Article
Chemistry, Multidisciplinary
Yanbang Li, Thomas J. Emge, Antonio Moreno-Vicente, William P. Kopcha, Yue Sun, Iram F. Mansoor, Mark C. Lipke, Gene S. Hall, Josep M. Poblet, Antonio Rodriguez-Fortea, Jianyuan Zhang
Summary: A new multicomponent reaction involving isocyanide, alkynes, and endohedral metallofullerene (EMF) Lu3N@C-80 has been developed to yield metallofulleroids characterized by various analytical techniques. Single crystal studies revealed ordered Lu3N cluster in one ketenimine metallofulleroid, which is rare for EMF monoadducts. Computational analysis confirmed that the motion of the endohedral cluster is influenced by the position of exohedral organic appendants.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Yelu Shi, Gianna Stella, Jia-Min Chu, Yong Zhang
Summary: This study reveals the importance of HNO binding and a proton-coupled electron transfer mechanism for HNO reaction through quantum chemical research on Cu cyclams. The results indicate that steric effect is the primary factor, and electronic factor is the secondary factor, but the combined effects can lead to unexpected reactions.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Boyli Ghosh, Ambar Banerjee, Lisa Roy, Rabindra Nath Manna, Rounak Nath, Ankan Paul
Summary: This study investigates the mechanistic pathways of copper-promoted formation of aryl isocyanate from aryl aldehyde. The analysis suggests that the reaction proceeds through radical-based pathways, consistent with experimental findings. Copper salts play a role as an electron pool in this nitrogen transfer reaction.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Pascal Vermeeren, Trevor A. Hamlin, F. Matthias Bickelhaupt
Summary: The catalytic effect of ionization on the Diels-Alder reaction between 1,3-butadiene and acrylaldehyde has been studied using relativistic density functional theory (DFT). The removal of an electron from the dienophile significantly accelerates the reaction and changes the reaction mechanism. Detailed analyses reveal two mechanisms by which ionization enhances the reactivity.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Physical
Daniele Loco, Isabelle Chataigner, Jean-Philip Piquemal, Riccardo Spezia
Summary: Modeling chemical reactions using Quantum Chemistry is a widely used predictive strategy that complements experimental studies to understand reaction mechanisms. This research benchmarked various computational approaches for predicting energy barriers in six Diels-Alder reactions of increasing complexity. The results showed that using economical Density Functional Theory methods combined with empirical dispersion corrections can provide high-quality results with minimal computational effort. This simulation protocol opens new prospects for studying Diels-Alder reactions with explicit solvent using hybrid QM/MM molecular dynamics simulations.
Article
Chemistry, Physical
Yanhong Liu, Aili Feng, Rongxiu Zhu, Chengbu Liu, Dongju Zhang
Summary: Density functional theory (DFT) calculations were performed to investigate the mechanism of copper-catalyzed four-component borocarbonylative coupling of alkenes with alkyl halides using bis(pinacolato)diboron as the boron reagent under CO atmosphere. The theoretical results revealed an unexpected reaction mechanism involving CuI as the sole catalyst, with a two-ligand relay mechanism and no radical participation, proceeding through SN2-type C-C coupling. The experimental observations of regio- and chemoselectivities, as well as the inhibition of the reaction by radical trapping reagents, were rationalized by the theoretical analysis.
JOURNAL OF CATALYSIS
(2023)
Article
Chemistry, Organic
Eveline H. Tiekink, Pascal Vermeeren, F. Matthias Bickelhaupt, Trevor A. Hamlin
Summary: The study demonstrates that Lewis acid catalysts efficiently accelerate the ene reaction by lowering the reaction barrier and inducing asymmetry in the pi-electronic system, thus relieving activation strain and Pauli repulsion.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Yong Wu, Shanshan Cao, Iskander Douair, Laurent Maron, Xihe Bi
Summary: The [2+1] cycloaddition reaction of a metal carbene with an alkene often suffers from side reactions, leading to lower yields of cyclopropanation products. By adding a low concentration of diazo compound to alkenes, it was found that AgOTf catalysis can efficiently produce cyclopropane products from hindered alkenes.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Green & Sustainable Science & Technology
Sajjad Hussain, Dhanasekaran Vikraman, Zeesham Abbas, Muhammad Faizan, Sikandar Aftab, Khalid Mujasam Batoo, Hyun-Seok Kim, Kyung-Wan Nam, Jongwan Jung
Summary: In this study, CoNiO2 nanowires (NWs)-embedded MoS2 hybrids were synthesized and found to exhibit superior bifunctional catalytic activity and stability. The strong interfacial contact between CoNiO2 NWs and MoS2 was also observed, contributing to the enhanced electrocatalytic performance. This development of cobalt-based oxide and transition metal dichalcogenide carrier bifunctional electrocatalysts provides a novel approach to enhance overall water splitting.
