Review
Biochemistry & Molecular Biology
Rosa Amoroso, Frank Hollmann, Cristina Maccallini
Summary: DES are mixtures of two or more compounds that can form liquids with lower freezing points due to specific hydrogen-bond interactions, making them customizable for pharmaceutical purposes. ChCl-based DES have been utilized in pharmaceutical compound synthesis as solvents, solvents/catalysts, or chemical donors.
Article
Chemistry, Physical
Wahiba Ramdani, Ines Rabadan Gonzales, Nora Benbakoura, Mohammed Ahmar, Charlie Verrier, Yves Queneau, Marc Pera-Titus, Francois Jerome, Karine De Oliveira Vigier
Summary: 1-(5-(Hydroxymethyl)furan-2-yl)-5-methylhex-1-en-3-one was synthesized from cellulose or glucose through a series of depolymerization/dehydration/aldol condensation reactions. The synthesis of HMF started from a highly concentrated feed of glucose and cellulose (31 wt.%) using choline chloride in MIBK/water biphasic media, followed by aldol condensation with MIBK over alkaline metal oxides. Among the catalysts used, commercial BaO exhibited the highest efficiency with an aldol product yield above 90%. BaO readily transformed into Ba(OH)(2), H2O, and BaO2 in air, which were considered as the active phases for the reaction. The catalyst basicity and solvent played crucial roles in determining the reaction selectivity by limiting secondary reactions.
Article
Chemistry, Physical
Si Ae Kim, Kihyuk Sung, June Young Jang, Sohee Bang, Seung Uk Son, Hye-Young Jang
Summary: Versatile homogeneous and heterogeneous catalysts are crucial for the sustainable conversion of carbohydrates into high-value chemicals such as DFF. This study presents an efficient catalytic system consisting of Br-, disulfide, and DMSO that enables the selective synthesis of DFF from various carbohydrates. Heterogeneous catalysts containing Br- also show promising results with recyclable high yields.
Article
Agricultural Engineering
Qing Qing, Wenxuan Wu, Xiaoran Tao, Zhuang Ma, Weigang He, Yuheng Tao, Liqun Wang
Summary: Aqueous choline chloride/acetone was developed as a green ternary solvent for catalytic conversion of glucose and raw corn stover into 5-HMF. The acidic choline chloride solution promoted the isomerization and dehydration of glucose to 5-HMF, while acetone acted as an efficient extracting solvent to remove 5-HMF from the aqueous phase. The composition of the ternary solvent system significantly affected the 5-HMF yield, reaction selectivity, and prevention of further degradation.
INDUSTRIAL CROPS AND PRODUCTS
(2022)
Article
Chemistry, Analytical
Eman O. Osman, Amr M. Mahmoud, Sally S. El-Mosallamy, Hala B. El-Nassan
Summary: This study reported the first synthesis of 4H-pyran derivatives using electrochemical synthesis conditions and deep eutectic solvents in a one pot reaction. By optimizing the reaction conditions, high yields of pure pyran derivatives could be obtained in a short amount of time. The use of deep eutectic solvents also eliminated the need for a supporting electrolyte, improving the sustainability of the catalyst.
JOURNAL OF ELECTROANALYTICAL CHEMISTRY
(2022)
Article
Chemistry, Physical
Usman Saeed, Asim Laeeq Khan, Mazhar Amjad Gilani, Muhammad Roil Bilad, Asad Ullah Khan
Summary: This study focused on utilizing deep eutectic solvents (DESs) impregnated into PVDF membranes for the separation of CO2 from CH4. The DES-SLMs showed high CO2 permeability and selectivity, indicating potential for new pathways in CO2 capture using DESs.
JOURNAL OF MOLECULAR LIQUIDS
(2021)
Article
Energy & Fuels
Lucas S. Silva, Bernardo D. Ribeiro, Ivaldo Itabaiana Jr
Summary: Babassu, a valuable fruit in Brazil, generates a large amount of residual mesocarp after oil extraction. Using deep eutectic solvents as pre-treatment can efficiently dissolve this residue and extract valuable compounds, offering significant biotechnological potential.
