Facile Synthesis of Dibenzopentalene Dianions and Their Application as New π‐Extended Ligands

Reduction of phenyl(silyl)ethynes with potassium followed by quenching with iodine gave dibenzopentalenes in moderate yields. The intermediates of the reactions, dipotassium dibenzopentalenides, were isolated. The first dibenzopentalene–transition‐metal complex was successfully synthesized. The ruthenium atoms are located above the six‐membered rings. However, X‐ray diffraction analysis and theoretical calculations revealed that the aromatic nature of the five‐membered rings was retained. The cyclic voltammetry of the Ru complex revealed two oxidation waves with relatively large separation.     

An “OFF–ON–OFF” fluorescence protein-labeling probe for real-time visualization of the degradation of short-lived proteins in cellular systems

The ability to monitor proteolytic pathways that remove unwanted and damaged proteins from cells is essential for understanding the multiple processes used to maintain cellular homeostasis. In this study, we have developed a new protein-labeling probe that employs an ‘OFF–ON–OFF’ fluorescence switch to enable real-time imaging of the expression (fluorescence ON) and degradation (fluorescence OFF) of PYP-tagged protein constructs in living cells. Fluorescence switching is modulated by intramolecular contact quenching interactions in the unbound probe (fluorescence OFF) being disrupted upon binding to the PYP-tag protein, which turns fluorescence ON. Quenching is then restored when the PYP-tag–probe complex undergoes proteolytic degradation, which results in fluorescence being turned OFF. Optimization of probe structures and PYP-tag mutants has enabled this fast reacting ‘OFF–ON–OFF’ probe to be used to fluorescently image the expression and degradation of short-lived proteins.

An “OFF–ON–OFF” fluorescence probe for real-time imaging of the expression (fluorescence ‘OFF’) and degradation (fluorescence ‘ON’) of short lived PYP-tag proteins in cellular systems.     

An Ultrastable,Small {Ag7}5+ Nanocluster within a Triangular Hollow Polyoxometalate Framework

Small Ag_n nanoclusters (n<10) have been emerging as promising materials as sensing, biolabeling, and catalysis because of their unique electronic states and optical properties. However, studying synthesis, structure determination, and exploration of their properties remain major challenges as a result of the low stability of small Ag nanoclusters. Herein, we synthesized an atomically precise face‐centered‐cubic‐type small {Ag₇}⁵⁺ nanocluster supported by a novel triangular hollow polyoxometalate (POM) framework [Si₃W₂₇O₉₆]^18?. The cluster showed unique {Ag₇}⁵⁺‐to‐POM charge transfer bands in both visible and UV light regions. Furthermore, this small {Ag₇}⁵⁺ nanocluster exhibited an unprecedented ultrastability in solution, despite having exposed Ag sites that can be accessed by small molecules, such as O₂, water, and solvents.     

Pd- and Cu-catalyzed C–H arylation of indazoles

The palladium- and copper-catalyzed C–H arylation reactions of 1H- and 2H-indazoles with haloarenes are described. A PdCl₂/phen/Ag₂CO₃/K₃PO₄ catalytic system is effective for the C–H arylation of 1H- and 2H-indazoles with haloarenes, whereas a less expensive CuI/phen/LiOt-Bu catalytic system is applicable to the C–H coupling of substituted 2H-indazoles and iodoarenes. The utility of newly developed catalyst was demonstrated in the rapid synthesis of YC-1 (an antitumor agent) and YD-3 (platelet anti-aggregating agent). These new reactions represent important direct functionalization tools of indazoles, well-known bioisosteres of pharmaceutically important indole core.     

Flattened chromatic dispersion in square photonic crystal fibers with low confinement losses

This research presents a simple index-guiding square photonic crystal fibers (SPCFs) that has a silica core surrounded by air hole with two different diameters. It is demonstrated that the designed two-different-size hole-arrayed index-guiding SPCFs has a ultra-flattened chromatic dispersion of 0 ± 0.9 ps/(nm·km) in a wavelength range of 1.34 to 1.61 μm and low confinement loss of less than 10⁻⁷ dB/m in a wavelength range of 1.2 to 1.7 μm. It has also been shown that the proposed SPCFs show reasonable dispersion tolerance.     

Water‐ and Temperature‐Triggered Reversible Structural Transformation of Tetranuclear Cobalt(II) Cores Sandwiched by Polyoxometalates

Although stimuli‐responsive structural transformations of inorganic materials have attracted considerable attention because of their potential use as functional switchable materials, multinuclear metal cores frequently suffer from unexpected dissociation of metal cations and/or irreversible transformations into infinite structures. In this study, we describe the successful demonstration of the water‐ and temperature‐triggered reversible structural transformation between cubane‐ and planar‐type tetranuclear Co^II cores sandwiched by polyoxometalates. The arrangements and coordination geometries of the Co^II cations were interconverted by simple hydration and dehydration, resulting in the manipulation of the magnetic and optical properties of these compounds. Moreover, this system showed unique thermochromism through temperature‐dependent reversible structural interconversion.     

Solitons and Fractal Kerr Response

Optical solitary waves that propagate in a Kerr medium exhibiting a power-law nonlocal response are studied analytically. The first-principles stability analysis based on quantum field theory shows that within the whole range of the exponent (the fractal dimension) the solitary wave can be stabilized.     

Parallel vs. anti-parallel orientation in a curdlan/oligo(dA) complex as estimated by a FRET technique

We already found that beta-1,3-glucan polysaccharides form polymeric complexes with certain polynucleotides, but the parallel vs. anti-parallel orientation in those complexes had remained unsolved. In this paper, this controversial problem has been discussed for curdlan/oligo(dA) complexes utilizing two different energy transfer techniques. The first system consists of a combination of fluorescein-labeled curdlan and 3'-(or 5'-)tetramethyl-rhodamine (TAMRA)-labeled oligo(dA). The second system utilizes gold nanoparticles: that is, two curdlan chains were linked by a disulfide bond and after complexation with oligo(dA), the complex was immobilized on gold nanoparticles. In this system, TAMRA was attached to the 3'(or 5') end of oligo(dA) and the gold particle acted as a fluorescence quencher (energy acceptor). These experiments have led us to conclude that in the curdlan/oligo(dA) complex, parallel orientation is more favourable than anti-parallel orientation. These findings have enabled us to envision a clearer image for the complexation mode between beta-1,3-glucan polysaccharides and polynucleotides.     

Single-molecule fluorescence imaging of the remote TiO2 photocatalytic oxidation

The remote TiO2 photocatalytic oxidation reaction of single dyes has been investigated by the single-molecule fluorescent imaging technique. The present results suggest that the active oxygen species (Ox) is most probably the .OH radical, which is generated from the photodecomposition of H2O2 by UV light. The analyses of the number, intensity, and spectrum of individual fluorescence spots at the single-molecule level also indicate that unoxidized and oxidized dyes exist during the bleaching processes of single dyes.