Self-assembling dendrimers have facilitated the discovery of periodic and quasiperiodic arrays of supramolecular architectures and the diverse functions derived from them. Examples are liquid quasicrystals and their approximants plus helical columns and spheres, including some that disregard chirality. The same periodic and quasiperiodic arrays were subsequently found in block copolymers, surfactants, lipids, glycolipids, and other complex molecules. Here we report the discovery of lamellar and hexagonal periodic arrays on the surface of vesicles generated from sequence-defined bicomponent monodisperse oligomers containing lipid and glycolipid mimics. These vesicles, known as glycodendrimersomes, act as cell-membrane mimics with hierarchical morphologies resembling bicomponent rafts. These nanosegregated morphologies diminish sugar–sugar interactions enabling stronger binding to sugar-binding proteins than densely packed arrangements of sugars. Importantly, this provides a mechanism to encode the reactivity of sugars via their interaction with sugar-binding proteins. The observed sugar phase-separated hierarchical arrays with lamellar and hexagonal morphologies that encode biological recognition are among the most complex architectures yet discovered in soft matter. The enhanced reactivity of the sugar displays likely has applications in material science and nanomedicine, with potential to evolve into related technologies.
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Entropic formation of a thermodynamically stable colloidal quasicrystal with negligible phason strain
Quasicrystals have been discovered in a variety of materials ranging from metals to polymers. Yet, why and how they form is incompletely understood. In situ transmission electron microscopy of alloy quasicrystal formation in metals suggests an error-and-repair mechanism, whereby quasiperiodic crystals grow imperfectly with phason strain present, and only perfect themselves later into a high-quality quasicrystal with negligible phason strain. The growth mechanism has not been investigated for other types of quasicrystals, such as dendrimeric, polymeric, or colloidal quasicrystals. Soft-matter quasicrystals typically result from entropic, rather than energetic, interactions, and are not usually grown (either in laboratories or in silico ) into large-volume quasicrystals. Consequently, it is unknown whether soft-matter quasicrystals form with the high degree of structural quality found in metal alloy quasicrystals. Here, we investigate the entropically driven growth of colloidal dodecagonal quasicrystals (DQCs) via computer simulation of systems of hard tetrahedra, which are simple models for anisotropic colloidal particles that form a quasicrystal. Using a pattern recognition algorithm applied to particle trajectories during DQC growth, we analyze phason strain to follow the evolution of quasiperiodic order. As in alloys, we observe high structural quality; DQCs with low phason strain crystallize directly from the melt and only require minimal further reduction of phason strain. We also observe transformation from a denser approximant to the DQC via continuous phason strain relaxation. Our results demonstrate that soft-matter quasicrystals dominated by entropy can be thermodynamically stable and grown with high structural quality––just like their alloy quasicrystal counterparts.
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- Award ID(s):
- 1808342
- NSF-PAR ID:
- 10218705
- Date Published:
- Journal Name:
- Proceedings of the National Academy of Sciences
- Volume:
- 118
- Issue:
- 7
- ISSN:
- 0027-8424
- Page Range / eLocation ID:
- e2011799118
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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Abstract Quasicrystals exhibit long-range order but lack translational symmetry. When grown as single crystals, they possess distinctive and unusual properties owing to the absence of grain boundaries. Unfortunately, conventional methods such as bulk crystal growth or thin film deposition only allow us to synthesize either polycrystalline quasicrystals or quasicrystals that are at most a few centimeters in size. Here, we reveal through real-time and 3D imaging the formation of a single decagonal quasicrystal arising from a hard collision between multiple growing quasicrystals in an Al-Co-Ni liquid. Through corresponding molecular dynamics simulations, we examine the underlying kinetics of quasicrystal coalescence and investigate the effects of initial misorientation between the growing quasicrystalline grains on the formation of grain boundaries. At small misorientation, coalescence occurs following rigid rotation that is facilitated by phasons. Our joint experimental-computational discovery paves the way toward fabrication of single, large-scale quasicrystals for novel applications.
