Article
Biochemistry & Molecular Biology
Insaf Abdouli, Frederic Dappozze, Marion Eternot, Chantal Guillard, Nadine Essayem
Summary: This paper provides evidence that the model reaction of aqueous dihydroxyacetone (DHA) conversion is influenced by both the acidity and basicity of TiO2 catalysts. Different products are obtained through two parallel pathways.
Article
Nanoscience & Nanotechnology
Nawras Abidi, Stephan N. Steinmann
Summary: Atomistic modeling of electrified interfaces is important in electrocatalysis, corrosion, electrodeposition, batteries, and related devices. The use of grand-canonical density functional theory (GCDFT) with implicit solvation models has become popular. However, the accuracy of these models for solvation effects at interfaces is not well known. Hybrid quantum mechanical/molecular mechanics (QM/MM) models have been proposed as a promising alternative. In this study, we demonstrate the implementation of electrostatic embedding in the VASP code and its application in GCDFT for studying the hydrogen evolution reaction (HER) on MoS2. Our results show that electrostatic embedding has a significant effect on polar sites, while having almost indistinguishable results compared to the implicit solvent for apolar systems.
ACS APPLIED MATERIALS & INTERFACES
(2023)
Article
Chemistry, Inorganic & Nuclear
S. S. Fouad, Eszter Baradacs, M. Nabil, Bence Parditka, S. Negm, Zoltan Erdelyi
Summary: In this study, a comparative analysis of TiO2/Cu/TiO2 thin films with different Cu interlayer thickness was conducted. The results showed that increasing the Cu interlayer thickness can enhance the photocatalytic activity and reduce the indirect optical band gap energy, making the films more efficient in absorbing visible light.
INORGANIC CHEMISTRY COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Davide Avagliano, Matteo Bonfanti, Artur Nenov, Marco Garavelli
Summary: This software provides an automated workflow and interface for simulating time-resolved transient absorption spectra of medium-to-big chromophores in complex environments using TD-DFT and QM/MM schemes, enabling simulations of systems previously computationally inaccessible. The implementation includes auxiliary scripts for system setup, evaluation of wavefunction overlap, and analysis of results.
JOURNAL OF COMPUTATIONAL CHEMISTRY
(2022)
Article
Materials Science, Multidisciplinary
Shyamapada Patra, Pritam Das, Shyamal Chatterjee
Summary: This work demonstrates the ability to tailor the bandgap, electrical conductivity, and wettability of anatase TiO2 nanotubes through low-energy argon ion irradiation. The effects of ion beam modification on the structure, morphology, and surface chemistry are analyzed using various techniques. The observed changes, such as morphological deformation, surface defects, and joining, are successfully predicted by simulation. The tunability of these properties can have significant impacts on various applications involving TiO2 nanotubes.
MATERIALS CHEMISTRY AND PHYSICS
(2023)
Article
Chemistry, Multidisciplinary
Leonardo F. G. Dias, Joao P. C. Rheinheimer, Orisson P. Gomes, Michael Noeske, Stephani Stamboroski, Erika S. Bronze-Uhle, Maria C. Mainardi, Welchy L. Cavalcanti, Augusto B. Neto, Paulo N. Lisboa-Filho
Summary: This paper presents insights into the surface properties of sputter-deposited titania modified with bisphosphonates. The functionalization process occurs in a short time and results in a predominantly side-on adsorbate configuration. Additionally, the modified titania surfaces exhibit hydrophilicity.
Article
Chemistry, Physical
Alejandro Suarez-Mendez, Myrna H. Matus, Victor M. Rivera
Summary: The photocatalytic evaluation of a novel material based on protonated thiophene-based oligomers as sensitizers of TiO2 nanoparticles supported on protonic zeolite-Y was investigated. Experimental results showed that the degradation rate depended on the amount of TiO2 supported on zeolite and the TiO2-OTn+/HY material was photochemically stable. Theoretical calculations indicated that oligothiophenes with protonation in the Ca atom exhibited the best performance as sensitizers in the TiO2OTn+/HY material.
JOURNAL OF PHOTOCHEMISTRY AND PHOTOBIOLOGY A-CHEMISTRY
(2022)
Article
Chemistry, Physical
Vinicius Manzoni, Rogerio Gester, Antonio R. da Cunha, Tarciso Andrade-Filho, Rodrigo Gester
Summary: The analysis of solvent effects on the fluorescence and NLO response of thieno[3,4-b]pyrazine was done using s-MC/QM method, showing potential applications in solar cells and biological markers. EC plays a key role in the first hyperpolarizability, with solvent effects being negligible.
