Divalent cation complexes

Sobalik, Z., Tvaruzkova, Z. and Wichterlova, B. (1998) Skeletal T-O-T vibrations as a tool for characterization of divalent cation complexation in ferrierite, J. Phys. Chem. B, 102, 1077. 

A single-atom bridging mode of urea is observed in 38 with rather long Hg—O bonds (2.66 A) (94). Such a situation is usually met in monovalent cation complexes of urea, while it is rare for divalent cation complexes, where in most cases nonbridging O coordination with shorter M—O distances is observed. Comparison with free urea reveals a noticeable lengthening of the C=0 bond and a slight shortening of the C—N bonds in 38. 

Figure 4. Stabilities of some class B divalent cation complexes at I = 0 based on published data. EN values for Hg Cd Pb Sn and Zn are 1.8,1.5, 1.6, 1.7, and 1.5, respectively (29).

Figure 3.7 Stabilities of some class B divalent cation complexes are shown at zero ionic strength, based on published data. Ligand EN values are 1 (2.66), Br (2.96), Cl- (3.16), F- (3.98), OH" (3.1), and SH (2.33). Cation EN values all range from 1.6 to 1.7, except EN = 2.00 for Hg -. Reprinted with permission from Techniques of estimating thermodynamic properties for some aqueous complexes of geochemical interest, D. Langmuir. In Chemical modeling in aqueous systems, ed. E. A. Jenne, Am. Chem. Soc. Symp. Sen 93. Copyright 1979 American Chemical Society.

Energy level diagram for a silver halide type of crystal containing divalent cation impurities. -B is the binding energy of a vacancy-divalent cation complex. The separation of a divalent cation from its associated vacancy is referred to as ionization in the text. 

A chromatographic separation of the polymer molecules and a divalent cation complexation behavior, resulting in lower relative viscosities, have been evidenced. 

Polyethers. Antibiotics within this family contain a number of cycHc ether and ketal units and have a carboxyHc acid group. They form complexes with mono- and divalent cations that ate soluble ia aoapolar organic solvents. They iateract with bacterial cell membranes and allow cations to pass through the membranes causiag cell death. Because of this property they have been classified as ionophores. Monensia, lasalocid, and maduramicia are examples of polyethers that are used commercially as anticoccidial agents ia poultry and as growth promotants ia mmiaants. 

Electroanalytical chemistry is one of the areas where advantage of the unique properties of SAMs is clear, and where excellent advanced analytical strategies can be utilized, especially when coupled with more complex SAM architectures. There are a number of examples where redox reactions are used to detect biomaterials (357,358), and where guest—host chemistry has been used to exploit specific interactions (356,359). Ion-selective electrodes are an apphcation where SAMs may provide new technologies. Selectivity to divalent cations such as Cu " but not to trivalent ions such as Fe " has been demonstrated (360). 

New chelating ion-exchange resins are able to selectively remove many heavy metals in the presence of high concentrations of univalent and divalent cations such as sodium and calcium. The heavy metals are held as weaMy acidic chelating complexes. The order of selectivity is Cu > Ni > Zn > Co > Cd > Fe + > Mn > Ca. This process is suitable for end-of-pipe polishing and for metal concentration and recovery. 

The type of catalyst influences the rate and reaction mechanism. Reactions catalyzed with both monovalent and divalent metal hydroxides, KOH, NaOH, LiOH and Ba(OH)2, Ca(OH)2, and Mg(OH)2, showed that both valence and ionic radius of hydrated cations affect the formation rate and final concentrations of various reaction intermediates and products.61 For the same valence, a linear relationship was observed between the formaldehyde disappearance rate and ionic radius of hydrated cations where larger cation radii gave rise to higher rate constants. In addition, irrespective of the ionic radii, divalent cations lead to faster formaldehyde disappearance rates titan monovalent cations. For the proposed mechanism where an intermediate chelate participates in the reaction (Fig. 7.30), an increase in positive charge density in smaller cations was suggested to improve the stability of the chelate complex and, therefore, decrease the rate of the reaction. The radii and valence also affect the formation and disappearance of various hydrox-ymethylated phenolic compounds which dictate the composition of final products. 

The effect of the nature of the divalent cation is very pronounced as illustrated in Figure 2 on sample A30. Pectins were found to be much more sensitive to copper than to calcium. A scale of affinity towards divalent cations can be easily obtained this way [18]. This result corroborates what has been measured by pH titration upon addition of increasing amount of cations [28,29], where the order of decreasing selectivity was Pb = Cu Zn > Cd = Ni > Ca. This scale does not follow the size of the radius of the cations but is in agreement with the sequence of complex stability of Irving-Williams [30]. 

