Fast atom bombardment mass spectrometric analysis of the partial ozonolysis products of poly(isoprene) and poly(chloroprene)

The low molecular weight compounds formed by partial ozonolysis of poly(isoprene) and poly(chloroprene) were analyzed by fast atom bombardment mass spectrometry (FABMS). In the poly(chloroprene) case, the ozonized mixtures were treated with piperidine before the MS analysis to transform in amide end groups the reactive acyl chlorides formed by the cleavage of double bonds along the main chain. Only one family of compounds having carboxyl and ketone or carboxyl and amide end groups were obtained from the ozonolysis of poly(isoprene) and poly(chloroprene), respectively. The assigned structures were confirmed by FAB-MS analysis of the GPC separation fractions [poly(chloroprene)] or by FAB-MS of the KOH-doped ozonolysis mixtures [poly(isoprene)]. It has been also ascertained, by GPC experiments, that poly(chloroprene) decomposes more rapidly than poly(isoprene) and poly(butadiene).     

Conformational behavior of nonfused biheterocycles: Part XVI. Isomeric phenyl-tetrazines and bitetrazines

We present here an ab-initio STO-3G and advanced semiempirical AM1 calculation for the structure and the conformational behavior of phenyltetrazine and bitetrazine molecules. Results for phenyltetrazine isomers show that in the absence of H-H interactions, the preferred conformation is the planar one. Instead, in the case of bitetrazines, the systems dominated by the lone pair-lone pair interactions are not planar. In the presence of direct H-H interaction as for 5-5-1,2,3,4 bitetrazine, the antiplanar conformation is the preferred one. Comparison with other systems (including one or more nitrogen lone pairs) shows that the compounds with the same ortho substituents have very similar conformational behavior irrespective of their composition. The AM1 results indicate that this method is able to give reliable conformational information for compounds in which H-H interactions are involved. A Fourier expansion of the torsional potential suggests that the first two terms fit the calculated torsional potentials well except in the case of two H-H interactions in the same molecule.     

A spectroscopic study of cobalt(III) furyldioximates

Summary The electronic properties of a series of cobalt(III)trans-furyldioximato-complexes of the type [CoB(FH)₂X] (B=NH₃, X=Cl, Br, I or NO₂; B=pyridine (py) or thiocarbamide (thio), X=Cl or Br; B=imidazole (imid), X=Br), [Co(FH₂)(FH)Cl₂] and [Co(thio)₂(FH)₂]NO₃ were studied by i.r., u.v. and¹H and¹³C n.m.r. spectra The results were compared with those from the corresponding dimethylglyoximato-complexes. It was concluded that -conjugation over the equatorial plane in the furyldioximates is greater than in the dimethylglyoximates. There is some evidence of thetrans-influence of the anionic ligands in the ammines which are in the order NO ₂ ^– >Br^–>Cl^–.     

Hydrophobic-phase-modified fused-silica columns for capillary electrophoresis

Coated capillaries modified with a hydrophobic layer were developed. Linear hydrocarbons and ethylbenzene modified surfaces greatly improved the electrophoretic performance of the capillaries. The column efficiency for organic compounds reached as high as 327 000 theoretical plate numbers per meter on a 50 microm I.D. linear hydrocarbon (C6) surface treated fused-silica capillary column. This value did not change during 50 repeated analyses and the columns showed strong stability against 0.1 M NaOH and 0.1 M HCl. The relative standard deviation of the run-to-run, day-to-day, and capillary-to-capillary coating with hydrophobic layer showed values of < or =2.5%, and good reproducibility. The separations of four aromatic amines and six pharmacological amines at pH 2.5 is reported.     

Mechanical properties and molecular mobility in oriented polyolefines

The static modulus of elasticity (E) and the correlation time of rotation ( _c ) of 2,-2,6,6-tetramethylpiperidine-1-oxyl are studied as a function of the temperature (210<T <350°K) for oriented films of isotactic polypropylene and polyethylene of high and low density.E and _c change both upon heating and polymer orientation; this result indicates that sample properties are influenced by the microstructure of the amorphous phase where probes are localized.     

Eptastigmine,nicotinamide and nicotinic acid determination using an inhibition enzyme sensor; application to pharmaceutical analysis

An enzyme inhibition biosensor, developed in our laboratory and previously used for the analysis of compounds with anticholinesterase activity (e.g. physostigmine, neostigmine, pyridostigmine nicotine and organophosphorus compounds) has now been tested for the analysis of another recently synthesized cholinesterase inhibitor, i.e. eptastigmine. In addition nicotinic acid and nicotinamide, although displaying weaker inhibition properties, were also tested in pharmaceutical products using the same inhibition enzyme sensor. The biosensor consisted of a hydrogen peroxide amperometric electrode coupled to a functionalised nylon membrane chemically bonding both the enzymes butyrylcholinesterase and choline oxidase; a butyrylcholine standard solution in glycine buffer acted as substrate. The response of the system to all the inhibitors considered was characterised completely and the analysis of several pharmaceutical formulations containing nicotinamide or nicotinic acid was also performed.     

Neutral organic lewis acids of π type

The interaction of some neutral acids of π type, bearing appropriate unsymmetrical substitutions at the C?C group with some selected bases (H₂O, NH₃, OH^?), is compared with that of the parent compound of a new set of neutral π acids, bearing symmetrical substitutions at the C?C group with the same bases. The analyses of the interaction energy, performed according to two decomposition schemes, with and without the counterpoise corrections, make clear the similarity of symmetrically and unsymmetrically substituted neutral organic acids.