Synthesis, electrochemistry and metal binding properties of monosubstituted ferrocenoyl peptides with thioether-containing sidechains

Scully, Conor C. G.; Lau, Yu Heng; Jensen, Paul R.; Rutledge, Peter J.

doi:10.1016/j.jorganchem.2010.09.056

Cited by 7 publications

(6 citation statements)

References 63 publications

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“…NMR experiments showed a change in the CH 2 S or CH 3 S signals, whereas a job plot confirmed the 1:1 binding stoichiometry of Hg(II) with these changes. The NMR data also implicated significant changes in the CH 2 S and SCH 3 signals upon addition of mercury(II) nitrate After addition of one equivalent of mercury(II) nitrate in 92 , a slight change in chemical shift was observed {CH 2 S (Δ δ = 0.041), SCH 3 (0.045), CαH (0.004), C 5 H 5 (0.003), OCH 3 (0.003) and NH (0.01)} …”

Section: Non‐biological Applicationsmentioning

confidence: 90%

Miscellaneous applications of ferrocene‐based peptides/amides

Lal

Badshah

Altaf

et al. 2011

Applied Organom Chemis

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This article provides a critical review of the different applications of ferrocene-based peptides/amides in biological as well as in non-biological systems. Ferrocene-based peptides/amides find many applications in different fields such as materials science, medicine, organic synthesis, bio-organometallic and biological chemistry, asymmetric catalysis, nonlinear optics, in polymer science as redox active polymers and dendrimers, in molecular recognition as biosensors and in electrochemistry). Extensive research is being done on ferrocene-based peptides/amides but we will highlight the various applications of ferrocene-based peptides/amides for the period 2006-2010. The main factors that govern the potential biological and nonbiological applications are an electroactive core, a conjugated linker that can act as a chromophore and lower the oxidation potential of the ferrocene part, an amino acid or peptide derivative that can interact with other molecules via hydrogen bonding or any secondary bonding, and symmetric and asymmetric substitution on the ferrocene moiety.

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Section: Non‐biological Applicationsmentioning

confidence: 90%

Miscellaneous applications of ferrocene‐based peptides/amides

Lal

Badshah

Altaf

et al. 2011

Applied Organom Chemis

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“…The frequent occurrence of 2 + k coordination (two strong short bonds and k weak bonds) has led to the introduction of the terms “characteristic coordination number” (i.e., 2) and “effective coordination number” (i.e., 2 + k ) . A case in point is methionine thioether (RSR′), which can form a weak Hg···S contact in proteins. , This interaction is the basis for the development of biologically inspired Hg sensors that incorporate thioether-containing side chains in de novo peptides . Similar Hg···S interaction may exist in NOM with inorganic sulfide (RSR) but is as yet unknown.…”

Section: Introductionmentioning

confidence: 99%

“…4,13 This interaction is the basis for the development of biologically inspired Hg sensors that incorporate thioether-containing side chains in de novo peptides. 14 Similar Hg•••S interaction may exist in NOM with inorganic sulfide (RSR) but is as yet unknown.…”

Section: Introductionmentioning

confidence: 99%

“…Multinuclear complexes made by associating three (14) and five (15) Hg(SR) 2 units were also considered for completeness and because crystals 3 and 16 feature 3[Hg(SR) 2 ] and 5[Hg(SR) 2 ] complexes, respectively. As when RSR groups are added, the linear geometry of the initial Hg(SR) 2 Optimized structures are in good agreement with those reported 7,8 for the n(HgX 2 ) (n = 2, 3; X = F, Cl, Br, I) complexes.…”

Section: Introductionmentioning

confidence: 99%

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Structure, Bonding, and Stability of Mercury Complexes with Thiolate and Thioether Ligands from High-Resolution XANES Spectroscopy and First-Principles Calculations

Manceau¹,

Lemouchi²,

Rovezzi

et al. 2015

Inorg. Chem.

