First coordination shell

C. Hydrated monovalent cation approaching an area of the membrane where an amphiphilic carrier is located with its lipid side in contact with the lipid layer and with polar oxygens directed outward into solution. On close approach to the carrier, water molecules in the first coordination shell become replaced by carrier oxygens. As the ion becomes enclosed, the carrier moves into the lipid layer. 

D. Hydrated monovalent cation approaching the carbonyl oxygens of a transmembrane channel. The carbonyl oxygens at the mouth replace water in the first coordination shell. As the ion moves through the channel, it retains one bound water molecule preceding and following it and the walls of the channel provide for lateral coordination. (Parts A through D reproduced with permission from Ref. 6>. 

The copper EXAFS of the ruthenium-copper clusters might be expected to differ substantially from the copper EXAFS of a copper on silica catalyst, since the copper atoms have very different environments. This expectation is indeed borne out by experiment, as shown in Figure 2 by the plots of the function K x(K) vs. K at 100 K for the extended fine structure beyond the copper K edge for the ruthenium-copper catalyst and a copper on silica reference catalyst ( ). The difference is also evident from the Fourier transforms and first coordination shell inverse transforms in the middle and right-hand sections of Figure 2. The inverse transforms were taken over the range of distances 1.7 to 3.1A to isolate the contribution to EXAFS arising from the first coordination shell of metal atoms about a copper absorber atom. This shell consists of copper atoms alone in the copper catalyst and of both copper and ruthenium atoms in the ruthenium-copper catalyst. 

This discussion of EXAFS on ruthenium-copper clusters has emphasized qualitative aspects of the data analysis. A quantitative data analysis, yielding information on the various structural parameters of interest, has also been made and published (8). Of particular Interest was the finding that the average compo tion of the first coordination shell of ruthenium and copper atoms about a ruthenium atom was about 90% ruthenium, while that about a copper atom was about 50% ruthenium. Details of the methods Involved in the quantitative analysis of EXAFS data on bimetallic clusters can be obtained from our original papers (8.12-15). 

There appears to be concentration of rhodium in the surface of the iridium-rhodium clusters, on the basis that the total number of nearest neighbor atoms about rhodium atoms was found to be smaller than the nunber about iridium atoms in both catalysts investigated. This conclusion agrees with that of other workers (35) based on different types of measurements. The results on the average compositions of the first coordination shells of atoms about iridium and rhodium atoms in either catalyst Indicate that rhodium atoms are also incorporated extensively in the interiors of the clusters. In this respect the iridium-rhodium system differs markedly from a system such as ruthenium-copper (8), in which the copper appears to be present exclusively at the surface. 

A. The structure of the first coordination shell in liquid water. Science 2004, 304, 995-999. 

Such a function exhibits peaks (Fig. 9C) that correspond to interatomic distances but are shifted to smaller values (recall the distance correction mentioned above). This finding was a major breakthrough in the analysis of EXAFS data since it allowed ready visualization. However, because of the shift to shorter distances and the effects of truncation, such an approach is generally not employed for accurate distance determination. This approach, however, allows for the use of Fourier filtering techniques which make possible the isolation of individual coordination shells (the dashed line in Fig. 9C represents a Fourier filtering window that isolates the first coordination shell). After Fourier filtering, the data is back-transformed to k space (Fig. 9D), where it is fitted for amplitude and phase. The basic principle behind the curve-fitting analysis is to employ a parameterized function that will model the... 

Table V shows redox potentials (Ey2) for ferric complexes of a series of natural and synthetic siderophores. The first coordination shell of the complex formed between iron and siderophore...

The kinetics and mechanism of iron-siderophore complex formation are influenced by the oxidation state and composition of the first coordination shell of iron. The iron sequestration... 

