Chemical organization in reaction-diffusion systems offers a strategy for the generation of materials with ordered morphologies and structural hierarchy. Periodic structures are formed by either molecules or nanoparticles. On the premise of new directing factors and materials, an emerging frontier is the design of systems in which the precipitation partners are nanoparticles and molecules. We show that solvent evaporation from a suspension of cellulose nanocrystals (CNCs) and l -(+)-tartaric acid [ l -(+)-TA] causes phase separation and precipitation, which, being coupled with a reaction/diffusion, results in rhythmic alternation of CNC-rich and l -(+)-TA–rich rings. The CNC-rich regions have a cholesteric structure, while the l -(+)-TA–rich bands are formed by radially aligned elongated bundles. The moving edge of the pattern propagates with a finite constant velocity, which enables control of periodicity by varying film preparation conditions. This work expands knowledge about self-organizing reaction-diffusion systems and offers a strategy for the design of self-organizing materials.
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Travelling colourful patterns in self-organized cellulose-based liquid crystalline structures
Abstract Cellulose-based systems are useful for many applications. However, the issue of self-organization under non-equilibrium conditions, which is ubiquitous in living matter, has scarcely been addressed in cellulose-based materials. Here, we show that quasi-2D preparations of a lyotropic cellulose-based cholesteric mesophase display travelling colourful patterns, which are generated by a chemical reaction-diffusion mechanism being simultaneous with the evaporation of solvents at the boundaries. These patterns involve spatial and temporal variation in the amplitude and sign of the helix´s pitch. We propose a simple model, based on a reaction-diffusion mechanism, which simulates the observed spatiotemporal colour behaviour.
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- Award ID(s):
- 1663041
- NSF-PAR ID:
- 10281751
- Date Published:
- Journal Name:
- Communications Materials
- Volume:
- 2
- Issue:
- 1
- ISSN:
- 2662-4443
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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Abstract The color patterns of butterflies moths are exceptionally diverse, but are very stable within a species, so that most species can be identified on the basis of their color pattern alone. The color pattern is established in the wing imaginal disc during a prolonged period of growth and differentiation, beginning during the last larval instar and ending during the first few days of the pupal stage. During this period, a variety of diffusion and reaction–diffusion signaling mechanisms determine the positions and sizes of the various elements that make up the overall color pattern. The patterning occurs while the wing is growing from a small imaginal disc to a very large pupal wing. One would therefore expect that some or all aspects of the color pattern would be sensitive to the size of the developmental field on which pattern formation takes place. To study this possibility, we analyzed the color patterns of Junonia coenia from animals whose growth patterns were altered by periodic starvation during larval growth, which produced individuals with a large range of variation in body size and wing size. Analyses of the color patterns showed that the positions and size of the pattern elements scaled perfectly isometrically with wing size. This is a puzzling finding and suggests the operation of a homeostatic or robustness mechanism that stabilizes pattern in spite of variation in the growth rate and final size of the wing.
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Arid ecosystems are known to be sensitive to climate change. The Jornada Basin in the USA, as one representative of arid land, has suffered from land degradation in recent decades. In order to disentangle the climate–vegetation feedback, we analyzed the vegetation dynamics under the effects of climate change via a mathematical model based on the reaction–diffusion mechanism. Using this model, we conducted a sensitive analysis of climate factors and concluded that the ecosystem might experience a catastrophic shift with the climatic deterioration. We considered the non-local interaction term to explain the competition among plants. Additionally, the PLR (power law range) metric was used to quantify the extent of the degradation and to compare the results of the vegetation patterns from the remote sensing data and the simulations. From the results, this model could simulate the trends of land degradation in this area. We found that the land degradation could be mainly attributed to climate changes in recent years. This approach suggests that vegetation patterns can provide hints as to whether the ecosystem is approaching desertification. These results can help with mapping vulnerable arid areas around the world through model simulation and satellite images.
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Mechanical decrystallization and water-promoted recrystallization of cellulose were studied to understand the effects of cellulose crystallinity on reaction engineering models of its acid-catalyzed hydrolysis. Microcrystalline cellulose was ball-milled for different periods of time, which decreased its crystallinity and increased the glucose yield obtained from acid hydrolysis treatment. Crystallinity increased after acid hydrolysis treatment, which has previously been explained in terms of rapid hydrolysis of amorphous cellulose, despite conflicting evidence of solvent promoted recrystallization. To elucidate the mechanism, decrystallized samples were subjected to various non-hydrolyzing treatments involving water exposure. Interestingly, all non-hydrolyzing hydrothermal treatments resulted in recovery of crystallinity, including a treatment consisting of heat-up and quenching that was selected as a way to estimate the crystallinity at the onset of hydrolysis. Therefore, the proposed mechanism involving rapid hydrolysis of amorphous cellulose must be incomplete, since the recrystallization rate of amorphous cellulose is greater than the hydrolysis rate. Several techniques (solid-state nuclear magnetic resonance, X-ray diffraction, and Raman spectroscopy) were used to establish that water contact promotes conversion of amorphous cellulose to a mixture of crystalline cellulose I and cellulose II. Crystallite size may also be reduced by the decrystallization-recrystallization treatment. Ethanolysis was used to confirm that the reactivity of the cellulose I/cellulose II mixture is distinct from that of truly amorphous cellulose. These results strongly point to a revised, more realistic model of hydrolysis of mechanically decrystallized cellulose, involving recrystallization and hydrolysis of the cellulose I/cellulose II mixture.more » « less
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We examine a nonreciprocally coupled dynamical model of a mixture of two diffusing species. We demonstrate that nonreciprocity, which is encoded in the model via antagonistic cross-diffusivities, provides a generic mechanism for the emergence of traveling patterns in purely diffusive systems with conservative dynamics. In the absence of nonreciprocity, the binary fluid mixture undergoes a phase transition from a homogeneous mixed state to a demixed state with spatially separated regions rich in one of the two components. Above a critical value of the parameter tuning nonreciprocity, the static demixed pattern acquires a finite velocity, resulting in a state that breaks both spatial and time-reversal symmetry, as well as the reflection parity of the static pattern. We elucidate the generic nature of the transition to traveling patterns using a minimal model that can be studied analytically. Our work has direct relevance to nonequilibrium assembly in mixtures of chemically interacting colloids that are known to exhibit nonreciprocal effective interactions, as well as to mixtures of active and passive agents where traveling states of the type predicted here have been observed in simulations. It also provides insight on transitions to traveling and oscillatory states seen in a broad range of nonreciprocal systems with nonconservative dynamics, from reaction–diffusion and prey–predators models to multispecies mixtures of microorganisms with antagonistic interactions.
- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1038/s43246-021-00182-7
