Article
Polymer Science
Yeasmin Nahar, James Horne, Vinh Truong, Alex C. Bissember, Stuart C. Thickett
Summary: Thermoresponsive poly(N-isopropylacrylamide) (polyNIPAM) hydrogels were prepared via free radical polymerization in deep eutectic monomer solvents (DEMs) for the first time, where NIPAM served as a polymerizable hydrogen bond donor. The hydrogels prepared with DEMs showed increased cross-linking density and mechanical strength compared to those prepared in aqueous polymerization, exhibiting unique thermoresponsive swelling behavior.
Article
Engineering, Chemical
Monia A. R. Martins, Dinis O. Abranches, Liliana P. Silva, Simao P. Pinho, Joao A. P. Coutinho
Summary: The study investigated the intermolecular interactions between urea and quaternary ammonium salts by measuring the solid-liquid equilibria of their binary mixtures. It was found that anion transfer increases with alkyl chain lengths, leading to negative deviations in urea-rich side. Using bromides instead of chlorides can dampen the nonideality of urea.
INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH
(2022)
Article
Agricultural Engineering
Barbara P. Moreira, Crisleine P. Draszewski, Dian Celante, Leoni Brondani, Daniel Lachos-Perez, Flavio D. Mayer, Ederson R. Abaide, Fernanda Castilhos
Summary: The composition of defatted rice bran was modified by deep eutectic solvent pretreatment, leading to increased content of lignin and hemicellulose. As a result, the yield of fermentable sugars during subcritical water hydrolysis was significantly improved.
BIORESOURCE TECHNOLOGY
(2022)
Editorial Material
Chemistry, Physical
Andrew P. Abbott, Karen J. Edler, Alister J. Page
Summary: When selecting a solvent for a given solute, the commonly used idiom "like dissolves like" suggests using polar solvents for polar solutes. However, in deep eutectic solvents (DES), the components can be of various types, allowing for the solubilization of a wide range of solutes and the control of phase behavior through mixture design.
JOURNAL OF CHEMICAL PHYSICS
(2021)
Article
Chemistry, Multidisciplinary
Tatsuya Umecky, Akihiro Goto, Naoki Hayashi, Kazuki Eguchi
Summary: The physicochemical properties of deep eutectic solvents (DESs) are influenced by the combination of hydrogen bond acceptors and hydrogen bond donors. The basicity of a DES has a significant impact on various processes such as CO2 absorption, biomass dissolution, protein dissolution, and catalytic reactions. This study introduces a strategy for fine-tuning the basicity of DESs by substituting molecules and demonstrates the potential applications of DESs in the future.
Article
Chemistry, Multidisciplinary
Guangrui Ma, Zhiguo Zhang, Jiachuan Chen, Guihua Yang, Ming He
Summary: In this study, a new method using a sulfamic acid-urea-choline chloride system is presented for treating cellulose. This method achieves both swelling and sulfation of cellulose, significantly reducing energy consumption in the cellulose nanoization process. The method is successfully applied to the preparation of food packaging films for odor elimination. Its simplicity and resource-efficiency suggest a broad impact on current (nano) cellulose modification protocols.
NANOSCALE ADVANCES
(2023)
Article
Chemistry, Physical
Bricker D. Like, Christina E. Uhlenbrock, Matthew J. Panzer
Summary: Deep eutectic solvents (DESs) are a rapidly expanding class of liquid phase mixtures that have many useful features. However, there is currently no widely accepted criterion for identifying whether a particular mixture is a DES or not. This study introduces a quantitative metric based on the molar excess Gibbs energy of a eutectic mixture and proposes a threshold value to classify a eutectic system as a DES.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2023)
Article
Biochemistry & Molecular Biology
Zhassulan Sailau, Abay Serikkanov, Ainagul Kemelbekova, Aigul Shongalova, Sultan Zhantuarov, Nurlan Almas, Anuar Aldongarov, Kainaubek Toshtay
Summary: The main challenge in large-scale biofuel production is the extraction of undesired impurities such as glycerol, water, methanol, soap/catalyst, free fatty acids, and glycerides. This study proposes the use of deep eutectic solvents (DES) for glycerol extraction from biodiesel. The formation mechanism of DES and the extraction process were investigated through density functional theory and molecular dynamics simulations, which showed that DES has a strong interaction with glycerol, facilitating its extraction.
