研究者詳細 - 伴野　太祐

論文 - 伴野　太祐

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Surface structures of cosmetic standard poly methyl methacrylate UV evaluation plates and their influence on the in vitro evaluation of UV protection abilities of cosmetic sunscreens

Kuroda A., Sakai K., Yahagi S., Mukawa T., Sato N., Nakamura N., Maezawa D., Masaki H., Banno T., Asakura K.

Journal of Oleo Science （Journal of Oleo Science） 68 （ 2 ） 175 - 182 2019年

査読有り, ISSN 13458957

Cosmetic standard poly methyl methacrylate (PMMA) UV evaluation plates, i.e., roughened PMMA plates, are used in the EU and the US for the in vitro evaluation of UV protection abilities of sunscreen, such as in vitro UVA-PF and critical wavelength for the Broad-spectrum approval. In our previous studies, inhomogeneity in the thickness of a pseudo-sunscreen layer applied on a flat quartz plate was observed to alter UV transmission. Thus, the surface roughness of the standard plates should have a significant influence on the in vitro evaluation. In the present study, we have analyzed the surface structures of three cosmetic standard PMMA UV evaluation plates: Helioplates HD6 (Sa = 6 µm) and ISO plates (Ra = 2 and 5 µm). A decamethylcyclopentasiloxane and 2-propanol-mixed solvent solution of acrylsilicone resin was prepared, and the solution was added dropwise onto the plates. After the evaporation of the solvents, the plates were cut and the cross section was analyzed using SEM-EDS. The distribution of silicon atoms at the cross-section suggested that the maximum depth of penetrating of acrylsilicone resin was larger than Ra for all the standard plates, and the surface structure was significantly different for each standard plate. In addition, cracks into which the acrylsilicone resin deeply penetrated were observed on the surface of some plates. Clear-solution-type pseudo-sunscreen samples in which UV absorbers and acrylsilicone resin were dissolved were deposited on the standard roughened PMMA plates. It was observed that the addition of acrylsilicone resin drastically changed the net UV transmission. The degree to which the hollows of the roughened surface were filled with the pseudo-sunscreen samples determined the variation of UV transmittance.

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Irreversible aggregation of alternating tetra-block-like amphiphile in water

Konno S., Banno T., Takagi H., Honda S., Toyota T.

PLoS ONE （PLoS ONE） 13 （ 8 ） e0202816 2018年08月

査読有り

As a frontier topic of soft condensed matter physics, irreversible aggregation has drawn attention for a better understanding of the complex behavior of biomaterials. In this study, we have described the synthesis of an artificial amphiphilic molecule, an alternating tetra-block-like amphiphile, which was able to diversify its aggregate structure in water. The aggregated state of its aqueous dispersion was obtained by slow evaporation of the organic solvent at room temperature, and it collapsed irreversibly at ~ 50C. By using a cryo-trans-mission electron microscope and a differential scanning calorimeter, it was revealed that two types of molecular nanostructures were formed and developed into submicro- and micrometer-sized fibrils in the aggregated material.

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Locomotion Mode of Micrometer-Sized Oil Droplets in Solutions of Cationic Surfactants Having Ester or Ether Linkages

Hirono A., Toyota T., Asakura K., Banno T.

Langmuir （Langmuir） 34 （ 26 ） 7821 - 7826 2018年07月

査読有り, ISSN 07437463

Micrometer-sized self-propelled oil droplets under a far-from-equilibrium condition have drawn much attention because of their potential as a dynamic model for the chemical machinery in living organisms. To clarify the effect of interactions between the system components (surfactant, oil, and water) on the locomotion mode of droplets, we investigated the behaviors of oil droplets composed of n-heptyloxybenzaldehyde (HBA) in solutions of cationic surfactants having or not having an ester or an ether linkage. It was observed that in solutions of cationic surfactants having an ester or an ether linkage, spherical HBA droplets self-propelled by changing their direction frequently. On the other hand, when this functional group is absent, a slow self-propelled motion of the oil droplets concurrent with the evolution of aggregates on their surface was observed. From the results of measurement of interfacial tension and assessment of self-emulsification, we determined that the attractive interactions of cationic surfactants without an ester or an ether linkage with HBA are stronger than those having the linkage. The difference in the locomotion mode of oil droplets is probably explained from the viewpoint of the interactions among the system components.

