Photochemical transformations of glycosyl bromides in the presence of amines.

Photochemical transformations of glycosyl bromides are investigated in the presence of amines. The choice of amines such as N,N-diisopropylethylamine and triphenylamine was found to be critical for product selectivity. Alkylation and alkenylation of anomeric carbon with 1,1-diphenylethene could be realized.

Temperature-Dependent Photoreactivity of 2-Azidomethylbenzophenone: Insights into the Triplet Imine Biradical Pathway.

Photoenols, formed through photoinduced intramolecular H atom abstraction in -alkyl-substituted arylketones, typically have limited utility as reactive intermediates owing to fast reversion to the starting material. Herein, we introduced an azido group on the -alkyl substituent to render the photoreaction irreversible. Irradiation of 2-azidomethylbenzophenone () in methanol yielded 2-(hydroxy(phenyl)methyl)benzonitrile ().

Design, Synthesis, and Biological Evaluation of BODIPY-Caged Resiquimod as a Dual-Acting Phototherapeutic.

Resiquimod, an imidazoquinoline scaffold, exhibits potent immunotherapeutic activity but is associated with off-target effects, limiting its clinical utility. To address this limitation, we developed a novel BODIPY-caged resiquimod that is responsive to red light, combining photocaging and photodynamic therapy functionalities. Molecular docking studies guided identification of the optimal caging site for resiquimod, effectively masking its immune activity.

The microcephaly-associated transcriptional regulator AUTS2 cooperates with Polycomb complex PRC2 to produce upper-layer neurons in mice.

AUTS2 syndrome is characterized by intellectual disability and microcephaly, and is often associated with autism spectrum disorder, but the underlying mechanisms, particularly concerning microcephaly, remain incompletely understood. Here, we analyze mice mutated for the transcriptional regulator AUTS2, which recapitulate microcephaly. Their brains exhibit reduced division of intermediate progenitor cells (IPCs), leading to fewer neurons and decreased thickness in the upper-layer cortex.

Central amygdala NPBWR1 neurons facilitate social novelty seeking and new social interactions.

The formation of new social interactions is vital for social animals, but the underlying neural mechanisms remain poorly understood. We identified CeA neurons, a population in central amygdala expressing neuropeptide B/W receptor-1 (NPBWR1), that play a critical role in these interactions. CeA neurons were activated during encounters with unfamiliar, but not with familiar, mice.

Influence of Curvature on the Physical Properties and Reactivity of Triplet Corannulene Nitrene.

Although nitrene chemistry is promising for the light-induced modification of organic compounds, the reactivity of large polycyclic aromatic compounds and the effects of their curvature remain unexplored. Irradiation of azidocorannulene () in methanol/acetonitrile followed by HCl addition produced diastereomers and . Azirine is apparently trapped by methanol to form diastereomeric acetal derivatives that are hydrolyzed with HCl to yield and '.

Impact of Transition-State Aromaticity on Selective Radical-Radical Coupling of Triarylimidazolyl Radicals.

Radical coupling reactions are generally known to have a low selectivity due to the high reactivity of radicals. In this study, high regio and substrate selectivity was discovered in the dimerization of triarylimidazolyl radicals (), a versatile photochromic reaction. When two different radicals, 2-(4-cyanophenyl)-4,5-diphenyl-1-imidazolyl radical () and 2-(4-methoxyphenyl)-4,5-diphenyl-1-imidazolyl radical (), were simultaneously generated in situ, a hexaarylbiimidazole, formed by selective coupling at the nitrogen atom at position 1 of and the carbon atom at position 2 of , was isolated with high selectivity as the main product among 24 possible radical dimer hexaarylbiimidazole derivatives.

Design and synthesis of a 2,5-Diarylthiophene chromophore for enhanced near-infrared two-photon uncaging efficiency of calcium ions.

The design and synthesis of two-photon-responsive chromophores have recently garnered significant attention owing to their potential applications in materials and life sciences. In this study, a novel π-conjugated system, 2-dimethylaminophenyl-5-nitrophenylthiophene derivatives, featuring a thiophene unit as the π-linker between the donor (NMeCH-) and acceptor (NOCH-) units was designed, synthesized, and applied for the development of two-photon-responsive chromophores as a photoremovable protecting group in the near-infrared region. Notably, the positional effect of the nitro group (NO), meta versus para position, was observed in the uncaging process of benzoic acid.

Generation of rat offspring from ovarian oocytes by xenotransplantation.

The idea of utilizing unused oocytes present in the ovaries has been tested in various ways to produce offspring. However, only a limited number of studies succeeded in offspring generation. They include transplantation of ovaries into autologous or allogeneic animals, and acquisition of pups from oocytes obtained by transplanting mouse ovaries into immunodeficient rats.

PCPE-1, a brown adipose tissue-derived cytokine, promotes obesity-induced liver fibrosis.

Metabolic dysfunction-associated steatohepatitis (MASH, previously termed non-alcoholic steatohepatitis (NASH)), is a major complication of obesity that promotes fatty liver disease. MASH is characterized by progressive tissue fibrosis and sterile liver inflammation that can lead to liver cirrhosis, cancer, and death. The molecular mechanisms of fibrosis in MASH and its systemic control remain poorly understood.

Organophotocatalytic access to -glycosides: multicomponent coupling reactions using glycosyl bromides.

Photochemical multi-component coupling reactions initiated by the activation of glycosyl bromides in the presence of 1,4-bis(diphenylamino)benzene (BDB) as an organic photocatalyst were developed. -glycosides accompanied by olefin (di)functionalization were obtained. This method allows us to access various -glycosides with alkene, carbonyl, alcohol, ether, and amide functionalities.

