»... da aber die Welt keine Brücken hat ...«

Schafer, Judith Kelleher; Ingelheim, Geschwister Boehringer; Bochum, Ruhr-Universität; Jagiellonska, Uniwersytet Biblioteka; Huber, Evi Ziegler c/o EDV Fotowerk

doi:10.30965/9783846760321

Cited by 4 publications

(4 citation statements)

References 0 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Both geometry optimizations and single-point calculations used the spin unrestricted B3LYP [39][40][41] hybrid functional and the Ahlrichs' valence triple-ξ with a polarization function basis set. 42 The molecular orbitals were visualized as Gaussian cubes and an isosurface of 0.08 au in Pymol. Hyperfine and g tensors were calculated by the coupled-perturbed self-consistent field (SCF) approach as implemented in ORCA 4.0 using the B3LYP hybrid functional and EPR-III basis 43,44 in combination with the accurate spin-orbit coupling operator [RI-SOMF(1X)].…”

Section: Dft Calculationsmentioning

confidence: 99%

The Elusive 5′-Deoxyadenosyl Radical: Captured and Characterized by Electron Paramagnetic Resonance and Electron Nuclear Double Resonance Spectroscopies

et al. 2019

View full text Add to dashboard Cite

The 5′-deoxyadenosyl radical (5′-dAdo·) abstracts a substrate H atom as the first step in radical-based transformations catalyzed by adenosylcobalamin-dependent and radical S-adenosyl-L-methionine (RS) enzymes. Notwithstanding its central biological role, 5′-dAdo· has eluded characterization despite efforts spanning more than a half-century. Here, we report generation of 5′-dAdo· in a RS enzyme active site at 12 K using a novel approach involving cryogenic photoinduced electron transfer from the [4Fe–4S]+ cluster to the coordinated S-adenosylmethionine (SAM) to induce homolytic S–C5′ bond cleavage. We unequivocally reveal the structure of this long-sought radical species through the use of electron paramagnetic resonance (EPR) and electron nuclear double resonance (ENDOR) spectroscopies with isotopic labeling, complemented by density-functional computations: a planar C5′ (2pπ) radical (~70% spin occupancy); the C5′(H)2 plane is rotated by ~37° (experiment)/39° (DFT) relative to the C5′–C4′–(C4′–H) plane, placing a C5′–H antiperiplanar to the ribose-ring oxygen, which helps stabilize the radical against elimination of the 4′–H. The agreement between φ from experiment and in vacuo DFT indicates that the conformation is intrinsic to 5-dAdo· itself, and not determined by its environment.

show abstract

Section: Dft Calculationsmentioning

confidence: 99%

The Elusive 5′-Deoxyadenosyl Radical: Captured and Characterized by Electron Paramagnetic Resonance and Electron Nuclear Double Resonance Spectroscopies

et al. 2019

View full text Add to dashboard Cite

show abstract

“…18 Pre-edge intensity was normalized relative to the tail of the fluorescence signal. 20 TZVP (Mn,O,and N) and SVP (C, F, and H) basis sets, [21][22][23] and the COSMO solvation model (for TFE). 24 Tight optimization and SCF criteria were invoked using the TightOpt and TightSCF keywords.…”

Section: Xas Data Analysismentioning

confidence: 99%

Mn^IV-Oxo complex of a bis(benzimidazolyl)-containing N5 ligand reveals different reactivity trends for Mn^IV-oxo than Fe^IV-oxo species

et al. 2019

View full text Add to dashboard Cite

show abstract

“…Density Functional Theory (DFT).-Computations were carried out according to the TZVP/B97-D scheme, as implemented in the TURBOMOLE 7.2 programs suite. [67][68][69] The pure B97-D functional, which intrinsically accounts for dispersive effects, has been chosen since it proved to reliably reproduce both geometries and reactive behavior of hydrogenaselike models. 70 The Resolution-of-the-Identity (RI) technique has been used to reduce the computational costs deriving by the treatment of the classical electron-electron repulsive contribution to the total energy.…”

Section: Supplementary Materialsmentioning

confidence: 99%

Synthetic Designs and Structural Investigations of Biomimetic Ni–Fe Thiolates

et al. 2019

View full text Add to dashboard Cite

Described are the syntheses of several Ni(μ-SR) 2 Fe complexes, including hydride derivatives, in a search for improved models for the active site of [NiFe]-hydrogenases. The nickel(II) precursors include (i) nickel with tripodal ligands: Ni(PS 3 ) − and Ni(NS 3 ) − (PS 3 3-= tris(phenyl-2thiolato)phosphine, NS 3 3-= tris(benzyl-2-thiolato)amine) (ii) traditional diphosphine-dithiolates, including chiral diphosphine R,R-DIPAMP, (iii) cationic Ni(phosphine-imine/amine) complexes,

show abstract

»... da aber die Welt keine Brücken hat ...«

Cited by 4 publications

References 0 publications

The Elusive 5′-Deoxyadenosyl Radical: Captured and Characterized by Electron Paramagnetic Resonance and Electron Nuclear Double Resonance Spectroscopies

The Elusive 5′-Deoxyadenosyl Radical: Captured and Characterized by Electron Paramagnetic Resonance and Electron Nuclear Double Resonance Spectroscopies

Mn^IV-Oxo complex of a bis(benzimidazolyl)-containing N5 ligand reveals different reactivity trends for Mn^IV-oxo than Fe^IV-oxo species

Synthetic Designs and Structural Investigations of Biomimetic Ni–Fe Thiolates

Contact Info

Product

Resources

About

»... da aber die Welt keine Brücken hat ...«

Cited by 4 publications

References 0 publications

The Elusive 5′-Deoxyadenosyl Radical: Captured and Characterized by Electron Paramagnetic Resonance and Electron Nuclear Double Resonance Spectroscopies

The Elusive 5′-Deoxyadenosyl Radical: Captured and Characterized by Electron Paramagnetic Resonance and Electron Nuclear Double Resonance Spectroscopies

MnIV-Oxo complex of a bis(benzimidazolyl)-containing N5 ligand reveals different reactivity trends for MnIV-oxo than FeIV-oxo species

Synthetic Designs and Structural Investigations of Biomimetic Ni–Fe Thiolates

Contact Info

Product

Resources

About

Mn^IV-Oxo complex of a bis(benzimidazolyl)-containing N5 ligand reveals different reactivity trends for Mn^IV-oxo than Fe^IV-oxo species