Prof. Dr. Ivan Huc
Academic Research Focus
- Foldamer design
- Molecular Recognition within foldamers
- Biological applications of foldamers
- Molecular Recognition within foldamers
- Biological applications of foldamers
Fields of Application
Publications
7.
J Wang, B Wicher, V Maurizot, I Huc
Directing the Self-Assembly of Aromatic Foldamer Helices using Acridine Appendages and Metal Coordination Journal Article
In: Chemistry – A European Journal, vol. 28, no. 62, pp. e202201345, 2022, ISSN: 0947-6539.
@article{nokey,
title = {Directing the Self-Assembly of Aromatic Foldamer Helices using Acridine Appendages and Metal Coordination},
author = {J Wang and B Wicher and V Maurizot and I Huc},
url = {https://doi.org/10.1002/chem.202201345},
doi = {https://doi.org/10.1002/chem.202201345},
issn = {0947-6539},
year = {2022},
date = {2022-11-07},
journal = {Chemistry \textendash A European Journal},
volume = {28},
number = {62},
pages = {e202201345},
abstract = {Abstract Folded molecules provide complex interaction interfaces amenable to sophisticated self-assembly motifs. Because of their high conformational stability, aromatic foldamers constitute suitable candidates for the rational elaboration of self-assembled architectures. Several multiturn helical aromatic oligoamides have been synthesized that possess arrays of acridine appendages pointing in one or two directions. The acridine units were shown to direct self-assembly in the solid state via aromatic stacking leading to recurrent helix-helix association patterns under the form of discrete dimers or extended arrays. In the presence of Pd(II), metal coordination of the acridine units overwhelms other forces and generates new metal-mediated multihelical self-assemblies, including macrocycles. These observations demonstrate simple access to different types of foldamer-containing architectures, ranging from discrete objects to 1D and, by extension, 2D and 3D arrays.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
Abstract Folded molecules provide complex interaction interfaces amenable to sophisticated self-assembly motifs. Because of their high conformational stability, aromatic foldamers constitute suitable candidates for the rational elaboration of self-assembled architectures. Several multiturn helical aromatic oligoamides have been synthesized that possess arrays of acridine appendages pointing in one or two directions. The acridine units were shown to direct self-assembly in the solid state via aromatic stacking leading to recurrent helix-helix association patterns under the form of discrete dimers or extended arrays. In the presence of Pd(II), metal coordination of the acridine units overwhelms other forces and generates new metal-mediated multihelical self-assemblies, including macrocycles. These observations demonstrate simple access to different types of foldamer-containing architectures, ranging from discrete objects to 1D and, by extension, 2D and 3D arrays.
6.
D Meier, B Schoof, J Wang, X Li, A Walz, A Huettig, H Schlichting, F Rosu, V Gabelica, V Maurizot, J Reichert, A C Papageorgiou, I Huc, J V Barth
Structural adaptations of electrosprayed aromatic oligoamide foldamers on Ag(111) Journal Article
In: Chemical Communications, vol. 58, no. 64, pp. 8938-8941, 2022, ISSN: 1359-7345.
@article{nokey,
title = {Structural adaptations of electrosprayed aromatic oligoamide foldamers on Ag(111)},
author = {D Meier and B Schoof and J Wang and X Li and A Walz and A Huettig and H Schlichting and F Rosu and V Gabelica and V Maurizot and J Reichert and A C Papageorgiou and I Huc and J V Barth},
url = {http://dx.doi.org/10.1039/D2CC03286D},
doi = {10.1039/D2CC03286D},
issn = {1359-7345},
year = {2022},
date = {2022-07-11},
journal = {Chemical Communications},
volume = {58},
number = {64},
pages = {8938-8941},
abstract = {Aromatic foldamers are promising for applications such as molecular recognition and molecular machinery. For many of these, defect free, 2D-crystaline monolayers are needed. To this end, submonolayers were prepared in ultra-high vacuum (UHV) on Ag(111) via electrospray controlled ion beam deposition (ES-CIBD). On the surface, the unfolded state is unambiguously identified by real-space single-molecule imaging using scanning tunnelling microscopy (STM) and it is found to assemble in regular structures.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
Aromatic foldamers are promising for applications such as molecular recognition and molecular machinery. For many of these, defect free, 2D-crystaline monolayers are needed. To this end, submonolayers were prepared in ultra-high vacuum (UHV) on Ag(111) via electrospray controlled ion beam deposition (ES-CIBD). On the surface, the unfolded state is unambiguously identified by real-space single-molecule imaging using scanning tunnelling microscopy (STM) and it is found to assemble in regular structures.
