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Drying of an aqueous suspension containing fine granules leads to the formation of a circular pattern, i.e., the coffee-ring effect. Here, we report the effect of mechanical rotation with drying of an aqueous suspension containing a large amount of granular particles as in the Turkish coffee. It was found that wavy fragmented stripes, or a “waggly pattern”, appear in the early stage of the drying process and a “polka-dot pattern” with many small circles is generated in the late stage. We discuss the mechanism of these patterns in terms of the kinetic effect on micro phase-segregation. We suggest that the waggly pattern is induced through a mechanism similar to spinodal decomposition, whereas polka-dot formation is accompanied by the enhanced segregation of a water-rich phase under mechanical rotation.

The UCST of phase separation for imidazolium-based ionic liquids [Cnmim][TFSI] and formamide (FA) binary solutions increases with elongation of the alkyl chain lengthn. This is opposite to previous 1,4-dioxane solutions.

Liquid–liquid phase separation of binary systems for imidazolium-based ionic liquids (ILs), 1-alkyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide ([Cnmim][TFSI], where n represents the alkyl chain length of the cation), with 1,4-dioxane (1,4-DIO) was observed as a function of temperature and 1,4-DIO mole fraction, x1,4-DIO. The phase diagrams obtained for [Cnmim][TFSI]–1,4-DIO systems showed that the miscible region becomes wider with an increase in the alkyl chain length, n. For n = 6 and 8, an upper critical solution temperature (UCST) was found. To clarify the mechanism of the UCST-type phase separation, small-angle neutron scattering (SANS) experiments were conducted on the [C8mim][TFSI]–1,4-DIO-d8 system at several x1,4-DIO. The critical exponents of γ and ν determined from the SANS experiments showed that phase separation of the system at the UCST mole fraction occurs via the 3D-Ising mechanism, while that on both sides of UCST occurs via the mean field mechanism. Thus, the crossover of mechanism was observed for this system. The microscopic interactions among the cation, anion, and 1,4-DIO were elucidated using 1H and 13C NMR and IR spectroscopic techniques, together with the theoretical method of molecular dynamics (MD) simulations. The results on the microscopic interactions suggest that 1,4-DIO molecules cannot strongly interact with H atoms on the imidazolium ring, while they interact with the octyl chain of the cation through dispersion force. With a decrease in temperature, 1,4-DIO molecules gradually aggregate to form 1,4-DIO clusters in the binary solutions. The strengthening of the C–H⋯O interaction between 1,4-DIO molecules by cooling is the key to the phase separation. Of course, the electrostatic interaction between the cations and anions results in the formation of IL clusters. When IL clusters are excluded from 1,4-DIO clusters, liquid–liquid phase separation occurs. Accordingly, the balance between the electrostatic force between the cations and anions and the C–H⋯O interaction between the 1,4-DIO determines the 3D-Ising or the mean field mechanism of phase separation.

Liquid-liquid phase separation of binary systems for imidazolium-based ionic liquids (ILs), 1-alkyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide ([C

The effect of monovalent cations on a cell-free transcription-translation (TX-TL) system is examined using a luciferase assay. It is found that the potency for all ions analyzed here is in the order Rb

