Evolution-inspired design of multicolored photoswitches from a single cyanobacteriochrome scaffold.

Cyanobacteriochromes (CBCRs) are small, bistable linear tetrapyrrole (bilin)-binding light sensors which are typically found as modular components in multidomain cyanobacterial signaling proteins. The CBCR family has been categorized into many lineages that roughly correlate with their spectral diversity, but CBCRs possessing a conserved DXCF motif are found in multiple lineages. DXCF CBCRs typically possess two conserved Cys residues: a first Cys that remains ligated to the bilin chromophore and a second Cys found in the DXCF motif. The second Cys often forms a second thioether linkage, providing a mechanism to sense blue and violet light. DXCF CBCRs have been described with blue/green, blue/orange, blue/teal, and green/teal photocycles, and the molecular basis for some of this spectral diversity has been well established. We here characterize AM1_1499g1, an atypical DXCF CBCR that lacks the second cysteine residue and exhibits an orange/green photocycle. Based on prior studies of CBCR spectral tuning, we have successfully engineered seven AM1_1499g1 variants that exhibit robust yellow/teal, green/teal, blue/teal, orange/yellow, yellow/green, green/green, and blue/green photocycles. The remarkable spectral diversity generated by modification of a single CBCR provides a good template for multiplexing synthetic photobiology systems within the same cellular context, thereby bypassing the time-consuming empirical optimization process needed for multiple probes with different protein scaffolds.

An Inorganic-Organic Hybrid Framework Composed of Polyoxotungstate and Long-Chained Bolaamphiphile.

Surfactants are functional molecules utilized in various situations. The self-assembling property of surfactants enables several molecular arrangements that can be employed to build up nanometer-sized architectures. This is beneficial in the construction of functional inorganic-organic hybrids holding the merits of both inorganic and organic components. Among several surfactants, bolaamphiphile surfactants with two hydrophilic heads are effective, as they have multiple connecting or coordinating sites in one molecule. Here, a functional polyoxotungstate inorganic anion was successfully hybridized with a bolaamphiphile to form single crystals with anisotropic one-dimensional alignment of polyoxotungstate. Keggin-type metatungstate ([H2W12O40]6-, H2W12) was employed as an inorganic anion, and 1,12-dodecamethylenediammonium (C12N2) derived from 1,12-dodecanediamine was combined as an organic counterpart. A simple and general ion-exchange reaction provided a hybrid crystal consisting of H2W12 and C12N2 (C12N2-H2W12). Single crystal X-ray structure analyses revealed a characteristic honeycomb structure in the C12N2-H2W12 hybrid crystal, which is possibly effective for the emergence of conductivity due to the dissociative protons of C12N2.

Photoluminescent Layered Crystal Consisting of Anderson-Type Polyoxometalate and Surfactant toward a Potential Inorganic-Organic Hybrid Laser.

The hybridization of inorganic and organic components is a promising strategy to build functional materials. Among several functions, luminescence is an important function which should be considered for practical usage. Inorganic-organic hybrid luminescent materials have been investigated as phosphors, sensors, and lasers. Organic luminescent centers such as dye molecules have often been hybridized with inorganic matrices. Polyoxometalate anions (POMs) are effective inorganic luminescent centers due to their luminescent properties and structural designability. However, most luminescent POM components are limited to lanthanide-based POMs. In this report, a photoluminescent inorganic-organic hybrid crystal based on a non-lanthanide POM was successfully synthesized as a single crystal. Anderson-type hexamolybdochromate ([CrMo6O18(OH)6]3-, CrMo6) anion exhibiting emission derived from Cr3+ was utilized with n-dodecylammonium ([C12H25NH3]+, C12NH3) surfactant cation to obtain a photoluminescent hybrid crystal. The grown single crystal of C12NH3-CrMo6 comprised a distinct layered structure consisting of inorganic CrMo6 layers and interdigitated C12NH3 layers. In the CrMo6 layers, the CrMo6 anions were associated with water molecules by hydrogen bonding to form a densely packed two-dimensional network. Steady-state and time-resolved photoluminescence spectroscopy revealed that the C12NH3-CrMo6 hybrid crystal exhibited characteristic emission from the CrMo6 anion. Preliminary lasing properties were also observed for C12NH3-CrMo6, which shows the possibility of using the C12NH3-CrMo6 hybrid crystal as an inorganic-organic hybrid laser.