JOURNAL OF MOLECULAR MODELING
(2023)
Article
Chemistry, Physical
Valentina Migliorati, Paola D'Angelo
Summary: The study found that the low melting points of deep eutectic solvents are related to the anion's ability to build favorable networks of interactions, maximizing hydrogen bonds among all parts of the system.
CHEMICAL PHYSICS LETTERS
(2021)
Article
Chemistry, Multidisciplinary
Magdalena Zdanowicz
Summary: In this study, deep eutectic solvents (DESs) with different urea (U) contents were prepared and used as plasticizers for potato-starch. The influence of different DES compositions on the physicochemical properties of thermoplastic starch (TPS) was investigated. The results showed that increasing the U content led to higher phase-transition temperatures and lower thermal stability. Additionally, higher U content resulted in higher elongation at break and a highly amorphous structure in the TPS.
APPLIED SCIENCES-BASEL
(2023)
Article
Chemistry, Physical
Dinis O. Abranches, Liliana P. Silva, Monia A. R. Martins, Joao A. P. Coutinho
Summary: This study investigates the impact of water on intermolecular interactions in deep eutectic solvents betaine/urea and choline/urea. The addition of water enhances intermolecular interactions in betaine/urea, hinting at the formation of aggregates, while in choline/urea, water has an asymmetric impact leading to weaker interactions in choline-rich mixtures and stronger interactions in urea-rich mixtures. This research provides insights into how water affects the interactions in these systems.
JOURNAL OF CHEMICAL PHYSICS
(2021)
Article
Materials Science, Paper & Wood
Xiaoyao Wei, Tao Lin, Hengli Du, Le Wang, Xuefeng Yin
Summary: Cellulose nanocrystal (CNC) suspensions can form chiral spiral structures, which can be maintained in films. The addition of a deep eutectic solvent as a green plasticizer can improve the flexibility of CNC films, while maintaining their optical properties and structural stability. However, excessive amounts of the solvent can destroy the CNC structure and result in the loss of optical properties.
Article
Engineering, Chemical
Syed Z. Islam, Md Arifuzzaman, Gernot Rother, Vera Bocharova, Robert L. Sacci, Jacek Jakowski, Jingsong Huang, Ilia Nicolaevich Ivanov, Ramesh R. Bhave, Tomonori Saito, David S. Sholl
Summary: This study presents a scalable and energy-efficient hollow fiber membrane contactor (HFMC)-based process for CO2 capture using a green solvent. The use of deep eutectic solvent (DES) in HFMC allows for effective interaction between DES and CO2, overcoming drawbacks of direct absorption in DES. The research evaluates the performance of commercial low-cost polymer hollow fiber membranes in CO2 capture with DES and provides insights into the CO2 separation mechanism.
INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH
(2023)
Article
Electrochemistry
Fariha Ahmed, Domenec Paterno, Gurneet Singh, Sophia Suarez
Summary: The ion dynamics of null solvents consisting of 1ZnCl2:4EtG and 1ChCl:1ZnCl2:6EtG with the incorporation of 1M water, propylene carbonate (PC) or acetonitrile (AcN) were investigated. Various measurements, including 1H NMR spectra, spin-lattice relaxation time (T1) measurements, ionic conductivity, density and viscosity, were conducted to study the properties as a function of temperature. The results revealed increased free volume and dynamic heterogeneities in the mixtures, as well as selective interactions between hydrogen bond donors and acceptors, as well as with the co-solvents.
