2011 |
Palma, Carlos-Andres ; Samori, Paolo Blueprinting macromolecular electronics Journal Article In: NATURE CHEMISTRY, 3 (6), pp. 431–436, 2011, ISSN: 1755-4330. @article{palma_blueprinting_2011, title = {Blueprinting macromolecular electronics}, author = {Palma, Carlos-Andres and Samori, Paolo}, doi = {10.1038/NCHEM.1043}, issn = {1755-4330}, year = {2011}, date = {2011-06-01}, journal = {NATURE CHEMISTRY}, volume = {3}, number = {6}, pages = {431--436}, abstract = {Recently, by mastering either top-down or bottom-up approaches, tailor-made macromolecular nano-objects with semiconducting properties have been fabricated. These engineered nanostructures for organic electronics are based on conjugated systems predominantly made up of sp(2)-hybridized carbon, such as graphene nanoribbons. Here, we describe developments in a selection of these nanofabrication techniques, which include graphene carving, stimulus-induced synthesis of conjugated polymers and surface-assisted synthesis. We also assess their potential to reproduce chemically and spatially precise molecular arrangements, that is, molecular blueprints. In a broad context, the engineering of a molecular blueprint represents the fabrication of an integrated all-organic macromolecular electronic circuit. In this Perspective, we suggest chemical routes, as well as convergent on-surface synthesis and microfabrication approaches, for the ultimate goal of bringing the field closer to technology.}, keywords = {}, pubstate = {published}, tppubtype = {article} } Recently, by mastering either top-down or bottom-up approaches, tailor-made macromolecular nano-objects with semiconducting properties have been fabricated. These engineered nanostructures for organic electronics are based on conjugated systems predominantly made up of sp(2)-hybridized carbon, such as graphene nanoribbons. Here, we describe developments in a selection of these nanofabrication techniques, which include graphene carving, stimulus-induced synthesis of conjugated polymers and surface-assisted synthesis. We also assess their potential to reproduce chemically and spatially precise molecular arrangements, that is, molecular blueprints. In a broad context, the engineering of a molecular blueprint represents the fabrication of an integrated all-organic macromolecular electronic circuit. In this Perspective, we suggest chemical routes, as well as convergent on-surface synthesis and microfabrication approaches, for the ultimate goal of bringing the field closer to technology. |
Luo, Guobin ; Karplus, Martin Determining the Conformational Change that Accompanies Donor-Acceptor Distance Fluctuations: An Umbrella Sampling Analysis Journal Article In: JOURNAL OF PHYSICAL CHEMISTRY B, 115 (24), pp. 7991–7995, 2011, ISSN: 1520-6106. @article{luo_determining_2011, title = {Determining the Conformational Change that Accompanies Donor-Acceptor Distance Fluctuations: An Umbrella Sampling Analysis}, author = {Luo, Guobin and Karplus, Martin}, doi = {10.1021/jp201998c}, issn = {1520-6106}, year = {2011}, date = {2011-06-01}, journal = {JOURNAL OF PHYSICAL CHEMISTRY B}, volume = {115}, number = {24}, pages = {7991--7995}, abstract = {The response of a protein to variation of a specific coordinate can provide insights into the role of the overall architecture in the structural change. Given that the calculated potential of mean force governing the fluctuation of an electron transfer donor-acceptor distance in the NAD(P)H:Flavin oxidoreductase (Fre)/FAD complex was shown to agree with experiment, an analysis of the structural response of the rest of the protein to that distance change was made. Significant displacements are found throughout much of the protein, and the coupling pathway resulting in the structural changes was determined. A covariance analysis based on the quasiharmonic modes of the unperturbed protein was used to provide information concerning how the residue motions are correlated. It is found that, of the three regions identified as moving together in an NMR study, two undergo significant structural changes when the electron donor acceptor distance is varied, and the third does not.}, keywords = {}, pubstate = {published}, tppubtype = {article} } The response of a protein to variation of a specific coordinate can provide insights into the role of the overall architecture in the structural change. Given that the calculated potential of mean force governing the fluctuation of an electron transfer donor-acceptor distance in the NAD(P)H:Flavin oxidoreductase (Fre)/FAD complex was shown to agree with experiment, an analysis of the structural response of the rest of the protein to that distance change was made. Significant displacements are found throughout much of the protein, and the coupling pathway resulting in the structural changes was determined. A covariance analysis based on the quasiharmonic modes of the unperturbed protein was used to provide information concerning how the residue motions are correlated. It is found that, of the three regions identified as moving together in an NMR study, two undergo significant structural changes when the electron donor acceptor distance is varied, and the third does not. |
Beermann, Jonas ; Sondergaard, Thomas ; Novikov, Sergey M; Bozhevolnyi, Sergey I; Devaux, Eloise ; Ebbesen, Thomas W Field enhancement and extraordinary optical transmission by tapered periodic slits in gold films Journal Article In: NEW JOURNAL OF PHYSICS, 13 , 2011, ISSN: 1367-2630. @article{beermann_field_2011, title = {Field enhancement and extraordinary optical transmission by tapered periodic slits in gold films}, author = {Beermann, Jonas and Sondergaard, Thomas and Novikov, Sergey M. and Bozhevolnyi, Sergey I. and Devaux, Eloise and Ebbesen, Thomas W.}, doi = {10.1088/1367-2630/13/6/063029}, issn = {1367-2630}, year = {2011}, date = {2011-06-01}, journal = {NEW JOURNAL OF PHYSICS}, volume = {13}, abstract = {We investigate field enhancements by one-dimensional periodic arrays of tapered slits fabricated to a high quality (nm precision) using focused ion beam milling in a 180 nm-thick gold film. Tapering of periodic slits in metal was recently shown to boost the extraordinary optical transmission (EOT) exhibited by similar, but non-tapered, plasmonic structures. Here, both simulated and experimental reflection spectra, along with high-resolution two-photon luminescence (TPL) scanning optical images and simulated electric field plots of the metal slits, are compared, revealing good correspondence between spectral dependences and field intensity enhancements (FEs) estimated via the local TPL. Experimentally investigated structures had a fixed taper angle alpha = 20.5 degrees for two different widths}, keywords = {}, pubstate = {published}, tppubtype = {article} } We investigate field enhancements by one-dimensional periodic arrays of tapered slits fabricated to a high quality (nm precision) using focused ion beam milling in a 180 nm-thick gold film. Tapering of periodic slits in metal was recently shown to boost the extraordinary optical transmission (EOT) exhibited by similar, but non-tapered, plasmonic structures. Here, both simulated and experimental reflection spectra, along with high-resolution two-photon luminescence (TPL) scanning optical images and simulated electric field plots of the metal slits, are compared, revealing good correspondence between spectral dependences and field intensity enhancements (FEs) estimated via the local TPL. Experimentally investigated structures had a fixed taper angle alpha = 20.5 degrees for two different widths |
Aouani, Heykel ; Mahboub, Oussama ; Devaux, Eloise ; Rigneault, Herve ; Ebbesen, Thomas W; Wenger, Jerome Plasmonic Antennas for Directional Sorting of Fluorescence Emission Journal Article In: NANO LETTERS, 11 (6), pp. 2400–2406, 2011, ISSN: 1530-6984. @article{aouani_plasmonic_2011, title = {Plasmonic Antennas for Directional Sorting of Fluorescence Emission}, author = {Aouani, Heykel and Mahboub, Oussama and Devaux, Eloise and Rigneault, Herve and Ebbesen, Thomas W. and Wenger, Jerome}, doi = {10.1021/nl200772d}, issn = {1530-6984}, year = {2011}, date = {2011-06-01}, journal = {NANO LETTERS}, volume = {11}, number = {6}, pages = {2400--2406}, abstract = {Spontaneous emission of fluorescent molecules or quantum dots is radiated along all directions when emitters are diluted in a liquid solution, which severely limits the amount of collected light. Besides, the emission direction does not carry any useful information and cannot be used to sort different molecules. To go beyond these limits, optical antennas have been recently introduced as conceptual tools to control the radiation properties for nanoemitters fixed on a substrate. Despite intense recent research, controlling the luminescence directivity remains a challenge for emitters with random positions and orientations, which is a key for several biomolecular screening applications. Here, we present full directional control of the fluorescence emission from molecules in water solution by an optical antenna made of a nanoaperture surrounded by a periodic set of shallow grooves in a gold film. For each emission wavelength, the fluorescence beam can be directed along a specific direction with a given angular width, hereby realizing a micrometer-size dispersive antenna. We demonstrate the fluorescence beaming results from an interference phenomenon and provide physical optics guidelines to control the fluorescence directivity by tuning the groove-nanoaperture distance. This photon-sorting capability provides a new approach for high-sensitivity screening of molecular species in solution.