Article
Chemistry, Multidisciplinary
Vageesha W. Liyana Gunawardana, Tyler J. Finnegan, Carson E. Ward, Curtis E. Moore, Jovica D. Badjic
Summary: Living systems use chemical fuels to assemble functional structures. In this study, the dissipative formation of covalent basket cage CBC 5 by reversible reactions is described.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Organic
Simon Lambert, Kristin Bartik, Ivan Jabin
Summary: This paper reports on a hexahomotrioxacalix[3]arene molecular container with exceptional binding properties, which enables the acid-base control of substrate protection/deprotection, catalytic recycling of the container, and the accumulation of non-symmetric difunctionalized products. This supramolecular protection strategy offers many synthetic advantages in the functionalization of polyfunctional substrates.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Multidisciplinary
Shao-Chuan Li, Li-Xuan Cai, Maochun Hong, Qihui Chen, Qing-Fu Sun
Summary: This study demonstrates a combinatorial self-assembly method to synthesize a family of palladium-organic cages with systematically varied shapes and cavities by using different ligand combinations. The formation of heteroleptic cages leads to the emergence of new functions, enabling the co-encapsulation of both aromatic and aliphatic guests and enhancing the catalytic power in the Knoevenagel condensation.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Hugh P. Ryan, Cally J. E. Haynes, Alyssa Smith, Angela B. Grommet, Jonathan R. Nitschke
Summary: A method for immobilizing coordination cages on alumina has been reported, allowing for the encapsulation and separation of guest and non-guest molecules. Quantification of cage loadings and guest displacement assays demonstrate the retained ability of the adsorbed cages.
ADVANCED MATERIALS
(2021)
Review
Chemistry, Inorganic & Nuclear
Tomoki Tateishi, Masahiko Yoshimura, Shun Tokuda, Fuyuki Matsuda, Daishi Fujita, Shuhei Furukawa
Summary: Cage-like molecules formed by the coordination of metal ions and organic links have unique chemical properties and design flexibility, and are pushing the boundaries of science. This review article compares coordination cages (CCs) and metal-organic cages (MOCs) from two distinct chemistry communities, highlighting their similarities and differences. The article provides insights into synthetic conditions and identifies new research directions in the field.
COORDINATION CHEMISTRY REVIEWS
(2022)
Article
Chemistry, Multidisciplinary
Bin Sun, Eva J. J. Meeus, Felix J. J. de Zwart, Eduard O. O. Bobylev, Tiddo J. J. Mooibroek, Simon Mathew, Joost N. H. Reek
Summary: Coordination chemistry is a powerful method for synthesizing supramolecular cages with specific applications. This study successfully synthesized discrete, homochiral (Fe2L3)-L-II cages through chirality-driven self-assembly. The size of these cages can be controlled by stereochemical manipulation of the iron(II) centers, and their formation requires chirality at both the vertices and ligand backbones. The smaller cages exhibit stereoselectivity with only chiral ligands, and their formation is driven by non-covalent interactions.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Wei Zuo, Yu Tao, Zhipeng Luo, Anyang Li, Shanshan Wang, Xinrui Qiao, Fen Ma, Chuandong Jia
Summary: Inspired by the signal transduction function of organophosphates, bioactive organophosphates were used as chiral nodes to control the stereoselective assembly of hydrogen-bonded anionic cages. Antibiotics such as phosphonomycin and clindamycin phosphate, antiviral drug tenofovir, and natural product AMP were assembled with an achiral bis-monourea ligand to form quadruple or triple helicates with stereoselectivity. The stereoselectivity could be enhanced by lowering temperature or using stronger-binding cations as templates. Enantioselectivity was achieved when binding chiral quaternary ammonium cations with the chiral anionic cages as hosts.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Irene Regeni, Bin Chen, Marina Frank, Ananya Baksi, Julian J. Holstein, Guido H. Clever
Summary: This study introduces a strategy to incorporate four members of the classic coal-tar dye family into [Pd2L4] self-assemblies, investigating their performance in different ligands and color ranges, showing potential applications in chiroptical recognition, photo-redox catalysis, and optical materials. The results demonstrate different behaviors of the self-assemblies based on this new ligand class, such as chiral induction, binding modes distinction, and rearrangement to new structures.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Kai Wu, Bo Zhang, Christoph Drechsler, Julian J. Holstein, Guido H. Clever
