Soft+Matter
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Nanoscale Self-Assembling Salt-Crystal ‘Origami’ Balls Envelop Liquids
Mechanical engineers have devised a ‘crystal capillary origami’ technique where salt crystals spontaneously encapsulate liquid droplets
Researchers have developed a technique whereby they can spontaneously encapsulate microscopic droplets of water and oil emulsion in a tiny sphere made of salt crystals—sort of like a minute, self-constructing origami soccer ball filled with liquid. The process, which they are calling ‘crystal capillary origami,’ could be used in a range of fields from more precise drug delivery to nanoscale medical devices.The technique is described in a paper appearing in the journal Nanoscale on September 21.
Capillary action, or ‘capillarity,’ will be familiar to most people as the way that water or other liquids can move up narrow tubes or other porous materials seemingly in defiance of gravity (for example within the vascular systems of plants, or even more simply, the drawing up of paint between the hairs of a paintbrush). This effect is due to the forces of cohesion (the tendency of a liquid’s molecules to stick together), which results in surface tension, and adhesion (their tendency to stick to the surface of other substances). The strength of the capillarity depends on the chemistry of the liquid, the chemistry of the porous material, and on the other forces acting on them both. For example, a liquid with lower surface tension than water would not be able to hold up a water strider insect.
Less well known is a related phenomenon, elasto-capillarity, that takes advantage of the relationship between capillarity and the elasticity of a very tiny flat sheet of a solid material. In certain circumstances, the capillary forces can overcome the elastic bending resistance of the sheet.
This relationship can be exploited to create ‘capillary origami,’ or three-dimensional structures. When a liquid droplet is placed on the flat sheet, the latter can spontaneously encapsulate the former due to surface tension. Capillary origami can take on other forms including wrinkling, buckling, or self-folding into other shapes. The specific geometrical shape that the 3D capillary origami structure ends up taking is determined by both the chemistry of the flat sheet and that of the liquid, and by carefully designing the shape and size of the sheet.
There is one big problem with these small devices, however. “These conventional self-assembled origami structures cannot be completely spherical and will always have discontinuous boundaries, or what you might call ‘edges,’ as a result of the original two-dimensional shape of the sheet,” said Kwangseok Park, a lead researcher on the project. He added, “These edges could turn out to be future defects with the potential for failure in the face of increased stress.” Non-spherical particles are also known to be more disadvantageous than spherical particles in terms of cellular uptake.
Professor Hyoungsoo Kim from the Department of Mechanical Engineering explained, “This is why researchers have long been on the hunt for substances that could produce a fully spherical capillary origami structure.”
The authors of the study have demonstrated such an origami sphere for the first time. They showed how instead of a flat sheet, the growth of salt-crystals can perform capillary origami action in a similar manner. What they call ‘crystal capillary origami’ spontaneously constructs a smooth spherical shell capsule from these same surface tension effects, but now the spontaneous encapsulation of a liquid is determined by the elasto-capillary conditions of growing crystals.
Here, the term ‘salt’ refers to a compound of one positively charged ion and another negatively charged. Table salt, or sodium chloride, is just one example of a salt. The researchers used four other salts: calcium propionate, sodium salicylate, calcium nitrate tetrahydrate, and sodium bicarbonate to envelop a water-oil emulsion. Normally, a salt such as sodium chloride has a cubical crystal structure, but these four salts form plate-like structures as crystallites or ‘grains’ (the microscopic shape that forms when a crystal first starts to grow) instead. These plates then self-assemble into perfect spheres.
Using scanning electron microscopy and X-ray diffraction analysis, they investigated the mechanism of such formation and concluded that it was ‘Laplace pressure’ that drives the crystallite plates to cover the emulsion surface. Laplace pressure describes the pressure difference between the interior and exterior of a curved surface caused by the surface tension at the interface between the two substances, in this case between the salt water and the oil.
The researchers hope that these self-assembling nanostructures can be used for encapsulation applications in a range of sectors, from the food industry and cosmetics to drug delivery and even tiny medical devices.
-Publication
Kwangseok Park, Hyoungsoo Kim “Crystal capillary origami capsule with self-assembled nanostructure,” Nanoscale, 13(35), 14656-14665 (DOI: 10.1039/d1nr02456f)
-Profile
Professor Hyoungsoo Kim
Fluid and Interface Laboratory
http://fil.kaist.ac.kr
Department of Mechanical Engineering
KAIST
2021.11.04 View 7447 -
Micropatch Made of DNA
Researchers reported the fabrication of microstructure arrays of DNA materials using topographic control. This method provides a platform for forming multiscale hierarchical orientations of soft and biomaterials using a process of simple shearing and controlled evaporation on a patterned substrate. This approach enables the potential of patterning applications using DNA or other anisotropic biomaterials.
