Potentiometric and spectrophotometric equilibrium study on Fe(III) and new catechol-bisphosphonate conjugates

Crisponi, Guido; Nurchi, Valeria Marina; Pivetta, Tiziana

doi:10.1016/j.jinorgbio.2007.07.038

Cited by 18 publications

(21 citation statements)

References 24 publications

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“…For quantification, only the peaks above 400 nm were used because the data below this range were too severely affected by overlap; the main absorption above 400 nm of the monospecies was found to be a doublet at 406 and 759 nm, the dimer had a peak at 575 nm while the trimer had a peak at 492 nm. These values agree with spectra reported in the literature for similar species (9,10,31). The areas of the peaks were then normalized to the maximum value for each peak.…”

Section: Methodssupporting

confidence: 82%

pH-induced metal-ligand cross-links inspired by mussel yield self-healing polymer networks with near-covalent elastic moduli

Holten‐Andersen

Harrington

Birkedal

et al. 2011

Proc. Natl. Acad. Sci. U.S.A.

1,384

1,326

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Growing evidence supports a critical role of metal-ligand coordination in many attributes of biological materials including adhesion, self-assembly, toughness, and hardness without mineralization [Rubin DJ, Miserez A, Waite JH (2010) Advances in Insect Physiology: Insect Integument and Color, eds Jérôme C, Stephen JS (Academic Press, London), pp . Coordination between Fe and catechol ligands has recently been correlated to the hardness and high extensibility of the cuticle of mussel byssal threads and proposed to endow self-healing properties [Harrington MJ, Masic A, HoltenAndersen N, Waite JH, Fratzl P (2010) Science 328:216-220]. Inspired by the pH jump experienced by proteins during maturation of a mussel byssus secretion, we have developed a simple method to control catechol-Fe 3þ interpolymer cross-linking via pH. The resonance Raman signature of catechol-Fe 3þ cross-linked polymer gels at high pH was similar to that from native mussel thread cuticle and the gels displayed elastic moduli (G′) that approach covalently cross-linked gels as well as self-healing properties.biomaterials | catecholate polymer | metal coordination | reversible cross-links | physical gels M ussel byssal threads are protected against wear by a cuticle, an outer proteinaceous coating, that despite a hardness of ∼0.1 GPa, accommodates large cyclic strains in the turbulent intertidal zone (1, 2). During strain, the cuticle suppresses macroscale failure by limiting crack propagation to the microscale (1, 3). It was recently demonstrated that a small amount of Fe (<1 wt%) plays an important role in this mechanism; bonding with the catechol-like amino acid dihydroxy-phenylalanine (dopa) in the cuticle protein, mfp-1 (4-6). Tris-and bis-catecholFe 3þ complexes possess some of the highest known stability constants of metal-ligand chelates (log K S ≈ 37-40, where K S is the equilibrium constant for the complex formation) (7-10) and single molecule tensile tests have demonstrated that the breaking of a metal-dopa bond requires a force only modestly lower than the force required to rupture a covalent bond under identical loading conditions (∼0.8 nN vs. ∼2 nN, respectively) (11). Harrington et al. proposed a model where the catecholFe 3þ complexes in the cuticle function as sacrificial load-bearing cross-links facilitating extensibility of the material (4). In contrast to covalent bonds, metal-dopa bonds can spontaneously reform after breaking (11) and the model predicts that the damage accumulated in the cuticle could self-heal via reformation of broken catechol-Fe 3þ complexes (4). Here we describe a strategy for introducing bis-and/or tris-catechol-Fe 3þ cross-links into a synthetic polymer network and demonstrate that such a network indeed displays high elastic moduli and self-healing properties. ResultsThe stoichiometry of catechol-Fe 3þ complexes (mono-, bis-, or tris-) is controlled by pH via the deprotonation of the catechol hydroxyls (Fig. 1A). The pH required to establish the bis-and tris-complexes is typically reported to be above pH...

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Section: Methodssupporting

confidence: 82%

pH-induced metal-ligand cross-links inspired by mussel yield self-healing polymer networks with near-covalent elastic moduli

Holten‐Andersen

Harrington

Birkedal

et al. 2011

Proc. Natl. Acad. Sci. U.S.A.

1,384

1,326

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“…In addition, the former complexes show LMCT bands at longer wavelengths than the latter (violet and red complexes, respectively, Fig. S2, ESI) A similar behavior has been reported for other ferric complexes [38]. Taking into account that the rate limiting step in most Fentonlike systems is the production of Fe(II) from Fe(III) species, we studied the reduction of the ferric complexes through dark pathways associated with the in situ formation of reducing intermediates.…”

Section: Formation Of Fe(iii) Complexessupporting

confidence: 68%

“…It has been reported that ML 2 and ML 3 complexes can be formed between Fe(III) and 2HBA at pH values higher than 4.0 [38]. The formation of complexes with higher L:M molar ratios is favored at high pH values since increasing pH leads to an increase in the fraction of LH − forms that participate in Reaction (5).…”

Section: Formation Of Fe(iii) Complexesmentioning

confidence: 98%

Iron cycling during the autocatalytic decomposition of benzoic acid derivatives by Fenton-like and photo-Fenton techniques

Nichela

Donadelli

Caram

et al. 2015

Applied Catalysis B: Environmental

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“…doi:10.1016/j.jinorgbio.2010.01.007 the design of new molecules with improved properties. In this context, since our research attention has been devoted in these last years to iron chelators [9,[18][19][20][21][22], we present here a study on Fe(III) and Al(III) complexation equilibria with the ligand proposed by Fox and Taylor. The study of complex formation equilibria between HKa and the two trivalent metal ions together to the X-ray structure of the complex Fe(Ka) 3 is also presented as the base to interpret the behavior of 6-[5-hydroxy-2-hydroxy methyl-pyran-4-one]-5-hydroxy-2-hydroxy methyl-pyran-4-one.…”

Section: Introductionmentioning

confidence: 99%

Iron(III) and aluminum(III) complexes with hydroxypyrone ligands aimed to design kojic acid derivatives with new perspectives

Nurchi

Crisponi

Lachowicz

et al. 2010

Journal of Inorganic Biochemistry

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Potentiometric and spectrophotometric equilibrium study on Fe(III) and new catechol-bisphosphonate conjugates

Cited by 18 publications

References 24 publications

pH-induced metal-ligand cross-links inspired by mussel yield self-healing polymer networks with near-covalent elastic moduli

pH-induced metal-ligand cross-links inspired by mussel yield self-healing polymer networks with near-covalent elastic moduli

Iron cycling during the autocatalytic decomposition of benzoic acid derivatives by Fenton-like and photo-Fenton techniques

Iron(III) and aluminum(III) complexes with hydroxypyrone ligands aimed to design kojic acid derivatives with new perspectives

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