Summary: By introducing covalent backbone bridges, the assembly structure can be diversified, and with the solvent and guest effects, it can modulate nuclearity, topology, and number of cavities. The nature of the linker in ligands would affect the structure of the assembly under different solvent conditions, resulting in different structural forms.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Shao-Jun Hu, Xiao-Qing Guo, Li-Peng Zhou, Dan-Ni Yan, Pei-Ming Cheng, Li-Xuan Cai, Xiao-Zhen Li, Qing-Fu Sun
Summary: Chiral luminescent lanthanide-organic cages have potential applications in enantioselective recognition, sensing, and asymmetric catalysis, but their structures are limited. This study introduces a guest-driven self-assembly and chiral induction approach to construct Ln(4)L(4)-type tetrahedral hosts, showcasing remarkable guest-adaptive cavity breathing and variation tolerance on coordination geometry of f-elements.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Multidisciplinary
Li-Xuan Cai, Dan-Ni Yan, Pei-Ming Cheng, Jin-Jin Xuan, Shao-Chuan Li, Li-Peng Zhou, Chong-Bin Tian, Qing-Fu Sun
Summary: Controlled self-assembly of three topologically unprecedented conjoined twin-cages was achieved in this study, with structural conversions between cages 3 and 4 enabled by changing solvents. This interconversion between topologically complex superstructures may lay a solid foundation for achieving a variety of functions within a switchable system.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Multidisciplinary
Sandipan Ghorai, Ramalingam Natarajan
Summary: In the coordination-driven self-assembly, the outcome of chiral self-sorting, either heterochiral or homochiral cages, can be controlled by specific anion encapsulation. Non-encapsulating anion results in a mixture of diastereomers, while anion exchange enables structural transformations and conversion of the mixture into homochiral diastereomers.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Chao Liu, Yucheng Jin, Dongdong Qi, Xu Ding, Huimin Ren, Hailong Wang, Jianzhuang Jiang
Summary: This paper reports a method for the preparation of heterochiral porous organic cages, achieving enantioselective assembly through chiral recognition, and demonstrating the ability of the organic cage to recognize chiral substrates and exhibit circularly polarized luminescence.
Article
Chemistry, Multidisciplinary
Wenyao Zhang, Yang Feng, Boyang Li, Dong Yang, Lekai Hou, Wei Zhao, Xiao-Juan Yang, Biao Wu
Summary: Sulfate cages, compared to phosphate cages, exhibit enhanced resistance in acidic and metal environments, making them potentially useful for applications requiring such conditions.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Multidisciplinary
Sandipan Ghorai, Suman Maji, Bhaswati Paul, Krishanu Samanta, Shovan Kumar Sen, Ramalingam Natarajan
Summary: This study reports the chiral self-sorting phenomenon in Pd6L12-type metal-organic cages. When a racemic mixture of axially chiral bis-pyridyl ligands undergoes self-assembly with Pd(II) ions to form Pd6L12-type cages, the system can undergo chiral self-sorting, resulting in at least 70 pairs of enantiomers and 5 meso isomers or a statistical mixture. However, the system exhibited diastereoselective self-assembly through high-fidelity chiral social self-sorting, forming a racemic mixture of D-3 symmetric heterochiral cages.
CHEMISTRY-AN ASIAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Francesca Guagnini, Alessando Pedrini, Enrico Dalcanale, Chiara Massera
Summary: The formation of supramolecular structural units through self-assembly is a powerful method for designing new architectures and materials. We synthesized four new V-shaped building blocks with distinctive properties, which formed co-crystals with tetraiododifluorobenzene, demonstrating potential applications in crystal engineering. The energetic contributions of the supramolecular interactions in the crystal lattice were evaluated to understand their nature and rationalize their role in designing molecular crystals.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Organic
Alessandro Pedrini, Anjali Devi Das, Roberta Pinalli, Neal Hickey, Silvano Geremia, Enrico Dalcanale
Summary: The study shows that as the alkyl chain length increases from 12 carbon atoms to 16 carbon atoms, the binding mode of viologens with cucurbit[8]uril in water switches from a 1:1 to 2:1 host/guest stoichiometry. This is due to the folding of the major portion of the longer alkyl chain in one CB[8] cavity and the inclusion of the full viologen unit by another host molecule.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Junyi Chen, Briana L. Hickey, Linlin Wang, Jiwon Lee, Adam D. Gill, Alessia Favero, Roberta Pinalli, Enrico Dalcanale, Richard J. Hooley, Wenwan Zhong
Summary: The study demonstrates a method using an array of synthetic hosts and dyes for fluorescence detection of nucleic acid secondary structures, enabling quick differentiation and classification of G-quadruplex structures. By employing a simple multivariate analysis approach, different G-quadruplex structures with similar topological types but different lengths can be identified, making it a simple and widely applicable non-invasive sensing method.