JOURNAL OF MOLECULAR LIQUIDS
(2021)
Article
Chemistry, Physical
Jia Lin, Xiaohua Chen, Yong Zheng, Yihong Xiao, Ying Zheng, Lilong Jiang
Summary: Improving the sulfur resistance of palladium-based catalysts is essential for the sustainable and efficient combustion of methane. In this study, the surface properties of the catalysts were adjusted to regulate the behavior of sulfur species on the active sites and supports. The results showed that the accumulation of sulfur species in the catalysts increased linearly with the surface basicity and was restrained in catalysts with high surface acidity. The zirconium-doped alumina supported palladium catalyst exhibited moderate surface acidity/basicity and showed excellent catalytic activity in the presence of SO2 and after regeneration. The enhanced sulfur resistance was attributed to the interaction between supports and sulfur species, the decomposition of zirconium sulfates, the suppression of surface/bulk aluminum sulfates formation, and the effective regeneration of PdO phase. The establishment of a quantitative correlation between the accumulated sulfur species, surface acidity/basicity, and catalytic performance provides a pathway for the development of sulfur-resistant palladium-based catalysts for oxidation reactions.
APPLIED SURFACE SCIENCE
(2022)
Review
Biochemistry & Molecular Biology
Christina Eleftheria Tzeliou, Markella Aliki Mermigki, Demeter Tzeli
Summary: The multiscaling quantum mechanics/molecular mechanics (QM/MM) approach is a powerful tool for investigating chemical reactions' mechanisms, drug delivery, molecular devices properties, etc. This review briefly discusses the main methodologies in multiscaling approaches and provides a review on calculations and reactions on metalloproteins.
Article
Engineering, Chemical
Faisal Alahmadi, Il Son Khan, Daria Poloneeva, Genrikh Shterk, Luis Carlos Garzon Tovar, Robert Schucker, Anastasiya Bavykina, Jorge Gascon
Summary: Research into the upgrading of methane is gaining attention due to the recent increase in natural gas reservoir discoveries. Among the different techniques explored, Oxidative Coupling of Methane (OCM) is a promising route for the production of ethylene. Lanthanum oxide has long been known as a promising catalyst for OCM, but the synthesis method plays a crucial role in its performance. This study compares the catalytic performance of La2O3 prepared through the use of a cheap La-based-Metal Organic Framework (LaMOF) to conventionally prepared La2O3 via sol-gel (La-SG) and a commercial La2O3 (La C). The results show that La-MOF catalyst exhibits smaller particle size and higher C2+ yield at high temperature.
INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH
(2022)
Article
Chemistry, Physical
Nikorn Shinsuphan, Sriprajak Krongsuk, Supawadee Namuangruk
Summary: Hybrid QM/MM calculations were used to study the binding interactions and properties of microhydration complexes of Span 60 center dot(H2O)n (n = 1-10) in the gas phase. The hydration energy and binding force of the monohydration complex were found to depend strongly on the hydration sites of the Span 60 head group, with the ether oxygen showing the highest hydration energy. For polyhydration complexes, steric hindrance and electrostatic repulsions between water molecules led to similar average hydration energies as monohydrated forms, with the interaction between the ether oxygen and water molecules remaining prominent. The charge transfer phenomenon altered noticeably as more water molecules bound to specific oxygen atoms of the Span 60 head group, affecting hydrogen bond lengths and conformation changes.
Article
Chemistry, Physical
Yabin Wang, Juan He, Xueli Li, Youmin Shi, Yantu Zhang, Xiuping Ding
Summary: The study introduces two types of catalytic components into dendritic mesoporous silica nanospheres for the first time, producing DMSTNs/ACN photocatalysts with excellent visible-light response for energy conversion applications. The novel catalyst shows superior efficiency in hydrogen production through water splitting under simulated sunlight condition, as well as high selectivity in carbon dioxide reduction.
