Article
Chemistry, Multidisciplinary
Kalipada Koner, Suvendu Karak, Yutaro Ogaeri, Yusuke Nishiyama, Rahul Banerjee
Summary: Covalent organic nanotubes (CONTs) are porous one-dimensional frameworks connected through imine bonds via Schiff base condensation. The presence of two amine groups at the ortho position in the structurally demanding tetraaminotriptycene (TAT) building block leads to multiple reaction pathways between the ditopic aldehyde and the tetratopic amine. The synthesis and characterization of CONT-1 monomers, including the conversion of imine to imidazole bonding and the structural connectivity of CONTs, are investigated using various experimental techniques.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Victor Paulino, Kaixuan Liu, Valentino Cesiliano, Ifigeneia Tsironi, Arindam Mukhopadhyay, Maria Kaufman, Jean-Hubert Olivier
Summary: A two-component stapling strategy is used to covalently tether a new class of water-soluble supramolecular polymers built from bay-functionalized perylene bisimide (PBI) units. By leveraging a novel combined strategy where excitonic coupling and fluorescence data are exploited as spectroscopic reporters, structural design principles are established to form light-harvesting superstructures whose ground-state electronic properties are not sensitive to solvation environments.
Article
Multidisciplinary Sciences
Minghao Liu, Shuai Yang, Xiubei Yang, Cheng-Xing Cui, Guojuan Liu, Xuewen Li, Jun He, George Zheng Chen, Qing Xu, Gaofeng Zeng
Summary: Covalent organic frameworks with ionic skeletons and C-N linkages were constructed through multilevel post-synthetic modification. These frameworks showed high activity and stability for electrocatalytic CO2 reduction. By modulating the linkers and linkages, the catalytic performance and structure of covalent organic frameworks were optimized, leading to controllable activity and selectivity. This study provides insights into developing covalent organic frameworks for CO2 reduction reaction.
NATURE COMMUNICATIONS
(2023)
Article
Chemistry, Inorganic & Nuclear
Ya-Jing Zhang, Hong-Xiang Nie, Mei-Hui Yu, Ze Chang
Summary: Post-Synthetic Modification (PSM) is an efficient method to regulate properties of metal-organic frameworks (MOFs). Through the inverse-electron demand Diels-Alder (IEDDA) reaction, a series of PSM derivatives were constructed, leading to MOFs with modified pore chemistry and tuned gas adsorption properties.
JOURNAL OF SOLID STATE CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Dong Luo, Zi-Jun Yuan, Lin-Jie Ping, Xiao-Wei Zhu, Ji Zheng, Chuang-Wei Zhou, Xian-Chao Zhou, Xiao-Ping Zhou, Dan Li
Summary: Post-synthetic modification is a general and efficient strategy to functionalize metal-organic cages. In this study, a covalent PSM approach was developed to modify PdnL2n metal-organic cages through Diels-Alder cycloaddition. The functionalized cages exhibited improved solubility and displayed concentration-dependent circular dichroism and aggregation-induced emission.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Akim Khobotov-Bakishev, Partha Samanta, Kornel Roztocki, Jorge Albalad, Sergio Royuela, Shuhei Furukawa, Felix Zamora, Arnau Carne-Sanchez, Daniel Maspoch
Summary: This study presents a new approach for the synthesis of robust aerogels using covalent chemistry and their post-synthetic functionalization through coordination chemistry. The ability to modify the macroscopic properties of the aerogels allows for the development of optimized adsorbents tailored to specific guests, making it a promising method for various applications.
ADVANCED FUNCTIONAL MATERIALS
(2023)
Article
Multidisciplinary Sciences
Elisa Ruffo, Adam A. Butchy, Yaniv Tivon, Victor So, Michael Kvorjak, Avani Parikh, Eric L. Adams, Natasa Miskov-Zivanov, Olivera J. Finn, Alexander Deiters, Jason Lohmueller
Summary: This study introduces engineered cell-surface receptors called chimeric antigen receptors (CARs) and synthetic Notch (synNotch) receptors, which can sense target antigens and respond accordingly. The authors develop universal receptor systems that can be post-translationally directed to specific antigens through covalent attachment of BG-conjugated antibodies. They demonstrate successful targeting of SNAP-CAR and SNAP-synNotch receptors using clinically relevant BG-conjugated antibodies, showing anti-tumor activity in a human tumor xenograft mouse model. A mathematical model is also developed to better understand the parameters affecting universal receptor signaling.
