We have developed photocatalytic oxidation of aromatic substrates using O as a terminal oxidant to afford only 2e-oxidized products without the reductive activation of O in acidic water under visible-light irradiation. A Ru complex () bearing a pyrazine moiety as the active site in tetrapyrido[3,2-:2',3'-:3″,2″-:2‴,3‴-]phenazine (tpphz) as a ligand was employed as a photocatalyst. The active species for the photocatalysis was revealed to be not complex itself but the protonated form, -H, protonated at the vacant diimine site of tpphz.
View Article and Find Full Text PDFA sequential process via photoredox catalysis and Lewis acid mediation for C-F bond transformation of the CF unit in perfluoroalkyl groups has been achieved to transform perfluoroalkylarenes into complex fluoroalkylated compounds. A phenothiazine-based photocatalyst promotes the defluoroaminoxylation of perfluoroalkylarenes with (2,2,6,6-tetramethylpiperidin-1-yl)oxyl (TEMPO) under visible light irradiation, affording the corresponding aminoxylated products. These products undergo a further defluorinative transformation with various organosilicon reagents mediated by AlCl to provide highly functionalized perfluoroalkyl alcohols.
View Article and Find Full Text PDFPhotochem Photobiol Sci
February 2024
Radiation detection plays an important role in diverse applications, including medical imaging, security, and display technologies. Scintillators, materials that emit light upon exposure to radiation, have garnered significant attention due to their exceptional sensitivity. Previous research explored polymer dots (P-dots) doped with iridium complexes as nano-sized scintillators for radiation detection, but these were constrained to emitting specific colors like red, green, and blue, limiting their utility.
View Article and Find Full Text PDFWe demonstrate that polymer dots doped with thermally activated delayed fluorescence (TADF) molecules clearly exhibit blue radio-luminescence upon hard X-ray and electron beam irradiation, which is a new design for nano-sized scintillators.
View Article and Find Full Text PDFIn this study, we synthesized radioexcitable luminescent polymer dots (P-dots) doped with heteroleptic tris-cyclometalated iridium complexes that emit red, green, and blue light. We investigated the luminescence properties of these P-dots under X-ray and electron beam irradiation, revealing their potential as new organic scintillators.
View Article and Find Full Text PDFNitric oxide (NO) is a signaling molecule that plays a variety of functions in the human body, but it is difficult to use it in biological experiments or for therapeutic purposes because of its high reactivity and instability in the biological milieu. Consequently, photocontrollable NO releasers, which enable spatiotemporal control of NO release, have an important role in elucidating the functions of NO. Our group has developed visible-light-controllable NO-releasing molecules that contain a fluorescent dye structure as a light-harvesting antenna moiety and an -nitrosoaminophenol structure as an NO-releasing moiety.
View Article and Find Full Text PDFPorphyrin covalent organic nanodisks (CONs) were synthesized by exfoliating covalent organic frameworks (COFs) in acidic aqueous solutions at pH 4. The synthesized CONs showed remarkable bactericidal activity against owing to enhanced generation of singlet oxygen upon visible light irradiation.
View Article and Find Full Text PDFPhotosensitizers (PSs) are critical substances with considerable potential for use in non-invasive photomedicine. Type I PSs, which generate reactive radical species by electron transfer from the excited state induced via photoirradiation, attracted much attention because of their suitability for photodynamic therapy (PDT) irrespective of the oxygen concentration. However, most organic PSs are type II, which activates only oxygen, generating singlet oxygen (O) via energy transfer from the triplet state.
View Article and Find Full Text PDFWe report the aggregation-induced photosensitizing activity of a cyanine dye in water and the mechanism. In addition, using the supramolecular assembly, visible-light-driven photooxidation of hydrophobic aromatic compounds in water was successfully performed.
View Article and Find Full Text PDFThe development of photocatalysts is an essential task for clean energy generation and establishing a sustainable society. This paper describes the aggregation-induced photocatalytic activity (AI-PCA) of amphiphilic rhodamines and photocatalytic functions of the supramolecular assemblies. The supramolecular assemblies consisting of amphiphilic rhodamines with octadecyl alkyl chains exhibited significant photocatalytic activity under visible light irradiation in water, while the corresponding monomeric rhodamines did not exhibit photocatalytic activity.
