Article
Multidisciplinary Sciences
Huang Wu, Yu Wang, Chun Tang, Leighton O. Jones, Bo Song, Xiao-Yang Chen, Long Zhang, Yong Wu, Charlotte L. Stern, George C. Schatz, Wenqi Liu, J. Fraser Stoddart
Summary: In order to maintain sustainable environments and improve resource utilization, it is urgently needed to develop an eco-friendly, efficient, and highly selective gold-recovery technology. Here, the authors present a gold recovery paradigm based on the controlled assembly of supramolecular polymers formed between beta-cyclodextrin and tetrabromoaurate anions. By co-occupying the binding cavity of beta-cyclodextrin with tetrabromoaurate anions, the additives initiate a rapid assembly process, resulting in the precipitation of cocrystals from aqueous solutions. The gold recovery efficiency reaches 99.8% with the use of dibutyl carbitol as the additive. This protocol offers a promising approach for the sustainable recovery of gold, with reduced energy consumption, low cost inputs, and environmental pollution avoidance.
NATURE COMMUNICATIONS
(2023)
Article
Chemistry, Multidisciplinary
Sebastian Haaf, Elisabeth Kaifer, Hubert Wadepohl, Hans-Joerg Himmel
Summary: In this study, the manipulation of the electronic structure of copper complexes with a redox-active guanidine ligand was achieved through the use of secondary coordination sphere motifs. The crown ether functions attached to the ligand allowed for control of the degree of intramolecular electron transfer between the guanidine ligand and the copper atom through metal encapsulation.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Multidisciplinary
Yida Zhang, Qingyu Wang, Shaokang Yang, Hengwei Wang, Dewei Rao, Tao Chen, Gongming Wang, Junling Lu, Junfa Zhu, Shiqiang Wei, Xusheng Zheng, Jie Zeng
Summary: This study demonstrates that the strong interaction between Ru single atoms and the second coordination sphere can enrich photogenerated electrons at Ru active sites and enhance N-2 photofixation activity. Mechanistic studies reveal that Ru-Co coordination serves as an additional photoelectron transfer channel, facilitating the photoreduction of N-2 into NH3.
ADVANCED FUNCTIONAL MATERIALS
(2022)
Review
Chemistry, Inorganic & Nuclear
Tesfay Gebretsadik, Qianqian Yang, Jinjiang Wu, Jinkui Tang
Summary: Hydrazone based ligand systems are gaining attention in coordination chemistry due to their straightforward synthesis, tunability, and stability. These ligand systems exhibit multi-functional spin state switching and have been successfully employed in constructing Fe(II/III), Co(II), and Mn(III) complexes exhibiting spin crossover events. This review highlights the advantages and applications of hydrazone based ligand systems in the field of coordination chemistry.
COORDINATION CHEMISTRY REVIEWS
(2021)
Article
Chemistry, Inorganic & Nuclear
Christophe Gourlaouen, Fethi Elaieb, Eric Brenner, Dominique Matt, Jack Harrowfield, Louis Ricard
Summary: This study investigated the conformational preference of a cavity-based biaryl phosphine, 5-(2-diphenylphosphinyl-phenyl)-25,26,27,28-tetrapropyloxycalix[4]arene (L), through density functional theory calculations. The analysis revealed that the rotation barrier of the biaryl unit around the C-C axis is only 10.7 kcal mol(-1), allowing the existence of two types of conformers: one with the P lone pair inside the cavity pointing to the calixarene interior, and the other with a more open structure where the P atom is located outside the cavity. Single crystal X-ray diffraction study showed that the biaryl phosphine is essentially an atropisomer in the solid state, with the phosphorus atom completely out of the cavity defined by the four phenoxy rings.
DALTON TRANSACTIONS
(2023)
Article
Chemistry, Multidisciplinary
Ming Liu, Na Li, Xuemin Wang, Jia Zhao, Di-Chang Zhong, Wei Li, Xian-He Bu
Summary: To improve the catalytic efficiency of the electrocatalytic oxygen evolution reaction (OER), proton transfer acceleration and kinetic mechanism elucidation are necessary. In this study, a series of OER electrocatalysts with FeO6/NiO6 units and carboxylate anions (TA(2-)) were developed, inspired by photosystem II. The optimized catalyst showed superior activity with low overpotential and excellent cycling stability, attributed to the synergistic effect of the metal units and TA(2-). A proton-transfer-promotion mechanism was proposed, which involved preferential proton acceptance by TA(2-) to optimize the O-H adsorption/activation process and reduce the kinetic barrier for O-O bond formation.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Inorganic & Nuclear
Christopher D. Hastings, Lucy S. X. Huffman, Chandan Kumar Tiwari, Jolaine Galindo Betancourth, William W. Brennessel, Brandon R. Barnett
Summary: In this study, a synthetic method for a tripodal ligand scaffold is reported, which forms a narrow and rigid cavity through a macrocyclization reaction. The resulting coordination complexes exhibit a narrow cavity and an open metal coordination site. It is shown that acetonitrile entry into the cavity is sterically precluded, disrupting anticipated coordination at the intracavity site. A new tripodal ligand system is used to access unsaturated metallates of cobalt(II), nickel(II), and zinc(II).
INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Daniel M. Beagan, John J. Kiernicki, Matthias Zeller, Nathaniel K. Szymczak
Summary: We propose a ligand platform with appended ditopic Lewis acids for the capture/activation of diatomic substrates. Incorporation of two 9-borabicyclo[3.3.1]nonane (9-BBN) units on a carbon tethered to a pyridine pyrazole scaffold allows for coordination of Fe-II, Zn-II, and Ni-II. The additive effect of ditopic boranes compared to monotopic analogues is demonstrated through hydride ion affinity and competition experiments. The platform achieves high selectivity for binding NO2- in the presence of competitive anions and enables unique activation pathways for hydrazine capture.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Mechanics
Susumu Goto, Yasufumi Horimoto, Takuro Kaneko, Kohei Oya, Yuji Sugitani, Shota Aritsu, Masato Yoshida, Haruka Ohyama, Kento Eguchi, Shota Kukimoto, Kazuo Matsuyama, Toru Nishimura, Kimikazu Fukuda, Keiichi Onoda
Summary: Through laboratory experiments, a high-shear-rate mixer (precession mixer) without any mixing blades can be constructed by using the precession of a cylindrical container for oil-in-water emulsification. The efficiency of emulsification is highest when the Poincare number Po, the ratio of spin and precession rotation speeds, is set to about 0.2-0.3. A systematic parameter survey has revealed an experimental law describing the maximum shear rate in the mixer, which provides useful information for practical use of the mixer by appropriately choosing the driving conditions according to the properties of the materials to be mixed.
Article
Chemistry, Multidisciplinary
Marta Meneghello, Alexandre Uzel, Marianne Broc, Rita R. Manuel, Axel Magalon, Christophe Leger, Ines A. C. Pereira, Anne Walburger, Vincent Fourmond
Summary: Metal-based formate dehydrogenases are enzymes that require molybdenum or tungsten ions to catalyze the conversion between formate and CO2. The coordination of the metal ion in the active form prevents direct binding of formate to the metal. The study's findings provide strong evidence for the hypothesis that the oxidation of formate occurs in the second coordination sphere of the metal.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Physical
Nilakshi Devi, Caroline K. Williams, Ashwin Chaturvedi, Jianbing ''Jimmy'' Jiang
Summary: The study introduces an iron porphyrin catalyst, FePEG8T, which shows excellent activity, stability, and selectivity in electrocatalytic reduction of CO2 to CO. Control experiments confirm the contribution of triazole units on high catalytic activity. Long-term electrolysis demonstrates high catalyst stability.
ACS APPLIED ENERGY MATERIALS
(2021)
Article
Engineering, Environmental
Weifeng Xu, Baihui Wang, Xiaojun Zeng, Kewen Tang
Summary: In this study, four types of amorphous coordination polymers (aCPs) were synthesized using a solvothermal method. These aCPs showed significant selectivity and reusability for the adsorption of Au(III). Among them, Cr-TDBP exhibited the fastest adsorption rate and the highest adsorption capacity.
CHEMICAL ENGINEERING JOURNAL
(2023)
Review
Chemistry, Multidisciplinary
Sahil Gandhi, Pravin Shende
Summary: The use of cyclodextrin-complexed metallic nanoparticles as a novel platform for cancer therapy can effectively overcome limitations of conventional chemotherapy. This approach improves the delivery efficiency of anticancer drugs, reduces toxic side effects, and holds great potential for clinical application.
JOURNAL OF CONTROLLED RELEASE
(2021)
Article
Chemistry, Multidisciplinary
Magdalena Barwiolek, Dominika Jankowska, Mateusz Chorobinski, Anna Kaczmarek-Kedziera, Iwona Lakomska, Slawomir Wojtulewski, Tadeusz M. Muziol
Summary: Two Zn(ii) complexes were successfully synthesized through template reactions and characterized by various methods. The complexes exhibited significant differences in structure and fluorescence properties, with different quantum yields in different solvents. Additionally, DFT calculations were performed to explain the structural and electronic spectral properties of the complexes.