In the room-temperature ionic liquid (IL) of 1-methyl-3-octylimidazolium bis(trifluoromethylsulfonyl)amide ([C8mim][TFSA]), the complex formation of Ni2+ with molecular liquids (MLs), dimethyl sulfoxide (DMSO), methanol (MeOH), and acetonitrile (AN), has been examined using ultraviolet (UV)-visible spectroscopy. The overall stability constants log βn, enthalpies , and entropies of the equilibria have been determined to elucidate the mechanism of complex formation. From a comparison of such thermodynamic parameters of the present [C8mim][TFSA] systems with those of the previous systems of 1-ethyl-3-methylimidazolium-based IL, [C2mim][TFSA], the effects of the octyl chain of the imidazolium cation, [C8mim]+, on the complex formation of Ni2+ with MLs have been demonstrated. In [C8mim][TFSA]–ML systems, more stable complexes are formed with MLs in the sequence of AN > DMSO ≫ MeOH. This sequence differs from that of DMSO ≫ AN > MeOH in [C2mim][TFSA]. For the AN systems, the stabilities of [Ni(an)n] in [C8mim][TFSA] are higher as compared to those in [C2mim][TFSA]. In contrast, for the DMSO systems, [Ni(dmso)n] is less stable in the IL with the longer alkyl chain than that in the IL with the shorter chain. The dependence of the alkyl chain length on the stabilities of [Ni(meoh)n] is the least significant among the three MLs. These varieties of the stabilities of Ni2+ complexes with the MLs have been interpreted from the thermodynamic parameters, together with the static interactions in the [C8mim][TFSA]–ML and [C2mim][TFSA]–ML solvents observed by means of 1H and 13C NMR, small-angle neutron scattering (SANS), and infrared (IR) with an ATR diamond prism.

Bacteriophages with long DNA genomes are of interest due to their diverse mutations dependent on environmental factors. By lowering the ionic strength of a hydrophobic (PPh4Cl) antagonistic salt (at 1 mM), single long T4 DNA strand fluctuations were clearly observed, while condensed states of T4 DNA globules were formed above 5–10 mM salt. These long DNA strands were treated with fluorescently labeled probes, for which photo bleaching is often unavoidable over a short time of measurement. In addition, long (few tens of $$\upmu m$$ μ m ) length scales are required to have larger fields of view for better sampling, with shorter temporal resolutions. Thus, an optimization between length and time is crucial to obtain useful information. To facilitate the challenge of detecting large biomacromolecules, we here introduce an effective method of live image data analysis for direct visualization and quantification of local thermal fluctuations. The motions of various conformations for the motile long DNA strands were examined for the single- and multi-T4 DNA strands. We find that the unique correlation functions exhibit a relatively high-frequency oscillatory behavior superimposed on the overall slower decay of the correlation function with a splitting of amplitudes deriving from local activities of the long DNA strands. This work shows not only the usefulness of an image–time correlation for analyzing large biomacromolecules, but also provides insight into the effects of a hydrophobic antagonistic salt on active T4 bacteriophage long DNA strands, including thermal translocations in their electrostatic interactions.

The aggregation of a dipeptide, l-leucine-glycine (Leu-Gly), at 100 mmol dm-3 has been observed in 1,1,1,3,3,3-hexafluoroisopropanol (HFIP)-water and 2-propanol (2-PrOH)-water solvents at various alcohol mole fractions, xA, using the dynamic light scattering technique and molecular dynamics (MD) simulations. Leu-Gly was dissolved into the HFIP solvents at the concentration over the entire xA range, while the dipeptide was not dissolved in the 2-PrOH solvents above xA = 0.6. Interestingly, the MD snapshots showed different shapes of Leu-Gly aggregates in the HFIP and 2-PrOH solvents. A linear-shaped aggregate forms in the former; in contrast, a spherical-shaped aggregate is generated in the latter. The solvation structure of each moiety of Leu-Gly in the HFIP and 2-PrOH solvents was observed using experimental and theoretical techniques,1H and 13C NMR, IR, and 19F-1H HOESY measurements and MD simulations. These results gave us the reasons for the different shapes of Leu-Gly aggregates in both solvents. In the HFIP solvents, most of the moieties of the dipeptide are easily solvated by HFIP. This induces the elongated structure of Leu-Gly, leading to the electrostatic interaction between the N- (NH3+ group) and C- (COO- group) terminals of dipeptide molecules. On the other hand, in the 2-PrOH solvents, water molecules that initially solvate the moieties of Leu-Gly, such as the N- and C-terminals and the peptide linkage, are not easily eliminated even as the xA is close to 0.6. The water molecules can bridge such moieties of Leu-Gly to form spherical-shaped aggregates. The diffusion coefficients of Leu-Gly in both alcohol-water binary solvents were experimentally determined by NMR DOSY to estimate the geometries of the aggregates in the solvents. The sizes of Leu-Gly aggregates obtained by DOSY for both solvent systems were consistent with those estimated from the MD snapshots.