}, keywords = {}, pubstate = {published}, tppubtype = {article} } Spontaneous emission of fluorescent molecules or quantum dots is radiated along all directions when emitters are diluted in a liquid solution, which severely limits the amount of collected light. Besides, the emission direction does not carry any useful information and cannot be used to sort different molecules. To go beyond these limits, optical antennas have been recently introduced as conceptual tools to control the radiation properties for nanoemitters fixed on a substrate. Despite intense recent research, controlling the luminescence directivity remains a challenge for emitters with random positions and orientations, which is a key for several biomolecular screening applications. Here, we present full directional control of the fluorescence emission from molecules in water solution by an optical antenna made of a nanoaperture surrounded by a periodic set of shallow grooves in a gold film. For each emission wavelength, the fluorescence beam can be directed along a specific direction with a given angular width, hereby realizing a micrometer-size dispersive antenna. We demonstrate the fluorescence beaming results from an interference phenomenon and provide physical optics guidelines to control the fluorescence directivity by tuning the groove-nanoaperture distance. This photon-sorting capability provides a new approach for high-sensitivity screening of molecular species in solution. |
Bonini, Massimo ; Zalewski, Leszek ; Orgiu, Emanuele ; Breiner, Thomas ; Doetz, Florian ; Kastler, Marcel ; Samori, Paolo H-Bonding Tuned Self-Assembly of Phenylene-Thiophene-Thiophene-Phenylene Derivatives at Surfaces: Structural and Electrical Studies Journal Article In: JOURNAL OF PHYSICAL CHEMISTRY C, 115 (19), pp. 9753–9759, 2011, ISSN: 1932-7447. @article{bonini_h-bonding_2011, title = {H-Bonding Tuned Self-Assembly of Phenylene-Thiophene-Thiophene-Phenylene Derivatives at Surfaces: Structural and Electrical Studies}, author = {Bonini, Massimo and Zalewski, Leszek and Orgiu, Emanuele and Breiner, Thomas and Doetz, Florian and Kastler, Marcel and Samori, Paolo}, doi = {10.1021/jp201556y}, issn = {1932-7447}, year = {2011}, date = {2011-05-01}, journal = {JOURNAL OF PHYSICAL CHEMISTRY C}, volume = {115}, number = {19}, pages = {9753--9759}, abstract = {Several physicochemical properties of molecular ensembles can be modulated by controlling intermolecular interactions. The design and synthesis of pi-conjugated rodlike molecules exposing groups that can undergo H-bondings was exploited to develop materials featuring tunable 2D self-assembly at surfaces, thermal stability, order in micrometer-thick films, and electrical characteristics in organic field-effect transistors (OFETs). As a model system, we have chosen phenylene thiophene thiophene phenylene derivatives with side groups exposing either COOH or COOMe moieties. The structure and dynamics within monolayers at the solid-liquid interface was explored by in-situ scanning tunneling microscopy (STM) experiments. The thermal behavior of the materials was investigated by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). The order in micrometer-thick films was studied by grazing-incidence small-angle X-ray scattering (GISAXS), whereas the electrical characteristics of the different systems were studied when self-assembled in thin films in a bottom-gate and bottom-contact field-effect transistor.}, keywords = {}, pubstate = {published}, tppubtype = {article} } Several physicochemical properties of molecular ensembles can be modulated by controlling intermolecular interactions. The design and synthesis of pi-conjugated rodlike molecules exposing groups that can undergo H-bondings was exploited to develop materials featuring tunable 2D self-assembly at surfaces, thermal stability, order in micrometer-thick films, and electrical characteristics in organic field-effect transistors (OFETs). As a model system, we have chosen phenylene thiophene thiophene phenylene derivatives with side groups exposing either COOH or COOMe moieties. The structure and dynamics within monolayers at the solid-liquid interface was explored by in-situ scanning tunneling microscopy (STM) experiments. The thermal behavior of the materials was investigated by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). The order in micrometer-thick films was studied by grazing-incidence small-angle X-ray scattering (GISAXS), whereas the electrical characteristics of the different systems were studied when self-assembled in thin films in a bottom-gate and bottom-contact field-effect transistor. |
Voignier, Julie ; Frey, Julien ; Kraus, Tomas ; Budesinsky, Milos ; Cvacka, Josef ; Heitz, Valerie ; Sauvage, Jean-Pierre Transition-Metal-Complexed Cyclic [3]- and [4]Pseudorotaxanes Containing Rigid Ring-and-Filament Conjugates: Synthesis and Solution Studies Journal Article In: CHEMISTRY-A EUROPEAN JOURNAL, 17 (19), pp. 5404–5414, 2011, ISSN: 0947-6539. @article{voignier_transition-metal-complexed_2011, title = {Transition-Metal-Complexed Cyclic [3]- and [4]Pseudorotaxanes Containing Rigid Ring-and-Filament Conjugates: Synthesis and Solution Studies}, author = {Voignier, Julie and Frey, Julien and Kraus, Tomas and Budesinsky, Milos and Cvacka, Josef and Heitz, Valerie and Sauvage, Jean-Pierre}, doi = {10.1002/chem.201003592}, issn = {0947-6539}, year = {2011}, date = {2011-05-01}, journal = {CHEMISTRY-A EUROPEAN JOURNAL}, volume = {17}, number = {19}, pages = {5404--5414}, abstract = {By using the “gathering-and-threading” effect of copper(I) with rigid ring-and-string conjugates, daisy-chain-type [3]- and [4]pseudorotaxanes could be prepared in high yields. The organic fragment used consisted of a 2,9-diphenyl-1,10-phenanthroline (dpp)-containing ring attached to a coordinating filament capable of threading through the ring of another molecule by coordination to copper(I). The bidentate chelate introduced in the axis was also a 1,10-phenanthroline (phen) derivative with two methyl groups ortho to the nitrogen atoms of the phen unit. The organic component was prepared following a multistep strategy, one of the key steps being the attachment of the ring to the lateral axis. This connection was done by a condensation reaction between an ortho dione located at the back of a ring-incorporated phen and an aromatic aldehyde, which was the end-function of the thread. An oxazole nucleus was obtained after the condensation, which provided a rigid connection between the ring and the axis. In this way, the coordination axes of the ring-incorporated bidentate chelate and of the ligand belonging to the lateral filament were approximately orthogonal to one another. The design was such that the tetrameric complex, a [4]pseudorotaxane, seemed to be the most stable species, owing to the mutual geometrical arrangement of the filament and the ring. Various spectroscopic techniques, such as (1)H NMR spectroscopy, including DOSY, and electrospray ionization mass spectroscopy (ESI-MS), clearly demonstrated that a mixture of cyclic [3]- and [4]pseudorotaxane was obtained; the proportions of both components depended on concentration and temperature. Copper(I) was not the only metal center leading to the formation of cyclic pseudorotaxanes. A similar effect was observed with silver(I) as the templating metal: quantitative formation of threaded species was observed, with a higher proportion of trimer over tetramer than in the copper(I) case. Concentration and temperature effects were investigated for both series of Cu(I)- and Ag(I)-complexed threaded species showing that formation of the trimer was favored upon dilution or heating of the solution.