ELECTROCHIMICA ACTA
(2023)
Article
Chemistry, Physical
Elizabeth A. Recker, David Hardy, Grace I. Anderson, Arsalan Mirjafari, Durgesh V. Wagle
Summary: This study investigated the impact of a covalent link between hydrogen bond donor species on the behavior of deep eutectic solvents (DES). The presence of a glycosidic bond in trehalose limited the movement of sugar units, resulting in fewer interactions with choline chloride in DES(t). This limitation influenced the physical state of DES(t), making it behave more like a semi-solid material compared to the liquid-like behavior of DES(g).
JOURNAL OF CHEMICAL PHYSICS
(2021)
Article
Chemistry, Multidisciplinary
Paul Geerlings, Frank De Proft
Summary: The necessity of incorporating new external variables in the context of conceptual DFT (CDFT) is discussed. Electric and magnetic fields, mechanical forces, and confinement are proposed as valuable new variables. The study shows that these new variables are important for understanding chemical phenomena under different conditions.
JOURNAL OF COMPUTATIONAL CHEMISTRY
(2023)
Article
Chemistry, Physical
Xavier Deraet, Jan Turek, Mercedes Alonso, Frederik Tielens, Bert M. M. Weckhuysen, Monica Calatayud, Frank De Proft
Summary: This paper investigates the adsorption behavior of single late transition metals on a defect-free anatase surface using periodic density functional theory calculations. The results reveal that the interaction strength between the transition metals and the support can be attributed to electron transfer, s-d orbital hybridization effects, or a synergistic effect between both factors. Palladium shows deviating adsorption behavior, which is likely associated with the lower dissociation enthalpy of the Pd-O bond. The reactivity of these systems is evaluated using the Fermi weighted density of states approach, and a model is proposed to predict the adsorption strength of CO on anatase-supported d-metal atoms.
Article
Chemistry, Organic
Javier E. Alfonso-Ramos, Ruben Van Lommel, David Hernandez-Castillo, Frank De Proft, Roy Gonzalez-Aleman, Erik V. Van der Eycken, Gerardo M. Ojeda-Carralero
Summary: 3-Dipolar cycloadditions are commonly used to form five-membered heterocycles, but the cycloadditions involving acyl-isocyanide ylides have not been well explored by the chemical community. In this study, we investigated the mechanistic features of the reaction between acyl-isocyanide ylides and dipolarophiles using density functional theory calculations. We explained the experimental results and predicted opposite regioselectivity for electron-poor and electron-rich dipolarophiles. This study provides insights for the design of new cycloaddition reactions based on the acyl-isocyanide ylides motif.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Mercedes Alonso, Frank De Proft, Tom Bettens, Paul Geerlings
Summary: Anti-Felkin-Anh diastereoselectivity can be achieved by stretching the ketone with a mechanical pulling force. A mechanochemical Felkin-Anh model is proposed based on the distance between the pulling points. The model is validated by density functional theory calculations and the risk of bond rupture is minimized.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Biochemistry & Molecular Biology
Ana V. Cunha, Remco W. A. Havenith, Jari van Gog, Freija De Vleeschouwer, Frank De Proft, Wouter Herrebout
Summary: In this study, the interaction between the halogen atom X and the aromatic ring in the halogen bond complexes CF(3)Xmiddot middot middot Y and C(2)F(3)Xmiddot middot middot Y (with Y = furan, thiophene, selenophene and X = Cl, Br, I) was investigated using DFT and CCSD(T) methods. It was found that the interaction with the pi-bonds in a perpendicular orientation is stronger than the interaction with the in-plane lone pairs of the heteroatom of the aromatic cycle. The interaction energy is dominated by electrostatic, orbital, and dispersion interactions, and the strength of the interaction follows the trend Cl < Br < I.