It is well known that polyamines induce a folding transition from an elongated coil to a compact globule state for giant DNA larger than several tens of kbp (kilo base pairs). Here, we studied the interaction between compact DNA molecules in the presence of linear and branched-chain isomers of polyamines. We compared the stability of the assembly among plural number of compact DNA molecules generated by laser trapping. As a result, the assembly of compact DNAs with a linear-chain polyamine is stable even after the laser is switched off. On the other hand, the assembly of DNAs with a branched-chain polyamine disperses into individual compact DNAs when the laser is switched off. Thus, compact DNAs with linear- and branched-chain polyamines attract and repel each other, respectively. This difference in the effects of linear and branched polyamines is discussed in terms of the steric interaction between negatively charged double-strand DNA and cationic polyamines.

The hydrogen bonds of the imidazolium-ring H atoms of ionic liquids (ILs), 1-alkyl-3-methylimidazolium bis(trifluoromethylsulfonyl)amides ([Cnmim][TFSA], n = 2 to 12 where n represents the alkyl chain length), with the O atom of dimethyl sulfoxide (DMSO) have been elucidated using 1H, 13C, and 15N NMR spectroscopy and soft X-ray absorption and emission spectroscopy (XAS and XES). Density functional theory (DFT) calculations have been performed on an isolated DMSO molecule and two cluster models of [Cnmim]+-DMSO by hydrogen bonding to interpret the XES spectra for the [Cnmim][TFSA]-DMSO solutions. The 1H and 13C NMR chemical shifts of the imidazolium ring showed that deshielding of the ring H and C atoms is moderate as the DMSO mole fraction xDMSO increases to ∼0.8; however, it becomes more significant with further increase of xDMSO. This finding suggests that the hydrogen bonds of the three ring H atoms with the DMSO O atoms are saturated in solutions with xDMSO increased to ∼0.8. The 1H and 13C chemical shifts of the alkyl chains revealed that the electron densities of the chain H and C atoms gradually decrease with increasing xDMSO, except for the N1-bound carbon atom C7 of the chain. The 15N NMR chemical shifts showed that the imidazolium-ring N1 atom which is bound to the alkyl chain is shielded with increasing xDMSO in the range from 0 to 0.8 and is then deshielded with further increase of xDMSO. In contrast, the imidazolium ring N3 atom is simply deshielded with increasing xDMSO. Thus, the electron densities of the alkyl chain may be condensed at the C7 and N1 atoms of [Cnmim]+ by the hydrogen bonding of the ring H atoms with DMSO. The hydrogen bonding of DMSO with the ring results in low-energy shifts of the XES peaks of the O K-edge of DMSO. Small-angle neutron scattering experiments showed that [Cnmim][TFSA] and DMSO are homogeneously mixed with each other on the mesoscopic scale. This results from the strong hydrogen bonds of DMSO with the imidazolium-ring H atoms.

We report that both rhythmic pendular motion and rotary motion are generated under stationary irradiation by a green laser for a centimeter-sized metallic sheet floating on an aqueous solution. For a hammer-shaped aluminum sheet, regular pendular motion is caused by CW laser irradiation when the “handle” of the pendulum is in contact with the wall of the glass containing vessel. This rhythmic pendular motion occurs as on/off switching from a stationary state with an increase in laser power. We discuss the mechanism of such stable pendular motion in terms of limit-cycle oscillation with the aid of phenomenological coupled differential equations, by incorporating the effects of a decrease in interfacial tension with an increase in temperature under laser absorption and of the dissipation of heat into the environment. Stable rotary motion of the metallic sheet was also generated, driven by stationary laser irradiation. The chirality of the rotary motion, either clockwise or anticlockwise, for the metallic ob...

