Assembly via Hydrogen Bonds of Low Molar Mass Compounds into Supramolecular Polymers

Bouteiller, Laurent

doi:10.1007/12_2006_110

Cited by 176 publications

(33 citation statements)

References 202 publications

(158 reference statements)

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“…15,16 Acting as one of the most significant noncovalent interactions, hydrogen bonds (H-bonds) are well-known to guide the construction of many examples of self-assembled structures. Yet, despite the expansion of various synthetic strategies to design supramolecular polymers, the investigation of phase segregation within such macromolecules opposing the ordering effects by H-bonding forces is a newly emerging field.…”

Section: Introductionmentioning

confidence: 99%

Dynamic Ordering and Phase Segregation in Hydrogen-Bonded Polymers

Chen

Binder

2016

Acc. Chem. Res.

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Hydrogen bonds (H-bonds) constitute highly relevant structural units of molecular self-assembly. They bridge biological and synthetic sciences, implementing dynamic properties into materials and molecules, not achieved via purely covalent bonds. Phase segregation on the other hand represents another important assembly principle, responsible for, e.g., cell compartimentation, membrane-formation, and microphase segregation in polymers. Yet, despite the expanding elegant synthetic strategies of supramolecular polymers, the investigation of phase behavior of macromolecules driven by H-bonding forces still remains in its infancy. Compared to phase segregation arising from covalently linked block copolymers, the generation of phase segregated nanostructures via supramolecular polymers facilitates the design of novel functional materials, such as those with stimuli-responsive, self-healing, and erasable-material properties. We here discuss the phase segregation of H-bonding polymers in both the solution and solid state, wherein the molecular recognition elements are based on multiple H-bonding moieties, such as thymine/2,6-diamino-pyridine (THY/DAP), thymine/diamino triazine (THY/DAT), and barbiturate/Hamilton wedge (Ba/HW) elements. The specific aggregation of a series of different H-bonding polymers in solution, both linear and dendritic polymers, bearing heterocomplementary H-bonding moieties are described, in particular focusing on the issue of phase segregation. The exploitation of H-bonded supramolecular dendrons with segregating polymer chains leads to the formation of three-phase segregated hierarchical micelles in solution, purely linking the components via H-bonds, in turn displaying a versatile spectrum of segregated morphologies. We also focus on segregation effects of H-bonded amorphous and crystalline polymers: thus the formation of nanostructures, such as disordered micelles and well-ordered body centered cubic (BCC) packed spheres from telechelic polymers bearing H-bonding moieties at the chain ends is observed. Finally, we discuss the discovery of novel functional microphase separated self-healing supramolecular architectures, illustrating dynamic and self-healing properties with an almost complete recovery of the initial mechanical performances healing within 24h at 30 °C. Collectively, our studies prove that phase segregation in H-bonding polymers is an important principle, capable to generate nanostructures and dynamic properties not achieved in covalently linked polymers. The results discussed illustrate that a rational architectural design within H-bonding polymer systems in interplay with phase segregation in both the amorphous and crystalline state opens perspectives to develop artificial supramolecular systems approaching the level of complexities and properties present in nature's biomaterials.

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Section: Introductionmentioning

confidence: 99%

Dynamic Ordering and Phase Segregation in Hydrogen-Bonded Polymers

Chen

Binder

2016

Acc. Chem. Res.

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“…By increasing the bis-DAN linker content, the virtual degree of polymerization decreased because the bis-DAN linker acted as a chain stopper [103]. Accordingly, the concentration dependence of the virtual degree of polymerization and, thus, the chain length can be blocked in a defined concentration range by the use of chain stoppers, which enables conclusions to be drawn about the hydrogen bonding interaction corrected for concentration effects [104][105][106]. In contrast, in the case of weaker hydrogen bonding interactions in urea-modified polyether polyols, no break-up of the supramolecular assembly was observed because the polymer ends were incorporated in the microphaseseparated hydrogen bonding arrays, resulting in the formation of phase-separated TPEs [107].…”

Section: Bis(urea)-based Hydrogen Bonding Interactionsmentioning

confidence: 97%

Intrinsic Self-Healing Polymers Based on Supramolecular Interactions: State of the Art and Future Directions

Enke

Döhler

Bode

et al. 2015

Self-Healing Materials

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Supramolecular polymers are an intriguing class of materials with dynamic behavior as a result of the presence of non-covalent bonds. These bonds include hydrogen bonds, metallopolymers, ionomers, host-guest as well as π-π interactions. The strength of these supramolecular bonds can be tuned by varying the binding motifs. Their reversible and dynamic character can be utilized to engineer self-healing polymers. This review briefly presents the preconditions for design of self-healing polymers and summarizes the development of supramolecular self-healing polymers based on various non-covalent interactions. Furthermore, challenges and perspectives for the understanding of self-healing mechanisms and the preparation of novel materials with enhanced properties are discussed.

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“…Polimer ini dapat kembali menjadi monomer atau oligomernya sehingga supramolekular polimer ini bersifat reversible (Lehn (2002), Bouteiller (2007), Shimizu (2007) dan Weck (2007)). Karena sifat reversible ini, supramolekular polimer memiliki beberapa kelebihan dibandingkan polimer murni, kelebihan tersebut diantaranya : 1) memiliki sifat yang dapat berubah sesuai dengan kondisi lingkungan (karena bersifat re v e r s i b l e ) , 2 ) m e m p e r mu d a h p r o s e s pengolahan material, dan 3) memiliki sifat healing ability (Ghosh, 2009).…”

Section: Supramolekular Polimerunclassified

Kajian Tentang Self-Healing Rubber Self Healing Rubber Review

Purbaya¹

2015

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Abstrak B a r a n g j a d i k a r e t s e l a m a m a s a pemakaiannya dapat mengalami cracking. Untuk mengatasi masalah ini maka konsep selfhealing dapat digunakan. Self-healing merupakan kemampuan dari suatu material untuk dapat memperbaiki dirinya sendiri setelah mengalami kerusakan. Konsep ini dapat digunakan untuk menambah umur pemakaian suatu produk. Strategi yang dapat digunakan dalam pembuatan material selfhealing adalah : 1) pembentukan ikatan silang pada polimer, 2) pelepasan healing agent pada s a a t m e m p r o d u k s i p o l i m e r, d a n 3 ) menggunakan teknologi khusus seperti konduktiviti, electro-fluid-dynamic (EFD), migrasi nano partikel, efek shape memori dan co-deposition. Salah satu supramolekular polimer yang memiliki sifat elastis dan healing ability adalah self-healing rubber. Self-healing rubber disintesis melalui dua tahap sintesis, yaitu 1) pembuatan oligoamide, dan 2) mereaksikan oligoamide yang diperoleh dari tahap pertama reaksi dengan urea untuk menghasilkan self-healing rubber. Karet yang diperoleh memiliki sifat elastis dan sifat healing ability setelah mengalami kerusakan. Sifat ini tidak ditemukan dalam karet alam maupun karet sintesis. Jenis karet baru ini sangat menarik untuk dipelajari dan diaplikasikan untuk teknologi karet.

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Assembly via Hydrogen Bonds of Low Molar Mass Compounds into Supramolecular Polymers

Cited by 176 publications

References 202 publications

Dynamic Ordering and Phase Segregation in Hydrogen-Bonded Polymers

Dynamic Ordering and Phase Segregation in Hydrogen-Bonded Polymers

Intrinsic Self-Healing Polymers Based on Supramolecular Interactions: State of the Art and Future Directions

Kajian Tentang Self-Healing Rubber Self Healing Rubber Review

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