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Droplets As Liquid Robots

J. Čejková, T. Banno, M. M. Hanczyc, F. Štěpánek

Artificial Life 23 528 - 549 2017年12月

筆頭著者, 最終著者, 責任著者, 査読有り

Locomotion and Transformation of Underwater Micrometer-Sized Molecular Aggregates under Chemical Stimuli

伴野太祐

JOURNAL OF THE PHYSICAL SOCIETY OF JAPAN （PHYSICAL SOC JAPAN） 86 （ 10 ） 528 - 549 2017年10月

研究論文（学術雑誌）, 査読有り, ISSN 0031-9015

In this review paper, we introduce the mobility and transformation of micrometer-sized molecular aggregates (i.e., oil droplets, liquid crystalline droplets and tubes, and giant vesicles) in water under chemical stimuli. These molecular aggregates comprising lipophilic and/or amphiphilic molecules have drawn much attention as plausible prebiotic cellular structures and dynamic microreactors related to the origins of life. Here, we highlight recent advances and issues concerning the construction of such systems and discuss the implications of these findings to our understanding of protocellular systems.

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Sequential dynamic structuralisation by in situ production of supramolecular building blocks

伴野太祐

CHEMICAL COMMUNICATIONS （ROYAL SOC CHEMISTRY） 53 （ 61 ） 8553 - 8556 2017年08月

研究論文（学術雑誌）, 査読有り, ISSN 1359-7345

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Self-Propelled Motion of Monodisperse Underwater Oil Droplets Formed by a Microfluidic Device

伴野太祐

LANGMUIR 33 （ 22 ） 5393 - 5397 2017年06月

研究論文（学術雑誌）, 査読有り, ISSN 0743-7463

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Phototactic behavior of self-propelled micrometer-sized oil droplets in a surfactant solution

Sho Kaneko, Kouichi Asakura, Taisuke Banno

CHEMICAL COMMUNICATIONS （ROYAL SOC CHEMISTRY） 53 （ 14 ） 2237 - 2240 2017年02月

筆頭著者, 最終著者, 責任著者, 査読有り, ISSN 1359-7345

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Self-Propelled Oil Droplets and Their Morphological Change to Giant Vesicles Induced by a Surfactant Solution at Low pH

Taisuke Banno, Yuki Tanaka, Kouichi Asakura, Taro Toyota

LANGMUIR （AMER CHEMICAL SOC） 32 （ 37 ） 9591 - 9597 2016年09月

筆頭著者, 最終著者, 責任著者, 査読有り, ISSN 0743-7463

Unique dynamics using inanimate molecular assemblies based on soft matter have drawn much attention for demonstrating far-from-equilibrium chemical systems. However, there are no soft matter systems that exhibit a possible pathway linking the self-propelled oil droplets to formation of giant vesicles stimulated by low pH. In this study, we conceived an experimental oil-in-water emulsion system in which flocculated particles composed of a imine-containing oil transformed to spherical oil droplets that self-propelled and, after coming to rest, formed membranovs figures. Finally, these figures became giant vesicles. From NMR, pH curves, and surface tension measurements, we determined that this far-from-equilibrium phenomenon was due to the acidic hydrolysis of the oil, which, produced a benzaldehyde derivative as an component and a primary amine as a surfactant precursor, and, the dynamic behavior of the hydrolytic products in the emulsion system. These findings afforded us a potential linkage between mobile droplet-based protocells and vesicle-based protocells stimulated by low pH.

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Deformable Self-Propelled Micro-Object Comprising Underwater Oil Droplets

Taisuke Banno, Arisa Asami, Naoko Ueno, Hiroyuki Kitahata, Yuki Koyano, Kouichi Asakura, Taro Toyota

SCIENTIFIC REPORTS （NATURE PUBLISHING GROUP） 6 31292 2016年08月

筆頭著者, 最終著者, 責任著者, 査読有り, ISSN 2045-2322

The self-propelled motion with deformation of micrometer-sized soft matter in water has potential application not only for underwater carriers or probes in very narrow spaces but also for understanding cell locomotion in terms of non-equilibrium physics. As far as we know, there have been no reports about micrometer-sized self-propelled soft matter mimicking amoeboid motion underwater. Here, we report an artificial molecular system of underwater oil droplets exhibiting self-propelled motion with deformation as an initial experimental model. We describe the heterogeneity in a deformable self-propelled oil droplet system in aqueous and oil phases and at their interface based on the behavior and interaction of surfactant and oil molecules. The current results have great importance for scientific frontiers such as developing deformable micro-swimmers and exploring the emergence of self-locomotion of oil droplet-type protocells.

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Controlled polymerization of acrylonitrile proceeded along with the Belousov–Zhabotinsky oscillator by changing its stirring conditions

Y. Furue, K. Okano, T. Banno, K. Asakura

Chemical Physics Letters （ELSEVIER SCIENCE BV） 645 210 - 214 2016年02月

筆頭著者, 最終著者, 責任著者, 査読有り, ISSN 0009-2614

Chemical oscillations of the manganese-ion catalyzed Belousov-Zhabotinsky (BZ) reaction system were found to be controlled by changing its stirring conditions. The oscillation stopped at a high stirring rate, while it reappeared immediately by reducing the stirring rate. It is known in the BZ reaction system, that the radical polymerization takes place along with the oscillation when acrylic monomers are added. By the addition of acrylonitrile to the system stirred at a high stirring rate, the oscillation as well as the polymerization of acrylonitrile stopped. The radical polymerization of acrylonitrile by the BZ oscillator is thus found to be made controllable by changing the mixing conditions. (C) 2015 Elsevier B.V. All rights reserved.

