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23 items found (0 items not approved), displaying 1 to 10.[First/Prev] 1, 2, 3 [Next/Last]

Instruments / Technical Area	Publication Details	Published
I19-Small Molecule Single Crystal Diffraction	BioMOF@PAN mixed matrix membranes as fast and efficient adsorbing materials for multiple heavy metals’ removal Paula Escamilla , Marcello Monteleone , Rita Maria Percoco , Teresa F. Mastropietro , Mariagiulia Longo , Elisa Esposito , Alessio Fuoco , Johannes C. Jansen , Rosangela Elliani , Antonio Tagarelli , Jesus Ferrando-Soria , Valeria Amendola , Emilio Pardo , Donatella Armentano Acs Applied Materials & Interfaces DOI: 10.1021/acsami.4c12363 Diamond Proposal Number(s): [28808] Show Abstract ▼ Abstract: Heavy metal ions are a common source of water pollution. In this study, two novel membranes with biobased metal–organic frameworks (BioMOFs) embedded in a polyacrylonitrile matrix with tailored porosity were prepared via nonsolvent induced phase separation methods and designed to efficiently adsorb heavy metal ions from oligomineral water. Under optimized preparation conditions, stable membranes with high MOF loading up to 50 wt % and a cocontinuous sponge-like morphology and a high water permeability of 50–60 L m–2 h–1 bar–1 were obtained. The tortuous flow path in combination with a low water flow rate guarantees maximum contact time between the fluid and the MOFs, and thus a high heavy metal capture efficiency in a single pass. The performances of these BioMOF@PAN membranes were investigated in the dynamic regime for the simultaneous removal of Pb2+, Cd2+, and Hg2+ heavy metals from aqueous environments in the presence of common interfering ions. The new composite adsorbing membranes are capable of reducing the concentration of heavy metal pollutants in a single pass and at much higher efficiency than previously reported membranes. The enhanced performance of the mixed matrix membranes is attributed to the presence of multiple recognition sites which densely decorate the BioMOF channels: (i) the thioether groups, deriving from the S-methyl-l-cysteine and (S)-methionine amino acid residues, able to recognize and capture Pb2+ and Hg2+ ions and (ii) the oxygen atoms of the oxamate moieties, which preferentially interact with Cd2+ ions, as revealed by single crystal X-ray diffraction. The flexibility of the pore environments allows these sites to work synergically for the simultaneous capture of different metal ions. The stability of the membranes for a potential regeneration process, a key-factor for the effective feasibility of the process in real life applications, was also evaluated and confirmed less than 1% capacity loss in each cycle.	Sep 2024
I19-Small Molecule Single Crystal Diffraction	Design of multivariate biological metal–organic frameworks: toward mimicking active sites of enzymes Javier Navarro-Alapont , Cristina Negro , Sergio Navalón , Amarajothi Dhakshinamoorthy , Donatella Armentano , Jesus Ferrando-Soria , Emilio Pardo Inorganic Chemistry DOI: 10.1021/acs.inorgchem.4c01988 Diamond Proposal Number(s): [28808] Open Access Show Abstract ▼ Abstract: Mimicking enzymatic processes carried out by natural enzymes, which are highly efficient biocatalysts with key roles in living organisms, attracts much interest but constitutes a synthetic challenge. Biological metal–organic frameworks (bioMOFs) are potential candidates to be enzyme catalysis mimics, as they offer the possibility to combine biometals and biomolecules into open-framework porous structures capable of simulating the catalytic pockets of enzymes. In this work, we first study the catalase activity of a previously reported bioMOF, derived from the amino acid L-serine, with formula {CaIICuII6[(S,S)-serimox]3(OH)2(H2O)} · 39H2O (1) (serimox = bis[(S)-serine]oxalyl diamide), which is indeed capable to mimic catalase enzymes, in charge of preventing cell oxidative damage by decomposing, efficiently, hydrogen peroxide to water and oxygen (2H2O2 → 2 H2O + O2). With these results