Behaviour of 5,6-dihydrothieno[2,3-h]cinnolin-3(2H)-one and 5,6-dihydrothieno[3,2-h]cinnolin-3(2H)-one towards hydrazine. Synthesis of thienocinnolinones and of 4-aminothienocinnolinones

The isomeric compounds 5,6-dihydrothieno[2,3-h]cinnolin-3(2H)-one ( 7a ) and 5,6-dihydrothieno-[3,2-h]cinnolin-3(2H)-one ( 7b ) rapidly tautomerise to the corresponding 1,4-dihydrothienocinnolinones 8a,b when kept in refluxing hydrazine hydrate. With longer reaction times the initially formed 8a,b dehydrogenate to the thienocinnolinones 9a,b which eventually are aminated to 4-aminothienocinnolinones 10a,b . This behaviour recalls that reported for the related 5,6-dihydrobenzocinnolin-3(2H)-one ( 1 ) which under the same conditions undergoes dehydrogenation to benzo[h]cinnolin-3(2H)-one ( 2 ) followed by 4-amination to 3 , but differs for the stability of the intermediates, for the mechanism of the final amination, and for the higher reaction rate. All these differences can be rationalised in terms of the heats of formation of the intermediates and products of the two series of transformations.     

The Ferrocenylethynyl Unit: a Stable Hormone Tag

We prepared the organometallic complex 17α‐(ferrocenylethynyl)estradiol (=[(3,17β‐dihydroxyestra‐1,3,5(10)‐trien‐17α‐yl)ethynyl]ferrocene; FcEE; 1 ) by a novel synthetic method. This metallocene possesses sufficient stability in aqueous media to permit the study of its biological properties. Thus, we were able to show that, despite the addition of a bulky substituent at the 17α position of the steroid, the metallocene is still well‐ recognized by an antibody specific to estradiol (CR=40%) and by both subtypes (ERα, ERβ) of the estrogen receptor (at 0°, RBA=28 and 37%, resp.). A DCI‐MS study of the stability of the carbocation [FcEE−OH]⁺ showed moderate stabilization of the carbocation, in agreement with the pK value of −0.72 found for the metallocene by means of Deno's method. The presence of the ferrocene allows the electrochemical detection of FcEE ( 1 ) by HPLC‐ED, with a detection limit of ca. 1 nM , suitable for quantitative pharmacological analysis.     

A numerical eigenvalue study of preconditioned non‐equilibrium transport equations

The finite element integration of non‐equilibrium contaminant transport in porous media yields sparse, unsymmetric, real or complex equations, which may be solved by iterative projection methods, such as Bi‐CGSTAB and TFQMR, on condition that they are effectively preconditioned. To ensure a fast convergence, the eigenspectrum of the preconditioned equations has to be very compact around unity. Compactness is generally measured by the spectral condition number. In difficult advection‐dominated problems, however, the condition number may be large and nevertheless, convergence may be good. A numerical study of the preconditioned eigenspectrum of a representative test case is performed using the incomplete triangular factorization. The results show that preconditioning eliminates most of the original complex eigenvalues, and that compactness is not necessarily jeopardized by a large condition number. Quite surprisingly, it is shown that the preconditioned complex problem may have a more compact real eigenspectrum than the equivalent real problem. Copyright © 1999 John Wiley & Sons, Ltd.     

Partially selective methanolysis of sebacic units in biodegradable multicomponent copolyesters

The composition and molar masses of equimolar multicomponent copolyesters, obtained from 1,4-butandiol and mixtures of succinic, adipic, sebacic, and terephthalic acids were characterized by ¹³C NMR, size exclusion chromatography (SEC), matrix assisted laser desorption ionization-time of flight mass spectroscopy (MALDI-TOF-MS), and viscosimetry. These copolyesters were subjected to partial methanolysis, and the composition and sequence of the oligomers obtained in the methanolysis were determined by the analysis of their fast atom bombardment (FAB-MS) mass spectra. The comparison of the composition data obtained by FAB-MS and ¹³C NMR indicates that for copolymers containing sebacic units the methanolysis is a partially selective process, and that oligomers containing sebacic units accumulate in the residue.     

Characterization of end groups in nylon 6 by MALDI-TOF mass spectrometry

Four samples of Ny6, each terminated by different end groups, i.e., diamino terminated, monoamino terminated (monocapped), dicarboxyl terminated, and amino-carboxyl terminated, were synthesized and analyzed by MALDI-TOF Mass Spectrometry, in order to accurately characterize their structure by direct identification of mass resolved chains. A self-calibrating method for the MALDI-TOF mass spectra of polymeric samples was used in order to distinguish the end groups existing in the four samples of Ny6. The MALDI-TOF spectra showed the presence of protonated, sodiated, and potassiated ions that were assigned to Ny6 chains containing the expecteted end groups. Furthermore, the MALDI-TOF spectra made possible the simultaneous detection of the cyclic oligomers of Ny6 present in these samples, thus achieving the full structural characterization of the molecular species present in these polyamides. © 1996 John Wiley & Sons, Inc.     

Sequence of polymers by mass spectrometry

Mass Spectrometry, being able to look at the mass of individual molecules in a mixture of homologues, is particularly suitable for the detection of a series of oligomers. However, mass spectra had not been exploited to estimate oligomers distributions, due to the diffuse notion that a lack of correlation existed between peak intensities and concentration of the oligomers in the mixture. The introduction of soft-ionization techniques has largely eliminated this problem. A novel method for the determination of the microstructure of copolymers is presented here. We have recently found that opportune decoding of the information contained in the mass spectral intensities leads to the determination of composition and microstructure in copolymers, and this represents a significant progress. Statistical modeling of the mass spectral intensities of copolymers has been used to derive information on the distribution of monomers along the copolymer chain, and an automated procedure to find the composition and the sequence of the copolymers analyzed has been developed. The statistical analysis of copolymers makes use of Bernoullian and Markovian models in order to characterize the microstructure of copolymer samples, and assuming a theoretical distribution and then fitting the calculated oligomer abundances with the experimental MS peak intensities, the copolymer composition can be determined. A method is also reported to obtain the copolymer conposition by direct analysis of the mass spectra. These theories have been applied to determine the composition and the microstructure of several copolymers whose mass spectra have been reported in the most recent literature.