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We report the discovery of a dodecagonal quasicrystal Mn 72.3 Si 15.6 Cr 9.7 Al 1.8 Ni 0.6 —composed of a periodic stacking of atomic planes with quasiperiodic translational order and 12-fold symmetry along the two directions perpendicular to the planes—accidentally formed by an electrical discharge event in an eolian dune in the Sand Hills near Hyannis, Nebraska, United States. The quasicrystal, coexisting with a cubic crystalline phase with composition Mn 68.9 Si 19.9 Ni 7.6 Cr 2.2 Al 1.4 , was found in a fulgurite consisting predominantly of fused and melted sand along with traces of melted conductor metal from a nearby downed power line. The fulgurite may have been created by a lightning strike that combined sand with material from downed power line or from electrical discharges from the downed power line alone. Extreme temperatures of at least 1,710 °C were reached, as indicated by the presence of SiO 2 glass in the sample. The dodecagonal quasicrystal is an example of a quasicrystal of any kind formed by electrical discharge, suggesting other places to search for quasicrystals on Earth or in space and for synthesizing them in the laboratory.more » « less
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Abstract We report the discovery of Al34Ni9Fe2, the first natural known periodic crystalline approximant to decagonite (Al71Ni24Fe5), a natural quasicrystal composed of a periodic stack of planes with quasiperiodic atomic order and ten-fold symmetry. The new mineral has been approved by the International Mineralogical Association (IMA 2018-038) and officially named proxidecagonite, which derives from its identity to periodic approximant of decagonite. Both decagonite and proxidecagonite were found in fragments from the Khatyrka meteorite. Proxidecagonite is the first natural quasicrystal approximant to be found in the Al-Ni-Fe system. Within this system, the decagonal quasicrystal phase has been reported to transform at ~940 °C to Al13(Fe,Ni)4, Al3(Fe,Ni)2and the liquid phase, and between 800 and 850 °C to Al13(Fe,Ni)4, Al3(Fe,Ni) and Al3(Fe,Ni)2. The fact that proxidecagonite has not been observed in the laboratory before and formed in a meteorite exposed to high pressures and temperatures during impact-induced shocks suggests that it might be a thermodynamically stable compound at high pressure. The most prominent structural motifs are pseudo-pentagonal symmetry subunits, such as pentagonal bipyramids, that share edges and corners with trigonal bipyramids and which maximize shortest Ni–Al over Ni–Ni contacts.
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In the world of soft-robotic medical devices, there is a growing need for low profile, non-rigid, and lower power actuators for soft exoskeletons and dynamic compression garments. Advanced compression garments with integrated shape memory materials have been developed recently to alleviate the functional and usability limitations associated with traditional compression garments. These advanced garments use contractile shape memory alloy (SMA) coil actuators to produce dynamic compression on the body through selective heating of the SMA material. While these garments can create spatially- and temporally-controllable compression, typical SMA materials (e.g., 70°C Flexinol) consume considerable power and require considerable thermal insulation to protect the wearer during the heating phase of the SMA actuation. Alternative SMA materials (e.g., NiTi #8 by Fort Wayne Metals, Inc.) transform below room temperature and do so using no applied electrical power and generate no waste heat. However, these materials are challenging to dynamically control and require active refrigeration to reset to material. In theory, low-temperature SMA actuators made from materials like NiTi #8 may maintain additional dynamic actuation capacity once equilibrated to room temperature (i.e., the material may not fully transform), as the SMA phase transformation temperature window expands when the material experiences applied stress. This paper investigates this possibility: we manufactured and tested low-temperature NiTi coil actuators to determine the magnitude of the additional force that can be generated via Joule heating once the material has equilibrated to room temperature. SMA spring actuators made from NiTi #8 consumed 84% less power and stabilized at significantly lower temperatures (26.0°C vs. 41.2°C) than SMA springs made from 70°C Flexinol, when actuated at identically fixed displacements (100% nominal strain) and when driven to produce equal forces (∼3.35N). This demonstration of low-power, minimal-heat exposure SMA actuation holds promise for many future wearable actuation applications, including dynamic compression garments.
- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1073/pnas.2011799118
