Synthesis of Diverse Aromatic Ketones through C−F Cleavage of Trifluoromethyl Group

An efficient synthetic method of aromatic ketones through C−F cleavage of trifluoromethyl group is disclosed. The high functional group tolerance of the transformation and the remarkable stability of trifluoromethyl group in various reactions enabled multi-substituted aromatic ketone synthesis in an efficient route involving useful transformations such as ortho-lithiation, aryne chemistry, and cross-couplings.     

Spectral and temporal optical signal generation using randomly distributed quantum dots

Optical Review - Quantum dots (QDs) have a great potential for realizing information processing because of their signal-modulation capability based on energy transfer. We present a method for...     

Highly polarized very cold neutrons through a permanent magnet quadrupole

We obtained highly polarized very cold neutrons through a quadrupole magnet with a large aperture. When neutrons go through a quadrupole magnet, parallel-spin neutrons are attracted to the magnet axis and anti-parallel-spin neutrons are repelled off the axis. Therefore, the neutrons through a sufficiently long quadrupole magnet have completely parallel-spin. At the downstream of the quadrupole magnet, we placed another quadrupole magnet to divide neutrons into two regions depending on their spin directions. We obtained the neutron polarization from the integrated count of the two regions and found it was 99.88±0.09 (stat.)±0.05 (syst.)%.     

Single C−F Bond Cleavage of Trifluoromethylarenes with an ortho‐Silyl Group

The transformation of a single C−F bond of trifluoromethylarenes bearing a hydrosilyl group at the ortho position was achieved. The activation of the hydrosilyl group with a trityl cation in the presence of nucleophiles allowed for selective C−F bond functionalization, for example, by allylation, carboxylation, or chlorination. Further derivatization of the resulting fluorosilylarenes afforded various aromatic difluoromethylene compounds.     

Magnetic hyperfine interaction of 59Fe in nickel

Nuclear magnetic resonance on oriented nuclei (NMR-ON) on ⁵⁹Fe isotope in Ni was performed. The magnetic hyperfine splitting frequency of was determined to be ν(B ₀?=?0)?=?48.32 (2) MHz. Using the known magnetic moment the magnetic hyperfine field was deduced as B _HF?=???28.32 (5) T. The effective nuclear spin-lattice relaxation time was also measured. The measured value is compared with experimental values of 3d-impurity in nickel host.     

Photodegradation of environmental mutagens by visible irradiation in the presence of xanthene dyes as photosensitizers

The photodegradation of environmental mutagens, such as 3-amino-1,4-dimethyl-5H-pyrido[4,3-b]indole (Trp-P-1), 3-amino-1-methyl-5H-pyrido[4,3-b]indole (Trp-P-2), 2-amino-3-methyl-9H-pyrido[2,3-b]indole (MeAαC), and 2-amino-3-methyl-imidazo[4,5-f]quinoline (IQ), was investigated by visible irradiation in the presence of xanthene dyes as photosensitizers. Although the environmental mutagens themselves were very stable during visible irradiation under the conditions in this study, they were effectively photodegraded in the presence of the xanthene dyes (erythrosine, rose bengal, and phloxine). Moreover, photodegradation of the mutagens was further enhanced for xanthene dyes loaded onto a water-soluble diethylaminoethyl (DEAE)-dextran anion-exchanger via ionic interactions (xanthene-dyeDEX). Photodegradation was inhibited by O2 removal from the reaction solution. In ESR spin-trapping experiments using 5,5-dimethyl-1-pyrroline-N-oxide (DMPO) as a trapping reagent, signals characteristic of DMPO-?OH (hydroxyl radical) were observed in the presence of xanthene-dyeDEX. These results suggest that reactive oxygen species derived from O2, such as singlet molecular oxygen (?1O2) and/or ?OH, were active participants in photodegradation of the mutagens in the presence of xanthene dyes or xanthene-dyeDEX.     

Development of a highly specific rhodamine-based fluorescence probe for hypochlorous acid and its application to real-time imaging of phagocytosis

The tetramethylrhodamine (TMR) fluorophore is a useful platform for fluorescence probes, being applicable, for example, to biological investigations utilizing fluorescence microscopy, owing to its excellent photochemical properties in aqueous media. We have developed new TMR derivatives that show different dependences of their behavior upon the environment. Among them, HMTMR showed unique characteristics, and its putative spirocyclic structure was confirmed by X-ray crystallography. Utilizing this discovery, we have established a strategy to modulate the fluorescence of TMR by regulating the spirocyclization, and we have obtained a new fluorescence probe that can detect hypochlorous acid specifically. This probe, HySOx, can work in 99.9% aqueous solution at pH 7.4 and was confirmed to be able to detect hypochlorous acid being generated inside phagosomes in real time. HySOx is tolerant to autoxidation and photobleaching under bioimaging conditions. Regulation of the spirocyclization of rhodamines, as we describe here, provides a new approach to the rational development of novel fluorescence probes.     

Femtosecond laser modification of living neuronal network

An all-wet femtosecond laser microprocessing technique was utilized for patterning and cutting functional network of living neuronal cells on a multi-electrode dish (MED). The neuronal cells cultured on a source substrate were transferred onto an electrode in a MED probe in solution by utilizing a femtosecond laser-induced impulsive force and a pattern of neuronal cells were formed on the MED probe. The cellular activity of the detached neurons was supported that neurites could be regenerated around the electrodes. As another processing method, the neurons stretching between electrodes were selectively cut by the direct femtosecond laser irradiation and the spontaneous electrical activity of the neuronal network was evaluated. While the spontaneous action potentials of neurons were synchronized before the cutting, the synchronization disappeared after the cutting, indicating that the neuronal network is locally disconnected by the laser cutting. The present method is applicable to artificial reconstruction of living neuronal network.     

Relationship between third-order nonlinear optical properties and magnetic interactions in open-shell systems: a new paradigm for nonlinear optics

Although most third-order nonlinear optical (NLO) materials are closed-shell singlet systems, this Letter theoretically shows that the third-order NLO properties are drastically enhanced in symmetric open-shell diradical systems with intermediate diradical character and further reveals that this enhancement is associated with the ferromagnetic and antiferromagnetic interactions. This new paradigm opens up a promising area for designing new third-order NLO materials.