Article
Chemistry, Multidisciplinary
Stephen E. Brown, Ioanna Mantaloufa, Ryan T. Andrews, Thomas J. Barnes, Martin R. Lees, Frank De Proft, Ana V. Cunha, Sebastian D. Pike
Summary: The molecular titanium-oxo cluster [Ti6O6((OPr)-Pr-i)(6)((O2CBu)-Bu-t)(6)] (1) can be activated by UV light to produce a mixed valent (photoreduced) Ti (iii/iv) cluster, along with alcohol and ketone organic products. Mechanistic studies show a two-electron mechanism utilizing the cluster structure for multielectron reactions. The photoreduced products [Ti6O6((OPr)-Pr-i)(4)((O2CBu)-Bu-t)(6)(sol)(2)] can be isolated and characterized, and undergo onward oxidation under air. The redox reactivity described is only possible in a cluster with multiple Ti sites.
Article
Materials Science, Multidisciplinary
Mingtao Wang, Liwei Wang, Wendi Yang, Yuxi Liu, Herman Terryn, Zhongyu Cui
Summary: The effect of bisulfite (HSO3-) on the stress corrosion cracking (SCC) behavior of 7050-T7451 aluminum alloy in the presence of Cl- in a thin electrolyte layer environment is investigated. The addition of HSO3- inhibits corrosion initiation but promotes corrosion propagation and hydrogen uptake. Quantitative calculation demonstrates that HSO3- significantly facilitates the synergistic effect among stress, corrosion, and hydrogen, causing a shift in the controlling step of SCC from corrosion-induced hydrogen to mechanical-electrochemical-hydrogen interactions. The buffer effect of HSO3- plays a dominant role in the HSO3--induced acceleration of SCC degradation.
Article
Chemistry, Inorganic & Nuclear
Bin Wang, Chunying Rong, Ming Lei, Shubin Liu, Frank De Proft
Summary: Designing efficient and selective catalysts for carbon dioxide reduction is an active area of research in homogeneous catalysis. In this study, the catalytic activity of a newly reported Mn(I)-PNP-pincer catalyst with an embedded aromatic ring is investigated. The study systematically examines the catalyst's capability to yield different products and explores the importance of ligand aromaticity and steric effects on metal-ligand cooperativity. The reactivity of the catalyst is probed using conceptual density functional theory and an information-theoretic approach, leading to a novel partitioning of the reaction coordinate into three relevant regions. The results demonstrate that different properties govern the reactivity in these different regions, such as steric effects, electrophilicity/nucleophilicity, or aromaticity. The methodology and analytical tools employed in this study have the potential to be generalized and extended to other catalytic systems, offering insights towards designing improved catalysts.
INORGANIC CHEMISTRY
(2023)
Article
Biochemistry & Molecular Biology
Lise Vermeersch, Frank De Proft, Vicky Faulkner, Freija De Vleeschouwer
Summary: This study analyzed the governing factors in Lewis acid and non-covalent catalysis of three types of Diels-Alder reactions. The stability of the non-covalent interaction donor-dienophile complex was found to significantly reduce the activation energy. Orbital interactions were shown to be the main driver for catalysis, with electrostatic interactions dominating.
INTERNATIONAL JOURNAL OF MOLECULAR SCIENCES
(2023)
Article
Chemistry, Physical
Lieven Bekaert, Suzuno Akatsuka, Naoto Tanibata, Frank De Proft, Annick Hubin, Mesfin Haile Mamme, Masanobu Nakayama
Summary: Rechargeable batteries are essential in the transition from fossil fuels to renewable energy. Solid-state sodium ion batteries are a promising alternative to lithium-based batteries, offering improvement in safety, lifespan, sustainability, and price. The chemical stability of Na3PS4 solid-state electrolyte with sodium metal electrode has been investigated, providing new design principles for optimizing solid-state electrolytes.
