Phase Diagrams of Anthracene Derivatives in Pyridinium Ionic Liquids.

Crystal engineering for single crystallization of π-conjugated molecules has attracted much attention because of their electronic, photonic, and mechanical properties. However, reproducibility is a problem in conventional printing techniques because control of solvent evaporation is difficult. We investigated the phase diagrams of two anthracene derivatives in synthesized ionic liquids for non-volatile crystal engineering to determine the critical points for nucleation and crystal growth. Anthracene and 9,10-dibromoanthracene were used as representative π-conjugated molecules that form crystal structures with different packing types. Ionic liquids with an alkylpyridinium cation and bis(fluorosulfonyl)amide were good solvents for the anthracene derivatives from ca. 0 °C to 200 °C. The solubilities (critical points for crystal growth) of the anthracene derivatives in the ionic liquids reached the 100 mM level, which is similar to those in organic solvents. Ionic liquids with phenyl and octyl groups tended to show high-temperature dependence (a high dissolution entropy) with 9,10-dibromoanthracene. The precipitation temperature (critical point for crystal nucleation) at each 9,10-dibromoanthracene concentration was lower than the dissolution temperature. The differences between the dissolution and precipitation temperatures (supersaturated region) in the ionic liquids were greater than those in an organic solvent.

Chemical Recycling and Physical Tuning of Necklace-Shaped Polydimethylsiloxanes Bearing Anthracene Dimer Units.

The problem of plastic waste in the environment calls for the development of new polymeric materials designed specifically for easy recycling at the end of their life cycle. Herein, a green polymer system comprising a series of necklace-shaped polydimethylsiloxanes bearing anthracene dimer units is developed. The polymers have low environmental impact and are easily recycled. Further, their flexibility and glass transition temperatures are easy to control. These necklace-shaped inorganic polymers are synthesized by photopolymerizing (dimerizing) anthracene-terminated oligo-dimethylsiloxane monomers. A key achievement of the present work is the successful chemical recovery of the monomers from the polymers through thermal depolymerization, enabling monomer-polymer recycling. By applying equilibrium polymerization with base catalysts, monomers with a controlled distributed chain length are synthesized from monomers with a constant chain length. The necklace-shaped polymers synthesized from these randomized monomers have amorphous structures and readily form transparent films. It is possible to modulate the thermal and mechanical properties of the polymers by controlling the average chain length of the polydimethylsiloxane between the anthracene dimers. This investigation presents a method for the synthesis and cyclic utilization of polymer materials with a wide range of applications, including plastics and elastomers.

Electrochemistry in bicontinuous microemulsions derived from two immiscible electrolyte solutions for a membrane-free redox flow battery.

HYPOTHESES: Bicontinuous microemulsions (BMEs) have attracted attention as unique heterogeneous mixture for electrochemistry. An interface between two immiscible electrolyte solutions (ITIES) is an electrochemical system that straddles the interface between a saline and an organic solvent with a lipophilic electrolyte. Although most BMEs have been reported with nonpolar oils, such as toluene and fatty acids, it should be possible to construct a sponge-like three-dimensionally expanded ITIES comprising a BME phase. EXPERIMENTS: Dichloromethane (DCM)-water microemulsions stabilized by a surfactant were investigated in terms of the concentrations of co-surfactants and hydrophilic/lipophilic salts. A Winsor III microemulsion three-layer system, consisting of an upper saline phase, a middle BME phase, and a lower DCM phase, was prepared, and electrochemistry was conducted in each phase. FINDINGS: We found the conditions for ITIES-BME phases. Regardless of where the three electrodes were placed in the macroscopically heterogeneous three-layer system, electrochemistry was possible, as in a homogeneous electrolyte solution. This indicates that the anodic and cathodic reactions can be divided into two immiscible solution phases. A redox flow battery comprising a three-layer system with a BME as the middle phase was demonstrated, paving the way for applications such as electrolysis synthesis and secondary batteries.

Single Crystallization of Cs4PbBr6 Perovskite from Supersaturated Organic Solutions Optimized Through Solubility Studies.

