1:1 Crystal Complexes of 2',6'‐Dimethoxyflavone with 3‐Bromo and 3‐Chloro‐2,6‐dimethoxybenzoic Acid

The structures of two solid inclusion compounds with the 2',6'‐dimethoxyflavone host molecule, 1, were investigated by single‐crystal X‐ray analysis. Both compounds, 1�3‐bromo‐2,6‐dimethoxybenzoic acid (1:1) and 1�3‐chloro‐2,6‐dimethoxybenzoic acid (1:1) crystallize in the centrosymmetric group P‐1. The complexation involves an intermolecular hydrogen bond between the carbonyl group of the flavone and the acidic hydrogen of the acid.     

An interlaboratory study to evaluate potential matrix reference materials for herbicides in water

Matrix reference materials (MRM) are essential tools for the validation of analytical protocols. Nowadays, there are no such materials for the determination of herbicides in water. Pesticides stored in acetonitrile and stored on solid phase extraction (SPE) cartridges previously percolated with a water sample spiked with triazines and phenylureas have proven to be good candidates for reference materials because of their satisfactory stability under appropriate temperature conditions. To evaluate the behaviors of these materials containing pesticides and to be analyzed by liquid chromatography, a collaborative study including 15 laboratories has been organized. Observed reproducibility on candidate materials after the removal of extreme results was 16.1% for the vials with pesticides in acetonitrile (at around 0.125 mg/L) directly analyzed, 29.2% for a water sample spiked with the pesticides (at around 0.5 microg/L) analyzed after preconcentration on a cartridge and 26.7% for the cartridges previously percolated with a water containing the pesticides (250 mL at around 0.5 microg/L for each pesticide) analyzed after elution. Such dispersion values are quite compatible with the requirement of a further certification for such materials.     

A simple access to ω-aminoalkyltrialkoxysilanes: Tunable linkers for self-organised organosilicas

A simple route to ω-aminoalkyltriethoxysilanes with variable alkylene chain lengths, (EtO)₃Si(CH₂)_nNH₂ (n = 5, 11) is described. These silyl linkers have been used to prepare urea-based compounds with H-bonding and hydrophobic interactions which enable the self-assembly of the molecules. These molecular precursors are suitable for the obtention of nano-structured hybrid silicas.     

Acquired biodegradability of polyethylenes containing pro-oxidant additives

Biodegrability of high density polyethylene film (HDPE) and low density polyethylene film (LDPE) both containing a balance of antioxidants and pro-oxidants was studied with defined microbial strains particularly with Rhodococcus rhodochrous and Nocardia asteroides in mineral medium. After an abiotic pre-treatment consisting of photooxidation and thermo-oxidation corresponding to about 3 years of outdoor weathering the samples were inoculated, incubated up to 200 days and during the period their metabolic activities were followed by measuring adenosine triphosphate content. Simultaneously the cultures were also monitored by optical microscopy and FTIR spectroscopy. The first initial phase of fast growth caused by the presence of low molecular extractable compounds was followed by a long period of stabilized metabolic activity suggesting that microorganisms continued to gain energy from the substrate but evidently at a much slower rate. Complementary analysis performed at the end of incubation revealed that during the experiment time biodegradation processes probably affected surface layer of materials only.     

Molecularly imprinted polymer for solid‐phase extraction of ephedrine and analogs from human plasma

A molecularly imprinted polymer (MIP) was synthesized and evaluated to selectively extract ephedrine from human plasma. The MIP synthesis was performed in chloroform with methacrylic acid as a functional monomer and the target alkaloid as a template molecule. The resulting MIP was applied to the selective extraction of ephedrine from a pure aqueous medium. A recovery about 74% was obtained using the MIP with only 7% on the nonimprinted polymer (NIP). A very straightforward selective SPE procedure was then successfully applied to the direct extraction of ephedrine from spiked human plasma with a high extraction recovery (68%) on the MIP with no recovery on the NIP. Moreover, the MIP was used for the selective extraction of catecholamine neurotransmitters, i.e. adrenaline and noradrenaline.     