in hand, we then prepared a new multivariate bioMOF (MTV-bioMOF) that combines two different types of bioligands derived from L-serine and L-histidine amino acids with formula CaIICuII6[(S,S)-serimox]2[(S,S)-hismox]1(OH)2(H2O)}·27H2O (2) (hismox = bis[(S)-histidine]oxalyl diamide ligand). MTV-bioMOF 2 outperforms 1 degrading hydrogen peroxide, confirming the importance of the amino acid residue from the histidine amino acid acting as a nucleophile in the catalase degradation mechanism. Despite displaying a more modest catalytic behavior than other reported MOF composites, in which the catalase enzyme is immobilized inside the MOF, this work represents the first example of a MOF in which an attempt is made to replicate the active center of the catalase enzyme with its constituent elements and is capable of moderate catalytic activity.	Jul 2024
I19-Small Molecule Single Crystal Diffraction	Translocation and confinement of tetraamines in adaptable microporous cavities Ana Rubio-Gaspar , Alechania Misturini , Reisel Millán , Neyvis Almora-Barrios , Sergio Tatay , Volodymyr Bon , Mickaele Bonneau , Vincent Guillerm , Mohamed Eddaoudi , Sergio Navalón , Stefan Kaskel , Donatella Armentano , Carlos Marti-Gastaldo Angewandte Chemie International Edition DOI: 10.1002/anie.202402973 Diamond Proposal Number(s): [28808] Open Access Show Abstract ▼ Abstract: Metal-Organic Frameworks can be grafted with amines by coordination to metal vacancies to create amine-appended solid adsorbents, which are being considered as an alternative to using aqueous amine solutions for CO2 capture. In this study, we propose an alternative mechanism that does not rely on the use of neutral metal vacancies as binding sites but is enabled by the structural adaptability of heterobimetallic Ti2Ca2 clusters. The combination of hard (Ti+4) and soft (Ca2+) metal centers in the inorganic nodes of the framework enables MUV-10 to adapt its pore windows to the presence of triethylenetetramine molecules. This dynamic cluster response facilitates the translocation and binding of tetraamine inside the microporous cavities to enable the formation of bis-coordinate adducts that are stable in water. The extension of this grafting concept from MUV-10 to larger cavities not restrictive to CO2 diffusion will complement other strategies available for the design of molecular sorbents for decarbonization applications.	Apr 2024
I19-Small Molecule Single Crystal Diffraction	A MOF-supported Pd1-Au1 dimer catalyses the semihydrogenation reaction of acetylene in ethylene with a nearly barrierless activation energy Jordi Ballesteros-Soberanas , Nuria Martín , Matea Bacic , Estefanía Tiburcio , Marta Mon , Juan Carlos Hernández-Garrido , Carlo Marini , Mercedes Boronat , Jesus Ferrando-Soria , Donatella Armentano , Emilio Pardo , Antonio Leyva-Pérez Nature Catalysis 7 DOI: 10.1038/s41929-024-01130-7 Diamond Proposal Number(s): [28808] Open Access Show Abstract ▼ Abstract: The removal of acetylene from ethylene streams is key in industry for manufacturing polyethylene. Here we show that a well-defined Pd1–Au1 dimer, anchored to the walls of a metal–organic framework (MOF), catalyses the selective semihydrogenation of acetylene to ethylene with ≥99.99% conversion (≤1 ppm of acetylene) and >90% selectivity in extremely rich ethylene streams (1% acetylene, 89% ethylene, 10% H2, simulated industrial front-end reaction conditions). The reaction proceeds with an apparent activation energy of ∼1 kcal mol–1, working even at 35 °C, and with operational windows (>100 °C) and weight hourly space velocities () within industrial specifications. A combined experimental and computational mechanistic study shows the cooperativity between both atoms, and between atoms and support, to enable the barrierless semihydrogenation of acetylene.	Mar 2024
