

Quantitative determination of amoxicillin in animal feed using liquid chromatography with tandem mass spectrometric detection

A liquid chromatographic tandem mass spectrometric (LC-MS/MS) method for the determination of amoxicillin (AMO) in animal feed was developed and validated. The method was used to examine the quality requirements for products intended for incorporation into animal feedingstuffs (medicated premixes), as documented in the EMEA/CVMP/080/95-Final guideline. After addition of the internal standard (ampicillin), the medicated feed samples were extracted using a 0.01 M potassium dihydrogenphosphate buffer solution (pH 4.5), followed by a centrifugation and filtration step. An appropriately diluted aliquot of the extract was analysed on a PLRP-S polymeric column (150 mm x 2.1 mm i.d., 100 A) using a mixture of 0.1% formic acid in water and acetonitrile as the mobile phase. Gradient elution was performed at a flow-rate of 0.2 mL min(-1). The mass spectrometer was used in the positive electrospray ionization MS/MS mode. The LC-MS/MS method was validated for linearity, trueness, precision, limit of quantification, limit of detection and specificity. The results fell within the ranges specified. The method was used for the homogeneity and stability testing of AMO in a commercial medicated feed. Some extracts were also injected onto a LC-UV and LC-fluorescence instrument (after pre-column derivatization with a formaldehyde reagent). These experiments showed that the LC-MS/MS method was superior with regard to speed of analysis, selectivity and sensitivity.     

A liquid chromatography – tandem mass spectrometry method to measure a selected panel of uremic retention solutes derived from endogenous and colonic microbial metabolism

Chronic kidney disease (CKD) is associated with an increased risk of mortality and cardiovascular disease, which is, at least partly, mediated by the accumulation of so-called uremic retention solutes. Although there has been an increasing interest in the behavior of these solutes, derived from both the endogenous and colonic microbial metabolism, methods to simultaneously and accurately measure a broad panel of relevant uremic retention solutes remain scarce.     

Synthesis of titanium dioxide nanoparticles with mesoporous anatase wall and high photocatalytic activity

Mesoporous titanium dioxide nanosized powder with high specific surface area and anatase wall was synthesized via hydrothermal process by using cetyltrimethylammonium bromide (CTAB) as surfactant-directing agent and pore-forming agent. The resulting materials were characterized by XRD, nitrogen adsorption, FESEM, TEM, and FT-IR spectroscopy. The as-synthesized mesoporous TiO2 nanoparticles have mean diameter of 17.6 nm with mean pore size of 2.1 nm. The specific surface area of the as-synthesized mesoporous nanosized TiO2 exceeded 430 m2/g and that of the samples after calcination at 600 degrees C still have 221.9 m2/g. The mesoporous TiO2 nanoparticles show significant activities on the oxidation of Rhodamine B (RB). The large surface area, small crystalline size, and well-crystallized anatase mesostructure can explain the high photocatalytic activity of mesoporous TiO2 nanoparticles calcined at 400 degrees C.