BIOENERGY RESEARCH
(2023)
Article
Chemistry, Physical
Reza Tabaraki, Fereshteh Nazari
Summary: This study synthesized carbon dots using a microwave method in ten choline chloride based deep eutectic solvents (DESs). The surface and optical characteristics of the carbon dots were influenced by the solvent used during synthesis. The quantum yield of the prepared carbon dots varied depending on the DES used, with choline chloride/urea, choline chloride/glycerol, and choline chloride/thiourea DESs having quantum yields of 41.3%, 38.7%, and 35.5% respectively. The doping of nitrogen and sulfur atoms in certain carbon dots enhanced their photoluminescence performance. TEM, FT-IR, EDXS, and fluorescence spectroscopy were used for characterization.
JOURNAL OF PHOTOCHEMISTRY AND PHOTOBIOLOGY A-CHEMISTRY
(2023)
Article
Engineering, Environmental
Chun-Chi Chen, Chiun-Yao Wang, Yen-Hui Huang
Summary: The study demonstrates a new strategy for capturing nitrogen dioxide (NO2) using deep eutectic solvents (DESs) and their aqueous mixtures. The results show that ChCl-based DESs have excellent NO2 absorption capability, which increases with increasing HBD content. Additionally, the DES aqueous mixtures retain high NO2 solubility while exhibiting a lower viscosity after the introduction of water.
CHEMICAL ENGINEERING JOURNAL
(2021)
Article
Chemistry, Multidisciplinary
Salvatore Romano, Antonio Rescifina, Giuseppina De Luca, Monica Nardi, Manuela Oliverio, Antonio Procopio
Summary: The synthesis of amides, a commonly used reaction in pharmaceutical chemistry, usually requires stoichiometric activators and impacts sustainability. Developing eco-friendly methods for amidation has become a challenge. This study explores the use of non-toxic biological molecule choline chloride (ChCl) as a promoter for direct amidation of carboxylic acids. Microwave-assisted amidation tests reveal that the reaction benefits from specific microwave effects, which accumulate energy and activate the reaction. FT-IR analysis and DFT calculations shed light on the reaction mechanism and uncover a new role for ChCl in stabilizing intermediates and coordinating reagents.
ACS SUSTAINABLE CHEMISTRY & ENGINEERING
(2023)
Article
Polymer Science
Doina Crucean, Bruno Pontoire, Gervaise Debucquet, Alain Le-Bail, Patricia Le-Bail
Summary: The aim of this research is to study the destructuration of three native starches and wheat flour in mixtures of water and choline chloride. The study shows that choline chloride impacts the gelatinization of starch and that the exotherm observed is not only related to depolymerization of the starch, but also to a crystalline rearrangement stage coexisting with this phenomenon.
Article
Chemistry, Multidisciplinary
Huai Liu, Xuejuan Cao, Xing Tang, Xianhai Zeng, Yong Sun, Xixian Ke, Lu Lin
Summary: By establishing hydrogen bonds between levulinic acid and choline chloride, the study successfully enhanced the hydrogenation efficiency of the acyl group in levulinic acid over Ru/C, achieving high yields of GVL synthesis under solvent-free conditions.
Article
Engineering, Environmental
JishaKuttiani Ali, Emad Alhseinat, Maguy Abi Jaoude, Inas M. Al Nashef, Idowu A. Adeyemi, Tejraj M. Aminabhavi, Hassan A. Arafat
Summary: This research developed novel composite mixed matrix membranes by incorporating choline chloride/malonic acid (ChCl-MA) deep eutectic solvent (DES) supported onto silica (SiO2) nanoparticles into polyimide (PI) membrane precursor solution. The membranes showed improved hydrophilicity, surface texture, water flux, and removal efficiency for bentazon, attributed to the functional groups in DES fragment and their interactions with bentazon in the feed solution.