The solvation states of the sodium ion (Na+) and the tetraphenylborate ion (BPh4−) in 3-methylpyridine (3MP) and its mixture with deuterium oxide (D2O) were investigated by Raman spectroscopy and DFT calculations. Raman spectra observed for the 3MP solutions systematically varied with increase in the amount of NaBPh4; the Raman band at 633 cm −1 weakened and that at 639 cm −1 strengthened with increase in the salt concentration. According to DFT calculations, the former was assigned to the 3MP molecule in the bulk and the latter to that bound to the Na+ ion. The number of 3MP molecules bound to Na+, n, was estimated to be 6.1, that is, a [Na(3MP)6] + complex was formed in the 3MP/NaBPh4 solution. On the other hand, n was estimated to be 1.6 in the D2O/3MP/NaBPh4 mixtures with χ3MP = 0.50, where χ3MP denotes the mole fraction of 3MP in the D2O/3MP mixtures. Furthermore, both integrated intensities at 633 cm −1 (free 3MP) and 640 cm −1 (hydrated 3MP by D2O) were almost independent of the salt concentration in the case of D2O/3MP mixtures with χ3MP = 0.09. Additionally, the position of the other Raman bands at 609, 616, 626, and 672 cm −1, arising from BPh4−, were almost independent of χ3MP between 1 and 0.09. These results suggest that Na+ is preferentially solvated with D2O, whereas BPh4− is preferentially solvated with 3MP in such mixtures.

Methylcellulose (MC) is one of the widely used bio-based polymers derived from cellulose. MC possesses an amphiphilic property, since it contains both the hydrophilic hydroxyl group and the hydrophobic methoxy group in its molecular structure. Due to the amphiphilicity, aqueous MC solution shows temperature-sensitive property i.e. the lower critical solution temperature (LCST) type of phase behavior. On the other hand, a special organic salt, sodium tetraphenylborate (NaBPh 4 ) also possesses an amphiphilic property, since it consists of hydrophilic cation Na + and hydrophobic anion BPh 4 − . Motivated by an interest in the combined effect of the dual amphiphilicity, here we studied the addition effects of NaBPh 4 on the cloud point of aqueous MC. When the additive amount of NaBPh 4 to aqueous MC was small, the cloud point was depressed with the amount of NaBPh 4 , namely the salting-out effect. However, when the additive amount of NaBPh 4 exceeded a certain value, the cloud point was elevated drastically with the amount of NaBPh 4 , namely the salting-in effect. We proposed a hypothesis that the switching from the salting-out to the salting-in is caused by concentration-specific binding of NaBPh 4 to MC; NaBPh 4 mostly dissociates into Na + and BPh 4 − acting as the salting-out salt when the concentration of NaBPh 4 is small, whereas the hydrophobic anions BPh 4 − are bound to the hydrophobic region of MC acting like a surfactant when the concentration of NaBPh 4 exceeds a critical value. The presence of such a concentration-specific binding of anions was confirmed by the electric conductivity measurements.

Synchronized motion between two self-running oil droplets floating on an aqueous phase is reported. We describe the results of our observation on the interference between a pair of centimeter-sized nitrobenzene droplets undergoing back-and-forth motion on a waterway. The two droplets exhibit a swinging type of synchronization when a thin glass capillary is placed at the midpoint of the waterway with a narrow rectangle shape. Furthermore, 2:1 synchronized oscillation of the periodicities of this back-and-forth motion is generated when the capillary is shifted away from the center of the waterway. We discuss the mechanism of the emergence of synchronized swinging motion for the pair of droplets based on a simple mathematical model with nonlinear coupled differential equations.

To better understand the regulation and function of cellular interactions, three-dimensional (3D) assemblies of single cells and subsequent functional analysis are gaining popularity in many research fields. While we have developed strategies to build stable cellular structures using optical tweezers in a minimally invasive state, methods for manipulating a wide range of cell types have yet to be established. To mimic organ-like structures, the construction of 3D cellular assemblies with variety of cell types is essential. Our recent studies have shown that the presence of nonspecific soluble polymers in aqueous solution is the key to creating stable 3D cellular assemblies efficiently. The present study further expands on the construction of 3D single cell assemblies using two different cell types. We have successfully generated 3D cellular assemblies, using GFP-labeled adipose tissue-derived stem cells and endothelial cells by using optical tweezers. Our findings will support the development of future applications to further characterize cellular interactions in tissue regeneration.