Article
Biochemistry & Molecular Biology
Takahide Yamaguchi, Attila Taborosi, Chihiro Sakai, Kohei Akao, Seiji Mori, Takamitsu Kohzuma
Summary: The rational structural and computational studies of pseudoazurin (PAz) and its Met16X variants provide insights into the functional significance of noncovalent interactions (NCIs) in the second coordination sphere. High-resolution X-ray crystal structures reveal that the substitution of Met16 significantly affects the active site geometry, which is in close proximity to the His81 imidazole ring at the copper active site. Computational chemistry calculations confirm the presence of S-π/CH-π (wild-type), π-π (Met16Phe), double CH-π (Met16Leu), and single CH-π (Met16Val and Met16Ile) NCIs. The estimated interaction energies demonstrate the fine-tuning of protein stability and Cu site properties in the second coordination sphere of PAz.
JOURNAL OF INORGANIC BIOCHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Dennis Larsen, Michel Ferreira, Sebastien Tilloy, Eric Monflier, Sophie R. Beeren
Summary: This study utilizes a native cyclodextrin glucanotransferase (CGTase) to drive the dynamic system of cyclodextrins (CDs), incorporating unnatural glucopyranose-derived building blocks. By controlling the relative concentrations of modified glucopyranoses, modified CDs can be accessed.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Inorganic & Nuclear
Guillaume Hoyez, Cyril Rousseau, Jolanta Rousseau, Sebastien Saitzek, Anne Ponchel, Eric Monflier
Summary: A series of isoreticular zirconium-organic frameworks based on UiO-66 family were synthesized through a co-modulated hydrothermal method, with alpha-cyclodextrin being used to modulate the textural properties of the analogues. The systematic study showed that the addition of alpha-CD to the reaction mixture can significantly impact the properties of UiO-66 Zr-MOFs.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Mona Alleshagh, Samahe Sadjadi, Hassan Arabi, Naeimeh Bahri-Laleh, Eric Monflier
Summary: In this study, a novel chitosan-based catalyst was designed for the hydrofinishing of polyalphaolefins. The optimized reaction conditions resulted in a high yield of hydrogenated oil. The catalyst demonstrated heterogeneous nature and could be recovered and reused.
JOURNAL OF PHYSICS AND CHEMISTRY OF SOLIDS
(2022)
Review
Energy & Fuels
Claudia Prestigiacomo, Martina Biondo, Alessandro Galia, Eric Monflier, Anne Ponchel, Dominique Prevost, Onofrio Scialdone, Sebastien Tilloy, Rudina Bleta
Summary: This study successfully fabricates SnO@gamma-Al2O3 composites with tuneable pore size and well-defined octahedral-shape crystal structure using a molecular-colloidal coassembly approach combined with an ultrasonic-assisted precipitation method. The cooperative action of the supramolecular template and gamma-Al2O3 nanoparticles plays a critical role in the growth and orientation of SnO microcrystals and ultimately determines their catalytic performance in ester exchange reactions.
Article
Chemistry, Multidisciplinary
Antonio Madureira, Sebastien Noel, Bastien Leger, Anne Ponchel, Eric Monflier
Summary: The hydrogenation of vegetable oil-derived compounds using ion-exchange resin-supported ruthenium nanoparticles has been achieved for the first time. These catalysts show high efficiency, low metal loading, and excellent recyclability, and exhibit remarkable catalytic activity.
ACS SUSTAINABLE CHEMISTRY & ENGINEERING
(2022)
Article
Chemistry, Physical
Walid Hamza Saadaoui, Cecile Machut, Sebastien Rio, Sandra Bigot, Vincent Wiatz, Eric Monflier, Anne Ponchel
Summary: The direct conversion of glucose to 5-hydroxymethylfurfural was investigated using phosphated niobium oxide-carbon catalysts in a biphasic system. A facile approach for generating Nb-based composites with high metal loadings (around 20%) was developed through hydrothermal carbonization, calcination, and H3PO4 adsorption. Catalysts were characterized through various techniques, and NbP@C-RB30 and NbP@C-RB15 prepared using oligosaccharides and low water volumes exhibited higher efficiency for HMF production.
