Article
Chemistry, Multidisciplinary
Ciera M. Wentworth, Alexander C. Castonguay, Pepijn G. Moerman, Caleb H. Meredith, Rebecca Balaj, Seong Ik Cheon, Lauren Zarzar
Summary: This study reports emulsions with a behavior opposite to the typical one where solubilization decreases the interfacial tension and leads to droplet attraction. By adjusting the oil chemical structure, nonionic surfactant structure, and surfactant concentration, three regimes corresponding to droplet attraction, repulsion, or inactivity are identified.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Physical
Yu Zhang, Weizhou Wang
Summary: This study investigates the unexpected attractive interactions between 2,3,4,5-tetrafluorothiophene (C4F4S) and 2,3,4,5-tetrafluoroselenophene (C4F4Se) complexes and Br-2, BrCl, BrF, Cl-2, and ClF using quantum chemical calculations. The interactions between positive sigma-holes and positive it-lumps are found to be electrostatically attractive rather than repulsive, contrary to expectations. These attractive interactions are attributed to short-range charge penetration. Additionally, the study reveals that dispersion, electrostatics, and induction all contribute to stabilizing these interactions.
COMPUTATIONAL AND THEORETICAL CHEMISTRY
(2022)
Article
Chemistry, Organic
Valerio Fasano, Varinder K. Aggarwal
Summary: The Matteson reaction is a highly selective synthetic method, with modern computational analysis revealing a novel Cl···H electrostatic interaction controlling selectivity. This interaction is crucial for determining the stereochemical outcome of the process.
Article
Energy & Fuels
Chengyong Wang, Yaowen Xing, Yangchao Xia, Rui Zhang, Shiwei Wang, Kaiyi Shi, Jinlong Tan, Xiahui Gui
Summary: The oxygen-containing group plays a crucial role in determining the water wettability of coal surfaces. Oxygen atoms in the oxygen-containing group enhance the hydrophilicity of coal surfaces by forming strong hydrogen bonds with water molecules. The impact of oxygen-containing groups on water adsorption capability follows the order -OOH > -OH > -CHO > -OCH3 based on the combined action of hydrogen bonds and van der Waals force.
Article
Chemistry, Physical
Samuel Stenberg, Clifford E. Woodward, Jan Forsman
Summary: The study demonstrates quantitative and qualitative differences in interactions between two perfectly conducting surfaces in a salt solution compared to those between equally charged non-conducting surfaces. Despite these differences, there are also similarities in behaviors. The dependence of the free energy barrier height on salt concentration displays a non-monotonic relationship, reaching a minimum when a flat profile of apparent surface charge density is achieved, outside the Stern layer.
Article
Physics, Multidisciplinary
Nuri Yazdani, Maryna I. Bodnarchuk, Federica Bertolotti, Norberto Masciocchi, Ina Fureraj, Burak Guzelturk, Benjamin L. Cotts, Marc Zajac, Gabriele Raino, Maximilian Jansen, Simon C. Boehme, Maksym Yarema, Ming-Fu Lin, Michael Kozina, Alexander Reid, Xiaozhe Shen, Stephen Weathersby, Xijie Wang, Eric Vauthey, Antonietta Guagliardi, Maksym V. Kovalenko, Vanessa Wood, Aaron M. Lindenberg
Summary: Understanding the electron-phonon coupling in lead halide perovskites is important for interpreting and utilizing their optical and electronic properties. This study shows that photoexcitation leads to lattice reorganization through deformation potential coupling to low-energy optical phonons. The coupling strength is stronger in FAPbBr3 due to its disordered crystal structure. The reorganizations induced by each exciton in a multi-excitonic state constructively interfere, resulting in a coupling strength that scales quadratically with the exciton number.
Review
Chemistry, Multidisciplinary
Samuel Botterbusch, Tobias Baumgart
Summary: Liquid-liquid phase separation in biological settings, specifically those interacting with membrane surfaces, play a crucial role in reshaping membranes, constructing protein structures, modulating functions, and organizing lipid vesicles dynamically. This review discusses the fundamental organizational phenomenon of phase-separated liquids in contact with bilayers and summarizes the common phenomena arising from these interactions.
