RESUMO
Boron-doped microcrystalline diamond (BMD) and nanocrystalline diamond (BND) thin films were grown on Si substrates by microwave-assisted chemical vapor deposition, and their field emission properties were evaluated. BND exhibited a lower turn-on field and higher field enhancement factor than BMD. Furthermore, in a long-term emission stability test, BND showed only a 4% increase in the current density after 12 h of emission, whereas the current density of BMD decreased by - 59%. These results indicate that BND is a more stable and viable current emitter than BMD.
RESUMO
This paper addresses the decades-old problem of gaining a measure of intellectual control over the fate of the diradical intermediate in not-obviously-concerted thermal rearrangements. It focuses mainly on the stereochemistry of the thermal rearrangement of cis- and trans-1-cyano-2-trans-propenylcyclobutane to the related ring-enlarged products, 4-cyano-3-methylcyclohexenes. The complete stereochemical profile is revealed by the incorporation of a pair of cis deuterons to serve as a stereochemical lighthouse. The striking result (besides providing a further example of the inapplicability of the orbital symmetry rules of Woodward and Hoffmann to not-obviously-concerted reactions) is the predominance of the same stereoisomer regardless whether starting from the cis or trans educt. This preference is rationalized by a simple conceptual scheme based on two premises of the behavior of the diradical as intermediate: removal of the diradical from the caldera of rotationally labile conformations occurs whenever the two radical centers come within bonding distance in an appropriate orientation of orbitals; relative internal rotational rates are in the order, cyanomethyl faster than methallyl, faster than internal rotation about the backbone.