}, keywords = {}, pubstate = {published}, tppubtype = {article} } By using the “gathering-and-threading” effect of copper(I) with rigid ring-and-string conjugates, daisy-chain-type [3]- and [4]pseudorotaxanes could be prepared in high yields. The organic fragment used consisted of a 2,9-diphenyl-1,10-phenanthroline (dpp)-containing ring attached to a coordinating filament capable of threading through the ring of another molecule by coordination to copper(I). The bidentate chelate introduced in the axis was also a 1,10-phenanthroline (phen) derivative with two methyl groups ortho to the nitrogen atoms of the phen unit. The organic component was prepared following a multistep strategy, one of the key steps being the attachment of the ring to the lateral axis. This connection was done by a condensation reaction between an ortho dione located at the back of a ring-incorporated phen and an aromatic aldehyde, which was the end-function of the thread. An oxazole nucleus was obtained after the condensation, which provided a rigid connection between the ring and the axis. In this way, the coordination axes of the ring-incorporated bidentate chelate and of the ligand belonging to the lateral filament were approximately orthogonal to one another. The design was such that the tetrameric complex, a [4]pseudorotaxane, seemed to be the most stable species, owing to the mutual geometrical arrangement of the filament and the ring. Various spectroscopic techniques, such as (1)H NMR spectroscopy, including DOSY, and electrospray ionization mass spectroscopy (ESI-MS), clearly demonstrated that a mixture of cyclic [3]- and [4]pseudorotaxane was obtained; the proportions of both components depended on concentration and temperature. Copper(I) was not the only metal center leading to the formation of cyclic pseudorotaxanes. A similar effect was observed with silver(I) as the templating metal: quantitative formation of threaded species was observed, with a higher proportion of trimer over tetramer than in the copper(I) case. Concentration and temperature effects were investigated for both series of Cu(I)- and Ag(I)-complexed threaded species showing that formation of the trimer was favored upon dilution or heating of the solution. |
Sauvage, Jean-Pierre ; Trolez, Yann ; Canevet, David ; Salle, Marc Intercalation of Tetrathiafulvalene between the Two Plates of a Copper(I)-Complexed [4]Rotaxane Journal Article In: EUROPEAN JOURNAL OF ORGANIC CHEMISTRY, (13), pp. 2413–2416, 2011, ISSN: 1434-193X. @article{sauvage_intercalation_2011, title = {Intercalation of Tetrathiafulvalene between the Two Plates of a Copper(I)-Complexed [4]Rotaxane}, author = {Sauvage, Jean-Pierre and Trolez, Yann and Canevet, David and Salle, Marc}, doi = {10.1002/ejoc.201100142}, issn = {1434-193X}, year = {2011}, date = {2011-05-01}, journal = {EUROPEAN JOURNAL OF ORGANIC CHEMISTRY}, number = {13}, pages = {2413--2416}, abstract = {The ability of a cyclic copper(I)-complexed [4]rotaxane to act as a receptor towards organic electron donors has been studied. In particular, tetrathiafulvalene (TTF), which is a flat and electron-rich molecule, forms a relatively stable complex with the rotaxane host. H-1 NMR spectroscopic measurements strongly suggest that the coordination mode involves intercalation of the TTF motif between the two electron-poor plates of the [4]rotaxane. By contrast, extended TTF (exTTF), which possesses pi-donating ability similar to that of TTF but which is a significantly bulkier molecule due to a concave structure, was not able to form any detectable complex. This observation tends to indicate that the recognition site of the [4]rotaxane receptor is rigid and can not adapt to thick substrates.}, keywords = {}, pubstate = {published}, tppubtype = {article} } The ability of a cyclic copper(I)-complexed [4]rotaxane to act as a receptor towards organic electron donors has been studied. In particular, tetrathiafulvalene (TTF), which is a flat and electron-rich molecule, forms a relatively stable complex with the rotaxane host. H-1 NMR spectroscopic measurements strongly suggest that the coordination mode involves intercalation of the TTF motif between the two electron-poor plates of the [4]rotaxane. By contrast, extended TTF (exTTF), which possesses pi-donating ability similar to that of TTF but which is a significantly bulkier molecule due to a concave structure, was not able to form any detectable complex. This observation tends to indicate that the recognition site of the [4]rotaxane receptor is rigid and can not adapt to thick substrates. |
Carretero-Palacios, S; Mahboub, O; Garcia-Vidal, F J; Martin-Moreno, L; Rodrigo, Sergio G; Genet, C; Ebbesen, T W Mechanisms for extraordinary optical transmission through bull's eye structures Journal Article In: OPTICS EXPRESS, 19 (11), pp. 10429–10442, 2011, ISSN: 1094-4087. @article{carretero-palacios_mechanisms_2011, title = {Mechanisms for extraordinary optical transmission through bull's eye structures}, author = {Carretero-Palacios, S. and Mahboub, O. and Garcia-Vidal, F. J. and Martin-Moreno, L. and Rodrigo, Sergio G. and Genet, C. and Ebbesen, T. W.}, doi = {10.1364/OE.19.010429}, issn = {1094-4087}, year = {2011}, date = {2011-05-01}, journal = {OPTICS EXPRESS}, volume = {19}, number = {11}, pages = {10429--10442}, abstract = {We analyze both experimentally and theoretically the physical mechanisms that determine the optical transmission through deep subwavelength bull's eye structures (concentric annular grooves surrounding a circular hole). Our analysis focus on the transmission resonance as a function of the distance between the central hole and its nearest groove. We find that, for that resonance, each groove behaves almost independently, acting as an optical cavity that couples to incident radiation, and reflecting the surface plasmons radiated by the other side of the same cavity. It is the constructive contribution at the central hole of these standing waves emitted by independent grooves which ends up enhancing transmission. Also for each groove the coupling and reflection coefficients for surface plasmons are incorporated into a phenomenological Huygens-Fresnel model that gathers the main mechanisms to enhance transmission. Additionally, it is shown that the system presents a collective resonance in the electric field that does not lead to resonant transmission, because the fields radiated by the grooves do not interfere constructively at the central hole. (C) 2011 Optical Society of America}, keywords = {}, pubstate = {published}, tppubtype = {article} } We analyze both experimentally and theoretically the physical mechanisms that determine the optical transmission through deep subwavelength bull's eye structures (concentric annular grooves surrounding a circular hole). Our analysis focus on the transmission resonance as a function of the distance between the central hole and its nearest groove. We find that, for that resonance, each groove behaves almost independently, acting as an optical cavity that couples to incident radiation, and reflecting the surface plasmons radiated by the other side of the same cavity. It is the constructive contribution at the central hole of these standing waves emitted by independent grooves which ends up enhancing transmission. Also for each groove the coupling and reflection coefficients for surface plasmons are incorporated into a phenomenological Huygens-Fresnel model that gathers the main mechanisms to enhance transmission. Additionally, it is shown that the system presents a collective resonance in the electric field that does not lead to resonant transmission, because the fields radiated by the grooves do not interfere constructively at the central hole. (C) 2011 Optical Society of America |
Schwartz, T; Hutchison, J A; Genet, C; Ebbesen, T W Reversible Switching of Ultrastrong Light-Molecule Coupling Journal Article In: PHYSICAL REVIEW LETTERS, 106 (19), 2011, ISSN: 0031-9007. @article{schwartz_reversible_2011, title = {Reversible Switching of Ultrastrong Light-Molecule Coupling}, author = {Schwartz, T. and Hutchison, J. A. and Genet, C. and Ebbesen, T. W.}, doi = {10.1103/PhysRevLett.106.196405}, issn = {0031-9007}, year = {2011}, date = {2011-05-01}, journal = {PHYSICAL REVIEW LETTERS}, volume = {106}, number = {19}, abstract = {We demonstrate that photochromic molecules enable switching from the weak- to ultrastrong-coupling regime reversibly, by using all-optical control. This switch is achieved by photochemically inducing conformational changes in the molecule. Remarkably, a Rabi splitting of 700 meV is measured at room temperature, corresponding to 32% of the molecular transition energy. A similar coupling strength is demonstrated in a plasmonic structure. Such systems present a unique combination of coupling strength and functional capacities.}, keywords = {}, pubstate = {published}, tppubtype = {article} } We demonstrate that photochromic molecules enable switching from the weak- to ultrastrong-coupling regime reversibly, by using all-optical control. This switch is achieved by photochemically inducing conformational changes in the molecule. Remarkably, a Rabi splitting of 700 meV is measured at room temperature, corresponding to 32% of the molecular transition energy. A similar coupling strength is demonstrated in a plasmonic structure. Such systems present a unique combination of coupling strength and functional capacities. |
