You can find below the publication list of all members of the theoretical chemistry group at ENS. For the list of each individual member, please consult their personal webpage from the Members page.
2021 |
Cation enrichment in the ion atmosphere is promoted by local hydration of DNA Article de journal Chun Yu Ma; Simone Pezzotti; Gerhard Schwaab; Magdalena Gebala; Daniel Herschlag; Martina Havenith Phys. Chem. Chem. Phys., 23 (40), p. 23203–23213, 2021. @article{Pezzotti_DNA2021, title = {Cation enrichment in the ion atmosphere is promoted by local hydration of DNA}, author = {Chun Yu Ma and Simone Pezzotti and Gerhard Schwaab and Magdalena Gebala and Daniel Herschlag and Martina Havenith}, year = {2021}, date = {2021-01-01}, journal = {Phys. Chem. Chem. Phys.}, volume = {23}, number = {40}, pages = {23203--23213}, keywords = {}, pubstate = {published}, tppubtype = {article} } |
Stripping away ion hydration shells in electrical double-layer formation: Water networks matter Article de journal Serena R Alfarano; Simone Pezzotti; Christopher J Stein; Zhou Lin; Federico Sebastiani; Sarah Funke; Claudius Hoberg; Inga Kolling; Chun Yu Ma; Katja Mauelshagen; others Proc. Natl. Acad. Sci., 118 (47), p. e2108568118, 2021. @article{Alfaranoe2108568118, title = {Stripping away ion hydration shells in electrical double-layer formation: Water networks matter}, author = {Serena R Alfarano and Simone Pezzotti and Christopher J Stein and Zhou Lin and Federico Sebastiani and Sarah Funke and Claudius Hoberg and Inga Kolling and Chun Yu Ma and Katja Mauelshagen and others}, year = {2021}, date = {2021-01-01}, journal = {Proc. Natl. Acad. Sci.}, volume = {118}, number = {47}, pages = {e2108568118}, keywords = {}, pubstate = {published}, tppubtype = {article} } |
Molecular fingerprints of hydrophobicity at aqueous interfaces from theory and vibrational spectroscopies Article de journal Simone Pezzotti; Alessandra Serva; Federico Sebastiani; Flavio Siro Brigiano; Daria Ruth Galimberti; Louis Potier; Serena Alfarano; Gerhard Schwaab; Martina Havenith; Marie-Pierre Gaigeot J. Phys. Chem. Lett., 12 (15), p. 3827–3836, 2021. @article{pezzotti2021molecular, title = {Molecular fingerprints of hydrophobicity at aqueous interfaces from theory and vibrational spectroscopies}, author = {Simone Pezzotti and Alessandra Serva and Federico Sebastiani and Flavio Siro Brigiano and Daria Ruth Galimberti and Louis Potier and Serena Alfarano and Gerhard Schwaab and Martina Havenith and Marie-Pierre Gaigeot}, year = {2021}, date = {2021-01-01}, journal = {J. Phys. Chem. Lett.}, volume = {12}, number = {15}, pages = {3827--3836}, keywords = {}, pubstate = {published}, tppubtype = {article} } |
Local Mutations Can Serve as a Game Changer for Global Protein Solvent Interaction Article de journal Ellen M Adams; Simone Pezzotti; Jonas Ahlers; Maximilian Rüttermann; Maxim Levin; Adi Goldenzweig; Yoav Peleg; Sarel J Fleishman; Irit Sagi; Martina Havenith JACS Au, 1 (7), p. 1076-1085, 2021. @article{Pezzotti_JACSau2021, title = {Local Mutations Can Serve as a Game Changer for Global Protein Solvent Interaction}, author = {Ellen M Adams and Simone Pezzotti and Jonas Ahlers and Maximilian R\"{u}ttermann and Maxim Levin and Adi Goldenzweig and Yoav Peleg and Sarel J Fleishman and Irit Sagi and Martina Havenith}, doi = {10.1021/jacsau.1c00155}, year = {2021}, date = {2021-01-01}, journal = {JACS Au}, volume = {1}, number = {7}, pages = {1076-1085}, keywords = {}, pubstate = {published}, tppubtype = {article} } |
The key role of solvent in condensation: mapping water in liquid-liquid phase-separated FUS Article de journal Jonas Ahlers; Ellen M Adams; Verian Bader; Simone Pezzotti; Konstanze F Winklhofer; Jörg Tatzelt; Martina Havenith Biophys. J., 120 (7), p. 1266–1275, 2021. @article{Pezzotti_LLPS2021, title = {The key role of solvent in condensation: mapping water in liquid-liquid phase-separated FUS}, author = {Jonas Ahlers and Ellen M Adams and Verian Bader and Simone Pezzotti and Konstanze F Winklhofer and J\"{o}rg Tatzelt and Martina Havenith}, year = {2021}, date = {2021-01-01}, journal = {Biophys. J.}, volume = {120}, number = {7}, pages = {1266--1275}, publisher = {Elsevier}, keywords = {}, pubstate = {published}, tppubtype = {article} } |
Size dependence of hydrophobic hydration at electrified gold/water interfaces Article de journal Alessandra Serva; Mathieu Salanne; Martina Havenith; Simone Pezzotti Proc. Natl. Acad. Sci., 118 (15), p. e2023867118, 2021. @article{serva2021size, title = {Size dependence of hydrophobic hydration at electrified gold/water interfaces}, author = {Alessandra Serva and Mathieu Salanne and Martina Havenith and Simone Pezzotti}, year = {2021}, date = {2021-01-01}, journal = {Proc. Natl. Acad. Sci.}, volume = {118}, number = {15}, pages = {e2023867118}, publisher = {National Acad Sciences}, keywords = {}, pubstate = {published}, tppubtype = {article} } |
The role of hydrophobic hydration in the free energy of chemical reactions at the gold/water interface: size and position effects Article de journal Alessandra Serva; Martina Havenith; Simone Pezzotti J. Chem. Phys., 155 (20), p. 204706, 2021. @article{serva2021JCP, title = {The role of hydrophobic hydration in the free energy of chemical reactions at the gold/water interface: size and position effects}, author = {Alessandra Serva and Martina Havenith and Simone Pezzotti}, year = {2021}, date = {2021-01-01}, journal = {J. Chem. Phys.}, volume = {155}, number = {20}, pages = {204706}, publisher = {AIP Publishing}, keywords = {}, pubstate = {published}, tppubtype = {article} } |
