The effect of shell side hydrodynamics on the performance of axial flow hollow fibre modules

Fluid flow and mass transfer experiments have been performed on axial flow hollow fibre modules of varying packing density (32 to 76%). Shell-side pressure drop was found to be proportional to (flowrate)ⁿ, where n varied from about 1.1 at high packing density to 1.5 at low packing density, for shellside Reynolds numbers < 350. Assuming an Ergun-type pressure drop relationship it was found that for packing densities < about 50% the inertial (turbulent) losses exceeded the viscous (laminar) losses. Inspection of cross-sections taken from the middle of modules revealed non-uniform fibre packing with regions of high and low packing density. The cross-sections also change along the length of the module. It is inferred that, in addition to axial flow along fibres, there is also a degree of stream splitting which provides transverse flow across fibres as fluid continuously seeks preferential paths through regions of lower packing density. The presence of transverse flow would explain the higher than expected velocity exponent. Mass transfer experiments involving the removal of oxygen from water flowing through the shell to a sweep gas in the fibre lumens produced higher than expected shell-side mass transfer coefficients. The results are correlated within ± 15% by Sh = (0.53 − 0.58φ)Re^0.53Sc^0.33. The exponent on Re is consistent with entry region conditions, caused by repeated stream splitting and transverse flow. Compared with mass transfer predicted for axial flow through a uniformly packed shell the experimental results are up to 2× higher, with the most significant enhancement at the lower packing densities. The implication of this work is that module design requires a more sophisticated approach than the traditional assumption of laminar flow through parallel axial ducts.     

Simulation of tethered oligomers in nanochannels using multi-particle collision dynamics

The effect of a high Reynold's number, pressure-driven flow of a compressible gas on the conformation of an oligomer tethered to the wall of a square channel is studied under both ideal solvent and poor solvent conditions using a hybrid multiparticle collision dynamics and molecular dynamics algorithm. Unlike previous studies, the flow field contains an elongational component in addition to a shear component as well as fluid slip near the walls and results in a Schmidt number for the polymer beads that is less than unity. In both solvent regimes the oligomer is found to extend in the direction of flow. Under the ideal solvent conditions, torsional twisting of the chain and aperiodic cyclical dynamics are observed for the end of the oligomer. Under poor solvent conditions, a metastable helix forms in the end of the chain despite the lack of any attractive potential between beads in the oligomeric chain. The formation of the helix is postulated to be the result of a solvent induced chain collapse that has been confined to a single dimension by a strong flow field.     

High-level ab initio studies of the electronic excited states of the hydroxyl radical and water-hydroxyl complex

The lowest-energy electronic transitions in the hydroxyl radical and the hydrogen bound complex H(2)O.HO have been studied using ab initio methods. We have used the complete active-space self-consistent field and multireference configuration interaction (MRCI) methods to calculate vertical excitation energies and oscillator strengths. At the MRCI level the lowest-lying (2)Sigma(+)<--(2)Pi electronic transition is redshifted by about 2500 cm(-1) upon formation of the H(2)O.HO complex. We propose that this transition could be used to identify the complex in the gas phase, which in turn could be used to examine the role of H(2)O.HO in atmospheric reactions.     

Ultrasonic propagation in slurries

Experimental measurements have been made of the ultrasonic velocity and attenuation in some simple suspensions of, mainly, silicon carbide in water and in ethylene glycol. These are compared with theoretical predictions based on a novel hydrodynamic model. Predicted ultrasonic velocities are in excellent agreement with the measured values. Predicted and measured ultrasonic attenuations do not agree as well. However, the suspensions give rise to excess attenuations rising to a few hundred nepers per metre and special experimental techniques were needed to measure ultrasonic properties. To predict attenuations to within, say, 20% for mixtures such as these is a major achievement.     

The unusual bifunctional catalysis of epimerization and desaturation by carbapenem synthase

High-level ab initio calculations have been used to study the mechanism for the conversion of (3S,5S)-carbapenam to the biologically active beta-lactam antibiotic, (5R)-carbapenem, catalyzed by carbapenem synthase. This process involves epimerization at C5 and desaturation at C2/C3. Our calculations suggest that the reaction proceeds via initial abstraction of the C5 hydrogen atom, followed by epimerization. In addition, we have identified an attractive mechanism for coupling the epimerization and desaturation in thermodynamically favorable steps with the aid of an external reductant. Other mechanisms that have been examined have significantly higher energy requirements or do not appear to be consistent with available experimental evidence.     

Sensitivity to disorder of the metallic state in the ruthenates

We report the results of transport measurements on SrRuO3, Sr3Ru2O7, and CaRuO3. In SrRuO3 and Sr3Ru2O7, our findings are consistent with the predictions of Fermi liquid theory, in contrast to previous reports based on samples with much shorter mean free paths. In CaRuO3, however, a T1.5 power law is seen in the resistivity in the high purity samples studied here. Our work gives concrete evidence that even the metallic state of the ruthenates is highly sensitive to disorder.     

Electroluminescent zinc(II) bis(8-hydroxyquinoline): structural effects on electronic states and device performance

We present direct evidence for stable oligomers in vacuum-deposited thin films of zinc(II) bis(8-hydroxyquinoline) (Znq(2)). The tetramer [(Znq(2))(4)] is the energetically favored configuration in both the single crystal and the vacuum-deposited thin film. Oligomerization leads to distinct, symmetry-driven differences between the electronic states in Znq(2) and those in the archetypal organic electroluminescent molecule tris(8-hydroxyquinoline) aluminum (Alq(3)). In the case of the Znq(2) tetramer, symmetry leads to an extended network of overlapping pyridyl and phenolato moieties in the solid film. Analysis of the electronic structure of (Znq(2))(4) calculated by ab initio Hartree-Fock (HF) methods reveals a localization and energy shift of high-lying occupied and low-lying unoccupied states on symmetry related ligands located on opposite sides of the supramolecular structure resulting in a dipole moment for (Znq(2))(4) tetramer close to zero. The optimal pi-overlap pathways, altered charge distributions, and extended electronic states of tetrameric Znq(2) may be expected to enable low operating voltage organic light-emitting devices (OLEDs) based on Znq(2). We present preliminary evidence that the operating voltage of (Znq(2))(4)-based OLEDs is indeed lower than that of identical devices made with Alq(3). Strategic substitution of 8-hydroxyquinoline ligands and control of the structural symmetry of the corresponding metal chelates may offer a route to high efficiency and low operating voltage small molecule OLEDs.     

Evidence for oxidation at C-3 of the flavonoid C-ring during anthocyanin biosynthesis

Evidence is presented for initial oxidation at the C-3 position of the flavonoid C-ring and for two bifurcating steps during catalysis by anthocyanidin synthase.