Photolysis of CH3C(O)CH3 (248 nm, 266 nm), CH3C(O)C2H5 (248 nm) and CH3C(O)Br (248 nm): pressure dependent quantum yields of CH3 formation

The formation of CH(3) in the 248 or 266 nm photolysis of acetone (CH(3)C(O)CH(3)), 2-butanone (methylethylketone, MEK, CH(3)C(O)C(2)H(5)) and acetyl bromide (CH(3)C(O)Br) was examined using the pulsed photolytic generation of the radical and its detection by transient absorption spectroscopy at 216.4 nm. Experiments were carried out at room temperature (298 +/- 3 K) and at pressures between approximately 5 and 1500 Torr N(2). Quantum yields for CH(3) formation were derived relative to CH(3)I photolysis at the same wavelength in back-to-back experiments. For acetone at 248 nm, the yield of CH(3) was greater than unity at low pressures (1.42 +/- 0.15 extrapolated to zero pressure) confirming that a substantial fraction of the CH(3)CO co-product can dissociate to CH(3) + CO under these conditions. At pressures close to atmospheric the quantum yield approached unity, indicative of almost complete collisional relaxation of the CH(3)CO radical. Measurements of increasing CH(3)CO yield with pressure confirmed this. Contrasting results were obtained at 266 nm, where the yields of CH(3) (and CH(3)CO) were close to unity (0.93 +/- 0.1) and independent of pressure, strongly suggesting that nascent CH(3)CO is insufficiently activated to decompose on the time scales of these experiments at 298 K. In the 248 nm photolysis of CH(3)C(O)Br, CH(3) was observed with a pressure independent quantum yield of 0.92 +/- 0.1 and CH(3)CO remained below the detection limit, suggesting that CH(3)CO generated from CH(3)COBr photolysis at 248 nm is too highly activated to be quenched by collision. Similar to CH(3)C(O)CH(3), the photolysis of CH(3)C(O)C(2)H(5) at 248 nm revealed pressure dependent yields of CH(3), decreasing from 0.45 at zero pressure to 0.19 at pressures greater than 1000 Torr with a concomitant increase in the CH(3)CO yield. As part of this study, the absorption cross section of CH(3) at 216.4 nm (instrumental resolution of 0.5 nm) was measured to be (4.27 +/- 0.2) x 10(-17) cm(2) molecule(-1) and that of C(2)H(5) at 222 nm was (2.5 +/- 0.6) x 10(-18) cm(2) molecule(-1). An absorption spectrum of gas-phase CH(3)C(O)Br (210-305 nm) is also reported for the first time.     

A microfluidic device for practical label-free CD4(+) T cell counting of HIV-infected subjects

Practical HIV diagnostics are urgently needed in resource-limited settings. While HIV infection can be diagnosed using simple, rapid, lateral flow immunoassays, HIV disease staging and treatment monitoring require accurate counting of a particular white blood cell subset, the CD4(+) T lymphocyte. To address the limitations of current expensive, technically demanding and/or time-consuming approaches, we have developed a simple CD4 counting microfluidic device. This device uses cell affinity chromatography operated under differential shear flow to specifically isolate CD4(+) T lymphocytes with high efficiency directly from 10 microliters of unprocessed, unlabeled whole blood. CD4 counts are obtained under an optical microscope in a rapid, simple and label-free fashion. CD4 counts determined in our device matched measurements by conventional flow cytometry among HIV-positive subjects over a wide range of absolute CD4 counts (R(2) = 0.93). This CD4 counting microdevice can be used for simple, rapid and affordable CD4 counting in point-of-care and resource-limited settings.     

Zinc-zinc bonded zincocene structures. Synthesis and characterization of Zn2(eta5-C5Me5)2 and Zn2(eta5-C5Me4Et)2

While, in general, decamethylzincocene, Zn(C5Me5)2, and other zincocenes, Zn(C5Me4R)2 (R = H, But, SiMe3), react with dialkyl and diaryl derivatives, ZnR'2, to give the half-sandwich compounds (eta5-C5Me4R)ZnR', under certain conditions the reactions of Zn(C5Me5)2 with ZnEt2 or ZnPh2 produce unexpectedly the dizincocene Zn2(eta5-C5Me5)2 (1) in low yields, most likely as a result of the coupling of two (eta5-C5Me5)Zn* radicals. An improved, large scale (ca. 2 g) synthesis of 1 has been achieved by reduction of equimolar mixtures of Zn(C5Me5)2 and ZnCl2 with KH in tetrahydrofuran. The analogous reduction of Zn(C5Me4R)2 (R = H, SiMe3, But) yields only decomposition products, but the isotopically labeled dimetallocene 68Zn2(eta5-C5Me5)2 and the related compound Zn2(eta5-C5Me4Et)2 (2) have been obtained by this procedure. Compound 2 has lower thermal stability than 1, but it has been unequivocally characterized by low-temperature X-ray diffraction studies. As for 1 a combination of structural characterization techniques has provided unambiguous evidence for its formulation as the Zn-Zn bonded dimer Zn2(eta5-C5Me4Et)2, with a short Zn-Zn bond of 2.295(3) A indicative of a strong Zn-Zn bonding interaction. The electronic structure and the bonding properties of 1 and those of related dizincocenes Zn2(eta5-Cp')2 have been studied by DFT methods (B3LYP level), with computed bond distances and angles for dizincocene 1 very similar to the experimental values. The Zn-Zn bond is strong (ca. 62 kcal.mol-1 for 1) and resides in the HOMO-4, that has a contribution of Zn orbitals close to 60%, consisting mostly of the Zn 4s orbitals (more than 96%).     