The role of CRMP4 in LPS-induced neuroinflammation.

Neuroinflammation has been gaining attention as one of the potential causes of neurodegenerative diseases such as Alzheimer's disease, Parkinson's disease, and amyotrophic lateral sclerosis in recent years. The suppression of excessive proinflammatory responses is expected to be a target for the treatment and prevention of neurodegenerative diseases. Collapsin response mediator protein 4 (CRMP4) is involved in cytoskeleton-associated axonal guidance in the developing brain.

α-Cleavage of 2,2-Diazido-2,3-dihydroinden-1-one in Solution and Cryogenic Matrices.

The Norrish type I (α-cleavage) reaction is an excellent photochemical method for radical-pair formation in solution. However, in cryogenic matrices, the starting material typically re-forms before the radical pair diffuses apart. This study focused on N extrusion from an azido alkyl radical to prevent radical-pair recombination.

Optochemical control of slow-wave sleep in the nucleus accumbens of male mice by a photoactivatable allosteric modulator of adenosine A receptors.

Optochemistry, an emerging pharmacologic approach in which light is used to selectively activate or deactivate molecules, has the potential to alleviate symptoms, cure diseases, and improve quality of life while preventing uncontrolled drug effects. The development of in-vivo applications for optochemistry to render brain cells photoresponsive without relying on genetic engineering has been progressing slowly. The nucleus accumbens (NAc) is a region for the regulation of slow-wave sleep (SWS) through the integration of motivational stimuli.

Generation and characterization of cerebellar granule neurons specific knockout mice of Golli-MBP.

Golli-myelin basic proteins, encoded by the myelin basic protein gene, are widely expressed in neurons and oligodendrocytes in the central nervous system. Further, prior research has shown that Golli-myelin basic protein is necessary for myelination and neuronal maturation during central nervous system development. In this study, we established Golli-myelin basic protein-floxed mice to elucidate the cell-type-specific effects of Golli-myelin basic protein knockout through the generation of conditional knockout mice (Golli-myelin basic proteins; E3CreN), in which Golli-myelin basic proteins were specifically deleted in cerebellar granule neurons, where Golli-myelin basic proteins are expressed abundantly in wild-type mice.

Temporal-Focusing Multiphoton Excitation Single-Molecule Localization Microscopy Using Spontaneously Blinking Fluorophores.

Single-molecule localization microscopy (SMLM) based on temporal-focusing multiphoton excitation (TFMPE) and single-wavelength excitation is used to visualize the three-dimensional (3D) distribution of spontaneously blinking fluorophore-labeled subcellular structures in a thick specimen with a nanoscale-level spatial resolution. To eliminate the photobleaching effect of unlocalized molecules in out-of-focus regions for improving the utilization rate of the photon budget in 3D SMLM imaging, SMLM with single-wavelength TFMPE achieves wide-field and axially confined two-photon excitation (TPE) of spontaneously blinking fluorophores. TPE spectral measurement of blinking fluorophores is then conducted through TFMPE imaging at a tunable excitation wavelength, yielding the optimal TPE wavelength for increasing the number of detected photons from a single blinking event during SMLM.

Limb-Clasping Response in NMDA Receptor Palmitoylation-Deficient Mice.

Proper regulation of N-methyl-D-aspartate-type glutamate receptor (NMDA receptor) expression is responsible for excitatory synaptic functions in the mammalian brain. NMDA receptor dysfunction can cause various neuropsychiatric disorders and neurodegenerative diseases. Posttranslational protein S-palmitoylation, the covalent attachment of palmitic acid to intracellular cysteine residues via thioester bonds, occurs in the carboxyl terminus of GluN2B, which is the major regulatory NMDA receptor subunit.

Crucial Roles of Leaving Group and Open-Shell Cation in Photoreaction of (Coumarin-4-yl)methyl Derivatives.

Photoreactions of (coumarin-4-yl)methyl derivatives have been extensively studied in many fields of chemistry, including organic synthesis and photoinduced drug delivery systems. The identification of the reaction intermediates involved in the photoreactions is crucial not only for elucidating the reaction mechanism but also for the application of the photoreactions. In this study, the photoreactions of 7-diethylamino(coumarin-4-yl)methyl thioester [-SC(O)CH], thionoester [-OC(S)CH], and ester [-OC(O)CH] were investigated to clarify the intermediary species and their chemical behavior.

Development of a Two-Photon-Responsive Chromophore, 2-(-Aminophenyl)-5,6-dimethoxy-1-(hydroxyinden-3-yl)methyl Derivative, as a Photoremovable Protecting Group.

Photoremovable protecting groups (PPGs) are powerful tools that are widely used to investigate biological events in cells. An important requirement for PPGs is the efficient release of bioactive molecules by using visible to near-infrared light in the biological window (650-1350 nm). In this study, we report a new two-photon (2P)-responsive PPG, 2-(-aminophenyl)-5,6-dimethoxy-1-(hydroxyinden-3-yl)methyl, with a donor-π-donor cyclic stilbene structure.

Behavioral analysis of kainate receptor KO mice and the role of GluK3 subunit in anxiety.

Kainate receptors (KARs) are one of the ionotropic glutamate receptors in the central nervous system (CNS) comprised of five subunits, GluK1-GluK5. There is a growing interest in the association between KARs and psychiatric disorders, and there have been several studies investigating the behavioral phenotypes of KAR deficient mice, however, the difference in the genetic background has been found to affect phenotype in multiple mouse models of human diseases. Here, we examined GluK1-5 single KO mice in a pure C57BL/6N background and identified that GluK3 KO mice specifically express anxiolytic-like behavior with an alteration in dopamine D2 receptor (D2R)-induced anxiety, and reduced D2R expression in the striatum.