Santiago Andres Toledo

American University

A new biomimetic model complex of the active site of acireductone dioxygenase (ARD) was synthesized and crystallographically characterized ([Ni(II)(N-(ethyl-N’Me2)(Py)(2-t-ButPhOH))(OTf)]-1). 1 displays carbon-carbon oxidative cleavage activity in the presence of O2...

We report the synthesis and biomimetic activity of a family of model complexes with relevance to acireductone dioxygenase (ARD), an enzyme that displays dual function based on metal identity found in the methionine salvage pathway (MSP). Three complexes with related structural motifs were synthesized and characterized derived from phenolate, and py...

This work explores the pivotal role that protein mobility plays in facilitating the catalytic activity of Copper-Zinc superoxide dismutase (SOD1). Through both localized active site distortions and correlated domain movement, these motions enable the enzyme to adopt the conformations necessary to achieve both substrate delivery and efficient cataly...

Studies have found that mutant, misfolded superoxide dismutase [Cu–Zn] (SOD1) can convert wild type SOD1 (wtSOD1) in a prion-like fashion, and that misfolded wtSOD1 can be propagated by release and uptake of protein aggregates. In developing a prion-like mechanism for this propagation of SOD1 misfolding we have previously shown how enervation of th...

Getting students to use grading feedback as a tool for learning is a continual challenge for educators. This work proposes a method for evaluating student performance that provides feedback to students based on standards of learning dictated by clearly delineated course learning outcomes. This method combines elements of standards-based grading int...

Reported herein is the structural, spectroscopic, redox, and reactivity properties of a series of iron complexes containing both a π-donating thiolate, and π-accepting N-heterocycles in the coordination sphere, in which we systematically vary the substituents on the N-heterocycle, the size of the N-heterocycle, and the linker between the imine nitr...

Herein we quantitatively investigate how metal ion Lewis acidity and steric properties influence the kinetics and thermodynamics of dioxygen binding versus release from structurally analogous Mn-O2 complexes, as well as the barrier to Mn peroxo O-O bond cleavage, and the reactivity of Mn oxo intermediates. Previously we demonstrated that the steric...

The synthesis and preliminary biomimetic reactivity of the first structural analogue for the resting state of the active site of the nickel oxygenase nickel acireductone dioxyegenase (Ni-ARD), is presented. Compound 1 ([NiII(OPhN4(6-H-DPEN)(H2O))](OTf)) is only the second model complex for Ni-ARD. The N4O ligand motif, mimics the contributions of t...

An emphasis on higher-order thinking within the curriculum has been a subject of interest in the chemical and STEM literature due to its ability to promote meaningful, transferable learning in students. The systematic use of learning taxonomies could be a practical way to scaffold student learning in order to achieve this goal. This work proposes t...

Understanding the metal ion properties that favor O-H bond formation versus cleavage should facilitate the development of catalysts tailored to promote a specific reaction, e.g., C-H activation or H2O oxidation. The first step in H2O oxidation involves the endothermic cleavage of a strong O-H bond (BDFE = 122.7 kcal/mol), promoted by binding the H2...

Presented here is a practical tool called the Active Reading Document (ARD) that can give students the necessary incentive to engage with the text/readings. By designing the tool to incrementally develop student understanding of the material through reading using Marzano's Taxonomy as a framework, the ARD offers support through scaffolding as they...

Dioxygen addition to coordinatively unsaturated [Fe(II)(O(Me2)N4(6-Me-DPEN))](PF6) (1) is shown to afford a complex containing a dihydroxo-bridged Fe(III)2(μ-OH)2 diamond core, [Fe(III)(O(Me2)N4(6-Me-DPEN))]2(μ-OH)2(PF6)2·(CH3CH2CN)2 (2). The diamond core of 2 resembles the oxidized methane monooxygenase (MMOox) resting state, as well as the active...

The synthesis, structural, and spectroscopic characterization of four new coordinatively unsaturated mononuclear thiolate-ligated manganese(II) complexes ([Mn(II)(S(Me2)N(4)(6-Me-DPEN))](BF(4)) (1), [Mn(II)(S(Me2)N(4)(6-Me-DPPN))](BPh(4))·MeCN (3), [Mn(II)(S(Me2)N(4)(2-QuinoPN))](PF(6))·MeCN·Et(2)O (4), and [Mn(II)(S(Me2)N(4)(6-H-DPEN)(MeOH)](BPh(4...