Activation barriers, aggregation

The aggregation behaviour and the structure in solution of two closely related dilithium compounds 90 and 91 (Figure 16) was studied by Gunther, Maercker and coworkers, using one- and two-dimensional NMR techniques ( H, C, Li) . While in diethyl ether, both compounds exist as a dimer, the dimeric structure is partly broken up in THF or by the addition of TMEDA. Also, activation barriers and thermodynamic parameters of aggregate exchanges were determined by temperature-dependent NMR studies. 

One of the main factors influencing the activation barrier in fast electron-transfer reactions is the change in the polarization of the immediate space surrounding the activated complex in solution. The more-well-known salt effects as well as the relatively new field of micellar effects can be used as mechanistic probes in this context. Since micelles have a hydrophobic as well as a hydrophilic part, this creates two different kinds of interfaces where electron transfer can occur if one of either the oxidant or reductant is contained or associated with these molecular aggregates. A futuristic approach could be that studies of this kind may serve as models for enzymatic reactions with complex bioaggregates such as membranes. 

Membrane surfaces act as a promoter of crystallization by lowering the activation barrier to the nucleation stage, thus allowing molecules to aggregate in conditions of supersaturation that would not be adequate for the spontaneous nucleation. The relatively small elapsed time for the appearance of biomolecular crystals demonstrates the existence of the molecule-membrane interactions that favorably affect the mechanisms of nucleation. A short list of biomolecnles tested by the authors is reported in Figure 10.7. 

Some end-use applications may prefer the characteristics of foundry solid waste. For instance, spent foundry sand is a uniformly graded fine aggregate containing chemically active iron and organics. Spent foundry sand can be superior to other types of granular materials, such as compacted soils or clays, for hydraulic barriers. In this case, spent foundry sand provides better performance at lower cost. 

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