Selective extraction of organophosphorus nerve agent degradation products by molecularly imprinted solid-phase extraction

The analysis of alkyl alkylphosphonic acids, the degradation products of V and G nerve agents as VX, Sarin or Soman, is an important task for the verification of compliance to the Chemical Weapons Convention. The detection of these contaminants at low concentration levels is often difficult in complex matrices due to the amount of interfering substances. Molecularly imprinted solid-phase extraction technique should allow a selective extraction of these compounds from complex samples, and thus make their detection easier. Two molecularly imprinted polymers (MIPs) prepared with methacrylic acid (MAA) as monomer and pinacolyl methylphosphonic acid (PMPA) as template molecule were synthesised and tested. The first polymer, MIP A, was prepared with ethylene glycol dimethacrylate (EGDMA) in dichloromethane. The second polymer, MIP B, was synthesised using trimethylolpropane trimethacrylate (TRIM) in acetonitrile. To evaluate the selectivity provided by these MIPs, the retention of the ethyl methylphosphonic acid (EMPA) target molecule was studied in parallel on a non-imprinted polymer (NIP). While MIP A does not show any difference compared to NIP A, a good selectivity was obtained for MIP B. After the optimisation of the extraction process, 60% of EMPA can be removed from the NIP B without affecting the retention on the MIP B. A recovery of extraction of 93% was then obtained on the MIP B. Its capacity was then measured and corresponds to 97 microg of EMPA per gram of MIP. Finally, the selectivity of MIP B was clearly demonstrated by applying it to the clean-up of a soil extract spiked with EMPA.     

Stereocontrolled synthesis and cycloaddition of 1,2,4-trioxygenated 1,3-dienes

A new stereocontrolled synthetic pathway to 1,2,4-trioxygenated 1,3-dienes from pyruvic aldehyde dimethyl acetal (14a) is described. Reacting the cyclohexylamine-derived imine of this starting material with chloroalkyl ethers under basic conditions affords ketoacetals 18-20, which were then transformed into eight different enoxysilanes 12. A delta-elimination triggered by tert-butyllithium yields 1,2,4-trioxygenated dienes 13. Increasing the bulkiness of the silyloxy group or that of the acetal moiety leads stereoselectively to the (1E,3E) or (1Z,3E) isomers of 13, respectively. Hyperbaric [4 + 2] cycloadditions between 13 (13c, 13d, 13g) and N-methylmaleimide or methyl- and phenylacrylates give access to the expected cycloadducts with fine stereo- and regiocontrol.     

On the gene delivery efficacies of pH-sensitive cationic lipids via endosomal protonation: a chemical biology investigation

In an effort to probe the importance of endosomal protonation in pH-sensitive, cationic, lipid-mediated, non-viral gene delivery, we have designed and synthesized a novel cholesterol-based, endosomal pH-sensitive, histidylated, cationic amphiphile (lipid 1), its less pH-sensitive counterpart with an electron-deficient, tosylated histidine head group (lipid 2) as well as a third new cholesterol-based, cationic lipid containing no histidine head group (lipid 3). For all the novel liposomes and lipoplexes, we evaluated hysicochemical characteristics, including lipid:DNA interactions, global surface charge, and sizes. As anticipated, lipid 2 showed lower efficacies than lipid 1 for the transfection of 293T7 cells with the cytoplasmic gene expression vector pT7Luc at lipid:DNA mole ratios of 3.6:1 and 1.8:1; both lipids were greatly inhibited in the presence of Bafilomycin A1. This demonstrates the involvement of imidazole ring protonation in the endosomal escape of DNA. Conversely, endosome escape of DNA with lipid 3 seemed to be independent of endosome acidification. However, with nuclear gene expression systems in 293T7, HepG2, and HeLa cells, the transfection efficacies of lipid 2 at a lipid:DNA mole ratio of 3.6:1 were found to be either equal to or somewhat lower than those of lipids 1 and 3. Interestingly, at a lipid:DNA mole ratio of 1.8:1, lipids 2 and 3 were remarkably more transfection efficient than lipid 1 in both HepG2 and HeLa cells. Mechanistic implications of such contrasting relative transfection profiles are delineated.