In the room-temperature ionic liquid (IL) of 1-methyl-3-octylimidazolium bis(trifluoromethylsulfonyl)amide ([C8mim][TFSA]), the complex formation of Ni2+ with molecular liquids (MLs), dimethyl sulfoxide (DMSO), methanol (MeOH), and acetonitrile (AN), has been examined using ultraviolet (UV)-visible spectroscopy. The overall stability constants log βn, enthalpies , and entropies of the equilibria have been determined to elucidate the mechanism of complex formation. From a comparison of such thermodynamic parameters of the present [C8mim][TFSA] systems with those of the previous systems of 1-ethyl-3-methylimidazolium-based IL, [C2mim][TFSA], the effects of the octyl chain of the imidazolium cation, [C8mim]+, on the complex formation of Ni2+ with MLs have been demonstrated. In [C8mim][TFSA]-ML systems, more stable complexes are formed with MLs in the sequence of ANDMSO ≫ MeOH. This sequence differs from that of DMSO ≫ ANMeOH in [C2mim][TFSA]. For the AN systems, the stabilities of [Ni(an)n] in [C8mim][TFSA] are higher as compared to those in [C2mim][TFSA]. In contrast, for the DMSO systems, [Ni(dmso)n] is less stable in the IL with the longer alkyl chain than that in the IL with the shorter chain. The dependence of the alkyl chain length on the stabilities of [Ni(meoh)n] is the least significant among the three MLs. These varieties of the stabilities of Ni2+ complexes with the MLs have been interpreted from the thermodynamic parameters, together with the static interactions in the [C8mim][TFSA]-ML and [C2mim][TFSA]-ML solvents observed by means of 1H and 13C NMR, small-angle neutron scattering (SANS), and infrared (IR) with an ATR diamond prism.

Recently, we revealed N-methylimidazole C1Im equimolar mixtures with superacids and strong acids such as trifluoromethanesulfonic acid HTfO (Tf: CF3SO2–), bis-(trifluoromethanesulfonyl)amide acid HTf2N or trifluoroacetic acid CF3COOH are essentially protic ionic liquids by means of potentiometry of direct pH measurement in such liquids. Here, we demonstrated Raman spectroscopic speciation analysis of [C1hIm+][TfO−] and [C1hIm+][Tf2N−] (C1hIm+: N-methylimidazolium) to elucidate both liquids are spectroscopically protic ionic liquids; much excess ionic species exist in these liquids and the amount of electrically neutral molecular species are practically negligible. In addition, to further insight into the hydrogen bond in the imidazolium-based protic ionic liquids, liquid structure of [C1hIm+][TfO−] were studied by high-energy X-ray total scattering HEXTS experiments with the aid of molecular dynamics simulations. Comparing with the hydrogen bond in [C1hIm+][Tf2N−] previously reported, the hydrogen bond in...

We report a novel method for constructing a stable three-dimensional cellular assembly in the absence of a solid or gel scaffold. A targeted cell was transferred to another cell, and the two were kept in contact for a few minutes by optical manipulation in an aqueous medium containing a hydrophilic polymer. Interestingly, this cell–cell adhesion was maintained even after elimination of the polymer. We discuss the mechanism of the formation of stable multi-cellular adhesion in terms of spontaneous rearrangement of the components embedded in the pair of facing membranes.

