Porphyrin-Polyoxotungstate Molecular Hybrid as a Highly Efficient, Durable, Visible-Light-Responsive Photocatalyst for Aerobic Oxidation Reactions.

Organic-polyoxometalate (POM) hybrids have recently attracted considerable interest because of their distinctive properties and wide-ranging applications. For the construction of organic-POM hybrids, porphyrins are promising building units owing to their optical properties and reactivity, including strong visible-light absorption and subsequent singlet-oxygen (O*) generation. However, the practical utilization of porphyrins as photocatalysts and photosensitizers is often hindered by their own degradation by O*.

Chiroptical Response Inversion and Enhancement of Room-Temperature Exciton-Polaritons Using 2D Chirality in Perovskites.

Although chiral semiconductors have shown promising progress in direct circularly polarized light (CPL) detection and emission, they still face potential challenges. A chirality-switching mechanism or approach integrating two enantiomers is needed to discriminate the handedness of a given CPL; additionally, a large material volume is required for sufficient chiroptical interaction. These two requirements pose significant obstacles to the simplification and miniaturization of the devices.

Better Peptides via Chemical Glycosylation: Somatostatin Analogues Having a Human Complex-Type N-Glycan with Improved Drug Properties.

Somatostatin (somatotropin release-inhibiting factor, SRIF) is a growth hormone inhibitory factor in the form of a 14- or 28-amino acid peptide. SRIF affects several physiological functions through its action on five distinct SRIF receptor subtypes (sst1-5). Native SRIF has only limited clinical applications due to its rapid degradation in plasma.

Two-photon, red light uncaging of alkyl radicals from organorhodium(III) phthalocyanine complexes.

A stepwise two-photon, red light excitation of organorhodium(III) phthalocyanine complexes was found to induce the activation of the axial metal-carbon bond to generate alkyl radicals/aldehydes. The cooperative action of the photouncaging reaction and the photochemical generation of reactive oxygen species were indicated to induce the cell deaths.

Organic deliquescence: organic vapor-induced dissolution of molecular salts.

This report demonstrates organic vapor-induced dissolution of several molecular salts (, organic deliquescence), like water vapor-induced deliquescence. Systematic experiments indicate that appropriate organic deliquescent responses to volatile organic compounds can be designed according to the principle, "like dissolves like". The phenomena will be useful for developing agents to collect various volatile organic compounds.

A Newly Developed Aerosol Exposure Apparatus for Heated Tobacco Products for In Vivo Experiments Can Deliver Both Particles and Gas Phase With High Recovery and Depicts the Time-Dependent Variation in Nicotine Metabolites in Mouse Urine.

Introduction: There is no standardized aerosol exposure apparatus to deliver heated tobacco products (HTPs) for in vivo experiments. Therefore, we developed a novel HTPs aerosol exposure apparatus for mice and demonstrated that nicotine and other chemicals in HTPs aerosol generated by the apparatus can be delivered to mice which replicate human smoke.

Aims And Methods: The amounts of nicotine, tar, and carbon monoxide (CO) in IQOS (Marlboro Regular HeatSticks) aerosol generated by two types of apparatuses were determined.

Chiral Induction in Buckminsterfullerene Using a Metal-Organic Framework.

Chiral induction is an emerging topic of interest in various areas of chemistry because of its relationship to the elusive mechanism of spontaneous symmetry breaking in nature. Buckminsterfullerene (C ) with the shape of a highly symmetric truncated icosahedron has rarely been referred for chiral induction due to the difficult symmetry breaking. In this work, we demonstrate that a chiral metal-organic framework (MOF) can provide a key field for chiral induction.

Distorted Porphyrins with High Stability: Synthesis and Characteristic Electronic Properties of Mono- and Di-Nuclear Tricarbonyl Rhenium Tetraazaporphyrin Complexes.

Mono- and di-nuclear tricarbonyl Re(I) tetraazaporphyrin complexes (Re TAP and Re TAP) are investigated and compared with Re(I) phthalocyanine complexes (Re Pc and Re Pc). Although Re Pc is unstable in polar solvents, and easily undergoes demetallation reaction, the coordination of the TAP ligand significantly improves the tolerance toward polar solvents, affording more stability to Re TAP. Additionally, the incorporation of [Re(CO) ] unit(s) and the TAP ligand results in remarkable positive shifts in both oxidation and reduction potentials.

