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DNA-Functionalized Supramolecular Polymers DNA-functionalized supramolecular polymers Citation for published version (APA): Wijnands, S. P. W., Meijer, E. W., & Merkx, M. (2019). DNA-functionalized supramolecular polymers: dynamic multicomponent assemblies with emergent properties. Bioconjugate Chemistry, 30(7), 1905-1914. https://doi.org/10.1021/acs.bioconjchem.9b00095 Document license: CC BY-NC-ND DOI: 10.1021/acs.bioconjchem.9b00095 Document status and date: Published: 17/07/2019 Document Version: Publisher’s PDF, also known as Version of Record (includes final page, issue and volume numbers) Please check the document version of this publication: • A submitted manuscript is the version of the article upon submission and before peer-review. There can be important differences between the submitted version and the official published version of record. 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If the publication is distributed under the terms of Article 25fa of the Dutch Copyright Act, indicated by the “Taverne” license above, please follow below link for the End User Agreement: www.tue.nl/taverne Take down policy If you believe that this document breaches copyright please contact us at: [email protected] providing details and we will investigate your claim. Download date: 24. Sep. 2021 This is an open access article published under a Creative Commons Non-Commercial No Derivative Works (CC-BY-NC-ND) Attribution License, which permits copying and redistribution of the article, and creation of adaptations, all for non-commercial purposes. Review Cite This: Bioconjugate Chem. 2019, 30, 1905−1914 pubs.acs.org/bc DNA-Functionalized Supramolecular Polymers: Dynamic Multicomponent Assemblies with Emergent Properties Sjors P.W. Wijnands,†,‡ E. W. Meijer,† and Maarten Merkx*,†,‡ † ‡ Institute for Complex Molecular Systems and Laboratory of Chemical Biology, Department of Biomedical Engineering, Eindhoven University of Technology, P.O. Box 513, 5600 MB Eindhoven, The Netherlands ABSTRACT: Recent years have witnessed an increasing interest in hybrid molecular systems in which the programmability of DNA hybridization is used to introduce enhanced molecular control in synthetic systems. The first examples of DNA-functionalized supramolecular polymers have been reported only recently, but have already revealed structural and functional properties that are not easily obtained in either synthetic supramolecular polymers or DNA-only based systems. In this Topical Review, we provide an overview of the various forms of additional control offered by DNA hybridization for different types of supramolecular polymers and discuss how orthogonal supramolecular interactions in these hybrid systems can give rise to emergent structural and functional properties. ■ INTRODUCTION an additional level of control on the structure and macroscopic At the cellular level, life is predominantly built from aqueous, properties of materials, allowing the construction of stimuli- dynamic molecular assemblies.1,2 The transient nature of these responsive materials such as hydrogels and other nanomateri- als, DNA-surfactants that can be applied as responsive drug complex multicomponent systems introduces adaptability and 16−22 allows for rapid response to biological triggers with great delivery systems, and materials for optoelectronic devices. − fi efficiency.3 5 In the quest to understand and emulate these Only recently have the rst examples of DNA-functionalized natural systems, supramolecular chemistry has become a supramolecular polymers been reported. In this Topical fi Review, we provide an overview of the various forms of topical research eld in which supramolecular polymers play ff ff a prominent role.6 Although the first synthetic supramolecular additional control o ered by DNA hybridization for di erent polymers were designed to assemble in organic solvents, many supramolecular polymers and discuss how orthogonal supra- water-soluble variants exist today, providing an interesting molecular interactions in these hybrid systems can give rise to platform for the development of molecular systems and emergent structural and functional properties. Downloaded via TU EINDHOVEN on August 7, 2019 at 08:23:49 (UTC). materials with life-like properties.7 Extensive studies using a wide variety of biophysical approaches have provided detailed ■ AROMATIC OLIGOMERS insight into the assembly mechanisms and exchange dynamics fi − Some of the rst examples of DNA-functionalized supra- of several of these water-soluble supramolecular polymers.8 12 ̈ See https://pubs.acs.org/sharingguidelines for options on how to legitimately share published articles. molecular polymers were reported by the group of Haner. In These studies have revealed a subtle interplay between various their pioneering work, DNA-grafted supramolecular polymers noncovalent interactions that together govern their structural consisting of oligomers of aromatic compounds and and dynamic properties, but also showed that tuning these oligonucleotides were constructed and used to study how properties and introducing functionality in these dynamic DNA can be used to gain control over the structural systems can be challenging. The latter is important as future characteristics of supramolecular polymers.23 One class of applications would require these systems to specifically interact hybrid supramolecular building blocks consists of phospho- with other components, materials, cells, or tissues. However, diester-linked pyrene oligomers modified with oligonucleotides synthesis of these building blocks is not straightforward. via solid-phase phosphoramidite chemistry (Figure 1a). The DNA has rapidly emerged as a highly versatile molecular supramolecular assembly of these monomers is initiated by the building block for the construction of precise nanometer formation of stair-like arrangements of the pyrenes within the structures and sophisticated molecular machines and networks. In contrast to synthetic supramolecular interactions, the Special Issue: Interfacing Biology with Materials using DNA programmability of DNA hybridization enables the modular Assemblies assembly of structures and reaction cascades with great precision and structural control.13 Recent years have witnessed Received: February 3, 2019 an increasing interest in hybrid molecular systems.14,15For Revised: March 11, 2019 example, DNA functionalization of covalent polymers provides Published: March 12, 2019 © 2019 American Chemical Society 1905 DOI: 10.1021/acs.bioconjchem.9b00095 Bioconjugate Chem. 2019, 30, 1905−1914 Bioconjugate Chemistry Review Figure 1. Using DNA to reversibly control the structural characteristics of supramolecular polymer assemblies. (a) Structure and schematic representation of a DNA-modified heptapyrene monomer with the sequences of the grafted, separator, and connector oligonucleotides. (b) DNA- modified heptapyrene monomers are assembled into DNA-grafted ribbons in water. Hybridization of the oligonucleotide on the heptapyrene with a complementary handle (1b) results in the formation of fibrous networks driven by the blunt-end stacking of the grafted DNA helices. This process is reversible via disruption of the hybridized oligonucleotides, either by thermal denaturation or by addition of an excess of a separator strand (1a). Adapted and reproduced with permission from ref 25. (c) Schematic representation of the assembly pathways of pyrene monomers functionalized with complementary oligonucleotides (Py-a and Py-b). The monomers separately assemble into supramolecular polymers which form networks upon mixing due to hybridization of the complementary grafted oligonucleotides. Thermal disruption of these networks or mixing of the different monomers leads to the formation of mixed polymers which do not form networks. Adapted and reproduced with permission from ref 26. monomers and subsequent assembly of multiple monomers. complementary to that on the hepta-oligopyrene units resulted The balance between the lengths of the oligopyrenes and in the formation of micrometer-size fibrous networks due to oligonucleotides directed the morphology of the supra- cross-links formed by blunt-end stacking of the grafted double- molecular assemblies. Oligopyrenes containing 7 pyrenes and stranded DNA (Figure 1b).9 The formation of these networks 10 base oligonucleotides reversibly formed fibers with lengths was reversible by thermal denaturation of the double-stranded up to several hundreds of nanometers, while no fibrous DNA or by the addition of a scavenger oligonucleotide which structures could be observed for oligopyrenes containing 4 or 1 separates the strand complementary
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