SUSTAINABLE MATERIALS AND TECHNOLOGIES
(2023)
Article
Chemistry, Multidisciplinary
Marin Puget, Viacheslav Shcherbakov, Sergey Denisov, Philippe Moreau, Jean-Pierre Dognon, Mehran Mostafavi, Sophie Le Caer
Summary: The nature of the primary species formed in FEC depends on the amount of FEC in the solution, which will affect its performance in the electrolyte.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Physical
Zhiyao Duan, Graeme Henkelman
Summary: This study uses global optimization and constant-potential density functional theory to simulate the complete process of Pt dissolution, revealing the formation and dissolution mechanism of a two-dimensional Pt surface oxide. The findings provide a fundamental understanding of Pt dissolution under potential cycling, which is essential for the rational design of durable Pt-based cathodes for fuel cells.
Article
Chemistry, Multidisciplinary
Raphael Robidas, Claude Y. Legault
Summary: A mechanism is proposed to explain the formation of benzobicyclo[3.2.0]heptane derivatives from 1,7-enyne derivatives bearing a terminal cyclopropane, which has been previously reported.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Pascal Vermeeren, Marco Dalla Tiezza, Michelle van Dongen, Israel Fernandez, F. Matthias Bickelhaupt, Trevor A. Hamlin
Summary: Various weakly interacting Lewis acids across the periodic table can catalyze the Diels-Alder cycloaddition reaction by lowering the reaction barrier and increasing the asynchronicity of the reaction, demonstrating the generality of the Pauli repulsion-lowering catalysis concept. The reactivity can be further enhanced with a stronger binding to the dienophile, as shown when transitioning from a Period 3 to a Period 5 Lewis acid.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Agricultural Engineering
Misa Mojca Cajnko, Jost Oblak, Miha Grilc, Blaz Likozar
Summary: Enzymes play a crucial role in lignin valorization, with different enzymes involved in various elementary reaction mechanisms. Degradation of lignin depends on enzyme activity and the interaction with proteins in ways that target specific covalent bonds in lignin. Various factors influence enzymatic activity, which must be taken into consideration for optimal functionality and synthesis yields.
BIORESOURCE TECHNOLOGY
(2021)
Article
Chemistry, Physical
Niklas Thoben, Tobias Kaper, Simon de Graaff, Luca Gerhards, Marc Schmidtmann, Thorsten Kluener, Rudiger Beckhaus, Sven Doye
Summary: Hybrid Density Functional Theory (DFT) calculations were used to investigate the multiple conformers of the insertion reactions of a methylenecyclopropane into the Ti-C bond of two differently α-substituted titanaaziridines. The calculations explained the experimentally observed differences in regioselectivity between catalytic hydroaminoalkylation reactions and corresponding stoichiometric reactions. The study also provided insights into the lack of reactivity of α-phenyl-substituted titanaaziridines and the diastereoselectivity of the reactions.
Article
Green & Sustainable Science & Technology
Lorenzo Bigiani, Alberto Gasparotto, Teresa Andreu, Johan Verbeeck, Cinzia Sada, Evgeny Modin, Oleg I. Lebedev, Juan Ramon Morante, Davide Barreca, Chiara Maccato
Summary: This study presents a versatile approach for preparing manganese oxide catalysts, focusing on gold-decorated manganese oxide-based OER electrocatalysts. By characterizing and controlling the composition of Mn(x)O(y) phases, high OER activity was achieved, demonstrating the potential for developing low-cost and efficient anode nanocatalysts for water splitting applications.
ADVANCED SUSTAINABLE SYSTEMS
(2021)
Article
Engineering, Environmental
Javier Fragoso, Davide Barreca, Lorenzo Bigiani, Alberto Gasparotto, Cinzia Sada, Oleg I. Lebedev, Evgeny Modin, Ivana Pavlovic, Luis Sanchez, Chiara Maccato
Summary: This study presents the use of heterostructures based on beta-Fe2O3 for De-NOx photocatalysis, fabricated by chemical vapor deposition of Fe2O3 and functionalized with CuO or WO3. The modulation of material performance by forming heterostructures enables efficient removal of nitrogen oxides. The improved photoactivity is attributed to matched band edges and increased oxygen defectivity in the target heterostructures.
CHEMICAL ENGINEERING JOURNAL
(2022)
Article
Materials Science, Multidisciplinary
Davide Barreca, Lorenzo Bigiani, Max Klotzsche, Alberto Gasparotto, Roberta Seraglia, Christian Jandl, Alexander Pothig, Ettore Fois, Laura Vanin, Gloria Tabacchi, Marco Roverso, Sara Bogialli, Emanuela Callone, Sandra Dire, Chiara Maccato
Summary: Iron(III) oxide nanomaterials show great potential in various applications, and the versatile iron(II) precursor Fe(tfa)(2)TMEDA can be used to fabricate high purity iron oxide nanomaterials with metastable phase and tunable nano-organization. This precursor combines molecular stability, volatility, and clean decomposition, making it ideal for chemical vapor deposition (CVD) applications.