View Article and Find Full Text PDFHard X-ray excited optical luminescence is a unique property of materials, which makes them promising for biological imaging applications. However, the preparation of biocompatible contrast agents for hard X-ray excited optical luminescence remains a considerable challenge that has, to date, not been overcome. In this study, we investigated the luminescence properties of protein-directed Au clusters upon hard X-ray irradiation, both in solution and when embedded in films.
View Article and Find Full Text PDFOptical manipulation of cellular function is one of the important targets in chemical biology and medicine. To achieve manipulation of cellular function using small molecules, photochemical reaction, such as photo-isomerization and photo-induced electron transfer, is one of the most promising reactions. Especially, photo-induced electron transfer process may be the crucial for their further development of photo-functional agents in living cells.
View Article and Find Full Text PDFFluorescence photoswitching using nanomaterials has recently emerged as a promising approach for the imaging of biological targets. However, despite intensive research efforts during the last decade, practical microscopy of biological targets using photoswitchable nanoparticles in real time remains challenging. To address this problem, we have developed live macrophage cell imaging and single particle imaging methods, using photoswitchable fluorescent diarylethene-doped polymer nanoparticles (P-dots) under Xe lamp irradiation.
View Article and Find Full Text PDFYakugaku Zasshi
December 2016
X-rays are widely used in imaging applications such as diffraction imaging of crystals and medical imaging. In particular, X-ray computed tomography (CT) is a critical tool for clinical and disease diagnostics. The principle of conventional CT is based on X-ray attenuation caused by photoelectric absorption and scattering.
View Article and Find Full Text PDFIntracellular recording of action potentials is important to understand electrically-excitable cells. Recently, vertical nanoelectrodes have been developed to achieve highly sensitive, minimally invasive and large-scale intracellular recording. It has been demonstrated that the vertical geometry is crucial for the enhanced signal detection.
View Article and Find Full Text PDFHere, we demonstrate that biomolecule-directed metal clusters are applicable in the study of hard X-ray excited optical luminescence, promising a new direction in the development of novel X-ray-activated imaging probes.
View Article and Find Full Text PDFRetrograde trophic signaling of nerve growth factor (NGF) supports neuronal survival and differentiation. Dysregulated trophic signaling could lead to various neurological disorders. Charcot-Marie-Tooth type 2B (CMT2B) is one of the most common inherited peripheral neuropathies characterized by severe terminal axonal loss.
View Article and Find Full Text PDFIn this study, cyclometalated iridium(III) complex-doped polymer dots were synthesized and shown to emit luminescence upon X-ray irradiation, potentially serving as a new probe for molecular imaging during X-ray computed tomography.
View Article and Find Full Text PDFChem Commun (Camb)
April 2012
The photochromic molecule diarylethene works as a "toggle switch" for biocompatible fluorescence polymer dots and enables fluorescence switching in biological samples.
View Article and Find Full Text PDFThe normal function of neurons depends on the integrity of microtubule-dependent transport of cellular materials and organelles to/from their cell bodies or axon terminus. In this chapter, we describe the design and implementation of a fluorescence imaging method to visualize axonal transport in neurons directly. We combine a pseudo total internal reflection microscopy, quantum dot fluorescence labeling, microfluidic neuronal culture chamber, and single molecule detection methods to achieve a high spatial and temporal resolution in tracking nerve growth factor transport in dorsal root ganglia neurons.
View Article and Find Full Text PDFThe dynamics of cargo movement in axons encodes crucial information about the underlying regulatory mechanisms of the axonal transport process in neurons, a central problem in understanding many neurodegenerative diseases. Quantitative analysis of cargo dynamics in axons usually includes three steps: (1) acquiring time-lapse image series, (2) localizing individual cargos at each time step, and (3) constructing dynamic trajectories for kinetic analysis. Currently, the later two steps are usually carried out with substantial human intervention.
View Article and Find Full Text PDFCharge-separation and charge-recombination dynamics and oxidative DNA degradation were investigated for DNA modified with a photosensitizer (Sens) naphthalimide (NI), naphthaldiimide (ND), or anthraquinone (AQ). In all three Sens-modified DNA systems, the formation of long-lived charge-separated states was observed in which the lifetime increased with increasing numbers of A-T base pairs between Sens and the neighboring G-C base pair. The lifetime of the charge-separated state correlated well with the DNA damage yield, indicating that the charge-separated state provides time for the irreversible DNA oxidative damage to occur.
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