Dr. Claudia Pigliacelli, Prof. Valentina Dichiarante, Prof. Francesca Baldelli Bombelli, Prof. Pierangelo Metrangolo, Prof. Giancarlo Terraneo and others have recently published an article on Nature Communications about "High-resolution crystal structure of a 20 kDa superfluorinated gold nanocluster".

The full paper can be found at the following link: High-resolution crystal structure of a 20 kDa superfluorinated gold nanocluster.

Abstract. Crystallization of atomically precise nanoclusters is gaining increasing attention, due to the opportunity of elucidating both intracluster and intercluster packing modes, and exploiting the functionality of the resulting highly pure crystallized materials. Herein, we report the design and single-crystal X-ray structure of a superfluorinated 20 kDa gold nanocluster, with an Au₂₅ core coated by a shell of multi-branched highly fluorinated thiols (SF₂₇) resulting in almost 500 fluorine atoms, i.e., ([Au₂₅(SF₂₇)₁₈]⁰). The cluster shows a switchable solubility in the fluorous phase. X-ray analysis and computational studies reveal the key role of both intracluster and intercluster F···F contacts in driving [Au₂₅(SF₂₇)₁₈]⁰ crystal packing and stabilization, highlighting the ability of multi-branched fluorinated thiols to endow atomically precise nanoclusters with remarkable crystallogenic behavior.

How to cite:
Claudia Pigliacelli, Angela Acocella, Isabel Díez, Luca Moretti, Valentina Dichiarante, Nicola Demitri, Hua Jiang, Margherita Maiuri, Robin H. A. Ras, Francesca Baldelli Bombelli, Giulio Cerullo, Francesco Zerbetto, Pierangelo Metrangolo & Giancarlo Terraneo, High-resolution crystal structure of a 20 kDa superfluorinated gold nanocluster, Nat Commun, 2022, 13, 2607
DOI: https://doi.org/10.1038/s41467-022-29966-2

Dr. Marta Rosati, Dr. Andrea Pizzi, Prof. Francesca Baldelli Bombelli, Prof. Gabriella Cavallo, Prof. Pierangelo Metrangolo and others have recently published an article on Macromolecules about "Janus-Type Dendrimers Based on Highly Branched Fluorinated Chains with Tunable Self-Assembly and ¹⁹F Nuclear Magnetic Resonance Properties".

The full paper can be found at the following link: Janus-Type Dendrimers Based on Highly Branched Fluorinated Chains with Tunable Self-Assembly and ¹⁹F Nuclear Magnetic Resonance Properties.

Abstract. Tuning the self-assembly of dendritic amphiphiles represents a major challenge for the design of advanced nanomaterials for biomimetic applications. The morphology of the final aggregates, in fact, critically depends on the primary structure of the dendritic building blocks as well as the environmental conditions. Here we report a new family of fluorinated Janus-type dendrimers (FJDs), based on a short-chain and branched fluorinated synthon with 27 magnetically equivalent fluorine atoms, linked to bis-MPA polyester dendrons of different generations. Increasing size, flexibility, and number of peripheral hydroxyl groups, we observed a peculiar self-assembly behavior in bulk and in aqueous media as a consequence of the subtle balance between their fluorinated and hydrophilic portions. The lowest generation FJDs formed spherical nanoparticles in water, e.g., micelles, showing a single 19F NMR peak with good signal-to-noise ratio and over time stability, making them promising as 19F-MRI traceable probes. The highest generation FJD, instead, presented an interesting morphological transition from multilamellar dendrimersomes to tubules as a consequence of a subtle balance of intra- and intermolecular forces that compete at the interface. Interestingly, a reduction of the local mobility of CF3 groups passing from dendrimersomes to tubules switches off the 19F NMR signal. The transition mechanism has been rationalized by coarse-grain simulations as well as demonstrated by using cosolvents of different nature (e.g., fluorinated) that promote conformational changes, ultimately reflected in the self-assembly behavior. Short and branched fluorinated chains have here been demonstrated as new moieties for the design of FJDs with tunable self-assembly behavior for potential applications as biocompatible 19F MRI probes in the construction of theranostic platforms.