We demonstrate the fabrication of millimeter-sized single crystals of 0D-Cs4PbBr6 grown in a supersaturated solution consisting of organic solvents without HBr (aq). One of the precursors, CsBr, was dissolved in ethylene glycol (EG) mixed with dimethyl sulfoxide, which is a good solvent for the other precursor, PbBr2. At a solvent ratio of 20 vol % EG, the solubility of cesium bromide decreased and the title compound, Cs4PbBr6, was selectively formed, whereas, with an EG ratio of 80 vol %, 3D-CsPbBr3 was formed. A phase diagram (solubility curve) of Cs4PbBr6 in the mixed solvent containing 20 vol % EG was obtained by visually observing dissolution and crystal precipitation while changing the temperature. Because the solubility was proportional to the temperature, the solubility curve demonstrated an upper critical solution phenomenon. The solubility near the boiling point of the solution (150 °C) was approximately 0.14 M. A single crystal of Cs4PbBr6 was formed by growing a seed crystal in a supersaturated solution on the low-temperature side of the solubility curve. X-ray analysis established the crystal structure; a fluorescence emission at 520 nm with a full width at half maximum of 20 nm confirms the composition of the single crystal to be Cs4PbBr6.

Infusion of Variable Chemical Structure to Tune Stacking among Metal-Organic Layers in 2D Nano MOFs.

Invited for the cover of this issue is the group of Biplab Manna at the University of Kumamoto. The image depicts various kinds of stacking between the metal-organic layers of MOFs. Read the full text of the article at 10.1002/chem.202201665.

Infusion of Variable Chemical Structure to Tune Stacking among Metal-Organic Layers in 2D Nano MOF.

Thickness of two-dimensional (2D) metal-organic frameworks (MOFs) govern their intriguing functionalities. Primarily this thickness is controlled by the stacking between the metal-organic layers (MOL). It is observed that until now such modulating factors for stacking efficiency of MOL are not well studied. Here, we report a fundamental hypothesis to comprehend regulation of stacking efficiency among MOLs as a function of chemical structure of organic ligands (dicarboxylic acids and pillar linkers). This basically involves a series of isostructural three-dimensional (3D) MOFs which contain linkers of variable chemical nature that could be depillared to generate 2D stacked MOFs of different thickness. Depending on the linkers, we encountered the formation of single MOL to stacked multiple MOLs as evidenced from atomic force microscopic and other experimental analysis. The present study gives a concrete correlation between the stacking within 2D MOFs (from monolayer to multilayers), and their 3D counter parts, which may provide a thickness tuning pathway for 2D MOFs.

Preparation of double-layered nanosheets containing pH-responsive polymer networks in the interlayers and their conversion into single-layered nanosheets through the cleavage of cross-linking points.

Double-layered nanosheets containing pH-cleavable polymer networks between two niobate layers were prepared by copolymerization of N-isopropylacrylamide and an acid-degradable crosslinker via surface-initiated atom transfer radical polymerization on the surface of hydrated interlayers (interlayer I) of K4Nb6O17·3H2O and subsequent exfoliation by the introduction of tetra-n-butylammonium (TBA) ions into anhydrous interlayers (interlayer II). Moreover, the double-layered nanosheets were converted into single-layered nanosheets by the cleavage of cross-linking points in polymer networks by lowering pH. Fourier transform infrared spectroscopy (FTIR) and thermogravimetry (TG) results showed that polymer networks were present, and nanosheets with a thickness of 10.8 ± 1.6 nm were observed by using an atomic force microscope (AFM) after exfoliation using TBA ions. The thickness of the nanosheets was decreased to 6.1 ± 0.9 nm by lowering the pH, and proton nuclear magnetic resonance (1H NMR) and UV-vis spectroscopy showed that the degradation of the cross-linkers proceeded, suggesting that the cleavage of the cross-linking points led to the conversion of double-layered nanosheets into single-layered nanosheets.

Lipophilic probe behavior in microemulsions evaluated by fluorescence correlation spectroscopy.

We evaluated the dispersion and diffusion of fluorescent-labeled lipophilic vitamin E (VE) in microemulsions (MEs) including water-in-oil (W/O) type ME, oil-in-water (O/W) type ME, and bicontinuous ME (BME), using fluorescence correlation spectroscopy (FCS). We prepared a fluorescent ATTO 488 or BODIPY group labeled VE (VE-ATTO or VE-BODIPY). VE-ATTO possesses lipophilic and hydrophilic parts, while VE-BODIPY consists solely of the lipophilic part. The VE-ATTO dissolved in heptane solution as an oil phase appeared hot pink in color due to the solvatochromism effect under room light and almost no fluorescent signal, which was unlike the VE-ATTO dissolved in ME solutions and all the VE-BODIPY solutions (typical fluorescent green color). The FCS measurement proved that VE-BODIPY diffuses faster than VE-ATTO. This is presumably because the "surfactant-like" VE-ATTO is localized and trapped at the micro-water/micro-oil interface of the MEs, while the VE-BODIPY exists in the ME phase and macro-oil phase with good dispersion. These results demonstrate that FCS is a powerful tool for the rapid evaluation of the lipophilic probe behavior in heterogeneous ME solutions.

