Article
Chemistry, Physical
Biswajit Biswas, Prashant Chandra Singh
Summary: Propofol, as the most common drug for general anesthesia, has been studied in terms of its structure and dissociation at the water interface under different pH conditions. The results show that propofol remains neutral and forms hydrogen bonds with water molecules at lower pH, while it becomes deprotonated and enhances the OH stretch of water at higher pH. The pK(a) of propofol at the water interface is lower than in bulk medium, indicating enhanced dissociation. These findings suggest that propofol prefers to be in the charged state at the water interface under physiological conditions, impacting its diffusion and acid-base equilibrium in the interfacial arterial blood region.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2021)
Article
Multidisciplinary Sciences
Hongxia Hao, Itai Leven, Teresa Head-Gordon
Summary: Reaction rates of common organic reactions can significantly increase by several orders of magnitude in aqueous microdroplets compared to bulk solution. However, the reasons for this rate acceleration are still poorly understood. By studying the electric field distributions at the air-water interface, it has been found that the electric field alignments along free O-H bonds at the surface are on average around 16 MV/cm larger than those in the interior of the water droplet. This difference in electric field distribution may contribute to the enhanced surface reactivity observed in microdroplets.
NATURE COMMUNICATIONS
(2022)
Article
Chemistry, Physical
Anna Chachaj-Brekiesz, Jan Kobierski, Rosa Grinon Echaniz, Anita Wnetrzak, Patrycja Dynarowicz-Latka
Summary: This paper presents a general protocol for interpreting the electric surface potential of Langmuir monolayers using a three-layer capacitor model. The protocol was successfully applied to different types of amphiphiles, obtaining the local dielectric permittivities and dipole-moment components of molecules in the monolayer. The findings are important for the design and preliminary characterization of molecules in sensor and material science applications.
JOURNAL OF PHYSICAL CHEMISTRY B
(2022)
Article
Environmental Sciences
Mark L. Brusseau, Sarah Van Glubt
Summary: This study investigated the influence of PFAS molecular structure on air-water interfacial adsorption in electrolyte solutions, finding significant impact of chain length trends on surface activities and interfacial adsorption coefficients. The QSPR analysis using a single molecular descriptor successfully characterized the impact of PFAS molecular structure on air-water interfacial adsorption.
Article
Chemistry, Multidisciplinary
Jiayuan Li, Zhaoming Xia, Qingyu Xue, Mingkai Zhang, Sai Zhang, Hai Xiao, Yuanyuan Ma, Yongquan Qu
Summary: The Lewis acid-base Ce···S pairs at the interface of CeO2-loaded CoS2 nanowire array electrodes effectively enhance catalytic activity and durability in alkaline hydrogen evolution reaction, reducing overpotential and maintaining activity stability over extended periods.
Article
Chemistry, Physical
Xiaolin Hu, Jichuan Fan, Ronghua Wang, Meng Li, Shikuan Sun, Chaohe Xu, Fusheng Pan
Summary: By combining vacancies and heterogeneous interfacial engineering, three-dimensional core-shell NiCoP/NiO heterostructures with dominated oxygen vacancies have been constructed for efficient electrocatalysis. These materials possess multiple exposed active sites, faster mass transfer behavior, optimized electronic structures, and improved electrochemical performance.
GREEN ENERGY & ENVIRONMENT
(2023)
Article
Engineering, Chemical
Bhuvanesh Eswaraswamy, Amit Suhag, Priya Goel, Priyabrata Mandal, Sujay Chattopadhyay
Summary: Bipolar membranes containing montmorillonite nanoclay interface as water dissociation catalyst were synthesized. The addition of nanoclay lowered the dissociation potential and increased the acid/base production rate. The nanoclay demonstrated good durability and cost-effectiveness, making it a potential interface material for developing bipolar membranes.