DNA is one of the most abundant biomaterials found in all living organisms in nature. It has unique characteristics of fine feature size and liquid crystalline phase, enabling to create various kinds of microstructure DNA arrays. Based on these characteristics, DNA has been used as a building block for “origami” and textile art at the nanometer scale.
A KAIST research team led by Professors Dong Ki Yoon and Hyungsoo Kim fabricated a DNA-based micropatch using the “coffee ring effect” and its multi-angle control technology, which was published online in Nature Communications on June 7.
The research team used cheap DNA material extracted from salmon to realize the micropatch structure with well-aligned knit or ice cream cone shapes. When the DNA material in an aqueous solution is rubbed between two solid substrates while water is evaporating, DNA chains are unidirectionally aligned to make a thin film such as in LCD display devices. The DNA chains can make more complex microstructures such as knit or a texture with ice cream cone shapes when the same procedure is carried out in topographical patterns like microposts (Figure 1). This can be applied to make metamaterials by mixing with functionalized gold nanorods to show plasmonic color.
Plasmon resonance is a phenomenon in which electrons vibrate uniformly on the surface of a substrate made of metal, reacting only to light that matches a specific energy to enhance the clarity and expression of colors. For this, the most important factor is the orientation in which the gold nanorods align. That is, when the rods are aligned side by side in one direction, the optical and electrical characteristics are maximized. The research team focused on this point and made the DNA micropatch as a frame to orient the gold nanorods in a unique shape and fabricated a plasmonic color film (Figure 2).
Professor Yoon said this study is meaningful in that it deals with the evaporation phenomenon, which has not been studied much in the field of polymers and biopolymers in terms of basic science. He explained, “This will also help maximize the efficiency of polymeric materials that can be orientated in coating, 2D, and 3D printing applications. Furthermore, DNA that exists infinitely in nature can be expected to have industrial application value as a new material since it can easily form complexes with other materials as described in this study.”
(Figure 1. The DNA micropatch using topographic control. (a) The experimental scheme.
(b) Enlarged image of (e). (c-e) Different micropatches made of DNA using different shearing directions.)
(Figure 2. The knit-like structures made of DNA-gold nanorod complex. (a,b) Optical
and polarized optical microscopy images. (c-f) Plasmonic colors reflected from aligned DNA-gold nanorod complex depending on the sample rotation.)
2019.07.01 View 32704 -
Undergrad's Paper Chosen as the Cover Article in Soft Matter
(from left: Research Professor KyuHan Kim and Undergrad Student Subeen Kim)
A KAIST undergraduate student, Subeen Kim, had his paper chosen as the cover article in an international journal during his senior year.
There have been an increasing number of undergraduate students who were published as the first author because the KAIST Undergraduate Research Participation program allows more active research participation by undergraduate students.
Through URP, Kim successfully published his paper in the internationally-renowned journal, Soft Matter, which is published by the Royal Society of Chemistry, and it was chosen as the cover article of that journal in February 2018.
This publication means a lot to him because he designed the cover image himself, based on his imagination and observations.
His research is about controllable one-step double emulsion formation. Double emulsion is a system in which dispersed droplets contain additional immiscible liquid droplets.
Having great retention ability, double emulsion has been used in various applications in the food industry, in cosmetics, and for drug delivery. Nevertheless, two-step emulsification is a conventional approach to produce double emulsions that typically leads to partial destabilization of the emulsion formed during the initial stage. Hence, it does not ensure the stability of a double emulsion. On the other hand, a microfluidic approach with various flow-focusing techniques has been developed, but it has low production efficiency and thus limited industrial applications.
Kim’s results came from the process of phase inversion to solve this problem. He identified the instant formation of double emulsions during the process of phase inversion. Based on this finding, he proposed criteria to achieve high stability of double emulsion.
Through constant research, he developed a quite general method using a combination of an oil soluble poly methyl methacrylate (PMMA) and hydrophobic silica nanoparticle (HDK H18). This new method enables one-step and stable production of double emersions in a stable manner. It also allows control of the number and the volume of inner oil droplets inside the outer water droplets by adjusting PMMA and HDK H18.
Kim enrolled at KAIST as a KAIST Presidential Fellowship and Presidential Science Scholarship in 2014. While studying both chemical and biomolecular engineering and chemistry he has been developing his hypothesis and conducting research.
He was able to begin conducting research because he has taken part in URP projects twice. In his sophomore year, he studied the formation of high internal phase double emulsions. After one year, he conducted research to produce superabsorbent resins, which are the base material for diapers, by using colloid particles. Using partial research outcomes, he published his paper in Nature Communications as a second author.
Kim said, “Double majoring the chemical and biomolecular engineering and chemistry has helped me producing this outcome. I hope that this research contributes to commercializing double emulsions. I will continue to identify accurate principles to produce chemicals that can be controlled exquisitely.”
Figure 1. The cover article of Soft Matter
2018.05.03 View 9280