5.
B Gole, B Kauffmann, A Tron, V Maurizot, N Mcclenaghan, I Huc, Y Ferrand
Selective and Cooperative Photocycloadditions within Multistranded Aromatic Sheets Journal Article
In: Journal of the American Chemical Society, 2022, ISSN: 0002-7863.
@article{nokey,
title = {Selective and Cooperative Photocycloadditions within Multistranded Aromatic Sheets},
author = {B Gole and B Kauffmann and A Tron and V Maurizot and N Mcclenaghan and I Huc and Y Ferrand},
url = {https://doi.org/10.1021/jacs.2c01269},
doi = {10.1021/jacs.2c01269},
issn = {0002-7863},
year = {2022},
date = {2022-04-05},
urldate = {2022-04-05},
journal = {Journal of the American Chemical Society},
abstract = {A series of aromatic helix-sheet-helix oligoamide foldamers composed of several different photosensitive diazaanthracene units have been designed and synthesized. Molecular objects up to 7 kDa were straightforwardly produced on a 100 mg scale. Nuclear magnetic resonance and crystallographic investigations revealed that helix-sheet-helix architectures can adopt one or two distinct conformations. Sequences composed of an even number of turn units were found to fold in a canonical symmetrical conformation with two helices of identical handedness stacked above and below the sheet segment. Sequences composed of an odd number of turns revealed a coexistence between a canonical fold with helices of opposite handedness and an alternate fold with a twist within the sheet and two helices of identical handedness. The proportions between these species could be manipulated, in some cases quantitatively, being dependent on solvent, temperature, and absolute control of helix handedness. Diazaanthracene units were shown to display distinct reactivity toward [4 + 4] photocycloadditions according to the substituent in position 9. Their organization within the sequences was programmed to allow photoreactions to take place in a specific order. Reaction pathways and kinetics were deciphered and product characterized, demonstrating the possibility to orchestrate successive photoreactions so as to avoid orphan units or to deliberately produce orphan units at precise locations. Strong cooperative effects were observed in which the photoreaction rate was influenced by the presence (or absence) of photoadducts in the structure. Multiple photoreactions within the aromatic sheet eventually lead to structure lengthening and stiffening, locking conformational equilibria. Photoproducts could be thermally reverted.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
A series of aromatic helix-sheet-helix oligoamide foldamers composed of several different photosensitive diazaanthracene units have been designed and synthesized. Molecular objects up to 7 kDa were straightforwardly produced on a 100 mg scale. Nuclear magnetic resonance and crystallographic investigations revealed that helix-sheet-helix architectures can adopt one or two distinct conformations. Sequences composed of an even number of turn units were found to fold in a canonical symmetrical conformation with two helices of identical handedness stacked above and below the sheet segment. Sequences composed of an odd number of turns revealed a coexistence between a canonical fold with helices of opposite handedness and an alternate fold with a twist within the sheet and two helices of identical handedness. The proportions between these species could be manipulated, in some cases quantitatively, being dependent on solvent, temperature, and absolute control of helix handedness. Diazaanthracene units were shown to display distinct reactivity toward [4 + 4] photocycloadditions according to the substituent in position 9. Their organization within the sequences was programmed to allow photoreactions to take place in a specific order. Reaction pathways and kinetics were deciphered and product characterized, demonstrating the possibility to orchestrate successive photoreactions so as to avoid orphan units or to deliberately produce orphan units at precise locations. Strong cooperative effects were observed in which the photoreaction rate was influenced by the presence (or absence) of photoadducts in the structure. Multiple photoreactions within the aromatic sheet eventually lead to structure lengthening and stiffening, locking conformational equilibria. Photoproducts could be thermally reverted.
4.
J Wang, B Wicher, A Méndez-Ardoy, X Li, G Pecastaings, T Buffeteau, D M Bassani, V Maurizot, I Huc
Loading linear arrays of Cu(II) inside aromatic amide helices Journal Article
In: Angewandte Chemie International Edition, vol. n/a, no. n/a, 2021, ISSN: 1433-7851.
