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Self-propelled droplets made of organic materials can be an influential candidate for understanding cell migration from the viewpoint of nonequilibrium physics and have attracted significant attention with regard to soft-matter-type rovers. Because self-propelled droplets are soft enough to be easily deformed, they should be useful as chemically artificial rovers that can move in small areas with many obstacles in water and can be applied as ‘motile’ carriers for exploring and curing of biological bodies or remediation of the natural environment. Here, we review recent research progress on designing self-propelled droplets of micrometer size.

Using water-floating 3D-printed models, we investigated the dynamics of camphor boats, which are composed of a one-holed board and a camphor grain, under constraint conditions where a rod hooks the camphor boat on the water surface. When a camphor boat was connected to a water-floating disk or another camphor boat through a rod, we found that regular dynamics of the camphor boat appear and depend on the mobility restriction of the disk, the rod length, and the position of a slit of the camphor boat. We performed numerical simulations to reproduce the observed motions with theoretical models including constraint conditions.

Design and fabrication of organic and polymeric soft materials exhibiting solvent-free isothermal changes in mechanical properties triggered by photostimulation are challenging. Here, we report dramatic changes in viscoelasticity of coumarin end-functionalized poly(dimethyl siloxane) with a branched macromolecular architecture under a solvent-free isothermal condition upon alternating irradiation of UV at the wavelength of 365 and 254 nm (UV365 and UV254). Significantly, it is disclosed that storage modulus (G′) was increased by a factor of more than 30000. Moreover, the subsequent UV254 irradiation caused sharp decrease in G′ and it became comparable to loss modulus. Furthermore, alternating irradiation of UV365 and UV254 caused repetitive increase and decrease in G′ of the material.

The self-propelled behaviors of macroscopic inanimate objects at surfaces and interfaces are ubiquitous phenomena of fundamental interest in interface science. However, given the existence of a large variety of systems with their own inherent chemical properties, the kinematics of the self-propelled motion and the dynamics of the forces driving these systems often remain largely unknown. Here, we experimentally investigate the spontaneous motion of a sodium oleate tablet at a water-nitrobenzene interface, under nonequilibrium and global isothermal conditions, through measurements of the interfacial tension with the noninvasive, quasi-elastic laser scattering method. The sodium oleate tablet was self-propelled due to an imbalance in the interfacial tension induced by the inhomogeneous adsorption of oleate/oleic acid molecules. The kinetics of the self-propelled motion of a boat-shaped plastic sheet bearing sodium oleate tablets at a sodium oleate aqueous solution-nitrobenzene interface was also studied. The interfacial tension difference between the front and rear of the boat was quantitatively identified as the force pushing the boat forward, although the Marangoni flow due to the uneven distribution of the interfacial tension behind the boat tended to decelerate the motion.

The Nobel Prize in Chemistry was awarded in 1987 and 2016 for research in supramolecular chemistry on the “development and use of molecules with structure-specific interactions of high selectivity” and the “design and production of molecular machines”, respectively. This confirmed the explosive development of supramolecular chemistry. In addition, attempts have been made in systems chemistry to embody the complex functions of living organisms as artificial non-equilibrium chemical systems, which have not received much attention in supramolecular chemistry. In this review, we explain recent developments in supramolecular chemistry through four categories: stimuli-responsiveness, time evolution, dissipative self-assembly, and hierarchical expression of functions. We discuss the development of non-equilibrium supramolecular systems, including the use of molecules with precisely designed properties, to achieve functions found in life as a hierarchical chemical system.

The characteristic amoeboid behavior of an oil droplet (decane with dissolved palmitic acid) on an aqueous phase containing a surfactant (stearyltrimethylammonium chloride) has been investigated and discussed. The formation and motion of assemblies of molecular aggregates were observed with the aid of a range of particle tracers. The quasi-elastic laser scattering method was employed to measure the surface tension of the aqueous phase as a function of time. From those measurements we found that the amoeboid behavior occurs in three stages. First, molecular aggregates formed at the oil-water interface and subsequently spread and absorbed at the aqueous surface thanks to a convective flow due to the Marangoni effect. In the second stage, the whole aqueous surface was saturated with those molecular aggregates and a phase transition to a liquid condensed monolayer membrane occurred. Finally, domains formed at the bottom of the oil droplet with permeable boundaries composed of branch-shaped assemblies of molecular aggregates. Blebs grew in those parts of the oil droplet rim with high accumulation of molecular aggregates.

