Article
Chemistry, Physical
Maximilian G. Muenst, Milan Oncak, Martin K. Beyer, Christian van der Linde
Summary: This study investigates the structure and chemical properties of hydrated molecular anions in the atmosphere, revealing their microsolvation characteristics through spectroscopic measurements. The experimental results show that the interaction of hydrogen atoms with the central ion affects the infrared spectra, while the high fluxionality of water molecules contributes to spectral broadening.
JOURNAL OF CHEMICAL PHYSICS
(2021)
Article
Chemistry, Physical
Debopriya Sadhukhan, Po-Jen Hsu, Jer-Lai Kuo, G. Naresh Patwari
Summary: This study investigates the dissociation of HCl embedded in DMSO clusters using various theoretical levels, revealing a bistable nature at the B3LYP-D3 level and minimal exceptions at the MP2 level. The critical electric field required for HCl dissociation is around 138 MV cm(-1) at the B3LYP-D3 level and approximately 181 MV cm(-1) at the MP2 level.
JOURNAL OF PHYSICAL CHEMISTRY A
(2021)
Article
Thermodynamics
Huiyu Zhao, Feng Wu, Qingwen Han, Chen Wang, Sibei Cao, Jiayu Ma
Summary: The solubility of potassium hexafluorosilicate (K2SiF6) was studied in pure water and acid solutions (HCl and H3PO4) using the isothermal method. The stability of K2SiF6 in these systems was analyzed through various techniques. The results indicated that the solubility of K2SiF6 increases with temperature in all systems, and in the presence of HCl and H3PO4, the solubility first increases and then decreases with increasing acid concentration. K2SiF6 is stable in pure water and acid solutions, and the experimental data can be successfully correlated using the Apelblat empirical equation.
JOURNAL OF CHEMICAL AND ENGINEERING DATA
(2023)
Article
Engineering, Environmental
Gong Chen, Yuanpu Cai, Hao Zhang, Dongsen Hong, Shijie Shao, Chensheng Tu, Yuexiang Chen, Feng Wang, Biao Chen, Yuting Bai, Xingyi Wang, Qiguang Dai
Summary: MnO2 nanorods with exposed (110), (100), or (310) facets were modified by Pt and/or Mo, showing enhanced activity and durability, with Pt promoting oxygen vacancies/Mn3+ formation and Mo inhibiting polychlorinated byproducts. The optimized Mo and Pt codecorated MnO2 demonstrated high resistance to harsh conditions and was considered a promising catalyst for practical applications in catalytic oxidation of actual Cl-VOCs emissions.
ENVIRONMENTAL SCIENCE & TECHNOLOGY
(2021)
Article
Chemistry, Physical
Alexander Zech, Martin Head-Gordon
Summary: This study investigated the ionic dissociation of small HCl-water nanoclusters and found that at least four water molecules are needed for the dissociation of HCl. The analysis revealed a push-pull mechanism for the destabilization of the HCl bond based on the synergy between forward and backward charge-transfer.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2021)
Article
Thermodynamics
Arnault Lassin, Laurent Andre
Summary: This article presents an improved model for accurately describing the CaCl2-H2O chemical system, covering a wide range of temperatures and concentrations. The model considers the aqueous speciation of the CaCl2 electrolyte and is applicable to ternary systems containing major cations.
JOURNAL OF CHEMICAL THERMODYNAMICS
(2023)
Article
Chemistry, Inorganic & Nuclear
Lifang Lin, Lulu Wang, Li Xu
Summary: The first examples of extended Mo-3(IV)-polyoxometalates (Mo-3(IV)-POMs), 1D-H-2 [(Ge2Mo6Mo4O31Zn)-Mo-IV-O-VI(H2O)py(9)]center dot 2Hpy center dot HOCH2CH2 OH(center dot)4H(2)O(H-2 [1]center dot 2Hpy(center.dot)glycol center dot H2O) and 2D-[P@(Mo3Mo9Zn6)-Mo-IV-Zn-VI(PO4)(6)O(32)py(8)]Cl center dot 2py center dot 7H(2)O ([2]center dot Cl(center.dot)2py center dot 7H(2)O), were prepared through the solvothermal partial oxidation of [(Mo3O2)-O-IV(O2CCH3)(6)(H2O)(3)]ZnCl4 in py/H2O containing glycol (for 1) or H3PO4 (for 2). They were characterized by X-ray crystallography and elemental analyses. Their electronic structure and bonding were discussed on the basis of density functional theory (DFT) theoretical calculations. X-ray photoelectron spectroscopy, IR/UV-vis spectra, powder X-ray diffraction, thermal gravimetric analysis, and mass spectrometry were also performed and discussed for 2D-2.
INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Physical
Xiaoxia Zhao, Zizhong Liu, Ruisheng Zhao, Tianzi Xu
Summary: This study examined the reaction mechanism and influencing factors of HONO and HCl, and found that the presence of water dimer plays an important role, which may explain the inconsistency between experimental and theoretical results.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2022)
Article
Multidisciplinary Sciences
Shi-Jun Wang, Long Wang, Xiang-Ying Tang
Summary: B(C6F5)(3)-H2O has been recognized as a common Bronsted acid, but the lack of X-ray crystal structure has hindered the development of a new catalytic mode. In this study, a B(C6F5)(3)-H2O and amide complex with hydrogen bonds and pi-pi interactions is characterized by X-ray diffraction. Noncovalent interactions are observed in solution and a photoredox catalysis for synthesizing a-aminoamides under mild conditions is developed based on the photoactive properties of the complex.
Article
Chemistry, Multidisciplinary
Liang Lu, Ren-Zhong Li, Xiao-Yang Xu
Summary: This study investigates the interaction between cysteine and Li+ and LiF in a microcosmic water environment, aiming to understand the interactions between ions and amino acids and the correlation effect between cations and anions. The results show that water prefers to interact with Li+/LiF. In the presence of Li+, Li+ interacts with amino nitrogen, carbonyl oxygen, and hydrophobic sulfur of cysteine, whereas in the presence of LiF, Li+ and F- cooperate to interact with carbonyl oxygen and hydroxyl hydrogen of cysteine. The study also reveals that the interaction between Li+/LiF and cysteine is mainly electrostatic, followed by dispersion, and the weakest interaction occurs during the transition from the neutral form to the zwitterionic form.
Article
Metallurgy & Metallurgical Engineering
A. Panova, Ya G. Avdeev, T. E. Andreeva, Yu Kuznetsov
Summary: The oxidizing ability of the HCl-H3PO4-H2O-Fe(III) system was investigated by measuring the electrode potentials of the Fe(III)/Fe(II) redox couple and the half-wave potentials. It was found that the values of these parameters were close under different conditions, while the formation of complexes of Fe(III) with phosphate anions in mixtures reduced the oxidizing ability. Temperature coefficients of the electrode potential for the Fe(III)/Fe(II) redox couple were experimentally determined, and the diffusion coefficients of Fe(III) in the solutions were calculated based on the Randles-Shevchik equation.
PROTECTION OF METALS AND PHYSICAL CHEMISTRY OF SURFACES
(2021)
Article
Green & Sustainable Science & Technology
Gengshu You, Le Liu, Jin Wang, Min Zhao, Chengjie Zhao, Xu Cai, Jin Tang, Fushen Lu, Tonggang Jiu
Summary: Polythiophene-acid-based conjugated polyelectrolytes have shown promising potential as hole-transport materials for inverted planar perovskite devices. A simple and effective strategy involving tris(pentafluorophenyl)borane as a Lewis acid has been developed to regulate the aggregation of the polyelectrolytes, leading to improved efficiency of perovskite solar cells.
ADVANCED SUSTAINABLE SYSTEMS
(2021)
Article
Electrochemistry
Ernesto Emmanuel Lopez-Lopez, Sergio J. Lopez-Jimenez, Joaquin Barroso-Flores, Esdrey Rodriguez-Cardenas, Melina Tapia-Tapia, Gustavo Lopez-Tellez, Luis D. Miranda, Bernardo A. Frontana-Uribe
Summary: The electrochemical behavior of a series of S-phenacyl-O-ethyl-xanthates was studied in hydroalcoholic and anhydrous media using carbon electrodes. Different behaviors were observed in the two media, with complications arising when using carbon electrodes in hydroalcoholic media. The problem was overcome by utilizing a Ti electrode instead.
ELECTROCHIMICA ACTA
(2021)
Article
Chemistry, Inorganic & Nuclear
Liqiang Ma, Pengpeng Wei, Jingfang Li, Liye Liang, Guangming Li
Summary: A novel catalyst, H4PVMo2W9O40@rht-MOF-1, was developed using a one-pot hydrothermal method. It exhibited high efficiency and reusability in esterification reactions.
JOURNAL OF SOLID STATE CHEMISTRY
(2024)
Article
Chemistry, Physical
Imane Merimi, Ruby Aslam, Belkheir Hammouti, Tadeusz Szumiata, Hassane Lgaz, Ill -Min Chung
Summary: This study investigated the corrosion inhibition performance and adsorption mechanism of a new corrosion inhibitor 2C on carbon steel in hydrochloric acid. Results showed that 2C could form a compact protective layer with high inhibition efficiency at a certain concentration. Furthermore, 2C was classified as a mixed class inhibitor affecting both anodic and cathodic reactions, with adsorption following the Langmuir adsorption isotherm.
