Article
Chemistry, Multidisciplinary
Sergiy V. Rosokha
Summary: The studies on anion-π interactions have progressed in the past two decades, moving from the mere existence of this counter-intuitive bonding to its practical applications in anion recognition and transport, catalysis, and other fields. However, there are still substantial differences in the interpretation of the nature and driving forces behind anion-π bonding. Surprisingly, there are also conflicting opinions on the definition of this term and which associations qualify as anion-π complexes. A proposed definition suggests that anion-π bonding occurs when there is evidence of a net attraction between a (close-shell) anion and the face of an electrophilic π-system, encompassing a wide range of supramolecular complexes. This widely accepted definition would facilitate the discussion of the nature and distinct driving forces of this fascinating interaction.
Article
Chemistry, Multidisciplinary
Valentina Milasinovic, Vedran Vukovic, Anna Krawczuk, Kresimir Molcanov, Christoph Hennig, Michael Bodensteiner
Summary: The investigated co-crystal of 3-chloro-N-methylpyridinium iodide with tetrabromoquinone exhibits a pi-hole interaction involving charge transfer. The quinoid ring displays partial negative charge and radical character, contributing to the black color of the crystals. X-ray charge density study confirms the interaction between iodide anions and carbon atoms in the ring. The energy of the interaction is comparable to moderate hydrogen bonding.
Article
Biochemistry & Molecular Biology
Fengying Lei, Qingyu Liu, Yeshuang Zhong, Xinai Cui, Jie Yu, Zuquan Hu, Gang Feng, Zhu Zeng, Tao Lu
Summary: In recent years, there has been substantial research interest in the non-covalent interactions between chalcogen centers. This study systematically investigates the pi-hole-type interactions between chalcogen centers in model complexes, and reveals their significant impact on the stability of the complexes.
INTERNATIONAL JOURNAL OF MOLECULAR SCIENCES
(2023)
Article
Materials Science, Composites
Tao Xu, Lilu Zhou, Lijuan Long, Shuhao Qin, Yushu Xiang, Min He, Jie Yu
Summary: In this study, a flame retardant structure (D-AB) with hydrogen bonds and pi-pi stacking effect was successfully synthesized and blended with poly (lactic acid) (PLA) to prepare flame-retardant films. The addition of D-AB significantly improved the viscoelasticity and complex viscosity of PLA due to synergistic effects. Furthermore, the PLA/D-ABs films exhibited excellent flame retardancy and achieved UL-94 VTM-0 rating and a high LOI value of 30.5% with only a 5 wt % addition of D-AB. The flame retardant mechanism of D-AB in PLA was also studied in detail, revealing the release of PO· radicals and non-combustible gas in the gas phase, as well as the formation of a dense and intact carbon layer in the condensed phase.
COMPOSITES COMMUNICATIONS
(2023)
Review
Chemistry, Multidisciplinary
Subhrakant Jena, Juhi Dutta, Kiran Devi Tulsiyan, Akshay Kumar Sahu, Shubhranshu Shekhar Choudhury, Himansu S. Biswal
Summary: This article discusses the significant relevance of noncovalent interactions (NCIs) in biomolecular structure and function, such as hydrogen bonding, halogen bonding, and the more recently discovered n→π* interactions. These interactions are crucial for understanding the dynamics of biological systems, enzymatic activities, and drug design.
CHEMICAL SOCIETY REVIEWS
(2022)
Article
Chemistry, Multidisciplinary
Elna Pidcock, Ghazala Sadiq, Joanna S. Stevens, Robert D. Willacy
Summary: An analysis of interaction geometries between C6H5-C aromatic rings and between substituted rings and pyridine rings showed high similarity when ring centroid-centroid separations are less than 6 angstrom, with variations in ring orientations. Molecular characteristics such as weight, shape, and aromaticity were found to influence the number of strong aromatic interactions observed in the solid state.
