Reaction of hexafluoropropene with halogenoalkanes

Insertion of hexafluoropropene under thermal and/ or photochemical conditions occurs into C-H bonds of the halogenomethanes MeCl, CH₂Cl₂, CHCl₃, MeF, CH₂F₂ and CHF₂Cl and the fluoroethanes EtF, MeCHF₂ and MeCF₃, into CH and CCl bonds of the monochloroalkanes EtCl, MeCHFCl, prⁿCl, prⁱCl, Bu^tCl and BuⁱCl and into CCl bonds of allyl chloride and the chloroalkanes CH₂ClCH₂Cl, MeCHCl₂, CH₂ClCHCl₂ and MeCCl₃.     

Measurement of franck-condon factors for the υ′= 0 progression in the BX system of PO

Laser fluorescence of PO produced in a microwave discharge through organophosphonate esters has been studied. The flourescence was pumped in the B²Σ⁺-X²Π 3250 Å system. Relative intensities of fluorescence for the υ′= 0 progression were measured. These intensities were used to derive Franck-Condon factors for the υ′= 0 progression.     

Polynitroalkyltetrazoles

5-(Fluorodinitromethyl)-and 5-(trinitromethyl)tetrazoles were synthesized in the reactions of fluorodinitroacetonitrile with sodium azide, and trinitroacetonitrile with trimethylsilyl azide, respectively, and characterized as their ammonium salts.     

Mechanistic and kinetic studies on the photoinitiated polymerization of tetrahydrofuran

Polymerization of tetrahydrofuran (THF) (bulk) promoted by a free radical source, 2,2-dimethoxy-2-phenyl acetophenone (DMPA), in the presence of 4,4′-di-(methylphenyl)iodonium hexafluorophosphate was studied in detail. Rate dependence of the polymerizing system on both DMPA and the iodonium salt was studied dilatometrically. Rate saturation for the iodonium salt was attributed to the formation of iodobenzene, which may react with propagating cations to form an iodonium salt. DMPA was shown to be an efficient transfer agent in the cationic polymerization of THF. A transfer constant for DMPA was estimated to be 2.8 and, whilst the precise details of the overall mechanism cannot be deduced from the present results, it may result in functionalized polytetrahydrofuran chains having photochemically active end groups.     

Aminopropargyl derivative of terpyridine-bis(methyl-enamine) tetraacetic acid chelate of europium (Eu (TMT)-AP3): a new reagent for fluorescent labelling of proteins and peptides

The synthesis and photophysical properties of a new terpyridine-based europium(III) chelate (Eu (TMT)-AP3) designed for peptide and protein labelling in aqueous solution phase is described. In order to obtain a stable, easy to handle, versatile and efficient labelling agent, a reactive aminopropargyl arm has been introduced onto the terpyridine moiety. As preliminary biochemical applications the chelate has been 1) efficiently covalently attached onto a representative biomolecule-monoclonal antibody-and 2) converted into iodoacetamido and aldehyde derivatives, and the photoluminescent Eu (TMT)-AP3 was grafted onto cysteine and lysine amino acid residues respectively. These two different solution phase labelling methods yielded original fluorogenic FRET based probes suitable for "in vitro" detection of caspase-3 protease, a key mediator of apoptosis of mammalian cells.     

New antitumour active platinum compounds containing carboxylate ligands in trans geometry: synthesis, crystal structure and biological activity

New asymmetric trans-platinum(II) complexes, composed of an isopropylamine, an azole and two carboxylate leaving groups, are presented. The crystal and molecular structures of one of the complexes has been determined and the cytotoxicity and reactivity with 5'-guanosine monophosphate is reported. The complexes show a reduced reactivity, but no decrease in cytotoxic activity compared to their chloro-counterparts. Furthermore the complexes largely overcome cisplatin resistance, they therefore present an interesting class of antitumour active trans-platinum complexes.     

Dihydrobis(methimazolyl)borate and methimazolyl complexes of titanium

The first poly(methimazolyl)borato complex of group 4, [Ti([double bond, length as m-dash]NCMe(3)){H(2)B(mt)(2)}(2)](mt = methimazolyl), results from the reaction of Na[H(2)B(mt)(2)] with [Ti([double bond, length as m-dash]NCMe(3))Cl(2)(py)(3)] and features both kappa(2)-S,S' and kappa(3)-H,S,S' coordination of H(2)B(mt)(2) ligands coincident within the same molecule.