Macromolecular and supramolecular chirality: a twist in the polymer tales

Bruin, Alexander G de; Barbour, Michele E; Briscoe, Wuge H.

doi:10.1002/pi.4639

Cited by 15 publications

(5 citation statements)

References 39 publications

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“…It is well known that twist is a chiral property and arises from chirality at some level of organization of substances, usually arising from molecular chirality. Many studies of twist and its chiral roots have been published and some studies of biological polymers have pointed back to the chiral centers in the polymers as the source of twist(de Bruin, Barbour & Briscoe, 2014;Fujiki, Koe, Terao, Sato, Teramoto & Watanabe, 2003;Khandelwal & Windle, 2014a;Lotz & Cheng, 2005). The chiral centers, however, and their specific chirality cannot determine the direction of twist or degree of twist in a polymer since there are other contributing factors, such as orientation of molecular associations.…”

Section: Introductionmentioning

confidence: 99%

The molecular origins of twist in cellulose I-beta

Himmel

Crowley

2015

Carbohydrate Polymers

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The observation of twisted microfibrils in cellulose Iβ both in imaging and in molecular simulations has been reported and studied for years. This article reports a computational modeling study of cellulose Iβ twist showing its strong dependence on fibril diameter and no dependence on fibril length. We report that an important contribution to the twist in the model, empirically and analytically, is the hydrogen bonding that spans the glycosidic linkage, and that the characteristics of the chiral centers involved in the trans-glycosidic-linkage hydrogen bonding determine the directions if those interactions and cause observed right-handed twist. Other crystalline forms of cellulose show evidence of twisting at the microfibril scale, but less than Iβ. The minimal twist in other forms of cellulose was shown previously to be due to inter-layer hydrogen bonds; this study shows it is also partially due to the primary alcohol not occurring in the TG orientation in those forms. Thus, only cellulose I has the primary alcohol in TG orientation, which leads to formation of the twist-causing hydrogen bonds.

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Section: Introductionmentioning

confidence: 99%

The molecular origins of twist in cellulose I-beta

Himmel

Crowley

2015

Carbohydrate Polymers

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“…Twisted architecture widely arises in nature from molecules to nano- and microscale materials to macroscopic objects such as DNA, RNA, peptide, and chromosome. , Such twisted architectures play an important role in improving mechanical properties as well as enabling biological functions. Inspired by the beauty and interesting properties of twisted structures, a wide range of artificial chiral materials with twisted or coiled structures have been prepared, from organic and inorganic nanorods, nanotubes, and nanobelts to macroscopic architectures and buildings. , …”

Section: Introductionmentioning

confidence: 99%

The Power of Fiber Twist

et al. 2021

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Conspectus Nature’s evolution over billions of years has led to the development of different kinds of twisted structures in a variety of biological species. Twisted fibers from nanoscale- to micrometer-scale diameter have been prepared by mimicking natural twisted structures. Mechanically inserting twist in a yarn is an efficient and important method, which generates internal stress, changes the macromolecular orientation, and increases compactness. Recently, twist insertion has been found to produce interesting fiber properties, including chemical, mechanical, electrical, and thermal properties. This Account summarizes recent progress in how twist insertion affects the chemical and physical properties of fibers and describes their applications in artificial spider silk, artificial muscles, refrigeration, and electricity generation. Twist and associated chirality widely arise in nature from molecules to nano- and microscale materials to macroscopic objects such as DNA, RNA, peptides, and chromosomes. Such twisted architectures play an important role in improving the mechanical properties and enabling biological functions. Inspired by the beauty and interesting properties of twisted structures, a wide range of artificial chiral materials with twisted or coiled structures have been prepared, from organic and inorganic nanorods, nanotubes, and nanobelts to macroscopic architectures and buildings. An efficient way to prepare twisted materials is by inserting twist in fibers or yarns, which is an ancient technique used to make yarns or ropes (Wang, R., et al. Science 2019, 366, 216–221. Mu, J., et al. Science 2019, 365, 150–155). During the twisting process, torque is generated in fibers or yarns, the structure of the polymer chains becomes helically oriented, and the fibers in a yarn become more compact. Therefore, the twisting of fibers and yarns can produce novel chemical, mechanical, electrical, and thermal properties (Dou, Y., et al. Nat. Commun. 2019, 10, 1–10. Kim, S. H., et al. Science 2017, 357, 773–778). This Account focuses on the novel properties generated by twist insertion. The mechanical stress and strain can be optimized in a yarn by twist insertion, and different types of fibers exhibit rather different mechanisms. In the first section, we will focus on recent progress in improving the mechanical properties of twisted fibers, including carbon nanotube yarns, single-filament fibers, and hydrogel fibers. Torque was generated by twist insertion in a fiber or a yarn, and the balance of internal torsional stress can be changed by causing a change in yarn volume. This will result in twist release and torsional and tensile actuations of the yarn, which will be described in the second section. Twisting a yarn generally makes it more compact, which will result in a mechanically induced change in capacitance, supercapacitance, and other useful electrochemical properties when a conducting yarn is in an electrolyte. Such processes were used to develop novel devices for twist-based electricity generation, called t...