No evidence for genotoxicity in mice due to exposure to intermediate-frequency magnetic fields used for wireless power-transfer systems.

Time varying magnetic fields (MFs) are used for the wireless power-transfer (WPT) technology. Especially, 85 kHz band MFs, which are included in the intermediate frequency (IF) band (300 Hz - 10 MHz), are commonly used WPT system for charging electric vehicles. Those applications of WPT technology have elicited public concern about health effects of IF-MF.

Vortex-Induced Harmonic Light Scattering of Porphyrin J-Aggregates.

An understanding of macroscopic vortex-induced chirality can provide insights into the origin of the homochirality of life. While circular dichroism measurements in stirred solutions are useful for the analysis of chiral supramolecular structures induced by vortex motion, there are no reports on the application of other spectroscopic methods. To obtain a deeper understanding of macroscopic vortex-induced chirality, it is essential to develop novel spectroscopic methods that provide information about changes in both the size and chirality in stirred solutions.

Recurrent Cerebral Venous Thrombosis Treated with Direct Oral Anticoagulants in a Japanese Man with Hereditary Protein C Deficiency.

We herein report a case involving a 32-year-old Japanese man with recurrent cerebral venous thrombosis due to hereditary protein C deficiency. He was admitted to our hospital with impaired consciousness. Brain magnetic resonance imaging demonstrated high intensities diffusely along the bilateral sulci and magnetic resonance venography revealed left transverse sinus and superior sagittal sinus stenoses.

Novel method for preparing stable near-infrared absorbers: a new phthalocyanine family based on rhenium(i) complexes.

Rational design of near-infrared (NIR) absorbing molecules is crucial for developing photofunctional materials. Here, we synthesized dinuclear and mononuclear Re(i) tricarbonyl phthalocyanine complexes that exhibit a sharp intense Q band in the NIR region. The unsymmetric coordination of electron-deficient metal unit(s) concomitantly produced a remarkable red shift of the Q band and improved the tolerance of the phthalocyanine ring to oxidation.

Direct Observation of the S → T Transition in Phosphorescent Platinum(II) Octaethylporphyrin, Evidenced by Magnetic Circular Dichroism.

In recent years, the importance of analyzing excited triplet states has increased dramatically because of their relevance in the design and development of photofunctional molecules. Since the second lowest excited triplet (T) state plays an important role in enhancing the nonradiative intersystem crossing (ISC) process from the lowest excited singlet (S) state to the lowest excited triplet (T) state, it is strongly desired to develop direct observation methods for the nonluminescent, short-lived T state. In this study, the excited triplet states of platinum(II) octaethylporphyrin (PtOEP), which was used as the first phosphorescent organic light emitting diode and oxygen sensor, are investigated using UV-vis absorption, magnetic circular dichroism, and phosphorescence spectroscopies.

Recent advances in studies on the magneto-chiral dichroism of organic compounds.

Magneto-chiral dichroism (MChD) is an interesting phenomenon in which the absorbance of a chiral molecule depends on the direction of the magnetic field. As the MChD of two enantiomers is opposite in nature, MChD has received considerable attention for the development of magneto-optical devices and new asymmetric synthetic methods, as well as being an explanation for the origin of the homochirality of life. In this perspective, the theoretical background behind MChD is introduced, and then, the first examples of metal complexes and aromatic π-conjugated systems are discussed.

Transcription of Chirality from Metal-Organic Framework to Polythiophene.

Here, we report an unprecedented chirality transfer from a metal-organic framework (MOF) to a polymer. In this work, unsubstituted polythiophene (PTh) was prepared in the nanochannels of a chiral MOF. Circular dichroism spectroscopy revealed that nanoconfinement of the polymer chains could endow optically inactive PTh with a chiral nature.

Chiral Supramolecular Nanoarchitectures from Macroscopic Mechanical Rotations: Effects on Enantioselective Aggregation Behavior of Phthalocyanines.