SEPARATION AND PURIFICATION TECHNOLOGY
(2022)
Article
Engineering, Environmental
Anton De Vylder, Jeroen Lauwaert, Maarten K. Sabbe, Marie-Francoise Reyniers, Jeriffa De Clercq, Pascal Van Der Voort, Joris W. Thybaut
Summary: The effects of water and silanol groups on the liquid-phase amine-catalyzed aldol reaction of acetone with 4-nitrobenzaldehyde have been elucidated with a comprehensive theoretical model. Water and silanol groups were found to reduce Gibbs free energy barriers for certain reaction steps, resulting in overall lower barriers and more efficient reactions. The effect of water was more pronounced in apolar hexane compared to DMSO, leading to less deactivation of the amine and lower barriers for reactions where water assists in the transition state.
CHEMICAL ENGINEERING JOURNAL
(2021)
Article
Chemistry, Physical
Nanna Myllys
Summary: New particle formation from acid and base molecules in the atmosphere is a common phenomenon, but the role of water in salt particle formation is still not fully understood. Increased relative humidity can enhance particle formation for nitric acid but slightly reduce it for sulfuric acid and methanesulfonic acid. Neglecting hydration or using the same value for different systems can introduce significant inaccuracies in large-scale models.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2023)
Article
Chemistry, Multidisciplinary
Alexandre Poirier, Antonio Stocco, Romain Kapel, Martin In, Laurence Ramos, Amelie Banc
Summary: The study investigated the adsorption process of sunflower protein extract at two air-water and oil-water interfaces, revealing a three-step mechanism. Initially, a diffusion-limited adsorption of proteins at interfaces occurs, followed by the formation of a three-dimensional saturated monolayer of proteins, and finally a thick layer expanding in the aqueous phase. The study also found that the adsorption mechanisms of proteins exhibit significant divergences at longer adsorption times.
Article
Chemistry, Physical
Subhadip Roy, Jahur Alam Mondal
Summary: Research shows that ions have a strong correlation with the structure of hydrogen bonding at the air/water interface and in bulk water. Specifically, structure-breaking anions decrease hydrogen bonding at the interface, while structure-making anions have the opposite effect. None of the electrolytes studied significantly affect the orientation of water molecules at the interface.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2021)
Article
Chemistry, Multidisciplinary
Enrico Lepre, Sylvain Rat, Cristian Cavedon, Peter H. Seeberger, Bartholomaeus Pieber, Markus Antonietti, Nieves Lopez-Salas
Summary: The influence of structural modifications on the catalytic activity of carbon materials is investigated using carbonaceous materials with different pore networks and high nitrogen content. Results show that CO2 cycloaddition and Knoevenagel reaction are dependent on Lewis basic sites, while the absence of large conjugated carbon domains due to the introduction of nitrogen leads to poor redox activity. The material with the highest Lewis acid catalytic activity demonstrates the most effective small molecule activation and the highest concentration of electron-poor nitrogen species.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Engineering, Chemical
Emad Al-Dhubhani, Ragne Pa, Jan W. Post, Michel Saakes, Michele Tedesco
Summary: The use of bipolar membranes (BPMs) is expanding due to their ability to enhance water dissociation and maintain a stable pH gradient. However, a comprehensive characterization of commercial BPM properties is still lacking, and further research is needed to lower proton leakage and electrical resistance to improve BPM performance in acid-base flow batteries and other energy applications. Testing BPMs in a single-cell acid-base flow battery system has shown promising round-trip efficiencies, highlighting the potential for future advancements in this field.
JOURNAL OF MEMBRANE SCIENCE
(2021)
Article
Chemistry, Multidisciplinary
Ryoji Kusaka, Satoshi Nihonyanagi, Tahei Tahara
Summary: The study directly observed a photochemical reaction occurring at the air-water interface using ultrafast phase-sensitive interface-selective nonlinear vibrational spectroscopy. The results showed that the reaction rate at the water surface is 10^4 times faster than in the bulk aqueous phase, indicating significant differences in photochemical reactions between water interfaces and bulk water.
