Covalently attached complexes immobilization techniques

A problem especially with oxidation catalysts is that the metals in their highest oxidation state tend to be less strongly associated with a support, so that the reaction conditions can lead to leaching of the metal complex from the support. To overcome this problem, microencapsulation, as an immobilization technique for metal complexes, has been introduced by Kobayashi and coworkers. In the microencapsulation method, the metal complex is not attached by covalent bonding but is physically enveloped by a thin film of a polymer, usually polystyrene. With this technique leaching of the metal can be prevented. In 2002, Lattanzi and Leadbeater reported on the use of microencapsulated VO(acac)2 for the epoxidation of allylic alcohols. In the presence of TBHP as oxidant, it was possible to oxidize a variety of substrates with medium to good yields (55-96%) and diastereomeric ratios (60/40 to >98/2) (equation 42). The catalyst is easily prepared and can be reused several times without significant loss in activity. 

However, the focus of the major part of the chapters lies on the coupling chemistry used for DNA immobilization. Successful immobilization techniques for DNA appear to either involve a multi-site attachment of DNA (preferentially by electrochemical and/or physical adsorption) or a single-point attachment of DNA (mainly by surface activation and covalent immobilization or (strept)avidin-biotin linkage). Immobilization methods described here comprise physical or electrochemical adsorption, cross-linking or entrapment in polymeric films, (strept)avidin-biotin complexation, a surface activation via self-assembled monolayers using thiol linker chemistry or silanization procedures, and finally covalent coupling strategies. 

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