New hierarchically porous titania monoliths for chromatographic separation media

Separation media based on hierarchically porous titania (TiO₂) monoliths for high‐performance liquid chromatography (HPLC) have been successfully fabricated by the sol–gel process of titanium alkoxide in a mild condition utilizing a chelating agent and mineral salt. The as‐gelled TiO₂ monoliths were subjected to a simple solvent exchange process from ethanol (EtOH) to H₂O followed by drying and calcination. The resultant monolithic TiO₂ columns consist of anatase crystallites with the typical specific surface area of more than 200 m²/g. The resultant monolithic TiO₂ column calcined at 200 and 400°C exhibited a good separation performance for organophosphates as well as for polar benzene derivatives in the normal‐phase mode.     

Evaluation of ferritin-overexpressing brain in newly developed transgenic mice

Aberrant expression of ferritin, a major iron-binding protein, has shown to be involved in neurodegenerative diseases. In this study, we generated transgenic (Tg) mice of human ferritin heavy chain (FTH) gene and investigated the effects of ferritin overexpression in FTH-Tg brain by ¹H-MRI and ¹H-MRS. The mice displayed no apparent neurological symptoms, and no specific morphological and T₂ alterations were found in the brain by MRI, and not even by histological studies. ¹H-MRS, however, revealed that some metabolic markers were significantly altered in FTH-Tg brains compared to wild-type control brains, such as decreases in myo-inositol and glutamine, and an increase in lactate. Our present studies suggested that despite the absence of neurological, morphological, T₂, and histological signatures, brain metabolisms were significantly affected in FTH-Tg mice. This study also highlights the usefulness of ¹H-MRS in the analysis of transgenic mouse models.     

Energy entanglement in neutron interferometry

Entanglement between degrees of freedom, namely between the spin, path and (total) energy degrees of freedom, for single neutrons is exploited. We implemented a triply entangled Greenberger-Horne-Zeilinger(GHZ)-like state and coherently manipulated relative phases of two-level quantum subsystems. An inequality derived by Mermin was applied to analyze the generated GHZ-like state: we determined the four expectation values and finally obtained M=2.558±0.004?2. This demonstrates the violation of a Mermin-like inequality for triply entangled GHZ-like state in a single-particle system, which, in turn, exhibits a clear inconsistency between noncontextual assumptions and quantum mechanics and confirms quantum contextuality.     

3D analysis of the lattice defects in the gyroid network structure of a block copolymer/homopolymer blend – The line-like defects in the gyroid network structure

The line-shaped defects formed in the gyroid bicontinuous microdomain structures in the solution-casting process of a blend of polystyrene-block-polyisoprene (SI) diblock copolymer and homopolystyrene (HS) were investigated using 3D electron tomography. The inclusion-type lattice defects composed of segregated HS formed during the morphological transition from the preexisted sponge phase to the stable gyroid phase induced by the phase separation between SI and HS. The gyroid grains grew by consuming the sponge phase and expelling excess HS as well as by impinging each other. Consequently, some expelled HS was trapped as the line-like inclusions in the gyroid grains. Structural rearrangement occurred so that low energy planes of the gyroid phase are facing the HS inclusions while the gyroid structure became continuous across/around the inclusions.     

Dynamic path bifurcation in the Beckmann reaction: support from kinetic analyses

The reactions of oximes to amides, known as the Beckmann rearrangement, may undergo fragmentation to form carbocations + nitriles when the migrating groups have reasonable stability as cations. The reactions of oxime sulfonates of 1-substituted-phenyl-2-propanone derivatives (7-X) and related substrates (8-X, 9a-X) in aqueous CH(3)CN gave both rearrangement products (amides) and fragmentation products (alcohols), the ratio of which depends on the system; the reactions of 7-X gave amides predominantly, whereas 9a-X yielded alcohols as the major product. The logk-logk plots between the systems gave excellent linear correlations with slopes of near unity. The results support the occurrence of path bifurcation after the rate-determining TS of the Beckmann rearrangement/fragmentation reaction, which has previously been proposed on the basis of molecular dynamics simulations. It was concluded that path-bifurcation phenomenon could be more common than thought and that a reactivity-selectivity argument based on the traditional TS theory may not always be applicable even to a well-known textbook organic reaction.     

GC-MS ultra trace analysis of dioxins produced through hydrothermal gasification of biowastes

Hydrogen gas and the valuable material hydroxylapatite have successfully been produced from biomass wastes by hydrothermal gasification. However, it was expected that toxic compounds might be produced through the reaction. It was therefore important to clarify whether toxic compounds were synthesized in hydrothermal gasification of biowastes since dioxins are categorized among the most toxic compounds for humans. This is particularly true of biomass wastes containing hetero-atoms in organic matrices. In this study, formation of the dioxins polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs) and certain dioxin-like polychlorinated biphenyls (PCBs) were examined. Chicken manure and cattle manure were tested as real biowastes for hydrothermal gasification and the produced compounds in the liquid and solid phases were analyzed for detection of dioxins by gas chromatography/mass spectrometry (GC/MS). The total toxic equivalent quantities (the total TEQ) of dioxins produced by the hydrothermal gasification were found to be much lower than regulation levels in Japan require and therefore the products require no additional post treatments.     