CRYSTAL GROWTH & DESIGN
(2022)
Article
Chemistry, Multidisciplinary
Steve Scheiner
Summary: The noncovalent interactions between halogen atoms on separate molecules can be categorized as Type I or II (T1 or T2). T2 is a standard halogen bond where the molecules are perpendicular to each other, while T1 has antiparallel molecules. Quantum calculations show that the T2 geometry is slightly more stable than T1 for FX pairs (X = Cl, Br, I). In mixed heterodimers FX1 center dot center dot center dot X2F, the heavier X atom prefers to be an electron acceptor. T1 conformation is held together by bent halogen bonds and positive cooperativity. The FX bond lengthens in the acidic subunit and shortens in the base, resulting in red and blue shifts in the FX stretching frequency. The NMR chemical shielding of X atoms increases upon complex formation, while the F atoms undergo smaller deshielding. These changes increase rapidly in the order Cl < Br < I.
CRYSTAL GROWTH & DESIGN
(2022)
Article
Chemistry, Inorganic & Nuclear
Jin-Fei Lan, Jie Li, Jia-Le Zhu, Gen-Ping Yan, Hua Ke, Jian-Zhen Liao
Summary: The study focused on obtaining lanthanide-based crystalline materials with significant photochromism and reactive organic radicals by combining water-soluble naphthalenediimide derivative with lanthanide nitrate solution. Photoswitchable near-infrared fluorescence was achieved in crystalline complex 1, with the structures of these materials studied to clarify the charge-transfer process. Multiple-interaction-assisted self-assembly, radical-doped nature, and the photochromic mechanism were thoroughly investigated through various techniques.
INORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Brigitte A. G. Lamers, Martin H. C. van Son, Freek de Graaf, Bart W. L. van den Bersselaar, Bas F. M. de Waal, Kazuki Komatsu, Hiroshi Sato, Takuzo Aida, Jose Augusto Berrocal, Anja R. A. Palmans, Ghislaine Vantomme, Stefan C. J. Meskers, E. W. Meijer
Summary: The assembly of highly ordered nanomaterials through charge transfer interactions is achieved in this study, where pyrene and naphthalenediimide functionalized oligodimethylsiloxanes are synthesized and co-assembled in bulk. By tuning the donor-acceptor interactions through connecting pyrene and NDI to the same oligomer or to two separate oligomers, different types of donor-acceptor molecules are obtained. The discreet length of the oligodimethylsiloxane units plays a crucial role in the formation of liquid crystalline materials and CT dimers.
MATERIALS HORIZONS
(2022)
Article
Chemistry, Physical
Ruth Chau-Ting Chan, Chensheng Ma, Allen Ka-Wa Wong, Chris Tsz-Leung Chan, Joshua Chiu-Lok Chow, Wai-Ming Kwok
Summary: In contrast to the extensive research on electronically excited DNA, little is known about the excited states of RNA. In this study, the intrinsic fluorescence and overall dynamics of a homopolymeric adenine center dot uracil RNA duplex with the A-form structure were investigated using ultrafast broadband time-resolved fluorescence and fluorescence anisotropy. The results revealed complex deactivation processes mediated by states of varied energy, involving charge transfer and lifetimes ranging from sub-picosecond to nanoseconds. Unique features, such as an unprecedented kinetic isotopic effect and unusual proton transfer, were observed. Additionally, a high-energy nanosecond emission with fluorescence anisotropy was attributed to long-lived weakly emissive excitons specific to the A-form conformation of the adenine center dot uracil double helix.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2022)
Article
Chemistry, Multidisciplinary
Dusan P. Malenov, Snezana D. Zaric
Summary: The study shows that aromatic ligands in half-sandwich compounds can form stronger anion-pi interactions, due to more pronounced dispersion and induction energy components. Compared to organic aromatic molecules, these aromatic ligands exhibit stronger anion-pi interactions and have a positive overall electrostatic potential surface. Additionally, C-H...anion interactions of aromatic ligands are stronger than anion-pi interactions.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Multidisciplinary
Tianyu Zheng, Rui Chen, Jingxian Huang, Theo P. Goncalves, Kuo-Wei Huang, Ying-Yeung Yeung
Summary: Bifunctional catalysis is important in synthesizing useful compounds. Confined bifunctional catalysts can achieve highly enantioselective reactions. This study demonstrates a proof-of-concept approach to formulating confined catalysts by linking catalytic species via non-covalent interactions. The reactions are optimized by changing the achiral catalyst.