CHEMICAL ENGINEERING JOURNAL
(2022)
Article
Polymer Science
Syed Asim Hussain Shah, Muggundha Raoov Ramachandran, Sity Aishah Mansur, Noorashikin Md Saleh, Saliza Asman
Summary: The synthesis and characterization of a deep eutectic solvent molecularly imprinted polymer (DES-MIP) has shown that it exhibits a higher selectivity and binding capacity for bisphenol A (BPA) compared to structurally similar compounds. The DES-MIP has been found to have optimal binding capacity at pH 7 and its adsorption follows pseudo-second-order kinetic and Langmuir isotherm models. Thermodynamic analysis indicates that the adsorption of BPA on DES-MIP is exothermic and spontaneous. The DES-MIP is a promising adsorbent with high adsorption capability, remarkable selectivity, and good reusability.
Article
Polymer Science
Penghui Li, Yuan Lu, Xiaoyu Li, Jianpeng Ren, Zhengwei Jiang, Bo Jiang, Wenjuan Wu
Summary: In this study, lignin was degraded using deep eutectic solvent (DES), and it was found that acidic DES was more effective in depolymerizing alkaline lignin. The degradation process was characterized using NMR hydrogen spectroscopy, FT-IR spectroscopy, and GPC.
Article
Chemistry, Multidisciplinary
I van Scodeller, Karine De Oliveira Vigier, Eric Muller, Changru Ma, Frederic Guegan, Raphael Wischert, Francois Jerome
Summary: In this study, a Diels-Alder/aromatization sequence is used to synthesize renewable aromatics from bio-based furfural derivatives and inexpensive alkenes. The control of ortho/meta selectivity in the Diels-Alder step is crucial for developing a wide range of renewable aromatics. Experimental and theoretical approaches show that ortho and meta cycloadducts are kinetic and thermodynamic products, respectively, and the feasibility of the reaction is significantly impacted by substituents on the reactants.
Article
Chemistry, Multidisciplinary
Anaelle Humblot, Laurie Grimaud, Audrey Allavena, Prince N. Amaniampong, Karine De Oliveira Vigier, Tony Chave, Stephane Streiff, Francois Jerome
Summary: This study demonstrates that cavitation bubbles created by ultrasonic irradiation of aqueous NH3 at a high frequency can activate and convert NH3 to hydrazine without the need for any catalyst. The in-situ-produced hydrazine is compartmentalized in the bulk solution maintained close to 30 degrees Celsius, preventing its thermal degradation. Additionally, this work suggests a pathway to scavenge (OH)-O-. radicals by adjusting the NH3 concentration.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Organic
Gongming Peng, Anaelle Humblot, Raphael Wischert, Karine De Oliveira Vigier, Fan Jiang, Marc Pera-Titus, Francois Jerome
Summary: The combination of bismuth triflate and hexafluoroisopropanol (HFIP) leads to highly active catalytic species for the hydroarylation of various nonactivated alkenes with aniline, achieving high selectivity (71-92%). Through experimental and computational investigations, a reaction pathway is proposed where HFIP stabilizes the rate-determining transition state by interacting with the triflate anion, assisting the acid catalyst in the hydroarylation of nonactivated alkenes. This work provides a catalytic access to C-functionalized aniline derivatives from inexpensive and abundant feedstocks in a 100% atom-economical fashion.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Walid Lamine, Frederic Guegan, Francois Jerome, Gilles Frapper
Summary: This study investigates the reaction mechanism of cellulose depolymerization under non-thermal plasma conditions. The degradation of glycosidic bonds triggered by reaction with hydroxyl radicals is explored. It is found that the hydrogen abstraction reactions by hydroxyl radicals on different sites of the pyranose ring are nonselective and exergonic, resulting in the formation of cellobiosyl carboradicals. These carboradicals protect against direct hydrolysis and a homolytic bond cleavage process allows the desired monomer to be obtained. Through molecular simulation and analysis, three feasible reaction pathways are identified based on their kinetics and thermodynamics.
