An overview of the wide range of nanoreactors that have been constructed from synthetic and biological building blocks using both covalent and noncovalent approaches is given. Focus is on self-assembled systems, varying in size from a few nanometers to tens of micrometers. The review is divided into several sections that cover the development of tailor-made nanoreactors, starting from small organic molecular containers expanding to large compartment-containing assemblies. First, the construction of capsules from low molecular weight compounds by means of covalent synthesis and self-assembly by highly directive and pre-designed interactions is discussed. Second, nanocapsules based on micellar and vesicular assemblies that are built up frow low molecular weight molecules are described. Finally, the construction of nanoreactors from macromolecular building blocks, as well as recent developments in the use of viruses as nanocontainers and reactors are outlined.

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Self-Assembled Nanoreactors

2. Thiol Oxidation to Disulfides 3007 3. Epoxidation of Alkenes 3007 4. Oxidation of Bromide 3008 5. Oxidation of Mercaptoethanol by Dioxygen 3008 V. Particle−Dendrimer Assemblies 3008 1. Hydrogenation 3008 2. Heck Reaction 3010 3. Anodic Oxidation of Ethanol 3010 VI. Redox Catalysis 3010 1. Anodic Oxygen Reduction 3010 2. Cathodic Reduction of CO2 to CO 3010 3. Ferrocenes as Redox Mediators for Glucose Oxidation 3010

Dendritic Catalysts and Dendrimers in Catalysis

Regulation of membrane enzymes by lipids

DNA-enhanced peroxidase activity of a DNA aptamer-hemin complex

Reverse micelles as hosts for proteins and small molecules.

Catalysis in micellar and macromolecular systems

Publisher Summary This chapter reviews the importance of micellar catalysis in relation to mechanistic physical–organic and bio-organic chemistry, to enable to design meaningful experiments in the area, and to guide one through the abundant literature of surfactants and solubilization. Although solubilization by surface active agents has found considerable utility in pharmaceutical and industrial processes, the attention is primarily focussed on the mechanistic aspects of micellar catalyzed organic reactions. The subject is in its rapidly growing infancy, and is scattered and involves interdisciplinary collaboration among colloid, electro, structural, biological, pharmaceutical and organic chemists. The effects of many charged macromolecules, such as polymers, on ionic reactions can be qualitatively predicted on the basis of simple electrostatic considerations analogous to those involved in Hartley's rule.

Micellar Catalysis in Organic Reactions: Kinetic and Mechanistic Implications

Micellar-catalyzed hydrolysis of nitrophenyl phosphates

Proton magnetic resonance investigations of alkylammonium carboxylate micelles in nonaqueous solvents. II. Effects of carboxylate structure in benzene and in carbon tetrachloride

Changes in the chemical shifts for butyl (BAP), hexyl (HAP), octyl (OAP), decyl (DeAP), and dodecyl (DAP) ammonium propionates in benzene and in carbon tetrachloride as functions of their concentrations have established the formation of micelles. Treatment of the 1H n.m.r. data afforded values for the critical micelle concentration, the aggregation number and the equilibrium constant for the formation of micelles in benzene listed in sequence as follows: BAP, (4.5–5.5)× 10–2 M, 4, 1 × 104 M1–n; HAP, (2.2–3.2)× 10–2 M, 7, 5 × 102 M1–n; OAP, (1.5–1.7)× 10–2 M, 5, 1 × 108 M1–n;; DeAP, (8–10)× 10–3 M; DAP, (3–7)× 10–3 M, and those in carbon tetrachloride: BAP, (2.3–2.6)× 10–2 M, 3, 9 × 102 M1–n; HAP, (2.1–2.4)× 10–2 M, 7, 7 × 1011 M1–n; OAP, (2.6–3.1)× 10–2 M, 5, 5 × 107 M1–n; DeAP, (2.2–2.7)× 10–2 M, 5, 1 × 107 M1–n; DAP, (2.1–2.5)× 10–2 M, 4, 5 × 104 M1–n. These micelles have their polar head groups in the interior of the aggregate while the hydrophobic carbon chain is in contact with the non-polar solvent.

Eleanor J. Fendler

Papers

Catalysis in micellar and macromolecular systems

Micellar Catalysis in Organic Reactions: Kinetic and Mechanistic Implications

Micellar-catalyzed hydrolysis of nitrophenyl phosphates

Proton magnetic resonance investigations of alkylammonium carboxylate micelles in nonaqueous solvents. II. Effects of carboxylate structure in benzene and in carbon tetrachloride

Proton magnetic resonance investigations of the formation of alkylammonium propionate micelles in benzene and in carbon tetrachloride