We evaluated the speed profile of self-propelled underwater oil droplets comprising a hydrophobic aldehyde derivative in terms of their diameter and the surrounding surfactant concentration using a microfluidic device. We found that the speed of the oil droplets is dependent on not only the surfactant concentration but also the droplet size in a certain range of the surfactant concentration. This tendency is interpreted in terms of combination of the oil and surfactant affording spontaneous emulsification in addition to the Marangoni effect.

A tetracyanoquaterthienoquinoid (TCT4Q)-based field effect transistor is characterized by the ambipolar transfer characteristics and the facile shift of the threshold voltage induced by the bias stress. The trapping and detrapping kinetics of charge carriers was investigated in detail by the temperature dependence of the decay of source-drain current (ISD). We found a repeatable formation of a molecular floating gate is derived from a ‘charge carrier-and-gate’ cycle comprising four stages, trapping of mobile carriers, formation of a floating gate, induction of oppositely charged mobile carriers, and recombination between mobile and trapped carriers to restore the initial state.

Liposomes encapsulating cytoskeletons have drawn much recent attention to develop an artificial cell-like chemical-machinery; however, as far as we know, there has been no report showing isothermally reversible morphological changes of liposomes containing cytoskeletons because the sets of various regulatory factors, that is, their interacting proteins, are required to control the state of every reaction system of cytoskeletons. Here we focused on hydrostatic pressure to control the polymerization state of microtubules (MTs) within cell-sized giant liposomes (diameters ∼10 μm). MT is the cytoskeleton formed by the polymerization of tubulin, and cytoskeletal systems consisting of MTs are very dynamic and play many important roles in living cells, such as the morphogenesis of nerve cells and formation of the spindle apparatus during mitosis. Using real-time imaging with a high-pressure microscope, we examined the effects of hydrostatic pressure on the morphology of tubulin-encapsulating giant liposomes. At ambient pressure (0.1 MPa), many liposomes formed protrusions due to tubulin polymerization within them. When high pressure (60 MPa) was applied, the protrusions shrank within several tens of seconds. This process was repeatedly inducible (around three times), and after the pressure was released, the protrusions regenerated within several minutes. These deformation rates of the liposomes are close to the velocities of migrating or shape-changing living cells rather than the shortening and elongation rates of the single MTs, which have been previously measured. These results demonstrate that the elongation and shortening of protrusions of giant liposomes is repeatedly controllable by regulating the polymerization state of MTs within them by applying and releasing hydrostatic pressure., 細胞サイズの人工膜小胞を可逆的に繰り返し変形させられることに成功 (生体運動マシナリーを使った分子ロボット構築の可能性を実証). 京都大学プレスリリース. 2016-04-19.

The effects of halide ions on the acceptor phase in the chemical oscillation in donor/membrane/acceptor systems were examined. The transfer of cetyltrimethylammonium (CTA(+)) ions from the donor phase and their adsorption and desorption at the membrane/acceptor interface led to spontaneous, nonlinear oscillations of the electric potential. Chloride ions stabilized the adsorption of CTA(+) ions and gave rise to a large-amplitude, long-interval, and a long relaxation-time constant. On the contrary, iodide ions, which are more hydrophobic than chloride ions, demonstrated opposite results. This mechanism was proposed based on the simultaneous time-resolved measurements of the interfacial tensions at both the donor/membrane and membrane/acceptor interfaces and observation of the convective flow due to Marangoni instability.

Using a quasi-elastic laser scattering (QELS) method, we determined the changes in the interfacial tension of a lipid monolayer membrane, composed of either 1,2-dioleoyl-sn-glycero-3-phospho- l -serine sodium salt (DOPS) or 1,2-dioleoyl-sn-glycero-3-phosphocholine (DOPC), at the water/chloroform interface upon the addition of lysozyme. The measurements were performed in the presence of electrolytes of different concentrations and using lipids that vary the net charge of the monolayer membrane. As a result, the interfacial tension was observed to decrease in three stages. In the case of DOPS, there was a lag time wherein the interfacial tension did not change, which lasted from several tens of seconds to several hundreds, following electrostatic interaction between lysozyme and the lipid monolayer membrane. On the other hand, the DOPC monolayer membrane decreased its interfacial tension without such a lag time after lysozyme addition. The lag time was attributed to the strong electrostatic interaction between the lysozyme and the DOPS monolayer membrane, which delayed the hydrophobic interaction that causes a change in the overall structure and conformation of lysozyme and lipids.

We demonstrate a novel system that exhibits both self-propelled motion and division of micrometer-sized oil droplets induced by chemical conversion of the system components. Such unique dynamics were observed in an oil-in-water emulsion of a benzaldehyde derivative, an alkanol and a cationic surfactant at a low pH.

