X-ray Magnetic Circular Dichroism of Pseudomonas aeruginosa Nickel(II) Azurin

We show that X-ray magnetic circular dichroism (XMCD) can be employed to probe the oxidation states and other electronic structural features of nickel active sites in proteins. As a calibration standard, we have measured XMCD and X-ray absorption (XAS) spectra for the nickel(II) derivative of Pseudomonas aeruginosa azurin (NiAz). Our analysis of these spectra confirms that the electronic ground state of NiAz is high-spin (S = 1); we also find that the L3-centroid energy is 853.1(1) eV, the branching ratio is 0.722(4), and the magnetic moment is 1.9(4) μ_B. Density functional theory (DFT) calculations on model NiAz structures establish that orbitals 3d_x^2-y^2 and 3d_z^2 are the two valence holes in the high-spin Ni(II) ground state, and in accord with the experimentally determined orbital magnetic moment, the DFT results also demonstrate that both holes are highly delocalized, with 3d_x^2_(-y)^2 having much greater ligand character

CHARACTERIZATION OF COPPER IN LEACHATES FROM ACQ- AND MCQ-TREATED WOOD AND ITS EFFECT ON BASIDIOSPORE GERMINATION

The unpenetrated interior of wood with a shell of preservative treatment may be exposed when the wood is cut or when checks open up. Mobile copper from wood shell-treated with chromated copper arsenate (CCA) has been shown to protect cut ends and checks against basidiospore germination. However, recent observations found that leachates from alkaline copper quat (ACQ)-treated wood failed to prevent basidiospore germination on untreated wood although copper levels were higher than toxic thresholds previously identified. It was hypothesized that the copper in leachate from ACQ-treated wood may be coordinated with monoethanolamine and/or lignin-based ligands and that this may result in poorer performance against basidiospores. In this study, electron paramagnetic resonance spectroscopy was used to determine the form of copper in leachates from ACQ, micronized copper quat (MCQ), and coppersulfate-treated wood. Leachates from ACQ-treated wood contained at least some degree of coordination with a nitrogen- and oxygen-containing ligand, probably monoethanolamine. This was not detected in leachates from MCQ and copper-sulfate-treated wood. These leachates were further evaluated for their ability to inhibit germination of Tyromyces palustris basidiospores. At low concentrations of copper, the CuSO4 and MCQ leachates were more effective than the ACQ leachate. At high concentrations CuSO4 and MCQ, leachates prevented germination in all samples, whereas ACQ leachates prevented germination in all but one sample

The Nature of S-N Bonding in Sulfonamides and Related Compounds: Insights into π-Bonding Contributions from Sulfur K-Edge XAS

Molecules containing sulfur-nitrogen bonds, like sulfonamides, have long been of interest due to their many uses and chemical properties. Understanding the factors that cause sulfonamide reactivity is important, yet their continues to be controversy regarding the relevance of S-N π bonding in describing these species. In this paper, we use sulfur K-edge x-ray absorption spectroscopy (XAS) in conjunction with density functional theory (DFT) to explore the role of S3p contributions to π-bonding in sulfonamides, sulfinamides and sulfenamides. We explore the nature of electron distribution of the sulfur atom and its nearest neighbors and extend the scope to explore the effects on rotational barriers along the sulfur-nitrogen axis. The experimental XAS data together with TD-DFT calculations confirm that sulfonamides, and the other sulfinated amides in this series, have essentially no S-N π bonding involving S3p contributions and that electron repulsion and is the dominant force that affect rotational barriers

The Nature of S-N Bonding in Sulfonamides and Related Compounds: Insights into π-Bonding Contributions from Sulfur K-Edge XAS

Molecules containing sulfur-nitrogen bonds, like sulfonamides, have long been of interest due to their many uses and chemical properties. Understanding the factors that cause sulfonamide reactivity is important, yet their continues to be controversy regarding the relevance of S-N π bonding in describing these species. In this paper, we use sulfur K-edge x-ray absorption spectroscopy (XAS) in conjunction with density functional theory (DFT) to explore the role of S&lt;sub&gt;3p&lt;/sub&gt; contributions to π-bonding in sulfonamides, sulfinamides and sulfenamides. We explore the nature of electron distribution of the sulfur atom and its nearest neighbors and extend the scope to explore the effects on rotational barriers along the sulfur-nitrogen axis. The experimental XAS data together with TD-DFT calculations confirm that sulfonamides, and the other sulfinated amides in this series, have essentially no S-N π bonding involving S&lt;sub&gt;3p&lt;/sub&gt; contributions and that electron repulsion and is the dominant force that affect rotational barriers.</jats:p

Catalytic Activation via π –Backbonding in Halogen Bonds?

The role of halogen bonding (XB) in chemical catalysis has largely involved using XB donors as Lewis acid activators to modulate the reactivity of partner Lewis bases. We explore a more uncommon scenario, where a Lewis base modulates reactivity via a spectator halogen bond interaction. Our computational studies reveal that spectator halogen bonds may play an important role in modulating the rate of SN2 reactions. Most notably, π acceptors such as PF3 significantly decrease the barrier to substitution by decreasing electron density in the very electron-rich transition state. Such π-backbonding represents an example of a heretofor unexplored situation in halogen bonding: the combination of both s-donation and π-backdonation in this “non-covalent” interaction.</jats:p

Catalytic Activation via π –Backbonding in Halogen Bonds?

The role of halogen bonding (XB) in chemical catalysis has largely involved using XB donors as Lewis acid activators to modulate the reactivity of partner Lewis bases. We explore a more uncommon scenario, where a Lewis base modulates reactivity via a spectator halogen bond interaction. Our computational studies reveal that spectator halogen bonds may play an important role in modulating the rate of S&lt;sub&gt;N&lt;/sub&gt;2 reactions. Most notably, π acceptors such as PF&lt;sub&gt;3&lt;/sub&gt; significantly decrease the barrier to subsitution by decreasing electron density in the very electron rich transition state. Such π-backbonding represents an example of a heretofor unexplored situation in halogen bonding: the combination of both s-donation and π-backdonation in this “non-covalent” interaction.</jats:p

Catalytic Activation via π –Backbonding in Halogen Bonds?

The role of halogen bonding (XB) in chemical catalysis has largely involved using XB donors as Lewis acid activators to modulate the reactivity of partner Lewis bases. We explore a more uncommon scenario, where a Lewis base modulates reactivity via a spectator halogen bond interaction. Our computational studies reveal that spectator halogen bonds may play an important role in modulating the rate of SN2 reactions. Most notably, π acceptors such as PF3 significantly decrease the barrier to substitution by decreasing electron density in the very electron-rich transition state. Such π-backbonding represents an example of a heretofor unexplored situation in halogen bonding: the combination of both s-donation and π-backdonation in this “non-covalent” interaction

Direct experimental evaluation of ligand-induced backbonding in nickel metallacyclic complexes

The details of ligand-induced backbonding in nickel diphosphine π complexes are explored using nickel L-edge (3d←2p) X-ray absorption spectroscopy as a means of quantifying the degree of backbonding derived from direct Ni 3d donation into the π ligand.</p