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Tuning the formal potential of ferrocyanide over a 2.1 V range.

ABSTRACT: We report the synthesis and characterization of homoleptic borane adducts of hexacyanoferrate(ii). Borane coordination blueshifts d-d transitions and CN IR and Raman frequencies. Control over redox properties is established with respect to borane Lewis acidity, reflected in peak anodic potential shifts per borane of +250 mV for BPh₃ and +350 mV for B(C₆F₅)₃. Electron transfer from [Fe(CN-B(C₆F₅)₃)₆]^4- to photogenerated [Ru(2,2'-bipyridine)₃]³⁺ is very rapid, consistent with voltammetry data. Coordination by Lewis acids provides an avenue for selective modification of the electronic structures and electrochemical properties of cyanometalates.

SUBMITTER: McNicholas BJ

PROVIDER: S-EPMC6430091 | biostudies-literature | 2019 Mar

REPOSITORIES: biostudies-literature

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Tuning the formal potential of ferrocyanide over a 2.1 V range.

McNicholas Brendon J BJ Grubbs Robert H RH Winkler Jay R JR Gray Harry B HB Despagnet-Ayoub Emmanuelle E

Chemical science 20190221 12

We report the synthesis and characterization of homoleptic borane adducts of hexacyanoferrate(ii). Borane coordination blueshifts d-d transitions and CN IR and Raman frequencies. Control over redox properties is established with respect to borane Lewis acidity, reflected in peak anodic potential shifts per borane of +250 mV for BPh3 and +350 mV for B(C6F5)3. Electron transfer from [Fe(CN-B(C6F5)3)6]4-</s ...[more]

PMID: 30996955

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Project description:The Panel on Food Additives and Nutrient Sources added to Food (ANS) provided a scientific opinion re-evaluating the safety of sodium ferrocyanide (E 535), potassium ferrocyanide (E 536), and evaluating the safety of calcium ferrocyanide (E 538) as food additives. The Panel considered that adequate exposure and toxicity data were available. Ferrocyanides (E 535-538) are solely authorised in two food categories as salt substitutes. To assess the dietary exposure to ferrocyanides (E 535-538) from their use as food additives, the exposure was calculated based on regulatory maximum level exposure assessment scenario (maximum permitted level (MPL)) and the refined exposure assessment scenario. Dietary exposure to ferrocyanides was calculated based on mean and high levels consumption of salts in both the regulatory maximum level and the refined scenario. In the MPL scenario, the exposure to ferrocyanides (E 535-538) from their use as a food additive was up to 0.009 mg/kg body weight (bw) per day in children and adolescents. In the refined estimated exposure scenario, the exposure was up to 0.003 mg/kg bw per day in children and adolescents. Absorption of ferrocyanides is low and there is no accumulation in human. There is no concern with respect to genotoxicity and carcinogenicity. Reproductive studies were not available, but a no observed adverse effect level (NOAEL) of 1,000 mg sodium ferrocyanide/kg bw per day (highest dose tested) was identified from a prenatal developmental toxicity study. The kidney appeared to be the target organ for ferrocyanides toxicity and 4.4 mg sodium ferrocyanide/kg bw per day was identified as the NOAEL for the renal effects in a chronic (2-year) study in rats. Assuming that the toxicity of this compound is due to the ferrocyanide ion only, the Panel established a group acceptable daily intake (ADI) for sodium, potassium and calcium ferrocyanide of 0.03 mg/kg bw per day expressed as ferrocyanide ion. The Panel concluded that ferrocyanides (E 535-538) are of no safety concern at the current authorised use and use levels.

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Tuning the formal potential of ferrocyanide over a 2.1 V range.

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Tuning the formal potential of ferrocyanide over a 2.1 V range.

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