Reversible Polymers Formed from Self-Complementary Monomers Using Quadruple Hydrogen Bonding

Sijbesma, Rint P.; Beijer, Felix H.; Brunsveld, Luc; Folmer, B. J. B.; Hirschberg, J.H.K.K.; Lange, Ronald F. M.; Lowe, Jimmy; Meijer, E. W.

doi:10.1126/science.278.5343.1601

Cited by 2,217 publications

(1,700 citation statements)

References 14 publications

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“…13 In contrast, it takes 11 kcal/mol to fully unfold the UPy folded module (based on K d of ~10 −8 M −1 in toluene). 8 The enhancement of energy dissipation by the modular cross-linker is supported by the much larger loss moduli measured by DMA for the real samples as compared to the controls (see Fig. S7).…”

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confidence: 75%

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Biomimetic Design of Reversibly Unfolding Cross-Linker to Enhance Mechanical Properties of 3D Network Polymers

et al. 2007

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Three-dimensional (3D) network polymers are an important family of materials. For many applications of 3D networks it is important to combine high modulus, high tensile strength, and high extensibility. 1 Rigid network materials tend to fail after only a short extension. While flexible elastomers are more extensible, they usually have low moduli and exhibit shallow stress-response. Although many engineering approaches and chemical modifications 2 have been developed to improve mechanical properties of network polymers, it remains a challenge to design ideal networks that have a combination of desired properties. Among chemical methods, interesting work has been reported on using interchain hydrogen bonding to improve polymer physical properties. 3 Given the importance of cross-linker structure on mechanical properties of network polymers, it is surprising that there is very limited investigation on designing molecularly engineered cross-linkers to enhance network properties. Herein we introduce a novel biomimetic design of a reversibly unfolding modular cross-linker that can increase elastomer stiffness without sacrificing extensibility leading to a dramatic tensile strength enhancement.Our biomimetic concept is based on the modular design observed in many biopolymers, such as the skeletal muscle protein titin and connective proteins in both soft and hard tissues, that have a remarkable combination of strength and elasticity. 4 Single-molecule nanomechanical studies have revealed that their combined mechanical properties originate from their unique modular structure, which sequentially unfolds upon deformation providing the molecular mechanism to sustain high force (strength) and to yield high elongation (elasticity). 5 Inspired by nature, our group has been mimicking this modular domain strategy in the pursuit of synthetic polymers with advanced mechanical properties. A number of biomimetic modules have been successfully designed and incorporated into linear polymers. 6,7 Single-molecule and bulk properties validated our biomimetic concept of using modular structures to enhance polymer properties. This communication describes the first example of introducing a reversibly unfolding modular cross-linker into 3D networks to enhance their mechanical properties.Our concept is illustrated in Figure 1. A stress applied from any direction to a 3D network will be ultimately transferred across the individual network junctions, where biomimetic modules can be reversibly unfolded. Since it requires significant forces to unfold the modules held by strong multiple hydrogen bonds, further extension can be gained without sacrificing the modulus. In addition, we propose that the enhanced energy dissipation capability by unfolding the biomimetic modules should lead to significant increases in both * zguan@uci.edu. Supporting Information Available:Synthesis and characterization of cross-linker and polymers, MALDI-TOF MS, MTS stressstrain experiments. This material is available free of charge at http//:pubs.acs.org. The biomimet...

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confidence: 75%

“…8 The synthesis of the module is shown in Scheme 1 (also see synthetic details in Support Information). Double alkylation of ethyl acetoacetate followed by guanidine condensation afforded the alkenyl-pyrimidone interme-diate 3.…”

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confidence: 99%

Biomimetic Design of Reversibly Unfolding Cross-Linker to Enhance Mechanical Properties of 3D Network Polymers

et al. 2007

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“…[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. [72][73][74][75] Some of the most compelling examples of mechanoactive hydrogen bonds in polymers have been inspired by the natural protein titin.…”

Section: Hydrogen-bondsmentioning

confidence: 99%

Mechanochemistry in Polymers with Supramolecular Mechanophores

Haehnel

Sagara

Simon

et al. 2015

Topics in Current Chemistry

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“…Coordination polymers represent a distinct group of supramolecular polymers, [1][2][3][4][5][6] which have attracted great attention in recent years. [7][8][9][10][11][12] The degree of polymerization in such polymers is primarily controlled by the concentration of the building blocks in solution and the strength of interaction between the ligand and the metal ion.…”

Section: Introductionmentioning

confidence: 99%

Novel Molecular Building Blocks Based on the Boradiazaindacene Chromophore: Applications in Fluorescent Metallosupramolecular Coordination Polymers

Bozdemir

Büyükçakır

Akkaya

2009

Chemistry A European J

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Bright polymers: Fluorescent coordination polymers made up of versatile functionalized bodipy (boron‐dipyrrin) chromophore building blocks, such as that depicted, are described. Polymerization is signaled by changes in fluorescence emission intensity and shifts in peak emission wavelengths.magnified imageWe designed and synthesized novel boradiazaindacene (Bodipy) derivatives that are appropriately functionalized for metal‐ion‐mediated supramolecular polymerization. Thus, ligands for 2‐terpyridyl‐, 2,6‐terpyridyl‐, and bipyridyl‐functionalized Bodipy dyes were synthesized through Sonogashira couplings. These fluorescent building blocks are responsive to metal ions in a stoichiometry‐dependent manner. Octahedral coordinating metal ions such as ZnII result in polymerization at a stoichiometry corresponding to two terpyridyl ligands to one ZnII ion. However, at increased metal ion concentrations, the dynamic equilibria are re‐established in such a way that the monomeric metal complex dominates. The position of equilibria can easily be monitored by 1H NMR and fluorescence spectroscopies. As expected, although open‐shell FeII ions form similar complex structures, these cations quench the fluorescence emission of all four functionalized Bodipy ligands.

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Reversible Polymers Formed from Self-Complementary Monomers Using Quadruple Hydrogen Bonding

Cited by 2,217 publications

References 14 publications

Biomimetic Design of Reversibly Unfolding Cross-Linker to Enhance Mechanical Properties of 3D Network Polymers

Biomimetic Design of Reversibly Unfolding Cross-Linker to Enhance Mechanical Properties of 3D Network Polymers

Mechanochemistry in Polymers with Supramolecular Mechanophores

Novel Molecular Building Blocks Based on the Boradiazaindacene Chromophore: Applications in Fluorescent Metallosupramolecular Coordination Polymers

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