Publications

2011

Liu, S.; Whisenhunt-Ioup, S. E.; Gibb, C. L. D.; Gibb, B. C. An improved synthesis of ’octa-acid’ deep-cavity cavitand.. Supramolecular chemistry 2011, 23, 480-485.
Publisher's Version

An improved synthesis of a water-soluble deep-cavity cavitand (octa-acid, 1) is presented. Previously (Gibb, C. L. D. & Gibb, B. C., J. Am. Chem. Soc., 2004, 126, 11408-11409) we documented access to host 1 in eight (non-linear) steps starting from resorcinol; a synthesis that required four steps involving chromatographic purification. Here we reveal a modified synthesis of host 1. Consisting of seven (non-linear) steps, this new synthesis involves only one chromatographic step, and avoids a minor impurity observed in the original approach. This improved synthesis will therefore be useful for the laboratories that are investigating the properties of these types of host.

Laughrey, Z.; Gibb, B. C. Water-soluble, self-assembling container molecules: an update. Chem. Soc. Rev. 2011, 40, 363-386.
Publisher's Version
Over the past five years, an important development in the area of self-assembling containers has been the increase in interest in those containers that function in aqueous solution. This progress is a reflection of a similar trend within supramolecular chemistry in general, and is driven in part by the need to address issues and challenges within the biological sciences, as well as a desire to develop new strategies for greener chemistries carried out in water. It is also an opportunity to learn more about fundamental topics such as the hydrophobic effect. In this critical review we discuss progress in aqueous-based self-assembling container molecules since 2005 (177 references).

2010

Liu, S.; Gan, H.; Hermann, A. T.; Rick, S. W.; Gibb, B. C. Kinetic resolution of constitutional isomers controlled by selective protection inside a supramolecular nanocapsule. Nature Chemistry 2010, 2, 847-852.
Publisher's Version
The concept of self-assembling container molecules as yocto-litre reaction flasks is gaining prominence. However, the idea of using such containers as a means of protection is not well developed. Here, we illustrate this idea in the context of kinetic resolutions. Specifically, we report on the use of a water-soluble, deep-cavity cavitand to bring about kinetic resolutions within pairs of esters that otherwise cannot be resolved because they react at very similar rates. Resolution occurs because the presence of the cavitand leads to a competitive binding equilibrium in which the stronger binder primarily resides inside the host and the weaker binding ester primarily resides in the bulk hydrolytic medium. For the two families of ester examined, the observed kinetic resolutions were highest within the optimally fitting smaller esters.
Grayson, S. M.; Gibb, B. C. Dendronized cavitands: A step towards a synthetic viral capsid?. Soft Matter 2010, 6, 1377-1382.
Publisher's Version
Dendronized cavitands represent unique macromolecular hosts for encapsulation of biologically relevant guests. They combine the highly specific guest binding exhibited by deep-cavity cavitands, with the modular yet monodisperse macromolecular structure provided by dendrimers. Because these structures retain the ability to assemble into dimeric capsules, they resemble a simplified synthetic analog of viral capsids, displaying a modular, functionalizable outer coating while providing a protective cavity for a range of small-molecule payloads. This article highlights their preparation, their characterization, and their unique potential for probing in vivo drug delivery.