Dual targeting of higher-order DNA structures by azacryptands induces DNA junction-mediated DNA damage in cancer cells Article de journal Joanna Zell; Katerina Duskova; Leïla Chouh; Madeleine Bossaert; Nicolas Chéron; Anton Granzhan; Sébastien Britton; David Monchaud Nucleic Acids Research, 49 (18), p. 10275-10288, 2021, ISSN: 0305-1048. @article{10.1093/nar/gkab796, title = {Dual targeting of higher-order DNA structures by azacryptands induces DNA junction-mediated DNA damage in cancer cells}, author = {Joanna Zell and Katerina Duskova and Le\"{i}la Chouh and Madeleine Bossaert and Nicolas Ch\'{e}ron and Anton Granzhan and S\'{e}bastien Britton and David Monchaud}, url = {https://doi.org/10.1093/nar/gkab796}, doi = {10.1093/nar/gkab796}, issn = {0305-1048}, year = {2021}, date = {2021-01-01}, journal = {Nucleic Acids Research}, volume = {49}, number = {18}, pages = {10275-10288}, abstract = {DNA is intrinsically dynamic and folds transiently into alternative higher-order structures such as G-quadruplexes (G4s) and three-way DNA junctions (TWJs). G4s and TWJs can be stabilised by small molecules (ligands) that have high chemotherapeutic potential, either as standalone DNA damaging agents or combined in synthetic lethality strategies. While previous approaches have claimed to use ligands that specifically target either G4s or TWJs, we report here on a new approach in which ligands targeting both TWJs and G4s in vitro demonstrate cellular effects distinct from that of G4 ligands, and attributable to TWJ targeting. The DNA binding modes of these new, dual TWJ-/G4-ligands were studied by a panel of in vitro methods and theoretical simulations, and their cellular properties by extensive cell-based assays. We show here that cytotoxic activity of TWJ-/G4-ligands is mitigated by the DNA damage response (DDR) and DNA topoisomerase 2 (TOP2), making them different from typical G4-ligands, and implying a pivotal role of TWJs in cells. We designed and used a clickable ligand, TrisNP-α, to provide unique insights into the TWJ landscape in cells and its modulation upon co-treatments. This wealth of data was exploited to design an efficient synthetic lethality strategy combining dual ligands with clinically relevant DDR inhibitors.}, keywords = {}, pubstate = {published}, tppubtype = {article} } DNA is intrinsically dynamic and folds transiently into alternative higher-order structures such as G-quadruplexes (G4s) and three-way DNA junctions (TWJs). G4s and TWJs can be stabilised by small molecules (ligands) that have high chemotherapeutic potential, either as standalone DNA damaging agents or combined in synthetic lethality strategies. While previous approaches have claimed to use ligands that specifically target either G4s or TWJs, we report here on a new approach in which ligands targeting both TWJs and G4s in vitro demonstrate cellular effects distinct from that of G4 ligands, and attributable to TWJ targeting. The DNA binding modes of these new, dual TWJ-/G4-ligands were studied by a panel of in vitro methods and theoretical simulations, and their cellular properties by extensive cell-based assays. We show here that cytotoxic activity of TWJ-/G4-ligands is mitigated by the DNA damage response (DDR) and DNA topoisomerase 2 (TOP2), making them different from typical G4-ligands, and implying a pivotal role of TWJs in cells. We designed and used a clickable ligand, TrisNP-α, to provide unique insights into the TWJ landscape in cells and its modulation upon co-treatments. This wealth of data was exploited to design an efficient synthetic lethality strategy combining dual ligands with clinically relevant DDR inhibitors. |
On the role of hydrogen-bond exchanges in the spectral diffusion of water Article de journal Zeke A Piskulich; Damien Laage; Ward H Thompson J Chem Phys, 154 (6), p. 064501, 2021. @article{Piskulich2021, title = {On the role of hydrogen-bond exchanges in the spectral diffusion of water}, author = {Zeke A Piskulich and Damien Laage and Ward H Thompson}, year = {2021}, date = {2021-01-01}, journal = {J Chem Phys}, volume = {154}, number = {6}, pages = {064501}, keywords = {}, pubstate = {published}, tppubtype = {article} } |
Confined Water’s Dielectric Constant Reduction Is Due to the Surrounding Low Dielectric Media and Not to Interfacial Molecular Ordering Article de journal Jean-François Olivieri; James T Hynes; Damien Laage J Phys Chem Lett, 12 , p. 4319–4326, 2021. @article{Olivieri2021a, title = {Confined Water’s Dielectric Constant Reduction Is Due to the Surrounding Low Dielectric Media and Not to Interfacial Molecular Ordering}, author = {Jean-Fran\c{c}ois Olivieri and James T Hynes and Damien Laage}, year = {2021}, date = {2021-01-01}, journal = {J Phys Chem Lett}, volume = {12}, pages = {4319\textendash4326}, keywords = {}, pubstate = {published}, tppubtype = {article} } |
2020 |
Wrapping Up Hydrophobic Hydration: Locality Matters Article de journal V Conti Nibali; S Pezzotti; F Sebastiani; D R Galimberti; G Schwaab; M Heyden; M -P Gaigeot; M Havenith J. Phys. Chem. Lett., 11 (12), p. 4809-4816, 2020. @article{Pezzotti_JPCL2020, title = {Wrapping Up Hydrophobic Hydration: Locality Matters}, author = {V Conti Nibali and S Pezzotti and F Sebastiani and D R Galimberti and G Schwaab and M Heyden and M -P Gaigeot and M Havenith}, doi = {10.1021/acs.jpclett.0c00846}, year = {2020}, date = {2020-01-01}, journal = {J. Phys. Chem. Lett.}, volume = {11}, number = {12}, pages = {4809-4816}, keywords = {}, pubstate = {published}, tppubtype = {article} } |
An Isolated Water Droplet in the Aqueous Solution of a Supramolecular Tetrahedral Cage Article de journal Federico Sebastiani; Trandon A Bender; Simone Pezzotti; Wan-Lu Li; Gerhard Schwaab; Robert G Bergman; Kenneth N Raymond; Dean F Toste; Teresa Head-Gordon; Martina Havenith Proc. Natl. Acad. Sci., 117 (52), p. 32954–32961, 2020. @article{sebastiani2020isolated, title = {An Isolated Water Droplet in the Aqueous Solution of a Supramolecular Tetrahedral Cage}, author = {Federico Sebastiani and Trandon A Bender and Simone Pezzotti and Wan-Lu Li and Gerhard Schwaab and Robert G Bergman and Kenneth N Raymond and Dean F Toste and Teresa {Head-Gordon} and Martina Havenith}, doi = {10.1073/pnas.2012545117}, year = {2020}, date = {2020-01-01}, journal = {Proc. Natl. Acad. Sci.}, volume = {117}, number = {52}, pages = {32954--32961}, keywords = {}, pubstate = {published}, tppubtype = {article} } |
