Strukturelle Untersuchungen einiger neutraler Komplexe des zweiwertigen Molybdäns

Unit cell parameters have been calculated from x-ray powder diffraction data of Mo₂Br₄ Py ₄ (A), Mo₂I₄ Py ₄ (B), Mo₂I₄ Pic ₄ (C), Mo₂(SCN)₄ Py ₄ (D) and Mo₂(SCN)₄ Pic ₄ (E), A, B and C crystallize tetragonal. A witha=9,4₂,c=15,O₂ Å; B witha=9,4₆,c=14,9₈ Å and C witha=9,6₆ andc=15,7₂ Å D and E crystallize orthorhombic. D witha=10,0₉,b=9,1₄,c=15,0₈ Å; E witha=10,2₂,b=9,4₁ andc=15,1₅ Å.Py=pyridine,Pic=4-methylpyridine.

     

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.     

Effect of molecular weight on synthesis and surface morphology of high-density poly(ethylene glycol) grafted layers

This work describes studying the permanent grafting of carboxylic acid end-functionalized poly(ethylene glycol) methyl ether (PEG) chains of different molecular weights from the melt onto a surface employing poly(glycidyl methacrylate) ultrathin film as an anchoring layer. The grafting led to the synthesis of the complete PEG brushes possessing exceptionally high grafting density. The maximum thickness of the attached PEG films was strongly dependent on the length of the polymer chains being grafted. The maximum grafting efficiency was close to the critical entanglement molecular weight region for PEG. All grafted PEG layers were in the "brush regime", since the distance between grafting sites for the layers was lower than the end-to-end distance for the anchored macromolecules. Scanning probe microscopy revealed that the grafting process led to complete PEG layers with surface smoothness on a nanometric scale. Practically all samples were partly or fully covered with crystalline domains that disappeared when samples were scanned under water. Due to the PEG hydrophilic nature, the surface with the grafted layer exhibited a low (up to 21 degrees ) water contact angle.