Solvent-free synthesis of bisferrocenylimines and their rhodium(I) complexes

The solvent-free reaction of ferrocenecarboxaldehyde and diaminoalkanes under solvent-free conditions gave bisferrocenylimines (L) in excellent yields. Cationic rhodium(I) complexes with the formulation [Rh(COD)(L)]ClO₄ were prepared by the reaction of [Rh(COD)Cl]₂ with the bisferrocenylimines in the presence of silver perchlorate. The compounds were characterised by NMR, IR, MS and elemental analysis. The X-ray crystal structures of two rhodium(I) complexes are also reported.     

Controlling dimensions of polymerized micelles: micelle template versus reaction conditions

The polymerization of elongated micellar structures offers a novel approach to the production of high aspect ratio, water-soluble amphiphilic nanoparticles. Three different surfactants were synthesized consisting of a cationic surfactant of the form (C(X)H(2X+1))trimethylammonium (where X = 14, 16, or 18) and a vinyl-containing counterion, 4-vinylbenzoate. The resulting polymer-surfactant aggregates have been polymerized to produce high aspect ratio nanoparticles which are insensitive to changes in solution conditions. The radius of the initial template is maintained on polymerization, whereas the template length is not. The aggregate radius is varied by changing the length of the surfactant tail, in this case producing aggregates with radii of 1.7, 2.0, or 2.4 nm. Variation of the initiator decomposition half-life, by means of using different initiators and varying temperature, is used to control the aggregate length between 80 and 500 nm. Through the process discussed here, both the radius and length of the aggregates are controlled independently.     

Wetting and spreading of a surfactant film on solid particles: influence of sharp edges and surface irregularities

In addition to particle size and surface chemistry, the shape of particles plays an important role in their wetting and displacement by the surfactant film in the lung. The role of particle shape was the subject of our investigations using a model system consisting of a modified Langmuir-Wilhelmy surface balance. We measured the influence of sharp edges (lines) and other highly curved surfaces, including sharp corners or spikes, of different particles on the spreading of a dipalmitoylphosphatidyl (DPPC) film. The edges of cylindrical sapphire plates (circular curved edges, 1.65 mm radius) were wetted at a surface tension of 10.7 mJ/m2 (standard error (SE) = 0.45, n = 20) compared with that of 13.8 mJ/m2 (SE = 0.20, n = 20) for cubic sapphire plates (straight linear edges, edge length 3 mm) (p < 0.05). The top surfaces of the sapphire plates (cubic and cylindrical) were wetted at 8.4 mJ/m2 (SE = 0.54, n = 20) and 9.1 mJ/m2 (SE = 0.50, n = 20), respectively, but the difference was not significant (p > 0.05). The surfaces of the plates showed significantly higher resistance to spreading compared to that of the edges, as substantially lower surface tensions were required to initiate wetting (p < 0.05). Similar results were found for talc particles, were the edges of macro- and microcrystalline particles were wetted at 7.2 mJ/m2 (SE = 0.52, n = 20) and 8.2 mJ/m2 (SE = 0.30, n = 20) (p > 0.05), respectively, whereas the surfaces were wetted at 3.8 mJ/m2 (SE = 0.89, n = 20) and 5.8 mJ/m2 (SE = 0.52, n = 20) (p < 0.05), respectively. Further experiments with pollen of malvaceae and maize (spiky and fine knobbly surfaces) were wetted at 10.0 mJ/m2 (SE = 0.52, n = 10) and 22.75 mJ/m2 (SE = 0.81, n = 10), respectively (p < 0.05). These results show that resistance to spreading of a DPPC film on various surfaces is dependent on the extent these surfaces are curved. This is seen with cubic sapphire plates which have at their corners a radius of curvature of about 0.75 microm, spiky malvaceae pollen with an even smaller radius on top of their spikes, or talc with various highly curved surfaces. These highly curved surfaces resisted wetting by the DPPC film to a higher degree than more moderately curved surfaces such as those of cylindrical sapphire plates, maize pollens, or polystyrene spheres, which have a surface free energy similar to that of talc but a smooth surface. The macroscopic plane surfaces of the particles demonstrated the greatest resistance to spreading. This was explained by the extremely fine grooves in the nanometer range, as revealed by electron microscopy. In summary, to understand the effects of airborne particles retained on the surfaces of the respiratory tract, and ultimately their pathological potential, not only the particle size and surface chemistry but also the particle shape should be taken in consideration.     

A transient stochastic simulation–optimization model for operational fuel planning in-theater

Army fuel planners are responsible for developing daily loading plans that specify which tankers to load, with what fuel, and where to send the loaded tankers. The tools used to accomplish this task are custom built spreadsheets which require large amounts of time and effort to use, update, and keep free of errors. This research presents a transient stochastic simulation–optimization model of the in-theater bulk fuel supply chain, where the simulation model is used to simulate the performance of the fuel supply chain under a particular fuel distribution policy and the optimization portion is used to update the policy so that it results in the performance desired by the Army fuel planner. The fuel distribution policy can then be used to derive the daily loading plan. Due to the multi-objective nature of the problem, the set of policies that form the efficient frontier are all candidate policies for the Army fuel planner to select from. Results of experimentation with a wide variety of supply chain scenarios indicate that, for a given supply chain scenario, the optimization portion of the model identifies a set of fuel distribution policies that address the objectives of the Army fuel planner. In addition, the simulation–optimization model comfortably solves the largest supply chain scenarios the Army fuel planner would reasonably be expected to encounter.     

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