Protein Preferential Solvation in Water:Glycerol Mixtures Article de journal Nicolas Chéron; Margaux Naepels; Eva Pluhařová; Damien Laage The Journal of Physical Chemistry B, 124 (8), p. 1424-1437, 2020. @article{doi:10.1021/acs.jpcb.9b11190, title = {Protein Preferential Solvation in Water:Glycerol Mixtures}, author = {Nicolas Ch\'{e}ron and Margaux Naepels and Eva Pluha\v{r}ov\'{a} and Damien Laage}, url = {https://doi.org/10.1021/acs.jpcb.9b11190}, doi = {10.1021/acs.jpcb.9b11190}, year = {2020}, date = {2020-01-01}, journal = {The Journal of Physical Chemistry B}, volume = {124}, number = {8}, pages = {1424-1437}, keywords = {}, pubstate = {published}, tppubtype = {article} } |
Activation energies and the extended jump model: How temperature affects reorientation and hydrogen-bond exchange dynamics in water Article de journal Zeke A Piskulich; Damien Laage; Ward H Thompson J Chem Phys, 153 (7), p. 074110, 2020. @article{Piskulich2020a, title = {Activation energies and the extended jump model: How temperature affects reorientation and hydrogen-bond exchange dynamics in water}, author = {Zeke A Piskulich and Damien Laage and Ward H Thompson}, year = {2020}, date = {2020-01-01}, journal = {J Chem Phys}, volume = {153}, number = {7}, pages = {074110}, keywords = {}, pubstate = {published}, tppubtype = {article} } |
Differences in thermal structural changes and melting between mesophilic and thermophilic dihydrofolate reductase enzymes Article de journal Irene Maffucci; Damien Laage; Guillaume Stirnemann; Fabio Sterpone Phys Chem Chem Phys, 22 (33), p. 18361–18373, 2020. @article{Maffucci2020, title = {Differences in thermal structural changes and melting between mesophilic and thermophilic dihydrofolate reductase enzymes}, author = {Irene Maffucci and Damien Laage and Guillaume Stirnemann and Fabio Sterpone}, year = {2020}, date = {2020-01-01}, journal = {Phys Chem Chem Phys}, volume = {22}, number = {33}, pages = {18361\textendash18373}, abstract = {A key aspect of life’s evolution on Earth is the adaptation of proteins to be stable and work in a very wide range of temperature conditions. A detailed understanding of the associated molecular mechanisms would also help to design enzymes optimized for biotechnological …}, keywords = {}, pubstate = {published}, tppubtype = {article} } A key aspect of life’s evolution on Earth is the adaptation of proteins to be stable and work in a very wide range of temperature conditions. A detailed understanding of the associated molecular mechanisms would also help to design enzymes optimized for biotechnological … |
Water dynamics at electrified graphene interfaces: a jump model perspective Article de journal Yiwei Zhang; Guillaume Stirnemann; James T Hynes; Damien Laage Phys Chem Chem Phys, 22 , p. 10581 – 10591, 2020. @article{Zhang2020a, title = {Water dynamics at electrified graphene interfaces: a jump model perspective}, author = {Yiwei Zhang and Guillaume Stirnemann and James T Hynes and Damien Laage}, year = {2020}, date = {2020-01-01}, journal = {Phys Chem Chem Phys}, volume = {22}, pages = {10581 \textendash 10591}, abstract = {Changes in water reorientation dynamics at electrified graphene interfaces arise from the interfaces’ impact on water hydrogen-bond exchanges; the asymmetric behavior with electrode potential sign is quantitatively described by an extended jump model.}, keywords = {}, pubstate = {published}, tppubtype = {article} } Changes in water reorientation dynamics at electrified graphene interfaces arise from the interfaces’ impact on water hydrogen-bond exchanges; the asymmetric behavior with electrode potential sign is quantitatively described by an extended jump model. |
Water Structure, Dynamics, and Sum-Frequency Generation Spectra at Electrified Graphene Interfaces Article de journal Yiwei Zhang; Hilton B de Aguiar; James T Hynes; Damien Laage J Phys Chem Lett, 11 , p. 624–631, 2020. @article{Zhang2020b, title = {Water Structure, Dynamics, and Sum-Frequency Generation Spectra at Electrified Graphene Interfaces}, author = {Yiwei Zhang and Hilton B de Aguiar and James T Hynes and Damien Laage}, year = {2020}, date = {2020-01-01}, journal = {J Phys Chem Lett}, volume = {11}, pages = {624\textendash631}, keywords = {}, pubstate = {published}, tppubtype = {article} } |
2019 |
Ions Control Interfacial Water Structure and Dynamics at Silica Surfaces Article de journal Aashish Tuladhar; Shalaka Dewan; Simone Pezzotti; Flavio Siro Brigiano; Fabrizio Creazzo; Marie-Pierre Gaigeot; and Eric Borguet J. Am. Chem. Soc., 142 , p. 6991-7000, 2019. @article{Pezzotti_ions_ordering2019, title = {Ions Control Interfacial Water Structure and Dynamics at Silica Surfaces}, author = {Aashish Tuladhar and Shalaka Dewan and Simone Pezzotti and Flavio Siro Brigiano and Fabrizio Creazzo and Marie-Pierre Gaigeot and and Eric Borguet}, year = {2019}, date = {2019-01-01}, journal = {J. Am. Chem. Soc.}, volume = {142}, pages = {6991-7000}, keywords = {}, pubstate = {published}, tppubtype = {article} } |
