Synthesis of novel chiral bidentate hydroxyalkyl-N-heterocyclic carbene ligands and their application in palladium-catalyzed Mizoroki–Heck couplings and asymmetric addition of diethylzinc to benzaldehyde

A small library of new chiral bidentate hydroxyalkyl-imidazolium salts 1 is conveniently synthesized on multi-gram scale from inexpensive and commercially available chiral pool amino acids. The corresponding carbenes, generated by deprotonation of imidazolium salts 1, in combination with palladium(II) chloride were tested in the Mizoroki–Heck coupling reaction. The most significant results in terms of yields and reactivities were achieved with low catalyst loading. The catalytic activities of these imidazolium salts were also investigated in the asymmetric addition of diethylzinc to benzaldehyde. The use of MgO nanoparticles as an additive in conjunction with these ligands played a crucial role in increasing the efficiency of these reactions.     

Anionic polymerisation of caprolactam at the small-scale via DSC investigations

This work was part of a major project aiming to produce polyamide 6 parts using an additive manufacturing process. This is by manufacturing 3D parts layer by layer. The influence of heating strategy (heating rate, cooling rate and maximum temperature) on anionic polymerisation of caprolactam in a small-scale was investigated by means of differential scanning calorimetry (DSC). The relationship between heating rate and the polymerisation–crystallisation processes was determined. Two different catalyst/activator compositions were used to study the influence of a di-functional activator on polymerisation. Results showed that unlike cooling rate, the heating rate and maximum heating temperature had a major effect on the final properties of polymer such as crystallinity, monomer conversion and polymer chains regularity. Using a di-functional activator resulted in slowing down the crystallisation process due to the enhanced rate of branching.     

An input relaxation measure of efficiency in stochastic data envelopment analysis

We introduce stochastic version of an input relaxation model in data envelopment analysis (DEA). The input relaxation model, recently developed in DEA, is useful to resource management [e.g. G.R. Jahanshahloo, M. Khodabakhshi, Suitable combination of inputs for improving outputs in DEA with determining input congestion, Appl. Math. Comput. 151(1) (2004) 263–273]. This model allows more changes in the input combinations of decision making units than those in the observed inputs of evaluating decision making units. Using this extra flexibility in input combinations we can find better outputs. We obtain a non-linear deterministic equivalent to this stochastic model. It is shown that under fairly general conditions this non-linear model can be replaced by an ordinary deterministic DEA model. The model is illustrated using a real data set.     

Biodegradable ultra high strength poly(L-lactide) rods for bone fixation

The hydrostatic molecular orientation technique was used to explore the highest mechanical improvements achievable for poly-L-lactide (PLLA). The mechanical attributes of these materials designed for bone fracture fixation devices, i.e. bending strength and modulus were measured and compared with those prepared by stretching method. The starting samples were prepared by conventional melt extrusion at 200 °C followed by hydrostatic extrusion at 140 °C using glycerin filled extruder. Uniaxially stretched rods were prepared by drawing in silicon oil at 120 °C. The physical properties of these rods are inadequate as mechanical supports in the dynamic healing process of the bone. Moreover, they underwent a marked strength deterioration when immersed in aqueous buffered solution for 90 days. On the other hand, the hydrostatic extrusion technique produced rods with progressively higher bending strength that showed only a small drop after 90 days hydrolytic degradation. Micrographs suggested a superior molecular orientation and packing, which could be associated with the improved performance. The hydrostatic extrusion technique proved to be a safe and effective approach for strengthening biodegradable polymeric materials for dynamic mechanical support in orthopedic medical devices.