Preparation of water-dispersible Janus nanosheets from K4Nb6O17·3H2O and their behaviour as a two-dimensional surfactant on air-water and water-toluene interfaces.

K4Nb6O17·3H2O-based Janus nanosheets with water dispersibility and surface activity were prepared via sequential regioselective surface modification. To provide individual Janus nanosheets with these two properties, phenylphosphonic acid and phosphoric acid were utilized for surface modification at interlayers I and II of K4Nb6O17·3H2O, respectively, and the resulting product was exfoliated into single-layered nanosheets by ultrasonication in water. The resulting aqueous dispersion of the Janus nanosheets showed lower surface tension than pure water, confirming that the Janus nanosheets had surface activity. An o/w emulsion was formed using the Janus nanosheet aqueous dispersion and toluene. In this emulsion, characteristic phenomena, coalescence and Ostwald ripening behaviour of toluene droplets were observed; the appearance of ellipsoidal droplets during coalescence and a rapid Ostwald ripening which differ from those observed for systems using conventional surfactants, were observed. These phenomena likely originated from the unique anisotropic structures of Janus nanosheets with their nm-scale thickness and µm-range lateral size.

Multimotion of Marangoni Propulsion Ships Controlled by Two-Wavelength Near-Infrared Light.

Multimode motion of Marangoni propulsion ships on a water surface as per a near-infrared, two-wavelength selective response is achieved for the first time. The ships are rhombus- or propeller-shaped polyacrylamide or siloxane resin-based gels in which Nd2O3 and Yb2O3 nanoparticles are incorporated separately for photothermal conversion at 808 and 980 nm, respectively. The rhombus geometry is for straight locomotion, and the propeller geometry is for rotation. On/off remote control of the forward and backward locomotion of a rhombus-shaped ship and of the clockwise and counterclockwise rotations of a propeller-shaped ship via irradiation with 808 or 980 nm near-infrared light is demonstrated. The nanoparticles are incorporated into the desired locations of the gels, enabling selective local heating of the gels without focusing the light. The temperature gradient of the ships by local heating, based on a photothermal conversion, generates a Marangoni propulsion force to move the ship in the desired direction.

Lipophilic Vitamin E Diffusion through Bicontinuous Microemulsions.

We studied the diffusion properties of lipophilic vitamin E (VE) through bicontinuous microemulsions (BME) using both electrochemical and fluorescence correlation spectroscopy (FCS) measurements. We investigated the effect of different composition ratios of micro-water and micro-oil phases in BMEs (W/OBME). When we employed the BME with a lower W/OBME value of 40/60 (oil-rich BME) as an electrolyte solution, we obtained a larger current response from VE at a fluorinated nanocarbon film electrode. Further voltammetric studies revealed that a higher VE diffusion coefficient was observed in the oil-rich BME. The FCS results also exhibited faster diffusion through the oil-rich BME, which played a significant role in accelerating the VE diffusion probably due to the widening of the micro-oil phase pathway in the BME. Moreover, the effect of increasing the VE diffusion was pronounced at the interface between the electrode surface and the BME solution. These results indicate that controlling the conditions of the BME as the measurement electrolyte is very effective for achieving superior electrochemical measurements in a BME.

Stand-Alone Semi-Solid-State Electrochemical Systems Based on Bicontinuous Microemulsion Gel Films.

Bicontinuous microemulsion (BME)-based hydrogel films were integrated with screen-printed electrodes (SPEs) comprising working, counter, and reference electrodes to form stand-alone, semi-solid-state electrochemical systems that do not require an outer electrolyte solution. The gel network of the BME hydrogel only exists in the microaqueous phase and retains the structure of the entire BME gel. Following gelation, a microaqueous phase with sufficient ionic strength ensured effective ionic conductivity, even in thin gel films. This enabled the electrochemical reaction to proceed using a thin gel film as an electrolyte solution. However, an intact micro-oil phase with no gel network enabled efficient extraction from an external oil solution and exhibited rapid electrochemistry that was comparable to that of a BME solution. Cyclic voltammograms of lipophilic redox species in oil using the gel-integrated SPE system demonstrated successfully in the oil itself and in the air with dropped oil onto the system.

