Generally covariant quantization and the Dirac field

Canonical Hamiltonian field theory in curved spacetime is formulated in a manifestly covariant way. Second quantization is achieved invoking a correspondence principle between the Poisson bracket of classical fields and the commutator of the corresponding quantum operators. The Dirac theory is investigated and it is shown that, in contrast to the case of bosonic fields, in curved spacetime, the field momentum does not coincide with the generators of spacetime translations. The reason is traced back to the presence of second class constraints occurring in Dirac theory. Further, it is shown that the modification of the Dirac Lagrangian by a surface term leads to a momentum transfer between the Dirac field and the gravitational background field, resulting in a theory that is free of constraints, but not manifestly hermitian.     

A formal finite element approach for open boundaries in transport and diffusion ground-water problems

In the application of the finite element method to diffusion and convection-dispersion equations over a ground-water domain, the Galerkin technique was used to incorporate Neumann (or second-type) and Cauchy (or third-type) boundary conditions. While mass movement through open boundaries is a priori unknown, these boundaries are usually treated as a zero Neumann condition at some far distance from the domain of interest. Nevertheless, cheaper and better solutions can be obtained if these unknown conditions are adequately incorporated in the weak formulation and in the transient solution schemes (open boundary condition). Theoretical and numerical proofs are given of the equivalences between this approach and a ‘well-posed’ problem in a semi-infinite domain with a zero Neumann condition at a boundary placed at infinity. Transport and diffusion equations were applied in one dimension to show the numerical performances and limitations of this procedure for some linear and non-linear problems. No a priori limitations are foreseen in order to find similar solutions in two or three dimensions. Thus the spatial discretization in the proximity of open boundaries could be drastically reduced to the domain of interest.     

Arbres et dimension des ordres

Nous montrons que la dimension d'un ordre partiel est au plus égale à n si et seulement si cet ordre est isomorphe à l'inclusion sur une famille de sous-arbres d'un arbre àn sommets pendants. La dimension de deux classes voisines de treillis est établie.     

Configuration interaction study of H2 using a modified slater-type orbital

A non-standard 1s basis function, χ = (1 + ar²) exp(?ζr), is used to approximate the ground state of the hydrogen molecule in a configuration interaction framework and using numerical integration over MO's. Results are compared to the traditional 1s STO.     

Emission energies and photophysical properties of ladder oligo(p-aniline)s

Emission properties and the photophysics of three ladder oligo(p-aniline)s; namely 5,11-diethyl-6,12-dimethylindolo[3,2-b]carbazole (DIMER 2P), 14-ethyl-5,8-dihydro-diindolo[3,2-b:2′,3′-h]carbazole (TRIMER 2P), and 5,8,14-triethyl-diindolo[3,2-b:2′,3′-h]carbazole (TRIMER 3P) are presented. The optimization (relaxation) of the first singlet excited electronic state (S₁) has been done using the restricted configuration interaction (singles) (RCIS/6-31G*) approach. The excitation to the S₁ state does not cause important changes in the geometrical parameters of the compounds, as is experimentally corroborated by the small Stokes shifts. Emission energies from the relaxed excited states have been obtained from TDDFT calculations performed on the S₁ optimized geometries and have been correlated with the corresponding fluorescence spectra of the derivatives dissolved in dichloromethane. A good agreement has been found between TDDFT emission energies and the (0,0) fluorescence bands. As predicted from theoretical calculations, all compounds exhibit small Stokes shift, which testify the rigidity of these ladder compounds. Moreover, this theoretical approach provides a good evaluation of the bathochromic shifts caused by the increase in the conjugation length or by the presence of alkyl chains on the nitrogen atoms. Finally, the fluorescence quantum yield and lifetime of the compounds in dichloromethane have been obtained. From these data, the radiative and nonradiative rate constants of the deactivation of the S₁ state have been determined.     

