Unusual hydrolase-like activity of a mononuclear Fe(III) complex

Heying, Renata S.; Silva, Marcos Paulo da; Wecker, Giovana S.; Peralta, Rosely A.; Bortoluzzi, Adaílton J.; Neves, Ademir

doi:10.1016/j.inoche.2019.01.035

Cited by 5 publications

(15 citation statements)

References 22 publications

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“…[49] The amino groups on the side chain could shift the λ max values of 2 and 3, compared to 1, due to its interaction with the phenolate ring, simulating a withdrawing effect. [23] All bands have λ max comparable with other iron(III) complexes described in the literature [23,32,38,48] (Table 1). TD-DFT calculations were performed based on the previously discussed optimized ground state geometries to confirm these attributions and obtain further information on the excited state configurations (Table S7).…”

Section: Electronic Absorption Spectroscopy and Dft Studiessupporting

confidence: 73%

“…The general vibrational profile in infrared (FTIR) spectra for complexes 1-3 is quite similar to their respective ligands (Figure S10 and Table S3), with shifts and distinct intensity upon coordination with the metallic center and the ClÀ O stretch for 2 and 3, related to the counterion. [32,35,38,48] The presence of the protonated amine, suggested for 3 is also corroborated by the large band in 3185 cm À 1 , which is not present in the HL 3 spectrum. [50] For 1, all bands agree with those described in the first reported characterization.…”

Section: Characterization Of Complexesmentioning

confidence: 81%

“…The electrochemical potentials (E pc = 0.06(2), 0.00(3); E pa = 0.17(2), 0.14(3)) along with the previously reported for 1, agree to similar compounds previously described in the literature to Fe III /Fe II oxidation-reduction process. [23,38,48] The anodic shift following the order 2 > 3 > 1 is attributed to the hydrogen bonds between the side chain and the coordinated atoms/ ligands in the first coordination sphere.…”

Section: Electrochemical Propertiesmentioning

confidence: 99%

“…[37] However, these reactions can work even with mononuclear compounds if the complex presents an available position to interact with the substrate and another to promote hydrolysis. [38,39] In addition, groups known as the second coordination sphere can perform one of these roles in catalysis. They are not directly coordinated to the metal center and can interact with the substrate, enhancing the catalytic activity.…”

Section: Introductionmentioning

confidence: 99%

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Phosphate Triester Hydrolysis by Mononuclear Iron(III) Complexes: The Role of Benzimidazole in the Second Coordination Sphere

Luiz,

Farias,

Alzamora

et al. 2024

Eur J Inorg Chem

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Over the years, phosphate ester hydrolysis promoted by coordination compounds has attracted extensive research on developing new bioinspired compounds. However, the literature lacks sufficient examples displaying activity toward phosphate triesters specifically, limiting the understanding of efficient strategies for its hydrolysis. Herein, we report the preparation and characterization of three mononuclear iron(III) complexes (1, 2, and 3) and their hydrolase‐like activity. Complexes 2 and 3 contained benzimidazole (BIMZ) moieties and were strategically designed to separate the BIMZ moiety from the first coordination sphere, and complex 1 was used as a reference. Several techniques provided structural information, including spectrophotometry, spectrometry, electrochemistry, elemental analysis, and 57Fe Mossbauer. Density functional theory (DFT) revealed distorted octahedral geometries due to the presence of the BIMZ groups. These groups also directly affected the protonation equilibria and catalytic activity. The phosphate triester diethyl‐2,4‐dinitrophenylphosphate (DEDNPP) hydrolysis was enhanced at least 27 times compared to the uncatalyzed reaction, with complexes 2 and 3, containing the BIMZ moiety showing higher catalytic rates (kcat). Moreover, a longer carbon chain led to a higher hydrolysis rate but less interaction with substrate. These findings provide a foundation for further investigations and developing into efficient catalysts for agrochemical degradation.

