A switching cascade of hydrazone-based rotary switches through coordination-coupled proton relays
| Autor: | Russell P. Hughes, Justin T. Foy, Debdas Ray, Ivan Aprahamian |
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| Rok vydání: | 2012 |
| Předmět: |
Magnetic Resonance Spectroscopy
Chemical Phenomena Stereochemistry General Chemical Engineering Static Electricity Molecular Conformation Hydrazone Ring (chemistry) Crystallography X-Ray chemistry.chemical_compound Isomerism Static electricity Imidazole Histidine chemistry.chemical_classification Chemistry Rotary switch Hydrazones Imidazoles General Chemistry Combinatorial chemistry Zinc Photosynthetic bacteria Protons Isomerization |
| Zdroj: | Nature chemistry. 4(9) |
| ISSN: | 1755-4349 |
| Popis: | Imidazole, a subunit of histidine, plays a crucial role in proton-relay processes that are important for various biological activities, such as metal efflux, viral replication and photosynthesis. We show here how an imidazolyl ring incorporated into a rotary switch based on a hydrazone enables a switching cascade that involves proton relay between two different switches. The switching process starts with a single input, zinc(II), that initiates an E/Z isomerization in the hydrazone system through a coordination-coupled proton transfer. The resulting imidazolium ring is unusually acidic and, through proton relay, activates the E/Z isomerization of a non-coordinating pyridine-containing hydrazone switch. We hypothesize that the reduction in the acid dissociation constant of the imidazolium ring results from a combination of electrostatic and conformational effects, the study of which might help elucidate the proton-coupled electron-transfer mechanism in photosynthetic bacteria. |
| Databáze: | OpenAIRE |
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