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Design of Reactive Surfactants that Control the Locomotion Mode of Cell-Sized Oil Droplets

T. Banno, T. Toyota

Current Physical Chemistry 5 （ 1 ） 37 - 51 2015年10月

筆頭著者, 最終著者, 責任著者, 査読有り

Molecular System for the Division of Self-Propelled Oil Droplets by Component Feeding

Taisuke Banno, Taro Toyota

LANGMUIR （AMER CHEMICAL SOC） 31 （ 25 ） 6943 - 6947 2015年06月

筆頭著者, 最終著者, 責任著者, 査読有り, ISSN 0743-7463

Unique dynamics using inanimate molecular assemblies have drawn a great amount of attention for demonstrating prebiomimetic molecular systems. For the construction of an organized logic combining two fundamental dynamics of life, we demonstrate here a molecular system that exhibits both division and self-propelled motion using oil droplets. The key molecule of this molecular system is a novel cationic surfactant containing a five-membered acetal moiety, and the molecular system can feed the self-propelled oil droplet composed of a benzaldehyde derivative and an alkanol. The division dynamics of the self-propelled oil droplets were observed through the hydrolysis of the cationic surfactant in bulk solution. The mechanism of the current dynamics is argued to be based on the supply of "fresh" oil components in the moving oil droplets, which is induced by the Marangoni instability. We consider this molecular system to be a prototype of self-reproducing inanimate molecular assembly exhibiting self-propelled motion.

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Micrometer-sized network structure of novel DNA–lipid conjugates induced by heat stimulation

K. Takahashi, M. Matsuo, T. Banno, T. Toyota

Soft Matter （ROYAL SOC CHEMISTRY） 11 （ 35 ） 7053 - 7058 2015年

筆頭著者, 最終著者, 責任著者, 査読有り, ISSN 1744-683X

We have developed a novel lipid-bearing DNA that forms hairpin modules, including a single RNA monomer; this can be used to create micrometer-sized structures from nanometer-sized building blocks during breakage at the RNA site. In the presence of divalent metal ions and heat stimulation, we observed transition of the self-assembly, which results in the formation of a three-dimensional network structure. To our knowledge, this is also the first report of heat-induced micrometer-sized molecular self-assembly of molecules that carry biological information.

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Multiple-division of self-propelled oil droplets through acetal formation

Taisuke Banno, Rie Kuroha, Shingo Miura, Taro Toyota

SOFT MATTER （ROYAL SOC CHEMISTRY） 11 （ 8 ） 1459 - 1463 2015年

筆頭著者, 最終著者, 責任著者, 査読有り, ISSN 1744-683X

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Giant Vesicle Formation of Novel Polymerizable Amphiphile Associated with Its Polymerization and Hydrolysis in Water

Taisuke Banno, Yuki Kazayama, Taro Toyota

CHEMISTRY LETTERS （CHEMICAL SOC JAPAN） 43 （ 11 ） 1707 - 1709 2014年11月

筆頭著者, 最終著者, 責任著者, 査読有り, ISSN 0366-7022

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Molecular Building Blocks and Their Architecture in Biologically/Environmentally Compatible Soft Matter Chemical Machinery

Taro Toyotat, Taisuke Banno, Sachiko Nitta, Masahiro Takinoue, Tomonori Nomoto, Yuno Natsume, Shuichi Matsumura, Masanori Fujinami

JOURNAL OF OLEO SCIENCE （JAPAN OIL CHEMISTS SOC） 63 （ 11 ） 1085 - 1098 2014年11月

筆頭著者, 最終著者, 責任著者, 査読有り, ISSN 1345-8957

This review briefly summarizes recent developments in the construction of biologically/environmentally compatible chemical machinery composed of soft matter. Since environmental and living systems are open systems, chemical machinery must continuously fulfill its functions not only through the influx and generation of molecules but also via the degradation and dissipation of molecules. If the degradation or dissipation of soft matter molecular building blocks and biomaterial molecules/polymers can be achieved, soft matter particles composed of them can be used to realize chemical machinery such as self-propelled droplets, drug delivery carriers, tissue regeneration scaffolds, protocell models, cell-/tissue-markers, and molecular computing systems.