The implications of these mechanistic studies for our understanding of environmental iron sequestration by siderophores is as follows. The hydroxyl containing aqua ferric ions will tend to form ferri-siderophore complexes more rapidly than the hexaaqua ion and ferrous ion will be sequestered more rapidly than the ferric ion. However, once in a siderophore binding site the ferrous ion will be air oxidized to the ferric ion, due to the negative redox potentials (see Section III.D). This also means that Fe dissolution from rocks will be influenced by mineral composition (other donors in the first coordination shell) as well as surface reductases in contact with the rock, and of course surface area (4,13). 

BLM transport systems for ferrioxamine B were also devised based on first coordination shell recognition via ternary complex formation utilizing vacant coordination sites on the Fe(III) center (Fig. 29) (199). The tetra-coordinated substrate complex selectively transported was partially dechelated diaqua-ferrioxamine B and coordinately unsaturated di-hydroxamato iron(III) complexes, which utilized a hydrophobic membrane bound bidentate chelator as a carrier for selective transport. Active transport for these systems was accomplished using a pH gradient (199). 

A combination first coordination shell-second coordination shell based recognition BLM transport system was devised, including active transport (200). This is based on a labile dihydroxamic acid system, including alcaligin, and a free lysine hydroxamic acid ligand capable of ternary complex formation to... 

Solvent exchange reactions on metal cations are among the most simple chemical reactions a solvent molecule situated in the first coordination shell of the ion is replaced by another one, normally entering from the second shell. They are generally considered as fundamental reactions for metal ions in solution, since they constitute an important step in complex-formation reactions on metal cations. The reaction is... 

Figure 6.15 Ru and Cu K-edge EXAFS spectra at 100 K with Fourier transforms and inverse transforms of the first coordination shell of Ru/Si02, Cu/Si02 and Ru-Cu/Si02 catalysts. The inverse transforms correspond to distances between 1.7 and 3.1 A (from Sinfelt et al. [39]).

Comparison of the Cu K-edge EXAFS signals for the monometallic Cu/Si02 and the bimetallic Ru-Cu/Si02 catalyst, on the other hand, provides clear evidence for the proximity of ruthenium to copper atoms in the latter. This is seen in the different shape of the measured EXAFS signal and the distorted inverse transform of the first coordination shell. Note that the intensity of the latter is weaker for the bimetallic catalyst, while the region between k=8 and k=15 A-1 has become more important, which points to the presence of a scattering atom heavier than copper in the first coordination shell. The reduced intensity in the Cu Fourier transform of the bimetallic catalyst is indicative of a lower coordination of the copper, which is characteristic of surface atoms. 

Quantitative analysis of the data revealed that the first coordination shell of the average Ru atom in the bimetallic catalyst contains 90% Ru and 10% Cu, whereas the first coordination shell of the average Cu atom contains 50% Cu and 50% Ru. This, together with the overall lower coordination of copper, is in agreement with particles consisting of an Ru core and an outer shell of Cu atoms. 

An analysis of the coordination numbers gives further understanding of the nature of the MoS2-like structure. For the catalyst recorded in situ it is seen that the first coordination shell contains about 6 atoms (Table II) which are in agreement with the 6 nearest neighbor sulfur atoms in well-crystallized MoS2. A similar result was previously obtained for alumina supported catalysts (12). 

We have also studied the coordination of the monocarbonate, bicarbonate, and tricarbonate complexes of neptunyl in water, by using both explicit water molecules and a continuum solvent model.84 The monocarbonate complex was shown to have a pentacoordinated structure, with three water molecules in the first coordination shell, and the bicarbonate complex has a hexacoordinated structure, with two water molecules in the first coordination shell. Overall good agreement with experimental results was obtained. 

Two coordination shells were found for Co in SAN, one at 2.33 and the other at 3.50 A (phase corrected). These two peaks correspond to Co-Si direct bonds (first coordination shell) and Co-Co scattering (second coordination shell). Only one major... 

T jo = nuclear relaxation times of solvent molecules outside the first coordination shell. 

---