APPLIED SURFACE SCIENCE
(2021)
Article
Nanoscience & Nanotechnology
Junnan Chen, Yujie Qi, Ming Lu, Shaoming Dong, Bingsen Zhang
Summary: In this study, the interface microstructures of Pt/TiO2 catalysts were characterized using electronic energy loss spectroscopy. The presence of TiOx coating on the surface of Pt metal particles was observed after high-temperature reduction processing. A quantitative analysis method based on Gaussian function fitting was established to determine the stoichiometric number of TiOx phases. The origins of TiOx and its effects on the electronic structure of the material were discussed and analyzed using density functional theory calculations.
ACS APPLIED MATERIALS & INTERFACES
(2023)
Article
Chemistry, Physical
Kushanava Bhaduri, Anindya Ghosh, Aline Auroux, Sauvik Chatterjee, Asim Bhaumik, Biswajit Chowdhury
Summary: The craftsmanship in catalyst synthesis is fascinating when catalytic activity of the material can be enhanced by tuning the synthesis conditions. By tailoring the structural and chemical behavior of tantalum phosphates (TaP) using different structure directing agents, it is possible to create efficient TaP catalysts for glycerol transformation reactions. The study provides a pathway for analytical architecture and construction of highly efficient TaP catalysts.
MOLECULAR CATALYSIS
(2022)
Article
Chemistry, Physical
Anu Baby, Laura Trovato, Cristiana Di Valentin
Summary: The study explores the properties of potential single atom catalysts in graphene, including stability and reactivity towards the hydrogen evolution reaction, by introducing nitrogen atoms and transforming the graphene structure to enhance stability and catalysis.
Article
Chemistry, Physical
Paulo Siani, Enrico Bianchetti, Hongsheng Liu, Cristiana Di Valentin
Summary: The study optimized CLASS2 force field parameters to describe Fe-O-water interactions by comparing with quantum mechanical calculations. The performance and transferability of the new parameters were evaluated through various simulations.
JOURNAL OF CHEMICAL PHYSICS
(2021)
Article
Chemistry, Multidisciplinary
Sonia Freddi, Daniele Perilli, Luca Vaghi, Mauro Monti, Antonio Papagni, Cristiana Di Valentin, Luigi Sangaletti
Summary: This study presents an easy and cost-effective method to functionalize graphene through thermally activated dimerization of 2,5-diaryltetrazoles, and introduces the use of tetrazoles to prepare graphene-based chemiresistors. The tests show that this method is sensitive to ammonia and the sensors perform better than bare graphene.
Article
Chemistry, Physical
Daniele Perilli, Raffaella Breglia, Cristiana Di Valentin
Summary: This article explains the electronic properties of single atom catalysts (SACs) embedded in 2D materials from the perspective of coordination chemistry. It highlights the role of the type of 2D material in determining the spin, charge, and stability of SACs.
JOURNAL OF PHYSICAL CHEMISTRY C
(2022)
Article
Chemistry, Physical
Federico A. Soria, Chiara Daldossi, Cristiana Di Valentin
Summary: Functionalized titanium dioxide nanoparticles with fluorescent dyes were studied for their adsorption behavior and optical properties. The study found that the adsorption mode of the dye on the nanoparticles affected the charge transfer mechanism, and manipulating the shape of the nanoparticles could control the injection mechanism.
MATERIALS TODAY ENERGY
(2022)
Article
Chemistry, Physical
Enrico Bianchetti, Cristiana Di Valentin
Summary: Through density functional theory calculations, it has been found that using multidentate ligands can inhibit the process of spin-canting in nanoparticles, and the presence of anchoring organic acids can also interfere with structural disorder.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2022)
Article
Chemistry, Physical
Aldo Ugolotti, Cristiana Di Valentin
Summary: This study focuses on two models of melem-based gCN structures and investigates their optical properties, including vibrational and electronic excitations, through computational calculations. The numerical results are compared with experimental data and the role of different polymeric arrangements is discussed.
APPLIED SURFACE SCIENCE
(2023)
Article
Chemistry, Physical
Marc G. Cuxart, Daniele Perilli, Sena Toemekce, Joel Deyerling, Felix Haag, Matthias Muntwiler, Francesco Allegretti, Cristiana Di Valentin, Willi Auwaerter
Summary: This work demonstrates how naturally occurring moire' patterns in Ir(111)-supported graphene can template the formation of ordered arrays of boron species. Experimental and theoretical studies provide a comprehensive understanding of the distribution, bonding configurations, interfacial interaction, and impact on graphene's electronic structure. The results show that boron prefers to form small aggregates by inducing local bending of graphene.