Controlling the Redox Catalytic Activity of a Cyclic Selenide Fused to 18-Crown-6 by the Conformational Transition Induced by Coordination to an Alkali Metal Ion.

trans-3,4-Dihydroxyselenolane (DHS), a water-soluble cyclic selenide, exhibits selenoenzyme-like unique redox activities through reversible oxidation to the corresponding selenoxide. Previously, we demonstrated that DHS can be applied as an antioxidant against lipid peroxidation and a radioprotector by means of adequate modifications of the two hydroxy (OH) groups. Herein, we synthesized new DHS derivatives with a crown-ether ring fused to the OH groups (DHS-crown-n (n = 4 to 7), 1-4) and investigated their behaviors of complex formation with various alkali metal salts. According to the X-ray structure analysis, it was found that the two oxygen atoms of DHS change the directions from diaxial to diequatorial by complexation. The similar conformational transition was also observed in solution NMR experiments. The 1H NMR titration in CD3OD further confirmed that DHS-crown-6 (3) forms stable 1:1 complexes with KI, RbCl and CsCl, while it forms a 2:1 complex with KBPh4. The results suggested that the 1:1 complex (3·MX) exchanges the metal ion with metal-free 3 through the formation of the 2:1 complex. The redox catalytic activity of 3 was evaluated using a selenoenzyme model reaction between H2O2 and dithiothreitol. The activity was significantly reduced in the presence of KCl due to the complex formation. Thus, the redox catalytic activity of DHS could be controlled by the conformational transition induced by coordination to an alkali metal ion.

Conductive Hybrid Crystal Composed from Polyoxomolybdate and Deprotonatable Ionic-Liquid Surfactant.

A polyoxomolybdate inorganic-organic hybrid crystal was synthesized with deprotonatable ionic-liquid surfactant. 1-dodecylimidazolium cation was employed for its synthesis. The hybrid crystal contained δ-type octamolybdate (Mo8) isomer, and possessed alternate stacking of Mo8 monolayers and interdigitated surfactant bilayers. The crystal structure was compared with polyoxomolybdate hybrid crystals comprising 1-dodecyl-3-methylimidazolium surfactant, which preferred ß-type Mo8 isomer. The less bulky hydrophilic moiety of the 1-dodecylimidazolium interacted with the δ-Mo8 anion by N-H···O hydrogen bonds, which presumably induced the formation of the δ-Mo8 anion. Anhydrous conductivity of the hybrid crystal was estimated to be 5.5 × 10(-6) S·cm(-1) at 443 K by alternating current (AC) impedance spectroscopy.

Decisive interactions between the heterocyclic moiety and the cluster observed in polyoxometalate-surfactant hybrid crystals.

Inorganic-organic hybrid crystals were successfully obtained as single crystals by using polyoxotungstate anion and cationic dodecylpyridazinium (C12pda) and dodecylpyridinium (C12py) surfactants. The decatungstate (W10) anion was used as the inorganic component, and the crystal structures were compared. In the crystal comprising C12pda (C12pda-W10), the heterocyclic moiety directly interacted with W10, which contributed to a build-up of the crystal structure. On the other hand, the crystal consisting of C12py (C12py-W10) had similar crystal packing and molecular arrangement to those in the W10 crystal hybridized with other pyridinium surfactants. These results indicate the significance of the heterocyclic moiety of the surfactant to construct hybrid crystals with polyoxometalate anions.

Blood-to-Testis Transport of Ribavirin Involves Carrier-Mediated Processes at the Blood-Testis Barrier.