Samori, Paolo ; Helman, Ana ; Biscarini, Fabio ; Cacialli, Franco Mastering Self-Organization of Functional Materials at Different Length Scale Journal Article In: ADVANCED FUNCTIONAL MATERIALS, 21 (7, SI), pp. 1210–1211, 2011, ISSN: 1616-301X. @article{samori_mastering_2011, title = {Mastering Self-Organization of Functional Materials at Different Length Scale}, author = {Samori, Paolo and Helman, Ana and Biscarini, Fabio and Cacialli, Franco}, doi = {10.1002/adfm.201100462}, issn = {1616-301X}, year = {2011}, date = {2011-04-01}, journal = {ADVANCED FUNCTIONAL MATERIALS}, volume = {21}, number = {7, SI}, pages = {1210--1211}, keywords = {}, pubstate = {published}, tppubtype = {article} } |
De Luca, Giovanna ; Pisula, Wojciech ; Credgington, Dan ; Treossi, Emanuele ; Fenwick, Oliver ; Lazzerini, Giovanni Mattia ; Dabirian, Reza ; Orgiu, Emanuele ; Liscio, Andrea ; Palermo, Vincenzo ; Muellen, Klaus ; Cacialli, Franco ; Samori, Paolo Non-conventional Processing and Post-processing Methods for the Nanostructuring of Conjugated Materials for Organic Electronics Journal Article In: ADVANCED FUNCTIONAL MATERIALS, 21 (7, SI), pp. 1279–1295, 2011, ISSN: 1616-301X. @article{de_luca_non-conventional_2011, title = {Non-conventional Processing and Post-processing Methods for the Nanostructuring of Conjugated Materials for Organic Electronics}, author = {De Luca, Giovanna and Pisula, Wojciech and Credgington, Dan and Treossi, Emanuele and Fenwick, Oliver and Lazzerini, Giovanni Mattia and Dabirian, Reza and Orgiu, Emanuele and Liscio, Andrea and Palermo, Vincenzo and Muellen, Klaus and Cacialli, Franco and Samori, Paolo}, doi = {10.1002/adfm.201001769}, issn = {1616-301X}, year = {2011}, date = {2011-04-01}, journal = {ADVANCED FUNCTIONAL MATERIALS}, volume = {21}, number = {7, SI}, pages = {1279--1295}, abstract = {In the search for new ways to combine the appealing simplicity of solution processing methods and the need for a high performance of the active layer of organic (opto)electronic devices, the possibilities given by the joint use of well-established casting techniques and post-treatment procedures are explored, as well as new and unconventional deposition protocols to tailor self-assembled architectures with a high degree of order at different length scales, from the subnanometer up to the macroscopic scale. In fact, even the same organic molecule can give rise to different molecular architectures which, in turn, may offer the possibility to exploit a large variety of new functionalities of the deposited materials, paving the way towards the fabrication multifunctional organic-based devices.}, keywords = {}, pubstate = {published}, tppubtype = {article} } In the search for new ways to combine the appealing simplicity of solution processing methods and the need for a high performance of the active layer of organic (opto)electronic devices, the possibilities given by the joint use of well-established casting techniques and post-treatment procedures are explored, as well as new and unconventional deposition protocols to tailor self-assembled architectures with a high degree of order at different length scales, from the subnanometer up to the macroscopic scale. In fact, even the same organic molecule can give rise to different molecular architectures which, in turn, may offer the possibility to exploit a large variety of new functionalities of the deposited materials, paving the way towards the fabrication multifunctional organic-based devices. |
Fischer, Stefan ; Olsen, Kenneth W; Nam, Kwangho ; Karplus, Martin Unsuspected pathway of the allosteric transition in hemoglobin Journal Article In: PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA, 108 (14), pp. 5608–5613, 2011, ISSN: 0027-8424. @article{fischer_unsuspected_2011, title = {Unsuspected pathway of the allosteric transition in hemoglobin}, author = {Fischer, Stefan and Olsen, Kenneth W. and Nam, Kwangho and Karplus, Martin}, doi = {10.1073/pnas.1011995108}, issn = {0027-8424}, year = {2011}, date = {2011-04-01}, journal = {PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA}, volume = {108}, number = {14}, pages = {5608--5613}, abstract = {Large conformational transitions play an essential role in the function of many proteins, but experiments do not provide the atomic details of the path followed in going from one end structure to the other. For the hemoglobin tetramer, the transition path between the unliganded (T) and tetraoxygenated (R) structures is not known, which limits our understanding of the cooperative mechanism in this classic allosteric system, where both tertiary and quaternary changes are involved. The conjugate peak refinement algorithm is used to compute an unbiased minimum energy path at atomic detail between the two end states. Although the results confirm some of the proposals of Perutz [Perutz MF (1970) Stereochemistry of cooperative effects in haemoglobin. Nature 228: 726-734], the subunit motions do not follow the textbook description of a simple rotation of one alpha beta-dimer relative to the other. Instead, the path consists of two sequential quaternary rotations, each involving different subdomains and axes. The quaternary transitions are preceded and followed by phases of tertiary structural changes. The results explain the recent photodissociation measurements, which suggest that the quaternary transition has a fast (2 mu s) as well as a slow (20 mu s) component and provide a testable model for single molecule FRET experiments.}, keywords = {}, pubstate = {published}, tppubtype = {article} } Large conformational transitions play an essential role in the function of many proteins, but experiments do not provide the atomic details of the path followed in going from one end structure to the other. For the hemoglobin tetramer, the transition path between the unliganded (T) and tetraoxygenated (R) structures is not known, which limits our understanding of the cooperative mechanism in this classic allosteric system, where both tertiary and quaternary changes are involved. The conjugate peak refinement algorithm is used to compute an unbiased minimum energy path at atomic detail between the two end states. Although the results confirm some of the proposals of Perutz [Perutz MF (1970) Stereochemistry of cooperative effects in haemoglobin. Nature 228: 726-734], the subunit motions do not follow the textbook description of a simple rotation of one alpha beta-dimer relative to the other. Instead, the path consists of two sequential quaternary rotations, each involving different subdomains and axes. The quaternary transitions are preceded and followed by phases of tertiary structural changes. The results explain the recent photodissociation measurements, which suggest that the quaternary transition has a fast (2 mu s) as well as a slow (20 mu s) component and provide a testable model for single molecule FRET experiments. |
Lehn, Jean-Marie Beyond synthesis: Self-organization Journal Article In: COMPTES RENDUS CHIMIE, 14 (4), pp. 348–361, 2011, ISSN: 1631-0748. @article{lehn_beyond_2011, title = {Beyond synthesis: Self-organization}, author = {Lehn, Jean-Marie}, doi = {10.1016/j.crci.2009.12.003}, issn = {1631-0748}, year = {2011}, date = {2011-04-01}, journal = {COMPTES RENDUS CHIMIE}, volume = {14}, number = {4}, pages = {348--361}, abstract = {The evolution of the universe from the particle to the thinking organism has taken place through self-organization. Chemistry has a major role to play in understanding these processes leading to the generation of complex matter. Chemistry has developed a highly powerful molecular synthetic chemistry, mastering the combination and recombination of atoms into increasingly complex molecules through selective chemical reactions. Supramolecular chemistry is harnessing intermolecular forces for the generation of informed supramolecular systems and processes through supramolecular synthetic chemistry implementing molecular information carried by electromagnetic interactions. Supramolecular chemistry has been actively exploring systems undergoing self-organization, i.e., systems capable of spontaneously generating well-defined functional supramolecular architectures by self-assembly from their components, under the control of interactional molecular recognition events, thus behaving as programmed chemical systems. Molecular chemistry may similarly take advantage of the selectivity of covalent reactions to assemble complex molecular architectures through self-organization processes implementing functional molecular recognition. Supramolecular/non-covalent and molecular/covalent SELF-ORGANIZATION may thus be considered as the ULTIMATE SYNTHETIC CHEMISTRY, whereby chemical objects at both levels are generated on the basis of recognition processes involving either interactional or reactional features. Illustrations from the supramolecular domain will serve as illustrations. Supramolecular entities as well as molecules containing reversible bonds are able to undergo a continuous change in constitution by reorganization and exchange of building blocks. This capability defines a Constitutional Dynamic Chemistry (CDC) on both the molecular and supramolecular levels. CDC introduces a paradigm shift with respect to constitutionally static chemistry. It takes advantage of dynamic constitutional diversity to allow variation and selection and thus leads towards the emergence of adaptive and evolutive chemistry. (C) 2009 Academie des sciences. Published by Elsevier Masson SAS. All rights reserved.