Molecular Encapsulation

Abstract

Louis Kahn, architect of the Salk Institute in La Jolla, said1 “even a common, ordinary brick wants to be something more than it is.” Suppose that were also true of molecules. We know that they can and do aggregate; they give complex structures, and by doing so they acquire new properties—functions that may not be apparent from a study of the individual components. This review is about molecular aggregates of a certain sort, namely, those that assemble and more or less completely surround other molecules. Taking part in this intimacy imparts unique properties to the participants, and new functions emerge from the aggregate as a whole. For the most part, we emphasize self‐complementary structures. Their ability to assemble—an expression of the molecule's desire to be something more than it is—results from instructions engineered into the molecules during their creation.

Aza Cope Rearrangement of Propargyl Enammonium Cations Catalyzed By a Self-Assembled “Nanozyme”

“…To emulate this mode of catalysis, many research groups have designed synthetic hosts capable of binding and directing the reactivity of guest molecules. [5][6][7][8][9][10][11][12][13] Upon encapsulation in either a synthetic host or an enzyme active site, the environment surrounding a guest molecule drastically differs from that of the bulk solution. Steric constraints, functional group positioning, and sequestration from other molecules can enforce reactivity and selectivity that is impossible when simpler catalysts are employed.…”

Chemical mimicry of viral capsid self-assembly

“…The idea of forming nonprotein molecular containers by total synthesis and assembly of small molecules has a rich history (3)(4)(5) and is an active area of research (6)(7)(8)(9). The field of molecular recognition is rapidly moving not only toward biomedical applications but also toward nanotechnology.…”

3α,6α-Bis(ethoxycarbonyl)glycoluril (diethyl 2,5-dioxoperhydroimidazo[4,5-d]imidazole-3a,6a-dicarboxylate)

“…For related literature, see: Burnett et al (2003); Chen et al (2007); Himes et al (1978); Hof et al (2002); Isaacs & Witt (2002); Kim et al (2000); Li et al (1994); Moon et al (2003); Rowan et al (1999); Wang et al (2006Wang et al ( , 2007; Wu et al (2002).…”

“…3) is an important building block for both molecular and supramolecular chemistry. Its derivatives have been used as the basis for molecular capsules (Hof et al, 2002), molecular clips (Rowan et al, 1999), self-complementary facial amphiphiles , and the cucurbit[n]uril (CB[n]) family (Kim et al, 2000), and its utilization has been explored as a platform for studies of crystal engineering (Wang et al, 2006;Chen et al, 2007). However, relatively few crystal structures are known for glycoluril derivatives without N-substituents.…”