JOURNAL OF COMPUTATIONAL CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Pablo G. Argudo, Lea Spitzer, Francois Jerome, Henri Cramail, Luis Camacho, Sebastien Lecommandoux
Summary: Sugar-based amphiphiles are a natural alternative to synthetic ones with biodegradable properties. An investigation of their structure-assembly relationship was conducted using various techniques in aqueous media. The results showed that the average degree of polymerization (DP) and the addition of a hydroxyl group to the hydrophobic tail affected their self-assembly. The critical micelle concentration was more influenced by changes in the hydrophobic molecular region than by variations in (DP) over bar. Amphiphiles with high (DP) over bar formed spherical micelles regardless of the presence of a hydroxyl group, while those with low (DP) over bar and only one hydrophilic moiety formed cylindrical micelles, and the addition of a hydroxyl group to the tail resulted in a spherical shape.
Article
Chemistry, Multidisciplinary
Anaelle Humblot, Tony Chave, Prince N. Amaniampong, Stephane Streiff, Francois Jerome
Summary: With the progressive defossilization of our industry, hydrogen (H-2) has been identified as a central molecule to store renewable electricity. In this context, ammonia (NH3) is now rapidly emerging as a promising hydrogen carrier for the future. This study demonstrates a novel method of cleaving the N-H bond of NH3 within cavitation bubbles, generated by ultrasonic irradiation, leading to the in situ formation of a diimide, which then catalyzes the hydrogenation of alkenes. This work offers a potential solution for hydrogenation reactions using ammonia directly, without the need for transition metals and with N-2 as the sole co-product.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Biochemistry & Molecular Biology
Somia Haouache, Yu Chen, Clara Jimenez-Saelices, Fabrice Cousin, Pan Chen, Yoshiharu Nishiyama, Francois Jerome, Isabelle Capron
Summary: This study compares the organization of nanocelluloses on oil-water interfaces. Both native and mercerized cellulose nanocrystals form strongly adsorbed layers at the interface, but the layer thickness depends on the concentration. Molecular dynamics simulations show that the migration of nanocelluloses to the interface is spontaneous and irreversible.
Review
Chemistry, Physical
Sophie Hameury, Hana Bensalem, Karine De Oliveira Vigier
Summary: This review provides an overview of the use of Borrowing Hydrogen methodology with bio-based alcohols, highlighting key parameters and remaining scientific hurdles in biomass amination.
Article
Chemistry, Multidisciplinary
Hang Hu, Muhammad Akif Ramzan, Raphael Wischert, Francois Jerome, Carine Michel, Karine de Oliveira Vigier, Marc Pera-Titus
Summary: The direct amination of biomass-derived isohexides over a Ru/C catalyst showed that the presence of hydrogen gas (H-2) and ammonia gas (NH3) played important roles in the selectivity of isohexide conversion to diamines and aminoalcohols. Isohexides with an exo-OH group formed aminoalcohols, while isohexides with two endo-OH groups produced a moderate yield of diamines due to higher reactivity. The adsorption of NH3 on the catalyst strongly suppressed isomerization of isohexides and discouraged the formation of byproducts promoted by H-2.
ACS SUSTAINABLE CHEMISTRY & ENGINEERING
(2023)
Article
Chemistry, Physical
Teseer Bahry, Shang Jiang, Umesh Jonnalagadda, Wen Liu, Benoit Teychene, Francois Jerome, Samir H. Mushrif, Prince N. Amaniampong
Summary: This study presents a novel catalytic chemistry for the demethylenation of benzyl alcohol to phenol using a combination of an earth-abundant transition metal oxide (CuO) catalyst and high frequency ultrasound (HFUS). The reaction takes place in water and at room temperature. By characterizing the catalyst, analyzing the chemistry and acoustics, using isotope labelling and density functional theory computations, the researchers unveil the molecular reaction mechanism, which involves benzaldehyde as an intermediate. Water is not only a benign solvation medium, but also directly participates in the reaction by undergoing dissociation due to sonolysis. The adsorption of the OH from water on the catalyst surface inhibits recombination and activates the C-H bond in benzyl alcohol, leading to the formation of benzaldehyde and its incorporation into the phenyl ring to form phenol.