Solvent effects on the vibrational spectrum of 3-hydroxyflavone Article de journal A P Seitsonen; A Idrissi; S Protti; A Mezzetti Journal of Molecular Liquids, 275 , p. 723–728, 2019. @article{Seitsonen:2019, title = {Solvent effects on the vibrational spectrum of 3-hydroxyflavone}, author = {A P Seitsonen and A Idrissi and S Protti and A Mezzetti}, url = {https://www.scopus.com/inward/record.uri?eid=2-s2.0-85057841646&doi=10.1016%2fj.molliq.2018.11.020&partnerID=40&md5=21ae25517ffabf644cd8eb8d94d34435}, doi = {10.1016/j.molliq.2018.11.020}, year = {2019}, date = {2019-01-01}, journal = {Journal of Molecular Liquids}, volume = {275}, pages = {723--728}, abstract = {3-hydroxyflavone (3HF) is a widely studied molecule that acts as a simplified prototype of biological, more complex flavonoids. Its solvation mechanism is still under investigation. Here we report a joint experimental and simulation study of the vibrational properties of 3HF in gas phase and in simple liquids tetrachloromethane, chloroform and acetonitrile using infra-red (IR) and Raman spectroscopies. We find reasonably good agreement between the static and molecular dynamics simulations employing density functional theory at the level of generalised gradient approximation (GGA) and hybrid functionals, but the agreement with the experimental spectra is only reasonable in the case of the IR spectroscopy and relatively poor in the case of Raman spectroscopy. The results can, however, be used as a starting point for discussing the solvation behaviour of the flavonoids. © 2018}, keywords = {}, pubstate = {published}, tppubtype = {article} } 3-hydroxyflavone (3HF) is a widely studied molecule that acts as a simplified prototype of biological, more complex flavonoids. Its solvation mechanism is still under investigation. Here we report a joint experimental and simulation study of the vibrational properties of 3HF in gas phase and in simple liquids tetrachloromethane, chloroform and acetonitrile using infra-red (IR) and Raman spectroscopies. We find reasonably good agreement between the static and molecular dynamics simulations employing density functional theory at the level of generalised gradient approximation (GGA) and hybrid functionals, but the agreement with the experimental spectra is only reasonable in the case of the IR spectroscopy and relatively poor in the case of Raman spectroscopy. The results can, however, be used as a starting point for discussing the solvation behaviour of the flavonoids. © 2018 |
Deconvolution of BIL-SFG and DL-SFG spectroscopic signals reveals order/disorder of water at the elusive aqueous silica interface Article de journal Simone Pezzotti; Daria Ruth Galimberti; Marie-Pierre Gaigeot Phys. Chem. Chem. Phys., 21 , p. 22188-22202" doi ="10.1039/C9CP02766A, 2019. @article{Pezzotti_PCCP2019, title = {Deconvolution of BIL-SFG and DL-SFG spectroscopic signals reveals order/disorder of water at the elusive aqueous silica interface}, author = {Simone Pezzotti and Daria Ruth Galimberti and Marie-Pierre Gaigeot}, year = {2019}, date = {2019-01-01}, journal = {Phys. Chem. Chem. Phys.}, volume = {21}, pages = {22188-22202" doi ="10.1039/C9CP02766A}, keywords = {}, pubstate = {published}, tppubtype = {article} } |
Molecular hydrophobicity at a macroscopically hydrophilic surface Article de journal Jenée D Cyran; Michael A Donovan; Doris Vollmer; Flavio Siro Brigiano; Simone Pezzotti; Daria R Galimberti; Marie-Pierre Gaigeot; Mischa Bonn; Ellen H G Backus Proc. Natl. Acad. Sci., 116 (5), p. 1520-1525, 2019. @article{Pezzotti_PNAS2019, title = {Molecular hydrophobicity at a macroscopically hydrophilic surface}, author = {Jen\'{e}e D Cyran and Michael A Donovan and Doris Vollmer and Flavio Siro Brigiano and Simone Pezzotti and Daria R Galimberti and Marie-Pierre Gaigeot and Mischa Bonn and Ellen H G Backus}, doi = {10.1073/pnas.1819000116}, year = {2019}, date = {2019-01-01}, journal = {Proc. Natl. Acad. Sci.}, volume = {116}, number = {5}, pages = {1520-1525}, keywords = {}, pubstate = {published}, tppubtype = {article} } |
Benzimidazoles as Metal-Free and Recyclable Hydrides for CO2 Reduction to Formate Article de journal C -H Lim; S Ilic; A Alherz; B T Worrell; S S Bacon; J T Hynes; K D Glusac; C B Musgrave Journal of the American Chemical Society, 141 (1), p. 272–280, 2019. @article{Lim:2019, title = {Benzimidazoles as Metal-Free and Recyclable Hydrides for CO2 Reduction to Formate}, author = {C -H Lim and S Ilic and A Alherz and B T Worrell and S S Bacon and J T Hynes and K D Glusac and C B Musgrave}, url = {https://www.scopus.com/inward/record.uri?eid=2-s2.0-85058544348&doi=10.1021%2fjacs.8b09653&partnerID=40&md5=538b0ec89a42c986b6e46df1217fc701}, doi = {10.1021/jacs.8b09653}, year = {2019}, date = {2019-01-01}, journal = {Journal of the American Chemical Society}, volume = {141}, number = {1}, pages = {272--280}, abstract = {We report a novel metal-free chemical reduction of CO2 by a recyclable benzimidazole-based organo-hydride, whose choice was guided by quantum chemical calculations. Notably, benzimidazole-based hydride donors rival the hydride-donating abilities of noble-metal-based hydrides such as [Ru(tpy)(bpy)H]+ and [Pt(depe)2H]+. Chemical CO2 reduction to the formate anion (HCOO-) was carried out in the absence of biological enzymes, a sacrificial Lewis acid, or a base to activate the substrate or reductant. 13CO2 experiments confirmed the formation of H13COO- by CO2 reduction with the formate product characterized by 1H NMR and 13C NMR spectroscopy and ESI-MS. The highest formate yield of 66% was obtained in the presence of potassium tetrafluoroborate under mild conditions. The likely role of exogenous salt additives in this reaction is to stabilize and shift the equilibrium toward the ionic products. After CO2 reduction, the benzimidazole-based hydride donor was quantitatively oxidized to its aromatic benzimidazolium cation, establishing its recyclability. In addition, we electrochemically reduced the benzimidazolium cation to its organo-hydride form in quantitative yield, demonstrating its potential for electrocatalytic CO2 reduction. These results serve as a proof of concept for the electrocatalytic reduction of CO2 by sustainable, recyclable, and metal-free organo-hydrides. © 2018 American Chemical Society.}, keywords = {}, pubstate = {published}, tppubtype = {article} } We report a novel metal-free chemical reduction of CO2 by a recyclable benzimidazole-based organo-hydride, whose choice was guided by quantum chemical calculations. Notably, benzimidazole-based hydride donors rival the hydride-donating abilities of noble-metal-based hydrides such as [Ru(tpy)(bpy)H]+ and [Pt(depe)2H]+. Chemical CO2 reduction to the formate anion (HCOO-) was carried out in the absence of biological enzymes, a sacrificial Lewis acid, or a base to activate the substrate or reductant. 