Article
Chemistry, Multidisciplinary
Shuguo An, Aiyou Hao, Pengyao Xing
Summary: This study reports the first example of polyhedral oligosilsesquioxane (POSS) derivatives that can self-assemble into well-defined chiral nanoassemblies. These chiral nanoassemblies exhibit active chiroptical responses and can bind guest molecules through charge-transfer interactions, offering a new design protocol for functional chiral materials.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Quoc Duy Ho, Eva Rauls
Summary: This report investigates the interaction between CO2 and different structures of pillar[n]arene (P[n]A) using DFTB and DFT calculations to understand the effect of P[n]A cavity sizes on CO2 adsorption. The adsorbed CO2 at different positions on P[4]A, P[5]A, and P[6]A have similar binding energies due to the role of hydrogen bonding. The number of CO2 molecules that can be adsorbed depends on the cavity size of P[n]A, with larger cavities allowing for more adsorption before saturation is reached. The study also highlights the potential CO2 capture capabilities of P[n]A structures through the interaction and increased binding energy between adsorbed CO2 molecules.
Article
Materials Science, Multidisciplinary
Quoc Duy Ho, Eva Rauls
Summary: In this study, the adsorption behaviors of NO, NH3, CO, and NO2 on Pillar[5]arenes (P[5]A) were investigated using DFTB and DFT calculations. The results showed that P[5]A structures can adsorb these gases at both the cavity site and OH group, facilitated by it-it interactions and hydrogen bonding. The findings provide valuable insights for the targeted design and optimization of P[5]A for effectively capturing toxic gases.
MATERIALS TODAY COMMUNICATIONS
(2023)
Review
Biochemistry & Molecular Biology
Yehong Huo, Jian Hu, Yuanyuan Yin, Peng Liu, Kaiyong Cai, Wei Ji
Summary: Peptides can self-assemble into hierarchical nanostructures with excellent chemical and physical properties, making them widely applicable in bio-/nanotechnology. This review presents the latest research progress on self-assembling peptide-based nanomaterials and their applications in biomedicine and optoelectronics.
Article
Chemistry, Multidisciplinary
Luka Dordevic, Hiroaki Sai, Yang Yang, Nicholas A. Sather, Liam C. Palmer, Samuel I. Stupp
Summary: This study reports on the synthesis, optoelectronic and electrochemical properties, aqueous supramolecular polymerization, and conductivity of polycyclic aromatic dicarboximide amphiphiles. The introduction of heterocycles, such as thiophene, pyridine or pyrrole rings, in the chemical structure of the model perylene monoimide amphiphile led to supramolecular polymerization in water. The presence of sulfur atoms in the thiophene-containing monomer resulted in crystalline nanoribbons with significantly higher electrical conductivity.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Physical
Michael Fischer
Summary: This study used electronic structure calculations to investigate the adsorption of carbamazepine (CBZ) in eleven all-silica zeolites. It was found that zeolites with one-dimensional channels formed by twelve-membered rings exhibited the highest affinity towards CBZ. The fit of CBZ into the zeolite pores, maximizing dispersion interactions, was identified as the dominant factor determining the interaction strength. The calculations also contributed to the understanding of the atomic-level interaction between functional organic molecules and all-silica zeolites.
