Article
Chemistry, Multidisciplinary
Suresh Moorthy, Alvaro Castillo Bonillo, Hugues Lambert, Elina Kalenius, Tung-Chun Lee
Summary: A new supramolecular approach has been reported to selectively deactivate the electrophilic alpha-carbon of phenyl diazonium ion through host-guest complexation, thus avoiding undesirable side reactions. This method holds great potential for the reactive chemistry of organic molecules in aqueous media.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Xue Yang, Chunyang Li, Michel Giorgi, Didier Siri, Xavier Bugaut, Bastien Chatelet, Didier Gigmes, Mehdi Yemloul, Virginie Hornebecq, Anthony Kermagoret, Sophie Brasselet, Alexandre Martinez, David Bardelang
Summary: Porous organic crystals based on macrocycles have recently shown exceptional sorption and separation properties. In this study, the inclusion of trimethoxybenzyl-azaphosphatrane in the macrocycle cucurbit[8]uril (CB[8]) resulted in the formation of molecular porous host.guest crystals (PHGC-1) with radically new properties. The PHGC-1 crystals demonstrated spontaneous and selective adsorption of iodine at room temperature and atmospheric pressure, offering potential advantages in energy cost reduction.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Multidisciplinary Sciences
Lin Xiao, Liang-Liang Wang, Chao-Qun Wu, Han Li, Qiu-Long Zhang, Yang Wang, Liang Xu
Summary: The study demonstrates the successful construction of a controllable DNA hybridization ligand invasion pathway using cucurbit[7]uril-based host-guest interactions. By introducing recognition handles, dynamic regulation of DNA hybridization is achieved, potentially applicable for switchable nanostructures and functional regulations of nucleic acids in both material developments and biological regulations.
NATURE COMMUNICATIONS
(2022)
Article
Chemistry, Organic
Xiaodong Zhang, Tao Sun, Xin-Long Ni
Summary: This study explores the host-guest interactions of cucurbit[8]uril with pi-conjugated bispyridinium guests in aqueous solution, resulting in a series of dynamic assemblies distinguishable by naked-eye observation and quantitative fluorescence emissions. The dissociation and control of host-stabilized charge-transfer interactions by N-substituted alkyl chains on cationic guests led to the discovery of new possible binding modes for the cucurbit[8]uril host.
ORGANIC CHEMISTRY FRONTIERS
(2021)
Article
Chemistry, Multidisciplinary
Sangmin Lee, Thi Vo, Sharon C. Glotzer
Summary: In this study, hard truncated triangular bipyramids self-assemble into seven different colloidal clathrate crystals, consisting of cages that are either empty or occupied by guest particles. Monte Carlo simulations reveal that the crystallization occurs through the compartmentalization of entropy between low- and high-entropy subsystems for the host and guest particles. The researchers also use entropic bonding theory to design host-guest colloidal clathrates with explicit interparticle attraction for experimental realization.
Article
Chemistry, Multidisciplinary
Yiming Zhao, Mengying Wei, Li-Li Tan, Zhixuan Luo, Jiahui Peng, Chunguang Wei, Feiyu Kang, Jian-Gan Wang
Summary: By manipulating the host-guest chemistry of CB[5] and zinc ions, the electric double layer (EDL) structure at the zinc interface can be reconstructed, inhibiting dendrite deposition and improving the Coulombic efficiency. The CB[5] also has a strong host-guest interaction with zinc ions, allowing rapid transport of zinc ions while hindering water radicals and sulfate ions. This work opens up a new avenue for the development of rechargeable zinc metal batteries.
Article
Chemistry, Multidisciplinary
Yulin Han, Anni Qin, Qian Zhang, Xue Zhang, Hui Qian, Shengming Ma
Summary: The Rh-catalyzed reaction allows for the efficient synthesis of cis-fused bicyclic products with excellent selectivity and tolerance towards synthetically useful functional groups. The proposed mechanism involves the rapid racemization of the allene moiety in the starting materials.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Physical
Liang Xiao Gan, Chun Ling Hao, Xiao Ming Jiang
Summary: The study focused on using cucurbituril (Q[7]) to modulate the adsorption and desorption of cationic surfactants on quartz surfaces.