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“…Delivery systems of controllable size and definable molecular response to stimuli are of great importance in the field of polymeric biomaterials where they are expected to induce specific biological responses. Block copolymers can be built from a plethora of polymeric building blocks linked by a variety of chemical connections …”

Section: Introductionmentioning

confidence: 99%

“…Block copolymers can be built from a plethora of polymeric building blocks linked by a variety of chemical connections. 6 One of the very first reports on the self-assembly of pentablock copolymers was published by Jones and colleagues 7 and indicates the ability of the poly(ethylene oxide)-poly(methylphenylsilane) amphiphilic multiblock copolymer to self-assemble into vesicles. Mallapragada and colleagues have utilized the self-assembly capabilities of pentablock copolymers in biomedical applications and have shown that their poly(amino methacrylate) terminated Pluronics form micelles and gels that lend themselves as non-viral vectors for gene delivery 8 and as polymer adjuvants for the controlled and sustained delivery of protein vaccines 9 using the block copolymers' pH and temperature dependent phase behavior.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of PEGylated poly(amino acid) pentablock copolymers and their self‐assembly

Iijima

Ulkoski

Sakuma

et al. 2016

Polymer International

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Pentablock copolymers with an ABCBA architecture were synthesized by ring‐opening polymerization of N‐carboxyanhydrides of l‐leucine and γ‐benzyl l‐glutamate using an α, ω‐diamino poly(ethylene glycol) (PEG) as macroinitiator. Three different PEGs with molecular weights of 2000, 4600 and 10 000 Da were used and the poly(amino acid) (PAA) block lengths were set to a combined 10 and 40, respectively, repeat units for p(l‐Leu) and 40 repeat units for p(l‐Glu). The molecular architecture of the resulting pentablock copolymers was determined by the order of monomer addition. The living character of the N‐carboxyanhydride ring‐opening polymerization enables the formation of multiblock copolymers. The degree of polymerization for the PAA blocks matched the monomer/initiator ratio. A structural switch element, which controls the hydrophilicity of the pentablock copolymers, was incorporated in the form of the p(l‐Glu) blocks. The pentablock copolymers became water soluble after hydrolyzing the benzyl ester protective groups. The pentablock copolymers self‐assembled into polymeric aggregates ranging in size between 160 and 340 nm. Hydrogels formed readily if the central PEG block had a molecular weight of at least 4600 Da and the terminal A‐blocks consisted of p(l‐Leu). SEM images confirmed the size ranges of the polymeric aggregates and showed non‐distinct spherical aggregates. © 2016 Society of Chemical Industry

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Macromolecular and supramolecular chirality: a twist in the polymer tales

Cited by 15 publications

References 39 publications

The molecular origins of twist in cellulose I-beta

The molecular origins of twist in cellulose I-beta

The Power of Fiber Twist

Synthesis of PEGylated poly(amino acid) pentablock copolymers and their self‐assembly

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