Coordination complexes metal-free copolymers

In the second approach, metal-ion/complex was first attached to one of the polymer blocks. A thin film of the resulting polymer metal complex was then obtained by spin coating/solution casting. Alternatively, the polymer metal complex may also be dissolved in a suitable solvent system that selectively dissolves one of the blocks. Micelles or nanosized aggregates formed in this case. The micellization of amphiphilic block copolymers and their use in the formation of metal nanoparticles has been discussed previously.44 A monolayer of micelles was introduced on a substrate surface by dipping or electrostatic attraction. The substrate was then subjected to further chemical or physical treatments as mentioned earlier. The third approach involves the formation of micelles from the metal-free block copolymer in a suitable solvent system. The micelle solution was then added with metal ion, which was selectively coordinated to one of the blocks. These micelle-metal complexes can also be processed by a procedures similar to the second approach. 

From the ratio of polyampholyte and metal ion concentrations at which a maximum reaction rate is observed one can ascertain the composition of catalytically active complexes [82]. The effect of [polyampholyte]/[metal ion] composition on Vq at a constant metal ion concentration for several polyampholyte-metal systems is illustrated in Fig. 7. For a majority of the systems the ratio is not higher than 3. These results support the contention that catalytic activity ctm occur only in the presence of free sites in the coordination sphere of a metal ion [83]. An exception to this is the styrene-A/ N-dimethylaminopropylmonoamide of maleic acid/copper(II) complex for which a maximum rate of H2O2 decomposition was found at [polyampholyte]/ [Cu ] = 16 1 and pH = 8.5. Because the isoelectric state of the polyampholyte is attained at pH 6.4 it is unlikely that the compression of the macromolecule coil has affected the complex composition. Apparently it is the presence of hydrophobic styrene units in the copolymer that affects the reaction rate. 

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