Article
Polymer Science
Xuefeng Li, Hanyu Chen, Xueyin Peng, Dapeng Li, Wei Wang, Mengfan Chen, Dezheng Hu, Shijun Long, Yiwan Huang
Summary: A method of fabricating a gel with high and adjustable interfacial adhesion has been developed by combining different interactions. The adhesion between gel-gel and gel-glass can be easily adjusted. This method also enables the creation of high-strength composites with good moldability and self-healing capability.
MACROMOLECULAR RAPID COMMUNICATIONS
(2022)
Article
Chemistry, Physical
Xudong Xiao, Siying Lin, Liping Zhang, Huiyuan Meng, Jing Zhou, Qi Li, Jianan Liu, Panzhe Qiao, Baojiang Jiang, Honggang Fu
Summary: The study demonstrates the use of an organic compound to produce tubular carbon nitride (TCN) as a support for Pd nanoparticles (NPs) to form a composite material (NP-Pd-TCN). It was found that preferentially bind with the electron-rich N atoms of TCN, leading to the formation of Pd-N bonds and improving charge transfer. The composite material showed excellent photocatalytic hydrogen evolution under visible-light irradiation, achieving a high evolution rate.
Article
Chemistry, Multidisciplinary
Dongmei Xi, Ning Xu, Xiang Xia, Chao Shi, Xiaojing Li, Dongsheng Wang, Saran Long, Jiangli Fan, Wen Sun, Xiaojun Peng
Summary: In this study, a photosensitizer assembly nanosystem was developed to enhance tumor retention for efficient photodynamic therapy. The long tumor retention time of the photosensitizer nanoparticles allowed for single-dose injection and multiple light treatments, resulting in a high inhibition rate of over 90% for tumor growth.
ADVANCED MATERIALS
(2022)
Article
Nanoscience & Nanotechnology
Greta Bergamaschi, Angelo Musico, Roberto Frigerio, Alessandro Strada, Andrea Pizzi, Benedetta Talone, Jacopo Ghezzi, Alfonso Gautieri, Marcella Chiari, Pierangelo Metrangolo, Renzo Vanna, Francesca Baldelli Bombelli, Marina Cretich, Alessandro Gori
Summary: This study presents a composite hydrogel obtained by combining a self-assembling peptide with low-temperature gelling agarose, which demonstrates simple and robust application in the fabrication of microdroplet arrays, overcoming hurdles and limitations commonly associated with 3D hydrogel assays.
ACS APPLIED MATERIALS & INTERFACES
(2022)
Article
Chemistry, Multidisciplinary
Riccardo Mobili, Giovanni Preda, Sonia La Cognata, Lucio Toma, Dario Pasini, Valeria Amendola
Summary: A chiral cage is proposed as an effective chiroptical sensor for detecting perrhenate in water, fruit juice, and artificial urine media. The key mechanism for chiroptical sensing involves changes in the dihedral angle of the binaphthyl unit and H-bonding with the guest, leading to significant changes in the CD signal.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Alessandro Marchetti, Andrea Pizzi, Greta Bergamaschi, Nicola Demitri, Ulrike Stollberg, Ulf Diederichsen, Claudia Pigliacelli, Pierangelo Metrangolo
Summary: Iodination is a successful labelling strategy to gain structural insights into proteins and biomolecules. However, interactions driven by iodine may significantly alter the self-assembly behavior of smaller biomolecular systems. In this study, an aliphatic bis-iodinated amino acid was synthesized and incorporated into a custom pentapeptide, leading to enhanced fibrillogenic behavior and amyloid fibril formation.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Review
Biochemistry & Molecular Biology
Greta Bergamaschi, Pierangelo Metrangolo, Valentina Dichiarante
Summary: Researchers are continuously seeking versatile and high-performing optical bioimaging and biosensing probes, including photoluminescent metal nanoclusters. These nanoclusters, with molecule-like quantization properties, have great potential for applications in biologically relevant molecules.