COLLOIDS AND SURFACES A-PHYSICOCHEMICAL AND ENGINEERING ASPECTS
(2021)
Article
Biochemical Research Methods
Carlos Redondo-Gomez, Soraya Padilla-Lopategui, Alvaro Mata, Helena S. Azevedo
Summary: The host-guest-mediated PA hydrogelation method relies on the formation of a host-guest homoternary complex with CB[8] and aromatic amino-acid-bearing PA nanofibers, resulting in hierarchical morphologies and increased stiffness compared to ion-based equivalents. This alternative cross-linking method can upgrade the design of PA materials and extend their biomedical applications, while maintaining similar biocompatibilities between the new and conventional hydrogels.
BIOCONJUGATE CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Siyang Jiang, Weipeng Mao, Dake Mao, Zhan-Ting Li, Da Ma
Summary: In this study, supramolecular AND logic gates based on host-guest complexation between acid-labile acyclic cucurbit[n]uril (CB[n]) molecular container and NaClO-responsive dye were reported. The supramolecular AND logic gate is activated by the acid-triggered degradation of the molecular container and the release of the dye, followed by the NaClO-induced fluorescence switch on effect of the dye. It has been confirmed that the supramolecular AND logic gate is operational in live MCF-7 and HeLa cancer cells.
CHINESE CHEMICAL LETTERS
(2022)
Article
Engineering, Chemical
Ying Wang, Song Zhao, Zhiyuan Zha, Zhi Wang, Jixiao Wang
Summary: A novel host-guest NF membrane based on CB-PEI was designed and fabricated, showing attractive separation performance for monovalent/divalent salts separation, purification and desalination of small molecule solutions.
Article
Multidisciplinary Sciences
Valerio Rizzi, Luigi Bonati, Narjes Ansari, Michele Parrinello
Summary: Atomistic computer simulations are commonly used for calculating ligand binding free energies, and the accuracy depends on the quality of the force field and sampling thoroughness. In this study, machine learning was combined with physical intuition to develop a non-local and efficient water-describing collective variable, resulting in highly accurate binding free energies for host-guest systems. The role of water during the binding process was analyzed in detail, highlighting the importance of computational approaches in predicting water's role in host-ligand binding.
NATURE COMMUNICATIONS
(2021)
Article
Chemistry, Multidisciplinary
Martin Dracinsky, Carina Santos Hurtado, Eric Masson, Jiri Kaleta
Summary: Solvent-free mechanochemical synthesis was used to prepare inclusion complexes with cucurbit[7]uril and four model guest molecules. Confirmation of successful formation of individual inclusions was independently confirmed by solid-state NMR techniques and differential scanning calorimetry. Mechanochemical synthesis is an alternative route towards new types of cucurbit[n]uril-guest inclusion complexes.
CHEMICAL COMMUNICATIONS
(2021)
Article
Chemistry, Multidisciplinary
Chun Liu, Yu Xia, Zhu Tao, Xin-Long Ni
Summary: An approach for constructing crystalline porous supramolecular organic frameworks (SOFs) using outer-surface interactions of cucurbit[6]uril (Q[6]) is presented. This method allows for the noncovalent integration of guest molecules into ordered topologies and the modification of pore wall surface using Q[6]-encapsulated guest molecules. One of the prepared solid Q[6]-SOFs exhibits high drug-loading capacity and potential control over drug release, making it suitable for drug-delivery applications.
CHINESE CHEMICAL LETTERS
(2022)
Article
Nanoscience & Nanotechnology
Han Wu, Hua Wang, Feilong Qi, Tian Xia, Yu Xia, Jiang-Fei Xu, Xi Zhang
Summary: A new strategy of activatable host-guest conjugate with self-inclusion property is proposed for supramolecular chemotherapy, which can achieve high-efficiency drug release triggered by intramolecular host-guest self-inclusion. The encapsulation of oxaliplatin in the conjugate leads to the formation of a stable supramolecular drug, and the release of oxaliplatin in the tumor microenvironment shows comparable anti-tumor bioactivity to naked oxaliplatin. This research may open new horizons for programmable and on-demand supramolecular chemotherapy with high anti-tumor efficiency.
ACS APPLIED MATERIALS & INTERFACES
(2021)
Article
Chemistry, Applied
Giuseppe Sciortino, Feliu Maseras
Summary: Cooperative multimetallic catalysis involves activating and coupling two substrates or functionalities simultaneously, leading to increased reaction rates and selectivity. Metal moieties are responsible for activation, while selectivity derives from interactions between substrates and catalysts.