}, keywords = {}, pubstate = {published}, tppubtype = {article} } The evolution of the universe from the particle to the thinking organism has taken place through self-organization. Chemistry has a major role to play in understanding these processes leading to the generation of complex matter. Chemistry has developed a highly powerful molecular synthetic chemistry, mastering the combination and recombination of atoms into increasingly complex molecules through selective chemical reactions. Supramolecular chemistry is harnessing intermolecular forces for the generation of informed supramolecular systems and processes through supramolecular synthetic chemistry implementing molecular information carried by electromagnetic interactions. Supramolecular chemistry has been actively exploring systems undergoing self-organization, i.e., systems capable of spontaneously generating well-defined functional supramolecular architectures by self-assembly from their components, under the control of interactional molecular recognition events, thus behaving as programmed chemical systems. Molecular chemistry may similarly take advantage of the selectivity of covalent reactions to assemble complex molecular architectures through self-organization processes implementing functional molecular recognition. Supramolecular/non-covalent and molecular/covalent SELF-ORGANIZATION may thus be considered as the ULTIMATE SYNTHETIC CHEMISTRY, whereby chemical objects at both levels are generated on the basis of recognition processes involving either interactional or reactional features. Illustrations from the supramolecular domain will serve as illustrations. Supramolecular entities as well as molecules containing reversible bonds are able to undergo a continuous change in constitution by reorganization and exchange of building blocks. This capability defines a Constitutional Dynamic Chemistry (CDC) on both the molecular and supramolecular levels. CDC introduces a paradigm shift with respect to constitutionally static chemistry. It takes advantage of dynamic constitutional diversity to allow variation and selection and thus leads towards the emergence of adaptive and evolutive chemistry. (C) 2009 Academie des sciences. Published by Elsevier Masson SAS. All rights reserved. |
Besenius, Pol ; van den Hout, Kelly P; Albers, Harald M H G; de Greef, Tom F A; Olijve, Luuk L C; Hermans, Thomas M; de Waal, Bas F M; Bomans, Paul H H; Sommerdijk, Nico A J M; Portale, Giuseppe ; Palmans, Anja R A; van Genderen, Marcel H P; Vekemans, Jef A J M; Meijer, E W Controlled Supramolecular Oligomerization of C-3-Symmetrical Molecules in Water: The Impact of Hydrophobic Shielding Journal Article In: CHEMISTRY-A EUROPEAN JOURNAL, 17 (18), pp. 5193–5203, 2011, ISSN: 0947-6539. @article{besenius_controlled_2011, title = {Controlled Supramolecular Oligomerization of C-3-Symmetrical Molecules in Water: The Impact of Hydrophobic Shielding}, author = {Besenius, Pol and van den Hout, Kelly P. and Albers, Harald M. H. G. and de Greef, Tom F. A. and Olijve, Luuk L. C. and Hermans, Thomas M. and de Waal, Bas F. M. and Bomans, Paul H. H. and Sommerdijk, Nico A. J. M. and Portale, Giuseppe and Palmans, Anja R. A. and van Genderen, Marcel H. P. and Vekemans, Jef A. J. M. and Meijer, E. W.}, doi = {10.1002/chem.201002976}, issn = {0947-6539}, year = {2011}, date = {2011-04-01}, journal = {CHEMISTRY-A EUROPEAN JOURNAL}, volume = {17}, number = {18}, pages = {5193--5203}, keywords = {}, pubstate = {published}, tppubtype = {article} } |
Woronoff, Gabrielle ; El Harrak, Abdeslam ; Mayot, Estelle ; Schicke, Olivier ; Miller, Oliver J; Soumillion, Patrice ; Griffiths, Andrew D; Ryckelynck, Michael New generation of amino coumarin methyl sulfonate-based fluorogenic substrates for amidase assays in droplet-based microfluidic applications Journal Article In: Analytical Chemistry, 83 (8), pp. 2852–2857, 2011, ISSN: 1520-6882. @article{woronoff_new_2011, title = {New generation of amino coumarin methyl sulfonate-based fluorogenic substrates for amidase assays in droplet-based microfluidic applications}, author = {Woronoff, Gabrielle and El Harrak, Abdeslam and Mayot, Estelle and Schicke, Olivier and Miller, Oliver J. and Soumillion, Patrice and Griffiths, Andrew D. and Ryckelynck, Michael}, doi = {10.1021/ac200373n}, issn = {1520-6882}, year = {2011}, date = {2011-04-01}, journal = {Analytical Chemistry}, volume = {83}, number = {8}, pages = {2852--2857}, abstract = {Droplet-based microfluidics is a powerful tool for biology and chemistry as it allows the production and the manipulation of picoliter-size droplets acting as individual reactors. In this format, high-sensitivity assays are typically based on fluorescence, so fluorophore exchange between droplets must be avoided. Fluorogenic substrates based on the coumarin leaving group are widely used to measure a variety of enzymatic activities, but their application in droplet-based microfluidic systems is severely impaired by the fast transport of the fluorescent product between compartments. Here we report the synthesis of new amidase fluorogenic substrates based on 7-aminocoumarin-4-methanesulfonic acid (ACMS), a highly water-soluble dye, and their suitability for droplet-based microfluidics applications. Both substrate and product had the required spectral characteristics and remained confined in droplets from hours to days. As a model experiment, a phenylacetylated ACMS was synthesized and used as a fluorogenic substrate of Escherichia coli penicillin G acylase. Kinetic parameters (k(cat) and K(M)) measured in bulk and in droplets on-chip were very similar, demonstrating the suitability of this synthesis strategy to produce a variety of ACMS-based substrates for assaying amidase activities both in microtiter plate and droplet-based microfluidic formats.}, keywords = {}, pubstate = {published}, tppubtype = {article} } Droplet-based microfluidics is a powerful tool for biology and chemistry as it allows the production and the manipulation of picoliter-size droplets acting as individual reactors. In this format, high-sensitivity assays are typically based on fluorescence, so fluorophore exchange between droplets must be avoided. Fluorogenic substrates based on the coumarin leaving group are widely used to measure a variety of enzymatic activities, but their application in droplet-based microfluidic systems is severely impaired by the fast transport of the fluorescent product between compartments. Here we report the synthesis of new amidase fluorogenic substrates based on 7-aminocoumarin-4-methanesulfonic acid (ACMS), a highly water-soluble dye, and their suitability for droplet-based microfluidics applications. Both substrate and product had the required spectral characteristics and remained confined in droplets from hours to days. As a model experiment, a phenylacetylated ACMS was synthesized and used as a fluorogenic substrate of Escherichia coli penicillin G acylase. Kinetic parameters (k(cat) and K(M)) measured in bulk and in droplets on-chip were very similar, demonstrating the suitability of this synthesis strategy to produce a variety of ACMS-based substrates for assaying amidase activities both in microtiter plate and droplet-based microfluidic formats. |
Crivillers, Nuria ; Orgiu, Emanuele ; Reinders, Federica ; Mayor, Marcel ; Samori, Paolo Optical Modulation of the Charge Injection in an Organic Field-Effect Transistor Based on Photochromic Self-Assembled-Monolayer-Functionalized Electrodes Journal Article In: ADVANCED MATERIALS, 23 (12), pp. 1447–1452, 2011, ISSN: 0935-9648. @article{crivillers_optical_2011, title = {Optical Modulation of the Charge Injection in an Organic Field-Effect Transistor Based on Photochromic Self-Assembled-Monolayer-Functionalized Electrodes}, author = {Crivillers, Nuria and Orgiu, Emanuele and Reinders, Federica and Mayor, Marcel and Samori, Paolo}, doi = {10.1002/adma.201003736}, issn = {0935-9648}, year = {2011}, date = {2011-03-01}, journal = {ADVANCED MATERIALS}, volume = {23}, number = {12}, pages = {1447--1452}, keywords = {}, pubstate = {published}, tppubtype = {article} } |