APPLIED SCIENCES-BASEL
(2021)
Review
Plant Sciences
Violeta Velikova, Kaidala Ganesha Srikanta Dani, Francesco Loreto
Summary: Photolytic generation of nitric oxide (NO), isoprene, and reactive oxygen species (ROS) predates life on Earth. Isoprene-ROS-NO interactions became relevant to climate chemistry when isoprene-emitting diatoms and angiosperms dominated aquatic and terrestrial ecosystems. NOx is a dangerous biogenic atmospheric pollutant, while isoprene acts as an antioxidant and hormone 'enabler' in plants. Isoprene-NO interactions vary among plant species and can impact growth and stress responses in a future NO-rich climate.
JOURNAL OF EXPERIMENTAL BOTANY
(2023)
Article
Chemistry, Multidisciplinary
Christopher Balzer, Jian Jiang, Ryan L. Marson, Valeriy V. Ginzburg, Zhen-Gang Wang
Summary: The study found that nonelectrostatic interactions with a surface have a significant impact on the adsorption of polyelectrolytes, potentially resulting in qualitatively different salt effects than the charge effects. Under certain conditions, the adsorbed polymer layers produce a long-range repulsive barrier that can overcome dispersive interactions causing surfaces to attract, and a short-range bridging attraction is observed when two polyelectrolyte layers span both surfaces. These phenomena depend on the charge density of the polymer backbone and the bulk salt concentration, rather than the chain length in the semidilute regime studied.
Article
Chemistry, Multidisciplinary
Wiktor Zierkiewicz, Mariusz Michalczyk, Thierry Maris, Rafal Wysokinski, Steve Scheiner
Summary: The inspection of tetrachloridopalladate(ii) centers in a crystalline solid reveals a pi-hole bond between Cl atoms, overcoming strong Coulombic repulsion. This arrangement is also applicable to other homodimers of Group 10 metals with [MX4](2-) structures.
CHEMICAL COMMUNICATIONS
(2021)
Article
Chemistry, Physical
Olivera Drecun, Cecilia Bernardini, Misbah Sarwar, Alberto Striolo
Summary: This study investigates the interactions and agglomeration of γ-alumina nanoparticles in water and salt solutions. Molecular dynamics simulations are used to characterize surface effects, and dynamic light scattering experiments are conducted to study agglomeration at the macroscale. The results highlight the capability of molecular simulations to explain macroscopic observations.
COLLOIDS AND SURFACES A-PHYSICOCHEMICAL AND ENGINEERING ASPECTS
(2023)
Article
Cell Biology
Samantha M. Richter, Lilyanna C. Massman, Dennis J. Stuehr, Elizabeth A. Sweeny
Summary: NADPH oxidase 5 (NOX5) is a transmembrane oxidative signaling enzyme that produces superoxide in response to intracellular calcium flux. It is involved in physiological processes and human disease, but its signaling pathways and targets of oxidative modifications remain poorly understood. This study demonstrates that NOX5 and actin interact in the cell and modulate each other's activity. Changes in actin dynamics affect NOX5 superoxide production, and NOX5 oxidatively modifies actin. Knockdown of NOX5 impairs cell migration. These findings reveal an important link between actin dynamics and oxidative signaling through NOX5.
FRONTIERS IN CELL AND DEVELOPMENTAL BIOLOGY
(2023)
Article
Environmental Sciences
Qi Yu, Jingyi Feng, Jie Li, Anfei He, G. Daniel Sheng
Summary: The presence of surface oxygen-containing functional groups (OFGs) on carbonaceous materials influenced the adsorption capacity at different sites, with OFGs on mesoporous surfaces inhibiting adsorption while those on external surfaces promoting it. Multiple linear relationships were established between monolayer adsorption capacity and the amounts of OFGs at different sites. Factors such as compound properties and molecular polarity influenced the inhibition or promotion effects of OFGs on adsorption behavior.
Article
Materials Science, Biomaterials
Paulina Chytrosz-Wrobel, Monika Golda-Cepa, Kamil Drozdz, Jakub Rysz, Piotr Kubisiak, Waldemar Kulig, Monika Brzychczy-Wloch, Lukasz Cwiklik, Andrzej Kotarba
Summary: This study investigates the effect of oxygen plasma treatment on the physicochemical properties of polyurethane surfaces and characterizes the polyurethane-water interfaces in detail through experiments and molecular dynamics simulations.
ACS BIOMATERIALS SCIENCE & ENGINEERING
(2023)
Review
Biochemistry & Molecular Biology
Gideon Ong, Susan E. Logue
Summary: Oxidative stress is caused by an imbalance in cellular redox state due to the accumulation of reactive oxygen species (ROS). It can lead to negative effects such as damage to biological macromolecules and disruption of organelle function. The unfolded protein response (UPR), a stress response initiated by cells to combat endoplasmic reticulum (ER) stress, is well characterized, but its response and influence on oxidative stress are less defined. This review evaluates the interplay between oxidative stress, ER stress, and UPR signaling networks, particularly focusing on how UPR signaling mediators can influence antioxidant responses.