MATERIALS CHEMISTRY AND PHYSICS
(2022)
Article
Polymer Science
Marco Paolino, Mario Saletti, Annalisa Reale, Vincenzo Razzano, Germano Giuliani, Alessandro Donati, Claudia Bonechi, Gianluca Giorgi, Andrea Atrei, Matteo Mauro, Andrea Scamporrino, Filippo Samperi, Ettore Fois, Gloria Tabacchi, Chiara Botta, Andrea Cappelli
Summary: Benzofulvene derivatives bearing complexed and un-complexed pyridine rings were designed and synthesized to evaluate the impact of bulky substituents capable of establishing metallophilic interactions on the spontaneous solid-state polymerization.
EUROPEAN POLYMER JOURNAL
(2022)
Review
Chemistry, Multidisciplinary
Davide Barreca, Chiara Maccato, Alberto Gasparotto
Summary: This review discusses the advancements in chemoresistive gas sensors based on metal oxide nanosystems for the detection of chemical warfare agents (CWAs). The sensing mechanisms and performance enhancement reasons are reviewed and summarized. The review also highlights the main challenges and prospects for future developments.
ADVANCED MATERIALS INTERFACES
(2022)
Article
Engineering, Environmental
Mattia Benedet, Gian Andrea Rizzi, Alberto Gasparotto, Oleg Lebedev, Leonardo Girardi, Chiara Maccato, Davide Barreca
Summary: This study presents a fabrication method for OER electrocatalysts based on graphitic carbon nitride. The catalysts were deposited on conductive glass substrates via electrophoretic technique and functionalized with noble metals using RF-sputtering. Functional tests showed that the catalysts exhibited high sensitivity to Vis light and their photoelectrocatalytic performances depended on the type of metal and the features of the carbon nitride deposit.
CHEMICAL ENGINEERING JOURNAL
(2022)
Article
Physics, Condensed Matter
Mattia Benedet, Alberto Gasparotto, Gian Andrea Rizzi, Davide Barreca, Chiara Maccato
Summary: In this study, the surface composition and elemental chemical states of graphitic carbon nitride (g-C3N4) materials decorated with highly dispersed noble metals were characterized using X-ray photoelectron spectroscopy. The results showed an intimate contact between the introduced noble metals and the underlying g-C3N4 matrix, resulting in functionalized structures of highly defective carbon nitride matrices.
SURFACE SCIENCE SPECTRA
(2022)
Article
Chemistry, Multidisciplinary
Serge Benedoue, Mattia Benedet, Alberto Gasparotto, Nicolas Gauquelin, Andrey Orekhov, Johan Verbeeck, Roberta Seraglia, Gioele Pagot, Gian Andrea Rizzi, Vincenzo Balzano, Luca Gavioli, Vito Di Noto, Davide Barreca, Chiara Maccato
Summary: This study reports on the synthesis of gCN flakes on Ni foam substrates by electrophoretic deposition and their decoration with Co-based cocatalysts. The developed systems were tested as (photo)anodes for water splitting and photoelectrocatalysts for the degradation of a recalcitrant water pollutant. Results showed that gCN decoration with Co-based cocatalysts enhanced water splitting performances, but bare gCN was more efficient in degrading the pollutant due to a different reaction mechanism. The insights from this study may provide guidelines for active nanomaterials in environmental remediation and solar-to-chemical energy conversion.
Article
Nanoscience & Nanotechnology
Gloria Tabacchi, Ilaria Armenia, Giovanni Bernardini, Norberto Masciocchi, Antonietta Guagliardi, Ettore Fois
Summary: Magnetic iron oxide nanoparticles (IONPs) have attracted attention for their biomedical applications. Through experiments and simulations, the mechanism of heat transfer from IONPs to their surroundings was revealed, providing a foundation for controlling the heat flow for activation or release of anchored molecules in medical and industrial applications.
ACS APPLIED NANO MATERIALS
(2023)
Article
Materials Science, Multidisciplinary
A. Martucci, N. Precisvalle, E. Fois, M. Ardit, G. Beltrami, L. Pasti, M. Cescon, E. Suard, G. Tabacchi
Summary: The concentration and location of Bronsted acid sites (BASs) in deuterated L-zeolite were determined using neutron powder diffraction and ab-initio molecular dynamics modelling. Two Bronsted acid sites, D1 and D2, were identified, with D2 showing a large degree of mobility and D1 showing static disorder. The study also found that the O1 BAS had a higher Bronsted base character compared to the average basicity of the framework oxygens of the 12-membered ring channels.
MATERIALS CHEMISTRY AND PHYSICS
(2023)
Article
Chemistry, Inorganic & Nuclear
Mattia Benedet, Davide Barreca, Ettore Fois, Roberta Seraglia, Gloria Tabacchi, Marco Roverso, Gioele Pagot, Cristiano Invernizzi, Alberto Gasparotto, Alexandra A. Heidecker, Alexander Poehig, Emanuela Callone, Sandra Dire, Sara Bogialli, Vito Di Noto, Chiara Maccato
Summary: The coordination sphere engineering of three heteroleptic Ni(ii) beta-diketonate-diamine adducts was studied, and it was found that the chemico-physical characteristics of the compounds directly depend on the functional groups in the diketonate ligands. Preliminary thermal CVD experiments demonstrated the suitability of the precursors for the obtainment of NiO films with flat and homogeneous surfaces.
DALTON TRANSACTIONS
(2023)