Quantitative Effect of Reducing Body Thickness on Visualizing Murine Deep Abdominal Lymph Nodes by In Vivo Fluorescence Reflectance Imaging

Scattering and absorption in the tissues are major problems for in vivo imaging based on a fluorescence reflectance imaging technique. We evaluated the quantitative relationship between body thickness and fluorescent signals from a deep abdominal source in intact mice. Mice were injected with quantum dots (peak emission, 800 nm) into the right rear footpad, and fluorescent signals from the iliac lymph node located deeply in the abdomen were assessed by fluorescence reflectance imaging. Stepwise compression of the mouse abdomen to reduce the body thickness was attained using a homemade simple device. The iliac node signals were weak and diffuse without compression but became stronger and more localized with decreasing body thickness. Using excitation light of approximately 710 nm wavelength, the lymph node/background contrast increased about 16 times with a 4 mm reduction in body thickness. Contrast enhancement was more evident using shorter wavelength excitation light. Overlying tissues profoundly affect signals from a deep source in fluorescence reflectance imaging. Our simple compression method may contribute to quantitatively assessing deep fluorescent sources.     

Very fast magic angle spinning (1)H-(14)N 2D solid-state NMR: sub-micro-liter sample data collection in a few minutes

Substantial resolution and sensitivity enhancements of solid-state (1)H detected (14)N HMQC NMR spectra at very fast MAS rates up to 80 kHz, in a 1mm MAS rotor, are presented. Very fast MAS enhances the (1)H transverse relaxation time and efficiently decouples the (1)H-(14)N interactions, both effects leading to resolution enhancement. The micro-coil contributes to the sensitivity increase via strong (14)N rf fields and high sensitivity per unit volume. (1)H-(14)N HMQC 2D spectra of glycine and glycyl-L-alanine at 70 kHz MAS at 11.7 T are observed in a few minutes with a sample volume of 0.8 μL.     

Common origin of the circular-dichroism pattern in angle-resolved photoemission spectroscopy of SrTiO3 and Cu(x)Bi2Se3

Circular dichroism in the angular distribution of photoelectrons from SrTiO(3):Nb and Cu(x)Bi(2)Se(3) is investigated by 7-eV laser angle-resolved photoemission spectroscopy. In addition to the well-known node that occurs in the circular dichroism pattern when the incidence plane matches the mirror plane of the crystal, we show that another type of node occurs when the mirror plane of the crystal is vertical to the incidence plane and the electronic state is two-dimensional. The flower-shaped circular dichroism patterns in the angular distribution occurring around the Fermi level of SrTiO(3):Nb and around the Dirac point of Cu(x)Bi(2)Se(3) are explained on equal footings. We point out that the penetration depth of the topological states of Cu(x)Bi(2)Se(3) depends on momentum.     

A stable dialkylphosphinyl radical

Dialkylphosphinyl radical 1 was synthesized as thermally stable yellow crystals and found to be monomeric both in solution and in the solid state. EPR spectrum showed that the spin density of 1 is mainly localized on the 3p orbital of the dicoordinated phosphorus atom. A distinct absorption band due to the electronic transition from nonbonding electron pair orbital to singly occupied 3p orbital on the phosphorus atom of 1 was observed at 445 nm in solution. Phosphinyl radical 1 underwent facile reaction with carbon tetrachloride, hydrogen abstraction, and a unique reaction with a persistent radical, galvinoxyl, giving a cyclic phosphaalkene and a silylether.     

Highly efficient, organocatalytic aerobic alcohol oxidation

5-Fluoro-2-azaadamantane N-oxyl (5-F-AZADO) realizes a simple, organocatalytic aerobic alcohol oxidation system that has a wide scope under mild conditions at ambient pressure and temperature and is weakly acidic and halogen- and transition-metal-free. The oxoammonium nitrate (5-F-AZADO(+)NO(3)(-)) works as a bifunctional catalyst of 5-F-AZADO and NO(x) that enables the catalytic aerobic oxidation of alcohols by itself (a metal-salt-free system).     

