A5002593523- Metalloenzymes and iron-sulfur proteins
- Electrocatalysts for Energy Conversion
- X-ray Diffraction in Crystallography
- Crystallization and Solubility Studies
- Organometallic Complex Synthesis and Catalysis
- Inorganic and Organometallic Chemistry
- Asymmetric Hydrogenation and Catalysis
- Hydrogen Storage and Materials
- Ammonia Synthesis and Nitrogen Reduction
- Metal complexes synthesis and properties
- Electrochemical Analysis and Applications
- Crystallography and molecular interactions
- Metal-Catalyzed Oxygenation Mechanisms
- CO2 Reduction Techniques and Catalysts
- Electrochemical sensors and biosensors
- Advanced battery technologies research
- Molecular Junctions and Nanostructures
- Inorganic Chemistry and Materials
- Chemical Reaction Mechanisms
- Conducting polymers and applications
- Magnetism in coordination complexes
- Chemical Synthesis and Characterization
- Iron oxide chemistry and applications
- Analytical Chemistry and Sensors
- Synthesis and characterization of novel inorganic/organometallic compounds
National Cancer Institute
2025
Swarthmore College
2024
University of Connecticut
2022
University of East Anglia
2008-2019
Norwich Research Park
2003-2019
Rutherford Appleton Laboratory
2008-2010
University of Strathclyde
2008-2010
University of Sussex
1987-2010
Merck & Co., Inc., Rahway, NJ, USA (United States)
2009
United States Military Academy
2009
Electrochemical reduction of Fe(2)(mu-pdt)(CO)(6) 1 (pdt = propane-1,3-dithiolate) leads initially to a short-lived species, 1-, then subsequently two-electron reduced products, including CO-bridged diiron compound, 1B. The assignment the redox level 1- is based on EPR and UV-vis spectra together with observation that CO-saturated solution decays give Hydride also results in formation 1B via relatively long-lived formyl 1(formyl). Despite its involvement hydride transfer reactions,...
The synthesis and characterisation of the first {2Fe2S}-cluster bearing both CO CN ligands is described; iron atoms are linked by bridging 1,3-propanedithiolate unit that has been identified in crystallographic structure {2Fe2S} sub-unit H-centre all-iron hydrogenase from Desulfovibrio desulfuricans.
Anecdotal observations suggested that poor quality of sleep is a frequent complaint during upper respiratory infections (URI). Nasal obstruction occurs frequently URI and causes apnea in some infants. Sleep disrupts normal could explain the complaints adults. Accordingly, 10 men had full night recordings stages breathing rhythm before nasal obstruction. The order obstructed nonobstructed nights was randomized after standard acclimatization night. During obstruction, time spent deep decreased...
Hitting water with a 2 iron: A novel nanophotocathode for hydrogen production is based on multilayer array of InP quantum dots activated synthetic diiron catalyst (see picture), which related to the subsite FeFe hydrogenase. Efficient solar fuels an imperative meeting future fossil-fuel-free energy demands. Hydrogen that derived from splitting by clearly attractive as clean vector, and there have been many attempts construct viable molecular biomolecular devices photohydrogen production.1...
Tripodal dithiolate thioether ligands MeC(CH2SH)2CH2SR (R = Me or Ph) provide a route to {2Fe3S}-complexes and syntheses are described. X-Ray crystal structures for two {2Fe3S}-pentacarbonyl derivatives that the first carbonyl cyanide reported, together with temperature dependent 1H-NMR, Mössbauer, FTIR redox potential data. The NMR data establish fluctionality associated inversion at sulfur in complexes. Mössbauer affirm coordination environment of iron atoms dicyanide bridging intermediate...
A scale of ligand constants, PL, is defined according to equation (1). This used analyse the E½ox PL=E½ox[Cr(CO)5L]–E½ox[Cr(CO)6](1) various closed-shell octahedral complexes [M3L], in terms linear approximation (2), where Es a E½ox[MsL]=Es+β. PL(2) measure electron-richness site Ms and β its polarisability. Other properties [MsL] such as type which binds Ms, spectroscopic properties, chemical reactivity are discussed parameters Es, β. It shown that (2) can be identification unknown...