13CO2 experiments confirmed the formation of H13COO- by CO2 reduction with the formate product characterized by 1H NMR and 13C NMR spectroscopy and ESI-MS. The highest formate yield of 66% was obtained in the presence of potassium tetrafluoroborate under mild conditions. The likely role of exogenous salt additives in this reaction is to stabilize and shift the equilibrium toward the ionic products. After CO2 reduction, the benzimidazole-based hydride donor was quantitatively oxidized to its aromatic benzimidazolium cation, establishing its recyclability. In addition, we electrochemically reduced the benzimidazolium cation to its organo-hydride form in quantitative yield, demonstrating its potential for electrocatalytic CO2 reduction. These results serve as a proof of concept for the electrocatalytic reduction of CO2 by sustainable, recyclable, and metal-free organo-hydrides. © 2018 American Chemical Society. |
Exciting vibrons in both frontier orbitals of a single hydrocarbon molecule on graphene Article de journal A Mehler; N Néel; M -L Bocquet; J Kröger Journal of Physics Condensed Matter, 31 (6), 2019. @article{Mehler:2019, title = {Exciting vibrons in both frontier orbitals of a single hydrocarbon molecule on graphene}, author = {A Mehler and N N\'{e}el and M -L Bocquet and J Kr\"{o}ger}, url = {https://www.scopus.com/inward/record.uri?eid=2-s2.0-85059370411&doi=10.1088%2f1361-648X%2faaf54c&partnerID=40&md5=5e541bf52c4692cc6d0c4ff3a4b4ec67}, doi = {10.1088/1361-648X/aaf54c}, year = {2019}, date = {2019-01-01}, journal = {Journal of Physics Condensed Matter}, volume = {31}, number = {6}, abstract = {Vibronic excitations in molecules are key to the fundamental understanding of the interaction between vibrational and electronic degrees of freedom. In order to probe the genuine vibronic properties of a molecule even after its adsorption on a surface appropriate buffer layers are of paramount importance. Here, vibrational progression in both molecular frontier orbitals is observed with submolecular resolution on a graphene-covered metal surface using scanning tunnelling spectroscopy. Accompanying calculations demonstrate that the vibrational modes that cause the orbital replica in the progression share the same symmetry as the electronic states they couple to. In addition, the vibrational progression is more pronounced for separated molecules than for molecules embedded in molecular assemblies. The entire vibronic spectra of these molecular species are moreover rigidly shifted with respect to each other. This work unravels intramolecular changes in the vibronic and electronic structure owing to the efficient reduction of the molecule-metal hybridization by graphene. © 2018 IOP Publishing Ltd.}, keywords = {}, pubstate = {published}, tppubtype = {article} } Vibronic excitations in molecules are key to the fundamental understanding of the interaction between vibrational and electronic degrees of freedom. In order to probe the genuine vibronic properties of a molecule even after its adsorption on a surface appropriate buffer layers are of paramount importance. Here, vibrational progression in both molecular frontier orbitals is observed with submolecular resolution on a graphene-covered metal surface using scanning tunnelling spectroscopy. Accompanying calculations demonstrate that the vibrational modes that cause the orbital replica in the progression share the same symmetry as the electronic states they couple to. In addition, the vibrational progression is more pronounced for separated molecules than for molecules embedded in molecular assemblies. The entire vibronic spectra of these molecular species are moreover rigidly shifted with respect to each other. This work unravels intramolecular changes in the vibronic and electronic structure owing to the efficient reduction of the molecule-metal hybridization by graphene. © 2018 IOP Publishing Ltd. |
Circular dichroism and angular deviation in x-ray absorption spectra of Dy2ScN@ C80 single-molecule magnets on h-BN/Rh(111) Article de journal T Greber; A P Seitsonen; A Hemmi; J Dreiser; R Stania; F Matsui; M Muntwiler; A A Popov; R Westerström Physical Review Materials, 3 (1), 2019. @article{Greber:2019, title = {Circular dichroism and angular deviation in x-ray absorption spectra of Dy2ScN@ C80 single-molecule magnets on h-BN/Rh(111)}, author = {T Greber and A P Seitsonen and A Hemmi and J Dreiser and R Stania and F Matsui and M Muntwiler and A A Popov and R Westerstr\"{o}m}, url = {https://www.scopus.com/inward/record.uri?eid=2-s2.0-85060612538&doi=10.1103%2fPhysRevMaterials.3.014409&partnerID=40&md5=b74a780f93dca9f124b95bcec5c689dc}, doi = {10.1103/PhysRevMaterials.3.014409}, year = {2019}, date = {2019-01-01}, journal = {Physical Review Materials}, volume = {3}, number = {1}, abstract = {Endohedral fullerenes, such as Dy2ScN@C80, are single-molecule magnets with long relaxation times of their magnetization. An open and anisotropic 4f electron shell in the lanthanides (here Dy) imposes a magnetic moment that maintains its orientation at liquid-helium temperatures for macroscopic times. If these molecules shall be used as single-bit information storage elements or for quantum operations, the orientation of the endohedral units and the orientation of the magnetic moments has to be controlled. X-ray absorption spectroscopy (XAS) and magnetic circular dichroism (XMCD) - with variation of the angle of x-ray incidence - allows for the detection of these two structural elements. We present XMCD data of Dy2ScN@C80 on an h-BN/Rh(111) nanomesh that display at 2 K a large hysteresis with a coercive field of 0.4 T. The angular dependence of the XAS data at the Dy M5 edge indicates partial ordering of the endohedral units. In order to quantify anisotropic orientation we introduce the "deviation" D as an operational quantity that measures differences between two spectra. © 2019 American Physical Society.