Functional Supramolecular Polymers

Aida, Takuzo; Meijer, E. W.; Stupp, Samuel I.

doi:10.1126/science.1205962

Cited by 3,282 publications

(2,617 citation statements)

References 59 publications

(63 reference statements)

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“…Unlike genetically encoded biomolecule organization, abiotic self‐assembly of a multiple‐component system often shows complex routes, whereby the self‐assembly pathway complexity is largely determined by ambient environment, intercomponent interaction, and structural similarity of components 1, 2, 3, 4. Normally, three scenarios can be expected when the self‐assembly is triggered in a multicomponent system, i.e., self‐sorting, synergistic assembly, and heterojunction 5.…”

Section: Introductionmentioning

confidence: 99%

Environment‐Adaptive Coassembly/Self‐Sorting and Stimulus‐Responsiveness Transfer Based on Cholesterol Building Blocks

Xing

Tham

et al. 2017

Advanced Science

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Manipulating the property transfer in nanosystems is a challenging task since it requires switchable molecular packing such as separate aggregation (self‐sorting) or synergistic aggregation (coassembly). Herein, a unique manipulation of self‐sorting/coassembly aggregation and the observation of switchable stimulus‐responsiveness transfer in a two component self‐assembly system are reported. Two building blocks bearing the same cholesterol group give versatile topological structures in polar and nonpolar solvents. One building block (cholesterol conjugated cynanostilbene, CCS) consists of cholesterol conjugated with a cynanostilbene unit, and the other one (C10CN) is comprised of cholesterol connected with a naphthalimide group having a flexible long alkyl chain. Their assemblies including gel, crystalline plates, and vesicles are obtained. In gel and crystalline plate phases, the self‐sorting behavior dominates, while synergistic coassembly occurs in vesicle phase. Since CCS having the cyanostilbene group can respond to the light irradiation, it undergoes light‐induced chiral amplification. C10CN is thermally responsive, whereby its supramolecular chirality is inversed upon heating. In coassembled vesicles, it is interestingly observed that their responsiveness can be transferred by each other, i.e., the C10CN segment is sensitive to the light irradiation, while CCS is thermoresponsive. This unprecedented behavior of the property transfer may shine a light to the precise fabrication of smart materials.

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Section: Introductionmentioning

confidence: 99%

Environment‐Adaptive Coassembly/Self‐Sorting and Stimulus‐Responsiveness Transfer Based on Cholesterol Building Blocks

Xing

Tham

et al. 2017

Advanced Science

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“…The non-covalent nature of SPs brings the additional feature of reversibility of the polymerization process. [28][29][30][31][32][33][34] Furthermore, it enables the formation of polymers with a high DNA grafting density. 25, 26 Herein we describe the hierarchical organization of DNA-grafted SPs.…”

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confidence: 99%

From Ribbons to Networks: Hierarchical Organization of DNA-Grafted Supramolecular Polymers

2015

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DNA-grafted supramolecular polymers (SPs) allow the programmed organization of DNA in a highly regular, one-dimensional array. Oligonucleotides are arranged along the edges of pyrene-based helical polymers. Addition of complementary oligonucleotides triggers the assembly of individual nanoribbons resulting in the formation of extended supramolecular networks. Network formation is enabled by cooperative coaxial stacking interactions of terminal GC base pairs. The process is accompanied by structural changes in the pyrene polymer core that can be followed spectroscopically. Network formation is reversible and disassembly into individual ribbons is realized either via thermal denaturation or by addition of a DNA separator strand.The creation of functional nanoscale structures represents a major goal of today's nanotechnology. DNA-based materials are of primary interest for the construction of functional platforms. [1][2][3][4] Proper choice of the nucleotide sequence provides control over aromatic stacking and hydrogen bonding interactions, 5-7 thus enabling the assembly of systems with a high degree of complexity. [8][9][10][11] Approaches towards the preparation of functional DNA materials include the designed DNA self-assembly, 12-15 the grafting of oligonucleotides onto metal nanoparticles (NPs) 16 and other surfaces, [17][18][19] as well as polymers. [20][21][22][23] The latter class, DNA-grafted polymers, has been pioneered by Nguyen and Mirkin and gained increasing attention over the last years. 24,25 We have recently introduced DNA-grafted supramolecular polymers (SPs). 26 These self-assembled structures appear as one-dimensional (1D) ribbons, consisting of an oligopyrenotide core 27 with arrays of singlestranded oligonucleotides appended onto its edges. The non-covalent nature of SPs brings the additional feature of reversibility of the polymerization process. [28][29][30][31][32][33][34] Furthermore, it enables the formation of polymers with a high DNA grafting density. 25,26 Herein we describe the hierarchical organization of DNA-grafted SPs. It is shown that individual ribbons assemble into extended networks through a highly cooperative mesh of DNA blunt end stacking interactions.Chimeric oligomers Py-a, Py-b and Py-c (Scheme 1) are all composed of a heptapyrenotide part and an appended oligonucleotide.They were prepared via solid-phase synthesis, purified by RP-HPLC and characterized by MS (SI). The two complementary oligonucleotides 1a (separator strand) and 1b (connector strand) have the same nucleobase sequence as the respective corresponding chimeric oligomers Py-a and Py-b; 1c is complementary to the oligonucleotide part of Py-c. DNA-grafted SPs are typically performed by slow annealing. Thus, a 2 μM solution of Py-a in aqueous buffer (10 mM sodium phosphate, pH=7.0 and 250 mM sodium chloride) is cooled from 95° to 20°C using a gradient of 0.1°C/min. Stacking interactions between pyrenes drive the self-assembly of polymeric ribbons. The polymerization process leads to the development ...

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“…Hydrogen bonds are one of the most commonly utilized types of intermolecular interaction in the fabrication of supramolecular polymers because of their directional character and the ideal strength. [64][65][66][67] Furthermore, the associative character of a given supramolecular motif can be fine-tuned by controlling the number of hydrogen-bonding sites. The inherent reversible nature of hydrogen bonds bestows supramolecular polymers made from such motifs with adaptive characters such as thermo-, photo-, chemo-and mechanoresponsive properties.…”

Section: Hydrogen-bondsmentioning

confidence: 99%

“…The inherent reversible nature of hydrogen bonds bestows supramolecular polymers made from such motifs with adaptive characters such as thermo-, photo-, chemo-and mechanoresponsive properties. [64][65][66][67][68][69] In the last 15 years, a large number of hydrogen-bonding supramolecular polymers has been investigated. [70,71] Interestingly, however, only few reports have described mechanically active hydrogen bonds in supramolecular polymers with unambiguous experimental evidence that show dissociation and formation of hydrogen bonds in response to mechanical stimulation.…”

Section: Hydrogen-bondsmentioning

confidence: 99%