Liberating Efimov Physics from Three Dimensions

When two particles attract via a resonant short-range interaction, three particles always form an infinite tower of bound states characterized by a discrete scaling symmetry. It has been considered that this Efimov effect exists only in three dimensions. Here we review how the Efimov physics can be liberated from three dimensions by considering two-body and three-body interactions in mixed dimensions and four-body interaction in one dimension. In such new systems, intriguing phenomena appear, such as confinement-induced Efimov effect, Bose?CFermi crossover in Efimov spectrum, and formation of interlayer Efimov trimers. Some of them are observable in ultracold atom experiments and we believe that this study significantly broadens our horizons of universal Efimov physics.     

Near‐Infrared‐III‐Absorbing and ‐Emitting Dyes: Energy‐Gap Engineering of Expanded Porphyrinoids via Metallation

The synthesis of organometallic complexes of modified 26π‐conjugated hexaphyrins with absorption and emission capabilities in the third near‐infrared region (NIR‐III) is described. Symmetry alteration of the frontier molecular orbitals (MOs) of bis‐Pd^II and bis‐Pt^II complexes of hexaphyrin via N‐confusion modification led to substantial metal d_π–p_π interactions. This MO mixing, in turn, resulted in a significantly narrower HOMO–LUMO energy gap. A remarkable long‐wavelength shift of the lowest S₀→S₁ absorption beyond 1700 nm was achieved with the bis‐Pt^II complex, t ‐Pt₂‐3 . The emergence of photoacoustic (PA) signals maximized at 1700 nm makes t ‐Pt₂‐3 potentially useful as a NIR‐III PA contrast agent. The rigid bis‐Pd^II complexes, t ‐Pd₂‐3 and c ‐Pd₂‐3 , are rare examples of NIR emitters beyond 1500 nm. The current study provides new insight into the design of stable, expanded porphyrinic dyes possessing NIR‐III‐emissive and photoacoustic‐response capabilities.     

Switching of Redox Properties Triggered by a Thermal Equilibrium between Closed‐Shell Folded and Open‐Shell Twisted Species

Thermally switchable redox properties have been reported to be due to a change in the spin state of newly designed overcrowded ethylenes, which can adopt closed‐shell folded and open‐shell twisted forms. In this study, tetrathienylanthraquinodimethane derivatives were designed to be in thermal equilibrium between a more stable folded form and less stable but more donating twisted diradical in solution, so that the oxidation potential can be controlled by heating/cooling. This is the first example of a switching of redox properties based on a thermally equilibrated twisted diradical, which can be more readily oxidized to the twisted dication.     

C1 Oxidation/C2 Reduction Isomerization of Unprotected Aldoses Induced by Light/Ketone

Unprotected aldoses in water undergo an isomerization reaction via a radical pathway when irradiated with light in the presence of water‐soluble benzophenone. Whereas its anomeric carbon (C1) is oxidized to a carboxy group, the hydroxy group on the C2 carbon is replaced by hydrogen. The generated 2‐deoxy lactones are readily reduced to the corresponding 2‐deoxy aldoses, which are often contained in bioactive compounds.     

N‐Methylated Peptide Synthesis via Generation of an Acyl N‐Methylimidazolium Cation Accelerated by a Brønsted Acid

The development of a robust amide‐bond formation remains a critical aspect of N‐methylated peptide synthesis. In this study, we synthesized a variety of dipeptides in high yields, without severe racemization, from equivalent amounts of amino acids. Highly reactive N‐methylimidazolium cation species were generated in situ to accelerate the amidation. The key to success was the addition of a strong Brønsted acid. The developed amidation enabled the synthesis of a bulky peptide with a higher yield in a shorter amount of time compared with the results of conventional amidation. In addition, the amidation can be performed by using either a microflow reactor or a conventional flask. The first total synthesis of naturally occurring bulky N‐methylated peptides, pterulamides I–IV, was achieved. Based on experimental results and theoretical calculations, we speculated that a Brønsted acid would accelerate the rate‐limiting generation of acyl imidazolium cations from mixed carbonic anhydrides.