@article{,
title = {Loading linear arrays of Cu(II) inside aromatic amide helices},
author = {J Wang and B Wicher and A M\'{e}ndez-Ardoy and X Li and G Pecastaings and T Buffeteau and D M Bassani and V Maurizot and I Huc},
url = {https://onlinelibrary.wiley.com/doi/abs/10.1002/anie.202104734},
doi = {https://doi.org/10.1002/anie.202104734},
issn = {1433-7851},
year = {2021},
date = {2021-05-20},
journal = {Angewandte Chemie International Edition},
volume = {n/a},
number = {n/a},
abstract = {The very stable helices of 8-amino-2-quinolinecarboxylic acid oligoamides are shown to uptake Cu(II) ions in their cavity through deprotonation of their amide functions with minimal alteration of their shape, unlike most metallo-organic structures which generally much differ from their organic precursors. The outcome is the formation of intramolecular linear arrays of a defined number of Cu(II) centers (up to sixteen in this study) at a 3 r{A} distance, forming a molecular mimic of a metal wire completely surrounded by an organic sheath. The helices pack in the solid state so that the arrays of Cu(II) extend intermolecularly. Conductive-AFM and cyclic voltammetry suggest that electrons are transported throughout the metal-loaded helices in contrast with hole transport observed for analogous foldamers devoid of metal ions.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
The very stable helices of 8-amino-2-quinolinecarboxylic acid oligoamides are shown to uptake Cu(II) ions in their cavity through deprotonation of their amide functions with minimal alteration of their shape, unlike most metallo-organic structures which generally much differ from their organic precursors. The outcome is the formation of intramolecular linear arrays of a defined number of Cu(II) centers (up to sixteen in this study) at a 3 Å distance, forming a molecular mimic of a metal wire completely surrounded by an organic sheath. The helices pack in the solid state so that the arrays of Cu(II) extend intermolecularly. Conductive-AFM and cyclic voltammetry suggest that electrons are transported throughout the metal-loaded helices in contrast with hole transport observed for analogous foldamers devoid of metal ions.
3.
F Devaux, X Li, D Sluysmans, V Maurizot, E Bakalis, F Zerbetto, I Huc, A-S Duwez
Single-molecule mechanics of synthetic aromatic amide helices: Ultrafast and robust non-dissipative winding Journal Article
In: Chem, 2021, ISSN: 2451-9294.
@article{,
title = {Single-molecule mechanics of synthetic aromatic amide helices: Ultrafast and robust non-dissipative winding},
author = {F Devaux and X Li and D Sluysmans and V Maurizot and E Bakalis and F Zerbetto and I Huc and A-S Duwez},
issn = {2451-9294},
year = {2021},
date = {2021-03-26},
journal = {Chem},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
2.
P Mateus, A Jacquet, A Méndez-Ardoy, A Boulloy, B Kauffmann, G Pecastaings, T Buffeteau, Y Ferrand, D M Bassani, I Huc
Sensing a binding event through charge transport variations using an aromatic oligoamide capsule Journal Article
In: Chemical Science, vol. 12, no. 10, pp. 3743-3750, 2021, ISSN: 2041-6520.