Knowing the exact location of gastrointestinal tumors both preoperatively and intraoperatively is essential for planning and performing laparoscopic surgery. Different techniques have been introduced to ascertain tumor locations during surgery, but none of these are fully satisfactory at establishing the minimum margins for organ resection while retaining curability. A new, non-blurring tissue marker, detectable by both X-ray computed tomography (CT) and near-infrared (NIR) fluorescence laparoscopy, has been developed, and we here examine its utility using an animal model. Liposomes, comprised phospholipids and an NIR fluorescent dye (an indocyanine green derivative), and emulsions, consisting of phospholipids and oily radiographic contrast medium, were combined with polyglycerol-polyricinoleate to form giant cluster-like vesicles. This vesicular dispersion (300 μl) was administered into the porcine gastric submucosa using a gastroendoscope, and the detectability of the marker was examined using X-ray CT and NIR fluorescence laparoscopy. One hour after the administration of the vesicular dispersion, X-ray CT identified four individual injection sites, each at a 1-cm radius of a metal hemostasis clip. NIR fluorescence laparoscopy detected individual fluorescent spots 18 hours after the administration of the vesicular dispersion. We anticipate that this newly developed tissue marker will contribute to the preoperative simulation of laparoscopic gastrointestinal cancer surgery and its intraoperative navigation.

Liposomally formulated indocyanine green (LP-ICG) has drawn much attention as a highly sensitive near-infrared (NIR)-fluorescence probe for tumors or lymph nodes in vivo. We synthesized ICG derivatives tagged with alkyl chains (ICG-Cn), and we examined NIR-fluorescence imaging for lymph nodes in the lower extremities of mice by using liposomally formulated ICG-Cn (LP-ICG-Cn) as well as conventional liposomally formulated ICG (LP-ICG) and ICG. Analysis with a noninvasive preclinical NIR-fluorescence imaging system revealed that LP-ICG-Cn accumulates in only the popliteal lymph node 1h after injection into the footpad, whereas LP-ICG and ICG accumulate in the popliteal lymph node and other organs like the liver. This result indicates that LP-ICG-Cn is a useful NIR-fluorescence probe for noninvasive in vivo bioimaging, especially for the sentinel lymph node.

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.

We have rationally designed and synthesized a novel near-infrared (NIR) photoactivating probe, designated by iDOPE, in which an indocyanine green (ICG) fluorophore is covalently conjugated with a phospholipid moiety, 1,2-dioleoyl- sn -glycero-3-phosphoethanolamine (DOPE), to incorporate into liposome bilayers. NIR irradiation showed that iDOPE retained the optical and fluorescence properties of ICG and demonstrated photoactivator characteristics: fluorescence emission at around 820 nm in a solvent, singlet oxygen production, and concentration-dependent heat generation. Additionally, iDOPE was incorporated into liposome bilayers and maintained stable liposomally formulated iDOPE (LP-iDOPE) over 1 week under physiological conditions. We also observed the tumor-specific biodistribution of LP-iDOPE of in vivo xenografts. These findings suggest that LP-iDOPE might be a promising tool for NIR optical imaging, photodynamic therapy, and photothermal therapy.

The production of giant lipid vesicles with controlled size and structure will be an important technology in the design of quantitative biological assays in cell-mimetic microcompartments. For establishing size control of giant vesicles, we investigated the vesicle formation process, in which inverted emulsion droplets are transformed into giant unilamellar vesicles (GUVs) when they pass through an oil/water interface. The relationship between the size of the template emulsion and the converted GUVs was studied using inverted emulsion droplets with a narrow size distribution, which were prepared by microfluidics. We successfully found an appropriate centrifugal acceleration condition to obtain GUVs that had a desired size and narrow-enough size distribution with an improved yield so that emulsion droplets can become the template for GUVs.

A major breakthrough in in vivo cellular imaging has been the clinical/preclinical use of magnetic resonance imaging (MRI) with contrast agent. Superparamagnetic iron oxide (SPIO) is a promising candidate for the development of smart MRI probes for cell-tracking. In the present study, we describe biodegradable probes made of giant vesicles (GVs; closed lipid membranes with diameters >1 μm) that encapsulate SPIO for use as an MRI contrast agent. These SPIO-containing GVs (SPIO-GVs) exhibited excellent contrast enhancement in the single cell of medaka fish (Oryzias latipes) embryos immediately after their microinjection, and this enhancement disappeared when the GV membranes were destroyed. Our results demonstrate that SPIO-GVs are useful MRI probes for single cell-tracking that have minimum cytotoxicity and will greatly improve clinical/preclinical in vivo cellular imaging techniques.

In an aqueous dispersion of a novel polymerizable amphiphile containing hydrolyzable linkages, spherical or tubular giant vesicles were formed after the polymerization reaction, even though the hyd...

