Dérives de l'imidazo[2,1-b]thiazole. V. Transposition allylique observée au cours de la synthése d'(imino-2 alkyl-3 thiazolinyl-4) acetates d'ethyle et de (dihydro-5,6 imidazo[2,1-b]thiazolyl-3) acetates d'éthyle

Ethyl (6-phenyl-5,6-dihydroimidazo[2,1-b]thiazol-3-yl) acetate hydrobromide shows an allylic transposition in alkaline medium and gives ethyl (6-phenyl-2,3,5,6-tetrahydroimidazo[2,1-b]thiazol-3-ylidene)acetate. This compound possesses an exocyclic double bond which is stable upon acidification. The intermediate ethyl (2-imino-3-alkylthiazolin-4-yl)-acetates undergo an analogous transposition upon treatment with base, which is reversible upon acidification. These transpositions were observed in the pmr data. The steric constraint and π p π conjugation are discussed in this work.     

Preparation of analyte-sensitive polymeric supports for biochemical sensors

The preparation and use of multiple polymers attached to a surface plasmon resonance (SPR) sensor for optimization of signal enhancement and minimization of fouling during sensing of biological species has been achieved. These polymers are advantageous compared to the current practice of carboxymethylated-dextran (CM-dextran). The polymers offer a wide range of functionalities and different molecular weights. Using these polymers, the SPR sensors can be fabricated as fast or faster than the CM-dextran sensor. In this study, we investigated the use of nine polymers for SPR biosensors. Polysaccharides, including CM-dextran, CM-hyaluronic acid, hyaluronic acid, and alginic acid, were investigated. Humic acid, polylactic acid, polyacrylic acid, orthopyridyldisulfide-polyethyleneglycol-N-hydroxysuccinimide (OPSS-PEG-NHS) and a synthesized polymer; polymethacrylic-acid-co-vinyl-acetate (PMAVA), were also used. The polymers were chemically attached to a thiol monolayer on the SPR biosensor using carbodiimide chemistry. The polymers were functionalized for binding of anti-myoglobin (anti-MG). The sensor performance was measured using myoglobin (MG) at 25 ng ml⁻¹, a biologically relevant level for myocardial infarction detection. Most polymers offered similar performance to CM-dextran for MG detection in HEPES buffer saline pH 7.4 (HBS). In preliminary studies in bovine serum, each of the candidate polymers demonstrated better performance than CM-dextran.     

Properties of acetate kinase activity inClostridium thermocellum cell extracts

Acetate kinase (EC 2.7.2.1) is involved in the wasteful production of acetate during conversion of cellulose to ethanol byClostridium thermocellum. The properties of this enzyme activity inC. thermocellum cell extracts were determined. Optimum enzyme activity was at 60 degrees C and between pH 7.5 and 9.0. In the presence of air, acetate kinase was stable to temperatures up to 60 degrees C, retaining 90% activity after 2 h, and was inactivated rapidly at higher temperatures. The enzyme exhibited a wide range of stability to pH (5.0-9.0) when incubated at 50 degrees C for 2 h. As with other acetate kinases, a divalent cation, such as Mg(2+), was required for enzyme activity. Optimum activity was observed at 20mM MgCl(2) when ATP was held constant at 10 mM. Acetate kinase activity was adversely affected by KCl, a salt commonly used in ion-exchange or affinity chromatography, with 0.3M KCl inhibiting by 50%. These results will be important in optimizing the direct microbial conversion process of cellulose to ethanol usingC. thermocellum in coculture withClostridium thermosaccharolyticum.     

Interactions of anthracyclines with zwitterionic phospholipid monolayers at the air-water interface

The present note describes the use of surface pressure measurements (Langmuir monolayer technique) for the analysis of interactions of two different anthracyclines (adriamycin and daunorubicin) with a non-ionic, zwitterionic phospholipid monolayer, at the air-water interface. Because the surface membrane of the cell is the first barrier encountered by the anthracyclines in the treatment of cancer, drug-membrane interactions studied in model (monolayers or bilayers) and natural systems play an important role in the understanding of the bioactivity properties of these molecules. We report here the rate constants of the adsorption process of adriamycin and daunorubicin in the presence of a zwitterionic phospholipid monolayer at the air-water interface. Because interactions with the lipid monolayer strongly depend on the molecular packing of the lipid, we investigated this process at a relatively low surface pressure (7 mN/m), the interactions being favoured by the gaseous and liquid expanded structure of the lipid monolayer. The apparent molecular area of these molecules during the insertion into the lipid film and their interactions with the phospholipid polar head groups was evaluated and the estimated percentage of anthracyclines at the interface after adsorption into the lipid monolayer is briefly discussed. The rate constants for the adsorption and desorption process at the water-monolayer interface have been calculated on the basis of a single-exponential model. The observed difference of these parameters for daunorubicin and adriamycin suggests a different interaction of these anthracyclines during the adsorption to and/or penetration across the phospholipid monolayer.     

Mean field at finite temperature and symmetry breaking

For an infinite system of nucleons interacting through a central spin-isospin schematic force we discuss how the Hartree-Fock theory at finite temperature T yields back, in the T=0 limit, the standard zero-temperature Feynman theory when there is no symmetry breaking. The attention is focused on the mechanism of cancellation of the higher order Hartree-Fock diagrams and on the dependence of this cancellation upon the range of the interaction. When a symmetry breaking takes place it turns out that more iterations are required to reach the self-consistent Hartree-Fock solution, because the cancellation of the Hartree-Fock diagrams of order higher than one no longer occurs. We explore in particular the case of an explicit symmetry breaking induced by a constant, uniform magnetic field B acting on a system of neutrons. Here we compare calculations performed using either the single-particle Matsubara propagator or the zero-temperature polarization propagator, discussing under which perturbative scheme they lead to identical results (if B is not too large). We finally address the issue of the spontaneous symmetry breaking for a system of neutrons using the technique of the anomalous propagator: in this framework we recover the Stoner equation and the critical values of the interaction corresponding to a transition to a ferromagnetic phase.     

Collective modes in a slab of interacting nuclear matter

We study the properties of a slab of nuclear matter. The behaviour with the slab thickness of the particle density, kinetic energy density and surface tension are given in the non-interacting case, together with the slab free response to an external field. Next we introduce a zero-range isovector interaction among the nucleons and analyze the slab collective excitations. For moderate momenta hard and soft modes are found, which exhaust most of the excitation strength. Their position and splitting in energy favourably compares with the splitted giant dipole resonance experimentally seen in deformed nuclei.     

The multilevel pairing Hamiltonian versus the degenerate case

We study the pairing Hamiltonian in a set of non-degenerate levels. First, we review in the path integral framework the spontaneous breaking of the U(1) symmetry occurring in such a system for the degenerate situation. Then the behaviors with the coupling constant of the ground state energy in the multilevel and in the degenerate case are compared. Next we discuss, in the multilevel case, an exact strong coupling expansion for the ground state energy which introduces the moments of the single particle level distribution. The domain of validity of the expansion, which is known in the macroscopic limit, is explored for finite systems and its implications for the energy of the latter is discussed. Finally the seniority and Gaudin excitations of the pairing Hamiltonian are addressed and shown to display the same gap in leading order.     

Reduced electron relaxation rate in multielectron quantum dots

We use a configuration-interaction approach and the Fermi golden rule to investigate electron-phonon interaction in multielectron quantum dots. Lifetimes are computed in the low-density, highly correlated regime. We report numerical evidence that electron-electron interaction generally leads to reduced decay rates of excited electronic states in weakly confined quantum dots, where carrier relaxation is dominated by the interaction with longitudinal acoustic phonons.