I19-Small Molecule Single Crystal Diffraction	Controlled supramolecular self-assembly in MOF confined spaces Rosario Bruno , Jesús Ferrando‐soria , Emilio Pardo , Donatella Armentano Controlled Supramolecular Self-Assembly In Mof Confined Spaces Chapter 3 DOI: 10.1002/9783527834044.ch3 Diamond Proposal Number(s): [16033, 18768, 22411, 28808] Show Abstract ▼ Abstract: The chapter is focused on our recent advances in the construction of well-defined metal organic framework (MOF)-driven self-assembly of supramolecular species. The experimental developments, which reside at the connection between supramolecular and reticular chemistry, are summarized. In particular, the discussion is focused on the use of MOFs – an emerging type of porous functional material capable of acting as vessels or as chemical nanoreactors to template the self-assembly of supramolecular coordination compounds (SCCs) or the growth of small aggregations of metal atoms, close to or within the subnanometric regime, so-called metal nanoclusters (MNCs) that are atomically precise nanoclusters, for application in heterogeneous catalysis. All that with a particular focus on how the MOFs' surface engineering, composition manipulation, and support effects can guarantee their stability while tuning their nuclearity/size and catalytic performance. We will show that their crystallographic characterization is still of critical importance in order to shed light on supramolecular host–guest interactions.	Aug 2023
I19-Small Molecule Single Crystal Diffraction	Exploring a metalloligand for construction of an oxamato-based metal-organic framework Javier Navarro-Alapont , Donatella Armentano , Emilio Pardo , Jesus Ferrando-Soria Journal Of Coordination Chemistry 341, 1 - 11 DOI: 10.1080/00958972.2022.2125303 Diamond Proposal Number(s): [22411] Show Abstract ▼ Abstract: We report the two-step synthesis of a heterobimetallic oxamato-based metal-organic framework (MOF). First, we prepared an oxamato functionalized carbazole-based dinuclear copper(II) complex, K4{Cu2(carbox)2]}·8H2O, where the carbozale linkers exhibited an uncommon substitution pattern, carbox = N,N’-1,6-carbazolebis(oxamate). Then, this building block was used as a metalloligand toward manganese(II) metal ions to assemble a neutral three-dimensional (3 D) MOF with formula [Mn2Cu2(carbox)2(H2O)4]·6CH3OH·2H2O (1) and single-crystal X-ray diffraction determined the structure. The resulting network constitutes one of the few examples of oxamato-based 3 D MOF.	Sep 2022
I19-Small Molecule Single Crystal Diffraction	A benzimidazolium-based organic cage with antimicrobial activity Sonia La Cognata , Donatella Armentano , Nicoletta Marchesi , Pietro Grisoli , Alessia Pascale , Marion Kieffer , Angelo Taglietti , Anthony P. Davis , Valeria Amendola Chemistry 4, 855 - 864 DOI: 10.3390/chemistry4030061 Diamond Proposal Number(s): [28808] Open Access Show Abstract ▼ Abstract: Considering the wide interest in (benz)imidazolium-based drugs, we here report our study on a benzimidazolium-based organic cage as potential antimicrobial and antifungal agent. Cytotoxicity studies on a human derived cell line, SH-SY5Y, showed that the cage is not cytotoxic at all at the investigated concentrations. Anion binding studies demonstrated that the cage can bind anions (chloride and nitrate, in particular) both in organic solvent and 20%v D2O/CD3CN mixture. The cage was also tested as anionophore, showing a weak but measurable transport of chloride and nitrate across LUVs vesicles. Nonetheless, the compounds have antimicrobial activity towards Staphylococcus aureus (Gram-positive bacteria). This is probably the first organic cage studied as anionophore and antimicrobial agent.	Aug 2022