Article
Materials Science, Multidisciplinary
Anton Kokalj, Matic Lozinsek, Barbara Kapun, Peyman Taheri, Shova Neupane, Patricia Losada-Perez, Chenyang Xie, Stojan Stavber, Daniel Crespo, Frank U. Renner, Arjan Mol, Ingrid Milosev
Summary: Research evaluated the correlation between molecular electronic parameters and experimentally determined corrosion inhibition efficiencies for a set of 24 heterocyclic organic compounds tested as corrosion inhibitors for copper in 3 wt.% NaCl aqueous solution. The study found no noticeable correlation between the molecular electronic descriptors and the inhibition efficiency. It also introduced a new metric called inhibition power for evaluating the performance of corrosion inhibitors.
Article
Materials Science, Multidisciplinary
Anton Kokalj
Summary: The hypothesis that inhibition efficiency increases with increasing electron-donating ability is critically reevaluated and shown to have no validity due to the practical limitation of Delta N always being smaller than 3.6. Additionally, a weak volcano-type dependence on the HOMO-LUMO gap for corrosion inhibitors for iron in acidic solutions indicates that a smaller HOMO-LUMO gap does not necessarily correspond to a better inhibitor.
Article
Materials Science, Multidisciplinary
Dzevad K. Kozlica, Anton Kokalj, Ingrid Milosev
Summary: The inhibitory action of 2-mercaptobenzimidazole (MBI) and octylphosphonic acid (OPA) on copper and aluminum in NaCl solution was investigated. While MBI was found to be a good inhibitor for copper but not for aluminum, OPA behaved complementarily. Evidence suggested that OPA changed the bonding of MBI on the copper surface, resulting in a thicker and more protective organic film.
Article
Chemistry, Physical
Chenyang Xie, Ingrid Milosev, Frank U. Renner, Anton Kokalj, Pere Bruna, Daniel Crespo
Summary: CuZr alloys serve as the basis for metallic glasses with good corrosion resistance, mainly controlled by the Zr-rich amorphous structure, with the inhibitors playing a secondary role. The results highlight a complex relationship between inhibitor performance, microstructure, and composition of CuZr alloys.
JOURNAL OF ALLOYS AND COMPOUNDS
(2021)
Article
Electrochemistry
Shova Neupane, Patricia Losada-Perez, Ursa Tiringer, Peyman Taheri, Derese Desta, Chenyang Xie, Daniel Crespo, Arjan Mol, Ingrid Milosev, Anton Kokalj, Frank Uwe Renner
Summary: This study compared the performance of two organic corrosion inhibitors in mitigating copper corrosion by examining the stability and intermolecular forces of their adsorbed layers using atomic force microscopy and X-ray photoelectron spectroscopy. The results showed that one inhibitor formed a stronger and more stable bond with the surface compared to the other, which was supported by computational modeling and electrochemical corrosion tests.
JOURNAL OF THE ELECTROCHEMICAL SOCIETY
(2021)
Article
Materials Science, Multidisciplinary
Anton Kokalj
Summary: The traditional criteria for distinguishing between physisorption and chemisorption based on the standard free energy of adsorption are not very reliable. Chemisorption may result in a rather weak standard adsorption free energy, and more reliable criteria from first principle computational modeling studies are recommended.
Article
Chemistry, Physical
Lea Gasparic, Matic Poberznik, Anton Kokalj
Summary: The study investigated hydrogen bonding between water molecules or metal hydroxides and small organic molecules with N, O, S, or P heteroatoms using DFT calculations. Results showed that Cu(OH)2 clusters are generally better H-bond acceptors and donors than water molecules, while Al(OH)3 clusters prefer to act as H-bond donors or form two H-bonds. Various organic molecules containing N, O, S, or P heteroatoms were analyzed, with imidazole and (CH3)2POOH forming the strongest H-bonds. Structural differences between surface and small-cluster calculations were identified, with small clusters unable to capture all H-bond interactions present on surfaces. Aqueous conditions were also examined using a continuum solvation model, showing an influence on H-bond properties and inducing deprotonation of adsorbed molecules in some cases.
