Marco Dalla Tiezza

• Ph.D. in Chemistry
• Ph.D. at University of Padua

In 1973, two major discoveries changed the face of selenium chemistry: the identification of the first mammal selenoenzyme, glutathione peroxidase 1, and the discovery of the synthetic utility of the so‐called selenoxide elimination. While the chemical mechanism behind the catalytic activity of glutathione peroxidases appears to be mostly unveiled,...

We performed a hierarchical ab initio benchmark study of the gas‐phase radical addition reactions of X⋅+C2H2 and X⋅+C2H4 (X⋅ = CH3⋅, NH2⋅, OH⋅, SH⋅). The hierarchical series of ab initio methods (HF, MP2, CCSD, CCSD(T)) were paired with a hierarchal series of Dunning basis sets with and without diffuse functions ((aug)–cc–pVDZ, (aug)–cc–pVTZ, (aug)...

Correction for ‘Pericyclic reaction benchmarks: hierarchical computations targeting CCSDT(Q)/CBS and analysis of DFT performance’ by Pascal Vermeeren et al. , Phys. Chem. Chem. Phys. , 2022, 24 , 18028–18042, https://doi.org/10.1039/D2CP02234F.

A series of macrocyclic ligands were considered for the chelation of Pb²⁺: 1,4,7,10-tetrakis[2-(methylsulfanyl)ethyl]-1,4,7,10-tetraazacyclododecane (DO4S), 1,4,7-tris[2-(methylsulfanyl)ethyl]-1,4,7,10-tetraazacyclododecane (DO3S), 1,4,7-tris[2-(methylsulfanyl)ethyl]-10-acetamido-1,4,7,10-tetraazacyclododecane (DO3SAm), 1,7-bis[2-(methylsulfanyl)et...

Chemical Quest is an innovative trivia game based on the 102 elements of the periodic table from H to No, developed collaboratively by upper secondary school and university teachers with the aim of increasing the interest of young students (age 14–18) in chemistry. As part of the project, a software version of the game was successfully played in 24...

We set up an in silico experiment and designed a chimeric compound integrating molecular features from different efficient ROS (Reactive Oxygen Species) scavengers, with the purpose of investigating potential relationships between molecular structure and antioxidant activity. Furthermore, a selenium centre was inserted due to its known capacity to...

We have quantum chemically studied activation of H n A–AH n bonds (AH n = CH 3 , NH 2 , OH, F) by PdL n catalysts with L n = no ligand, PH 3 , (PH 3 ) 2 , using relativistic density functional theory at ZORA-BLYP/TZ2P. The activation energy associated with the oxidative addition step decreases from H 3 C–CH 3 to H 2 N–NH 2 to HO–OH to F–F, where th...

Hierarchical, convergent ab initio benchmark computations were performed followed by a systematic analysis of DFT performance for five pericyclic reactions comprising Diels-Alder, 1,3-dipolar cycloaddition, electrocyclic rearrangement, sigmatropic rearrangement, and double group transfer prototypes. Focal point analyses (FPA) extrapolating to the a...

We have quantum chemically studied the palladium‐mediated activation of C(spⁿ)−X bonds (n=1–3; X=F, Cl, Br, I) in the archetypal model substrates H3C−CH2−X, H2C=CH−X, and HC≡C−X by a model bare palladium catalyst, using relativistic density functional theory at ZORA‐BLYP/TZ2P. The bond activation reaction barrier decreases, for all sp‐hybridized ca...

The C−X bond activation (X = H, C) of a series of substituted C(n°)−H and C(n°)−C(m°) bonds with C(n°) and C(m°) = H3C− (methyl, 0°), CH3H2C− (primary, 1°), (CH3)2HC− (secondary, 2°), (CH3)3C− (tertiary, 3°) by palladium were investigated using relativistic dispersion‐corrected density functional theory at ZORA‐BLYP‐D3(BJ)/TZ2P. The effect of the s...