Some divalent cations such as Cu and Pb form very stable complexes with pectate, but are unlikely to be present at sufiScient concentration in the apoplast of plants to form a major fraction of the counterions associated with the pectic fraction in vivo. The Al ion may deserve closer examination, as it is certainly able to displace Ca from cell walls and reaches substantial concentrations in plant roots under some conditions [60,61]. aluminium is not usually considered to be freely translocated, however. Basic peptides with their negative charges spaced at a similar interval to galacturonans (0.43 nm or a small multiple thereof) can in principle have a very high afiBnity for pectate [62,63], but the extensins that are associated with the most insoluble pectic fractions [M] do not appear to have this type of structure. The possibility that the non-extractable pectic polymers in most cell walls are very strongly complexed with some cation other than Ca " cannot be ruled out, but there is little evidence to support it at present. 

The effect of pH and cation concentration on pectinesterase (PE) activation and permeation on 30 kD MWCO ultrafiltration (UF) membrane was evaluated. In order of increasing effectiveness, PE activity was stimulated by monovalent and divalent cations, poly amines and trivalent cations. A similar trend was observed for permeation on UF membranes. Cation addition and higher pH releases PE from an inactive complex, increases activity, and increases permeation. Higher cation concentration decreases activity and permeation. These results suggest a common mechanism is involved in PE activation and permeation. 

Some of these divalent cations form part of the Irving-Williams series Mn, Fe, Co, Ni, Cu and Zn. Irving Williams (1953) examined the stability constants of complexes of a number of divalent ions and found that the order... 

Setting times and hydrolytic stability of these cements are given in Table 8.3. In some cases the speed of reaction was very high, and practical cements could not be formed from ZnO or CaO even when these oxides were deactivated by heating. All the faster-setting cements exhibited good hydrolytic stability. The stability of the complexes between divalent cations and PVPA was found by a titrametric procedure to follow the order Mg Ca < Cu Zn (Ellis Wilson, 1991). This result was... 

Interactions of Metal Salts with the Formation. Interactions of metal salts with the formation and distribution of the retained aluminum in a porous medium may significantly affect the location and strength of gels. This interaction was demonstrated with polyacrylamide-aluminum citrate gels [1514]. Solutions were displaced in silica sand. The major findings of this study are that as the aluminum-to-citrate ratio increases, the aluminum retention increases. Furthermore, the amount of aluminum retained by silica sand increases as the displacing rate decreases. The process is reversible, but the aluminum release rate is considerably slower than the retention rate. The amount of aluminum released is influenced by the type and the pH level of the flowing solution. The citrate ions are retained by silica sand primarily as a part of the aluminum citrate complex. Iron, cations, and some divalent cations cannot be used in the brine environment. 

Another material based on the crown ether extractant 4,4 (5 )-bis(t-butyl-cyclohexano)-18 crown-6, marketed under the name Sr-Spec, is useful for separations involving divalent cations including Pb, Ba, and Ra (Horwitz et al. 1991). For Ra analysis by TIMS, Ra-Ba separations are required because the presence of Ba drastically decreases the ionization efficiency of fg Ra samples from 10% to <1%. This material has been widely used for separations of Ra from Ba (e.g., Chabaux et al. 1994 Lundstrom et al. 1998 Rihs et al. 2000 Joannon and Pin 2001 Pietruszka et al. 2002) and is a complement or alternative to cation exchange separations for EDTA complexes of these elements (Volpe et al. 1991 Cohen and O Nions 1991). Sr-Spec material would also be useful for °Pb analysis, since Pb has a greater distribution coefficient than Sr with this extractant. 

Triphenylformazan behaves as a bidentate ligand forming 2 1 complexes (217) with divalent copper, nickel, and cobalt.377 Formazan metal complexes can be compared to complexes of azo dyes or beta diketones due to structural similarity.301,302 In general, formazan metal complexes have low stability toward acids. However, when electron-donating substituents are added to the aromatic ring, a considerable enhancement in stability is observed. Cationic complexes of type 218 are also known. The complexation of formazan with metal cation can be accompanied by oxidation to the tetrazolium salt and the formation of a complex... 

Divalent cations, although not essential, can favor complexing of heparin by lipoproteins,440 with possible formation of bridges between an-... 

A number of substances have been discovered in the last thirty years with a macrocyclic structure (i.e. with ten or more ring members), polar ring interior and non-polar exterior. These substances form complexes with univalent (sometimes divalent) cations, especially with alkali metal ions, with a stability that is very dependent on the individual ionic sort. They mediate transport of ions through the lipid membranes of cells and cell organelles, whence the origin of the term ion-carrier (ionophore). They ion-specifically uncouple oxidative phosphorylation in mitochondria, which led to their discovery in the 1950s. This property is also connected with their antibiotic action. Furthermore, they produce a membrane potential on both thin lipid and thick membranes. 

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