Ribavirin, an antiretroviral agent targeting the hepatitis C virus, causes male reproductive toxicity. This study investigated the mechanism of ribavirin transport at the blood-testis barrier (BTB). In vivo mouse integration plot analysis after intravenous administration revealed that the net influx clearance of [3H]ribavirin in the testis was 3.6-fold greater than that of [14C]D-mannitol, a paracellular transport marker, implying transcellular transport of ribavirin across the BTB. Moreover, [3H]ribavirin uptake by TM4 cells, mouse-derived Sertoli cells, was time- and concentration-dependent, with a Km value of 2.49 mM. S-[(4-nitrophenyl)methyl]-6-thioinosine, an inhibitor of Na+-independent equilibrative nucleoside transporters (ENTs), strongly inhibited the [3H]ribavirin uptake by TM4 cells at 100 µM. Compared to the uptake of [3H]adenosine, a typical endogenous nucleoside, [3H]ribavirin uptake was relatively similar to ENT2 transport. [3H]Ribavirin uptake was also observed in mouse ENT2-expressing Xenopus laevis oocytes, and gene silencing via the transfection of ENT2 small interfering RNA significantly reduced the [3H]ribavirin transport into TM4 cells by 13%. Taken together, these results suggest that ENT2 partially contributes to ribavirin transport at the BTB.

Phylogenetic, population structure, and population demographic analyses reveal that Vicia sepium in Japan is native and not introduced.

Vicia sepium (bush vetch) is a perennial legume widely distributed throughout the Eurasian continent. However, its distribution in Japan is limited to Mt. Ibuki and small parts of central and southern Hokkaido. Therefore, each Japanese V. sepium lineage has been considered to have been introduced separately from Europe. Here, we examined whether the species was introduced or not on the basis of cpDNA sequences and genome-wide SNPs from Japanese and overseas samples. Both the cpDNA haplotype network and the nuclear DNA phylogenetic tree showed that Japanese V. sepium is monophyletic. Furthermore, although the nuclear DNA phylogenetic tree also showed that each lineage is clearly monophyletic, genetic admixture of the genetic cluster dominated in the Hokkaido lineage was also detected in the Mt. Ibuki lineage. Population divergence analysis showed that the two lineages diverged during the last glacial period. The Mt. Ibuki lineage showed a sudden population decline 300-400 years ago, indicating that some anthropogenic activity might be involved, while the Hokkaido lineage showed a gradual population decline from 5000 years ago. Consequently, these two lineages show low current genetic diversity compared with overseas lineages. These results show that the Japanese V. sepium is not introduced but is native.

A redox-active inorganic crown ether based on a polyoxometalate capsule.

Cation-uptake has been long researched as an important topic in materials science. Herein we focus on a molecular crystal composed of a charge-neutral polyoxometalate (POM) capsule [MoVI72FeIII30O252(H2O)102(CH3CO2)15]3+ encapsulating a Keggin-type phosphododecamolybdate anion [α-PMoVI12O40]3-. Cation-coupled electron-transfer reaction occurs by treating the molecular crystal in an aqueous solution containing CsCl and ascorbic acid as a reducing reagent. Specifically, multiple Cs+ ions and electrons are captured in crown-ether-like pores {MoVI3FeIII3O6}, which exist on the surface of the POM capsule, and Mo atoms, respectively. The locations of Cs+ ions and electrons are revealed by single-crystal X-ray diffraction and density functional theory studies. Highly selective Cs+ ion uptake is observed from an aqueous solution containing various alkali metal ions. Cs+ ions can be released from the crown-ether-like pores by the addition of aqueous chlorine as an oxidizing reagent. These results show that the POM capsule functions as an unprecedented "redox-active inorganic crown ether", clearly distinguished from the non-redox-active organic counterpart.

Functional characteristics of 3'-azido-3'-deoxythymidine transport at the blood-testis barrier.