Monomolecular covalent honeycomb nanosheets produced by surface-mediated polycondensation between 1,3,5-triamino benzene and benzene-1,3,5-tricarbox aldehyde on Au(111).

Fabrication of a two-dimensional covalent network of honeycomb nanosheets comprising small 1,3,5-triamino benzene and benzene-1,3,5-tricarboxaldehyde aromatic building blocks was conducted on Au(111) in a pH-controlled aqueous solution. In situ scanning tunneling microscopy revealed a large defect-free and homogeneous honeycomb π-conjugated nanosheet at the Au(111)/liquid interface. An electrochemical potential dependence indicated that the nanosheets were the result of thermodynamic self-assembly based not only on the reaction equilibrium but also on the adsorption (partition) equilibrium, which was controlled by the building block surface coverage as a function of electrode potential.

Study of Gases Permeation in Necklace-Shaped Dimethylsiloxane Polymers Bearing POSS Cages.

The transport of small gases (H2, CO2, N2, O2) through a series of novel membranes based on necklace-shaped inorganic polymers (DMS@POSS), in which a polyhedral oligomeric silsesquioxane (POSS) cage unit and soft chains of oligo-dimethyl siloxane (DMS) were alternately connected, was investigated. The influence of the DMS chain length and crosslinking density of the DMS@POSS on membrane properties were studied. The membranes revealed characteristic structure-property relation towards both glass transition and gases transport. Specifically, clear dependence of properties from the length of DMS units (or overall siloxane content) was revealed. Gas transport properties, when compared to state-of-art polydimethylsiloxane and commercial silicone rubber, demonstrated significantly higher selectivity of DMS@POSS for carbon dioxide (in CO2/N2), hydrogen (in H2/N2) and oxygen (in O2/N2) but lowered permeability, proportional to the amount of POSS in the material. With a precise control over mechanical and thermal properties compared to conventional silicone rubbers, described materials could be considered as materials of choice in niche gas separation or other applications.

Two-wavelength infrared responsive hydrogel actuators containing rare-earth photothermal conversion particles.

Two-wavelength infrared responsive soft actuators composed of rare-earth-oxide particles composited in a thermoresponsive hydrogel have been constructed. Because Nd2O3 and Yb2O3 particles possess independent narrow infrared adsorption at 808 and 980 nm, respectively, the vicinity of the particles in the gel can be individually heated by irradiation at each adsorption wavelength, inducing a local volume phase transition. The wavelength-selective volume phase transition can be controlled based on the combination of the particles incorporated in the gels and the wavelength of the irradiation laser at the optimized water temperature. Only the alternatively correct combinations successfully induced selective local clouding at the irradiation spots in the gel sheets. The original transparency of the gel was immediately recovered by turning off the light. Furthermore, rod-shaped block gels with Nd2O3 and Yb2O3 particles separately arranged on the left and right sides at the bottom of the rods were prepared to demonstrate wavelength-selective bending motion. The correct light combination caused reversible bending motion of only the side of the rod gel with the corresponding adsorbed particles.

Inorganic Janus nanosheets bearing two types of covalently bound organophosphonate groups via regioselective surface modification of K4Nb6O17·3H2O.

Janus nanosheets were prepared from K4Nb6O17·3H2O by modifying surfaces of their two distinct interlayers in a regioselective and sequential manner and subsequent exfoliation. The surface properties of nanosheets were investigated by phase atomic force microscopy imaging and two types of surfaces were discriminated, indicating that Janus nanosheets were successfully prepared.

Quasi-Phase Diagrams at Air/Oil Interfaces and Bulk Oil Phases for Crystallization of Small-Molecular Semiconductors by Adjusting Gibbs Adsorption.