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Section: Electronic Absorption Spectroscopy and Dft Studiessupporting

confidence: 73%

Section: Characterization Of Complexesmentioning

confidence: 81%

Section: Electrochemical Propertiesmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Phosphate Triester Hydrolysis by Mononuclear Iron(III) Complexes: The Role of Benzimidazole in the Second Coordination Sphere

Luiz,

Farias,

Alzamora

et al. 2024

Eur J Inorg Chem

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“…Effects such as the flexibility of the whole system as well as the position of the metal complexes were investigated in order to shed light on the mechanism in some hydrolytic processes. 210 In more recent studies, the hydrolase activity of mononuclear iron complexes, 211 and dinuclear nickel complexes, 212 have been demonstrated.…”

Section: Synzymatic Supramolecular Catalystsmentioning

confidence: 99%

Pseudopeptidic Macrocyclic Systems with Preorganized Cavities

Franch¹

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6.1.2. Introduction 6.1.3. Experimental section 6.1.4. Results and discussion 6.1.4.1.Synthesis of the pseudopeptidic macrocycles 6.1.4.2.Evaluation of the macrocyclic systems as catalysts under homogenous conditions 6.1.4.3.Immobilization of the macrocycles on hydrophobic supports 6.1.4.4.Heterogenous catalysis experiments 6.1.5. Conclusions 6.1.6. References 6.2. Supporting information 7. Chapter 7 -Highly Active and Enantioselective Multifunctional One-Component Supramolecular Catalysts for the Cycloaddition of CO2 to Epoxides 7.1. Main text 7.1.1. Abstract 7.1.2. Introduction 7.1.3. Experimental section 7.1.4. Results and discussion 7.1.5. Conclusions 7.1.6. References 7.2. Supporting information 8. Chapter 8 -Doubly Chiral Pseudopeptidic Macrobicyclic Molecular cages: Water-assisted Dynamic Covalent Self-Assembly and Chiral Self-sorting 8.1. Main text 8.1.1. Abstract 8.1.2. Introduction Pseudopeptidic Macrocyclic Systems with Preorganized Cavities 36 8.1.3. Experimental section 8.1.4. Results and discussion 8.1.4.1. Synthesis and characterisation of the pseudopeptidic cryptands 8.1.4.2. Competition studies with the parent achiral component TREN 8.1.4.3. Effect of the sidechain in the self-sorting between components 8.1.4.4. Effect of component chirality in the self-sorting processes 8.1.5. Conclusions 8.1.6. References 8.2. Supporting information 9. Chapter 9 -Unravelling the Supramolecular Driving Forces in the Formation of CO2-Responsive Pseudopeptidic Low Molecular Weight Hydrogelators 9.1. Main text 9.1.1. Abstract 9.1.2. Introduction 9.1.3. Experimental section 9.1.4. Results and discussion 9.1.4.1. Synthesis of the pseudopeptidic compounds and gelation properties as LMWGs 9.1.4.2. Supramolecular driving forces 9.1.4.3. CO2 stimulus responsiveness 9.1.5. Conclusions 9.1.6. References 9.2. Supporting information 10. Chapter 10 -Conclusions Chapter 1 General Introduction Chapter 1 38 1.1. Supramolecular chemistry Supramolecular chemistry is a relatively recent domain of chemistry, frequently defined as the "non-covalent chemistry" or the "chemistry beyond molecules". 1 These non-covalent interactions are comparatively weaker than covalent bonds, although they have been proved to be essential in a wide range of fundamental biological functions. 2 Supramolecular interactions include, among others, electrostatic interactions, hydrogen bonding, van der Waals forces, π-interactions, hydrophobic interactions or halogen bonding. 3However, before delving further into this topic, it is important to set the discovery of these interactions in their historical background. At the end of the nineteenth century, the forces between molecules were being studied by authors such as J. D. van der Waals (Nobel Prize in Physics in 1910) and H. E. Fischer (Nobel Prize in Chemistry in 1902). In 1894, Fischer postulated the fundamental roots of supramolecular chemistry when he suggested that substrate-enzyme interactions could be defined in terms of the "lock and key" principle, paving the way for understanding host-guest chemist...

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