Fluid dynamics, resulting from the macroscopic mechanical rotation of either a rotary evaporator or a magnetic stirrer, has been shown to selectively induce one of two enantiomers (mirror-image structures) in certain nanoscale supramolecules. As an alternative to giving a chiral twist to synthesized supramolecules or polymers, it is a challenge to reproducibly prepare chiral species by only using macroscopic mechanical rotations. Demonstrated here is a highly reproducible method for rotary-evaporation-induced enantioselective H-aggregation of achiral phthalocyanines.

Differential oxidation processes of peroxiredoxin 2 dependent on the reaction with several peroxides in human red blood cells.

Peroxiredoxins (Prxs) detoxify hydrogen peroxide (HO), peroxynitrite, and various organic hydroperoxides. However, the differential oxidative status of Prxs reacted with each peroxide remains unclear. In the present study, we focused on the oxidative alteration of Prxs and demonstrated that, in human red blood cells (RBCs), peroxiredoxin 2 (Prx2) is readily reactive with HO, forming disulfide dimers, but was not easily hyperoxidized.

Molecular ground-state dissociation in the condensed phase employing plasmonic field enhancement of chirped mid-infrared pulses.

Selective bond cleavage via vibrational excitation is the key to active control over molecular reactions. Despite its great potential, the practical implementation in condensed phases have been hampered to date by poor excitation efficiency due to fast vibrational relaxation. Here we demonstrate vibrationally mediated, condensed-phase molecular dissociation by employing intense plasmonic near-fields of temporally-shaped mid-infrared (mid-IR) pulses.

Global Analysis of Transcriptional Expression in Mice Exposed to Intermediate Frequency Magnetic Fields Utilized for Wireless Power Transfer Systems.

Background: Intermediate frequency magnetic fields (IF-MFs) at around 85 kHz are a component of wireless power transfer systems used for charging electrical vehicles. However, limited data exist on the potential health effects of IF-MFs. We performed a comprehensive analysis of transcriptional expression in mice after IF-MF exposure.

Molecular Power Spring: Circular Dichroism Inversion of Polythiophene Aggregates from the Right-Handed Helix to Left-Handed Helix.

In molecular rotors, a type of molecular machine, spontaneous rotors without the need for an external stimulus are promising because conventional molecular rotors require a continuous energy supply. In this study, we demonstrate spontaneous transformation from kinetically favored metastable right-handed helical aggregates to thermodynamically stable left-handed helical aggregates after an evaporation procedure. In addition, we propose the conditions for preparation of metastable right-handed helical aggregates, whose chirality can be spontaneously inverted, based on kinetic analysis.

Soft Crystals: Flexible Response Systems with High Structural Order.

A new material concept of soft crystals is proposed. Soft crystals respond to gentle stimuli such as vapor exposure and rubbing but maintain their structural order and exhibit remarkable visual changes in their shape, color, and luminescence. Various interesting examples of soft crystals are introduced in the article.

Whole-cell circular dichroism difference spectroscopy reveals an in vivo-specific deca-heme conformation in bacterial surface cytochromes.

We established whole-cell circular dichroism difference spectroscopy to identify the inter-heme interaction in deca-heme cytochrome protein MtrC in whole cell. Our data showed that the heme alignment of reduced MtrC in whole cell is distinct from that in purified one, suggesting the in vivo specific electron transport kinetics.

Spiral Eu(iii) coordination polymers with circularly polarized luminescence.

A spiral-type chiral Eu(iii) coordination polymer showed strong luminescence (emission quantum yield Φf-f = 57% and photosensitized energy transfer efficiency ηsens = 53%) and effective CD and CPL properties (gCPL = 0.17) when compared with a mono-nuclear chiral Eu(iii) complex in the solid state (Φf-f = 36%, ηsens = 14%, and gCPL = 0.09).

Pulsed laser induced heat transfer from a phthalocyanine-based thin film to a Bi, Al-substituted DyIG substrate: photothermal demagnetization observed by magnetic circular dichroism and numerical analysis.

We have investigated the demagnetization of a ferrimagnetic substrate, Bi, Al-substituted dysprosium iron garnet (Bi0.8Dy2.2Fe4.