We have studied the palladium‐mediated activation of C(spⁿ)−X bonds (n = 1–3 and X = H, CH3, Cl) in archetypal model substrates H3C−CH2−X, H2C=CH−X and HC≡C−X by catalysts PdLn with Ln = no ligand, Cl⁻, and (PH3)2, using relativistic density functional theory at ZORA‐BLYP/TZ2P. The oxidative addition barrier decreases along this series, even though...

The reactivity of phenothiazine (PS), phenoselenazine (PSE), and phenotellurazine (PTE) with different reactive oxygen species (ROS) has been studied using density functional theory (DFT) in combination with the QM‐ORSA (Quantum Mechanics‐based Test for Overall Free Radical Scavenging Activity) protocol for an accurate kinetic rate calculation. Fou...

The Cu2+ complexes formed by a series of cyclen derivatives bearing sulfur pendant arms, 1,4,7,10-tetrakis[2-(methylsulfanyl)ethyl]-1,4,7,10-tetraazacyclododecane (DO4S), 1,4,7-tris[2-(methylsulfanyl)ethyl]-1,4,7,10-tetraazacyclododecane (DO3S), 1,4,7-tris[2-(methylsulfanyl)ethyl]-10-acetamido-1,4,7,10-tetraazacyclododecane (DO3SAm), and 1,7-bis[2-...

The catalytic effect of various weakly interacting Lewis acids (LAs) across the periodic table, based on hydrogen (Group 1), pnictogen (Group 15), chalcogen (Group 16), and halogen (Group 17) bonds, on the Diels‐Alder cycloaddition reaction between 1,3‐butadiene and methyl acrylate was studied quantum chemically by using relativistic density functi...

Invited for this month's cover are collaborating groups from Università degli Studi di Padova, Vrije Universiteit Amsterdam, and Universidad de la República Uruguay. The cover picture shows two lorries along the road directed to the destination ‘H2O2 reduction’, and the selenol (SeH) lorry is faster than the thiol (SH) lorry. This cartoon represent...

The Front Cover shows two lorries along the road directed to ‘H2O2 reduction’ destination. The selenol (SeH) lorry is in front, being faster than the thiol (SH) lorry. This cartoon represents the situation of glutathione peroxidase, in which the presence of selenium rather than sulfur warrants a significantly faster hydroperoxide reduction along th...

The so‐called peroxidatic cysteines and selenocysteines in proteins reduce hydroperoxides through a dual attack to the peroxide bond in a two‐step mechanism. First, a proton dislocation from the thiol/selenol to a close residue of the enzymatic pocket occurs. Then, a nucleophilic attack of the anionic cysteine/selenocysteine to one O atom takes pla...

Dear Colleagues, Thank you for the possibility to present recent investigations in the Special Issue Edited by Professor Sérgio F. Sousa, which has been published in open access journal Applied Sciences (https://www.mdpi.com/journal/applsci/special_issues/Appl_Quantum_Mechanics) and united recognized scientists worldwide (Italy, Germany, Morocco, P...

With a half-life of 7.45 days, silver-111 (βmax 1.04 MeV, Eγ 245.4 keV [Iγ 1.24%], Eγ 342.1 keV [Iγ 6.7%]) is a promising candidate for targeted cancer therapy with β - emitters as well as for associated SPECT imaging. For its clinical use, the development of suitable ligands that form sufficiently stable Ag+-complexes in vivo is required. In this...

Methylmercury is a highly toxic compound and human exposure is mainly related to consumption of polluted fish and seafood. The inactivation of thiol‐based enzymes, promoted by the strong affinity binding of electrophilic mercuric ions to thiol and selenol groups of proteins, is likely an important factor explaining its toxicity. A key role is playe...

Macrocyclic ligands obtained by N-functionalization of 1,4,7,10-tetraazacyclododecane (cyclen) have been widely studied due to their remarkable complexing properties toward a variety of transition metals and lanthanides. Despite the large plethora...

The (seleno)cysteine residues in some protein families react with hydroperoxides with rate constants far beyond those of fully dissociated low molecular weight thiol or selenol compounds. In case of the glutathione peroxidases, we could demonstrate that high rate constants are achieved by a proton transfer from the chalcogenol to a residue of the a...