3'-Azido-3'-deoxythymidine (AZT), an antiretroviral drug, is often adopted in the therapy for human immunodeficiency virus (HIV) infection, and the characteristics of AZT transport at the blood-testis barrier (BTB) were investigated in this study. In the integration plot analysis that evaluates the transport activity in vivo, the apparent influx clearance of [3H]AZT was significantly greater than that of [14C]D-mannitol, a non-permeable paracellular transport marker. In the uptake study in vitro with TM4 cells derived from mouse Sertoli cells, [3H]AZT uptake exhibited a time- and concentration-dependent manner, of which Km and Vmax values being 20.3 µM and 102 pmol/(min·mg protein), respectively. In the inhibition analysis, [3H]AZT uptake was not affected by extracellular inorganics and some substrates of transporters putatively involved in AZT transport. In the further inhibition analyses to elucidate the characteristics of AZT transport, [3H]AZT uptake was strongly reduced in the presence of several nucleosides, that are categorized as 2'-deoxynucleosides with pyrimidine, whereas little effect on [3H]AZT uptake was exhibited in the presence of other nucleosides, nucleobases, and antiretrovirals. These results suggest the influx transport of AZT from the circulating blood to the testis, and the involvement of carrier-mediated process at the BTB, which selectively recognizes 2'-deoxynucleosides with a pyrimidine base.

Involvement of TauT/SLC6A6 in Taurine Transport at the Blood-Testis Barrier.

Taurine transport was investigated at the blood-testis barrier (BTB) formed by Sertoli cells. An integration plot analysis of mice showed the apparent influx permeability clearance of [3H]taurine (27.7 µL/(min·g testis)), which was much higher than that of a non-permeable paracellular marker, suggesting blood-to-testis transport of taurine, which may involve a facilitative taurine transport system at the BTB. A mouse Sertoli cell line, TM4 cells, showed temperature- and concentration-dependent [3H]taurine uptake with a Km of 13.5 µM, suggesting that the influx transport of taurine at the BTB involves a carrier-mediated process. [3H]Taurine uptake by TM4 cells was significantly reduced by the substrates of taurine transporter (TauT/SLC6A6), such as ß-alanine, hypotaurine, γ-aminobutyric acid (GABA), and guanidinoacetic acid (GAA), with no significant effect shown by L-alanine, probenecid, and L-leucine. In addition, the concentration-dependent inhibition of [3H]taurine uptake revealed an IC50 of 378 µM for GABA. Protein expression of TauT in the testis, seminiferous tubules, and TM4 cells was confirmed by Western blot analysis and immunohistochemistry by means of anti-TauT antibodies, and knockdown of TauT showed significantly decreased [3H]taurine uptake by TM4 cells. These results suggest the involvement of TauT in the transport of taurine at the BTB.

Polyoxomolybdate Layered Crystals Constructed from a Heterocyclic Surfactant: Syntheses, Pseudopolymorphism and Introduction of Metal Cations.

Crystals with layered structures are crucial for the construction of functional materials exhibiting intercalation, ionic conductivity, or emission properties. Polyoxometalate crystals hybridized with surfactant cations have distinct layered packings due to the surfactants which can form lamellar structures. Introducing metal cations into such polyoxometalate-surfactant hybrid crystals is significant for the addition of specific functions. Here, polyoxomolybdate-surfactant hybrid crystals were synthesized as single crystals, and unambiguously characterized by X-ray structure analyses. Octamolybdate ([Mo8O26]4-, Mo8) and heterocyclic surfactant of 1-dodecylpyridinium (C12py) were employed. The hybrid crystals were composed of α-type and ß-type Mo8 isomers. Two crystalline phases containing α-type Mo8 were obtained as pseudopolymorphs depending on the crystallization conditions. Crystallization with the presence of rubidium and cesium cations caused the formation of metal cation-introduced hybrid crystals comprising ß-Mo8 (C12py-Rb-Mo8 and C12py-Cs-Mo8). The yield of the C12py-Rb-Mo8 hybrid crystal was almost constant within crystallization temperatures of 279-303 K, while that of C12py-Cs-Mo8 decreased over 288 K. This means that the C12py-Mo8 hybrid crystal can capture Rb+ and Cs+ from the solution phase into the solids as the C12py-Rb-Mo8 and C12py-Cs-Mo8 hybrid crystals. The C12py-Mo8 hybrid crystals could be applied to ion-capturing materials for heavy metal cation removal.