TOPICS IN CATALYSIS
(2022)
Article
Chemistry, Inorganic & Nuclear
Ya-Qiong Zhang, Ying-Ying Li, Feliu Maseras, Rong-Zhen Liao
Summary: The phosphine-substituted Ru(ii) polypyridyl complex RuP was shown to be an efficient photocatalyst for selective reduction of CO2 to CO. Density functional calculations revealed the reaction mechanism, showing that the Ru center had an oxidation state of +2 after two one-electron reductions and Ru-II(L2-) nucleophilically attacked CO2. Protonation to generate Ru-II-hydride for formate and H-2 production was thermodynamically favorable but kinetically less so due to the presence of a Ru2+ ion in the reduced catalyst.
DALTON TRANSACTIONS
(2022)
Article
Chemistry, Organic
Lucia Moran-Gonzalez, Maria Besora, Feliu Maseras
Summary: This study statistically analyzed over 600 density functional theory (DFT)-computed barriers for bimolecular nucleophilic substitution at methyl derivatives, identifying numerical descriptors that best represent the entering and leaving ability of 26 different nucleophiles. The results reveal a hidden descriptor methodology that can be extended to other chemical fragments and reactions, showing correlations with thermodynamic and geometric parameters but not with commonly expected orbital or solvation descriptors.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Physical
Manuel R. Rodriguez, Anabel M. Rodriguez, Sara Lopez-Resano, Miquel A. . Pericas, M. Mar Diaz-Requejo, Feliu Maseras, Pedro J. Perez
Summary: In the context of copper-catalyzed nitrene transfer to olefins, this study challenges the general assumption that the X ligand is displaced from the coordination sphere. Through experiments with well-defined copper(I) complexes, it is demonstrated that the catalytic and mechanistic behavior depends on the presence or absence of the chloride ligand bonded to the metal center, with different turnover-limiting steps.
Article
Chemistry, Multidisciplinary
Arup Mondal, Marina Diaz-Ruiz, Fritz Deufel, Feliu Maseras, Manuel van Gemmeren
Summary: The regioselective C-H activation of arenes is a promising technique for accessing functionalized molecules. We report a unique approach using weak charge-charge and charge-dipole interactions to enable the meta-selective activation and olefination of arenes, addressing challenges in Pd catalysis.
Article
Chemistry, Multidisciplinary
Eric Palomo, Akhilesh K. Sharma, Zhaofeng Wang, Liyin Jiang, Feliu Maseras, Marcos G. Suero
Summary: We report the first successful generation of Fischer-type acyloxy Rh(II)-carbenes from carboxylic acids and Rh(II)-carbynoids. This novel class of transient donor/acceptor Rh(II)-carbenes evolves through a cyclopropanation process and allows access to densely functionalized cyclopropyl-fused lactones with excellent diastereoselectivity. DFT calculations were performed to analyze the properties of both Rh(II)-carbynoids and acyloxy Rh(II)-carbenes, as well as to characterize the reaction mechanism.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Aleria Garcia-Roca, Raul Perez-Soto, Georgiana Stoica, Jordi Benet-Buchholz, Feliu Maseras, Arjan W. Kleij
Summary: Metal-catalyzed propargylic transformations are a powerful tool in organic synthesis for forming new carbon-carbon and carbon-heteroatom bonds. However, there is limited knowledge about the mechanistic intricacies of asymmetric propargylic reactions with challenging heteroatom substitution, presenting an inspiring challenge. This study presents a detailed mechanistic analysis of a propargylic sulfonylation reaction promoted by a chiral Cu catalyst through experimental techniques and computational studies. Surprisingly, the enantio-discriminating step was found to be the proto-demetalation step, rather than the coupling between the nucleophile and the propargylic precursor.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Physical
Maria Biosca, Pol de la Cruz-Sanchez, Jorge Faiges, Jessica Margalef, Ernest Salomo, Antoni Riera, Xavier Verdaguer, Joan Ferre, Feliu Maseras, Maria Besora, Oscar Pamies, Montserrat Dieguez
Summary: Ir-MaxPHOX-type catalysts exhibit high catalytic performance in the hydrogenation of a wide range of nonchelating olefins with different geometries, substitution patterns, and degrees of functionalization. These air-stable and readily available catalysts have been successfully used in the asymmetric hydrogenation of di-, tri-, and tetrasubstituted olefins (ee ' s up to 9996). The combination of theoretical calculations and deuterium labeling experiments has revealed the factors responsible for the observed enantioselectivity, allowing for the rationalization of suitable substrates for these Ircatalysts.