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pH-Induced Motion Control of Self-Propelled Oil Droplets Using a Hydrolyzable Gemini Cationic Surfactant

Shingo Miura, Taisuke Banno, Taishi Tonooka, Toshihisa Osaki, Shoji Takeuchi, Taro Toyota

LANGMUIR （AMER CHEMICAL SOC） 30 （ 27 ） 7977 - 7985 2014年07月

筆頭著者, 最終著者, 責任著者, 査読有り, ISSN 0743-7463

Self-propelled motion of micrometer-sized substances has drawn much attention as an autonomous transportation system. One candidate vehicle is a chemically driven micrometer-sized oil droplet. However, to the best of our knowledge, there has been no report of a chemical reaction system controlling the three-dimensional motion of oil droplets underwater. In this study, we developed a molecular system that controlled the self-propelled motion of 4-heptyloxybenzaldehyde oil droplets by using novel gemini cationic surfactants containing carbonate linkages (2G12C). We found that, in emulsions containing sodium hydroxide, the motion time of the self-propelled oil droplets was longer in the presence of 2G12C than in the presence of gemini cationic surfactants without carbonate linkages. Moreover, in 2G12C solution, oil droplets at rest underwent unidirectional, self-propelled motion in a gradient field toward higher concentration of sodium hydroxide. Even though they stopped within several seconds, they restarted in the same direction. 2G12C was gradually hydrolyzed under basic conditions to produce a pair of the corresponding monomeric surfactants, which exhibit different interfacial properties from 2G12C. The prolonged and restart motion of the oil droplets were explained by the increase in the heterogeneity of the interfacial tension of the oil droplets.

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Mode Changes Associated with Oil Droplet Movement in Solutions of Gemini Cationic Surfactants

Taisuke Banno, Shingo Miura, Rie Kuroha, Taro Toyota

LANGMUIR （AMER CHEMICAL SOC） 29 （ 25 ） 7689 - 7696 2013年06月

筆頭著者, 最終著者, 責任著者, 査読有り, ISSN 0743-7463

Micrometer-sized self-propelled oil droplets in nonequilibrium systems have attracted much attention, since they form stable emulsions composed of oil, water, and surfactant which represent a primitive type of inanimate chemical machinery. In this work, we examined means of controlling the movement of oil droplets by studying the dynamics of n-heptyloxybenzaldehyde droplets in phosphate buffers containing alkanediyl-alpha,omega-bis(N-dodecyl-N,N-dimethylammonium bromide) (nG12) with either tetramethylene (4G12), octaethylene (8G12), or dodecamethylene (12G12) chains in the linker moiety. Significant differences in droplet dynamics were observed to be induced by changes in the linker structure of these gemini cationic surfactants. In a phosphate buffer containing 30 mM 4G12, self-propelled motion of droplets concurrent with the formation of molecular aggregates on their surfaces was observed, whereas the fusion of oil droplets was evident in both 8G12 and 12G12 solutions. We also determined that the surface activities and the extent of molecular self-assembly of the surfactants in phosphate buffer were strongly influenced by the alkyl chain length in the linker moiety. We therefore conclude that the surface activities of the gemini cationic surfactant have important effects on the oil water interfacial tension of oil droplets and the formation of molecular aggregates and that both of these factors induce the unique movement of the droplets.

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pH-Sensitive Self-Propelled Motion of Oil Droplets in the Presence of Cationic Surfactants Containing Hydrolyzable Ester Linkages

Taisuke Banno, Rie Kuroha, Taro Toyota

LANGMUIR （AMER CHEMICAL SOC） 28 （ 2 ） 1190 - 1195 2012年01月

筆頭著者, 最終著者, 責任著者, 査読有り, ISSN 0743-7463

Self-propelled oil droplets in a nonequilibrium system have drawn much attention as both a primitive type of inanimate chemical machinery and a dynamic model of the origin of life. Here, to create the pH-sensitive self-propelled motion of oil droplets, we synthesized cationic surfactants containing hydrolyzable ester linkages. We found that n-heptyloxybenzaldehyde oil droplets were self-propelled in the presence of ester-containing cationic surfactant. In basic solution prepared with sodium hydroxide, oil droplets moved as molecular aggregates formed on their surface. Moreover, the self-propelled motion in the presence of the hydrolyzable cationic surfactant lasted longer than that in the presence of nonhydrolyzable cationic surfactant. This is probably due to the production of a fatty acid by the hydrolysis of the ester-containing cationic surfactant and the subsequent neutralization of the fatty acid with sodium hydroxide,. A complex surfactant was formed in the aqueous solution because of the cation and anion combination. Because such complex formation can induce both a decrease in the interfacial tension of the oil droplet and self-assembly with n-heptyloxybenzaldehyde and lauric acid in the aqueous dispersion, the prolonged movement of the oil droplet may be explained by the increase in heterogeneity of the interfacial tension of the oil droplet triggered by the; hydrolysis of the ester-containing surfactant.

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伴野 太祐

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伴野　太祐

論文 - 伴野　太祐