On the behaviour of solid particles in a horizontal boundary layer with turbulence and saltation effects

 A horizontal turbulent boundary layer of air carrying heavy solid particles is investigated experimentally. Mean and r.m.s. velocities of air and particles are measured by LDA, and particle mass flux distributions are obtained by means of a sampling method. The influence of the saltation mechanism is revealed by the large particle r.m.s. velocity in the near-wall region, and by the velocity lag of the particles in the outer region of the boundary layer, which is shown to be closely related to their free fall velocity. The present original results are discussed and compared with available experimental data concerning other kinds of horizontal flows. Received: 17 June 1996/Accepted: 3 April 1997     

The Anomaly Line Bundle of the Self-Dual Field Theory

In this work, we determine explicitly the anomaly line bundle of the abelian self-dual field theory over the space of metrics modulo diffeomorphisms, including its torsion part. Inspired by the work of Belov and Moore, we propose a non-covariant action principle for a pair of Euclidean self-dual fields on a generic oriented Riemannian manifold. The corresponding path integral allows one to study the global properties of the partition function over the space of metrics modulo diffeomorphisms. We show that the anomaly bundle for a pair of self-dual fields differs from the determinant bundle of the Dirac operator coupled to chiral spinors by a flat bundle that is not trivial if the underlying manifold has middle-degree cohomology, and whose holonomies are determined explicitly. We briefly sketch the relevance of this result for the computation of the global gravitational anomaly of the self-dual field theory, that will appear in another paper.     

3-(D-Erythro-Trihydroxypropyl)-1-Neopentyl Pyrrole-2-Carboxaldehyde. A Novel Nonenzymatic Browning Product of Glucose

Abstract

The reaction of equimolar amounts of D-glucose and neopentyl-amine in phosphate buffer under physiological conditions of pH and temperature has been investigated. From the diethyl ether extract, we have identified a C-8 condensation product and have demonstrated that its formation does not proceed via a free-radical mechanism. Based on ¹H and ¹³C NMR and other spectroscopic techniques, including UV, IR, EI-MS, CI-MS of the TMS derivative, the structure 3-(D-erythro-trihydroxypropyl)-1-neopentyl pyrrole-2-carboxaldehyde, was assigned to this advanced Maillard reaction product.     

Search for the rare decays K(L)→π0π0μ+μ- and K(L)→π0π0X0→π0π0μ+μ-

The KTeV E799 experiment has conducted a search for the rare decays, K(L)→π(0)π(0)μ(+)μ(-) and K(L)→π(0)π(0)X(0)→π(0)π(0)μ(+)μ(-), where the X(0) is a possible new neutral boson that was reported by the HyperCP experiment with a mass of (214.3 ± 0.5) MeV/c(2). We find no evidence for either decay. We obtain upper limits of Br(K(L)→π(0)π(0)X(0)→π(0)π(0)μ(+)μ(-)) < 1.0 × 10(-10) and Br(K(L)→π(0)π(0)μ(+)μ(-)) < 9.2 × 10(-11) at the 90% confidence level. This result rules out the pseudoscalar X(0) as an explanation of the HyperCP result under the scenario that the dsX(0) coupling is completely real.     

Particle Size Determination by Laser Reflection: Methodology and problems

The particle size distribution of crystalline solids has progressively become a key parameter in manufacturing processes, as important as chemical purity. Among the particle size determination and counting systems available on the market, very few offer the possibility of continuous in situ monitoring of the particle size evolution during crystallization. For this reason, much interest has been aroused by the appearance of the Par Tec 100, patented by Laser Sensor Technology [1, 2]. A study has been carried out in a stirred vessel to verify the precision and reproducibility of particle size measurement and elucidate the influence of experimental parameters on data accessible with this instrument. Optimum reproducibility has logically been achieved by fixing the highest possible cycle time and taking the mean of several cycles. Determinations with the Par Tec 100 are influenced variously, according to whether they relate to the total number of particles counted or to the mean size. Thus, the number of counts measured by a particle size probe largely depends on the operating conditions and more particularly on the hydrodynamic conditions, solvent, temperature and focal point position. Its dependence relative to the concentration of the solid in suspension is normal and linear for a solid and for a given monodisperse sample. To establish the relationship between the number of counts and the population density would therefore necessitate delicate calibration on a case-by-case basis. The mean size determined does not depend on suspension homogeneity, provided that the stirring speed is sufficient for a statistically significant total count. On the other hand, for a given sample, a displacement of the focal point can lead to considerable variations in the size determined. The optimal focal point position for small sizes is in fact highly sensitive. Lastly, the optimal position of the focal point is considerably dependent on the true size of the particles, which means that this counter is unsuitable for the precise analysis of a dispersed sample since each particle size class would require a different setting of the focal point. In addition, the sizes determined, irrespective of the products studied, appear to be underestimated for large particles and over estimated for small particles.     

