Highly accurate determinations of CO(2) line strengths using intensity-stabilized diode laser absorption spectrometry

An intensity-stabilized laser absorption spectrometer, which incorporates a mirror-extended cavity diode laser, a temperature-stabilized gas cell, and a Michelson interferometer, was developed and applied to a highly accurate investigation of line intensity factors within the nu(1)+2nu(2) (0)+nu(3) combination band of carbon dioxide, around 2 microm wavelength, at a temperature of 296.0 K. This relatively complex apparatus enables one to observe the absorption line shape with high precision and accuracy in such a way that it is possible to retrieve the integrated absorbance with a relative uncertainty better than 0.1%. The absorption spectra were interpolated with the uncorrelated strong-collision model of Rautian and Sobel'man in order to take into account Dicke narrowing effects, thus obtaining an agreement at a level of a few parts per 10(-5). We report line strength values for the R(2)-R(18) transitions with an unprecedented level of accuracy, in the range between 0.1% and 0.15%. Finally, we discuss the possibility of providing a first experimental test of the theoretical model for molecular line strengths based on the Herman-Wallis expansion.     

Intermolecular proton transfer in solid phase: a rare example of crystal-to-crystal transformation from hydroxo- to oxo-bridged iron(III) molecule-based magnet

Intermolecular proton transfer in solid phase from the hydroxo bridge to a water molecule occurs in a new mu-hydroxo iron(III) compound of formula {EtNH3[Fe2(ox)2Cl2(mu-OH)].2H2O}n leading to a still crystalline compound in which the mu-oxo bridge replaces the mu-hydroxo one. Both three-dimensional compounds exhibit magnetic ordering at Tc ca. 70 K due to a spin canting.     

Structure-based optimization of a non-beta-lactam lead results in inhibitors that do not up-regulate beta-lactamase expression in cell culture

Bacterial expression of beta-lactamases is the most widespread resistance mechanism to beta-lactam antibiotics, such as penicillins and cephalosporins. There is a pressing need for novel, non-beta-lactam inhibitors of these enzymes. One previously discovered novel inhibitor of the beta-lactamase AmpC, compound 1, has several favorable properties: it is chemically dissimilar to beta-lactams and is a noncovalent, competitive inhibitor of the enzyme. However, at 26 microM its activity is modest. Using the X-ray structure of the AmpC/1 complex as a template, 14 analogues were designed and synthesized. The most active of these, compound 10, had a K(i) of 1 microM, 26-fold better than the lead. To understand the origins of this improved activity, the structures of AmpC in complex with compound 10 and an analogue, compound 11, were determined by X-ray crystallography to 1.97 and 1.96 A, respectively. Compound 10 was active in cell culture, reversing resistance to the third generation cephalosporin ceftazidime in bacterial pathogens expressing AmpC. In contrast to beta-lactam-based inhibitors clavulanate and cefoxitin, compound 10 did not up-regulate beta-lactamase expression in cell culture but simply inhibited the enzyme expressed by the resistant bacteria. Its escape from this resistance mechanism derives from its dissimilarity to beta-lactam antibiotics.     

Mechanistic studies on the asymmetric alkylation of amino ester enolates using a copper(II)salen catalyst

Hammett data indicate that the asymmetric alkylation of enolates catalysed by copper(II)salen complex 1, proceeds by an asynchronous S(N)2 reaction and that the role of the catalyst is to enhance the nucleophilicity of the enolate.     

Carotenoid triplet states associated with the long-wavelength-emitting chlorophyll forms of photosystem I in isolated thylakoid membranes

The carotenoid triplet populations associated with the long-wavelength-emitting chlorophyll forms of photosystem I (PS I)(dagger) have been investigated in isolated spinach thylakoids by means of fluorescence-detected magnetic resonance in zero field. The spectra collected in the 730-800 nm emission range can be globally fitted assuming the presence of four different carotenoid triplet states coupled to long-wavelength-emitting forms of PS I, having zero-field-splitting parameters /D/ = 0.0359 cm(-1) and /E/ = 0.00371 cm(-1), /D/ = 0.0382 cm(-1) and /E/ = 0.00388 cm(-1), /D/ = 0.0395 cm(-1) and /E/ = 0.00397 cm(-1), and /D/ = 0.0405 cm(-1) and /E/ = 0.00411 cm(-1). On the basis of the triplet-associated fluorescence emission profile, it is suggested that those triplets are associated with light-harvesting complex I, the peripheral antenna complex of PS I.     