}, keywords = {}, pubstate = {published}, tppubtype = {article} } Endohedral fullerenes, such as Dy2ScN@C80, are single-molecule magnets with long relaxation times of their magnetization. An open and anisotropic 4f electron shell in the lanthanides (here Dy) imposes a magnetic moment that maintains its orientation at liquid-helium temperatures for macroscopic times. If these molecules shall be used as single-bit information storage elements or for quantum operations, the orientation of the endohedral units and the orientation of the magnetic moments has to be controlled. X-ray absorption spectroscopy (XAS) and magnetic circular dichroism (XMCD) - with variation of the angle of x-ray incidence - allows for the detection of these two structural elements. We present XMCD data of Dy2ScN@C80 on an h-BN/Rh(111) nanomesh that display at 2 K a large hysteresis with a coercive field of 0.4 T. The angular dependence of the XAS data at the Dy M5 edge indicates partial ordering of the endohedral units. In order to quantify anisotropic orientation we introduce the "deviation" D as an operational quantity that measures differences between two spectra. © 2019 American Physical Society. |
Effect of Ions on Water Dynamics in Dilute and Concentrated Aqueous Salt Solutions. Article de journal D Laage; G Stirnemann J Phys Chem B, 123 (15), p. 3312–3324, 2019. @article{Laage2019, title = {Effect of Ions on Water Dynamics in Dilute and Concentrated Aqueous Salt Solutions.}, author = {D Laage and G Stirnemann}, year = {2019}, date = {2019-01-01}, journal = {J Phys Chem B}, volume = {123}, number = {15}, pages = {3312\textendash3324}, address = {PASTEUR, D\'{e}partement de chimie, \'{E}cole normale sup\'{e}rieure, PSL University, Sorbonne Universit\'{e}, CNRS, 75005 Paris, France. CNRS Laboratoire de Biochimie Th\'{e}orique, Institut de Biologie Physico-Chimique, PSL University, Sorbonne Paris Cit\'{e}, 13 rue Pierre et Marie Curie, 75005 Paris, France.}, abstract = {Aqueous ionic solutions are ubiquitous in chemistry and in biology. Experiments show that ions affect water dynamics, but a full understanding of several questions remains needed: why some salts accelerate water dynamics while others slow it down, why the effect of a given salt can be concentration-dependent, whether the effect of ions is rather local or more global. Numerical simulations are particularly suited to disentangle these different effects, but current force fields suffer from limitations and often lead to a poor description of dynamics in several aqueous salt solutions. Here, we develop an improved classical force field for the description of alkali halides that yields dynamics in excellent agreement with experimental measurements for water reorientational and translational dynamics. These simulations are analyzed with an extended jump model, which allows to compare the effects of ions on local hydrogen-bond exchange dynamics and on more global properties like viscosity. Our results unambiguously show that the ion-induced changes in water dynamics are usually mostly due to a local effect on the hydrogen-bond exchange dynamics; in contrast, the change in viscosity leads to a smaller effect, which governs the retardation only for a minority of salts and at high concentrations. We finally show how the respective importance of these two effects can be directly determined from experimental measurements alone, thus providing guidelines for the selection of an electrolyte with specific dynamical properties.}, keywords = {}, pubstate = {published}, tppubtype = {article} } Aqueous ionic solutions are ubiquitous in chemistry and in biology. Experiments show that ions affect water dynamics, but a full understanding of several questions remains needed: why some salts accelerate water dynamics while others slow it down, why the effect of a given salt can be concentration-dependent, whether the effect of ions is rather local or more global. Numerical simulations are particularly suited to disentangle these different effects, but current force fields suffer from limitations and often lead to a poor description of dynamics in several aqueous salt solutions. Here, we develop an improved classical force field for the description of alkali halides that yields dynamics in excellent agreement with experimental measurements for water reorientational and translational dynamics. These simulations are analyzed with an extended jump model, which allows to compare the effects of ions on local hydrogen-bond exchange dynamics and on more global properties like viscosity. Our results unambiguously show that the ion-induced changes in water dynamics are usually mostly due to a local effect on the hydrogen-bond exchange dynamics; in contrast, the change in viscosity leads to a smaller effect, which governs the retardation only for a minority of salts and at high concentrations. We finally show how the respective importance of these two effects can be directly determined from experimental measurements alone, thus providing guidelines for the selection of an electrolyte with specific dynamical properties. |