Article
Chemistry, Inorganic & Nuclear
Kate L. Flint, David M. Huang, Oliver M. Linder-Patton, Christopher J. Sumby, F. Richard Keene
Summary: In this study, ligands containing a 1,4-disubstituted 1,2,3-triazole unit were used to form triple-stranded dinuclear Ru(II) complexes with stereoisomeric mixtures. The introduction of a more flexible spacer resulted in the detection of isomeric mixtures and successful separation of mesocate and helicate forms. Additionally, photoconversion behavior was observed in these Ru(II) compounds. Partial separation of compounds containing a different spacer was achieved via chromatographic resolution, confirming the existence of a mesocate/helicate pair.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2022)
Review
Chemistry, Multidisciplinary
Akhil Venugopal, Lorena Ruiz-Perez, K. Swamynathan, Chidambar Kulkarni, Annalisa Calo, Mohit Kumar
Summary: Supramolecular systems chemistry is a thriving field of research focused on developing nanomaterials with lifelike functions. Progress in this field relies on our ability to study the formation of nanostructures in solution. Visualizing the dynamic transformation of these structures over time is often challenging, requiring a shift from dry imaging techniques to solution-based ones. In this review, we discuss the application of state-of-the-art techniques such as optical super-resolution microscopy, solution-state atomic force microscopy, liquid-phase transmission electron microscopy, molecular dynamics simulations, and other emerging techniques for real-time, in situ visualization of dynamic self-assembly processes. This review provides valuable insights and a visionary approach to exploring the potential of dynamic nanomaterials.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Quoc Duy Ho, Eva Rauls
Summary: P[n]A-based supramolecular organic frameworks (SOF) have shown promise as materials for capturing and separating carbon dioxide (CO2). Experimental studies have demonstrated their high adsorption rates and selectivity for CO2 over methane (CH4) and nitrogen (N-2). However, a comprehensive understanding of CO2 adsorption in P[n]A is still lacking.
Article
Chemistry, Physical
Irina Osadchuk, Riina Aav, Victor Borovkov, Eric Clot
Summary: In this study, the influence of various controlling factors on electronic circular dichroism (ECD) spectra was investigated by modeling sixteen different zinc porphyrins using DFT and TD-DFT approaches. The factors mainly affected the excitation energy of electronic transitions and their intensity.
Article
Chemistry, Multidisciplinary
Markus Bursch, Jan-Michael Mewes, Andreas Hansen, Stefan Grimme
Summary: This work provides best-practice guidance on various methodological and technical aspects of DFT calculations, including how to choose computational protocols, functionals, basis sets, and achieve an optimal balance between accuracy, robustness, and efficiency through multi-level approaches.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Physical
Hyejin Kwon, Carson J. Bruns
Summary: Researchers have discovered and characterized a family of all-hydrocarbon, all-p-conjugated [n]cycloparaphenylene-PAH host-guest complexes. They have built a theoretical framework to select these complexes and predict their stabilities. This research offers new opportunities for bespoke PAH separation or remediation materials.
Article
Chemistry, Physical
Peter M. Spurgeon, Da-Jiang Liu, Theresa L. Windus, James W. Evans, Patricia A. Thiel
Summary: Chemisorbed species, particularly sulfur, can enhance the decay rate of 2D Au islands on metal surfaces, leading to surface pitting and reconstruction. The formation and diffusion of Au-S complexes contribute to the enhanced coarsening of Au islands at lower sulfur coverages.
Article
Chemistry, Physical
Michal Fecik, Philipp N. Plessow, Felix Studt
Summary: The influence of confinement from eight different zeotypes on the formation of alkoxides from 13 primary alcohols was studied using dispersion corrected density functional theory calculations. It was found that van der Waals interactions between substrates and zeolite frameworks largely govern the variations in adsorption and transition state energies. Additionally, trends between different reactants are mainly due to the size of the molecules and can be quantitatively described by the number of atoms constituting them. Adsorbate stabilization was found to be largest for frameworks that are neither too small nor too spacious.
Article
Chemistry, Multidisciplinary
Jiajing Zhou, Matthew Penna, Zhixing Lin, Yiyuan Han, Rene P. M. Lafleur, Yijiao Qu, Joseph J. Richardson, Irene Yarovsky, Jesse V. Jokerst, Frank Caruso
Summary: The study introduces a versatile and robust coating (pBDT-TA) self-assembled from tannic acid (TA) and a self-polymerizing aromatic dithiol (BDT), which can be precisely tuned in thickness on diverse substrates and exhibits high stability in various harsh aqueous environments. Moreover, the coating enables secondary reactions and easy integration of other compounds, showcasing its potential for diverse applications.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Applied
Gion Calzaferri, Samuel H. Gallagher, Dominik Bruhwiler
Summary: This study extends the analysis of compounds with multiple coordination sites to the description of adsorption isotherms, accurately determining adsorption enthalpy through particle distribution theory. Experimental data shows that the shape of all adsorption isotherms is primarily determined by entropy decrease with increasing coverage, with different sites exhibiting substantial differences in adsorption enthalpies. The information provided by the lc2-L analysis allows calculating the evolution of coverage of different sites as pressure increases.