NATURE COMMUNICATIONS
(2023)
Article
Multidisciplinary Sciences
Natali Ozber, Samuel C. Carr, Jeremy S. Morris, Siyu Liang, Jacinta L. Watkins, Kristian M. Caldo, Jillian M. Hagel, Kenneth K. S. Ng, Peter J. Facchini
Summary: This study reveals the functional role of major latex proteins in aiding opium poppy accumulate alkaloids through protein aggregation. Major latex proteins are a family of alkaloid-binding proteins that undergo conformational changes in the presence of specific ligands.
NATURE COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Xuhao Zhou, Shengyi Su, Bram Vanthournout, Ziying Hu, Florencia A. Son, Kexin Zhang, Zofia E. Siwicka, Xinyi Gong, Navjit Paul, Karthikeyan Gnanasekaran, Christopher Forman, Omar K. Farha, Matthew D. Shawkey, Nathan C. Gianneschi
Summary: Researchers have developed a method to modify synthetic hydrophilic melanin into hydrophobic derivatives through post-synthetic modifications. By introducing amine-terminated alkyl groups on melanin nanoparticles, large-scale and uniform structural colors can be generated.
Article
Chemistry, Applied
Li-Li Ma, Yuan-Yuan An, Ya-Wen Zhang, Yang Li, Le Zhang, Ying-Feng Han
Summary: The study demonstrates the synthesis of diverse three-nuclear organometallic assemblies through coordination-driven self-assembly, followed by transmetalation and oxidation addition reactions to obtain gold(I) and gold(III) complexes. Irradiation of the complexes in solution leads to structural transformation into cyclobutane-bridged complexes with quantitative yields.
APPLIED ORGANOMETALLIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Yue Xu, Xu Zhai, Xuan-He Wang, Lin-Lin Li, Huan Chen, Fu-Qiang Fan, Xiao-Jue Bai, Jun-Yi Chen, Yu Fu
Summary: A covalent post-assembly strategy was used to prepare a composite of MOF particles dispersed in an aerogel matrix. The resulting UiO-66-PI aerogel exhibited outstanding catalytic activity in CO2 cycloaddition and excellent adsorption capacity for dyes.
CHEMICAL COMMUNICATIONS
(2021)
Article
Biochemical Research Methods
Tian-Tian Ma, Cheng Yang, Hai-Long Qian, Xiu-Ping Yan
Summary: Separation of isomers is crucial in various fields, but remains challenging due to their similar properties. In this study, a new hydroxyl-functionalized covalent organic framework (COF) was post-modified with [(1-phenylethyl)amino]acetic acid (PEAA) to construct a functionalized COF for the efficient gas chromatographic separation of isomers. The introduced functional groups significantly improved the resolution of isomers.
JOURNAL OF CHROMATOGRAPHY A
(2022)
Article
Chemistry, Multidisciplinary
Bo Gui, Xuefen Liu, Yuanpeng Cheng, Ya Zhang, Pohua Chen, Minghui He, Junliang Sun, Cheng Wang
Summary: Three-dimensional covalent organic frameworks (3D COFs) have attracted increasing attention for their unique features, but face challenges in development due to synthetic difficulty and complex structure determination. This study presents a new strategy of post-synthetic modification to incorporate functional moieties into predetermined frameworks, offering a promising way to construct functional 3D COFs for various applications in the future.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Applied
Soraia P. S. Fernandes, Laura Frey, Krystal M. Cid-Seara, Orlando Oliveira, Noelia Guldris, Enrique Carbo-Argibay, Carlos Rodriguez-Abreu, Yury Kolen'ko, Artur M. S. Silva, Dana D. Medina, Laura M. Salonen
Summary: A post-synthetic modification strategy was proposed to extend the pi-system of covalent organic framework (COF) backbone, resulting in boronic ester based pyrene-fused azaacene COFs. Optimized catalyst-free reaction conditions led to COFs with up to 33% conversion and intriguing optical properties. This chemistry is expected to be useful for tailoring the optical properties of COFs.
MICROPOROUS AND MESOPOROUS MATERIALS
(2022)
Article
Chemistry, Multidisciplinary
Lei Zhu, Hai-Ruo Li, Zhao-Fei Liu, Zhengyi Di, Wengui Xu, Libo Zhang, Cheng-Peng Li
Summary: By grafting imidazole-based ionic liquids onto the backbone of covalent organic framework, we developed a COF-polyILs sorbent that efficiently removes TcO4- in high acidity and salinity environments.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Review
Chemistry, Multidisciplinary
Jake L. Greenfield, Jonathan R. Nitschke
Summary: Metal-containing polymers, or metallopolymers, have diverse applications in various fields. The self-assembly of metal-templated subcomponents allows the formation of complex structures. The control of parameters in metallopolymers can influence their growth behavior and properties, potentially meeting specific application requirements.
