One-dimensional ion transport in self-organized columnar ionic liquids

New fan-shaped ionic liquids forming columnar liquid crystalline phases have been prepared to obtain one-dimensional ion-transporting materials. The ionic liquids consist of two incompatible parts: an imidazolium-based ionic part as an ion-conducting part and tris(alkyloxy)phenyl parts as insulating parts. Two compounds having octyl and dodecyl chains have been synthesized. Self-assembly of these materials leads to the formation of thermotropic hexagonal columnar liquid crystalline states at room temperature. Anisotropic one-dimensional ionic conductivities have been successfully measured by the cells having comb-shaped gold electrodes. The self-organized columns have been aligned macroscopically in two directions by shearing perpendicular and parallel to the electrodes. The ionic conductivities parallel to the column axis are higher than those perpendicular to the axis. The incorporation of lithium salts in these columnar materials leads to the enhancement of the ionic conductivities and their anisotropy. These materials would be useful for anisotropic transportation of ions at the nanometer level.     

Iridium-catalyzed addition of aroyl chlorides and aliphatic acid chlorides to terminal alkynes

Iridium complexes show high catalytic activity in intermolecular additions of acid chlorides to terminal alkynes to afford valuable (Z)-β-chloro-α,β-unsaturated ketones. Ligands in the catalytic system play a crucial role in this reaction. An N-heterocyclic carbene (NHC) is an efficient ligand for the addition of aroyl chlorides, while dicyclohexyl(2-methylphenyl)phosphine (PCy(2)(o-Tol)) is indispensable for the reaction of aliphatic acid chlorides. The addition reactions proceed regio- and stereoselectively with suppression of decarbonylation and β-hydrogen elimination, which have been two major intrinsic problems in transition-metal-catalyzed reactions. Stoichiometric reactions of active iridium catalysts with aroyl chlorides and aliphatic acid chlorides are carried out to gain insights into the reaction mechanisms.     

Mechanism underlying bioinertness of self-assembled monolayers of oligo(ethyleneglycol)-terminated alkanethiols on gold: protein adsorption, platelet adhesion, and surface forces

The mechanism underlying the bioinertness of the self-assembled monolayers of oligo(ethylene glycol)-terminated alkanethiol (OEG-SAM) was investigated with protein adsorption experiments, platelet adhesion tests, and surface force measurements with an atomic force microscope (AFM). In this work, we performed systematic analysis with SAMs having various terminal groups (-OEG, -OH, -COOH, -NH(2), and -CH(3)). The results of the protein adsorption experiment by the quartz crystal microbalance (QCM) method suggested that having one EG unit and the neutrality of total charges of the terminal groups are essential for protein-resistance. In particular, QCM with energy dissipation analyses indicated that proteins absorb onto the OEG-SAM via a very weak interaction compared with other SAMs. Contrary to the protein resistance, at least three EG units as well as the charge neutrality of the SAM are found to be required for anti-platelet adhesion. When the identical SAMs were formed on both AFM probe and substrate, our force measurements revealed that only the OEG-SAMs possessing more than two EG units showed strong repulsion in the range of 4 to 6 nm. In addition, we found that the SAMs with other terminal groups did not exhibit such repulsion. The repulsion between OEG-SAMs was always observed independent of solution conditions [NaCl concentration (between 0 and 1 M) and pH (between 3 and 11)] and was not observed in solution mixed with ethanol, which disrupts the three-dimensional network of the water molecules. We therefore concluded that the repulsion originated from structured interfacial water molecules. Considering the correlation between the above results, we propose that the layer of the structured interfacial water with a thickness of 2 to 3 nm (half of the range of the repulsion observed in the surface force measurements) plays an important role in deterring proteins and platelets from adsorption or adhesion.     

Molecularly defined graphitic interface toward proton manipulation

Proton plays a critical role in electrochemical systems to control electrochemical reactivity or isotopic enrichment. Graphene is intensively investigated owing to its unique electronic structure and device fabrication. Through the structural tunability of graphitic materials by chemical or physical modification of the surface, graphene is revealed to be an ideal material for proton manipulation. Here, we review the use of graphene or graphitic materials toward the manipulation of proton with regard to the following three points. (1) Electronic properties of graphene: The electronic band structure of graphene can be modified by metal contacts owing to the interaction with a metal surface. (2) Molecular control of graphitic interface: The chemical structure of graphene can be modified, as is done in molecular chemistry, and can be used as a catalytic platform. (3) Proton conduction by graphene: Proton transport through a graphene layer occurs with a unique mechanism such as tunneling. We provide a perspective on the use of graphitic materials toward controlling the behavior of protons on the basis of the aforementioned points. From the above, graphene can be used as a platform for proton manipulation.     

Universal fluorescent labeling of amplification products using locked nucleic acids

Amplification/hybridization‐based genetic analyses using primers containing locked nucleic acids (LNAs) present many benefits. Here, we developed a novel design for universal fluorescent PCR using LNAs. Universal fluorescent PCR generates intermediate nonlabeled fragments and final fluorescent fragments in a two‐step amplification process that uses locus‐specific primers with universal tails and universal fluorescent primers. In this study, a few standard nucleotides were replaced with LNAs only in the fluorescent universal primers. The sequence of the fluorescent universal primer significantly affected the amplification efficiency. For primers with three LNAs, the fluorescent primers with stable M13(‐47) sequences provided the most efficient signal (approximately tenfold higher than the primers with M13(‐21) sequences at lower Tm values). Moreover, AT‐rich LNA substitutions in the fluorescent primers produced much lower amplification efficiencies than GC‐rich substitutions. GC‐rich LNAs produced greater differences in Tm values among primers, and resulted in the preferential production of fluorescently labeled amplicons. The specificity and sensitivity of LNA‐containing fluorescent primers were assessed by genotyping eight STRs in Japanese individuals, and full STR profiles could be generated using as little as 0.25 ng of genomic DNA. The method permitted clear discrimination of alleles and represents sensitive STR genotyping at a reduced cost.     

Visualizing Hepatic Copper Release in Long–Evans Cinnamon Rats Using Single-Photon Emission Computed Tomography

The potential utility of an imaging agent for the detection of hepatic copper was investigated in a Wilson’s disease animal model. Solid-phase peptide synthesis was used to construct an imaging agent which consisted of a copper-binding moiety, taken from the prion protein, and a gamma ray-emitting indium radiolabel. Long–Evans Cinnamon (LEC) rats were used for the Wilson’s disease animal model. Our evaluation methodology consisted of administering the indium-labeled agent to both LEC and genetically healthy Long–Evans (LE) cohorts via a tail vein injection and following the pharmacokinetics with single-photon emission computed tomography (SPECT) over the course of an hour. The animals were then sacrificed and their livers necropsied. An additional control agent, lacking the copper-binding moiety, was used to gauge whether any change in the hepatic uptake might be caused by other physiological differences between the two animal models. LEC rats injected with the indium-labeled agent had roughly double the amount of hepatic radioactivity as compared to the healthy control animals. The control agent, without the copper-binding moiety, displayed a hepatic signal similar to that of the control LE animals. Additional intraperitoneal spiking with CuSO₄ in C57BL/6 mice also found that the pharmacokinetics of the indium-labeled, prion-based imaging agent is profoundly altered by exposure to in vivo pools of extracellular copper. The described SPECT application with this compound represented a significant improvement over a previous MRI application using the same base peptide sequence.