In 1981, the macrocyclic methylene-bridged glycoluril hexamer (CB[6]) was dubbed "cucurbituril" by Mock and co-workers because of its resemblance to the most prominent member of the cucurbitaceae family of plants--the pumpkin. In the intervening years, the fundamental binding properties of CB[6]-high affinity, highly selective, and constrictive binding interactions--have been delineated by the pioneering work of the research groups of Mock, Kim, and Buschmann, and has led to their applications in waste-water remediation, as artificial enzymes, and as molecular switches. More recently, the cucurbit[n]uril family has grown to include homologues (CB[5]-CB[10]), derivatives, congeners, and analogues whose sizes span and exceed the range available with the alpha-, beta-, and gamma-cyclodextrins. Their shapes, solubility, and chemical functionality may now be tailored by synthetic chemistry to play a central role in molecular recognition, self-assembly, and nanotechnology. This Review focuses on the synthesis, recognition properties, and applications of these unique macrocycles.

The cucurbit[n]uril family

Dynamic combinatorial chemistry.

2.2.1. Polyisocyanates 6117 2.2.2. Polysilanes 6118 2.2.3. Polyacetylenes 6120 2.3. Foldamer-Based Helical Polymers 6124 2.3.1. Click Polymerization 6126 2.3.2. Ring-Closing Reaction 6126 2.4. Other Types of Helical Polymers 6127 2.4.1. π-Conjugated Helical Polymers 6127 2.4.2. Metallosupramolecular Helical Polymers 6128 2.5. Induced Helical Polymers 6130 2.5.1. Induced Helical Polyacetylenes 6130 2.5.2. Other Induced Helical Polymers and Oligomers 6132

Helical polymers: synthesis, structures, and functions

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

Enzyme-like catalysis by molecularly imprinted polymers.

Highly crosslinked polymers are prepared by radical copolymerization of β-D-fructopyranose 2,3:4,5-bis-O-((4-vinylphenyl)boronate) and α-D-galactopyranose 1,2:3,4-bis-O-((4-vinylphenyl)boronate) with a large amount of cross-linking agent. After splitting off the respective templates these polymers were used for racemic resolution of the racemates of the templates with separation factors α as high as α=2.36 in the batch procedures. The influence of the arrangement of functional groups within the cavities versus the spatial requirements (shape selectivity) on selectivity is discussed in detail. In the examples presented here, the orientation of the functional groups inside the cavity is the dominating factor; shape selectivity is only of secondary importance

Racemic resolution of free sugars with macroporous polymers prepared by molecular imprinting. Selectivity dependence on the arrangement of functional groups versus spatial requirements

Guenter Wulff

Papers

Enzyme-like catalysis by molecularly imprinted polymers.

Racemic resolution of free sugars with macroporous polymers prepared by molecular imprinting. Selectivity dependence on the arrangement of functional groups versus spatial requirements

Enzyme-Like Catalysis by Molecularly Imprinted Polymers

Microgel-supported Oxazaborolidines: Novel Catalysts for Enantioselective Reductions

On the synthesis of C-glycosyl compounds containing double bonds without the use of protecting groups