Article
Environmental Sciences
Jing He, Hong Zhang, Wenxin Wang, Yingxue Ma, Miao Yang, Yuwei He, Zhuo Liu, Kai Yu, Jie Jiang
Summary: This study explored the autoxidation process of oleic acid and found that it is an important pathway for SOAs formation. The autoxidation mechanism was divided into addition intermediates and Criegee intermediates pathways. Moreover, the MS approach of selectively probing the interfacial substances at the scale of sub-seconds opens new opportunities to study heterogeneous chemistry in atmosphere.
ENVIRONMENTAL RESEARCH
(2022)
Article
Chemistry, Physical
Adriano Santana, Andreia S. F. Farinha, Aniela Zarzar Torano, Mahmoud Ibrahim, Himanshu Mishra
Summary: This study compared the efficacy of different functional groups for removing cationic dyes from water, with hydrogen bonding playing a key role in the adsorption process. Experimental results showed that the hydrophobicity of functionalized beads had a significant impact on dye uptake.
INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY
(2021)
Article
Chemistry, Physical
Ryuichi Wada, Kenichi Tonokura, Shohei Koba, Tomonobu Imamura, Kosuke Nakai, Hiroshi Ushiyama, Koichi Yamashita, Yutaka Matsumi, Shinichi Enami, Paul W. Seakins
Summary: The equilibrium geometries and enthalpies of adduct formations between alkyl iodides and chlorine atoms were studied. It was found that the enthalpies decreased as the number of alkyl substituents on the carbon atom bonded to the iodine increased. This suggests that the charge transfer from the alkyl group to I-Cl increases with the number of substituents, leading to adduct stabilization. Charge density distribution between the Cl and H atoms also plays a role in stabilizing the adducts.
CHEMICAL PHYSICS LETTERS
(2021)
Article
Chemistry, Physical
Shinichi Enami
Summary: Understanding the fate of organic hydroperoxides (ROOHs) in atmospheric condensed phases is crucial for assessing the oxidative and toxicological potentials of particulate matter. Recent studies have shown that liquid-phase alpha-hydroxyalkyl hydroperoxides can decompose to geminal diols and H2O2 depending sensitively on water content, pH, and temperature, with H+-catalyzed conversion playing a key role in the process.
JOURNAL OF PHYSICAL CHEMISTRY A
(2021)
Article
Engineering, Environmental
Mingxi Hu, Kenichi Tonokura, Yu Morino, Kei Sato, Shinichi Enami
Summary: In this study, the effects of atmospherically relevant metal ions on the decomposition of alpha-hydroxyalkyl-hydroperoxides derived from the ozonolysis of alpha-terpineol in aqueous solutions were investigated using mass spectrometry. It was found that in acidic aqueous media, the reaction of alpha-HHs with Fe2+ is outcompeted by H+-catalyzed decomposition of alpha-HHs, producing aldehydes and H2O2 which can in turn react with Fe2+ to form hydroxyl radicals.
ENVIRONMENTAL SCIENCE & TECHNOLOGY
(2021)
Article
Chemistry, Physical
Muhammad Ghifari Ridwan, Buddha Ratna Shrestha, Nischal Maharjan, Himanshu Mishra
Summary: This study explores the electrostatic contribution of zwitterions in colloidal processes. The results show that zwitterions do not affect the surface potentials, electrostatic surface forces, and ionic conductivity of solutions, but contribute to the osmolality of solutions. This is because the structure of zwitterions imposes an inseparability among positive and negative charges, preventing the buildup of a counter-charge.
JOURNAL OF PHYSICAL CHEMISTRY B
(2022)
Article
Chemistry, Multidisciplinary
Adair Gallo, Nayara H. Musskopf, Xinlei Liu, Ziqiang Yang, Jeferson Petry, Peng Zhang, Sigurdur Thoroddsen, Hong Im, Himanshu Mishra
Summary: Recent research on the formation of hydrogen peroxide (H2O2) in water microdroplets has attracted significant attention. The presence of ozone (O-3) in the air has been found to have the most significant impact on H2O2 formation in these water microdroplets. Increased gas-liquid surface area facilitates the conversion of O-3 into H2O2.