Viscoelastic properties of durum wheat and common wheat dough of different strengths

Linear viscoelastic properties (LVP) were determined for five durum wheat doughs and five common wheat doughs (representing four different classes of Canadian common wheat) of different strength using creep testing. A creep time of 10,000 s was sufficient to reach a state of steady state flow for all of the doughs. Creep compliances were analyzed in terms of a Burgers model. For the durum doughs, the entire elastic compliance curve was shifted to higher values as the strength of the dough (as measured by extensigraph) decreased, while the steady state viscosity increased with strength. For common wheat doughs, the elastic compliance curves were steeper and the steady state viscosities were lower than for durum doughs of comparable extensigraph strength. The retardation strengths associated with a maximum in the retardation spectra were lower for the stronger durum doughs than for common wheat doughs of comparable strength. Differences in the LVP between durum and common wheat doughs of similar extensigraph strength were interpreted in the context of physical gels with crosslinks and entanglements, whose contributions to material properties are difficult to distinguish in short-time creep or dynamic measurements. The increased extensibility of common wheat doughs relative to durum doughs of comparable extensigraph strength was attributed to a higher molecular weight fraction in the polypeptide chains, similar in some respects to end-linked bimodal polymer networks. The idea of considering these doughs as physical gels was supported by their stress relaxation behavior. Received: 6 February 2000 Accepted: 22 August 2000     

DNA damage induced by organotins on ­trout‐nucleated erythrocytes

The effect of tributyltin‐chloride (TBTC), dibutyltin‐chloride (DBTC) and monobutyltin‐chloride (MBTC) on rainbow trout (Salmo irideus) nuclear DNA, was investigated by means of single cell gel electrophoresis (‘comet’ assay). Our data show that TBTC presents a marked genotoxic effect, whereas the genotoxic effect is less pronounced for DBTC and it is completely absent for MBTC. These results could be important in evaluating the environmental risks deriving from the use of these molecules as a antifouling agents in marine paints and as agricultural biocides. Copyright © 2001 John Wiley & Sons, Ltd.

Abbreviations:

TBTC,

tributyltin‐chloride;

DBTC,

dibutyltin‐chloride;

MBTC,

monobutyltin‐chloride;

Hb,

hemoglobin.

     

A parallel domain reduction method

We relate a particular version of a parallel multigrid method to a domain decomposition method, showing that the parallel multigrid method reduces computation to a small portion of the domain and then extends the solution to the entire domain using the correct reflections to get the exact solution. We extend a particular example to double the parallelism in a nonobvious manner. While the techniques of this paper are applied to twodimensional problems, they can be applied to higher dimensional problems in an obvious manner.     

Analytical methods to determine Po and Pb in marine samples

This paper describes the methods of sampling, preconcentration, chemical separation and final count of ²¹⁰Po and ²¹⁰Pb present in different marine matrices to determine their background levels in a marine ecosystem. Complex, time consuming and selective radioanalytical methods have been used to prepare final clear sources for alpha spectrometry and beta count; in fact, gamma spectrometry, a method direct and non destructive, cannot be taken into account because the ²¹⁰Pb activity is very low which does not allow to carry out sufficiently accurate measurements and ²¹⁰Po is not a gamma emitter but it emits only alpha particle at 5.40 MeV. The results of ²¹⁰Po and ²¹⁰Pb activity concentrations obtained in different marine samples collected in the first two campaigns are still very few to discuss about the ²¹⁰Po and ²¹⁰Pb behavior in marine environment.     

A Multidimensional Model for the Combustion of Compressible Fluids

We consider a multidimensional model for the combustion of compressible reacting fluids. The flow is governed by the Navier–Stokes in Eulerian coordinates and the chemical reaction is irreversible and is governed by the Arrhenius kinetics. The existence of globally defined weak solutions is established by using weak convergence methods, compactness and interpolation arguments in the spirit of Feireisl [16] and P.L. Lions [24].