Zalewski, Leszek ; Brovelli, Sergio ; Bonini, Massimo ; Mativetsky, Jeffrey M; Wykes, Michael ; Orgiu, Emanuele ; Breiner, Thomas ; Kastler, Marcel ; Doetz, Florian ; Meinardi, Francesco ; Anderson, Harry L; Beljonne, David ; Cacialli, Franco ; Samori, Paolo Self-Assembled Conjugated Thiophene-Based Rotaxane Architectures: Structural, Computational, and Spectroscopic Insights into Molecular Aggregation Journal Article In: ADVANCED FUNCTIONAL MATERIALS, 21 (5), pp. 834–844, 2011, ISSN: 1616-301X. @article{zalewski_self-assembled_2011, title = {Self-Assembled Conjugated Thiophene-Based Rotaxane Architectures: Structural, Computational, and Spectroscopic Insights into Molecular Aggregation}, author = {Zalewski, Leszek and Brovelli, Sergio and Bonini, Massimo and Mativetsky, Jeffrey M. and Wykes, Michael and Orgiu, Emanuele and Breiner, Thomas and Kastler, Marcel and Doetz, Florian and Meinardi, Francesco and Anderson, Harry L. and Beljonne, David and Cacialli, Franco and Samori, Paolo}, doi = {10.1002/adfm.201001135}, issn = {1616-301X}, year = {2011}, date = {2011-03-01}, journal = {ADVANCED FUNCTIONAL MATERIALS}, volume = {21}, number = {5}, pages = {834--844}, abstract = {A comparative study of the self-assembly at a variety of surfaces of a dithiophene rotaxane 1 subset of beta-CD and its corresponding dumbbell, 1, by means of atomic force microscopy (AFM) imaging and scanning tunneling microscopy (STM) imaging on the micrometer and nanometer scale, respectively. The dumbbell is found to have a greater propensity to form ordered supramolecular assemblies, as a result of pi-pi interactions between dithiophenes belonging to adjacent molecules, which are hindered in the rotaxane. The fine molecular structure determined by STM was compared to that obtained by molecular modelling. The optical properties of both rotaxane and dumbbell in the solid state were investigated by steady-state and time-resolved photoluminescence (PL) experiments on spin-cast films and diluted solutions. The comparison between the optical features of the threaded and unthreaded systems reveals an effective role of encapsulation in reducing aggregation and exciton migration for the rotaxanes with respect to the dumbbells, thus leading to higher PL quantum efficiency and preserved single-molecule photophysics for longer times after excitation in the threaded oligomers.}, keywords = {}, pubstate = {published}, tppubtype = {article} } A comparative study of the self-assembly at a variety of surfaces of a dithiophene rotaxane 1 subset of beta-CD and its corresponding dumbbell, 1, by means of atomic force microscopy (AFM) imaging and scanning tunneling microscopy (STM) imaging on the micrometer and nanometer scale, respectively. The dumbbell is found to have a greater propensity to form ordered supramolecular assemblies, as a result of pi-pi interactions between dithiophenes belonging to adjacent molecules, which are hindered in the rotaxane. The fine molecular structure determined by STM was compared to that obtained by molecular modelling. The optical properties of both rotaxane and dumbbell in the solid state were investigated by steady-state and time-resolved photoluminescence (PL) experiments on spin-cast films and diluted solutions. The comparison between the optical features of the threaded and unthreaded systems reveals an effective role of encapsulation in reducing aggregation and exciton migration for the rotaxanes with respect to the dumbbells, thus leading to higher PL quantum efficiency and preserved single-molecule photophysics for longer times after excitation in the threaded oligomers. |
Liscio, Andrea ; Palermo, Vincenzo ; Fenwick, Oliver ; Braun, Slawomir ; Muellen, Klaus ; Fahlman, Mats ; Cacialli, Franco ; Samori, Paolo Local Surface Potential of pi-Conjugated Nanostructures by Kelvin Probe Force Microscopy: Effect of the Sampling Depth Journal Article In: SMALL, 7 (5), pp. 634–639, 2011, ISSN: 1613-6810. @article{liscio_local_2011, title = {Local Surface Potential of pi-Conjugated Nanostructures by Kelvin Probe Force Microscopy: Effect of the Sampling Depth}, author = {Liscio, Andrea and Palermo, Vincenzo and Fenwick, Oliver and Braun, Slawomir and Muellen, Klaus and Fahlman, Mats and Cacialli, Franco and Samori, Paolo}, doi = {10.1002/smll.201001770}, issn = {1613-6810}, year = {2011}, date = {2011-03-01}, journal = {SMALL}, volume = {7}, number = {5}, pages = {634--639}, abstract = {Kelvin probe force microscopy (KPFM) is usually applied to map the local surface potential of nanostructured materials at surfaces and interfaces. KPFM is commonly defined as a `surface technique', even if this assumption is not fully justified. However, a quantification of the surface sensitivity of this technique is crucial to explore electrical properties at the nanoscale. Here a versatile 3D model is presented which provides a quantitative explanation of KPFM results, taking into account the vertical structure of the sample. The model is tested on nanostructured films obtained from two relevant semiconducting systems for field-effect transistor and solar cell applications showing different interfacial properties, i.e., poly(3-hexylthiophene) (P3HT) and perylene-bis-dicarboximide (PDI). These findings are especially important since they enable quantitative determination of the local surface potential of conjugated nanostructures, and thereby pave the way towards optimization of the electronic properties of nanoscale architectures for organic electronic applications.}, keywords = {}, pubstate = {published}, tppubtype = {article} } Kelvin probe force microscopy (KPFM) is usually applied to map the local surface potential of nanostructured materials at surfaces and interfaces. KPFM is commonly defined as a `surface technique', even if this assumption is not fully justified. However, a quantification of the surface sensitivity of this technique is crucial to explore electrical properties at the nanoscale. Here a versatile 3D model is presented which provides a quantitative explanation of KPFM results, taking into account the vertical structure of the sample. The model is tested on nanostructured films obtained from two relevant semiconducting systems for field-effect transistor and solar cell applications showing different interfacial properties, i.e., poly(3-hexylthiophene) (P3HT) and perylene-bis-dicarboximide (PDI). These findings are especially important since they enable quantitative determination of the local surface potential of conjugated nanostructures, and thereby pave the way towards optimization of the electronic properties of nanoscale architectures for organic electronic applications. |
Aprahamian, Marc ; Bour, Gaetan ; Akladios, Cherif Y; Fylaktakidou, Konstantina ; Greferath, Ruth ; Soler, Luc ; Marescaux, Jacques ; Egly, Jean-Marc ; Lehn, Jean-Marie ; Nicolau, Claude Myo-InositolTrisPyroPhosphate Treatment Leads to HIF-1 alpha Suppression and Eradication of Early Hepatoma Tumors in Rats Journal Article In: CHEMBIOCHEM, 12 (5), pp. 777–783, 2011, ISSN: 1439-4227. @article{aprahamian_myo-inositoltrispyrophosphate_2011, title = {Myo-InositolTrisPyroPhosphate Treatment Leads to HIF-1 alpha Suppression and Eradication of Early Hepatoma Tumors in Rats}, author = {Aprahamian, Marc and Bour, Gaetan and Akladios, Cherif Y. and Fylaktakidou, Konstantina and Greferath, Ruth and Soler, Luc and Marescaux, Jacques and Egly, Jean-Marc and Lehn, Jean-Marie and Nicolau, Claude}, doi = {10.1002/cbic.201000619}, issn = {1439-4227}, year = {2011}, date = {2011-03-01}, journal = {CHEMBIOCHEM}, volume = {12}, number = {5}, pages = {777--783}, abstract = {Myo-inositol trispyrophosphate (ITPP), a synthetic allosteric effector of hemoglobin, increases the regulated oxygen-releasing capacity of red blood cells (RBCs), leading to suppression of hypoxia-inducible factor 1 alpha (HIF-1 alpha) and to down-regulation of hypoxia-inducible genes such as vascular endothelial growth factor (VEGF). As a consequence, tumor growth is markedly affected. The effect of weekly intravenous injection of ITPP on an orthotopic, syngenic rat hepatocellular carcinoma (HCC) model was compared to that for untreated animals and animals subjected to conventional Doxorubicin chemotherapy. The longitudinal examination of HCC was performed by microCT imaging, and the cellular and molecular changes were evaluated by histology and Western blotting analysis of HIF-1 alpha, VEGF, and caspase-3 gene expression in the tumor and in the surrounding liver. Hematologic impact was evaluated by blood cell-count measurement and determination of P50 (oxygen partial pressure for a 50% oxygen saturation of hemoglobin). The HCC evaluation by microCT revealed a high potency of ITPP for tumor growth inhibition, thus allowing long-term survival and even cure of almost all the treated animals. The P50 value of hemoglobin in RBCs underwent a shift of 30% following ITPP injection. Under these conditions, HIF-1 alpha activity was strongly decreased, VEGF expression was down-regulated, and apoptosis was induced in HCC and surrounding liver cells, as indicated by Caspase-3 expression. ITPP did not affect hematologic parameters during treatment. The observations of in vivo tumor eradication suggest a significant clinical potential for ITPP in cancer therapy.