Review
Nanoscience & Nanotechnology
Sourabh Bera, Hemanta Kumar Datta, Parthasarathi Dastidar
Summary: A self-drug-delivery system against melanoma has been developed using metallogelators derived from coordination polymers. Amongst these metallogelators, CPG3 showed promising results in inhibiting melanoma cell growth by inducing apoptosis through mitochondrial membrane potential depolarization.
ACS APPLIED MATERIALS & INTERFACES
(2023)
Article
Chemistry, Multidisciplinary
Yosuke Akae, Jun Sawada, Ken Nakajima, Toshikazu Takata
Summary: A rotaxane crosslinker (RC) toughens rotaxane crosslinked polymer (RCP) through a stress dispersion effect attributed to the movable nature of the crosslinking structure. In this study, a series of structure-definite RCs with different axle end structures or wheel components were synthesized and used to create RCPs. Analysis showed that the size of the axle end structure and the type of rotaxane crosslinker affected the toughening effect, with [3]rotaxane crosslinker being more effective than [2]rotaxane. The mobility of the crosslinking points, specifically rotational and flipping movements, was found to be crucial for toughening RCPs.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Organic
Yu Wang, Shuai Lu, Xu-Qing Wang, Yan-Fei Niu, Heng Wang, Wei Wang
Summary: Novel sulfonamide [2]catenanes were successfully synthesized using a self-templation approach, with the confirmation of catenated skeletons by TWIMS combined with gMS(2). Two pyrene units were further introduced into the [2]catenane through alkylation reaction, resulting in a novel pyrene-functionalized [2]catenane with switchable optical output controlled by cation-induced conformation transformation.
ORGANIC CHEMISTRY FRONTIERS
(2021)
Article
Chemistry, Physical
Areli A. Molina-Paredes, Jesus A. Lara-Ceron, Marisol Ibarra-Rodriguez, Casiano del Angel-Mosqueda, H. Rasika Dias, Victor M. Jimenez-Perez, Blanca M. Munoz-Flores
Summary: Nowadays, designing eco-friendly synthesis with high atom economy and low E-factor is one of the biggest challenges for chemists worldwide. Solvent-free reactions are considered one of the best approaches to avoid waste. In this study, a series of solvent-free synthesis of five oxalamides was reported, yielding high purity products. NMR and X-ray diffraction results revealed the characteristic interactions of N,N'-oxalamides.
JOURNAL OF MOLECULAR STRUCTURE
(2022)
Article
Chemistry, Inorganic & Nuclear
Lisa Sturm, Christian R. Gob, Iris M. Oppel
Summary: By adjusting the stoichiometry of different co-ligands, a series of different metallocycles and carboxylate-bridged compounds have been successfully synthesized, with control over the occupation of co-ligands in metallocycles. These metallocycles show promising application prospects in host-guest chemistry due to their cavities and porosity in the solid state.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Zhenwen Wang, Lei Mei, Chenxing Guo, Song Huang, Wei-Qun Shi, Xiaowei Li, Wen Feng, Xiaopeng Li, Cheng Yang, Lihua Yuan
Summary: Here we report a ring-in-ring(s) system comprising a hydrogen-bonded macrocycle and cyclobis(paraquat-o-phenylene) tetracation (o-Box) or cyclobis(paraquat-p-phenylene) tetracation (CBPQT(4+), p-Box) that assembles to construct discrete higher order structures with adaptive conformation. This ring-in-ring(s) system features the box-directed aggregation of multiple macrocycles, leading to generation of several stable species such as H4G (1 a/o-Box) and H5G (1 a/o-Box). Remarkably, a dimeric shish-kebab-like ring-in-rings superstructure H7G2 (1 a/o-Box) or H8G2 (1 a/p-Box) is formed from the coaxial stacking of two ring-in-rings units. The formation of such unique dimeric superstructures is attributed to the large pi-surface of this 2D planar macrocycle and the conformational variation of both host and guest.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Chi-You Tsai, Hung-Te Cheng, Sheng-Hsien Chiu
Summary: A new approach for synthesizing improbable rotaxanes using malonate-centered rotaxanes as interlocked surrogate precursors has been developed. This method allows for the assembly of a desired dumbbell-shaped structure from completely separate portions with flexibility in structural design.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Andre Seco, Shilin Yu, Arnaud Tron, Nathan D. McClenaghan, Fernando Pina, A. Jorge Parola, Nuno Basilio
Summary: A linear double pyridinium-terminated thread with a central chalcone moiety provides two independent binding sites for cucurbit[7]uril macrocycles in water. The association leads to [2] and [3] pseudorotaxanes, which are pH and photosensitive, with enhanced association upon switching to the cationic flavylium form. Threading the flavylium moiety into CB7 results in a significant increase in fluorescence quantum yield.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Physical
Eric C. Moinet, Olivier Tardif, Lea-Sophie Hornberger, Friederike Adams, Ca''cilia Maichle-Moessmer, Reiner Anwander
Summary: It was discovered in this study that discrete complexes Ln[N(SiMe3)(2)](HAliBu(3))(AliBu(4)) can effectively promote the polymerization of isoprene with high cis selectivity. Mechanistic studies revealed the key reaction steps and products involved.