The temperature and concentration dependencies of the crystallization of two small-molecular semiconductors were clarified by constructing quasi-phase diagrams at air/oil interfaces and in bulk oil phases. A quinoidal quaterthiophene derivative with four alkyl chains (QQT(CN)4) in 1,1,2,2-tetrachroloethane (TCE) and a thienoacene derivative with two alkyl chains (C8-BTBT) in o-dichlorobenzene were used. The apparent crystal nucleation temperature (Tn) and dissolution temperature (Td) of the molecules were determined based on optical microscopy examination in closed glass capillaries and open dishes during slow cooling and heating processes, respectively. Tn and Td were considered estimates of the critical temperatures for nuclear formation and crystal growth, respectively. The Tn values of QQT(CN)4 and C8-BTBT at the air/oil interfaces were higher than those in the bulk oil phases, whereas the Td values at the air/oil interfaces were almost the same as those in the bulk oil phases. These Gibbs adsorption phenomena were attributed to the solvophobic effect of the alkyl chain moieties. The temperature range between Tn and Td corresponds to suitable supercooling conditions for ideal crystal growth based on the suppression of nucleation. The Tn values at the water/oil and oil/glass interfaces did not shift compared with those of the bulk phases, indicating that adsorption did not occur at the hydrophilic interfaces. Promotion and inhibition of nuclear formation for crystal growth of the semiconductors were achieved at the air/oil and hydrophilic interfaces, respectively.

Cohelical Crossover Network by Supramolecular Polymerization of a 4,6-Acetalized ß-1,3-Glucan Macromer.

Natural polysaccharides represent a renewable resource whose effective utilization is of increasing importance. Chemical modification is a powerful tool to transform them into processable materials but usually sacrifices the original structures and properties of value. Here we introduce a chemical modification of Curdlan, a ß-1,3-glucan, via 4,6-acetalization. This modification has successfully combined a helix-forming ability of Curdlan with new solubility in organic media. Furthermore, it has operationalized efficient cohelical crossovers (CCs) among the helices to demonstrate the formation of an extensive supramolecular network that goes well beyond the nanoscopic regime, allowing for preparation of flexible self-supporting films with macroscopic dimensions. This protocol, which is now viewed as supramolecular polymerization of a helical polysaccharide macromer, can add a new dimension to "polysaccharide nanotechnology", opening a door for the creation of unconventional polymer materials based on the cohelical crossover network (CCN).

Direct Analysis of Lipophilic Antioxidants of Olive Oils Using Bicontinuous Microemulsions.

Quantitative analyses of olive oil for lipophilic antioxidants, such as α-tocopherol and phenolics, by simple electrochemical measurements were conducted in a bicontinuous microemulsion (BME), which was bicontinuously composed of saline and toluene microphases with a surfactant system. Lipophilic antioxidants in oils were directly monitored in BME solutions using a lipophilic, fluorinated nanocarbon-film electrode (F-ECR). The combination of a well-balanced BME and extremely biased electrodes, such as strongly hydrophilic indium/tin oxide and strongly lipophilic (hydrophobic) F-ECR, allowed individual monitoring of hydrophilic and lipophilic antioxidants in the same BME solution without any required extraction. Furthermore, values for the charge Q, integrated from observed currents, showed good linear relationships with the results of conventional assays for antioxidant activity, namely, total phenolics and oxygen radical absorbance capacity assays, even with practical food samples. This proposed methodology provided a very simple, rapid, easily serviceable, and highly reproducible analysis that possesses great potential for applications to a wide range of chemical mixtures, in terms of analyte and media, beyond food oils.

Simultaneous electrochemical analysis of hydrophilic and lipophilic antioxidants in bicontinuous microemulsion.

Qualitative and quantitative analyses of hydrophilic and lipophilic antioxidants, such as polyphenols, by simple electrochemical measurements were conducted in a bicontinuous microemulsion (BME), in which water and oil phases coexisted bicontinuously on a microscopic scale. Hydrophilic and lipophilic antioxidants were individually monitored in the same BME solution using a hydrophilic indium tin oxide (ITO) electrode and a lipophilic fluorinated nanocarbon film electrode (F-ECR), respectively. The combination of well-balanced BME and extremely biased electrodes, such as ITO and F-ECR, in terms of hydrophilic-lipophilic balance allowed us to achieve individual monitoring of hydrophilic and lipophilic antioxidants in the same BME solution without extraction. Furthermore, the antioxidant activities of functional liquid foods, such as coffee and olive oil, were also evaluated by means of electrochemical measurements in BME solutions containing analytes in concentrations of several percent. The technique we propose provides a very simple, rapid, easily serviceable, and highly reproducible analysis and can be extended to a wide range of analytes and media.