A5050529895- Electrochemical Analysis and Applications
- Photosynthetic Processes and Mechanisms
- Electrochemical sensors and biosensors
- Crystallization and Solubility Studies
- X-ray Diffraction in Crystallography
- Metal complexes synthesis and properties
- Metal-Catalyzed Oxygenation Mechanisms
- Crystal structures of chemical compounds
- Protein Structure and Dynamics
- Spectroscopy and Quantum Chemical Studies
- Hemoglobin structure and function
- Molecular Junctions and Nanostructures
- Electron Spin Resonance Studies
- Enzyme Structure and Function
- Enzyme-mediated dye degradation
- Metalloenzymes and iron-sulfur proteins
- Molecular Sensors and Ion Detection
- Porphyrin Metabolism and Disorders
- Chemical Synthesis and Analysis
- Trace Elements in Health
- Lanthanide and Transition Metal Complexes
- Porphyrin and Phthalocyanine Chemistry
- Analytical Chemistry and Sensors
- Protein Interaction Studies and Fluorescence Analysis
- Magnetism in coordination complexes
University of Modena and Reggio Emilia
2015-2024
Azienda Unita' Sanitaria Locale Di Modena
2020
Istituto Nanoscienze
2010-2015
In-Q-Tel
2013
Newcastle University
2010
University of Bologna
1963-2007
Leiden University
2001-2007
Tel Aviv University
2007
Russian Academy of Sciences
2007
Institute of Bioorganic Chemistry
2007
Recent work has disclosed the critical role played by enamel peptides in sex classification of old skeletal remains. In particular, protein AMELY (amelogenin isoform Y) is present dental tissue male individuals only, while AMELX (isoform X) can be found both sexes. easily detected LC-MS/MS ion extracted chromatograms SM(ox)IRPPY peptide (monoisotopic [M + 2 H]+2 mass = 440.2233 m/z). this paper, we exploited dimorphic features amelogenin to determine so-called 'Lovers Modena', two Late...
Lytic polysaccharide monooxygenases (LPMOs) are Cu-containing enzymes that facilitate the degradation of recalcitrant polysaccharides by oxidative cleavage glycosidic bonds. They gaining rapidly increasing attention as key players in biomass conversion, especially for production second-generation biofuels. Elucidation detailed mechanism LPMO reaction is a major step toward assessment and optimization efficacy industrial biotechnology, paving way to utilization sustainable fuel sources. Here,...
Axial iron ligation and protein encapsulation of the heme cofactor have been investigated as effectors reduction potential (E°') cytochrome c through direct electrochemistry experiments. Our approach was that partitioning E°' changes resulting from binding imidazole, 2-methyl-imidazole, ammonia, azide to both microperoxidase-11 (MP11), into enthalpic entropic contributions. N-Acetylmethionine MP11 also investigated. These ligands replace Met80 a water molecule axially coordinated in MP11,...
ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTProton NMR spectroscopy and the electronic structure of high potential iron-sulfur protein from Chromatium vinosumIvano Bertini, Fabrizio Briganti, Claudio Luchinat, Andrea Scozzafava, Marco SolaCite this: J. Am. Chem. Soc. 1991, 113, 4, 1237–1245Publication Date (Print):February 1, 1991Publication History Published online1 May 2002Published inissue 1 February...
Dynamic protein–solvent interactions are fundamental for life processes, but their investigation is still experimentally very demanding. Molecular dynamics simulations up to hundreds of nanoseconds can bring light unexpected events even extensively studied biomolecules. This paper reports a combined computational/experimental approach that reveals the reversible opening two distinct fluctuating cavities in Saccharomyces cerevisiae iso-1-cytochrome c. Both channels allow water access heme...
The thermodynamic parameters of protein reduction (ΔH°'rc and ΔS°'rc) were measured for a number blue copper proteins including spinach plastocyanin, cucumber Pseudomonas aeruginosa azurin, Rhus vernicifera stellacyanin, horseradish umecyanin through voltammetric techniques in nonisothermal experiments at neutral pH. Including previous estimates other members the same family, we discuss here thermodynamics electron-exchange reaction twelve from different sources. enthalpic term (-ΔH°'rc/F)...
The reduction potentials of beef heart cytochrome c and cytochromes c2 from Rhodopseudomonas palustris, Rhodobacter sphaeroides, capsulatus were measured through direct electrochemistry at a surface-modified gold electrode as function temperature in nonisothermal experiments carried out neutral alkaline pH values. thermodynamic parameters for protein (ΔS°rc ΔH°rc) determined the native conformers. Enthalpy entropy terms underlying species-dependent differences E° pH- temperature-induced...
ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTRedox chemistry of superoxide dismutase. Cyclic voltammetry wild-type enzymes and mutants on functionally relevant residuesH. A. Azab, L. Banci, M. Borsari, C. Luchinat, Sola, S. ViezzoliCite this: Inorg. Chem. 1992, 31, 22, 4649–4655Publication Date (Print):October 1, 1992Publication History Published online1 May 2002Published inissue 1 October 1992https://pubs.acs.org/doi/10.1021/ic00048a037https://doi.org/10.1021/ic00048a037research-articleACS...
Elucidation of the molecular determinants reorganization energy λ is central to understanding fundamental biological processes based on transduction pathways. Here, we use a combined experimental/theoretical approach electrochemically determine for number cytochrome c variants and compute structure-related properties relevant kinetics electron transfer process through dynamics simulations. We find that exposure heme group solvent controls investigated proteins. Therefore, fine-tuning can be...