Very fast-growing (VFG) broiler chickens tend to have marked right ventricular hypertrophy when compared with slower growing chickens. We hypothesized that, in the setting of rapid growth, a hypoxic stimulus would cause greater pulmonary hypertension and (RVH). studied relationship between artial oxygenation (SaO90), RVH, artery pressure (Ppa) 28 awake VFG found that hypoxemic had Ppa was linearly related SaO90. The however, best described by broken line (p < 0.05). Thus, at higher...
IR spectroelectrochemistry of Fe4{Me(CH2S)3}2(CO)8 (4Fe6S) in the ν(CO) region shows that neutral and anion forms have all their CO groups terminally bound to Fe atoms; however, for dianion there is a switch coordination mode at least one groups. The available structural spectra are closely reproduced by density-functional theory calculations. calculated structure 4Fe6S2- mirrors diiron subsite [Fe−Fe] hydrogenase H cluster with bridging group an open site on outer atom pairs...
Natural model: The synthesis of a close structural analogue the active site [Fe]-hydrogenase is described (see structure; C gray, H dark blue, Fe green, N light O red, S yellow). Nature most probably constructs five membered ferracyclic ring to poise 2-hydroxy pyridine substituent in position assist heterolytic cleavage dihydrogen, and accessibility should now provide opportunities for probing this. Detailed facts importance specialist readers are published as ”Supporting Information”. Such...
Infrared data for mono-iron complexes possessing two cis-CO together with Mössbauer the enzyme and a model complex support assignment that iron centre of cluster-free hydrogenase Hmd is low-spin Fe(II).
Iron(I) in biology?: one-electron oxidation of an (Fe(I)-Fe(I)) carbonyl cyanide precursor bearing a proximal thioether group leads to (Fe(I)-Fe(II)) bridging transient with spectral features similar the di-iron sub-site CO inhibited paramagnetic centre all-iron hydrogenase.
The substituted d0 metallocene dichloro-complexes [M(η-C5H4R)2Cl2](M = TiIV, ZrIV, or HfIV; R Me, Et, Pri But, SiMe3), (1)–(11), have been prepared from MCl4 and 2Li[C5H4R] in tetrahydrofuran (thf). From the appropriate dichloride either (i) MgR′Cl CH2Cl2 there was obtained chloro (alkyl)[M(η-C5H4R)2R′Cl](R′= CH2SiMe3) [Zr(η-C5H5)2(CH2CMe3)Cl], (ii) alkyl-lithium OEt2 dialkyl [M′(η-C5H4R″)2–(CH2XMe3)2](M′= Zr Hf; R″= H, Pri, But; X C Si), (13)–(16), produced; treatment of [Hf(η-C5H4But)2Cl2]...
The electron-transfer reactions of several binary metal carbonyls at a Pt electrode in aprotic solvents have been investigated. In tetrahydrofuran, cathodic reduction the M(CO)n leads to anions [M2(CO)2n– 2]2–(M = Cr, Mo, W, and Fe) [M(CO)n]–(M V), while binuclear M2(CO)10(M Mn Re) gives [M(CO)5]–. Of anodic reactions, particular interest are oxidations Cr(CO)6 which, acetonitrile, produce cations [Cr(CO)6]+ [M(CO)5(NCMe)]+ respectively. mechanisms these studied.
The [Fe]-hydrogenase, also known as "H2-forming methylenetetrahydromethanopterin dehydrogenase" (Hmd) or "iron−sulfur cluster-free hydrogenase", is the third distinct class of hydrogenase enzyme to be discovered. In presence its carbocation substrate, it catalyzes reversible cleavage dihydrogen into H+ and H−, placing later concomitantly onto substrate molecule. This review describes emerging chemistry behind this fascinating enzyme.