CATALYSIS SCIENCE & TECHNOLOGY
(2023)
Article
Chemistry, Multidisciplinary
Prince Nana Amaniampong, Quang Thang Trinh, Teseer Bahry, Jia Zhang, Francois Jerome
Summary: The study demonstrated a base-free strategy for the selective oxidation of microcrystalline cellulose to oxalic acid using low frequency ultrasound and Au/Fe2O3 catalyst. The combination of low frequency ultrasound and catalyst led to enhanced catalytic oxidation of cellulose particles, resulting in a significant yield of oxalic acid. Density functional theory and X-ray photoelectron spectroscopy confirmed the charge transfer from Au nanoparticles to Fe2O3, forming active catalytic species for cellulose oxidation.
Article
Chemistry, Multidisciplinary
Julien Dieu, Francois Jerome, Catherine Batiot-Dupeyrat
Summary: Non-thermal atmospheric plasma is capable of cleaving the N-H bond of NH3 to form aminium radicals, which then react with ethylene to produce ethylamine with a yield of 17%. This technology can also be applied to n-octene, leading to the formation of 1-octylamine, demonstrating anti-Markovnikov addition of NH3.
REACTION CHEMISTRY & ENGINEERING
(2021)
Article
Chemistry, Physical
H. Hu, A. Ramzan, R. Wischert, F. Jerome, C. Michel, K. de Olivera Vigier, M. Pera-Titus
Summary: By combining experiments with DFT computations, it is possible to reduce the required H-2 pressure for isosorbide isomerisation, which can benefit the economy and safety of a potential industrial process.
CATALYSIS SCIENCE & TECHNOLOGY
(2021)
Review
Chemistry, Multidisciplinary
Tianjian Zhang, Changhui Liu, Yanlong Gu, Francois Jerome
Summary: Glycerol, with its abundant feedstock and unique properties, is an ideal candidate for catalysis, high-value-added chemical conversion, and energy transportation. Recent advances in the utilization of glycerol in energy transportation were summarized, showcasing its potential in industrial processes.
Review
Chemistry, Multidisciplinary
Stephane Streiff, Francois Jerome
Summary: Alkyl amines are important chemicals with various applications, and catalytic hydroamination is a highly interesting route. However, catalytic hydroamination of linear alkenes with ammonia remains a challenging unsolved reaction.
CHEMICAL SOCIETY REVIEWS
(2021)
Article
Chemistry, Multidisciplinary
Xuemei Liu, Chaonan Cui, Shuoshuo Wei, Jinyu Han, Xinli Zhu, Qingfeng Ge, Hua Wang
Summary: This study presents a new strategy for designing efficient photocatalysts that can convert CO2 into hydrocarbons by utilizing synergistic catalytic sites. The findings provide a solution for the selective photocatalytic reduction of CO2 to CH4.
Article
Chemistry, Multidisciplinary
Chengxian Hu, Dan Wang, Lu Wang, Ying Fu, Zhengyin Du
Summary: A novel one-pot, three-component reaction conducted under electrochemical conditions was studied. The reaction involved 2-aminothiophenols, aldehydes, and malononitrile, using TBABF4 as an electrolyte and CuI as a catalyst. The proposed reaction mechanism suggested that CuI served as an electron relay. This method offers simplified operation, high atom economy, and mild reaction conditions.
Article
Chemistry, Multidisciplinary
Zhi Yang, Yu Chen, Linxi Wan, Yuxiao Li, Dan Chen, Jianlin Tao, Pei Tang, Fen-Er Chen
Summary: A highly enantioselective method for the complete hydrogenation of pyrimidinium salts using Ir/(S,S)-f-Binaphane complex as the catalyst was developed. This method provides easy access to fully saturated chiral hexahydropyrimidines, which are prevalent in many bioactive molecules. The reactions exhibit high yields and enantioselectivities under mild reaction conditions without additives. Successful application of this methodology in a continuous flow fashion further extends its practical utility.
Article
Chemistry, Multidisciplinary
Tina Jeoh, Jennifer Danger Nill, Wujun Zhao, Sankar Raju Narayanasamy, Liang Chen, Hoi-Ying N. Holman
Summary: In this study, the enzymatic hydrolysis of cellulose was investigated using real-time infrared spectromicroscopy. The spatial heterogeneity of cellulose was found to impact the hydrolysis kinetics. Hydration affected cellulose ordering, and Cel7A preferentially removed less extensively hydrogen bonded cellulose.