Diastereoselective aldolization of alpha-aminonitriles. Diastereoselective synthesis of beta-amino alcohols and beta,gamma-diamino alcohols

Aldolization performed by addition of lithiated N-benzyl-N-tert-butylaminoacetonitrile to aldehydes provides diastereomerically pure anti-beta-hydroxy-alpha-aminonitriles. They are transformed into syn,anti-protected beta,gamma-diamino alcohols by a two-step procedure, involving addition of a Grignard reagent and reduction. The cleavage of the N-tert-butyl group is achieved by a simple acidic treatment. The application of this methodology to chiral, nonracemic aldehydes is studied. Starting from D-isopropylideneglyceraldehyde, an anti, anti, syn, anti-(2R,3S,4S,5R,6R)-diaminotriol is prepared in acceptable yield and with a good level of diastereoselectivity.     

Synthesis of diindolocarbazoles by Ullmann reaction: a rapid route to ladder oligo(p-aniline)s

[structure: see text] New and facile synthesis of symmetric diindolocarbazoles was developed using the copper-catalyzed Ullmann reaction. The key step is a double-intramolecular cyclization reaction realized on N-alkyl-3,6-dibromo-2,7-bis(2'aminophenyl)carbazole derivatives which offers the desired symmetric ladder oligo(p-aniline)s. Depending upon the nature of the side- and/or end-groups, well-defined thin films and/or semiladder polymers could be obtained. These electroactive ladder oligomers may have great potential in organic electronics.     

Determination of falintolol, a new aliphatic beta-adrenergic antagonist, in whole blood by gas chromatography with electron-capture detection: geometric isomers resolution

Falintolol oxalate, a new beta-adrenergic antagonist, is characterized by the presence of an oxime function and exists in a racemic form as a mixture of syn- and anti- isomers in a ratio of about 8:2. This article describes a selective gas chromatographic method for the resolution of the geometric isomers and the quantitation of the drug. The unchanged falintolol and internal standard, a related compound, are separated from blood by a solvent extraction under alkaline conditions, and then the drug is derivatized. The heptafluorobutyric derivatives are chromatographed on an SE-30 capillary quartz column and detected with a nickel-63 electron-capture detector. Because the syn- and anti- isomers of falintolol display comparable chromatographic responses, the sum of the two geometrical isomers is used for the quantitation of falintolol in blood. This method allows small serial blood samples in conscious rats, and 0.05 microgram of falintolol/0.1 mL of blood can be routinely determined. A calibration curve is prepared for the blood extracts. Linearity is observed in the study range (0.05 to 1 microgram/0.1 mL of blood). No interference by endogenous substances is observed. The procedure is applied successfully to drug absorption in rats when repeated oral doses are administered.     

High-performance liquid chromatographic determination of mitoxantrone in plasma utilizing non-bonded silica gel for solid-phase isolation to reduce adsorptive losses on glass during sample preparation

Mitoxantrone, a highly active antineoplastic agent, was found to bind strongly to non-bonded silica gel and glassware. When a Hamilton syringe was used to load and inject a mitoxantrone solution (0.4 microgram/ml in water) on to a high-performance liquid chromatographic (HPLC) system, about 95% of the loaded compound was found to bind to the glass surface of the syringe barrel and could not be removed by rinsing with water. It could, however, be removed slowly with an acidic solution and thus a small peak of mitoxantrone was present on the chromatogram whenever a blank acidic solution was injected with the syringe. The bound mitoxantrone could be removed effectively from the syringe surface with a solution of tetramethylammonium chloride, citric acid, methanol and water (elution solvent). This binding introduces a large error in assay results and might be one of the major factors responsible for contradictory pharmacokinetic data that have been reported. A new plasma preparation scheme and an HPLC method for mitoxantrone were developed to address this binding problem. Mitoxantrone was extracted directly from plasma samples with a plastic mini-column packed with non-bonded silica gel and eluted with the above elution solvent. The eluent was analysed by HPLC on an ODS column with an absorbance detector at 658 nm. The mobile phase was 0.1 M triethylamine phosphate (pH 3.0) in water-tetrahydrofuran-methanol (69:1:30) containing 0.02 M tetramethylammonium chloride. Methylene blue was added as an internal standard. Preliminary results showed that mitoxantrone levels in human plasma followed a triphasic decay curve after an intravenous bolus injection. The terminal elimination half-lives measured in three patients (mean t1/2 gamma = 25 min) were all shorter than the published values which ranged from 56 min to 9 days.