Self-assembling catalysis

Scheme 12.21 Self-assembling catalysis via a ternary complex involving a bisubstrate reaction template.30...

Kreiter R, Kleij AW, Klein Gebbink RJM, van Koten G (2001) In Vogllc F, Schalley CA (eds) Dendrimers IV Metal Coordination, Self Assembly, Catalysis 217 163. Springer, Berlin Heidelberg New York... 

Vogtle, F. Schalley, C.A. Ed. Dendrimers - IV Metal Coordination, Self Assembly, Catalysis Topics in Current Chemistry Springer Berlin, 2001 Vol. 217. 

Adsorption on solid surfaces is an important elemental step that leads to various chemical processes including self assembly, catalysis and separation. For this reason the determination of molecular orientation rind intrastructure in the adsorbed phase have been the target of numerous studies in the field of surface science. Large body of these works, however, has been limited to metal or semiconductor substrates placed under vacuum conditions, mainly due to the requirements posed by the techniques employed to obtain such information. The present work demonstrates that with AFM similar information can be obtained on nonconductive surfaces, even under liquid-phase... 

Most studies of ORR catalysis by metalloporphyrins have been carried out using water-insoluble catalysts absorbed on a graphite electrode in contact with aqueous solution. In a limited number of cases, four other approaches have been used catalysts imbedded in an inert film (i.e., Nafion or lipid) on the electrode surface self-assembled monolayers of catalysts catalysts in aqueous or mixed organic/aqueous solutions in contact with an electrode and catalysis in mixed aqueous/organic medium using... 

Relatively little work has been done on ORR catalysis by self-assembled mono-layers (SAMs) of metalloporphyrins. The advantages of this approach include a much better defined morphology, structure, and composition of the catalytic film, and the surface coverage, and the capacity to control the rate at which the electrons ate transferred from the electrode to the catalysts [CoUman et al., 2007b Hutchison et al., 1993]. These attributes are important for deriving the catal5d ic mechatfism. The use of optically transparent electrodes aUows characterization of the chemical... 

The unique power of synthesis is the ability to create new molecules and materials with valuable properties. This capacity can be used to interact with the natural world, as in the treatment of disease or the production of food, but it can also produce compounds and materials beyond the capacity of living systems. Our present world uses vast amounts of synthetic polymers, mainly derived from petroleum by synthesis. The development of nanotechnology, which envisions the application of properties at the molecular level to catalysis, energy transfer, and information management has focused attention on multimolecular arrays and systems capable of self-assembly. We can expect that in the future synthesis will bring into existence new substances with unique properties that will have impacts as profound as those resulting from syntheses of therapeutics and polymeric materials. 

The scale of components in complex condensed matter often results in structures having a high surface-area-to-volume ratio. In these systems, interfacial effects can be very important. The interfaces between vapor and condensed phases and between two condensed phases have been well studied over the past four decades. These studies have contributed to technologies from electronic materials and devices, to corrosion passivation, to heterogeneous catalysis. In recent years, the focus has broadened to include the interfaces between vapors, liquids, or solids and self-assembled structures of organic, biological, and polymeric nature. 

Chemical scientists will seek new methods of generating nanostructures with a range of materials and processes that rely on ideas common in chemistry—self-assembly, diffusion, phase-separation, catalysis, wetting—to make these structures accessible and inexpensive. 

Self-assembly processes in nature are sometimes catalyzed by enzymes. Zeolites are, in many ways, the inorganic counterparts of enzymes, with their ability to selectively bind other substances and perform catalysis. Can templates or catalysts be effective in increasing rates and reducing defects in a wide range of nanostructured materials ... 

Recently, a ternary complex of cytochrome c with a polyanionic /1-cyclodextrin has been reported (85). A self-assembled supra-molecular bidentate N,P ligand for aqueous organometallic catalysis was also described (86). Although related, such systems are out of the scope of this review and will not be discussed further here. 

The self-assembly of a chiral Ti catalyst can be achieved by using the achiral precursor Ti(OPr )4 and two different chiral diol components, (R)-BINOL and (R,R)-TADDOL, in a molar ratio of 1 1 1. The components of less basic (R)-BINOL and the relatively more basic (R,R)-TADDOL assemble with Ti(OPr )4 in a molar ratio of 1 1 1, yielding chiral titanium catalyst 118 in the reaction system. In the asymmetric catalysis of the carbonyl-ene reaction, 118 is not only the most enantioselective catalyst but also the most stable and the exclusively formed species in the reaction system. 

Thermodynamically controlled self-assembly of an equilibrated ensemble of POMs with [AlVWnO40]6 as the main component could act as a catalyst for the selective delignification of wood (lignocellulose) fibers (Figure 13.2) [55], Equilibration reactions typical of POMs kept the pH of the system near 7 during the catalysis that avoided acid or base degradation of cellulose. 

---