Origin of NMR shielding in fluorides
In this work, we analyze in detail the relation between electronic structure and fluorine nuclear magnetic resonance (NMR) shielding in a series of solid state alkali fluorides (LiF, NaF, KF, RbF, and CsF). For that purpose, we use solid-state NMR calculations implemented in the density functional theory full potential WIEN2K code (APW + lo). Both measurements and calculations show that the NMR shielding varies across the series by approximately 200 ppm. We focus our discussion on an explanation of the origin of the observed trend, and we show that the variation is mainly determined by contributions from “semicore” metal-p and valence F-p bands. More specifically, the trend in fluorine shielding can be related to the small but significant change in the hybridization of these states. A second important ingredient determining the value of the shielding is the presence and position of metal-d states in the unoccupied part of the Kohn-Sham bands. Although the present analysis has been demonstrated for the 19F nucleus in alkali fluorides, the main results are more general and can explain similar trends observed in other solids and for other nuclei.
Superposition model for isotropic chemical shift in ionic fluorides: from basic metal fluorides to transition metal fluoride glasses
Abstract Experimental measurements of 19 F isotropic chemical shifts on a large set of mainly ionic fluoride compounds (from simple metal fluorides to transition metal fluoride glasses) obtained by MAS NMR at 15 kHz spinning rate are simultaneously investigated. First, Ramsey's theory of the chemical shift with molecular orbitals obtained by Lodwin's orthogonalisation method is used to evaluate the isotropic part of the 19 F chemical shift in ionic fluorides for which the crystallographic structure and the atomic radial wavefunctions are known. Then, assuming that the paramagnetic part of the 19 F shielding in a given material is simply the summation of the paramagnetic contributions due to all the cations in the neighbourhood of the considered fluorine, a superposition model of the 19 F isotropic chemical shift is developed. Finally, this empirical approach is applied to complex fluoride compounds of unknown structure and it is demonstrated that it allows to obtain reliable structural informations. More generally, it can be applied to all the ionic fluorides.
Complications of motility peg placement for porous hydroxyapatite orbital implants
Aim: To evaluate the complications associated with pegging of porous hydroxyapatite orbital implants. Methods: Complications associated with pegging were retrospectively reviewed from the charts of 100 of 133 patients with hydroxyapatite implantation from 1993 to 2000. Results: 48 (48%) of the 100 hydroxyapatite implanted patients who had undergone pegging were found to have problems with their pegs, including discharge (45.8%), peg falling out (20.8%), pyogenic granulomas (16.7%), popping peg (14.6%), hydroxyapatite visible around peg hole (8.3%), part of peg shaft visible (6.2%), peg drilled off centre (6.2%), peg drilled at an angle (4.2%), and excess movement of peg (4.2%). The standard peg fell out statistically more often than the peg and sleeve system (Yates's corrected χ2, p=0.038). There was a trend towards complications of the peg with use of a standard peg (versus sleeved peg) (p=0.226). Conclusions: There are several potential complications of pegging. Most complications are minor and can be managed successfully.