Language：English   Publishing type：Research paper (scientific journal)   Publisher：Springer Science and Business Media LLC  

Abstract

Photoremovable protecting groups (PPGs) represent one of the main contemporary implementations of photochemistry in diverse fields of research and practical applications. For the past half century, organic and metal-complex PPGs were considered mutually exclusive classes, each of which provided unique sets of physical and chemical properties thanks to their distinctive structures. Here, we introduce the meso-methylporphyrin group as a prototype hybrid-class PPG that unites traditionally exclusive elements of organic and metal-complex PPGs within a single structure. We show that the porphyrin scaffold allows extensive modularity by functional separation of the metal-binding chromophore and up to four sites of leaving group release. The insertion of metal ions can be used to tune their spectroscopic, photochemical, and biological properties. We provide a detailed description of the photoreaction mechanism studied by steady-state and transient absorption spectroscopies and quantum-chemical calculations. Our approach applied herein could facilitate access to a hitherto untapped chemical space of potential PPG scaffolds.

DOI： 10.1038/s41467-022-31288-2

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Other Link： https://www.nature.com/articles/s41467-022-31288-2

Language：English   Publishing type：Research paper (scientific journal)  

DOI： 10.1021/acs.orglett.7b00957

Language：English   Publishing type：Research paper (scientific journal)   Publisher：Springer Science and Business Media LLC  

Abstract

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. Adenosine emerges as a promising candidate molecule for activating indirect pathway neurons of the NAc expressing adenosine A_2A receptors (A_2ARs) to induce SWS. Here, we developed a brain-permeable positive allosteric modulator of A_2ARs (A_2AR PAM) that can be rapidly photoactivated with visible light (λ > 400 nm) and used it optoallosterically to induce SWS in the NAc of freely behaving male mice by increasing the activity of extracellular adenosine derived from astrocytic and neuronal activity.

DOI： 10.1038/s41467-024-47964-4

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Other Link： https://www.nature.com/articles/s41467-024-47964-4

Language：English   Publishing type：Research paper (scientific journal)   Publisher：Oxford University Press (OUP)  

Abstract

In recent decades, various types of aryl-substituted 1,3,5-triazine derivatives have been applied in many research fields, including biomedical chemistry, non-linear optics, and organic electronics. However, the substituent scope for 4,6-diaryl-1,3,5-triazines (DAr-TRZs) remains limited. Here, we present our work on the synthesis of 2-amino- and 2-bromo-DAr-TRZ derivatives bearing electron-withdrawing groups on the aryl rings. Our synthetic methods successfully provided trifluoromethyl-, nitrile-, and nitro-substituted DAr-TRZs. These will expand the structural diversity of conventional triazine-based functional materials.

DOI： 10.1093/chemle/upae059

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Other Link： https://academic.oup.com/chemlett/article-pdf/53/4/upae059/57335721/upae059.pdf

Language：English   Publishing type：Research paper (scientific journal)   Publisher：Wiley  

Abstract

Photon‐upconversion in organic molecular systems is one of the promising technologies for future energy harvesting systems because these systems can generate excitons that possess higher energy than excitation energy. The photon‐upconversion caused by absorbing ambient heat as additional energy is particularly interesting because it could ideally provide a light‐driving cooling system. However, only a few organic molecular systems have been reported. Here, we report the anti‐Stokes photoluminescence (ASPL) derived from hot‐band absorption in a series of multi‐resonance‐type thermally‐activated delayed fluorescence (MR‐TADF) molecules. The MR‐TADF molecules exhibited an anti‐Stokes shift of approximately 0.1 eV with a high PL quantum yield in the solution state. The anti‐Stokes shift corresponded well to the 1–0 vibration transition from the ground state to the excited singlet state, and we further evaluated a correlation between the activation energy for the ASPL intensity and the TADF process. Our demonstration underlines that MR‐TADF molecules have become a novel class of ASPL materials for various future applications, such as light‐driving cooling systems.

DOI： 10.1002/anie.202312326

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Language：English  

DOI： 10.1039/9781788013598-00219

Language：English  

Venue：University College Dublin, Dublin, Ireland   Country：Ireland  

Language：English  

Country：Austria  

Language：Japanese  

Venue：同志社大学　京田辺キャンパス   Country：Japan  

Language：Japanese  

Venue：東広島市   Country：Japan  

Language：Japanese  

Country：Japan  

Language：Japanese  

Language：English   Publishing type：Article, review, commentary, editorial, etc. (scientific journal)  

DOI： 10.1055/s-0036-1590813

Type：Peer review 

Number of peer-reviewed articles in foreign language journals：3