I19-Small Molecule Single Crystal Diffraction	Highly efficient MOF-driven silver subnanometer clusters for the catalytic buchner ring expansion reaction Estefanía Tiburcio , Yongkun Zheng , Marta Mon , Nuria Martín , Jesus Ferrando-Soria , Donatella Armentano , Antonio Leyva-Pérez , Emilio Pardo Inorganic Chemistry 57 DOI: 10.1021/acs.inorgchem.2c01508 Diamond Proposal Number(s): [22411] Open Access Show Abstract ▼ Abstract: The preparation of novel efficient catalysts─that could be applicable in industrially important chemical processes─has attracted great interest. Small subnanometer metal clusters can exhibit outstanding catalytic capabilities, and thus, research efforts have been devoted, recently, to synthesize novel catalysts bearing such active sites. Here, we report the gram-scale preparation of Ag20 subnanometer clusters within the channels of a highly crystalline three-dimensional anionic metal–organic framework, with the formula [Ag20]@AgI2NaI2{NiII4[CuII2(Me3mpba)2]3}·48H2O [Me3mpba4– = N,N′-2,4,6-trimethyl-1,3-phenylenebis(oxamate)]. The resulting crystalline solid catalyst─fully characterized with the help of single-crystal X-ray diffraction─exhibits high catalytic activity for the catalytic Buchner ring expansion reaction.	Jul 2022
I19-Small Molecule Single Crystal Diffraction	Click amidations, esterifications and one–pot reactions catalyzed by Cu salts and multimetal–organic frameworks (M–MOFs) Rossella Greco , Estefanía Tiburcio , Brenda Palomar-De Lucas , Jesus Ferrando-Soria , Donatella Armentano , Emilio Pardo , Antonio Leyva-Pérez Molecular Catalysis 522 DOI: 10.1016/j.mcat.2022.112228 Diamond Proposal Number(s): [22411] Open Access Show Abstract ▼ Abstract: Amides and esters are prevalent chemicals in Nature, industry and academic laboratories. Thus, it is not surprising that a plethora of synthetic methods for these compounds has been developed along the years. However, these methods are not 100% atom economical and generally require harsh reagents or reaction conditions. Here we show a “spring–loaded”, 100% atom–efficient amidation and esterification protocol which consists in the ring opening of cyclopropenones with amines or alcohols. Some alkyl amines react spontaneously at room temperature in a variety of solvents and reaction conditions, including water at different pHs, while other alkyl amines, aromatic amines and alcohols react in the presence of catalytic amounts of simple Cu2+ salts or solids. A modular reactivity pattern (alkyl amines >> alkyl alcohols >> phenols >> aromatic amines) enables to design orthogonal and one–pot reactions on well–defined catalytic Multimetal–Organic Frameworks (M–MOFs, M= Cu, Ni, Pd), to easily functionalize the resulting cinnamides and cinnamic esters to more complex molecules. The strong resemblance of the amidation and esterification reaction conditions here reported with the copper–catalyzed azide–alkyne cycloaddition (CuAAC) allows to define this fast, clean and flexible protocol as a click reaction.	Apr 2022
I19-Small Molecule Single Crystal Diffraction	MOF–stabilized perfluorinated palladium cages catalyze the additive–free aerobic oxidation of aliphatic alcohols to acids Rossella Greco , Estefanía Tiburcio-Fortes , Antonio Fernandez , Carlo Marini , Alejandro Vidal-Moya , Judit Oliver-Meseguer , Donatella Armentano , Emilio Pardo , Jesus Ferrando-Soria , Antonio Leyva-Perez Chemistry – A European Journal DOI: 10.1002/chem.202103781 Diamond Proposal Number(s): [22411] Show Abstract ▼ Abstract: Extremely high electrophilic metal complexes, composed by a metal cation and very electron poor σ–donor ancillary ligands, are expected to be privileged catalysts for oxidation reactions in organic chemistry. However, their low lifetime prevents any use in catalysis. Here we show the synthesis of fluorinated pyridine–Pd 2+ coordinate cages within the channels of an anionic tridimensional metal organic framework (MOF), and their use as efficient metal catalysts for the aerobic oxidation of aliphatic alcohols to carboxylic acids without any additive. Mechanistic studies strongly support that the MOF–stabilized coordination cage with perfluorinated ligands unleashes the full electrophilic potential of Pd 2+ to dehydrogenate primary alcohols, without any base, and also to activate O 2 for the radical oxidation to the aldehyde intermediate. This study opens the door to design catalytic perfluorinated complexes for challenging organic transformations, where an extremely high electrophilic metal site is required.	Dec 2021

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