ACCOUNTS OF CHEMICAL RESEARCH
(2022)
Article
Chemistry, Multidisciplinary
Jack A. Davies, Andrew Tarzia, Tanya K. Ronson, Florian Auras, Kim E. Jelfs, Jonathan R. Nitschke
Summary: We have derived design principles for assembling rectangular tetramines into Zn8L6 pseudo-cubic coordination cages. The ligand panels' rectangular geometry and the handedness of each metal center at the corners of the pseudo-cube result in multiple possible cage diastereomers. However, our experiments showed that each tetra-aniline subcomponent assembled with zinc(II) and 2-formylpyridine into a single Zn8L6 pseudo-cube diastereomer. The preferred diastereomer depended on the subcomponent's aspect ratio and conformational flexibility.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Ina Heckelmann, Zifei Lu, Joseph C. A. Prentice, Florian Auras, Tanya K. Ronson, Richard H. Friend, Jonathan R. Nitschke, Sascha Feldmann
Summary: We report the self-assembly of a supramolecular pseudo-cube formed from six perylene diimides (PDIs), which suppresses aggregation and allows for non-aggregated, monomer-like properties. The stabilized excited state in the cage enables delayed fluorescence, acting as an excited-state reservoir. This self-assembly technique provides a powerful tool for controlling the electronic properties of chromophores and advancing molecular electronics devices.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Zifei Lu, Tanya K. K. Ronson, Andrew W. W. Heard, Sascha Feldmann, Nicolas Vanthuyne, Alexandre Martinez, Jonathan R. R. Nitschke
Summary: The selective chemical modification of C-60 remains a challenge, and achieving enantioselective functionalization is even more difficult due to the lack of suitable chiral reagents or separation methods. In this study, we demonstrate a strategy for introducing up to six stereocenters on C-60 with high enantioselectivity. By using a metal-organic cage built from a chiral formylpyridine, we can selectively react fullerenes inside the cage with the cage edges through chemo-, regio-, and stereo-selective Diels-Alder reactions, controlling the stereochemistry of the resulting chiral fullerene adducts. These chiral fullerene adducts hold promise for applications in devices requiring circularly polarized light manipulation.
Article
Chemistry, Multidisciplinary
Samuel E. Clark, Andrew W. Heard, Charlie T. McTernan, Tanya K. Ronson, Barbara Rossi, Petr Rozhin, Silvia Marchesan, Jonathan R. Nitschke
Summary: A double-walled tetrahedral metal-organic cage was assembled in solution using silver(I), 2-formyl-1,8-naphthyridine, halide, and a threefold-symmetric triamine. The cage has an inner set of tetrahedron walls that are surrounded by the outer four, with significant interior volume for binding anionic guests. External binding clefts located at the edges of the cage can bind small aromatic guests. The exchange of halide ions on the silver clusters allows for modulation of the cavity volume, enabling targeted binding behavior.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Weichao Xue, Kai Wu, Nianfeng Ouyang, Thierry Brotin, Jonathan R. Nitschke
Summary: The self-assembly of flexible tritopic aniline and 3-substituted 2-formylpyridine subcomponents around iron(II) templates produced a low-spin (Fe4L4)-L-II capsule, while a high-spin (Fe3L2)-L-II sandwich species formed when a sterically hindered 6-methyl-2-formylpyridine was used. The (Fe4L4)-L-II cage was found to have a new structure type with S-4 symmetry, consisting of two mer-Delta and two mer-Delta metal vertices, as confirmed by NMR and X-ray crystallographic analysis. The flexibility of the face-capping ligand allowed the resulting (Fe4L4)-L-II framework to adapt structurally from S-4 to T or C-3 symmetry upon guest binding, and it also displayed negative allosteric cooperativity in binding different guests within its cavity and at the apertures between its faces.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Carles Fuertes Espinosa, Tanya K. Ronson, Jonathan R. Nitschke
Summary: The structural complexity of metal-organic capsules can be increased by incorporating different ligands. A rational design strategy was used to selectively prepare a heteroleptic cage with a large cavity volume. The cage was able to bind multiple polycyclic aromatic hydrocarbon guests simultaneously.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Kai Wu, Tanya K. K. Ronson, Leonard Goh, Weichao Xue, Andrew W. W. Heard, Pingru Su, Xiaopeng Li, Mladen Vinkovic, Jonathan R. R. Nitschke
Summary: The allosteric regulation of biomolecules and the reconfiguration of synthetic coordination cages allow for adaptive responses to stimuli, leading to functional changes. A non-biological system consisting of organic subcomponents and Zn-II metal ions demonstrates complex responses to simple stimuli. It can transform into different architectures through subcomponent exchange and self-assembly, showing the potential for broader applications.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Amit Ghosh, Laura Slappendel, Bao-Nguyen T. Nguyen, Larissa K. S. von Krbek, Tanya K. Ronson, Ana M. Castilla, Jonathan R. Nitschke