Article
Chemistry, Multidisciplinary
Alessia Favero, Andrea Rozzi, Chiara Massera, Alessandro Pedrini, Roberta Pinalli, Enrico Dalcanale
Summary: The unique temperature, solvent and pH driven vase to kite equilibrium in quinoxaline cavitands allows reversible uptake and release of guests, but the associated cavity breathing reduces complexation strength. This study reports the synthesis and structural characterization of quinoxaline-based cavitand baskets, suggesting potential solutions for cavity rigidification.
SUPRAMOLECULAR CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Neal Hickey, Barbara Medagli, Alessandro Pedrini, Roberta Pinalli, Enrico Dalcanale, Silvano Geremia
Summary: The host-guest inclusion complexes of cucurbiturils with alkyl viologen exhibit various combinations in crystal structures, showcasing complex and interesting architectures. The coexistence of different stoichiometries in the crystal reveals the impact of packing effects on supramolecular complexes.
CRYSTAL GROWTH & DESIGN
(2021)
Article
Chemistry, Multidisciplinary
Mattia Amorini, Nicolo Riboni, Lucia Pesenti, Valentina Antonia Dini, Alessandro Pedrini, Chiara Massera, Chiara Gualandi, Federica Bianchi, Roberta Pinalli, Enrico Dalcanale
Summary: This study introduces a regenerable membrane for the efficient removal of toxic and carcinogenic PAHs from water, utilizing a cavitand receptor in electrospun PAN fibers. The effective uptake/release of PAHs is demonstrated through the design and synthesis of the cavitand receptor BenzoQxCav, with a removal efficiency ranging from 32% to 99%. The membrane's regeneration is achieved by exploiting the pH-driven conformational switching of the cavitand between vase and kite forms.
Article
Chemistry, Multidisciplinary
Giuseppe Soavi, Alessandro Pedrini, Anjali Devi Das, Francesca Terenziani, Roberta Pinalli, Neal Hickey, Barbara Medagli, Silvano Geremia, Enrico Dalcanale
Summary: The effect of the host-guest interaction between cucurbit[8]uril and a model trimethine indocyanine on dye spectral properties and aggregation in water was investigated. The addition of cucurbit[8]uril disrupted the dye aggregates, forming a 1:1 host-guest complex. Supramolecular polymer formation and precipitation were observed at suitable concentrations for NMR experiments.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Multidisciplinary
Andrea Rozzi, Alessandro Pedrini, Roberta Pinalli, Enrico Cozzani, Ivan Elmi, Stefano Zampolli, Enrico Dalcanale
Summary: A highly efficient quinoxaline-based preconcentrator material, in which the intrinsic adsorption capacity of the QxCav has been maximized, was reported. The material consists of silica particles covalently coated with a suitable functionalized QxCav derivative, and the preconcentrator's adsorption capacity is independent of the relative humidity of the incoming air.
Article
Chemistry, Multidisciplinary
Danilo Marchetti, Francesca Portone, Francesco Mezzadri, Enrico Dalcanale, Mauro Gemmi, Alessandro Pedrini, Chiara Massera
Summary: The dynamic behavior of supramolecular organic frameworks (SOFs) based on TPM organic tecton has been studied. The SOF undergoes a reversible single-crystal-to-single-crystal transformation when exposed to organic solvents, resulting in changes in structure and fluorescence. The selectivity of the transformation is dictated by the fitting of the guest in the expanded SOF.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Environmental Sciences
N. Riboni, M. Amorini, F. Bianchi, A. Pedrini, R. Pinalli, E. Dalcanale, M. Careri
Summary: A sensitive and selective method based on solid-phase microextraction-gas chromatography-mass spectrometry was developed for the simultaneous determination of 16 PAHs in snow samples. The method achieved low detection limits and demonstrated reliability in the analysis of these compounds at ultra-trace levels.