Sums of even powers in Archimedean rings

This note is devoted to the study of totally archimedean rings of regular functions. We extend Schmüdgen's theorem to this class of rings. Moreover, we show that, in such rings, every totally positive element is a sum of even powers of totally positive elements, and hence is a sum of even powers of units. Received: 21 October 1999; in final form: 10 November 2000 / Published online: 18 January 2002     

Alpha-phenyl-N-tert-butylnitrone-type derivatives bound to beta-cyclodextrins: syntheses, thermokinetics of self-inclusion and application to superoxide spin-trapping

alpha-Phenyl-N-tert-butylnitrone (PBN) derivatives bound to beta-cyclodextrin derivatives have been synthesized. Inclusion of the PBN group into the beta-cyclodextrin moiety is host- and temperature-dependent. In the case of the nitrone linked to permethylated cyclodextrin (Me3CD-PBN), the thermokinetic parameters are in favour of a slow chemical exchange between a tight and a loose complex. In contrast, 2,6-di-O-Me-beta-cyclodextrin-grafted PBN (Me2CD-PBN) exists either in a fast exchange or as a strongly self-associated complex. The covalent cyclodextrin-PBN compounds have been used to trap carbon and oxygen-centred free radicals. The self-associated forms of the beta-CD-spin-traps are compatible with effective spin-trapping, affording spin-adducts with enhanced EPR signal intensities relative to noncovalent CD-nitrone systems or the nitrone alone. This kind of cyclodextrin-bound nitrone is the first type of covalent supramolecular spin-trap and should open new possibilities for the study of biological free radicals in vivo.     

Selective ruthenium-catalyzed transformations of enynes with diazoalkanes into alkenylbicyclo[3.1.0]hexanes

Reaction of a variety of CCH bond-containing 1,6-enynes with N2CHSiMe3 in the presence of RuCl(COD)Cp* as catalyst precursor leads, at room temperature, to the general formation of alkenylbicyclo[3.1.0]hexanes with high Z-stereoselectivity of the alkenyl group and cis arrangement of the alkenyl group and an initial double-bond substituent, for an E-configuration of this double bond. The stereochemistry is established by determining the X-ray structures of three bicyclic products. The same reaction with 1,6-enynes bearing an R substituent on the C1 carbon of the triple bond results in either cyclopropanation of the double bond with bulky R groups (SiMe3, Ph) or formation of alkylidene-alkenyl five-membered heterocycles, resulting from a beta elimination process, with less bulky R groups (R = Me, CH2CH=CH2). The reaction can be applied to in situ desilylation in methanol and direct formation of vinylbicyclo[3.1.0]hexanes and to the formation of some alkenylbicyclo[4.1.0]heptanes from 1,7-enynes. The catalytic formation of alkenylbicyclo[3.1.0]hexanes also takes place with enynes and N2CHCO2Et or N2CHPh. The reaction can be understood to proceed by an initial [2+2] addition of the Ru=CHSiMe3 bond with the enyne CCH bond, successively leading to an alkenylruthenium-carbene and a key alkenyl bicyclic ruthenacyclobutane, which promotes the cyclopropanation, rather than metathesis, into bicyclo[3.1.0]hexanes. Density functional theory calculations performed starting from the model system Ru(HCCH)(CH2=CH2)Cl(C5H5) show that the transformation into a ruthenacyclobutane intermediate occurs with a temporary eta3-coordination of the cyclopentadienyl ligand. This step is followed by coordination of the alkenyl group, which leads to a mixed alkyl-allyl ligand. Because of the non-equivalence of the terminal allylic carbon atoms, their coupling favors cyclopropanation rather than the expected metathesis process. A direct comparison of the energy profiles with respect to those involving the Grubbs catalyst is presented, showing that cyclopropanation is favored with respect to enyne metathesis.     

Ruthenium-catalysed synthesis of fluorinated bicyclic amino esters through tandem carbene addition/cyclopropanation of enynes

The reaction of fluorinated 1,6- and 1,7-enynes, containing the moiety N(PG)C(CF(3))(CO(2)R), with diazo compounds in the presence of [RuCl(cod)(Cp*)] (cod=cycloocta-1,5-diene, Cp*=C(5)Me(5) , PG=protecting group) as the catalyst precursor leads to the formation of fluorinated 3-azabicyclo[3.1.0]hexane-2-carboxylates and 4-azabicyclo-[4.1.0]heptane-3-carboxylates. This catalytic transformation was applied to various protecting groups and has proved to be a selective and a general synthetic tool to form constrained proline or homoproline derivatives in good yields. Z stereoselectivity of the created alkenyl group is obtained with N(2)CHSiMe(3), whereas N(2)CHCO(2)Et favours selectively the E configuration for the same double bond. The diastereoselectivity exo/endo depends on the size of the created ring. The X-ray structures of two products have been determined, showing the stereochemistry of the compounds. The reaction can be understood by initial [2+2] addition of the Ru=CHY bond, generated from diazoalkane, with the C≡CH bond of the enyne leading to a key bicyclic ruthenacyclobutane, which promotes the cyclopropanation, rather than metathesis. This selective formation of bicyclic [n.1.0] compounds results from the ruthenium-catalysed creation of three carbon-carbon bonds in a single step under mild conditions.