@article{nokey,
title = {Sensing a binding event through charge transport variations using an aromatic oligoamide capsule},
author = {P Mateus and A Jacquet and A M\'{e}ndez-Ardoy and A Boulloy and B Kauffmann and G Pecastaings and T Buffeteau and Y Ferrand and D M Bassani and I Huc},
url = {http://dx.doi.org/10.1039/D0SC06060G},
doi = {10.1039/D0SC06060G},
issn = {2041-6520},
year = {2021},
date = {2021-01-22},
journal = {Chemical Science},
volume = {12},
number = {10},
pages = {3743-3750},
abstract = {The selective binding properties of a 13-mer oligoamide foldamer capsule composed of 4 different aromatic subunits are reported. The capsule was designed to recognize dicarboxylic acids through multiple-point interactions owing to a combination of protonation/deprotonation events, H-bonding, and geometrical constraints imparted by the rigidity of the foldamer backbone. Compared to tartaric acid, binding of 2,2-difluorosuccinic acid or 2,2,3,3-tetrafluorosuccinic acid resulted in symmetry breaking due to deprotonation of only one of the two carboxylic acid groups of the encapsulated species as shown by NMR studies in solution and by single-crystal X-ray diffraction in the solid state. An analogous 14-mer foldamer capsule terminated with a thiol anchoring group was used to probe the complexation event in self-assembled monolayers on Au substrates. Ellipsometry and polarization-modulation infrared absorption-reflection spectroscopy studies were consistent with the formation of a single molecule layer of the foldamer capsule oriented vertically with respect to the surface. The latter underwent smooth complexation of 2,2-difluorosuccinic acid with deprotonation of one of the two carboxylic acid groups. A significant (80-fold) difference in the charge transport properties of the monolayer upon encapsulation of the dicarboxylic acid was evidenced from conducting-AFM measurements (S = 1.1 × 10−9vs. 1.4 × 10−11 ohm−1 for the empty and complexed capsule, respectively). The modulation in conductivity was assigned to protonation of the aromatic foldamer backbone.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
The selective binding properties of a 13-mer oligoamide foldamer capsule composed of 4 different aromatic subunits are reported. The capsule was designed to recognize dicarboxylic acids through multiple-point interactions owing to a combination of protonation/deprotonation events, H-bonding, and geometrical constraints imparted by the rigidity of the foldamer backbone. Compared to tartaric acid, binding of 2,2-difluorosuccinic acid or 2,2,3,3-tetrafluorosuccinic acid resulted in symmetry breaking due to deprotonation of only one of the two carboxylic acid groups of the encapsulated species as shown by NMR studies in solution and by single-crystal X-ray diffraction in the solid state. An analogous 14-mer foldamer capsule terminated with a thiol anchoring group was used to probe the complexation event in self-assembled monolayers on Au substrates. Ellipsometry and polarization-modulation infrared absorption-reflection spectroscopy studies were consistent with the formation of a single molecule layer of the foldamer capsule oriented vertically with respect to the surface. The latter underwent smooth complexation of 2,2-difluorosuccinic acid with deprotonation of one of the two carboxylic acid groups. A significant (80-fold) difference in the charge transport properties of the monolayer upon encapsulation of the dicarboxylic acid was evidenced from conducting-AFM measurements (S = 1.1 × 10−9vs. 1.4 × 10−11 ohm−1 for the empty and complexed capsule, respectively). The modulation in conductivity was assigned to protonation of the aromatic foldamer backbone.
1.
J Wang, B Wicher, V Maurizot, I Huc
Oligo-Quinolylene–Vinylene Foldamers Journal Article
In: Chemistry – A European Journal, vol. 27, no. 3, pp. 1031-1038, 2021, ISSN: 0947-6539.
@article{nokey,
title = {Oligo-Quinolylene\textendashVinylene Foldamers},
author = {J Wang and B Wicher and V Maurizot and I Huc},
url = {https://doi.org/10.1002/chem.202003559},
doi = {https://doi.org/10.1002/chem.202003559},
issn = {0947-6539},
year = {2021},
date = {2021-01-13},
journal = {Chemistry \textendash A European Journal},
volume = {27},
number = {3},
pages = {1031-1038},
abstract = {Abstract Quinoline based aromatic amide foldamers are known to adopt stable folded conformations. We have developed a synthetic approach to produce similar oligomers where all amide bonds, or part of them, have been replaced by an isosteric vinylene group. The results of solution and solid state structural studies show that oligomers exclusively containing vinylene linkages are not well folded, and adopt predominantly flat conformations. In contrast, a vinylene segment flanked by helical oligoamides also folds in a helix, albeit with a slightly lower curvature. The presence of vinylene functions also result in an extension of π-conjugation across the oligomer that may change charge transport properties. Altogether, these results pave the way to foldamers in which both structural control and specific electronic properties may be engineered.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
Abstract Quinoline based aromatic amide foldamers are known to adopt stable folded conformations. We have developed a synthetic approach to produce similar oligomers where all amide bonds, or part of them, have been replaced by an isosteric vinylene group. The results of solution and solid state structural studies show that oligomers exclusively containing vinylene linkages are not well folded, and adopt predominantly flat conformations. In contrast, a vinylene segment flanked by helical oligoamides also folds in a helix, albeit with a slightly lower curvature. The presence of vinylene functions also result in an extension of π-conjugation across the oligomer that may change charge transport properties. Altogether, these results pave the way to foldamers in which both structural control and specific electronic properties may be engineered.