Excited-State Dynamics of Non-Luminescent and Luminescent π-Radicals

Recently, the potential use of organic π-radicals and related spin systems has been expanded to modern technological applications. The unique excited-state dynamics of organic π-radicals can be useful to improve the stability of photochemically unstable organic compounds, make the polarization transfer applicable to information technology, and achieve effective up-conversion of interest for luminescence bioimaging, among others. Furthermore, highly luminescent stable π-radicals have been recently reported, which are especially interesting for application in organic light-emitting devices owing to their potential to provide an internal quantum efficiency of 100 %. Thus, the excited-state nature of stable π-radicals as well as the control of their excited-state spin dynamics are emerging topics both in terms of fundamental science and related technological applications. In this minireview, we focus on the excited-state dynamics of both photostable non(weakly)-luminescent and luminescent π-radicals, which are opposites of each other. In particular, we cover the following topics: 1) effective generation of high-spin photoexcited states and control of the excited-state dynamics by using non-luminescent π-radicals, 2) unique excited-state dynamics of luminescent π-radicals and radical excimers, and 3) applications utilizing excited-state dynamics of π-radicals.     

Opposed type double stage cell for Mbar pressure experiment with large sample volume

ABSTRACT

A new opposed type double-stage large volume cell has been developed to compress large volume samples to more than 100?GPa (Mbar) pressure. A pair of second-stage diamond anvils is introduced into the first-stage Paris–Edinburgh press. The double-stage large volume cell allows the generation of ultrahigh pressures using a large culet diameter of the second-stage diamond anvils (diameters of 0.5–1.2?mm). Pressure generation up to 131?GPa has been achieved by using the culet diameter of 0.5?mm. Sample volume of the double-stage large volume cell can be more than ～100 times larger than that of conventional Mbar experiment using a diamond anvil cell. The double-stage large volume cell has a large opening in the horizontal plane for X-ray measurements, which is particularly suited for the multi-angle energy dispersive X-ray diffraction measurement, thus opening a new way of in situ structural determinations of amorphous materials at Mbar pressures.     

Development of Sulfonic-Acid-Functionalized Mesoporous Materials: Synthesis and Catalytic Applications

Sulfonic acid based mesostructures (SAMs) have been developed in recent years and have important catalytic applications. The primary applications of these materials are in various organic synthesis reactions, such as multicomponent reactions, carbon–carbon bond couplings, protection reactions, and Fries and Beckman rearrangements. This review aims to provide an overview of the recent developments in the field of SAMs with a particular emphasis on the reaction scope and advantages of heterogeneous solid acid catalysts.     

Synthesis and radical polymerization of acrylate and methacrylate bearing an isocyanurate core with adamantyl bisurethane moieties

In this article, we report the synthesis of acrylate and methacrylate bearing an isocyanurate core with two adamantyl urethane moieties and their radical homo- and copolymerization with n-butyl methacrylate (BMA). The synthesized polyacrylate exhibits higher 5% weight loss and glass transition temperatures (T_d5 and T_g) than those of the comparative polyacrylate, synthesized from the isocyanurate-based acrylate with two hexyl urethane moieties, suggesting that the rigid adamantane core incorporated in the side chains of polymer largely contributes to increase in thermal stability of polymer. Similarly, the obtained copolymers show higher T_g values than that of homopolymer derived from BMA, leading to the synthesized monomers are useful as a comonomer to enhance thermal property of polymer.     

In silico modeling of PAX8–PPARγ fusion protein in thyroid carcinoma: influence of structural perturbation by fusion on ligand-binding affinity

Journal of Computer-Aided Molecular Design - Paired box 8 (PAX8)–peroxisome proliferator-activated receptor γ (PPARγ) rearrangement is believed to play an important role in...     

Spatial mode compensation technique using progressive phase conjugation

Optical Review - We propose a spatial mode compensation method using progressive phase conjugation (PPC) to establish a dynamic control technology for mode distribution in multi-mode fiber (MMF)....     

2‐Oxazoline Formation for Selective Chemical Labeling of 5‐Hydroxylysine

Hydroxylation of lysine, one of posttranslational modifications of proteins, generates 5‐hydroxylysine (Koh) and plays a crucial role in regulating protein functions in cellular activity. We have developed a chemical labeling method of Koh. The 1,2‐aminoalcohol moiety of Koh in synthetic peptide sequences was trapped by an alkyne‐containing benzimidate to form a 2‐oxazoline ring. An additional ammonia treatment process removed the undesirable amidine residue formed between benzimidate and lysine. During the ammonia treatment, the oxazoline residue formed at Koh mainly remained intact, and the ring opening to the amide form was observed for only part of oxazoline, indicating that the chemical labeling is amino acid selective. Azide‐substituted biotin or fluorescent dye was attached to the peptide through Huisgen cycloaddition at Koh and converted into an alkyne‐labeled oxazoline form. The Koh‐labeling assay could provide a platform to enhance proteomic research of lysine hydroxylation.     

A far-red emitting probe for unambiguous detection of mobile zinc in acidic vesicles and deep tissue

Imaging mobile zinc in acidic environments remains challenging because most small-molecule optical probes display pH-dependent fluorescence. Here we report a reaction-based sensor that detects mobile zinc unambiguously at low pH. The sensor responds reversibly and with a large dynamic range to exogenously applied Zn²⁺ in lysosomes of HeLa cells, endogenous Zn²⁺ in insulin granules of MIN6 cells, and zinc-rich mossy fiber boutons in hippocampal tissue from mice. This long-wavelength probe is compatible with the green-fluorescent protein, enabling multicolor imaging, and facilitates visualization of mossy fiber boutons at depths of >100 μm, as demonstrated by studies in live tissue employing two-photon microscopy.     

Clinical Perspectives of Theranostics

Theranostics is a precision medicine which integrates diagnostic nuclear medicine and radionuclide therapy for various cancers throughout body using suitable tracers and treatment that target specific biological pathways or receptors. This review covers traditional theranostics for thyroid cancer and pheochromocytoma with radioiodine compounds. In addition, recent theranostics of radioimmunotherapy for non-Hodgkin lymphoma, and treatment of bone metastasis using bone seeking radiopharmaceuticals are described. Furthermore, new radiopharmaceuticals for prostatic cancer and pancreatic cancer have been added. Of particular, F-18 Fluoro-2-Deoxyglucose (FDG) Positron Emission Tomography (PET) is often used for treatment monitoring and estimating patient outcome. A recent clinical study highlighted the ability of alpha-radiotherapy with high linear energy transfer (LET) to overcome treatment resistance to beta--particle therapy. Theranostics will become an ever-increasing part of clinical nuclear medicine.