Synthesis of the sulfonated condensed polynuclear aromatic (S-COPNA) resins as strong protonic acids

The mixture (PXG/PR=1.00) of pyrene (PR) and p-xylylene glycol (1,4-benzenedimethanol) (PXG) in the presence of 5 wt % of p-toluenesulfonic acid (TsOH) was heated at 140 °C for 45 min under nitrogen to give the highly viscous condensed polynuclear aromatic (COPNA) resin. It was converted into an infusible and insoluble solid by further heating at 300 °C for 1 h. The obtained material was treated with fuming sulfuric acid at 80 °C for 15 h under nitrogen to give the sulfonated COPNA resin. The similar acidic resin was prepared by the reaction of phenanthrene or naphthalene with PXG in the presence of TsOH followed by sulfonation. The performance of the sulfonated polymers as the strong protonic acids was evaluated.     

Device for co-culture of sympathetic neurons and cardiomyocytes using microfabrication

Rat superior cervical ganglion (SCG) neurons and ventricular myocytes (VMs) were co-cultured separately in a minichamber placed on a microelectrode-array (MEA) substrate. The minichamber, fabricated photolithographically using polydimethylsiloxane (PDMS), had 2 compartments, 16 microcompartments and 8 microconduits. The SCG neurons were seeded into one of the compartments and all of the microcompartments using a glass pipette controlled by a micromanipulator and a microinjector. The VMs were seeded into the other compartment. Three days after seeding of the VMs, the SCG neurons were still confined to one compartment and all of the microcompartments, and the neurites of the SCG neurons had connected with the VMs via the microconduits. Constant-voltage stimulation, using a train of biphasic square pulses (1 ms at +1 V, followed by -1 ms at 1 V), was applied to the SCG neurons in the microcompartments using 16 electrodes. Evoked responses were observed in several electrodes while electrical stimulation was applied to the SCG neurons. Two-way analysis of variance (ANOVA) revealed that the frequency of the stimulation pulses had significant effects in increasing the beat rate of the VMs, and that the interaction between the frequency and the number of the pulses also had a significant effect on the ratio. No significant increases in the beat rate were observed when propranolol, a β-adrenergic receptor antagonist, was added to the culture medium. These results suggest that synaptic pathways were formed between the SCG neurons and the VMs, and that this co-culture device can be utilized for studies of network-level interactions between sympathetic neurons and cardiomyocytes.     

Luminescence tuning of imidazole-based lanthanide(III) complexes [Ln = Sm, Eu, Gd, Tb, Dy

To tune the lanthanide luminescence in related molecular structures, we synthesized and characterized a series of lanthanide complexes with imidazole-based ligands: two tripodal ligands, tris{[2-{(1-methylimidazol-2-yl)methylidene}amino]ethyl}amine (Me(3)L), and tris{[2-{(imidazol-4-yl)methylidene}amino]ethyl}amine (H(3)L), and the dipodal ligand bis{[2-{(imidazol-4-yl)methylidene}amino]ethyl}amine (H(2)L). The general formulas are [Ln(Me(3)L)(H(2)O)(2)](NO(3))(3)·3H(2)O (Ln = 3+ lanthanide ion: Sm (1), Eu (2), Gd (3), Tb (4), and Dy (5)), [Ln(H(3)L)(NO(3))](NO(3))(2)·MeOH (Ln(3+) = Sm (6), Eu (7), Gd (8), Tb (9), and Dy (10)), and [Ln(H(2)L)(NO(3))(2)(MeOH)](NO(3))·MeOH (Ln(3+) = Sm (11), Eu (12), Gd (13), Tb (14), and Dy (15)). Each lanthanide ion is 9-coordinate in the complexes with the Me(3)L and H(3)L ligands and 10-coordinate in the complexes with the H(2)L ligand, in which counter anion and solvent molecules are also coordinated. The complexes show a screw arrangement of ligands around the lanthanide ions, and their enantiomorphs form racemate crystals. Luminescence studies have been carried out on the solid and solution-state samples. The triplet energy levels of Me(3)L, H(3)L, and H(2)L are 21?000, 22?700, and 23?000 cm(-1), respectively, which were determined from the phosphorescence spectra of their Gd(3+) complexes. The Me(3)L ligand is an effective sensitizer for Sm(3+) and Eu(3+) ions. Efficient luminescence of Sm(3+), Eu(3+), Tb(3+), and Dy(3+) ions was observed in complexes with the H(3)L and H(2)L ligands. Ligand modification by changing imidazole groups alters their triplet energy, and results in different sensitizing ability towards lanthanide ions.     

Phospholipids with a stimuli-responsive thermotropic liquid-crystalline moiety

Lyotropic liquid-crystalline phospholipids having an electro- and/or light-responsive mesogenic core were prepared. These LCs show lyotropic smectic A, smectic C, rectangular columnar, and nematic phases. We succeeded in the dynamic control of these LC phases by applying an electric field, which could lead to electrically switchable phospholipid bilayers.