}, keywords = {}, pubstate = {published}, tppubtype = {article} } Myo-inositol trispyrophosphate (ITPP), a synthetic allosteric effector of hemoglobin, increases the regulated oxygen-releasing capacity of red blood cells (RBCs), leading to suppression of hypoxia-inducible factor 1 alpha (HIF-1 alpha) and to down-regulation of hypoxia-inducible genes such as vascular endothelial growth factor (VEGF). As a consequence, tumor growth is markedly affected. The effect of weekly intravenous injection of ITPP on an orthotopic, syngenic rat hepatocellular carcinoma (HCC) model was compared to that for untreated animals and animals subjected to conventional Doxorubicin chemotherapy. The longitudinal examination of HCC was performed by microCT imaging, and the cellular and molecular changes were evaluated by histology and Western blotting analysis of HIF-1 alpha, VEGF, and caspase-3 gene expression in the tumor and in the surrounding liver. Hematologic impact was evaluated by blood cell-count measurement and determination of P50 (oxygen partial pressure for a 50% oxygen saturation of hemoglobin). The HCC evaluation by microCT revealed a high potency of ITPP for tumor growth inhibition, thus allowing long-term survival and even cure of almost all the treated animals. The P50 value of hemoglobin in RBCs underwent a shift of 30% following ITPP injection. Under these conditions, HIF-1 alpha activity was strongly decreased, VEGF expression was down-regulated, and apoptosis was induced in HCC and surrounding liver cells, as indicated by Caspase-3 expression. ITPP did not affect hematologic parameters during treatment. The observations of in vivo tumor eradication suggest a significant clinical potential for ITPP in cancer therapy. |
Leproult, Emeline ; Barluenga, Sofia ; Moras, Dino ; Wurtz, Jean-Marie ; Winssinger, Nicolas Cysteine Mapping in Conformationally Distinct Kinase Nucleotide Binding Sites: Application to the Design of Selective Covalent Inhibitors Journal Article In: JOURNAL OF MEDICINAL CHEMISTRY, 54 (5), pp. 1347–1355, 2011, ISSN: 0022-2623. @article{leproult_cysteine_2011, title = {Cysteine Mapping in Conformationally Distinct Kinase Nucleotide Binding Sites: Application to the Design of Selective Covalent Inhibitors}, author = {Leproult, Emeline and Barluenga, Sofia and Moras, Dino and Wurtz, Jean-Marie and Winssinger, Nicolas}, doi = {10.1021/jm101396q}, issn = {0022-2623}, year = {2011}, date = {2011-03-01}, journal = {JOURNAL OF MEDICINAL CHEMISTRY}, volume = {54}, number = {5}, pages = {1347--1355}, abstract = {Kinases have emerged as one of the most prolific therapeutic targets. An important criterion in the therapeutic success of inhibitors targeting the nucleotide binding pocket of kinases is the inhibitor residence time. Recently, covalent kinase inhibitors have attracted attention since they confer terminal inhibition and should thus be more effective than reversible inhibitors with transient inhibition. The most robust approach to design irreversible inhibitors is to capitalize on the nucleophilicity of a cysteine thiol group present in the target protein. Herein, we report a systematic analysis of cysteine residues present in the nucleotide binding site of kinases, which could be harnessed for irreversible inhibition, taking into consideration the different kinase conformations. We demonstrate the predictive power of this analysis with the design and validation of an irreversible inhibitor of KIT/PDGFR kinases. This is the first example of a covalent kinase inhibitor that combines a pharmacophore addressing the DFG-out conformation with a covalent trap.}, keywords = {}, pubstate = {published}, tppubtype = {article} } Kinases have emerged as one of the most prolific therapeutic targets. An important criterion in the therapeutic success of inhibitors targeting the nucleotide binding pocket of kinases is the inhibitor residence time. Recently, covalent kinase inhibitors have attracted attention since they confer terminal inhibition and should thus be more effective than reversible inhibitors with transient inhibition. The most robust approach to design irreversible inhibitors is to capitalize on the nucleophilicity of a cysteine thiol group present in the target protein. Herein, we report a systematic analysis of cysteine residues present in the nucleotide binding site of kinases, which could be harnessed for irreversible inhibition, taking into consideration the different kinase conformations. We demonstrate the predictive power of this analysis with the design and validation of an irreversible inhibitor of KIT/PDGFR kinases. This is the first example of a covalent kinase inhibitor that combines a pharmacophore addressing the DFG-out conformation with a covalent trap. |
Ciesielski, Artur ; Stefankiewicz, Artur R; Hanke, Felix ; Persson, Mats ; Lehn, Jean-Marie ; Samori, Paolo Rigid Dimers Formed through Strong Interdigitated Ħ-Bonds Yield Compact 1D Supramolecular Helical Polymers Journal Article In: SMALL, 7 (3), pp. 342–350, 2011, ISSN: 1613-6810. @article{ciesielski_rigid_2011, title = {Rigid Dimers Formed through Strong Interdigitated Ħ-Bonds Yield Compact 1D Supramolecular Helical Polymers}, author = {Ciesielski, Artur and Stefankiewicz, Artur R. and Hanke, Felix and Persson, Mats and Lehn, Jean-Marie and Samori, Paolo}, doi = {10.1002/smll.201001419}, issn = {1613-6810}, year = {2011}, date = {2011-02-01}, journal = {SMALL}, volume = {7}, number = {3}, pages = {342--350}, abstract = {Hierarchical self-assembly of small abiotic molecular modules interacting through noncovalent forces is increasingly being used to generate functional structures and materials for electronic, catalytic, and biomedical applications. The greatest control over the geometry in H-bond supramolecular architectures, especially in H-bonded supramolecular polymers, can be achieved by using conformationally rigid molecular modules undergoing self-assembly through strong H-bonds. Their binding strength depends on the multiplicity of the H-bonds, the nature of donor/acceptor pairs and their secondary attractive/repulsive interactions. Here a functionalized molecular module is described, which is capable of self-associating through self-complementary H-bonding patterns comprising four strong and two medium-strength H-bonds to form dimers. The self-association of these phenylpyrimidine-based dimers through directional H-bonding between two lateral pyridin-2(1H)-one units of neighboring molecules allows the formation of highly compact 1D supramolecular polymers by self-assembly on graphite. A concentration-dependent study by scanning tunneling microscopy at the solid-liquid interface, corroborated by dispersion-corrected density functional studies, reveals the controlled generation of either linear supramolecular 2D arrays, or long helical supramolecular polymers with a high shape persistence.}, keywords = {}, pubstate = {published}, tppubtype = {article} } Hierarchical self-assembly of small abiotic molecular modules interacting through noncovalent forces is increasingly being used to generate functional structures and materials for electronic, catalytic, and biomedical applications. The greatest control over the geometry in H-bond supramolecular architectures, especially in H-bonded supramolecular polymers, can be achieved by using conformationally rigid molecular modules undergoing self-assembly through strong H-bonds. Their binding strength depends on the multiplicity of the H-bonds, the nature of donor/acceptor pairs and their secondary attractive/repulsive interactions. Here a functionalized molecular module is described, which is capable of self-associating through self-complementary H-bonding patterns comprising four strong and two medium-strength H-bonds to form dimers. The self-association of these phenylpyrimidine-based dimers through directional H-bonding between two lateral pyridin-2(1H)-one units of neighboring molecules allows the formation of highly compact 1D supramolecular polymers by self-assembly on graphite. A concentration-dependent study by scanning tunneling microscopy at the solid-liquid interface, corroborated by dispersion-corrected density functional studies, reveals the controlled generation of either linear supramolecular 2D arrays, or long helical supramolecular polymers with a high shape persistence. |