Article
Chemistry, Physical
Silvia Gaspa, Giuseppe Sciortino, Andrea Porcheddu, Chiara Dell'Osa, Giuseppe Satta, Ugo Azzena, Luisa Pisano, Massimo Carraro, Daniele Sanna, Eugenio Garribba, Feliu Maseras, Lidia De Luca
Summary: Oxidovanadium(IV) sulfate, (VOSO4)-O-IV, efficiently catalyzes the amidation of aldehydes by N-chloramine derivatives for selective amide synthesis under visible light irradiation. The reaction occurs at room temperature in ethyl acetate, a green solvent. The catalyst, an inexpensive and stable inorganic salt, outperforms other tested transition metal salts and complexes. Experimental and computational techniques reveal a mechanistic proposal involving an interaction between the amine and (VO2+)-O-IV ion, as well as the formation of V-IV/V-V and radical organic intermediates through a light-induced radical mechanism.
MOLECULAR CATALYSIS
(2023)
Article
Chemistry, Multidisciplinary
Giuseppe Zuccarello, Leonardo J. Nannini, Ana Arroyo-Bondia, Nicolas Fincias, Isabel Arranz, Alba H. Perez-Jimeno, Matthias Peeters, Inmaculada Martin-Torres, Anna Sadurni, Victor Garcia-Vazquez, Yufei Wang, Mariia S. Kirillova, Marc Montesinos-Magraner, Ulysse Caniparoli, Gonzalo D. Nunez, Feliu Maseras, Maria Besora, Imma Escofet, Antonio M. Echavarren
Summary: A new generation of chiragold(I) catalysts based on variations of complexes with JohnPhos-type ligands have been synthesized and tested in various reactions. The chiral binding pockets of the catalysts have been analyzed by DFT calculations and attractive non-covalent interactions between substrates and catalysts have been identified. Additionally, an open-source tool called NEST has been introduced for predicting experimental enantioselectivities in these systems.
Article
Chemistry, Multidisciplinary
Eduardo Garcia-Padilla, Feliu Maseras, Antonio M. Echavarren
Summary: This study identifies the factors influencing the selectivity in single-cleavage skeletal rearrangements promoted by gold(I) catalysts. It is found that stereoconvergence is achieved through a rotational equilibrium when electron-rich substituents are utilized. The anomalous Z-selective skeletal rearrangement is primarily governed by electronic factors, while endo-selectivity relies on both steric and electronic factors.
ACS ORGANIC & INORGANIC AU
(2023)
Article
Chemistry, Multidisciplinary
Giuseppe Sciortino, Feliu Maseras
Summary: The factors driving the Ni-0(binap)/Cu-I(phospherrox) cooperative asymmetric propargylation of aldimine esters are elucidated through DFT calculations. The system is thoroughly explored, taking into account conformational complexity and aggregation steps. Substrate activation occurs independently, while intercatalyst communication takes place through indirect cooperation (exchanging non-innocent MeOCO2-) and direct cooperation (driving stereoselective C-C coupling through intercatalyst interactions).
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Inorganic & Nuclear
Nsikak B. Essien, Antal Galvacsi, Csilla Kallay, Youssra Al-Hilaly, Ramon Gonzalez-Mendez, Geoffrey R. Akien, Graham J. Tizzard, Simon J. Coles, Maria Besora, George E. Kostakis
Summary: We synthesised and characterised two Zn salan fluorine-based complexes, both racemic and chiral, using commercially available materials. These complexes readily absorb H2O from the atmosphere. In solution (DMSO-H2O), both experimental and theoretical studies reveal that these complexes exist in a dimeric-monomeric equilibrium at the millimolar level. Additionally, we investigated their ability to sense amines via (19)F NMR, finding that the exchange with analytes requires an extreme excess due to the strong coordination of water or DMSO in CDCl3 or d(6)-DMSO.
DALTON TRANSACTIONS
(2023)
