Self‐Assembled Nanoreactors

Vriezema, Dennis M.; Aragones, M. Comellas; Elemans, Johannes A. A. W.; Cornelissen, Jeroen J. L. M.; Rowan, Alan E.; Nolte, Roeland J. M.

doi:10.1002/chin.200532290

Cited by 51 publications

(62 citation statements)

References 169 publications

(206 reference statements)

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“…A good approach to overcome these challenges has been the introduction of surfactants and water-soluble dendrimers as reaction pockets. [24,25] By carrying out organic reactions in the presence of surfactant-type micelles, enhancement of rates and/or specificity has been observed for different reactions based on hydrophobic forces. The high concentration created in the hydrophobic core enhances the reaction rates and induces selectivity in the same way as enzymes in biological systems.…”

Section: Well-defined Polymeric Nanostructuresmentioning

confidence: 99%

Catalytic polymeric nanoreactors: more than a solid supported catalyst

2012

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Polymeric nanostructures can be synthesized where the catalytic motif is covalently attached within the core domain and protected from the environment by a polymeric shell. Such nanoreactors can be easily recycled, and have shown unique properties when catalyzing reactions under pseudohomogeneous conditions. Many examples of how these catalytic nanostructures can act as nanosized reaction vessels have been reported in the literature. This prospective will focus on the exclusive features observed for these catalytic systems and highlight their potential as enzyme mimics, as well as the importance of further studies to unveil their full potential.

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Section: Well-defined Polymeric Nanostructuresmentioning

confidence: 99%

Catalytic polymeric nanoreactors: more than a solid supported catalyst

2012

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“…A toolbox initially developed by supramolecular chemists quickly expanded into an interdisciplinary field aiming at the manipulation of matter at the molecular scale (3,4). Up until recently self-assembly in dilute aqueous environments has predominantly dealt with linear amphiphiles that form closed structures (5)(6)(7)(8)(9), such as spherical micelles, cylindrical or rod-like micelles, and vesicles using, for example, phospholipids (10,11), synthetic block copolymers (12,13), or dendrimers (14). Morphological control in objects of defined size or shape, and transitions between different morphologies are increasingly well understood (15)(16)(17)(18).…”

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confidence: 99%

Controlling the growth and shape of chiral supramolecular polymers in water

Besenius

Portale²,

Bomans

et al. 2010

Proc. Natl. Acad. Sci. U.S.A.

206

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A challenging target in the noncovalent synthesis of nanostructured functional materials is the formation of uniform features that exhibit well-defined properties, e.g., precise control over the aggregate shape, size, and stability. In particular, for aqueousbased one-dimensional supramolecular polymers, this is a daunting task. Here we disclose a strategy based on self-assembling discotic amphiphiles that leads to the control over stack length and shape of ordered, chiral columnar aggregates. By balancing out attractive noncovalent forces within the hydrophobic core of the polymerizing building blocks with electrostatic repulsive interactions on the hydrophilic rim we managed to switch from elongated, rod-like assemblies to small and discrete objects. Intriguingly this rod-tosphere transition is expressed in a loss of cooperativity in the temperature-dependent self-assembly mechanism. The aggregates were characterized using circular dichroism, UV and 1H-NMR spectroscopy, small angle X-ray scattering, and cryotransmission electron microscopy. In analogy to many systems found in biology, mechanistic details of the self-assembly pathways emphasize the importance of cooperativity as a key feature that dictates the physical properties of the produced supramolecular polymers.aqueous self-assembly | controlled architecture | supramolecular polymerization | dynamic materials M olecular self-assembly has emerged as a fascinating area in its own right (1, 2). A toolbox initially developed by supramolecular chemists quickly expanded into an interdisciplinary field aiming at the manipulation of matter at the molecular scale (3, 4). Up until recently self-assembly in dilute aqueous environments has predominantly dealt with linear amphiphiles that form closed structures (5-9), such as spherical micelles, cylindrical or rod-like micelles, and vesicles using, for example, phospholipids (10, 11), synthetic block copolymers (12, 13), or dendrimers (14). Morphological control in objects of defined size or shape, and transitions between different morphologies are increasingly well understood (15)(16)(17)(18). Surprisingly, however, the generality of these concepts has not been translocated into another area of increasing interest, namely, the self-assembly of one-dimensional arrays. In that context the development of discotic monomers has proven to be a valuable route to allow for the synthesis of rod-like supramolecular polymers (19), whose potential applications in functional soft matter include electronics, biomedical engineering, and sensors (20)(21)(22)(23)(24)(25)(26). Considering the enormous interest in such systems, it is surprising that efforts to control the size and shape of nano-and micrometer size one-dimensional objects are rare (27-29); successful strategies rely on the use of templates (30, 31), end cappers (32), or selective solvent techniques (33).In order to control the growth of aqueous one-dimensional supramolecular polymers, we propose to utilize electrostatic repulsive contributions in analogy to surfactant...

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“…In recent reports, protein capsids and viruses have been studied as containers, as potential reaction vessels [5][6][7][8] , as well-defined hosts [9][10][11][12] , as nanotemplates [13][14][15][16][17][18] and as synthetic platforms [19][20][21] . To the best of our knowledge, no enzyme-loaded nanocontainer has been assembled, let alone studied, at the single-enzyme level.…”

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confidence: 99%