123

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We present results obtained from high energy-resolution L3-edge XANES spectroscopy and first-principles calculations for the structure, bonding, and stability of mercury(II) complexes with thiolate and thioether ligands in crystalline compounds, aqueous solution, and macromolecular natural organic matter (NOM). Core-to-valence XANES features that vary in intensity differentiate with unprecedented sensitivity the number and identity of Hg ligands and the geometry of the ligand environment. Post-Hartree-Fock XANES calculations, coupled with natural population analysis, performed on MP2-optimized Hg[(SR)2···(RSR)n] complexes show that the shape, position, and number of electronic transitions observed at high energy-resolution are directly correlated to the Hg and S (l,m)-projected empty densities of states and occupations of the hybridized Hg 6s and 5d valence orbitals. Linear two-coordination, the most common coordination geometry in mercury chemistry, yields a sharp 2p to 6s + 5d electronic transition. This transition varies in intensity for Hg bonded to thiol groups in macromolecular NOM. The intensity variation is explained by contributions from next-nearest, low-charge, thioether-type RSR ligands at 3.0-3.3 Å from Hg. Thus, Hg in NOM has two strong bonds to thiol S and k additional weak Hg···S contacts, or 2 + k coordination. The calculated stabilization energy is -5 kcal/mol per RSR ligand. Detection of distant ligands beyond the first coordination shell requires precise measurement of, and comparison to, spectra of reference compounds as well as accurate calculation of spectra for representative molecular models. The combined experimental and theoretical approaches described here for Hg can be applied to other closed-shell atoms, such as Ag(I) and Au(I). To facilitate further calculation of XANES spectra, experimental data, a new crystallographic structure of a key mercury thioether complex, Cartesian coordinates of the computed models, and examples of input files are provided as Supporting Information .

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“…We have chosen a ferrocene coupled‐peptide design, involving a disulfide‐linked dimer of an N ‐terminal ferrocene‐coupled Phe‐Cys. Ferrocene (Fc) is a widely used metallocene, with well‐characterized redox behaviour that is vastly used in a variety of applications, particularly in electrochemical systems [37–39] . Ferrocene‐coupling to peptides results in a redox‐providing modification to a simple molecule, imparting further characteristics that may be beneficial to the material's applications [38–40] .…”

Section: Introductionmentioning

confidence: 99%

Ferrocene‐Peptide Conjugate for the Detection and Quantification of Ascorbic Acid

Shao,

Wang,

Noroozifar

et al. 2023

ChemElectroChem

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Ferrocene (Fc) is a widely used metallocene, with well‐characterized redox behaviour that is vastly used in a variety of applications. Ferrocene‐coupling to peptides renders the resulting bioorganometallic peptide conjugate redox active and sensitive to changes in the chemical environment. The disulfide‐linked ferrocene peptide conjugate (FcCO‐Phe‐Cys‐OH)2 was synthesized and characterized by NMR, MS, and FT‐IR spectroscopies and then exploited for the detection of ascorbic acid. Here we demonstrate that the Cu(II) complex of this peptide conjugate allows the detection of ascorbic acid with a limit of detection of 0.02 μM with a linear range of 0.1–25 μM. This is the first report of the use of a peptide metal complex for direct modification of a glass carbon electrode and its application for ascorbic acid detection and quantification, including in commercial beverages. The modified GCE exhibited excellent selectivity, stability, and sensitivity.

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Synthesis, electrochemistry and metal binding properties of monosubstituted ferrocenoyl peptides with thioether-containing sidechains

Cited by 7 publications

References 63 publications

Miscellaneous applications of ferrocene‐based peptides/amides

Miscellaneous applications of ferrocene‐based peptides/amides

Structure, Bonding, and Stability of Mercury Complexes with Thiolate and Thioether Ligands from High-Resolution XANES Spectroscopy and First-Principles Calculations

Ferrocene‐Peptide Conjugate for the Detection and Quantification of Ascorbic Acid

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