JOURNAL OF MOLECULAR STRUCTURE
(2021)
Article
Physics, Multidisciplinary
Gerhard Schwaab, Ricardo Perez de Tudela, Devendra Mani, Nitish Pal, Tarun Kumar Roy, Fabio Gabas, Riccardo Conte, Laura Duran Caballero, Michele Ceotto, Dominik Marx, Martina Havenith
Summary: We investigate the microsolvation of glycine with water molecules under astrophysical conditions in our laboratory. By analyzing the infrared spectra, we identify two bands that correspond to specific stretching modes, confirming the formation of zwitter ions with only few water molecules under extreme conditions.
PHYSICAL REVIEW LETTERS
(2022)
Article
Chemistry, Multidisciplinary
Anna Kaczmarek-Kedziera, Borys Osmialowski, Piotr S. Zuchowski, Dariusz Kedziera
Summary: This study investigates the influence of hydrogen bonding on the one- and two-photon absorption of squaraine dyes using quantum chemistry tools, focusing on the effect of sulfur-oxygen substitution on the properties of the dyes. Various structural modifications were found to lead to controlled adjustment of electron density distribution and absorption properties, with calculations supporting tailored one- or two-photon absorption and highlighting the impact of substituents on the interaction energy.
FRONTIERS IN CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Simone Pezzotti, Federico Sebastiani, Eliane P. van Dam, Sashary Ramos, Valeria Conti Nibali, Gerhard Schwaab, Martina Havenith
Summary: Hydration free energies are determined by the delicate balance between hydrophobic and hydrophilic interactions. A spectroscopic approach using THz spectroscopy allows direct access to the contributions of cavity formation and hydrophilic interactions, and enables the separate determination of the thermodynamic effects of hydrophobic and hydrophilic interactions.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Physical
Marta Dudek, Anna Kaczmarek-Kedziera, Radoslaw Deska, Jakub Trojnar, Patryk Jasik, Piotr Mlynarz, Marek Samoc, Katarzyna Matczyszyn
Summary: This study investigates the linear and nonlinear optical properties of two-photon absorbing azobenzene compounds through experimental and theoretical approaches. The effects of pi-conjugation and substituents on these properties are also explored.
JOURNAL OF PHYSICAL CHEMISTRY B
(2022)
Article
Chemistry, Physical
Devendra Mani, Tarun Kumar Roy, Jai Khatri, Gerhard Schwaab, Sebastian Blach, Christoph Hoelzl, Harald Forbert, Dominik Marx, Martina Havenith
Summary: The application of external electric and magnetic fields is a powerful tool for controlling the alignment of molecules when thermal fluctuations are small. This study demonstrates that internal electric fields in a molecular cluster can also be used for such control. By utilizing the electric field of a single molecular dipole, researchers were able to manipulate the aggregation mechanism of subsequently added acetonitrile molecules. The presence of the internal electric field created by an HCl molecule resulted in the formation of exotic linear acetonitrile chains at 0.37K.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2022)
Article
Biochemistry & Molecular Biology
Magdalena Barwiolek, Dominika Jankowska, Anna Kaczmarek-Kedziera, Slawomir Wojtulewski, Lukasz Skowronski, Tomasz Rerek, Pawel Popielarski, Tadeusz M. Muziol
Summary: Two macrocyclic Schiff bases derived from o-phenylenediamine and 2-hydroxy-5-methylisophthalaldehyde or 2-hydroxy-5-tert-butyl-1,3-benzenedicarboxaldehyde were synthesized and characterized. The study determined their geometry in solution and in the solid phase, and analyzed the intermolecular interactions in the crystal structure. Luminescence studies showed significant quantum efficiency and emission in various solvents and in the solid state. Thin layers of the compounds deposited on Si(111) exhibited broad emission, suggesting potential applications in LED diodes.
Article
Chemistry, Inorganic & Nuclear
Magdalena Barwiolek, Dominika Jankowska, Anna Kaczmarek-Kedziera, Tadeusz M. Muzio
Summary: Two compounds were synthesized and their crystal structures were determined by X-ray crystallography. The intermolecular interactions in the crystal structures were analyzed, and the influence of solvents on the crystal lattice was investigated. The fluorescence properties of the compounds in different states and solvents were studied, and their sensing abilities towards Zn2+ ions were evaluated. Thin layers of the compounds were also prepared and examined using various microscopy techniques.