The binary and ternary (2,2'-bipyridine) complexes of dipositive lead formed by N-carbonyl N-sulfonyl amino acids, which are ligands containing the peptide sulfonamide group, respectively, were investigated in aqueous solution NMR differential pulse polarography, some also characterized crystallographically. N-Tosylglycine, N-tosyl-beta-alanine, N-benzoylglycine behave as simple carboxylate at acid pH, while around neutrality they switch to dianionic N,O-bidentate chelating due involvement...
ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTCoordination behavior of L-glutamic acid: spectroscopic and structural properties (L-glutamato)(imidazole)copper(II), (L-glutamato)(2,2'-bipyridine)copper(II), aqua(L-glutamato)(1,10-phenanthroline)copper(II) trihydrate complexesL. Antolini, G. Marcotrigiano, L. Menabue, C. Pellacani, M. Saladini, SolaCite this: Inorg. Chem. 1985, 24, 22, 3621–3626Publication Date (Print):October 1, 1985Publication History Published online1 May 2002Published...
Myeloperoxidase (MPO) (donor, hydrogen peroxide oxidoreductase, EC 1.11.1.7) is the most abundant neutrophil enzyme and catalyzes predominantly two-electron oxidation of ubiquitous chloride (Cl-), to generate potent bleaching oxidant hypochlorous acid (HOCl), thus contributing bacterial killing inflammatory reactions neutrophils. Here, thermodynamics one-electron reduction ferric heme in its high-spin cyanide-bound low-spin forms were determined through spectroelectrochemical experiments....
Cytochromes c (cytc) are ubiquitous heme-containing metalloproteins that shuttle electrons in a variety of electron-transport chains, most often central to the production chemical energy necessary for cell life. The reduction potential (E°′) Fe3+/2+ couple is physiological role these species it influences thermodynamic and kinetic features electron-exchange reactions with redox partners. In last two decades, voltammetric techniques exploiting heterogeneous electron exchange between cytc...
The thermodynamics of Fe3+ to Fe2+ reduction for the five-coordinate high-spin native form horseradish peroxidase and its six-coordinate low-spin cyanide adduct have been determined from variable-temperature UV−vis spectroelectrochemical experiments. In both cases, ΔH°'rc ΔS°'rc values are positive. Hence, negative potentials turn out be result two opposing partially compensating contributions: a large enthalpic term, which is determinant E°' species, smaller, yet relevant, entropic...
The reduction thermodynamics (ΔH°'rc and ΔS°'rc) for native Paracoccus versutus amicyanin, Alcaligenes faecalis S-6 pseudoazurin, the G45P, M64E, K27C variants of Pseudomonas aeruginosa azurin were measured electrochemically. Comparison with data available other mutated blue copper proteins indicates that features metal coordination electrostatic potential due to protein matrix solvent control enthalpy in a straightforward way. However, effects on are rather unpredictable owing entropic...
Cyclic voltammetry experiments were carried out on native Saccharomyces cerevisiae iso-1-cytochrome c and its C102T/N62C variant immobilized bare polycrystalline gold electrode through the S−Au bond formed by a surface cysteine. Experiments at different temperatures (5−65 °C) pH values (1.5−7). The E°' value 7 (+370 mV vs SHE) is approximately 100 higher than that for protein in solution. This difference enthalpic origin proposed to be result of electrostatic repulsion among densely packed...
Replacement of the axial Met80 heme ligand in electrode-immobilized cytochrome c with a noncoordinating Ala residue and alteration hydrogen bonding network region nearby following substitution Tyr67 were investigated as effectors thermodynamics kinetics protein−electrode electron transfer (ET) heme-mediated electrocatalytic reduction H2O2. To this end, voltammetry Met80Ala, Met80Ala/Tyr67His, Met80Ala/Tyr67Ala variants yeast iso-1-cytochrome chemisorbed on carboxyalkanethiol self-assembled...
The low-pH conformational equilibria of ferric yeast iso-1 cytochrome c (ycc) and its M80A, M80A/Y67H, M80A/Y67A variants were studied from pH 7 to 2 at low ionic strength through electronic absorption, magnetic circular dichroism, resonance Raman spectroscopies. For wild-type ycc, the protein structure, axial heme ligands, spin state iron atom convert native folded His/Met low-spin (LS) form a molten globule His/H(2)O high-spin (HS) totally unfolded bis-aquo HS state, in single cooperative...
The hydrophobic patch of azurin (AZ) from Pseudomonas aeruginosa is an important recognition surface for electron transfer (ET) reactions. influence changing the size this region, by mutating C-terminal copper-binding loop, on ET reactivity AZ adsorbed gold electrodes modified with alkanethiol self-assembled monolayers (SAMs) has been studied. distance-dependence kinetics measured cyclic voltammetry using SAMs variable chain length, demonstrates that activation barrier short-range dominated...
The redox potential of horse and bovine heart cytochromes c determined through cyclic voltammetry is exploited to probe for anion–protein interactions, using a Debye–Hückel‐based model. In parallel, protein charge neutralization resulting from specific anion binding allows monitoring surface‐charge/ E o relationships. This approach shows that number anions, most which are biological relevance, namely Cl ‐ , HPO 2‐ 4 HCO 3 NO SO ClO citrate 3‐ oxalate bind specifically the surface, often in...