PHOTOCHEMICAL & PHOTOBIOLOGICAL SCIENCES
(2022)
Article
Chemistry, Multidisciplinary
Nazeeha Ayaz, Valentina Dichiarante, Claudia Pigliacelli, Jacopo Repossi, Lara Gazzera, Marta Borreggio, Daniele Maiolo, Cristina Chirizzi, Greta Bergamaschi, Linda Chaabane, Elisa Fasoli, Pierangelo Metrangolo, Francesca Baldelli Bombelli
Summary: Fluorine-magnetic resonance imaging (F-19-MRI) is a promising diagnostic technique that can be easily translated for clinical use, requiring appropriate delivery systems for highly omniphobic fluorinated probes. The use of the film-forming protein hydrophobin offers a sustainable method to change the wettability of fluorinated surfaces, demonstrated here to stabilize F-19-MRI probes in aqueous solution as nanoparticles for imaging applications.
ADVANCED MATERIALS INTERFACES
(2022)
Article
Biochemistry & Molecular Biology
Carlo Ciarrocchi, Donatella Sacchi, Massimo Boiocchi, Maduka Lankani Weththimuni, Alessio Orbelli Biroli, Maurizio Licchelli
Summary: Copper(II) azacyclam complexes containing naphthyl or dansyl subunits were synthesized as chemical probes for the fluorogenic detection of sulfite. The complexes showed poor fluorescence due to the quenching behavior of Cu2+ ions, but the fluorescence could be recovered upon decomposition of the complexes.
Article
Chemistry, Multidisciplinary
Sonia La Cognata, Riccardo Mobili, Chiara Milanese, Massimo Boiocchi, Mattia Gaboardi, Donatella Armentano, Johannes C. Jansen, Marcello Monteleone, Ariana R. Antonangelo, Mariolino Carta, Valeria Amendola
Summary: Two novel imide/imine-based organic cages were prepared and studied as materials for selective separation of CO2 from N-2 and CH4. The cages showed selectivity for CO2 over N-2 and CH4 in gas adsorption and membrane filling, leading to improved gas transport properties and CO2 selectivity in mixed-matrix membranes.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Multidisciplinary
Andrea Pizzi, Lorenzo Sori, Claudia Pigliacelli, Alfonso Gautieri, Clara Andolina, Greta Bergamaschi, Alessandro Gori, Pierre Panine, Antonio Mattia Grande, Markus B. Linder, Francesca Baldelli Bombelli, Monica Soncini, Pierangelo Metrangolo
Summary: Bromination is used to promote elastic behavior in a short peptide derived from resilin, resulting in elastic and resilient hydrogels with self-healing behavior. The increased non-covalent interactions, particularly halogen bonds, contribute to the structural recovery of the peptide-based hydrogel.
Article
Biochemistry & Molecular Biology
Valentina Gazzola, Pietro Grisoli, Valeria Amendola, Giacomo Dacarro, Carlo Mangano, Piersandro Pallavicini, Antonio Poggi, Silvia Rossi, Barbara Vigani, Angelo Taglietti
Summary: This paper reports on the preparation of Imidazole-functionalized glass surfaces and demonstrates the use of a dinuclear Cu(II) complex to interact with deprotonated grafted imidazole moieties. This supramolecular approach leads to the development of an antimicrobial surface with a strong microbicidal effect using low amounts of the copper complex.