Article
Chemistry, Physical
Silvia D'Auria, Alessandro Pedrini, Ilaria Ferraboschi, Jerome Vachon, Cristina Sissa, Roberta Pinalli, Enrico Dalcanale
Summary: In this study, the researchers used two-photon microscopy (2PM) to investigate the compatibility between PE-HEMA and EVOH at the sub-micrometer level. 2PM is a nonlinear fluorescence imaging technique commonly used for thick biological tissue analysis. Polymer blending was visualized using 3D images obtained through 2PM. It was observed that the functionalized PE-HEMA, when reacted with ODIN, formed uniformly distributed blends on the surface and in the bulk, and repeated reprocessing partially reversed the compatibilization by forming ODIN dimers as the most stable H-bonding array in the solid state.
Article
Chemistry, Multidisciplinary
Francesca Portone, Mattia Amorini, Matteo Montanari, Roberta Pinalli, Alessandro Pedrini, Roberto Verucchi, Roberto Brighenti, Enrico Dalcanale
Summary: This study presents the first example of a synthetic molecular auxetic polymer obtained by embedding a conformationally expandable cavitand as a crosslinker into a rigid polymer of intrinsic microporosity. The auxetic behavior of the material is predicted and supported by a specific micromechanical model, and experimentally verified through mechanical tests. The results show that the conformational expansion of the cavitand crosslinker is responsible for the observed negative Poisson's ratio.
ADVANCED FUNCTIONAL MATERIALS
(2023)
Article
Chemistry, Multidisciplinary
Francesco Bertocchi, Danilo Marchetti, Sandra Doria, Mariangela di Donato, Cristina Sissa, Mauro Gemmi, Enrico Dalcanale, Roberta Pinalli, Andrea Lapini
Summary: Our study investigates the impact of hydrogen bond-assisted H-aggregate formation on the optical properties of two functionalized naphthyridine derivatives, ODIN-EtPh and ODIN-But. Through a combination of techniques including X-ray and electron crystallography, spectroscopy, and pump-probe spectroscopy, we reveal that the formation of dimers for ODIN derivatives is inhibited in polar solvents while favored in solvents with poor hydrogen bond-forming capabilities. The presence of a phenyl group linked to the ureidic unit stabilizes the charge-transfer excited state of ODIN derivatives, leading to a reduction in fluorescence emission.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Andrea Cesari, Daniele Rosa-Gastaldo, Alessandro Pedrini, Federico Rastrelli, Enrico Dalcanale, Roberta Pinalli, Fabrizio Mancin
Summary: This study presents a novel strategy for NMR chemosensors by utilizing self-assembled cavity structures on silica nanoparticles. These nanohybrids demonstrate selective detection of physiologically relevant compounds through STD-based NMR experiments.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Andrea Rozzi, Alessandro Pedrini, Roberta Pinalli, Chiara Massera, Ivan Elmi, Stefano Zampolli, Enrico Dalcanale
Summary: The selectivity and efficiency of benzene and toluene uptake at the gas-solid interface can be greatly improved by partially rigidifying the receptor cavity of quinoxaline cavitands and immobilizing them onto silica gel particles.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Organic
Fuying Zhu, Yamei Lin
Summary: In this study, a low-metal iron-supported catalyst (Fe20/NC-Mg) was reported for the efficient synthesis of quinoxaline compounds, using water as a solvent and without additional bases. The synergistic effect of FeNx site and Mg (OH)2 nanorods in the catalyst played a key role in achieving high yields (82-91%) in 16 examples. The gram-level synthesis and reusability of the catalysts after four cycles demonstrated its industrial application potential.
Article
Chemistry, Organic
Mikhail Kozlov, Alexey Tyurin, Andrey Dmitrenok, Vyacheslav Rusak, Aleksander Fedorov, Igor Zavarzin, Yulia Volkova
Summary: This study presents a novel and practical synthesis method for phosphorus-substituted 1,3,4-thiadiazolines using phosphorylthioformic acid hydrazides and ketones. The protocol demonstrates operational simplicity, availability of reagents, and tolerance towards different functional groups.
Article
Chemistry, Organic
Jisna Jose, Thomas Mathew
Summary: 2-Cyclopentenone and its derivatives are highly esteemed synthetic intermediates with exceptional utility in organic synthesis. They are favored structural motifs in numerous pharmaceutical drugs and natural products, highlighting their significance. The review discusses the various methods used to synthesize cyclopentenones from 2016 to 2023.