MOLECULAR CATALYSIS
(2023)
Article
Chemistry, Applied
Abdelghani El Mouat, Taha El Assimi, Mustapha Raihane, Jeremy Ternel, Herve Beicout, Eric Monflier, Sebastien Tilloy, Mohammed Lahcini
Summary: In this study, hyperbranched poly(epsilon-caprolactones) were synthesized and used as coating materials for slow-release DAP fertilizer. The prepared polymers (SFO-O-g-PCL) were confirmed by NMR and FTIR analysis. The coated DAP fertilizer granules showed a significant decrease in the release of P2O5 compared to the uncoated DAP fertilizer. This research opens up possibilities for the production of biodegradable coating agents using hydrophobic polyesters and bio-based oils.
PROGRESS IN ORGANIC COATINGS
(2023)
Article
Chemistry, Inorganic & Nuclear
Jiao Wang, Mengfan Wang, Bastien Leger, Anne Ponchel, Lei Bai
Summary: The NiCo2O4-ZnO-Co3O4-/N-C micro-cage was successfully synthesized by calcination of the precursor obtained from a hollow ZIF-8/ZIF-67 with nickel nitrate. The composition and structure of the composites were investigated to illustrate the preparation process involving ion exchange and leaching. The presence of NiCo2O4-Co3O4-ZnO/N-C showed more efficient degradation of BPA in the presence of persulfate, indicating a sevenfold increase in the apparent reaction rate. Further electrochemical analysis confirmed that the electron transfer was more easily achieved in the BPA-PDS-NiCo2O4-Co3O4-ZnO/N-C system. The enhanced activity of NiCo2O4-Co3O4-ZnO/N-C was attributed to its hollow structure, synergistic effect of NiCo2O4, and smaller size of the active species, which facilitated molecule and ion transport as well as PDS activation.
INORGANIC CHEMISTRY
(2023)
Article
Engineering, Environmental
Dario Lacalamita, Guillaume Hoyez, Chiara Mongiovi, Anne Ponchel, Nadia Morin-Crini, Cyril Rousseau, Christophe Loup, Jolanta Rousseau, Marina Raschetti, Eric Monflier, Vincent Placet, Gregorio Crini
Summary: In recent years, there have been numerous studies on the use of metal organic frameworks (MOFs) to remove contaminants from aqueous solutions. However, little is known about using MOFs as adsorbents for the removal of fluoride ions from real effluents. In this study, a highly porous MOF, UiO-66-NH2, was used for the final treatment of complex discharge waters containing fluoride ions. The batch experiments showed that the MOF exhibited high adsorption capacities for fluoride ions, effectively reducing their concentrations in the effluent.
JOURNAL OF WATER PROCESS ENGINEERING
(2023)
Article
Chemistry, Multidisciplinary
Thomas Roth, Rebecca Evertz, Niklas Kopplin, Sebastien Tilloy, Eric Monflier, Dieter Vogt, Thomas Seidensticker
Summary: Aqueous hydroaminomethylation (HAM) is a Green process for the efficient production of amines from basic chemicals. In this study, a continuous process for HAM in an aqueous multiphase system was successfully established. By adding randomly methylated-beta-cyclodextrin as a mass transfer agent, high yields and selectivities were achieved in several continuous experiments. The addition of cyclodextrin made it unnecessary to use solvents.
Article
Chemistry, Multidisciplinary
Chryslain Becquet, Michel Ferreira, Herve Bricout, Baptiste Quienne, Sylvain Caillol, Eric Monflier, Sebastien Tilloy
Summary: Jojoba oil ester was functionalized with alcohol groups via hydrohydroxymethylation catalyzed by a Rh/amine system. Under optimized conditions, a full conversion and a 99% yield of alcohol products were achieved. The catalytic system could be recycled at least 10 times without significant loss of activity. The hydrohydroxymethylated products were successfully used as monomers for the synthesis of a new biobased polyurethane with good thermal and mechanical properties.
Article
Polymer Science
Cedric Decarpigny, Anne Ponchel, Eric Monflier, Rudina Bleta
Summary: Surface modification is crucial for the production of highly efficient and stable enzymatic nanoreactors. This study investigates the impact of various functional groups on the catalytic performance of lipase B from Candida antarctica (CALB) in a supramolecular hydrogel. Results show that different functional groups have different effects on the catalytic activity and stability of CALB. Additionally, the use of cationic cross-linked beta-CD as an enzyme-stabilizing agent enhances the operational stability of the biocatalyst. These findings suggest that the supramolecular silicified hydrogel monoliths with hierarchical porosity have potential applications in biocatalytic continuous flow processes.