Spin in a Closed-Shell Organic Molecule on a Metal Substrate Generated by a Sigmatropic Reaction Article de journal M -L Bocquet; N Lorente; R Berndt; M Gruber Angewandte Chemie - International Edition, 58 (3), p. 821–824, 2019. @article{Bocquet:2019, title = {Spin in a Closed-Shell Organic Molecule on a Metal Substrate Generated by a Sigmatropic Reaction}, author = {M -L Bocquet and N Lorente and R Berndt and M Gruber}, url = {https://www.scopus.com/inward/record.uri?eid=2-s2.0-85058418932&doi=10.1002%2fanie.201812121&partnerID=40&md5=c9d1bd9afea90765f3df231c03cd706d}, doi = {10.1002/anie.201812121}, year = {2019}, date = {2019-01-01}, journal = {Angewandte Chemie - International Edition}, volume = {58}, number = {3}, pages = {821--824}, abstract = {Inert metal surfaces present more chances of hosting organic intact radicals than other substrates, but large amounts of delocalized electronic states favor charge transfer and thus spin quenching. Lowering the molecule\textendashsubstrate interaction is a usual strategy to stabilize radicals on surfaces. In some works, thin insulating layers were introduced to provide a controllable degree of electronic decoupling. Recently, retinoid molecules adsorbed on gold have been manipulated with a scanning tunneling microscope (STM) to exhibit a localized spin, but calculations failed to find a radical derivative of the molecule on the surface. Now the formation of a neutral radical spatially localized in a tilted and lifted cyclic end of the molecule is presented. An allene moiety provokes a perpendicular tilt of the cyclic end relative to the rest of the conjugated chain, thus localizing the spin of the dehydrogenated allene in its lifted subpart. DFT calculations and STM manipulations give support to the proposed mechanism. © 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim}, keywords = {}, pubstate = {published}, tppubtype = {article} } Inert metal surfaces present more chances of hosting organic intact radicals than other substrates, but large amounts of delocalized electronic states favor charge transfer and thus spin quenching. Lowering the molecule–substrate interaction is a usual strategy to stabilize radicals on surfaces. In some works, thin insulating layers were introduced to provide a controllable degree of electronic decoupling. Recently, retinoid molecules adsorbed on gold have been manipulated with a scanning tunneling microscope (STM) to exhibit a localized spin, but calculations failed to find a radical derivative of the molecule on the surface. Now the formation of a neutral radical spatially localized in a tilted and lifted cyclic end of the molecule is presented. An allene moiety provokes a perpendicular tilt of the cyclic end relative to the rest of the conjugated chain, thus localizing the spin of the dehydrogenated allene in its lifted subpart. DFT calculations and STM manipulations give support to the proposed mechanism. © 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim |
2018 |
Water Dynamics in Concentrated Electrolytes: Local Ion Effect on Hydrogen-Bond Jumps Rather than Collective Coupling to Ion Clusters Article de journal Guillaume Stirnemann; Pavel Jungwirth; D Laage Proceedings of the National Academy of Sciences of the United States of America, 115 (22), p. E4953-E4954, 2018, ISSN: 0027-8424, (WOS:000433283700001). @article{Stirnemann:2018, title = {Water Dynamics in Concentrated Electrolytes: Local Ion Effect on Hydrogen-Bond Jumps Rather than Collective Coupling to Ion Clusters}, author = {Guillaume Stirnemann and Pavel Jungwirth and D Laage}, doi = {10.1073/pnas.1803988115}, issn = {0027-8424}, year = {2018}, date = {2018-05-01}, journal = {Proceedings of the National Academy of Sciences of the United States of America}, volume = {115}, number = {22}, pages = {E4953-E4954}, note = {WOS:000433283700001}, keywords = {}, pubstate = {published}, tppubtype = {article} } |
Elemental Identification by Combining Atomic Force Microscopy and Kelvin Probe Force Microscopy Article de journal F Schulz; J Ritala; O Krejčí; A P Seitsonen; A S Foster; P Liljeroth ACS Nano, 12 (6), p. 5274–5283, 2018. @article{Schulz:2018, title = {Elemental Identification by Combining Atomic Force Microscopy and Kelvin Probe Force Microscopy}, author = {F Schulz and J Ritala and O Krej\v{c}\'{i} and A P Seitsonen and A S Foster and P Liljeroth}, url = {https://www.scopus.com/inward/record.uri?eid=2-s2.0-85047773715&doi=10.1021%2facsnano.7b08997&partnerID=40&md5=0f4b1ad25f886b3a2a8f9b440c657685}, doi = {10.1021/acsnano.7b08997}, year = {2018}, date = {2018-01-01}, journal = {ACS Nano}, volume = {12}, number = {6}, pages = {5274--5283}, abstract = {There are currently no experimental techniques that combine atomic-resolution imaging with elemental sensitivity and chemical fingerprinting on single molecules. The advent of using molecular-modified tips in noncontact atomic force microscopy (nc-AFM) has made it possible to image (planar) molecules with atomic resolution. However, the mechanisms responsible for elemental contrast with passivated tips are not fully understood. Here, we investigate elemental contrast by carrying out both nc-AFM and Kelvin probe force microscopy (KPFM) experiments on epitaxial monolayer hexagonal boron nitride (hBN) on Ir(111). The hBN overlayer is inert, and the in-plane bonds connecting nearest-neighbor boron and nitrogen atoms possess strong covalent character and a bond length of only ∼1.45 r{A}. Nevertheless, constant-height maps of both the frequency shift Δf and the local contact potential difference exhibit striking sublattice asymmetry. We match the different atomic sites with the observed contrast by comparison with nc-AFM image simulations based on the density functional theory optimized hBN/Ir(111) geometry, which yields detailed information on the origin of the atomic-scale contrast. © 2018 American Chemical Society.}, keywords = {}, pubstate = {published}, tppubtype = {article} } There are currently no experimental techniques that combine atomic-resolution imaging with elemental sensitivity and chemical fingerprinting on single molecules. The advent of using molecular-modified tips in noncontact atomic force microscopy (nc-AFM) has made it possible to image (planar) molecules with atomic resolution. However, the mechanisms responsible for elemental contrast with passivated tips are not fully understood. Here, we investigate elemental contrast by carrying out both nc-AFM and Kelvin probe force microscopy (KPFM) experiments on epitaxial monolayer hexagonal boron nitride (hBN) on Ir(111). The hBN overlayer is inert, and the in-plane bonds connecting nearest-neighbor boron and nitrogen atoms possess strong covalent character and a bond length of only ∼1.45 Å. Nevertheless, constant-height maps of both the frequency shift Δf and the local contact potential difference exhibit striking sublattice asymmetry. We match the different atomic sites with the observed contrast by comparison with nc-AFM image simulations based on the density functional theory optimized hBN/Ir(111) geometry, which yields detailed information on the origin of the atomic-scale contrast. © 2018 American Chemical Society. |