Synthesis of 4-Selenothreofuranose Derivatives via Pummerer-Type Reactions of trans-3,4-Dioxygenated Tetrahydroselenophenes Mediated by a Selenonium Intermediate.

Selenosugars are interesting targets of organic synthesis as they would possess potential biological activities. However, 4-selenotherofuranose derivatives, which have trans configuration for the two dihydroxy substituents at the 2,3-positions and a glycoside bond at the anomeric position, are not available in the current selenosugar library. In this study, racemic 4-selenothreofuranose derivatives were synthesized from trans-3,4-dioxygenated tetrahydroselenophenes in 77-99% yields with the α/ß selectivity about 7:3 via oxidation and subsequent seleno-Pummerer rearrangement. The acetoxy group introduced at the anomeric position was then substituted with various nucleophiles, including activated 6-chloropurine, which afforded 4'-selenothreonucleoside derivatives, in the presence of BF3·OEt2 or TMSOTf. The stereochemistry of the selenosugar products was established by 1H NMR spectroscopy as well as X-ray analysis. The similar α/ß selectivity observed in the latter glycosylation reaction to that in the former seleno-Pummerer rearrangement suggested the mediation of a common selenonium intermediate (-Se+=C<). It was also suggested that an unexpected interaction between the ester protecting group at the 3-position of the selenofuranose ring and the anomeric carbon atom decreases the α/ß selectivity.

Integrating molecular design and crystal engineering approaches in non-humidified intermediate-temperature proton conductors based on a Dawson-type polyoxometalate and poly(ethylene glycol) derivatives.

Anionic metal-oxygen clusters known as polyoxometalates (POMs) have been widely researched as components of proton conductors. While proton conduction under non-humidified intermediate-temperature (100-250 °C) conditions is advantageous from the viewpoint of kinetics, few solid-state materials, not to mention POM-based crystals, show truly effective proton conduction without the aid of water vapor. In this context, non-volatile proton-conductive polymers have been confined into POM-based frameworks, while fast proton conduction was infeasible. Herein, we demonstrate a new strategy to synthesize POM-polymer composites exhibiting fast proton conduction under non-humidified intermediate-temperature conditions. Specifically, a molecular design approach utilizing poly(ethylene glycol)s (PEGs) of different terminal groups or chain lengths controls the proton carrier density, and a crystal engineering approach using a large Dawson-type POM ([α-P2W18O62]6-) with an anisotropic molecular shape and alkali metal ions as counter cations fine-tunes the mobility of the confined PEGs as proton carriers. By integrating these approaches, proton conductivity over 10-4 S cm-1 at 150 °C, comparable to the well-known highly proton-conductive solid-state materials, is achieved. The proton conduction mechanism is discussed with alternative current impedance spectroscopy jointly with specific heat capacity measurements and solid-state NMR spectroscopy.

Dual-emissive photoluminescent Langmuir-Blodgett films of decatungstoeuropate and an amphiphilic iridium complex.

Langmuir monolayers and Langmuir-Blodgett (LB) films of the decatungstoeuropate [Eu(W(5)O(18))(2)](9-) (EuW(10)) and the amphiphilic Ir complex 1 have been successfully fabricated by using the adsorption properties of the EuW(10) polyanion dissolved in the aqueous subphase onto a positively charged 1 monolayer at the air-water interface. The compression isotherms and Brewster angle microscopy (BAM) of monolayers of 1 on pure water (1 monolayer) and on a subphase containing 10(-6) M EuW(10) and 10(-3) M NaCl (1/EuW(10) monolayer) have been studied. Infrared and UV-vis spectroscopy of the transferred LB films indicate that EuW(10) and 1 molecules are incorporated within these LB films. X-ray reflectivity (SXR) and atomic force microscopy (AFM) experiments indicate that LB films of 1 present a heterogeneous morphology while 1/EuW(10) films show a flatter and more homogeneous surface as well as a layered structure with a periodicity of 4.1 nm. Mixed monolayers of 1 and DODA (dimethyldioctadecylammonium bromide) have been prepared with EuW(10) polyanions in the subphase to control the concentration of 1 and EuW(10) polyanions within the LB films. AFM and SXR experiments with the transferred LB films show that the dilution of 1 with DODA improves the layered structure. The luminescence of 1 is partially quenched by EuW(10) in the 1/EuW(10) LB films, while emission from EuW(10) is not detected. On the other hand, emission from both entities is preserved in the LB films prepared from mixed DODA/1 monolayers, in which the red and yellow emissions arise independently from EuW(10) and 1, respectively. The different DODA:1 ratios lead to changes in the emission color. Therefore, they constitute a promising color-tunable luminescent material.

