Cerium model

The aforementioned inconsistencies between the paralinear model and actual observations point to the possibility that there is a different mechanism altogether. The common feature of these metals, and their distinction from cerium, is their facility for dissolving oxygen. The relationship between this process and an oxidation rate which changes from parabolic to a linear value was first established by Wallwork and Jenkins from work on the oxidation of titanium. These authors were able to determine the oxygen distribution in the metal phase by microhardness traverses across metallographic sections comparison of the results with the oxidation kinetics showed that the rate became linear when the metal surface reached oxygen... 

The diastereoselectivity of the reaction may be rationalized by assuming a chelation model, which has been developed in the addition of Grignard reagents to enantiomerically pure a-keto acetals7,8. Cerium metal is fixed by chelation between the N-atom, the methoxy O-atom and one of the acetal O-atoms leading to a rigid structure in the transition state of the reaction (see below). Hence, nucleophilic attack from the Si-face of the C-N double bond is favored4. 

Fig. 2b. Bone and liver uptake of inhaled cerium in Class D, W and Y compounds (no radioactive decay) as projected from the TGLD model coupled with the ICRP committee II model for radiocerium,...

Fig. 17. Biological model recommended for describing the uptake and retention of cerium by humans after inhalation or ingestion. Numbers in parentheses give the fractions of the material in the originating compartments which are cleared to the indicated sites of deposition. Clearance from the pulmonary region results from competition between mechanical clearances to the lymph nodes and gastrointestinal tract and absorption of soluble material into the systemic circulation. The fractions included in parentheses by the pulmonary compartment indicate the distribution of material subject to the two clearance rates however, these amounts will not be cleared in this manner if the material is previously absorbed into blood. Transfer rate constants or functions, S(t), are given in fractions per unit time. Dashed lines indicate clearance pathways which exist but occur at such slow rates as to be considered insignificant compared to radioactive decay of the cerium isotopes.

Kurshakova, N. N. and Ivanov, A. E. (1963). A model of experimental lung cancer caused by intratracheal introduction of radioactive cerium, Bull. Exp. Biol. Med. USSR 54, 787. 

A typical chemical system is the oxidative decarboxylation of malonic acid catalyzed by cerium ions and bromine, the so-called Zhabotinsky reaction this reaction in a given domain leads to the evolution of sustained oscillations and chemical waves. Furthermore, these states have been observed in a number of enzyme systems. The simplest case is the reaction catalyzed by the enzyme peroxidase. The reaction kinetics display either steady states, bistability, or oscillations. A more complex system is the ubiquitous process of glycolysis catalyzed by a sequence of coordinated enzyme reactions. In a given domain the process readily exhibits continuous oscillations of chemical concentrations and fluxes, which can be recorded by spectroscopic and electrometric techniques. The source of the periodicity is the enzyme phosphofructokinase, which catalyzes the phosphorylation of fructose-6-phosphate by ATP, resulting in the formation of fructose-1,6 biphosphate and ADP. The overall activity of the octameric enzyme is described by an allosteric model with fructose-6-phosphate, ATP, and AMP as controlling ligands. 

The oxidation of D-fructose with cerium(IV) in sulfuric acid medium is inhibited by an increase in the acidity. A cationic surfactant, CTAB, catalyses the reaction, whereas SDS has no effect. The catalytic role of CTAB has been explained using the pseudophase model of Menger and Portnoy. A mechanism involving the formation of an intermediate complex between /3-D-fructopyranose and Ce(S04)32- has been proposed.61 The oxidation of cycloalkanones with cerium(IV) in sulfuric acid medium showed a negligible effect of acidity. Formation of an intermediate complex, which decomposes in the rate-determining step, has been suggested.62... 

Comparison of model fit variances for cerium indicates a definite superiority of the DFO model over single-site sorption models. The large data scatter in groundwater cerium concentrations, and the ambiguity in extraction inventory trends, indicate that systems producing significant colloidal material may require more specialized models and experimental methods to fully understand their transport mechanisms ... 

Fig. 7.4 High-resolution transmission electron microscopy (TEM) image of a rhodium on a modified cerium oxide (Ceo.gTbo.202 x) after reduction, showing how the metal is almost epitaxially attached to the support, (a) TEM image (b,c) digital diffraction patterns obtained by Fourier transformation from the images (d) structure model ...

Figure 4.27 (a) Ortep plot of one molecule and (b) stick bond model projection of Ce(OEP)2 [42]. (Reprinted with permission from J.W. Buchler, et ah, Metal complexes with tetrapyrrole ligands. 40. Cerium(IV) bis(octaethylporphyrinate) and dicerium(III) tris(octaethylporphyrinate) parents of a new family of lanthanoid double-decker and triple-decker molecules, Journal of the American Chemical Society, 108, no. 13, 3652-3659, 1986. 1986 American Chemical Society.)... 

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