Article
Materials Science, Multidisciplinary
Matjaz Dlouhy, Anton Kokalj
Summary: The adsorbed species (X(ads)) on metal surfaces have different effects on the adsorption bonding of imidazole, with O and Cl enhancing the bonding, H having almost no effect, and OH either diminishing or negligibly impacting the adsorption. The influence of X(ads) usually diminishes with increasing distance between X(ads) and imidazole, as well as decreasing X(ads) coverage. Three coadsorption effects were identified, including stabilizing effects due to hydrogen bond formation and enhanced N-Cu bonding, as well as a destabilizing effect caused by work function change.
Article
Electrochemistry
Dzevad K. Kozlica, Ingrid Milosev
Summary: The optimal surface pre-treatment conditions for improved adsorption of 2-mercaptobenzimidazole (MBI) and octylphosphonic acid (OPA) on copper and aluminium substrates were investigated. It was found that the method of film formation played a crucial role in the effectiveness of the inhibitors on copper and aluminium.
ELECTROCHIMICA ACTA
(2022)
Article
Chemistry, Physical
Milutin Smiljanic, Stefan Panic, Marjan Bele, Francisco Ruiz-Zepeda, Luka Pavko, Lea Gasparic, Anton Kokalj, Miran Gaberscek, Nejc Hodnik
Summary: In this study, the overall catalytic performance of Pt, the best monometallic catalyst for the hydrogen evolution reaction (HER), was improved by supporting it on conductive titanium oxynitride (TiONx) dispersed over reduced graphene oxide nanoribbons. The strong metal-support interaction (SMSI) between TiONx and Pt was identified as the cause of the improved HER activity and stability.
Article
Materials Science, Multidisciplinary
Anton Kokalj, Matjaz Dlouhy
Summary: In this study, DFT calculations showed that chemisorbed O and OH species on copper surfaces promote the deprotonation of azole molecules. The activation energy for deprotonation via N-H bond cleavage is lower than that for deprotonation via C-H bond cleavage, leading to increased stability and persistence of adsorbed molecules.
Article
Chemistry, Physical
Gorazd Koderman Podborsek, Luka Suhadolnik, Anja Loncar, Marjan Bele, Armin Hrnjic, Ziva Marinko, Janez Kovac, Anton Kokalj, Lea Gasparic, Angelja Kjara Surca, Ana Rebeka Kamsek, Goran Drazic, Miran Gaberscek, Nejc Hodnik, Primoz Jovanovic
Summary: The study investigated nanotubular titanium oxynitride (TiON) as a support for iridium nanoparticles and their structural and compositional transformations during the oxygen evolution reaction (OER). Experimental findings demonstrate that both iridium nanoparticles and single atoms stabilize the ceramic support by suppressing the oxidation tendency of TiON under OER conditions.
Article
Materials Science, Multidisciplinary
Anton Kokalj
Summary: This article explores the synergy in corrosion inhibition and how to quantify it effectively. The equation for the synergistic parameter evaluates the inhibition efficiency of a mixture against a threshold based on the performance of pure compounds. However, the choice for the threshold value is not unique. The paper presents several reasonable alternatives, including using the Langmuir adsorption model, requiring the mixture's inhibition efficiency to be higher than the highest efficiency of pure compounds, or having a higher corrosion resistance in the mixture compared to the sum of resistances in pure compounds. The synergistic models are also extended to multi-component mixtures.
Article
Materials Science, Multidisciplinary
Anton Kokalj
Summary: A new general-purpose Type-I adsorption isotherm has been proposed to improve the estimation of standard adsorption Gibbs energy. This new isotherm takes into account the functional dependence of various adsorption models on the c/theta vs. c plot, where theta represents the fractional surface coverage and c represents the concentration. It has the ability to accurately describe multiple adsorption isotherms, indicating its flexibility in describing various adsorption scenarios. The tested adsorption models that can be described by this new isotherm include those considering lateral inter-adsorbate interactions, molecular size, surface heterogeneity, and mobile adsorption.
Article
Materials Science, Multidisciplinary
Anton Kokalj
Summary: The standard adsorption Gibbs energy (Delta G degrees -ads) is often estimated based on the assumption that corrosion inhibition efficiency is equivalent to fractional surface coverage. However, Lindsay et al. demonstrated that this assumption may not be valid. Therefore, this study presents a model that maps inhibition efficiency to fractional surface coverage to provide a more reliable estimation of Delta G-degrees ads. The model is validated using experimental data and confirms the significant error in Delta G degrees -ads estimation when using inhibition efficiency as a proxy for surface coverage.