Summary: A strategy for light-powered guest release from a tetrahedral capsule was developed by introducing azobenzene units at its vertices. The tetrahedral capsule containing 12 diazo moieties at its metal-ion vertices was prepared and could undergo isomerization upon ultraviolet irradiation, leading to guest release. Cage re-assembly and guest re-uptake could be achieved by visible-light irradiation. 19F NMR study provided a detailed understanding of how switching led to guest release.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Weichao Xue, Luca Pesce, Adinarayana Bellamkonda, Tanya K. Ronson, Kai Wu, Dawei Zhang, Nicolas Vanthuyne, Thierry Brotin, Alexandre Martinez, Giovanni M. Pavan, Jonathan R. Nitschke
Summary: This article reports on a tetrahedral FeII4L4 cage formed by the coordination of triangular chiral, face-capping ligands to iron(II). This cage exists as two diastereomers in solution, which differ in the stereochemistry of their metal vertices but share the same point chirality of the ligand. Guest binding subtly perturbs the equilibrium between these cage diastereomers, and atomistic well-tempered metadynamics simulations provide insight into the interplay between stereochemistry and fit. Understanding the stereochemical impact on guest binding enables the design of a straightforward process for the resolution of enantiomers.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Gen Li, Tanya K. Ronson, Roy Lavendomme, Zehuan Huang, Carles Fuertes-Espinosa, Dawei Zhang, Jonathan R. Nitschke
Summary: Chiral recognition is crucial in various biological processes and understanding its mechanism can lead to the design of synthetic systems with similar functions. However, current synthetic hosts can only recognize small chiral molecules. This study presents the self-assembly of triazatruxene trialdehyde into chiral FeII4L4 cages that can recognize complex steroids through non-covalent interactions. The recognition events are enantioselective and diastereoselective, showing different binding behaviors between the two enantiomers of the cage. Microcalorimetry experiments provide insight into the enthalpy and entropy contributions during enantioselective binding.
Article
Chemistry, Multidisciplinary
Yuchong Yang, Tanya K. Ronson, Jieyu Zheng, Nozomi Mihara, Jonathan R. Nitschke
Summary: The binding of fluoride to boron centers within metal-organic cages can regulate cage conformations and modulate host-guest binding. Tetrahedral and octahedral cages respond differently to fluoride binding, inhibiting or enhancing the binding of a second guest, respectively. Allosteric regulation between the tetrahedral and octahedral cages is also possible, with guests transferring between the two cages upon binding of fluoride to both.
Article
Chemistry, Multidisciplinary
Jieyu Zheng, Yuchong Yang, Tanya K. Ronson, Daniel M. Wood, Jonathan R. Nitschke
Summary: Precise control over guest release and recapture can be achieved by introducing redox-active azo groups into metal-organic capsules. These new azopyridine-based capsules have larger cavities compared to their iminopyridine-based counterparts, allowing for the encapsulation of bigger guests. The redox centers on the ligand arms can be attached to various ligand cores, making this a promising approach for design redox-controlled guest release and uptake systems.
ADVANCED MATERIALS
(2023)
Article
Chemistry, Multidisciplinary
Ilma Jahovic, Yuchong Yang, Tanya K. K. Ronson, Jonathan R. R. Nitschke
Summary: The anthracene panels of two tetrahedral (M4L6)-L-II cages, where M-II=Co-II or Fe-II, react with photogenerated singlet oxygen (O-1(2)) in a hetero-Diels-Alder reaction. The cobalt(II) cages undergo complete transformation of all anthracene panels into endoperoxides, whereas the iron(II) congeners undergo incomplete conversion. The reaction is partially reversible in the case of the 1-Fe-II cage. The dioxygen-cage cycloadducts bind guest molecules more weakly than the parent cages, with affinity dropping by more than two orders of magnitude in some cases, serving as a stimulus for guest release and reuptake.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Yuchong Yang, Tanya K. Ronson, Dingyu Hou, Jieyu Zheng, Ilma Jahovic, Kai Hong Luo, Jonathan R. Nitschke
Summary: A trigonal prismatic cage containing anthracene-centered ligands was formed through a reaction involving photogenerated singlet oxygen. Heating resulted in the reversion to the initial equilibrium system. Guest binding was observed to influence the formation of specific structures.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