Article
Chemistry, Physical
Enrico Bianchetti, Augusto F. Oliveira, Andreas C. Scheinost, Cristiana Di Valentin, Gotthard Seifert
Summary: This study investigates the chemistry of TcVIIO4- and TcIV species at the Fe3O4(001) surface using a hybrid DFT functional (HSE06) method. The results indicate that the interaction between TcVIIO4- and the magnetite surface leads to the formation of reduced TcVI species without any change in the Tc coordination sphere. Additionally, several model structures for the immobilized TcIV final products are explored, showing that TcIV can be incorporated into a subsurface octahedral site or adsorbed on the surface as TcIVO2 center dot xH2O chains.
JOURNAL OF PHYSICAL CHEMISTRY C
(2023)
Article
Chemistry, Physical
Paulo Siani, Giulia Frigerio, Edoardo Donadoni, Cristiana Di Valentin
Summary: Nonequilibrium molecular dynamics simulations were used to investigate the electrokinetic properties of different TIPxP water models in NaCl aqueous solutions near a negatively charged TiO2 surface. The study showed that lack of water flexibility slows down the forward electro-osmotic flow, and in some cases, can even cause flow reversal. Zeta potential determination using the Helmholtz-Smoluchowski formula was improved by considering water flexibility.
JOURNAL OF PHYSICAL CHEMISTRY C
(2023)
Article
Chemistry, Physical
Enrico Bianchetti, Daniele Perilli, Cristiana Di Valentin
Summary: Doping magnetite surfaces with transition-metal atoms is a promising strategy to improve the catalytic performance of the oxygen evolution reaction (OER). In this study, we investigated the Fe3O4(001) surface as a support material for single-atom catalysts of the OER. We prepared and optimized models of transition-metal atoms on the Fe3O4(001) surface and studied their properties and performance using computational methods.
Article
Materials Science, Biomaterials
Edoardo Donadoni, Giulia Frigerio, Paulo Siani, Stefano Motta, Jacopo Vertemara, Luca De Gioia, Laura Bonati, Cristiana Di Valentin
Summary: This study investigates the mechanism of targeting activity by biomedical nanodevices using atomistic molecular dynamics simulations, free energy calculations, and machine learning approaches. The results demonstrate the crucial role of parameters such as the spacer, folic acid protonation state, and density in controlling the targeting efficiency of spherical TiO2 nanoparticles.
ACS BIOMATERIALS SCIENCE & ENGINEERING
(2023)
Article
Chemistry, Multidisciplinary
Stefano Motta, Paulo Siani, Edoardo Donadoni, Giulia Frigerio, Laura Bonati, Cristiana Di Valentin
Summary: Inorganic nanoparticles have promising properties for drug delivery, with the main limitation being drug loading capacity, which can be overcome through functionalizing the nanoparticle surface. This study presents a computational method using metadynamics to estimate the binding free energy of a drug (DOX) to a functionalized TiO2 nanoparticle under different pH conditions. The approach proves robust in capturing the mechanism of pH-triggered drug release, and the binding free energy estimations align well with expectations for a pH-sensitive drug delivery system. Metadynamics shows potential as a computational tool for designing and optimizing ligands for drug carriers.
Article
Chemistry, Multidisciplinary
Edoardo Donadoni, Paulo Siani, Giulia Frigerio, Cristiana Di Valentin
Summary: Strategies based on the active targeting of tumor cells are emerging as smart and efficient nanomedical procedures. This study focuses on the functionalization of TiO2 nanoparticles with folic acid (FA) and polyethylene glycol (PEG) spacers for tumor targeting. The researchers use Quantum Mechanics and Molecular Dynamics simulations to analyze the behavior of the nanoconjugates in different environments and determine the optimal density of FA molecules and the mode of anchoring to the carrier. The results provide valuable insights for the design and optimization of nanocarriers for targeted drug delivery.
Article
Chemistry, Multidisciplinary
Paulo Siani, Cristiana Di Valentin
Summary: This article investigates the interaction between dopamine-functionalized TiO2 nanoparticles and PARP1 and HSP90 proteins through molecular dynamics simulations. The results suggest that intracellular pH conditions and ionic strength affect the interaction between the nanoparticles and PARP1 and HSP90.