Article
Chemistry, Multidisciplinary
Hongxia Hao, Ellen M. Adams, Sarah Funke, Gerhard Schwaab, Martina Havenith, Teresa Head-Gordon
Summary: Transport mechanisms of solvated protons in reverse micelles containing NaAOT or CTABr were studied using reactive force field simulations. The proton hopping events were found to be suppressed for NaAOT and completely ceased for CTABr. The sluggish proton dynamics in both charged reverse micelles were attributed to the expulsion of hydronium and chloride ions from the interface, resulting in increased pH of the acid pools compared to nonionic reverse micelles. The localized oscillatory hopping dominated in the charged micelles, especially for CTABr, where the proton residence time was significantly increased.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Physical
Simone Pezzotti, Benedikt Koenig, Sashary Ramos, Gerhard Schwaab, Martina Havenith
Summary: Water actively participates in liquid-liquid phase separation (LLPS) by driving and being involved in the process. LLPS is governed by changes in hydration entropy and enthalpy. To tune LLPS for biological and medical applications, a general model is required to quantify thermodynamic driving forces. In this study, we develop such a model based on measured THz features of hydration populations, revealing the thermodynamic changes and providing a rational means to manipulate LLPS.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2023)
Article
Chemistry, Physical
Simon Schulke, Melinda Nolten, Gerhard Schwaab, Martina Havenith
Summary: This study demonstrates the potential of using Terahertz-FTIR spectroscopy as a label-free probe to measure the pH-dependent spectra of solvated amine compounds and correlate them with pKa values, thus allowing investigation of the charge state of biomolecules in water.
Article
Chemistry, Physical
Sampad Bag, Simone Pezzotti, Debasish Das Mahanta, Simon Schulke, Gerhard Schwaab, Martina Havenith
Summary: This study reports the THz measurement results of aqueous acetic acid solutions and explores the spectral characteristics of hydration motifs. By quantitatively correlating these changes to mixing entropy and enthalpy, a quantitative relationship between the balance of local hydrophobic and hydrophilic solvation motifs and macroscopic mixing thermodynamic properties is established.
JOURNAL OF PHYSICAL CHEMISTRY B
(2023)
Article
Chemistry, Multidisciplinary
Debasish Das Mahanta, Dennis Robinson Brown, Simone Pezzotti, Songi Han, Gerhard Schwaab, M. Scott Shell, Martina Havenith
Summary: Based on experimental and theoretical study, it is found that global thermodynamic mixing properties of glycerol and water are determined by local solvation structures. Three hydration water populations, including bulk water, bound water, and cavity wrap water, are identified. The study shows a 1:1 connection between the population of bound waters and the mixing enthalpy, which can be further confirmed by simulation results. This allows for rational design of polyol water and other aqueous mixtures to optimize technological applications.
Article
Chemistry, Physical
Svenja Jaeger, Philipp Meyer, Kai-Stephan Feichtner, Stefan Henkel, Gerhard W. Schwaab, Viktoria H. Gessner, Martina Havenith
Summary: The study demonstrates that the reaction of alkali metal amides with water is close to barrierless even at ultra-cold conditions, leading to aggregation induced reaction to form specific products in helium nanodroplets at ultra-low temperatures.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2022)
Article
Chemistry, Physical
Eliane P. van Dam, Benedikt Koenig, Sashary Ramos, Ellen M. Adams, Gerhard Schwaab, Martina Havenith
Summary: The conformational changes of the hydrogen bond network during gelation of aqueous hyaluronan solutions were studied using Terahertz reflection absorption spectroscopy. It was found that solvated protons form ion pairs with hyaluronan within a specific pH range (2.4-2.8) when it forms a hydrogel. The elasticity of hyaluronan solutions can be altered by adding urea or glucose, which is attributed to the formation and destruction of these ion pairs.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2022)
Article
Chemistry, Physical
Sergi Ruiz-Barragan, Federico Sebastiani, Philipp Schienbein, Jijo Abraham, Gerhard Schwaab, Rahul R. Nair, Martina Havenith, Dominik Marx
Summary: The properties of water at interfaces differ from those of bulk water, and specific confinement effects have been discovered when water is enclosed in nanotubes and slit pores. This study uses experimental and theoretical THz spectroscopy to investigate the nanoconfinement effects on the H-bond network of stratified water lamellae hosted within graphene-based two-dimensional pores. The results show characteristic changes in the THz response due to the structural dynamics and molecular effects, providing insights into the impact of nanoconfinement on water.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2022)