Featured Application Due to the seriousness of depressive disorders and their social implications, any strategy to improve clinical symptoms are of considerable importance. It is recognized that oxidative stress negatively impacts on this and other psychiatric diseases. Fluoxetine, a well-known and largely prescribed antidepressant drug, has antiox...

In the paper by Orian et al. on page 679, the catalytic activity of anti- and syn-Rh/Cr indenyl complexes in alkyne [2+2+2] cycloadditions is investigated by means of quantum chemistry calculations, and the catalysts are built like a jigsaw puzzle. In fact, the mechanistic features of the parent monometallic rhodium indenyl and rhodium cyclopentadi...

Metal-catalyzed alkyne [2+2+2] cycloadditions provide a variety of substantial aromatic compounds of interest in the chemical and pharmaceutical industries. Herein, the mechanistic aspects of the acetylene [2+2+2] cycloaddition mediated by bimetallic half-sandwich catalysts [Cr(CO)3IndRh] (Ind = (C9H7)−, indenyl anion) are investigated. A detailed...

Supporting information

The interest in diphenyl ditelluride (Ph2Te2) is related to its strict analogy to diphenyl diselenide (Ph2Se2), whose capacity to reduce organic peroxides is largely exploited in catalysis and green chemistry. Since the latter is also a promising candidate as an antioxidant drug and mimic of the ubiquitous enzyme glutathione peroxidase (GPx), the u...

Zolpidem (N,N-Dimethyl-2-[6-methyl-2-(4-methylphenyl)imidazo[1,2-a]pyridin-3-yl]acetamide) is a well-known drug for the treatment of sleeping disorders. Recent literature reports on positive effects of zolpidem therapy on improving renal damage after cisplatin and on reducing akinesia without sleep induction. This has been ascribed to the antioxida...

The Cover Feature shows the glacier of Marmolada, the highest Dolomite (3343 m), with superimposed the aromatic ligand of the group 9 half‐matallocene catalysts for [2+2+2] cycloadditions of unsaturated molecules. When large changes of metal slippage from the centroid of the coordinated cyclopentadienyl moiety occur during catalysis, the turnover f...

Half‐sandwich RhI compounds display good catalytic activity toward alkyne [2+2+2] cycloadditions. A peculiar structural feature of these catalysts is the coordination of the metal to an aromatic moiety, typically a cyclopentadienyl anion, and, in particular, the possibility to change the bonding mode easily by the metal slipping over this aromatic...

Organodiselenides are an important class of compounds characterized by the presence of two adjacent covalently bonded selenium nuclei. Among them, diaryldiselenides and their parent compound diphenyl diselenide, attract continuing interest in chemistry as well as in close disciplines like medicinal chemistry, pharmacology and biochemistry. A search...

The reactivity of diselenides and ditellurides of general formula (RX)2 (X=Se, Te; R=H, CH3, C6H5) toward hydrogen peroxide was studied through a computational approach based on accurate Density Functional Theory (DFT) calculations. The aliphatic and aromatic dichalcogenides have been chosen in light of their activity in glutathione peroxidase (GPx...

The reaction between the gold(I) dicarbene complexes [Au2(μ²-MeIm(CH2)nImMe)2](PF6)2 (Im = imidazol-2-ylidene, n = 1, 2, 3) and N-bromosuccinimide affords the gold(III) complexes [{AuBr(N-suc)}2(μ²-MeIm(CH2)nImMe)2](PF6)2, in which both gold centres have a bromide and a N-succinimidate anion in the coordination sphere. In the case of the CH2CH2 bri...

The intramolecular oxidative addition converting a bis‐acetylene complex of formula CpM(C2H2)2 (Cp = C5H5‐; M = Co, Rh, Ir) into a 16 electron metallacycle is studied in silico. This reaction is paradigmatic in acetylene [2+2+2] cycloaddition to benzene catalyzed by CpM fragments, being the step with the highest activation energy, and thus affectin...