Cluster sites

The Fe proteins are homodimers containing a single Fe4S4 cluster. Site-directed mutagenesis experiments showed that the cluster was probably held between the two subunits by ligation to two of the invariant cysteine residues from each subunit (16). This observation was confirmed later by X-ray crystallography (1) of the Fe protein... 

Fig. 6. A schematic view of the [3Fe-4S] Emd [4Fe-4S] cores, as versatile structures. The absence of one site leads to the formation of a [3Fe-4S] core. The cubane structure can incorporate different metals (in proteins, M = Fe, Co, Zn, Cd, Ni, Tl, Cs), and S, N, O may be coordinating atoms from hgands (Li). The versatihty csm be extended to higher coordination number at the iron site and a water molecule can even be a ligand, exchangeable with substrate (as in the case of aconitase (,87)). The most characteristic binding motifs are schematically indicated, for different situations proteins accommodating [3Fe-4S], [4Fe-4S], [3Fe-4S] + [4Fe-4S], and [4Fe-4S] -I- [4Fe-4S] clusters. A disulfide bridge may replace a cluster site (see text).

Cluster sites should be established for synoptic surface water surveys. This approach is discussed in detail in Chapter 3. 

Clustered sites would be located within a single ecoregion or at least have similar ecological characteristics (e.g., southeastern coastal plain streams), and would consist of a series of geographically proximal locations (approximately 10 to 20 water bodies) where similar atmospheric loads (or load reductions) are anticipated. Cluster sites would be sampled on a routine basis (e.g., quarterly) for a prolonged period of time. Individual sites within a cluster would be specifically chosen to represent a range of site characteristics that are known to affect Hg cycling (e g., pH, DOC,... 

The primary considerations discussed in this book for sampling the indicators include the scale of measurements needed the type of sampling location (e.g., undisturbed sites, clustered sites) the frequency of sampling (e.g., hourly, weekly, armually, bierrrrially) and the duration of sampling needed to detect trends. 

While an exact number of site clusters has not been proposed, the authors consider from approximately 3 to 10 clusters of sites to be appropriate. These clusters should represent different ecoregions with different ecological characteristics as well as different loadings (both in amount and source) of mercury deposition. Care should be taken to monitor different types of water bodies and watersheds (e.g., seepage lakes, drainage lakes, old reservoirs, rivers, and estuaries). Areas that should be considered as potential cluster site locations include lakes in northern New England/the Adirondacks, lakes in the upper Midwest, rivers and streams in the southeastern coastal plain, lakes in south-central and southeastern Canada, western... 

Figure 2.9.3 shows typical maps [31] recorded with proton spin density diffusometry in a model object fabricated based on a computer generated percolation cluster (for descriptions of the so-called percolation theory see Refs. [6, 32, 33]).The pore space model is a two-dimensional site percolation cluster sites on a square lattice were occupied with a probability p (also called porosity ). Neighboring occupied sites are thought to be connected by a pore. With increasing p, clusters of neighboring occupied sites, that is pore networks, begin to form. At a critical probability pc, the so-called percolation threshold, an infinite cluster appears. On a finite system, the infinite cluster connects opposite sides of the lattice, so that transport across the pore network becomes possible. For two-dimensional site percolation clusters on a square lattice, pc was numerically found to be 0.592746 [6]. 

Precise placement of metal complexing sites within the infrastructure of a cascade molecule is of importance from a variety of perspectives. In the construction of the above noted Micellane family (cf. Sect. 3.1), we reported the construction of dendrimers with four alkyne moieties at sites equidistant from each other in the interior (17, Fig. 8) [60]. These were treated with decaborane (B10H14) to afford 1,2-dicarba-closo-dodecaboranes (o-carboranes) [71]. Rendering boron clusters soluble in water is of interest because of their use in cancer treatment by Boron Neutron Cancer Therapy. First and second generation water-soluble dendrimers containing four and twelve precisely located boron cluster sites, respectively, were synthesized (e.g., 18). These water soluble dendrimers and their precursors were characterized by 13C-, and nB-NMR spectroscopy (Fig. 8). 

Figure 21. Comparison of the spectroscopically effective models for azide binding at the blnuclear copper active site in hemocyanln and the trlnuclear copper cluster site in laccase.

A finite array of charges is built taking into account the symmetry elements of the crystal. The charges of the outermost ions are adjusted in order to provide the correct value of the Madelung potential on each cluster site as well as the electrical neutrality... 

In Table 2 we present the shells which correspond to our best choice as well as the values of the scaling factors which result from the solution of the system of equations (1). The Madelung potential values on each cluster site calculated with the finite adjusted array are given in Table 3. When these values are compared to that of the Table... 

The cluster site approximation, CSA, has the great advantage that the required number of equations to handle the necessary variables is given by the product Cn (Oates and Wentl 1996) as compared to the exponential value C" aassociated with a full CVM treatment (Inden and Pitsch 1991). The CSA is a variant of the quasichemical model proposed by Li as early as 1949, where the number of clusters that are considered to contribute to the entropy are reduced by excluding all clusters that share edges or bonds. Kikuchi (1977) has deduced the consequential changes in entropy for an f.c.c. structure (Eqs 7.32 and 7.33), which places CSA intermediate... 

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