Carbon Dioxide Fixation and Sulfate Sequestration by a Supramolecular Trigonal Bipyramid

The subcomponent self‐assembly of a bent dialdehyde ligand and different cationic and anionic templates led to the formation of two new metallosupramolecular architectures: a Fe^II₄L₆ molecular rectangle was isolated following reaction of the ligand with iron(II) tetrafluoroborate, and a M₅L₆ trigonal bipyramidal structure was constructed from either zinc(II) tetrafluoroborate or cadmium(II) trifluoromethanesulfonate. The spatially constrained arrangement of the three equatorial metal ions in the M₅L₆ structures was found to induce small‐molecule transformations. Atmospheric carbon dioxide was fixed as carbonate and bound to the equatorial metal centers in both the Zn₅L₆ and Cd₅L₆ assemblies, and sulfur dioxide was hydrated and bound as the sulfite dianion in the Zn₅L₆ structure. Subsequent in situ oxidation of the sulfite dianion resulted in a sulfate dianion bound within the supramolecular pocket.     

MODELING HARVEST SCHEDULING IN MULTIFUNCTIONAL PLANNING OF FORESTS FOR LONGTERM WATER YIELD OPTIMIZATION

In this study, wood production and hydrologic functions of forests were accommodated within a planning procedure for separate working circles (areas dedicated to certain forest functions) that were delineated according to an Ecosystem‐Based Functional Planning approach. Mixed integer goal programming was used as the optimization technique. The timing and scheduling of a maintenance cutting (partial harvest) was the decision variable in the modeling effort, and an original formulation was developed as a multiobjective planning procedure. Four sample planning strategies were developed and model outputs were evaluated according to these strategies. Spatial characteristics of stands were considered, and used to prohibit the regeneration of adjacent stands during the same time period. Because of the positive relationship between qualified water production and standing timber volume in the forest, the model attempts to maximize qualified water production levels by increasing standing volume stocks in the forest through the delay of regeneration activities.     

Calibration ofX-probes for turbulent flow measurements

We compare two methods of calibrating the yaw response of hot-wire probes: (i) the assumption that an effective angle, independent of the flow speed, can be deduced; (ii) the more general approach of determining the yaw response at a number of different speeds. The first, simpler, approach is shown to give surprisingly reasonable results for the usual turbulence statistics, even in high turbulence intensity flows. Some differences in the distribution of the inclination of the instantaneous velocity vector are observed. There is no advantage in using thek ² factor to allow for longitudinal cooling.     

A Simple Model for the Variation of Permeability due to Partial Saturation in Dual Scale Porous Media

The main focus of this work is to model macroscopically the effects of partial saturation upon the permeability of dual scale fibrous media made of fiber bundles when a Newtonian viscous fluid impregnates it. A new phenomenological model is proposed to explain the discrepancies between experimental pressure results and analytical predictions based on Darcy's law. This model incorporates the essential features of relative permeability but without the necessity of measuring saturation of the liquid for its prediction. The model is very relevant for the small scale industrial systems where a liquid is forced to flow through a fibrous porous medium. It requires four parameters. Two of them are the two permeability values based on the two length scales. One length scale is of the order of magnitude of the individual fiber radius and corresponds to the permeability of the completely staurated medium, the other is of the order of magnitude of the distance between the fiber bundles and corresponds to the permeability of the partially saturated medium. The other two parameters are the lengths of the two partially saturated regions of the flow domain. The two lengths of the partially saturated region and the permeability of the fully saturated flow domain can be directly measured from the experiments. The excellent agreement between the model and the experimental results of inlet pressure profile with respect to time suggests that this model may be used to describe the variation of the permeability behind a moving front in such porous media for correct pressure prediction. It may also be used to characterize the fibrous medium by determining the two different permeabilities and the relative importance of the unsaturated portion of the flow domain for a given architecture.     

Forward scattering theory of electric-field-gradient-induced birefringence

We attempt to resolve the discrepancy between the Buckingham—Longuet-Higgins (BLH) and Imrie—Raab (IR) theories of linear birefringence induced in a gas of dipolar molecules by an electric field gradient. To this end we present a new calculation of the effect, based on forward scattering of a light beam incident on a thin lamina of gas molecules. We work to electric quadrupole—magnetic dipole order. The beam undergoes a time delay which is proportional to the thickness of the lamina and the electric field gradient, and can therefore be interpreted in terms of a contribution to the refractive index of the gas due to the field gradient. The birefringence is obtained by considering appropriate polarizations of the incident beam. To avoid the occurrence of a divergent quantity, such as appears in the BLH theory, it is essential to take account of the finite beam width. Calculations are performed using both primitive (traced) and traceless molecular quadrupole moments; as required on basic grounds, these results are equivalent. They are also identical to the BLH result. By contrast, the IR result is physically unacceptable because it is not invariant with respect to the use of traced and traceless moments. The source of error in the IR theory remains unclear.     

Synthesis and mesomorphic properties of perfluorinated rod-like liquid crystals with sulphur-containing spacers

In order to determine the influence of 'sulphur-containing' spacers on the formation of mesophases in low molecular mass compounds, we have examined the mesomorphic behaviour of molecules which consists of a 4-biphenyl unit linked to an unbranched fluorinated chain via a short spacer including at least a sulphur atom. The synthesis of these compounds has been carried out from 2-F-butylethyl iodide or from the 2-F-alkylethyl mercaptans in the case of the F-hexyl and F-octyl tails. The mesomorphic properties have been characterized by polarized light microscopy and by differential thermal analysis showing the peculiar contribution of each of the spacers. The influence of the fluorinated chain and the shape of the connector on the stability of the mesophases has been investigated. The compounds with a thioether or a hemithioacetal spacer showed no mesomorphic properties, whereas the structures with a thioester spacer showed a very interesting enantiotropic behaviour of the smectic A type over a wide temperature range. Furthermore from the series exhibiting liquid crystalline behaviour, increasing the number of fluoromethylene units simultaneously increases both the melting and the clearing temperature. These mesomorphic properties within the fluorinated series are compared with those of their monocatenar hydrocarbon homologues.     

On the theory of the Buckingham effect

We apply general arguments (based on spatial transformation properties, intrinsic symmetry and dimensional analysis) to the theory of the Buckingham effect (electric-field–gradient-induced birefringence in a gas). These yield, in a simple manner, the temperature-dependent and temperature-independent terms in the birefringence (each to within a numerical factor), and also the expression, derived by Buckingham and Longuet-Higgins, for the effective quadrupole centre of a molecule. We show in addition how the calculation of the two numerical factors can be simplified in our approach.