Predictors of recurrent febrile seizures during the same febrile illness in children with febrile seizures.

Febrile seizures (FS) are common in childhood. Of children who experience an FS, 14-24% experience recurrence within 24 h, during the same febrile illness (RFS). The aim of this pilot study was to identify the predictors of RFS among children who experience FS. We conducted a retrospective cohort study of children aged 6-60 months, who visited the emergency department (ED) at Atsugi City Hospital in Japan for treatment of an FS between December 1, 2018 and February 28, 2019. Exclusion criteria included multiple seizures before visiting the ED, diazepam administration before visiting the ED or on departure, seizures lasting >15 min, underlying diseases such as epilepsy, and absence of laboratory test results. The primary outcome was RFS. Fifty-one patients fulfilled the inclusion criteria, of whom nine (17.6%) had RFS. The incidence of RFS was significantly higher in children with a body temperature ≤ 39.8 °C during the ED visit (P = .01). The combination of male sex and a body temperature ≤ 39.8 °C had a sensitivity, specificity and negative predictive value of 88.9%, 76.2%, and 97.0%, respectively. In conclusion, the incidence of RFS was 17.6%. The major predictors of RFS were male sex and a body temperature ≤ 39.8 °C.

Clinical and genetic study of Japanese patients with type 3 Gaucher disease.

Information on the phenotypic variations seen in patients with type 3 (chronic neuronopathic) Gaucher disease (GD) is still limited compared with type 1 GD. We retrospectively investigated the clinical features of 42 Japanese patients with type 3 GD. The 42 patients classified as type 3 fell into two groups: those diagnosed as having type 3 GD at diagnosis (group A; n = 24) and those thought to have type 1 at diagnosis but who later developed neurological symptoms (group B; n = 18). The genotype of group A patients varied widely; however, L444P/L444P and L444P/F213I genotypes accounted for 83% in group B. All the patients who did not receive enzyme replacement with alglucerase or imiglucerase (4 in group A, 2 in group B) died. Nineteen patients received enzyme replacement in group A; however, 7 of these died despite the therapy. On the other hand, 14 patients received enzyme replacement alone in group B and 13 of them survived. Among the ERT-treated patients who survived, only one of 12 in group A and 12 out of 13 in group B can walk unaided. In conclusion, some Japanese GD patients who are thought to have type 1 at diagnosis develop neurological symptoms during their clinical course, and careful observation is essential for patients with characteristic genotypes. Moreover, enzyme replacement alone might not have a sufficient effect on the early onset neurological symptoms in type 3 patients. A different treatment strategy is needed to improve the prognosis of these patients.

Efficacy of Brazilian Propolis Supplementation for Japanese Lactating Women for Atopic Sensitization and Nonspecific Symptoms in Their Offspring: A Randomized, Double-Blind, Placebo-Controlled Trial.