Article
Chemistry, Multidisciplinary
Alejandro Lopez-Moreno, Susana Ibanez, Sara Moreno-Da Silva, Luisa Ruiz-Gonzalez, Natalia Martin Sabanes, Eduardo Peris, Emilio M. Perez
Summary: Mechanically interlocked derivatives of carbon nanotubes (MINTs) are interesting and stable nanotube products. This study explores the encapsulation of single-walled carbon nanotubes within a palladium-based metallosquare, revealing the sensitivity of MINT formation to structural variations of the metallo-assemblies. The study also demonstrates the potential application expansion of MINTs through supramolecular coordination complexes.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Organic
Maxime Gauthier, Frederic Coutrot
Summary: This study synthesized and characterized four new DB24C8-based ammonium-containing pseudorotaxanes, and found that the perfluorobutyl extremity of the axle allows for dethreading of DB24C8, with the rate depending on the strength of the template-to-DB24C8 complex and the nature of the axle. The dethreading process may be assisted by the presence of a poor secondary site of interaction for the DB24C8 in the threaded axle, especially when this site is close to the DB24C8.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Hirokazu Miyoshi, Ichiro Hisaki, Yoshito Tobe
Summary: The crystal structures of tetramesityl-substituted tetracyclopenta[def,jkl,pqr,vwx]tetraphenylene (TCPTP) derivative were determined in different solvents and temperatures, showing a preference for the D-2h geometry. At room temperature, disorder of two perpendicularly oriented D-2h structures was observed, leading to slightly different bond length distributions in the crystals.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Inorganic & Nuclear
Jun Zheng, Ye Meng, Lin Zhang, Xinan Yang, Peihua Ma
Summary: In this paper, four supramolecular complexes were successfully constructed and characterized using single-crystal X-ray diffraction. The Pb2+ coordination in complex 4 formed a unique one-dimensional supramolecular chain, while the coordination of Hg2+ ion in complex 3 differed from that in complex 1 and 2.
INORGANICA CHIMICA ACTA
(2022)
Article
Chemistry, Multidisciplinary
Baoqiu Yu, Rui-Biao Lin, Gang Xu, Zhi-Hua Fu, Hui Wu, Wei Zhou, Shanfu Lu, Qian-Wen Li, Yucheng Jin, Jing-Hong Li, Zhenguo Zhang, Hailong Wang, Zier Yan, Xiaolin Liu, Kang Wang, Banglin Chen, Jianzhuang Jiang
Summary: Single-crystal X-ray diffraction demonstrates the single-crystal-to-single-crystal transformations of imine linkages in a flexible covalent organic framework with interpenetrating quartz topology. The material exhibits large anisotropic positive thermal expansion and can undergo structural transformations upon removal of solvent molecules. Redox-induced linkage conversions improve the stability of the COFs towards strong acids and enable high anhydrous proton conductivity.
Article
Chemistry, Multidisciplinary
Andrew. T. Turley, Magnus W. D. Hanson-Heine, Stephen. P. Argent, Yaoyang Hu, Thomas. A. Jones, Michael Fay, Simon Woodward
Summary: Large S-8-corona[n]arene macrocycles with alternating aryl and 1,4-C6F4 subunits were successfully synthesized on large scales using new high acceleration SNAr substitution protocols. The size and functionality of the macrocycles can be adjusted by selecting the appropriate precursor and catalyst. Furthermore, the inclusion of solvent controls the conformation and fluorine-fluorine interactions of the macrocycles, leading to spontaneous self-assembly into honeycomb-like lattices.