MICROPOROUS AND MESOPOROUS MATERIALS
(2021)
Article
Chemistry, Applied
Marco Fabbiani, Giorgia Confalonieri, Sara Morandi, Rossella Arletti, Simona Quartieri, Mario Santoro, Francesco Di Renzo, Julien Haines, Riccardo Fantini, Gloria Tabacchi, Ettore Fois, Giovanna Vezzalini, Gabriele Ricchiardi, Gianmario Martra
Summary: Zeolites serve as scaffolds for organizing molecules via non-covalent interactions, but their potential in promoting covalent bond formation in low-dimensional systems remains unexplored. By incorporating 1,5-hexadiene into high-silica mordenite channels, it was found that due to limited acid sites, 1,5-hexadiene slowly converted to a polymer mainly composed of cyclopentane units with short side chains that fit the channels. Zeolite frameworks play a dual role in directing monomer organization in void spaces and linear chain growth determined by channel geometry, highlighting their ability to control covalent bond transformations at ambient conditions for potential confined polymers applications.
MICROPOROUS AND MESOPOROUS MATERIALS
(2021)
Article
Chemistry, Physical
Ettore Fois, Mario Oriani, Gloria Tabacchi
Summary: The study shows that the cis and trans forms of the OMC molecule are equally stable in the gas phase, despite predictions favoring the trans structures, and that the stability of the cis-OMC is underestimated due to intra-molecular dispersion interactions leading to a more compact structure compared to the trans isomer.
JOURNAL OF CHEMICAL PHYSICS
(2021)
Article
Chemistry, Multidisciplinary
Massimiliano Curcio, Federico Nicoli, Erica Paltrinieri, Ettore Fois, Gloria Tabacchi, Luigi Cavallo, Serena Silvi, Massimo Baroncini, Alberto Credi
Summary: Innovative properties and processes can be achieved by mechanically interlocking molecular components, which are potentially valuable for applications in nanoscience, sensing, catalysis, and materials science. This study demonstrates a unique [3]rotaxane structure with adjustable recognition sites on the axle component controlled by acid-base inputs, leading to different properties and a fine tuning of pK(a) values.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Biochemistry & Molecular Biology
Davide Barreca, Ettore Fois, Alberto Gasparotto, Chiara Maccato, Mario Oriani, Gloria Tabacchi
Summary: By using density functional theory and ab initio molecular dynamics simulations, the study investigates the dissociation mechanism of metal-ligand bonds on the growth surface, showing that hydrogen bonding with surface hydroxyl groups plays a key role in aiding the dissociation of metal-oxygen bonds.
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
Chemistry, Applied
Gion Calzaferri, Samuel H. Gallagher, Dominik Bruehwiler
Summary: The adsorption of simple gases involves the formation of a monolayer, cluster formation and cavity filling, depending on the properties of the surface. The isotherms of different adsorbents show distinct shapes. Quantitative analysis can describe these isotherms. The properties of the adsorbent play a significant role in the adsorption process.
MICROPOROUS AND MESOPOROUS MATERIALS
(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)
Article
Materials Science, Multidisciplinary
Gion Calzaferri, Samuel H. Gallagher, Simon Lustenberger, Fabian Walther, Dominik Bruhwiler
Summary: We investigated the argon adsorption/desorption isotherms of MCM-41 and SBA-15 and found that the shape of the observed hysteresis loops corresponds to type H1. By applying the concept of metastable thermodynamic equilibrium and multiple equilibria description, we quantitatively analyzed the data. Interestingly, for both mesoporous materials, the desorption process can be understood according to this description, with a corresponding equilibrium constant. This analysis allowed us to determine the thermodynamic values for the enthalpy and the free enthalpy of cavity desorption, providing previously unavailable information.
MATERIALS CHEMISTRY AND PHYSICS
(2023)
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)
