Anion-induced switching of the helical orientation of a chiral indolocarbazole dimer

An indolocarbazole dimer, containing chiral urea appendages, that adopts a helically folded conformation by intramolecular hydrogen bonds as proven by ¹H NMR and circular dichroism (CD) spectroscopy has been prepared. Owing to the preferential formation of one helical conformer, strong CD signals appear in relatively non-polar solvents such as chloroform (CHCl₃) and dichloromethane (CH₂Cl₂) but the signal is negligible in dimethyl sulfoxide (DMSO). In addition, the optical rotation of the dimer is highly sensitive to the polarity of solvents. For example, the magnitude of the specific rotation ([α]_D) is ? 934° in CH₂Cl₂ and ? 657° in CHCl₃ but it is only ? 75° in DMSO. These observations suggest that the dimer folds to a helical structure by intramolecular hydrogen bonds in relatively non-polar solvents but exists in an unfolded extended conformation in polar solvents such as DMSO. The dimer strongly binds anions such as chloride, acetate and sulfate by multiple hydrogen bonds. In addition, anion binding leads to considerable CD spectral changes with the different pattern and degree of Cotton effects depending on the kind of anions. The dimer may be therefore utilised for the construction of an anion-responsive chiroptical sensor or switch.     

Size‐Controlled Construction of Magnetic Nanoparticle Clusters Using DNA‐Binding Zinc Finger Protein

Nanoparticle clusters (NPCs) have attracted significant interest owing to their unique characteristics arising from their collective individual properties. Nonetheless, the construction of NPCs in a structurally well‐defined and size‐controllable manner remains a challenge. Here we demonstrate a strategy to construct size‐controlled NPCs using the DNA‐binding zinc finger (ZnF) protein. Biotinylated ZnF was conjugated to DNA templates with different lengths, followed by incubation with neutravidin‐conjugated nanoparticles. The sequence specificity of ZnF and programmable DNA templates enabled a size‐controlled construction of NPCs, resulting in a homogeneous size distribution. We demonstrated the utility of magnetic NPCs by showing a three‐fold increase in the spin–spin relaxivity in MRI compared with Feridex. Furthermore, folate‐conjugated magnetic NPCs exhibited a specific targeting ability for HeLa cells. The present approach can be applicable to other nanoparticles, finding wide applications in many areas such as disease diagnosis, imaging, and delivery of drugs and genes.     

Synthesis and Reactivity of a Neutral,Three‐Coordinate Platinum(II) Complex Featuring Terminal Amido Ligation

A crystallographically characterized three‐coordinate, formally 14 electron Pt^II complex 1 featuring terminal amido ligation is reported. Computational analysis revealed relatively weak π donation from the amide lone pair to platinum and supports a 14‐electron assignment for 1 . Stoichiometric reactivity studies confirmed the viability of net O? H and C? H addition across, as well as isonitrile insertion into, the terminal platinum–amido linkage of 1 .     

Reconfigurable Photonic Capsules Containing Cholesteric Liquid Crystals with Planar Alignment

Cholesteric liquid crystals (CLCs) reflect selected wavelengths of light owing to their periodic helical structures. The encapsulation of CLCs leads to photonic devices that can be easily processed and might be used as stand‐alone microsensors. However, when CLCs are enclosed by polymeric membranes, they usually lose their planar alignment, leading to a deterioration of the optical performance. A microfluidics approach was employed to integrate an ultrathin alignment layer into microcapsules to separate the CLC core and the elastomeric solid membrane using triple‐emulsion drops as the templates. The thinness of the alignment layer provides high lubrication resistance, preserving the layer integrity during elastic deformation of the membrane. The CLCs in the microcapsules can thus maintain their planar alignment, rendering the shape and optical properties highly reconfigurable.     

Chemical‐Bath‐Deposited Indium Oxide Microcubes for Solar Water Splitting

We fabricated films of cubic indium oxide (In₂O₃) by chemical bath deposition (CBD) for solar water splitting. The fabricated films were characterized by X‐ray diffraction analysis, Raman scattering, X‐ray photoelectron spectroscopy, and scanning electron microscopy, and the three‐dimensional microstructure of the In₂O₃ cubes was elucidated. The CBD deposition time was varied, to study its effect on the growth of the In₂O₃ microcubes. The optimal deposition time was determined to be 24 h, and the corresponding film exhibited a photocurrent density of 0.55 mA cm^?2. Finally, the film stability was tested by illuminating the films with light from an AM 1.5 filter with an intensity of 100 mW cm^?2.     

Boron‐Based Drug Design

The use of the element boron, which is not generally observed in a living body, possesses a high potential for the discovery of new biological activity in pharmaceutical drug design. In this account, we describe our recent developments in boron‐based drug design, including boronic acid containing protein tyrosine kinase inhibitors, proteasome inhibitors, and tubulin polymerization inhibitors, and ortho‐carborane‐containing proteasome activators, hypoxia‐inducible factor 1 inhibitors, and topoisomerase inhibitors. Furthermore, we applied a closo‐dodecaborate as a water‐soluble moiety as well as a boron‐10 source for the design of boron carriers in boron neutron capture therapy, such as boronated porphyrins and boron lipids for a liposomal boron delivery system.     

Laryngeal Gestures During Stop Production Using High-Speed Digital Images

On acoustic and fiberscopic studies of stop consonants, voice onset time and glottal width have been shown to be greatest in heavily aspirated stops, next greater for slightly aspirated stops, and least for unaspirated stops. Integrated activity of the thyroarytenoid and posterior cricoarytenoid muscles has been reported to be involved in differentiating aspirate characteristics of the stops. However, the fine movement of mucosal edges of vocal folds during the production of stops has not been well documented. In recent years, a new method for high-speed digital recording of laryngeal dynamics has made this possible. In the current study, the movements of vocal fold edges were documented during the period of stop production using a fiberscopic system of high-speed digital images. By observing the glottal width and the visual vibratory movements of vocal folds before voice onset, the heavily aspirated stop was characterized as being more prominent and dynamic than the slightly aspirated and unaspirated stops.     

Application of a continued-fraction-based theory to magneto-optical intraband transition in GaAs and CdS

The quantum theory of intraband magneto-optical transition in semiconductors introduced previously in terms of continued-fraction-based power-series-expansion technique is reviewed in connection with examination of temperature- and dimensional-dependence of the width in GaAs and CdS in which piezoelectric scattering is dominant. With the same values of the piezoelectric coupling constant K and the expansion parameter the width in two-dimensions increases with temperature as in three-dimensions. Furthermore, the width becomes smaller uniformly as the dimension is reduced in the direction of static magnetic field in the quantum limit, which is physical. Therefore, the continued-fraction-based theory gives quite good interpretation of the acoustic phonon scattering in the quantum limit.