Article
Chemistry, Physical
Junting Qiu, Michiya Fujita, Kenichi Tonokura, Shinichi Enami
Summary: Secondary ozonides (SOZs), key products of the ozonolysis of biogenic terpenoids, have been found to persist in atmospheric condensed phases until they are delivered to the epithelial lining fluid of the pulmonary alveoli via inhaled particulate matter, potentially exerting previously unrecognized adverse health effects.
JOURNAL OF PHYSICAL CHEMISTRY A
(2022)
Editorial Material
Chemistry, Physical
Agustin J. Colussi, Shinichi Enami
Summary: A recent paper reported that photoelectron spectroscopy could not detect any products on the surface of aqueous Fe2+ jets dosed with gaseous hydrogen peroxide. However, the conclusion drawn in this paper is untenable because undetected species cannot be asserted.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2022)
Article
Chemistry, Multidisciplinary
Shinichi Enami
Summary: Organic hydroperoxides play important roles in atmospheric, environmental, and biological chemistry, and their H+ catalyzed decomposition can generate H2O2 and multifunctionalized compounds.
ACS EARTH AND SPACE CHEMISTRY
(2022)
Article
Chemistry, Physical
Naoki Numadate, Shota Saito, Yuki Nojima, Taka-aki Ishibashi, Shinichi Enami, Tetsuya Hama
Summary: Ultraviolet photolysis of fatty acid surfactants can generate hydroxyl radicals, but the dimerization structure of nonanoic acid's surface inhibits its photochemical reactivity.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2022)
Article
Chemistry, Physical
Shinichi Enami, Yu Morino, Kei Sato
Summary: This study reports the oxidation of Levoglucosan (Levo) in aqueous solutions using Fenton's reagent. The major products were oxygen-atom incorporated species. The results indicate that hydroxyl radicals (OH) preferentially abstract H atoms from carbon atoms with attached hydroxyl groups (-OH), followed by the formation of carbonyl groups (-C=O).
JOURNAL OF PHYSICAL CHEMISTRY A
(2023)
Article
Environmental Sciences
Mingxi Hu, Kunpeng Chen, Junting Qiu, Ying-Hsuan Lin, Kenichi Tonokura, Shinichi Enami
Summary: Organic hydroperoxides play important roles in the atmosphere, but the decomposition mechanisms in the liquid phase are not well understood. In this study, the decomposition of alpha-alkoxyalkyl-hydroperoxides derived from the ozonolysis of alpha-terpineol was investigated. Experimental and theoretical analysis revealed that a proton-catalyzed mechanism plays a central role in the decomposition, with water molecules also affecting the kinetics. These findings provide insights into the formation and transformation processes of organic hydroperoxides in the atmosphere.
ENVIRONMENTAL SCIENCE-ATMOSPHERES
(2022)
Article
Chemistry, Physical
Zi Qiang Yang, Peng Zhang, Meng Shi, Ali Al Julaih, Himanshu Mishra, Enzo Di Fabrizio, Sigurdur T. Thoroddsen
Summary: Polymer filaments have important applications in biology, tissue engineering, and molecular machines. Researchers have developed a simple method to deposit stretched polymer fibers between micro-pillars, allowing for characterization of filament-forming configurations and their properties.
Article
Chemistry, Physical
Yasuyuki Endo, Yosuke Sakamoto, Yoshizumi Kajii, Shinichi Enami
Summary: This study investigates the liquid-phase decomposition kinetics of multifunctionalized alpha-alkoxyalkyl-hydroperoxides (alpha-AHs). The results reveal that hemiacetal species are the main decomposition products and the reaction rate is influenced by pH and temperature.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2022)
Article
Multidisciplinary Sciences
Kennedy Odokonyero, Adair Gallo, Himanshu Mishra
Summary: Post-harvest storage of grains is crucial for food security, but jute bags' water-loving nature has been a major cause of post-harvest losses. Wax-coated jute bags have shown significant water-repellency and improved germination efficacy of stored grains, offering a promising solution to reduce post-harvest losses in developing countries.
SCIENTIFIC REPORTS
(2021)