JOURNAL OF PHYSICAL CHEMISTRY C
(2023)
Article
Chemistry, Physical
Ramon Alain Miranda-Quintana, Alberto Vela, Frank De Proft, Marco Martinez Gonzalez, Jose L. Gazquez
Summary: The hard/soft acid/base (HSAB) principle is fundamental to understanding chemical reactivity preferences. However, the local HSAB principle often fails in making accurate predictions for regioselectivity preferences. By considering both the charge transferred between reacting centers and the charge reorganization within non-reacting parts of the molecule, we propose different reorganization models and corresponding regioselectivity rules.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2023)
Review
Chemistry, Physical
Mercedes Alonso, Tom Bettens, Jochen Eeckhoudt, Paul Geerlings, Frank De Proft
Summary: Mechanochemistry has undergone a renaissance in recent years, with a remarkable interplay between theory and experiment at the molecular level. Quantum mechanochemistry has incorporated various quantum-chemical methods to investigate the impact of external mechanical forces on molecular properties. This contribution provides an overview of recent work on quantum mechanochemistry, covering fundamental topics on reactivity descriptors and applied topics on molecular force probes and stereoselectivity tuning.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2023)
Article
Chemistry, Multidisciplinary
Wouter Stuyck, Kwinten Janssens, Mats Denayer, Free De Schouwer, Robin Coeck, Katrien Bernaerts, Jelle Vekeman, Frank De Proft, Dirk E. De Vos
Summary: This study reports a green and efficient ammonolysis process for polyamide plastics using a hard Lewis acid catalyst and a simple glycol solvent at 200 degrees C and 1 bar NH3 pressure. Computational studies reveal that the vicinal diol moiety of the glycol solvent plays a key role in activating the ammonia nucleophile, with glycerol being the most effective solvent.
Article
Chemistry, Multidisciplinary
J. Eeckhoudt, T. Bettens, P. Geerlings, R. Cammi, B. Chen, M. Alonso, F. De Proft
Summary: High pressure chemistry offers possibilities for controlling chemical reactivity, developing new materials, and fine-tuning chemical properties. However, the focus has primarily been on volume changes and thermodynamics, neglecting the electronic effects at the molecular scale. This study combines the DFT framework with the XP-PCM method to analyze the effects of high pressure on chemical properties. The results reveal the relationship between pressure and various properties, such as ionization potential, electron affinity, electronegativity, chemical hardness, softness, and electron density. The findings provide insights into the periodic trends and correlations between these properties under pressure.
Article
Chemistry, Physical
Andrew M. Teale, Trygve Helgaker, Andreas Savin, Carlo Adamo, Balint Aradi, Alexei Arbuznikov, Paul W. Ayers, Evert Jan Baerends, Vincenzo Barone, Patrizia Calaminici, Eric Cances, Emily A. Carter, Pratim Kumar Chattaraj, Henry Chermette, Ilaria Ciofini, T. Daniel Crawford, Frank De Proft, John F. Dobson, Claudia Draxl, Thomas Frauenheim, Emmanuel Fromager, Patricio Fuentealba, Laura Gagliardi, Giulia Galli, Jiali Gao, Paul Geerlings, Nikitas Gidopoulos, Peter M. W. Gill, Paola Gori-Giorgi, Andreas Gorling, Tim Gould, Stefan Grimme, Oleg Gritsenko, Hans Jorgen Aagaard Jensen, Erin R. Johnson, Robert O. Jones, Martin Kaupp, Andreas M. Koster, Leeor Kronik, Anna Krylov, Simen Kvaal, Andre Laestadius, Mel Levy, Mathieu Lewin, Shubin Liu, Pierre-Francois Loos, Neepa T. Maitra, Frank Neese, John P. Perdew, Katarzyna Pernal, Pascal Pernot, Piotr Piecuch, Elisa Rebolini, Lucia Reining, Pina Romaniello, Adrienn Ruzsinszky, Dennis R. Salahub, Matthias Scheffler, Peter Schwerdtfeger, Viktor N. Staroverov, Jianwei Sun, Erik Tellgren, David J. Tozer, Samuel B. Trickey, Carsten A. Ullrich, Alberto Vela, Giovanni Vignale, Tomasz A. Wesolowski, Xin Xu, Weitao Yang
Summary: This paper provides an informal review and discussion on the history, present status, and future of density-functional theory (DFT) by 70 workers in the field. The format of a roundtable discussion allowed participants to express their views through 302 individual contributions to a preset list of 26 questions. Supported by a bibliography of 777 entries, the paper offers a comprehensive snapshot of DFT in 2022.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2022)