Article
Chemistry, Multidisciplinary
Erin Day, Brice Kauffmann, Matthieu Scarpi-Luttenauer, Alain Chaumont, Marc Henry, Pierre Mobian
Summary: The formation of a novel tetranuclear self-assembled species constructed around a TiO4N2 motif is reported, and its structure and stability were investigated using DFT calculations. It was found that the exclusive formation of an unprecedented chiral alternate [2x2] grid is driven by CH... interactions.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Applied
Mathilde Bayard, Brice Kauffmann, Jean-Michael Vauvre, Fernando Leal-Calderon, Maud Cansell
Summary: This study employed a multiscale approach to investigate the impact of low concentration pure exogenous compounds on the crystallization of TAGs in AMF. The results showed that the presence of additives did not alter the nanostructure of TAG crystals, but significantly changed the microstructure of AMF.
Article
Chemistry, Multidisciplinary
Dawei Zhang, Quan Gan, Alex J. Plajer, Roy Lavendomme, Tanya K. Ronson, Zifei Lu, Jesper D. Jensen, Bo W. Laursen, Jonathan R. Nitschke
Summary: This study reports the construction of three structurally distinct self-assembled architectures formed from a single triazatriangulenium subcomponent A under different reaction conditions. The largest structure, pseudoicosahedral capsule 1, was formed at higher concentrations, while helicate 2 exclusively formed at lower concentrations. Conversion of pseudoicosahedron 1 or helicate 2 into tetrahedron 3 occurred following the addition of a CB11H12- or B12F122- template.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Multidisciplinary Sciences
Chi Zhang, Dongyao Li, Guangdi Zhang, Xujie Wang, Li Mao, Quan Gan, Tao Ding, Hongxing Xu
Summary: This study demonstrates a method to reversibly modulate the nanogap plasmons between classical and quantum tunneling regimes using supramolecular interactions. The detailed plasmon shift near the quantum tunneling limit is revealed, and it is shown that plasmonic hot electron tunneling can further blue shift the quantum plasmons.
Article
Chemistry, Multidisciplinary
Bappaditya Gole, Brice Kauffmann, Arnaud Tron, Victor Maurizot, Nathan McClenaghan, Ivan Huc, Yann Ferrand
Summary: Aromatic helix-sheet-helix foldamers composed of photosensitive diaza-anthracene units were designed and synthesized. Their conformations can be manipulated by solvent, temperature, and helix handedness control. The photoreactivity of diazaanthracene units was found to be dependent on their position. Cooperative effects were observed in the photoreactions, which could be programmed to occur in a specific order.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Biochemical Research Methods
Pradeep K. Mandal, Gavin W. Collie, Brice Kauffmann, Ivan Huc
Summary: The use of racemic mixtures has been shown to improve the success rate of protein crystallization experiments and may also extend to other macromolecules including nucleic acids, potentially aiding in determining enantiopure DNA crystal structures. Racemates may favor the emergence of new conformations and provide new possibilities for the design of precise self-assembled nanomaterials and nanostructures.
ACTA CRYSTALLOGRAPHICA SECTION D-STRUCTURAL BIOLOGY
(2022)
Article
Biochemistry & Molecular Biology
Lauriane Giraud, Stephane Grelier, Etienne Grau, Laurent Garel, Georges Hadziioannou, Brice Kauffmann, Eric Cloutet, Henri Cramail, Cyril Brochon
Summary: The synthesis of environmentally friendly pi-conjugated polymers is challenging. In this study, divanillin-based polyazomethines were synthesized using a potentially bio-based monomer. The polymerization process was achieved in 5 minutes with microwave irradiation and without any metallic catalyst, resulting in water as the only by-product. The structure and properties of the polyazomethines were characterized, and model compounds were used to confirm the E configuration and cross-conjugated nature of the divanillin-based polymers.
Article
Chemistry, Organic
Friedericke S. S. Menke, Daniela Mazzier, Barbara Wicher, Lars Allmendinger, Brice Kauffmann, Victor Maurizot, Ivan Huc
Summary: The first abiotic foldamer tertiary structures have been reported, consisting of aromatic helix-turn-helix motifs based on oligo-quinolinecarboxamides held together by intramolecular hydrogen bonds. Computational modelling predicted and X-ray crystallography verified the tertiary folds. Investigation into the conformational preference of each helix revealed that the removal of some hydrogen bonds did not strongly destabilize the tertiary folds.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2023)
Article
Biotechnology & Applied Microbiology
Thierry Mourer, Mennat El Ghalid, Gerard Pehau-Arnaudet, Brice Kauffmann, Antoine Loquet, Sebastien Brule, Vitor Cabral, Christophe d'Enfert, Sophie Bachellier-Bassi
Summary: The human commensal fungus Candida albicans can form biofilms that are highly tolerant to antifungal drugs and can evade the immune response. The cell surface protein Pga59 influences adhesion and biofilm formation and displays amyloid properties. Mutations impairing Pga59 amyloid assembly result in diminished adhesion and reduced biofilm production. Pga59 is used by the fungal cell to assemble amyloids within the cell wall in response to adhesion.
