The many applications of photon upconversion-conversion of low-energy photons into high-energy photons-raises the question of the possibility of "electron upconversion". In this Review, we illustrate how the reduction potential can be increased by using the free energy of exergonic chemical reactions. Electron (reductant) upconversion can produce up to 20-25 kcal mol of additional redox potential, thus creating powerful reductants under mild conditions. We will present the two common types of electron-upconverting systems-dissociative (based on unimolecular fragmentations) and associative (based on the bimolecular formation of three-electron bonds). The possible utility of reductant upconversion encompasses redox chain reactions in electrocatalytic processes, photoredox cascades, design of peroxide-based medicines, firefly luminescence, and reductive repair of DNA photodamage.
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http://dx.doi.org/10.1002/anie.201807247 | DOI Listing |
Front Chem
October 2024
Institute of Biology and Biomedicine, Lobachevsky State University of Nizhny Novgorod, Nizhny Novgorod, Russia.
Targeted drug delivery for primary brain tumors, particularly gliomas, is currently a promising approach to reduce patient relapse rates. The use of substitutable scaffolds, which enable the sustained release of clinically relevant doses of anticancer medications, offers the potential to decrease the toxic burden on the patient's organism while also enhancing their quality of life and overall survival. Upconversion nanoparticles (UCNPs) are being actively explored as promising agents for detection and monitoring of tumor growth, and as therapeutic agents that can provide isolated therapeutic effects and enhance standard chemotherapy.
View Article and Find Full Text PDFChem Sci
August 2024
Aix Marseille Univ, CNRS, ICR, Institut de Chimie Radicalaire, Faculté de Pharmacie 13005 Marseille France
Catalytic amounts of 1,3-di(methyl)imidazole-2-ylidene, one of the simplest and most prototypical N-heterocyclic carbenes, can up-convert aldehydes into powerful stoichiometric sources of electrons (Super Electron Donors) for reductive transformations of iodoaryls ( < -2 V). In particular, the hydroarylation of 1,1'-diarylethylenes, which may require high temperatures and inherently generate stoichiometric amounts of oxidized waste, was performed at room temperature, with the concomitant formation of esters as oxidized co-products.
View Article and Find Full Text PDFAdv Healthc Mater
November 2024
Department of Medical Biochemistry and Molecular Biology, School of Medicine, Jinan University, Guangzhou, Guangdong, 510632, China.
Synergistic therapy has become the major therapeutic method for malignant tumors in clinical. Photodynamic therapy (PDT) and radiotherapy (RT) always combine together because of their identical anti-tumor mechanisms, that is reactive oxygen species are generated by the use of radiosensitizers after irradiation by X-ray to efficiently kill cancer cells, PDT also follows similar mechanism. Full exposure of energy-absorbing species in nanomaterials to X-ray or near-infrared light irradiation makes the energy interchange between nanomaterials and surrounding HO or dissolved oxygen easier, however, it remains challenging.
View Article and Find Full Text PDFACS Appl Mater Interfaces
May 2024
Shenzhen Research Institute, Shandong University, Shenzhen, Guangdong 518057, P. R. China.
Photodynamic therapy (PDT) based on upconversion nanoparticles (UCNPs) has been widely used in the treatment of a variety of tumors. Compared with other therapeutic methods, this treatment has the advantages of high efficiency, strong penetration, and controllable treatment range. PDT kills tumors by generating a large amount of reactive oxygen species (ROS), which causes oxidative stress in the tumor.
View Article and Find Full Text PDFJ Am Chem Soc
April 2024
Department of Chemistry, University of Basel, St. Johanns-Ring 19, 4056 Basel, Switzerland.
Substituting precious elements in luminophores and photocatalysts by abundant first-row transition metals remains a significant challenge, and iron continues to be particularly attractive owing to its high natural abundance and low cost. Most iron complexes known to date face severe limitations due to undesirably efficient deactivation of luminescent and photoredox-active excited states. Two new iron(III) complexes with structurally simple chelate ligands enable straightforward tuning of ground and excited state properties, contrasting recent examples, in which chemical modification had a minor impact.
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