The distribution of surface tension on the front and rear sides of a camphor boat continuously moving on an aqueous-phase camphor solution was observed by the time-resolved quasi-elastic laser scat...

This review covers the drastic morphological changes, including division or birthing dynamics, and even spontaneous movements performed by molecular self-assemblies constructed by reactive amphiphiles with the imine group that connects hydrophilic and hydrophobic moieties. It turns out that the formation (dehydrocondensation) of such amphiphiles or their cleavage (hydrolysis) into individual moieties occurs depending on the reaction fields, such as in membranes, or at interfaces between water and selfassemblies constructed by the amphiphiles. Moreover these chemical conversions induce outstanding dynamics aforementioned. Hence these findings give a hint to understand hierarchical dynamics occurring in a living system.

Directional migration of neuronal cells over long distances is critical for the developing and regenerating nervous system. A scaffold, which includes radial glia, provides a route between the germinal zone and the destination, with the direction of migration being attributed mainly to chemotaxis. However, the decrease in chemokine concentration with distance complicates cell guidance control over long distances. Our working hypothesis is that neuronal cells migrate directionally on an anisotropic and periodic scaffold. We tested this in a model involving neuronal PC12 cells cultured in a ratchet wheel-shaped microchamber. The microchamber was constructed by printing a patterned, thin film of polydimethylsiloxane (PDMS), to which the cells adhere weakly, onto a collagen-coated dish, to which the cells adhere strongly, using a microcontact printing technique. The cells can attach, extend neurites, and migrate on the anisotropic and periodic collagen-coated area between the ratchet wheel-shaped outer frame and round inner frame of the PDMS. We found that the microchamber geometry affected the direction of migration, even though the mean length of the longest neurite was independent of microchamber geometry. The time-course trace of cell body migration and neurite tips showed that the neurite tips remained around the tips of the ratchet teeth. These results suggested that neuronal cells migrate directionally on a scaffold, even in the absence of chemokine, and reveal a new conceptual framework for neuronal migration.

Real-time observation of a morphologies of a multi-component tubular giant vesicle (tGV), which is a self-assembly composed of plural amphiphiles with different packing parameters, was carried out under application of a magnetic field. A tGV, one of the terminals of which was fixed to a bottom of a cell, exhibited the bending deformation under a magnetic field along the perpendicular direction of the long axis. Moreover, the hysteretic behavior in this deformation was observed associated with the increase and decrease of the magnetic fields repeatedly, regardless of the presence or absence of a paramagnetic species. To understand the hysteretic behavior, the molecular cooperative effect, which stabilizes the bending deformation by replacing of the plural kinds of amphiphiles with different packing parameters within a membrane, must be taken into consideration.

Population analysis of a system of self-reproducing giant multilamellar vesicles (GMVs) was carried out by means of flow cytometry. The multidimensional distribution of forward light scattering (FS), side light scattering (SS), and fluorescence (FL) intensities originating from each GMV provided information about changes in a population composed of 104 vesicles. FS-FL dot plots indicated that, after the addition of the membrane precursor, the size distribution of the newly generated vesicles was nearly the same as that of the original, but the catalyst content was reduced. This result can be interpreted as evidence for the occurrence of the self-reproduction of GMVs. Moreover, the new GMVs recovered the amount of catalyst to the initial value, keeping their size distribution constant, when a solution of the catalyst was added to the new GMVs. These results are the first experimental evidence for a novel phenomenon on GMV size distribution during their self-reproducing cycle.

Collagen-containing tubular giant vesicles (Col–tGVs) under a high static magnetic field were found to constitute characteristic curved structures (e.g. circular, 8-figure, and hairpin-loop), which were sustained by polymerization of collagen units inside the tGV. We ascribed the formation of these structures to the elasticity of the tGV and to the competing diamagnetic anisotropies between collagen and the tGV. These curved structures can be well expressed by the equation of elastica.

A morphological transformation from hybrid micelles to giant vesicles was observed in aqueous dispersion associated with formation of a double-chained amphiphile as a result of the migration of dodecylamine from the amphiphilic imine to the amphiphilic aldehyde within the hydrophobic environment of amphiphilic aggregates.

We aimed to obtain giant vesicles (GVs) confining microspheres with a volume fraction of 20–30 vol %, analogous to biological macromolecules contained in cytosols, through simple and quick steps. T...

Giant vesicles (GVs) comprising zwitterionic and anionic phospholipids (DOPC and POPG, respectively) at a molar ratio of 90:10 formed a sparse network of aggregates that dissociated into isolated G...

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-α,ω-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.