How to cite the article:
Marta Rosati, Angela Acocella, Andrea Pizzi, Giorgio Turtù, Giulia Neri, Nicola Demitri, Nonappa, Giuseppina Raffaini, Bertrand Donnio, Francesco Zerbetto, Francesca Baldelli Bombelli, Gabriella Cavallo, and Pierangelo Metrangolo, Janus-Type Dendrimers Based on Highly Branched Fluorinated Chains with Tunable Self-Assembly and ¹⁹F Nuclear Magnetic Resonance Properties, Macromolecules, 2022, 55, 7, 2486-2496
DOI: 10.1021/acs.macromol.2c00129

All the authors would like to express their gratitude to Prof. Ulf Diederichsen, whose premature departure left us with a deep sorrow.

Alessandro Marchetti, Dr. Andrea Pizzi, Dr. Claudia Pigliacelli, Prof. Pierangelo Metrangolo and others have recently published an article on Chemistry A European Journal about "Fibril Structure Demonstrates the Role of Iodine Labelling on a Pentapeptide Self-Assembly".
The full paper can be found at the following link: Fibril Structure Demonstrates the Role of Iodine Labelling on a Pentapeptide Self-Assembly.

Abstract. Iodination has long been employed as a successful labelling strategy to gain structural insights into proteins and other biomolecules via several techniques, including Small Angle X-ray Scattering, Inductively Coupled Plasma Mass Spectrometer (ICP-MS), and single-crystal crystallography. However, when dealing with smaller biomolecular systems, interactions driven by iodine may significantly alter their self-assembly behaviour. The engineering of amyloidogenic peptides for the development of ordered nanomaterials has greatly benefitted from this possibility. Still, to date, iodination has exclusively been applied to aromatic residues. In this work, an aliphatic bis-iodinated amino acid was synthesized and included into a custom pentapeptide, which showed enhanced fibrillogenic behaviour. Peptide single crystal X-ray structure and powder X-ray diffraction on its dried water solution demonstrated the key role of iodine atoms in promoting intermolecular interactions that drive the peptide self-assembly into amyloid fibrils. These findings enlarge the library of halogenated moieties available for directing and engineering the self-assembly of amyloidogenic peptides.

How to cite the article:
Alessandro Marchetti, Andrea Pizzi, Greta Bergamaschi, Nicola Demitri, Ulrike Stollberg, Ulf Diederichsen, Claudia Pigliacelli, Pierangelo Metrangolo, Fibril Structure Demonstrates the Role of Iodine Labelling on a Pentapeptide Self-Assembly, ChemEurJ, 2022, e202104089
DOI: https://doi.org/10.1002/chem.202104089

Prof. Pierangelo Metrangolo, Prof. Giancarlo Terraneo, Prof. Gabriella Cavallo and others have recently published an article on CrystEngComm about "Dissecting the packing forces in mixed perfluorocarbon/aromatic co-crystals".
The full paper can be found at the following link: Dissecting the packing forces in mixed perfluorocarbon/aromatic co-crystals.

Abstract. We carried out a systematic evaluation of the packing forces in co-crystals featuring monoiodo- and diiodo-perfluoroalkanes and 1,2,4-oxadiazoles through single crystal X-ray diffraction and theoretical analysis. The molecules assemble via a combination of halogen bonding and specific dispersive interactions involving the perfluorinated units. We quantitatively elucidated the nature and strength of such interactions through solid-state calculations and Hirshfeld surface analysis. One of the co-crystals, formed by two monoiodoperfluorodecane molecules, the longest perfluorinated chain ever solved at the atomic level, allowed us to fully highlight the role of fluorous interactions.

How to cite the article:
Marco Saccone, Andrea Pace, Ivana Pibiri, Gabriella Cavallo, Pierangelo Metrangolo, Tullio Pilati, Giuseppe Resnati and Giancarlo Terraneo, Dissecting the packing forces in mixed perfluorocarbon/aromatic co-crystals, CrystEngComm, 2021, 23, 7324
DOI: https://doi.org/10.1039/d1ce01001h