Development of the energy flow in light-harvesting dendrimers

Modeling the multistep flow of energy in light-harvesting dendrimers presents a considerable challenge. Recent studies have introduced an operator approach based on a matrix representation of the connectivity between constituent chromophores. Following a review of the theory, detailed applications are now shown to exhibit the time development of the core excitation following pulsed laser irradiation and the steady-state behavior that can be expected under conditions of constant illumination. It is also shown how energy capture by whole dendrimers can be analytically related to chromophore pair-transfer properties and, in particular, the spectroscopic gradient toward the core. Indicative calculations also illustrate the consequences of tertiary folding. In each respect, the model affords opportunities to derive new, physically meaningful information on the photophysical and structural features of dendrimeric systems.     

Caractérisation et contrôle de l'asymétrie tourbillonnaire autour d'un côneAerodynamic caracteristics and vortex asymmetry control around a circular cone

The structure of the vortex asymetry around a circular cone at high incidence and Reynolds numbers of order 10⁴, is related to the existence of at least four vortices shed from the apex and exhibiting vortex breakdown points correlated with the sign of the lateral force. Control of the lateral force by injection points out three regimes, and not two as usually admitted, corresponding to inversions of the lateral force direction. To cite this article: O. Rodriguez, J. Pruvost, C. R. Mecanique 332 (2004).     

Temperature effects in the Rayleigh problem for a convected Jeffreys fluid

We use a thermodynamic approach to non-linear viscoelasticity which predicts a coupling between the stress tensor and the heat flux, to generalize the Rayleigh problem for an Oldroyd B model of a fluid. For a special choice of the external temperature gradient, we show that thermal effects do alter the hydrodynamic velocity field as well as the first and second normal stress differences. These quantities depend on renormalized parameters wich explicitly depend on temperature and on the strength of the coupling. In particular we find that in contrast to the isothermal situation, the second normal stress difference does not vanish. The possibility of an experimental verification of our theoretical predictions is also mentioned.On sabbatical leave from Laboratorio de Energia Solar, IIM-UNAM, Zona Cultural Xochicalco, Temixco, Mor. 62580, MéxicoOn leave from Departamento de Polimeros, IIM-UNAM, México, D.F. 04510, México     

Coacervation of Elastin‐Like Recombinamer Microgels

The investigation of the coacervation (self‐aggregation) behavior of biomicrogels which can potentially be used as drug carriers is an important topic, because self‐aggregation can not only cause loss of activity, but also toxicity and immunogenicity. To study this effect microgels from elastin‐like recombinamer are synthesized using miniemulsion technique. The existence of coacervation for such microgels, at different concentrations and temperatures, is studied and proved by cryo‐field emission scanning clectron microscopy (cryo‐FESEM), cryo‐transmission electron microscopy (cryo‐TEM), and by a novel ¹H high‐resolution magic angle sample spinning (HRMAS), nuclear magnetic resonance (NMR) spectroscopy, and relaxometry methods. The findings by ¹H HRMAS NMR spectroscopy and relaxometry show simultaneous processes of volume phase temperature transition and coacervation with different sensitivity for hydrophobic and hydrophilic amino acid side‐chains in the microgel. The coacervation process is more evidential by the behavior of glycine α‐CH₂, ¹H NMR peak as compared to the proline β‐CH₂.

     

A study by holographic velocimetry of the behaviour of free small particles in a flow

The aim of this paper is to calculate the motion of small dilute particles carried by a given flow with the help of two models of behaviour, and then to compare this motion to that measured by a method of multiple exposure holography. The results lead to the specification of the field of validity of each model. Also they provide information about the ability of the holographic method to be used as a velocimetry technique in fluid mechanics.     

Study on the Influence of Waves on Coastal Diffusion Using Image Analysis

A series of novel image analysis techniques have been used to study surf-zone hydrodynamics taking advantage of recent advances in digital processing of images taken from video recordings of the sea surface near the coast. The use of image analysis allows the estimation of both spatial and temporal characteristics of wave fields, surface circulation and mixing in the surf zone. The dispersion of blobs of dye released at different distances from the coastline under very different sea conditions is used to measure surface eddy diffusivities. A preliminary set of field measurements were done in the Ebro Delta where the methodology was tested. Further experiments have been performed at Vilanova, Spain and Recife, Brazil.There is an increase of diffusivity with wave height but only if the wave Reynolds number, Rw, is greater than 10³. No such trend is observed for Rw greater than 10⁶. The other important factors are wind speed and tidal and longshore currents.     

Iron Cyclopentadienone Complexes: Discovery,Properties, and Catalytic Reactivity

Iron cyclopentadienone complexes have recently received particular attention in organic chemistry. This is due to their easy synthesis from simple and cheap materials, air–water stability, and most importantly for their unique catalytic features arising from the presence of a non‐innocent ligand, triggering powerful redox properties. Herein we discuss the properties of such complexes from synthetic and mechanistic points of view, and their applications in original redox‐neutral transformations in both racemic and enantioselective series.