Substitution of phosphine in the complex [RhCl(cyclooctadiene)(phosphine)] by 1-hexene

Summary The substitution of phosphine in the [RhCl(COD)(phosphine)] complex (1), where phosphine is PPh₃ or 1/2 BPS-2 [bis(diphenylphosphinoethyl)tetramethyldisiloxane] and COD is cycloocta-1,5-diene, by 1-hexene is a two-step reversible reaction. All individual rate constants and equilibrium constants were determined spectrophotometrically and associative mechanism occurring via the formation of five-coordinated [RhCl(COD)(phosphine)(1-hexene)] (2) was inferred. The rate-determining step changes from the first- to the second-one as the concentration of 1-hexene increases. An excess of phosphine shifts the equilibrium towards complex (2).     

Multipeak distributions of first passage times in bistable dynamics in a model of a thermochemical system.

A master equation is used to study transitions between the stable limit cycle and stable focus in the two-variable bistable system. The distribution function of the mean first passage time between these attractors and the relative dispersion of the mean first return time from the stable focus to itself as a function of the intensity of fluctuations are calculated and discussed. A coherence resonance is observed for the return time from the focus to itself.     

Evolution and potential of the BiAS procedure for the determination of non-ionic surfactants

The evolution of the BiAS procedure is reviewed and its standard recommended version was compared with the modified version combined with the indirect tensammetric method (BiAS-ITM). New applications of the use of BiAS-ITM for the determination of nonionic surfactants (in the presence of hydrocarbons or adsorbed on particles) and polyethylene glycols were discussed.     

Alkoxy/siloxy group exchange in the system vinyltrialkoxysilane-iridium(I) siloxide complex

A study of reactions of dimeric siloxide iridium complex, [[(cod)Ir(mu-OSiMe3)]2] (1) with vinyltriethoxysilane and vinyltrimethoxysilane has revealed a new type of the reation--alkoxy group transfer from silicon to iridium with a simultaneous transfer of a siloxy group from iridium to silicon--as a result of which vinyldialkoxytrimethyldisiloxane and dimeric alkoxide iridium complex [[(cod)Ir(mu-OR)]2] (3) are formed. The structure of [[(cod)Ir(mu-OEt)]2] (3a) has been solved by X-ray diffraction.     

Fluorogenic reaction between adenine derivatives and chloroacetaldehyde and its application to the determination of 9-(2-chloro-6-fluorobenzyl)adenine in human plasma

A sensitive (1 ng ml^?1) liquid chromatographic method with fluorescence detection is described for the determination of arprinocid and analogous compounds in human plasma. The method is based on chemical derivatization with chloroacetaldehyde to form highly fluorescent derivatives. Extraction of the drug from plasma and separation of the derivative from the reaction mixture are accomplished by solid-phase extraction with two silica cartridges. The effects of pH, solvent, and concentration of the reagents on the efficiency of derivatization were studied. The assay in plasma was validated in the 1–50 ng ml^?1 range. The fluorescent derivatives were synthesized and fully characterized. The derivatives were also found to be efficient as energy acceptors in the oxalate ester/hydrogen peroxide chemiluminescent system.     

Highly stereoselective synthesis, structure, and application of (E)-9-[2-(silyl)ethenyl]-9H-carbazoles

(E)-N-(Silyl)vinylcarbazole has been easily prepared via a new catalytic route, silylative coupling (SC) of vinylcarbazole with vinyltrisubstituted silanes catalyzed by [RuH(Cl)(CO)(PCy3)2]. X-ray structures of two silylvinylcarbazoles as first N-vinylcarbazole derivatives have been resolved. The Pd-catalyzed Hiyama coupling reaction (also as the tandem reaction with SC) of synthesized (E)-N-(triethoxysilyl)vinylcarbazole with iodobenzene has been performed to afford (E)-N-(phenylvinyl)carbazole with high yield and stereoselectivity.     

The solid-phase synthesis of 2-5-linked oligoriboadenylates containing 8-bromoadenine

To increase the accessibility of 8-bromo-2′,5′-oligoadenylates, we developed a synthesis of 2′-5′-linked oligoriboadenylates containing varying numbers of 8-bromoadenosine residues based on the use of a CPG-LCA solid support and the phosphoramidite approach. Although N⁶benzoyl protection was satisfactory for incorporation of nonmodified adenine residues into 2′,5′-oligonucleotides, the effective incorporation of 8-bromoadenine into such 2′,5′-linked oligomers required use of a non acyl protecting group. Amidine protection of the purine exocyclic amino function proved compatible with all aspects of the phophoramidite approach and with the hydroxyl protection groups employed.     

Biosensors based on highly sensitive acetylcholinesterases for enhanced carbamate insecticides detection

This paper presents the construction of amperometric biosensors for the highly sensitive detection of carbamate insecticides based on the inhibition of acetylcholinesterase (AChE). This enzyme was immobilised by entrapment in an optimised sol-gel matrix on TCNQ-modified screen-printed electrodes. The enzyme activity was estimated by measuring the thiocholine produced by the enzymatic hydrolysis of the acetylthiocholine using TCNQ as mediator. Wild and genetically engineered AChEs from Drosophila melanogaster (Dm) were chosen for their high sensitivity towards insecticides, which substantially improves the LOD compared with cholinesterases from other sources. The wild type and three mutant enzymes were tested against three carbamate insecticides: carbaryl, carbofuran and pirimicard. The best LOD were obtained with the Y370A mutant for carbaryl (1 × 10⁻⁸ M), the E69W mutant for pirimicarb (2 × 10⁻⁸ M) and the I161V mutant for carbofuran (8 × 10⁻¹⁰ M). The biosensors were applied to the analysis of two potable water samples.     

Oxidatively truncated docosahexaenoate phospholipids: total synthesis,generation, and Peptide adduction chemistry

The recent immunological detection of extraordinarily high levels of carboxyethylpyrrole (CEP) modifications of proteins from the retinas of individuals with age-related macular degeneration provided presumptive evidence for the involvement of docosahexaenoate-derived oxidatively truncated phospholipids in retinal pathology. To facilitate the in vivo detection and characterization of the chemistry and biological activities of these postulated naturally occurring molecules, a family of oxidatively truncated phospholipids was prepared by total syntheses. Their formation in oxidation reactions of a docosahexaenoate ester of 2-lysophosphatidylcholine (DHA-PC) was also demonstrated. Free radical-induced oxidative cleavage of DHA-PC promoted by myeloperoxidase or copper ions generates similar mixtures of these phospholipids. The most abundant products were 1-palmitoyl-2-succinoyl-sn-glycero-3-phosphatidylcholine (4.7%) and 2-(6-carboxy-4-oxohex-5-enoyl)-1-palmitoyl-sn-glycero-3-phosphatidylcholine (1.7%). Both of these oxidatively truncated phospholipids are homologues of biologically active arachidonate-derived phospholipids. A minor product from DHA-PC, 2-(4-hydroxy-7-oxohept-5-enoyl)-1-palmitoyl-sn-glycero-3-phosphatidylcholine (0.4% yield), reacted with the epsilon-amino group of a peptide lysyl residue to produce a CEP derivative in 0.7% yield. These observations support the previous conclusion, based on immunological evidence, that CEPs are generated by the reaction of an oxidatively truncated phospholipid with proteins in the retina and further indicate that CEP protein modifications probably represent only a tiny fraction of the products generated upon oxidative damage of DHA-PC in photoreceptor disk membranes.