Simultaneous determination of ferrocyanide and ferricyanide in aqueous solutions using infrared spectrometry

Drew, D. M.

doi:10.1021/ac60336a029

Cited by 14 publications

(6 citation statements)

References 13 publications

(7 reference statements)

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“…This means that the ferro-species has a much stronger transition dipole for the cyano stretch. The difference in the transition dipole strength of the cyano stretch in ferri- and ferro-species has been observed earlier by Drew . Such a difference is caused by the charge of ferro- versus ferri-ions, as well as by the quadrupole interactions, as has been explained by Stanghellini .…”

Section: Resultssupporting

confidence: 65%

“…The difference in the transition dipole strength of the cyano stretch in ferri-and ferro-species has been observed earlier by Drew. 49 Such a difference is caused by the charge of ferro-versus ferri-ions, as well as by the quadrupole interactions, as has been explained by Stanghellini. 50 In addition, for each species, the solvent isotope effect on the IR absorption profile is not significant: there is only slight broadness in D 2 O as compared with H 2 O in the case of ferricyanide and only slight red shift of the peak position in D 2 O with respect to H 2 O in the case of ferrocyanide.…”

Section: Resultsmentioning

confidence: 86%

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Hydration Dynamics of Cyanoferrate Anions Examined by Ultrafast Infrared Spectroscopy

Yang

Zhao

et al. 2014

J. Phys. Chem. B

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In this work, we carried out steady-state IR absorption, transient IR pump-probe, and waiting-time-dependent two-dimensional (2D) IR measurements on ferrocyanide and ferricyanide ions solvated in water and deuterated water. These two anions are highly symmetric and have distributed cyano groups with IR-active stretching modes in the 5 μm wavelength region. The line width of their linear IR spectra and the initial value of the vibrational frequency-frequency correlation function extracted from their 2D IR spectra indicate water molecules in the hydration shell of the ferro-species are more inhomogeneously distributed but more tightly bound to the cyano groups than those of the ferri-species. Different charges and their distributions in the two anions cause different hydrogen bonding strengths with solvent. The frequency correlation relaxes somewhat slower in ferrocyanide, agreeing with stronger solute-solvent hydrogen-bonding interaction in this case. Mechanisms of the solvent isotope effect on the vibrational relaxation dynamics of the cyano stretching mode are discussed. These results also suggest that in the hydration shell the ferro-species breaks more water structure than the ferri-species, which is opposite to the situation of the bulk water region (beyond the hydration shell) reported previously. This work demonstrated that combined IR methods can be very useful for understanding the molecular details of the structure and dynamics of the hydrated ions.

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Section: Resultssupporting

confidence: 65%

Section: Resultsmentioning

confidence: 86%

Hydration Dynamics of Cyanoferrate Anions Examined by Ultrafast Infrared Spectroscopy

Yang

Zhao

et al. 2014

J. Phys. Chem. B

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“…As displayed in Figure (black curve), Pim exhibits absorption at 3092, 3137, 1161, 1550, and 1637 cm –1 , of which the absorption at 3092 and 3137 cm –1 was assigned to the stretching vibration of C 2 –H in an imidazole ring, and the absorption at 1161, 1550, and 1637 cm –1 was attributed to the stretching vibration of the C–N bonds in imidazole ring . The mixture of K 3 Fe(CN) 6 and K 4 Fe(CN) 6 shows absorption at 2117 and 2030 cm –1 (blue curve), which was assigned to the stretching vibration of CN of K 3 Fe(CN) 6 and K 4 Fe(CN) 6 , , respectively (Figure S6, Supporting Information). Upon the formation of the composite with Pim, the stretching vibration of CN of K 3 Fe(CN) 6 at 2117 cm –1 was red shifted to 2108 cm –1 , while no obvious shift was observed for the stretching vibration of CN of K 4 Fe(CN) 6 at 2030 cm –1 .…”

Section: Resultsmentioning

confidence: 95%

Strong Interaction between Imidazolium-Based Polycationic Polymer and Ferricyanide: Toward Redox Potential Regulation for Selective In Vivo Electrochemical Measurements

Zhuang,

Wang,

Lin

et al. 2012

Anal. Chem.

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This study effectively demonstrates a strategy to enable the ferricyanide-based second-generation biosensors for selective in vivo measurements of neurochemicals, with glucose as an example. The strategy is based on regulation of redox potential of ferricyanide mediator by carefully controlling the different adsorption ability of ferricyanide (Fe(CN)(6)(3-)) and ferrocyanide (Fe(CN)(6)(4-)) onto electrode surface. To realize the negative shift of the redox potential of Fe(CN)(6)(3-/4-), imidazolium-based polymer (Pim) is synthesized and used as a matrix for surface adsorption of Fe(CN)(6)(3-/4-) due to its stronger interaction with Fe(CN)(6)(3-) than with Fe(CN)(6)(4-). The different adsorption ability of Fe(CN)(6)(3-) and Fe(CN)(6)(4-) onto electrodes modified with a composite of Pim and multiwalled carbon nanotubes (MWNTs) eventually enables the stable surface adsorption of both species to generate integrated biosensors and, more importantly, leads to a negative shift of the redox potential of the surface-confined redox mediator. Using glucose oxidase (GOD) as the model biorecognition units, we demonstrate the validity of the ferricyanide-based second-generation biosensors for selective in vivo neurochemical measurements. We find that the biosensors developed with the strategy demonstrated in this study can be used well as the selective detector for continuous online detection of striatum glucose of guinea pigs, by integration with in vivo microdialysis. This study essentially paves a new avenue to developing electrochemical biosensors effectively for in vivo neurochemical measurements, which is envisaged to be of great importance in understanding the molecular basis of physiological and pathological events.

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“…5 are reported as relative changes in absorbance with a reference spectrum taken at the positive potential. The more intense signal arising from the increasing ferrocyanide (Red) signal at 2040 cm À1 , compared to the decreasing ferricyanide(Ox) signal at 2115 cm À1 , is explained by their well-known differences in molar absorptivity [31]. The signal-to-noise ratio for the 2040 cm À1 band at the longest time is over 400 even though no more than $200 femtomoles are interrogated by the beam.…”

Section: Time and Spatial Resolved Studiesmentioning

confidence: 99%

Spatiotemporal Mapping of Diffusion Layers Using Synchrotron Infrared Radiation

Lardner

Rosendahl

et al. 2015

Electrochimica Acta

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Simultaneous determination of ferrocyanide and ferricyanide in aqueous solutions using infrared spectrometry

Cited by 14 publications

References 13 publications

Hydration Dynamics of Cyanoferrate Anions Examined by Ultrafast Infrared Spectroscopy

Hydration Dynamics of Cyanoferrate Anions Examined by Ultrafast Infrared Spectroscopy

Strong Interaction between Imidazolium-Based Polycationic Polymer and Ferricyanide: Toward Redox Potential Regulation for Selective In Vivo Electrochemical Measurements

Spatiotemporal Mapping of Diffusion Layers Using Synchrotron Infrared Radiation

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