Article
Infectious Diseases
Tecla Ciociola, Laura Giovati, Tiziano De Simone, Greta Bergamaschi, Alessandro Gori, Valerio Consalvi, Stefania Conti, Alberto Vitali
Summary: Antimicrobial resistance, including fungal resistance, is a global public health concern. This study aimed to search for potential alternatives to conventional drugs, focusing on proline-rich antimicrobial peptides (PrAMPs) from plants. Two candidates showed potent activity against Candida albicans and Candida glabrata strains, including resistant isolates, with unique mechanistic properties.
Review
Chemistry, Medicinal
Alessandro Gori, Giulia Lodigiani, Stella G. Colombarolli, Greta Bergamaschi, Alberto Vitali
Summary: Cell-penetrating peptides (CPPs) are a class of peptides with the remarkable ability to cross cell membranes and deliver various cargoes into cells. They are extensively investigated for drug delivery in diseases such as cancer, diabetes, and genetic disorders. Despite sharing common structural features, CPPs are a highly diverse group of elements. This review summarizes their characteristics, distinctive features, mechanisms, and commonly used techniques for studying their structure and function, highlighting current gaps and future perspectives in the field of drug delivery and therapeutics.
Article
Cell Biology
Andrea Ridolfi, Laura Conti, Marco Brucale, Roberto Frigerio, Jacopo Cardellini, Angelo Musico, Miriam Romano, Andrea Zendrini, Laura Polito, Greta Bergamaschi, Alessandro Gori, Costanza Montis, Stefano Panella, Lucio Barile, Debora Berti, Annalisa Radeghieri, Paolo Bergese, Marina Cretich, Francesco Valle
Summary: The overlapping physicochemical properties of lipoproteins and extracellular vesicles pose challenges in isolating and characterizing these biogenic lipid nanoparticles. This study presents a rapid nanomechanical screening method using atomic force microscopy to determine the diameter and stiffness of individual nanometric objects in mixed lipoprotein and extracellular vesicle samples. The method enables discrimination of co-isolated vesicles and lipoproteins based on their specific nanomechanical readouts and provides insights into the relationship between mechanical behavior and structural features. The approach is label-free and can be used to assess the purity of lipoprotein and extracellular vesicle isolates efficiently.
JOURNAL OF EXTRACELLULAR VESICLES
(2023)
Review
Chemistry, Multidisciplinary
Sonia La Cognata, Valeria Amendola
Summary: Organic cages have attracted great interest in the scientific community due to their unique features, such as simple synthesis, structural tunability, and high selectivity. In the past decade, organic cages have been extensively studied and applied as chemosensors, separation agents, and membrane materials.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Multidisciplinary
Sonia La Cognata, Donatella Armentano, Nicoletta Marchesi, Pietro Grisoli, Alessia Pascale, Marion Kieffer, Angelo Taglietti, Anthony P. Davis, Valeria Amendola
Summary: This study reports a novel organic cage as a potential antimicrobial and antifungal agent. Experimental results demonstrate that the cage can bind and transport specific anions and exhibit antimicrobial activity against Staphylococcus aureus.
CHEMISTRY-SWITZERLAND
(2022)
Article
Chemistry, Multidisciplinary
Carlo Ciarrocchi, Guido Colucci, Massimo Boiocchi, Donatella Sacchi, Maduka L. Weththimuni, Alessio Orbelli Biroli, Maurizio Licchelli
Summary: In this paper, a series of novel 2,6-di(imino)pyridine ligands with different electron-rich aromatic substituents and their 1:2 complexes with zinc(II) were synthesized and characterized. The formation of charge-transfer species was promoted by the coordination of the metal ion. Absorption studies confirmed the presence of charge-transfer absorption bands in complexes with donor groups.
CHEMISTRY-SWITZERLAND
(2022)
