Optical enrichment of a racemic chiral crystal by X-ray irradiation
GENERATION of optical activity in a racemic mixture of enantiomers, a process relevant to the origin of life and of naturally chiral compounds1, requires chirality in the interaction responsible for the transformation or the environment in which it occurs. Without violating this strict requirement, we have found a way in which optical enrichment of a racemic mixture can occur without any chiral specificity in the mechanism. A racemic mixture of (1-cyanoethyl)(piperidine)cobaloxime, which contains the chiral 1-cyanoethyl group, crystallizes in a chiral space group (P212121) in which R and S enantiomers occupy crystallographically distinct (diastereoisomeric) positions in the asymmetric unit cell. We have prepared single crystals of the D configuration. Irradiating the crystal with X-rays at 343 K causes racemization of the S en-antiomer while the R enantiomer remains unaltered. This racemization is thought to be due solely to the different volume constraints on the two enantiomers in their different crystal environments. The result is that the number of R molecules is increased at the expense of S, and so the overall composition of the crystal changes from racemic to enriched in the R enantiomer.
Photochrome-coupled metal complexes: molecular processing of photon stimuli.
The frontiers of novel photoresponsive materials constructed with photochromes and transition metal complexes are surveyed in this review. Strategies to develop new photofunctions are categorized into four types. In the first category, intramolecular electronic interactions between photochromes and metal complexes produce entangled responses such as redox-regulated photochromic reactions or tristable photochromism. In the second, light-induced molecular structural rearrangements of photochromes induce the transformation of flexible and labile coordination structures, which can be applied to complex photomechanics or photoelectron conversion. In the third, the photochromic moiety also acts as a photonic switch, transmitting a metal-metal interaction when it is located between two metal complex moieties. The last category concerns the development of new photochromic reactions, involving metal-ligand bond rearrangements. These reactions potentially induce drastic electronic tuning of the metal center, and can be used to develop light-driven molecular machines.
Ignition and burning rates of segregated waste combustion in packed beds.
Recent developments in national recycling and re-use programmes for municipal waste have led to segregation of an increasing proportion of waste to enhance material recovery. Several of the segregated streams contain materials that can not viably be re-used or recycled but can be used for energy recovery. In this study, the combustion of cardboard and waste wood was investigated in a small-scale packed bed reactor in order to provide fundamental data for the design/operation of moving bed furnaces. Key parameters of combustion including the ignition and burning rates were evaluated for various air flowrates and compared to the modelling results. Two successive stages of combustion were identified for both samples: the propagation of ignition front into the bed and combustion of the fuel above the ignition front. The burning rate of cardboard reached a peak of about 300 kg/m(2)h at the air flowrate of 936 kg/m(2)h and decreased at higher air flowrates. For waste wood, both the ignition and burning rates increased in the tested range of the air flowrate up to 702 kg/m(2)h, of which the values were very close to those for the cardboard. The model prediction was in good agreement with the test results for waste wood. However, the burning rate for cardboard was under-predicted due to strongly irregular shapes of the fuel.