Two (ONO pincer)ruthenium‐complex‐bound norvalines, Boc−[Ru(pydc)(terpy)]Nva−OMe (1; Boc=tert‐butyloxycarbonyl, terpy=terpyridyl, Nva=norvaline) and Boc−[Ru(pydc)(tBu‐terpy)]Nva−OMe (5), were successfully synthesized and their molecular structures and absolute configurations were unequivocally determined by single‐crystal X‐ray diffraction. The robustness of the pincer Ru complexes and norvaline scaffolds against acidic/basic, oxidizing, and high‐temperature conditions enabled us to perform selective transformations of the N‐Boc and C−OMe termini into various functional groups, such as alkyl amide, alkyl urea, and polyether groups, without the loss of the Ru center or enantiomeric purity. The resulting dialkylated Ru‐bound norvaline, n‐C11H23CO−l‐[Ru(pydc)(terpy)]Nva−NH‐n‐C11H23 (l‐4) was found to have excellent self‐assembly properties in organic solvents, thereby affording the corresponding supramolecular gels. Ru‐bound norvaline l‐1 exhibited a higher catalytic activity for the oxidation of alcohols by H2O2 than parent complex [Ru(pydc)(terpy)] (11 a).

We discovered that vesicles with hierarchical structure, multilamellar vesicles, are formed spontaneously in an aqueous solution of an organic solvent by the addition of an antagonistic salt, of which range of size are from 1 nm to 10 μ m. In the present study, we investigated the influence of ionic substance (PPh 4 Cl) for the stability of the vesicles. Experimental results have indicated that multilamellar structure of vesicle was destroyed due to the addition of PPh 4 Cl and alternative structure was formed. We expect that the experimental results provide fundamental understandings on the stability of multilamellar vesicles.

We propose a novel methodology for constructing a stable three-dimensional cellular assembly by laser tweezer under depletion interaction in a natural polymer solution, without the usage any artificial scaffold such as gel or solid substrate. Successful construction of 3D cellular assembly is attained by forming stable cell-cell contacts within a few minutes. Our newly established method is expected to be useful for next-generation 3D single-cell assembly systems in the field of regenerative medicine and tissue engineering. The present study shows a concrete further extension of our recent reports on the use of soluble polymers for the construction of 3D single-cell assemblies.

Sodium tetraphenylborate (NaBPh 4 ) induces the highly ordered structures, such as multi-lamellar vesicles, in the water/3-methylpridine mixture. In this sense, NaBPh 4 can behave as a surfactant in the organic solvent mixtures. It is then expected that NaBPh 4 also behaves as a surfactant in neat water. To examine this assumption, the effects of NaBPh 4 on the surface structure and the bulk structure of the water were measured. It was shown that the surface tension of water decreases by dissolving NaBPh 4 . Additionally, micelle-like structure was confirmed in the water/NaBPh 4 mixtures.

We report the successful generation of directional liquid-flow under stationary laser irradiation at a fixed position in a chamber. We adopt a homogeneous solution consisting of a mixture of water and triethylamine (TEA), with a composition near the critical point for phase segregation. When geometrical asymmetry is introduced around the laser focus in the chamber, continuous directional flow is generated, accompanied by the emergence of water-rich microdroplets at the laser focus. The emerging microdroplets tend to escape toward the surrounding bulk solution and then merge/annihilate into the homogeneous solution. The essential features of the directional flow are reproduced through a simple numerical simulation using fluid dynamic equations.

Antagonistic salts are composed of hydrophilic and hydrophobic ions. In a binary mixture, such as water and organic solvent, these ion pairs preferentially dissolve to those phases, respectively, and there is a coupling between the charge density and the composition. The heterogeneous distribution of ions forms a large electric double layer at the interface between these solvents. This reduces the interfacial tension between water and organic solvent, and stabilizes an ordered structure, such as a membrane. These phenomena have been extensively studied from both theoretical and experimental point of view. In addition, the numerical simulations can reproduce such ordered structures.

Regenerative medicine and tissue engineering offer several advantages for the treatment of intractable diseases, and several studies have demonstrated the importance of 3-dimensional (3D) cellular assemblies in these fields. Artificial scaffolds have often been used to construct 3D cellular assemblies. However, the scaffolds used to construct cellular assemblies are sometimes toxic and may change the properties of the cells. Thus, it would be beneficial to establish a non-toxic method for facilitating cell-cell contact. In this paper, we introduce a novel method for constructing stable cellular assemblies by using optical tweezers with dextran. One of the advantages of this method is that it establishes stable cell-to-cell contact within a few minutes. This new method allows the construction of 3D cellular assemblies in a natural hydrophilic polymer and is expected to be useful for constructing next-generation 3D single-cell assemblies in the fields of regenerative medicine and tissue engineering.