Epitaxial Synthesis of Blue Phosphorene Article de journal W Zhang; H Enriquez; Y Tong; A Bendounan; A Kara; A P Seitsonen; A J Mayne; G Dujardin; H Oughaddou Small, 14 (51), 2018. @article{Zhang:2018b, title = {Epitaxial Synthesis of Blue Phosphorene}, author = {W Zhang and H Enriquez and Y Tong and A Bendounan and A Kara and A P Seitsonen and A J Mayne and G Dujardin and H Oughaddou}, url = {https://www.scopus.com/inward/record.uri?eid=2-s2.0-85055703645&doi=10.1002%2fsmll.201804066&partnerID=40&md5=8f4837161dc29a33bfa5b4c3a35fab0d}, doi = {10.1002/smll.201804066}, year = {2018}, date = {2018-01-01}, journal = {Small}, volume = {14}, number = {51}, abstract = {Phosphorene is a new 2D material composed of a single or few atomic layers of black phosphorus. Phosphorene has both an intrinsic tunable direct bandgap and high carrier mobility values, which make it suitable for a large variety of optical and electronic devices. However, the synthesis of single-layer phosphorene is a major challenge. The standard procedure to obtain phosphorene is by exfoliation. More recently, the epitaxial growth of single-layer phosphorene on Au(111) was investigated by molecular beam epitaxy and the obtained structure described as a blue phosphorene sheet. In the present study, large areas of high-quality monolayer phosphorene, with a bandgap value equal to at least 0.8 eV, are synthesized on Au(111). The experimental investigations, coupled with density functional theory calculations, give evidence of two distinct phases of blue phosphorene on Au(111), instead of one as previously reported, and their atomic structures are determined. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim}, keywords = {}, pubstate = {published}, tppubtype = {article} } Phosphorene is a new 2D material composed of a single or few atomic layers of black phosphorus. Phosphorene has both an intrinsic tunable direct bandgap and high carrier mobility values, which make it suitable for a large variety of optical and electronic devices. However, the synthesis of single-layer phosphorene is a major challenge. The standard procedure to obtain phosphorene is by exfoliation. More recently, the epitaxial growth of single-layer phosphorene on Au(111) was investigated by molecular beam epitaxy and the obtained structure described as a blue phosphorene sheet. In the present study, large areas of high-quality monolayer phosphorene, with a bandgap value equal to at least 0.8 eV, are synthesized on Au(111). The experimental investigations, coupled with density functional theory calculations, give evidence of two distinct phases of blue phosphorene on Au(111), instead of one as previously reported, and their atomic structures are determined. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim |
Electrostatic Interaction across a Single-Layer Carbon Shell Article de journal R Stania; A P Seitsonen; D Kunhardt; B Büchner; A A Popov; M Muntwiler; T Greber Journal of Physical Chemistry Letters, 9 (13), p. 3586–3590, 2018. @article{Stania:2018, title = {Electrostatic Interaction across a Single-Layer Carbon Shell}, author = {R Stania and A P Seitsonen and D Kunhardt and B B\"{u}chner and A A Popov and M Muntwiler and T Greber}, url = {https://www.scopus.com/inward/record.uri?eid=2-s2.0-85048726599&doi=10.1021%2facs.jpclett.8b01326&partnerID=40&md5=cedea2bb7be44b0fd895ba245c6ef72e}, doi = {10.1021/acs.jpclett.8b01326}, year = {2018}, date = {2018-01-01}, journal = {Journal of Physical Chemistry Letters}, volume = {9}, number = {13}, pages = {3586--3590}, abstract = {Ions inside of fullerene molecules are model systems for the study of the electrostatic interaction across a single layer of carbon. For TbSc2N@C80 on h-BN/Ni(111), we observe with high-resolution X-ray photoelectron spectroscopy a splitting of the C 1s core level. The data may be explained quantitatively with density functional theory. The correlation of the C 1s eigenvalues and the Coulomb potential of the inside ions at the corresponding carbon sites indicates incomplete screening of the electric field due to the endohedral ions. The screening comprises anisotropic charge transfer to the carbon atoms and their polarization. This behavior is essential for the ordering of endohedral single-molecule magnets and is expected to occur in any single-layer material. Copyright © 2018 American Chemical Society.}, keywords = {}, pubstate = {published}, tppubtype = {article} } Ions inside of fullerene molecules are model systems for the study of the electrostatic interaction across a single layer of carbon. For TbSc2N@C80 on h-BN/Ni(111), we observe with high-resolution X-ray photoelectron spectroscopy a splitting of the C 1s core level. The data may be explained quantitatively with density functional theory. The correlation of the C 1s eigenvalues and the Coulomb potential of the inside ions at the corresponding carbon sites indicates incomplete screening of the electric field due to the endohedral ions. The screening comprises anisotropic charge transfer to the carbon atoms and their polarization. This behavior is essential for the ordering of endohedral single-molecule magnets and is expected to occur in any single-layer material. Copyright © 2018 American Chemical Society. |