NPJ BIOFILMS AND MICROBIOMES
(2023)
Article
Chemistry, Multidisciplinary
Nagendar Pendem, Yella-Reddy Nelli, Leonie Cussol, Claude Didierjean, Brice Kauffmann, Christel Dolain, Gilles Guichard
Summary: Oligomers with a helix-turn-helix super-secondary structure were prepared by covalently bridging aliphatic oligourea foldamer helices with either rigid aromatic or flexible aliphatic spacers. The relative orientation of the helices in these dimers was studied using high-resolution X-ray diffraction analysis. Racemic crystallography was employed in some cases to facilitate crystallization and structure determination. All structures were solved using direct methods. Well-defined parallel helical hairpin motifs were observed in all cases when 4,4'-methylene diphenyl diisocyanate was used as a dimerizing agent, regardless of the primary sequence and chain length.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Physical
Johal Ruiz, Josephine G. LoRicco, Laurent Soulere, Marta Salvador Castell, Axelle Grelard, Brice Kauffmann, Erick J. Dufourc, Bruno Deme, Florence Popowycz, Judith Peters
Summary: Archaeal membrane lipids have unique structures that enable them to withstand extreme temperature and pressure conditions. A study on the synthesis of an archaeal lipid called 1,2-di-O-phytanyl-sn-glycero-3-phosphoinositol (DoPhPI) derived from myo-inositol reveals its resistance mechanisms. The experiments show that DoPhPI and DoPhPC can form small vesicles in aqueous dispersions, and these dispersions undergo phase transitions from lamellar to cubic and hexagonal phases with increasing temperature. The phytanyl chains in the lipid also contribute to the bilayer's dynamic properties over a wide temperature range. These findings suggest that the unique properties of archaeal lipids provide plasticity and aid in resisting extreme conditions.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2023)
Article
Chemistry, Multidisciplinary
Yulong Zhong, Thomas A. Sobiech, Brice Kauffmann, Bo Song, Xiaopeng Li, Yann Ferrand, Ivan Huc, Bing Gong
Summary: Two aromatic oligoamides, H8 and H16, were found to wrap around octyl viologen (OV2+) and para-bis(trimethylammonium)benzene (TB2+) to form 2:2 and 1:2 complexes, respectively. The longer H16 exhibited higher binding affinity with OV2+ and showed negative cooperativity. Interestingly, H16 selectively bound OV2+ over TB2+. This study highlights the pairwise placement of OV2+ ions, negative cooperativity, and the adaptability of hosts and guests, resulting in stable [2]-, [3]-, and [4]pseudo-foldaxanes.
Article
Chemistry, Multidisciplinary
Aline Delamare, Guillaume Naulet, Brice Kauffmann, Gilles Guichard, Guillaume Compain
Summary: The hexafluoroisobutyl group is a commonly found hydrophobic group in drugs, and its introduction can provide new advantages to compounds. However, the lack of a general and practical synthetic methodology has hindered the exploration of this modification. In this study, the first general method for introducing the hexafluoroisobutyl group into various compounds was reported. This method overcomes the usual fluoride beta-elimination observed with other CF3-vinyl groups, and it has been successfully applied to the multigram-scale synthesis of enantiopure (S)-5,5,5,5',5',5'-hexafluoroleucine.
Article
Chemistry, Multidisciplinary
Victor Koehler, Maxime Gauthier, Chenhao Yao, Karine Fournel-Marotte, Philip Waeles, Brice Kauffmann, Ivan Huc, Frederic Coutrot, Yann Ferrand
Summary: This study investigates the wrapping of an aromatic oligoamide helix around an active ester-containing [2]rotaxane, which enforces the sliding and sequestration of the surrounding macrocycle around a part of the axle without any formal affinity. The foldamer-mediated compartmentalization of the [2]rotaxane shuttle was subsequently used to prepare an improbable rotaxane.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Chenhao Yao, Brice Kauffmann, Ivan Huc, Yann Ferrand
Summary: Two oligoamide macrocycles composed of eight and twelve monomers were synthesized by utilizing helicity disruptors. The resulting macrocyclic ribbons adopt figure-of-eight and pseudoplectoneme shapes and are capable of self-assembly.
CHEMICAL COMMUNICATIONS
(2022)