Article
Chemistry, Multidisciplinary
Tiphaine Richard, Walid Abdallah, Xavier Trivelli, Mathieu Sauthier, Clement Dumont
Summary: An effective method of grafting functionalities onto lignin based on glycerol carbonate has been developed using an efficient nickel-catalysed telomerisation reaction. This method allows lignin to have new reactive functions and reduces the glass transition temperatures of modified lignins, thereby expanding the application range of lignin-based resins.
Article
Chemistry, Multidisciplinary
Jing Qi, Xiyan Wang, Gan Wang, Srinivas Reddy Dubbaka, Patrick ONeill, Hwee Ting Ang, Jie Wu
Summary: This study presents a green and environmentally friendly approach for the synthesis of imides using electrocatalytic oxidation with H2O as the oxygen source. The method eliminates the need for toxic or expensive oxidants and achieves high yields under mild reaction conditions. It shows broad substrate compatibility and potential for industrial applications.
Article
Chemistry, Multidisciplinary
Babasaheb Sopan Gore, Lin-Wei Pan, Jun-Hao Lin, Yi-Chi Luo, Jeh-Jeng Wang
Summary: Here, we report a visible light-promoted intramolecular radical cascade reaction for the construction of fluorenol and naphthalene-fused cyclopropyl carbaldehyde derivatives. This method offers mild reaction conditions, a broad substrate scope, excellent step efficiency, and scalability, without the need for external chemical oxidants. The novelty of this protocol was demonstrated by synthesizing chrysene analogs and performing late-stage functionalizations.
Article
Chemistry, Multidisciplinary
Juho Antti Sirvio, Idamaria Romakkaniemi, Juha Ahola, Svitlana Filonenko, Juha P. Heiskanen, Ari Ammala
Summary: This article discusses the method of using supramolecular interaction between an aromatic hydrogen bond donor and lignin to achieve rapid delignification of softwood at low temperatures.
Article
Chemistry, Multidisciplinary
Yunyan Meng, Chunxiang Pan, Na Liu, Hongjiang Li, Zixiu Liu, Yao Deng, Zixiang Wei, Jianbin Xu, Baomin Fan
Summary: A novel visible light-driven synthesis method for 2,3-diamines has been developed, which has mild conditions, avoids the use of metal reagents, and can synthesize diamines and diols in one pot.
Article
Chemistry, Multidisciplinary
Mingqing Huang, Haiyang Huang, Mengyao You, Xinxin Zhang, Longgen Sun, Chao Chen, Zhichao Mei, Ruchun Yang, Qiang Xiao
Summary: A direct air-oxidized strategy for the synthesis of benzo[b]phosphole oxides was developed in this study. Arylphosphine oxides were transformed into phosphinoyl radicals, which were further combined with various alkynes to achieve the desired products. DFT calculations revealed the mechanism of phosphinoyl radical formation.
Article
Chemistry, Multidisciplinary
Anwei Wang, Jiayin Huang, Chunsheng Zhao, Yu Fan, Junfeng Qian, Qun Chen, Mingyang He, Weiyou Zhou
Summary: This study demonstrates an innovative strategy for the aerobic oxidation of C(sp(3))-H bonds using gamma-valerolactone. By optimizing the reaction conditions and utilizing specific catalysts, efficient oxidation of C(sp(3))-H bonds is achieved with good chemoselectivity in certain cases.
Article
Chemistry, Multidisciplinary
Shun Li, Likai Tong, Zhijian Peng, Bo Zhang, Xiuli Fu
Summary: Sulfide compounds show promise as electrocatalysts for water splitting, but their performance is limited by factors such as limited active sites and hindered substance transport. This study successfully prepared a high-entropy sulfide (ZnCoMnFeAlMg)(9)S-8, which reduced grain size and increased specific surface area, enabling the realization of a dual-functional catalyst with multiple catalytic sites. High entropy also modulated the electronic properties of sulfides, reducing the potential energy barrier for hydrolysis. This research introduces a new approach for functionalizing high entropy nanomaterials and improves the performance of water splitting catalysts.
