Solid structural features

The practical development of plant sterol drugs as cholesterol-lowering agents will depend both on structural features of the sterols themselves and on the form of the administered agent. For example, the unsaturated sterol sitosterol is poorly absorbed in the human intestine, whereas sitostanol, the saturated analog, is almost totally unabsorbable. In addition, there is evidence that plant sterols administered in a soluble, micellar form (see page 261 for a description of micelles) are more effective in blocking cholesterol absorption than plant sterols administered in a solid, crystalline form. 

Six members of this series could be isolated in modest yields as highly air-sensitive, dark blue or dark purple crystalline solids for which analytical, spectroscopic, and single-crystal X-ray analyses were fully consistent with the side-on-biidged N2 structures shown in Scheme 102. These complexes show unusual structural features as well as a unique reactivity. An extreme degree of N = N bond elongation was manifested in rf(N-N) values of up to 1.64 A, and low barriers for N-atom functionalization allowed functionalization such as hydrogenation, hydrosilylation, and, for the first time, alkylation with alkyl bromides at ambient temperature. ... 

Incorporation into a Polymer Layer In recent years a new electrode type is investigated which represents a layer of conducting polymer (such as polyaniline) into which a metal catalyst is incorporated by chemical or electrochemical deposition. In some cases the specific catalytic activity of the platinum crystallites incorporated into the polymer layer was found to be higher than that of ordinary dispersed platinum, probably because of special structural features of the platinum crystallites produced within the polymer matrix. A variant of this approach is that of incorporating the disperse catalyst directly into the surface layer of a solid polymer electrolyte. 

In its solid state, however, the basic structural features of ordinary hexagonal ice (ice I) are well established. In this structure (Figure 1.2), each water molecule is hydrogen bonded to four others in nearly perfect tetrahedral coordination. This arrangement leads to an open lattice in which intermolecular cohesion is large. 

At this stage it could be useful to make a comment on the structural features of complexes 4-17. The coordination number of the metal affects strongly the shape of the calix[4]arene fragment. In the case of five-coordinate and, eventually, four-coordinate metals, the calix[4]arene moiety displays a cone, which changes to an elliptical conformation in the case of a six-coordinate metal.4,10 Such conformation changes, which appear in the solid state, are also detectable in solution, as in the... 

A diverse coordination chemistry is emerging for bismuth(III) made possible by a spacious and flexible coordination environment, allowing for coordination numbers in excess of 9. Although the available data are still limited, distinct trends are evident, and the polymeric solid-state features that may be assumed on the basis of high coordination numbers can be mediated by appropriate selection of organic-based ligands. The unusual structural arrangements observed for many types of complex may prove to be representative as the number of examples of such systems increases. 

There are three broad categories of materials that have been utilized in this endeavor. In the first, even in fully stoichiometric compounds, the ionic conductivity is high enough to be useful in devices because the cation or anion substructure is mobile and behaves rather like a liquid phase trapped in the solid matrix. A second group have structural features such as open channels that allow easy ion transport. In the third group the ionic conductivity is low and must be increased by the addition of defects, typically impurities. These defects are responsible for the enhancement of ionic transport. 

There are a number of ways in which this desirable state of affairs can be achieved. In one, a material that is a good ionic conductor by virtue of structural features (the layer structure (3-alumina, for example) can have the rest of the structure modified to become electronically conducting. In another approach, impurities can be introduced into a matrix to balance populations of both electronic and structural defects to generate a mixed conducting solid. Both approaches have been exploited in practice. 

The epoxide selectivity did not depend noticeably on the gross structural features of the catalyst. For instance, the selectivity in the epoxidation of 4 is about 85% on all solids (Table XIII). 

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