Shape-oscillations and synchronization are intriguing phenomena in many biological and physical systems. Here, we report the rhythmic mechanical oscillations and synchronization of aniline oil droplets on a water phase, which is induced by Marangoni convection during transfer of the solute. The repetitive increase and decrease in the surface concentration in the vicinity of the contact line leads to the oscillations of droplets through an imbalance in surface tensions. The nature of the oscillations depends on the diameter of the droplet, the depth of the bulk aqueous phase, and the concentration of the aqueous phase. A numerical simulation reproduces the essential behaviors of active oscillations of a droplet. Droplets sense each other through a surface tension gradient and advection, and hydrodynamic coupling in the bulk solution induces the synchronization of droplet oscillations.

Artificial scaffolds such as synthetic gels or chemically-modified glass surfaces that have often been used to achieve cell adhesion are xenobiotic and may harm cells. To enhance the value of cell studies in the fields of regenerative medicine and tissue engineering, it is becoming increasingly important to create a cell-friendly technique to promote cell–cell contact. In the present study, we developed a novel method for constructing stable cellular assemblies by using optical tweezers in a solution of a natural hydrophilic polymer, dextran. In this method, a target cell is transferred to another target cell to make cell–cell contact by optical tweezers in a culture medium containing dextran. When originally non-cohesive cells are held in contact with each other for a few minutes under laser trapping, stable cell–cell adhesion is accomplished. This method for creating cellular assemblies in the presence of a natural hydrophilic polymer may serve as a novel next-generation 3D single-cell assembly system with future applications in the growing field of regenerative medicine.

The effects of adding an antagonistic salt, sodium tetraphenylborate (\(\hbox {NaBPh}_4\)), to a binary mixture of deuterated water and 2,6-dimethylpyridine were investigated by visual inspection, optical microscopy, and small-angle neutron scattering. With increasing salt concentration, the two-phase region shrinks. When the concentration of \(\hbox {NaBPh}_4\) is \(85\hbox { mmol}{\cdot} \hbox {L}^{-1}\), a temperature-induced lamellar/disorder phase transition is observed at 338 K. These trends are similar to those observed for a mixture of water/3-methylpyridine/\(\hbox {NaBPh}_4\) (Sadakane et al., Phys. Rev. Lett. 103, 167803 (2009)).

Knowledge of hydrogen bonds is important in a wide range of scientific fields. However, information on the electronic state of hydrogen bonded molecules in liquids and solutions is still limited. We applied X-ray emission and absorption spectroscopy to observe the electronic state around oxygen of water and investigate the solvent dependence of occupied and unoccupied valence electronic states of water in acetonitrile, 3-methylpyridine, and ethylenediamine at room temperature under atmospheric pressure. Based on the direct comparison of the spectra, the pronounced variation of the unoccupied 2b2 state of water in acetonitrile and 3-methylpyridine was assigned to the difference of the dipole-dipole interaction and the donor hydrogen bond. For ethylenediamine solution, an enhancement of the peak structure in the post-edge region of X-ray absorption spectra and an evident shoulder structure on the higher energy side of the occupied 1b1 state in X-ray emission spectra were observed. Although ethylenediamine has two amino groups that can form the hydrogen bonds as a proton donor, the obtained results indicate that the amino groups of ethylenediamine also act as a proton acceptor in the hydrogen bond between water molecules. A systematic peak intensity variation of the pre-edge peak corresponding to the lowest unoccupied molecular orbital, 4a1, was also found through the comparison of three organic solvents. Since the peak intensity tends to decrease with increasing number of hydrogen bonds, the results can be interpreted by the covalency of hydrogen bonds.