Chemical fuel-driven living and transient supramolecular polymerization

Jain, Ankit; Dhiman, Shikha; Dhayani, Ashish; Vemula, Praveen Kumar; George, Subi J.

doi:10.1038/s41467-019-08308-9

Cited by 142 publications

(109 citation statements)

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“…The notion that this dynamics can be tuned and biased at will by both external stimuli (like solvents) and internal conversions, is only one of the aspects that gives supramolecular polymers a bright future. These ideas have recently been explored to arrive at out‐of‐equilibrium systems and illustrate another new aspect of supramolecular polymer science; an emerging field that is only at its beginning . Similarly, using supramolecular polymers to switch liquid‐crystals is just one of other new features where the dynamics of the system is used …”

Section: Comparison Between Macromolecular and Supramolecular Polymersmentioning

confidence: 99%

Supramolecular Polymers – we've Come Full Circle

Aida

Meijer

2020

Israel Journal of Chemistry

175

142

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Since the first polymers were discovered, scientists have debated their structures. Before Hermann Staudinger published the brilliant concept of macromolecules, polymer properties were generally believed to be based on the colloidal aggregation of small particles or molecules. From 1920 onwards, polymers and macromolecules are synonymous with each other; i. e. materials made by many covalent bonds connecting monomers in 2 or 3 dimensions. Although supramolecular interactions between macromolecular chains are evidently important, e. g. in nylons, it was unheard of to proposing polymeric materials based on the interaction of small molecules. Breakthroughs in supramolecular chemistry, however, showed that polymer materials can be made by small molecules using strong directional secondary interactions; the field of supramolecular polymers emerged. In a way, we have come full circle. In this essay we give a personal story about the birth of supramolecular polymers, with special emphasis on their structures, way of formation, and the dynamic nature of their bonding. The adaptivity of supramolecular polymers has become a major asset for novel applications, e. g. in the direction for the sustainable use of polymers, but also in biomedicine and electronics as well as self‐healing materials. The lessons learned in the past years include aspects that forecast a bright future for the use of supramolecular interactions in polymer materials in general and for supramolecular polymers in particular. In order to give full tribute to Staudinger in the year celebrating 100 years of macromolecules, we will show that many of the concepts of macromolecular polymers apply to supramolecular polymers, with only one important difference with fascinating consequences: the dynamic nature of the bonds that form polymer chains.

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Section: Comparison Between Macromolecular and Supramolecular Polymersmentioning

confidence: 99%

Supramolecular Polymers – we've Come Full Circle

Aida

Meijer

2020

Israel Journal of Chemistry

175

142

View full text Add to dashboard Cite

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“…Recently, George and co‐workers used a dynamic imine bond to form a charge‐transfer surfactant that self‐assembles into fibers (Figure 1g, Cat. 3) 54. The substrate is converted from its aldehyde‐containing inactive state to an amphiphile, upon the addition of an aliphatic primary amine as the chemical fuel.…”

Section: Progress So Farmentioning

confidence: 99%

“…Until recently, scientists have successfully developed reaction cycles that are applicable to widely used functional groups like carboxylic acids,36,39 thiols,50 alkenes,49 and imines 54. Usually, the chemical fuels that have been used, are commonly available.…”

Section: Challenges and Opportunitiesmentioning

confidence: 99%

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Devising Synthetic Reaction Cycles for Dissipative Nonequilibrium Self‐Assembly

et al. 2020

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Fuel‐driven reaction cycles are found in biological systems to control the assembly and disassembly of supramolecular materials such as the cytoskeleton. Fuel molecules can bind noncovalently to a self‐assembling building block or they can react with it, resulting in covalent modifications. Overall the fuel can either switch the self‐assembly process on or off. Here, a closer look is taken at artificial systems that mimic biological systems by making and breaking covalent bonds in a self‐assembling motif. The different chemistries used so far are highlighted in chronological order and the pros and cons of each system are discussed. Moreover, the desired traits of future reaction cycles, their fuels, and waste management are outlined, and two chemistries that have not been explored up to now in chemically fueled dissipative self‐assembly are suggested.

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“…Within systems chemistry there is a need for new fuel‐driven chemical reaction networks as they will allow powering and out of equilibrium operation of chemical systems. Inspired by the functional behavior seen in living systems, fuel‐driven chemical reaction networks have been used in many exciting examples, including oscillators, self‐replicating systems, fuel‐driven transient hydrogel formation, polymerization, fuel‐controlled chemical reactivity, and fuel‐driven molecular motion . At the base of many of these discoveries are chemical reaction networks where a fuel can reversibly and thereby temporarily change the properties of a chemical building block.…”

Section: Figurementioning

confidence: 99%

A Fuel‐Driven Chemical Reaction Network Based on Conjugate Addition and Elimination Chemistry

et al. 2019

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Fuel‐driven chemical reaction networks provide an opportunity to develop chemical systems that operate out‐of‐equilibrium. There remains a need to design and develop new fuel‐driven chemical reaction networks capable of repeated operation using simple and benign chemistry. Herein, we propose a new chemical reaction network for fuel‐driven transient formation of covalent bonds, based on redox‐controlled conjugate addition and elimination chemistry. By investigating the separate reactions making up the cycle, we find that the bond formation, breaking and regeneration processes can be realized. At present, substantial side reactivity prevents achieving repeated operation of a full cycle in a single system. If such obstacles would be overcome, this chemical reaction network could be a valuable addition to the toolbox for out‐of‐equilibrium systems chemistry.

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Chemical fuel-driven living and transient supramolecular polymerization

Cited by 142 publications

References 50 publications

Supramolecular Polymers – we've Come Full Circle

Supramolecular Polymers – we've Come Full Circle

Devising Synthetic Reaction Cycles for Dissipative Nonequilibrium Self‐Assembly

A Fuel‐Driven Chemical Reaction Network Based on Conjugate Addition and Elimination Chemistry

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