Propolis is a natural product collected from several plants by honeybees and mixed with beeswax and salivary enzymes. In animal models, propolis suppressed IgE-mediated allergies. However, there is no clinical evidence that propolis prevents human atopic sensitization, to the best of our knowledge. Therefore, a randomized, double-blind, placebo-controlled trial was conducted to assess whether propolis supplementation for lactating women increases or decreases the level of total IgE and antigen-specific IgE in the serum of their offspring (i.e., atopic sensitization) at the time of their first birthday. In addition, whether propolis supplementation improves or worsens nonspecific symptoms (e.g., eczema) in the lactating women and their offspring was also investigated. This trial is registered with UMIN000020794. Eligible pairs of mothers and their offspring (n=80) were randomized to two groups: propolis (n=40) and placebo (n=40). Participants were evaluated every month, and 31 (78%) of the propolis group and 23 (58%) of the placebo group underwent blood tests at the first birthday of the offspring. Total IgE ≥ 10 UA/ml was seen in 26 (84%) infants whose mothers were given propolis, which was not significantly different from the 19 (86%) given placebo (P=0.80). Total IgE as a continuous variable was not significantly different between the propolis and placebo groups (P=0.70). Antigen-specific IgE levels for mites, egg white, cow's milk, and wheat, as both dichotomous and continuous variables, were not significantly different between the two groups. Both in mothers and their offspring, there were no significant differences in the subjective improvements of nonspecific symptoms between the two groups. Except for one mother who had transient and mild nausea, none of the other mothers or their offspring developed severe adverse events during the follow-up period. In conclusion, compared with placebo, Brazilian propolis supplementation did not influence the risk of atopic sensitization in infants and neither did it improve nor worsen nonspecific symptoms in either mothers or their infants.

Dimensional Control in Polyoxometalate Crystals Hybridized with Amphiphilic Polymerizable Ionic Liquids.

Ionic liquids are an important component for constructing functional materials, and polyxometalate cluster anion is a promising partner for building inorganic-organic hybrid materials comprising ionic liquids. In such hybrid materials, the precise control of the molecular arrangement in the bulk structures is crucial for the emergence of characteristic functions, which can be realized by introducing an amphiphilic moiety into the ionic liquids. Here, an amphiphilic polymerizable imidazolium ionic liquid with a methacryloyl group was firstly hybridized with polyoxometalate anions of octamolybdate ([Mo8O26]4-, Mo8) and silicotungstate ([SiW12O40]4-, SiW12) to obtain inorganic-organic hybrid crystals. The polymerizable ionic liquid with a octyl chain (denoted as MAImC8) resulted in the formation of anisotropic molecular arrangements in the bulk crystal structure, which was compared with the hybrid crystals composed from the polymerizable ionic liquid without a long alkyl chain (denoted as MAIm). Rather densely packed isotropic molecular arrangements were observed in the hybrid crystals of MAIm-Mo8 and MAIm-SiW12 due to the lack of the amphiphilic moiety. On the other hand, using the amphiphilic MAImC8 cation gave rise to a honeycomb-like structure with the Mo8 anion and a layered structure with the SiW12 anion, respectively.

Polymerizable Ionic Liquid Crystals Comprising Polyoxometalate Clusters toward Inorganic-Organic Hybrid Solid Electrolytes.

Solid electrolytes are crucial materials for lithium-ion or fuel-cell battery technology due to their structural stability and easiness for handling. Emergence of high conductivity in solid electrolytes requires precise control of the composition and structure. A promising strategy toward highly-conductive solid electrolytes is employing a thermally-stable inorganic component and a structurally-flexible organic moiety to construct inorganic-organic hybrid materials. Ionic liquids as the organic component will be advantageous for the emergence of high conductivity, and polyoxometalate, such as heteropolyacids, are well-known as inorganic proton conductors. Here, newly-designed ionic liquid imidazolium cations, having a polymerizable methacryl group (denoted as MAImC1), were successfully hybridized with heteropolyanions of [PW12O40]3- (PW12) to form inorganic-organic hybrid monomers of MAImC1-PW12. The synthetic procedure of MAImC1-PW12 was a simple ion-exchange reaction, being generally applicable to several polyoxometalates, in principle. MAImC1-PW12 was obtained as single crystals, and its molecular and crystal structures were clearly revealed. Additionally, the hybrid monomer of MAImC1-PW12 was polymerized by a radical polymerization using AIBN as an initiator. Some of the resulting inorganic-organic hybrid polymers exhibited conductivity of 10-4 S·cm-1 order under humidified conditions at 313 K.