Ovchinnikov, Victor ; Karplus, Martin ; Vanden-Eijnden, Eric Free energy of conformational transition paths in biomolecules: The string method and its application to myosin VI Journal Article In: JOURNAL OF CHEMICAL PHYSICS, 134 (8), 2011, ISSN: 0021-9606. @article{ovchinnikov_free_2011, title = {Free energy of conformational transition paths in biomolecules: The string method and its application to myosin VI}, author = {Ovchinnikov, Victor and Karplus, Martin and Vanden-Eijnden, Eric}, doi = {10.1063/1.3544209}, issn = {0021-9606}, year = {2011}, date = {2011-02-01}, journal = {JOURNAL OF CHEMICAL PHYSICS}, volume = {134}, number = {8}, abstract = {A set of techniques developed under the umbrella of the string method is used in combination with all-atom molecular dynamics simulations to analyze the conformation change between the prepower-stroke (PPS) and rigor (R) structures of the converter domain of myosin VI. The challenges specific to the application of these techniques to such a large and complex biomolecule are addressed in detail. These challenges include (i) identifying a proper set of collective variables to apply the string method, (ii) finding a suitable initial string, (iii) obtaining converged profiles of the free energy along the transition path, (iv) validating and interpreting the free energy profiles, and (v) computing the mean first passage time of the transition. A detailed description of the PPS. R transition in the converter domain of myosin VI is obtained, including the transition path, the free energy along the path, and the rates of interconversion. The methodology developed here is expected to be useful more generally in studies of conformational transitions in complex biomolecules. (C) 2011 American Institute of Physics. [doi:10.1063/1.3544209]}, keywords = {}, pubstate = {published}, tppubtype = {article} } A set of techniques developed under the umbrella of the string method is used in combination with all-atom molecular dynamics simulations to analyze the conformation change between the prepower-stroke (PPS) and rigor (R) structures of the converter domain of myosin VI. The challenges specific to the application of these techniques to such a large and complex biomolecule are addressed in detail. These challenges include (i) identifying a proper set of collective variables to apply the string method, (ii) finding a suitable initial string, (iii) obtaining converged profiles of the free energy along the transition path, (iv) validating and interpreting the free energy profiles, and (v) computing the mean first passage time of the transition. A detailed description of the PPS. R transition in the converter domain of myosin VI is obtained, including the transition path, the free energy along the path, and the rates of interconversion. The methodology developed here is expected to be useful more generally in studies of conformational transitions in complex biomolecules. (C) 2011 American Institute of Physics. [doi:10.1063/1.3544209] |
Buchs (nee Levrand), Barbara ; Godin, Guillaume ; Trachsel, Alain ; de Saint Laumer, Jean-Yves ; Lehn, Jean-Marie ; Herrmann, Andreas Reversible Aminal Formation: Controlling the Evaporation of Bioactive Volatiles by Dynamic Combinatorial/Covalent Chemistry Journal Article In: EUROPEAN JOURNAL OF ORGANIC CHEMISTRY, (4), pp. 681–695, 2011, ISSN: 1434-193X. @article{buchs_nee_levrand_reversible_2011, title = {Reversible Aminal Formation: Controlling the Evaporation of Bioactive Volatiles by Dynamic Combinatorial/Covalent Chemistry}, author = {Buchs (nee Levrand), Barbara and Godin, Guillaume and Trachsel, Alain and de Saint Laumer, Jean-Yves and Lehn, Jean-Marie and Herrmann, Andreas}, doi = {10.1002/ejoc.201001433}, issn = {1434-193X}, year = {2011}, date = {2011-02-01}, journal = {EUROPEAN JOURNAL OF ORGANIC CHEMISTRY}, number = {4}, pages = {681--695}, abstract = {Dynamic mixtures generated by reversible aminal formation efficiently prolong the duration of evaporation of bioactive volatile aldehydes. Secondary diamines used for the generation of dynamic mixtures are obtained by treatment of primary diamines with carbonyl compounds and reduction of the diimines with NaBH(4). The reversibilities of the reactions were demonstrated by NMR measurements in buffered aqueous solutions. Kinetic rate constants and equilibrium constants for the formation and hydrolysis of aminals were determined. The performance of dynamic mixtures as delivery systems for perfumery ingredients was tested after deposition onto cotton, and the long-lastingness of fragrance evaporation was investigated by dynamic headspace analysis against a reference sample. The simplicity of the concept together with its excellent performance makes this delivery system highly interesting for applied perfumery. Reversible aminal formation might also be successfully applicable to dynamic combinatorial/covalent chemistry for screening of pharmaceutically or catalytically active ligands and receptors.}, keywords = {}, pubstate = {published}, tppubtype = {article} } Dynamic mixtures generated by reversible aminal formation efficiently prolong the duration of evaporation of bioactive volatile aldehydes. Secondary diamines used for the generation of dynamic mixtures are obtained by treatment of primary diamines with carbonyl compounds and reduction of the diimines with NaBH(4). The reversibilities of the reactions were demonstrated by NMR measurements in buffered aqueous solutions. Kinetic rate constants and equilibrium constants for the formation and hydrolysis of aminals were determined. The performance of dynamic mixtures as delivery systems for perfumery ingredients was tested after deposition onto cotton, and the long-lastingness of fragrance evaporation was investigated by dynamic headspace analysis against a reference sample. The simplicity of the concept together with its excellent performance makes this delivery system highly interesting for applied perfumery. Reversible aminal formation might also be successfully applicable to dynamic combinatorial/covalent chemistry for screening of pharmaceutically or catalytically active ligands and receptors. |
Smith, Thierry ; Dupuis, Christian ; Folie, Annelise ; Quesnel, Florence ; Storme, Jean-Yves ; Iacumin, Paola ; Riveline, Janine ; Missiaen, Pieter ; Ladeveze, Sandrine ; Yans, Johan A new terrestrial vertebrate site just after the Paleocene-Eocene boundary in the Mortemer Formation of Upper Normandy, France Journal Article In: COMPTES RENDUS PALEVOL, 10 (1), pp. 11–20, 2011, ISSN: 1631-0683. @article{smith_new_2011, title = {A new terrestrial vertebrate site just after the Paleocene-Eocene boundary in the Mortemer Formation of Upper Normandy, France}, author = {Smith, Thierry and Dupuis, Christian and Folie, Annelise and Quesnel, Florence and Storme, Jean-Yves and Iacumin, Paola and Riveline, Janine and Missiaen, Pieter and Ladeveze, Sandrine and Yans, Johan}, doi = {10.1016/j.crpv.2010.11.004}, issn = {1631-0683}, year = {2011}, date = {2011-02-01}, journal = {COMPTES RENDUS PALEVOL}, volume = {10}, number = {1}, pages = {11--20}, abstract = {European terrestrial vertebrate sites of the Upper Paleocene-Lower Eocene deposits are predominantly known from the central and eastern parts of the Paris Basin. However, several outcrops covering this interval are scattered along the Upper Normandy coast, in the western part of the Paris Basin. Here we report the discovery of a new terrestrial vertebrate site in the Mortemer Formation, at the top of the cliffs of Sotteville-sur-Mer in Upper Normandy, France. The vertebrate level is situated about 1.5 m above the onset of the Paleocene Eocene Carbon Isotope Excursion (CIE) based on dispersed organic carbon and is therefore Earliest Eocene in age. The vertebrate fauna is composed of fish, amphibians, lizards and mammals, including the earliest peradectid marsupials and paromomyid plesiadapiform of Europe. A diverse and rich charophyte flora is well represented throughout the lower part of the outcrop and allows the conclusion that the CIE falls in the Peckichara disermas biozone. (C) 2010 Academie des sciences. Published by Elsevier Masson SAS. All rights reserved.}, keywords = {}, pubstate = {published}, tppubtype = {article} } European terrestrial vertebrate sites of the Upper Paleocene-Lower Eocene deposits are predominantly known from the central and eastern parts of the Paris Basin. However, several outcrops covering this interval are scattered along the Upper Normandy coast, in the western part of the Paris Basin. Here we report the discovery of a new terrestrial vertebrate site in the Mortemer Formation, at the top of the cliffs of Sotteville-sur-Mer in Upper Normandy, France. The vertebrate level is situated about 1.5 m above the onset of the Paleocene Eocene Carbon Isotope Excursion (CIE) based on dispersed organic carbon and is therefore Earliest Eocene in age. The vertebrate fauna is composed of fish, amphibians, lizards and mammals, including the earliest peradectid marsupials and paromomyid plesiadapiform of Europe. A diverse and rich charophyte flora is well represented throughout the lower part of the outcrop and allows the conclusion that the CIE falls in the Peckichara disermas biozone. (C) 2010 Academie des sciences. Published by Elsevier Masson SAS. All rights reserved. |
Briggs, Breeze N; Durola, Fabien ; McMillin, David R; Sauvage, Jean-Pierre Luminescence studies of copper(I)-containing [2]pseudorotaxanes Journal Article In: CANADIAN JOURNAL OF CHEMISTRY, 89 (2), pp. 98–103, 2011, ISSN: 0008-4042. @article{briggs_luminescence_2011, title = {Luminescence studies of copper(I)-containing [2]pseudorotaxanes}, author = {Briggs, Breeze N. and Durola, Fabien and McMillin, David R. and Sauvage, Jean-Pierre}, doi = {10.1139/V10-093}, issn = {0008-4042}, year = {2011}, date = {2011-02-01}, journal = {CANADIAN JOURNAL OF CHEMISTRY}, volume = {89}, number = {2}, pages = {98--103}, abstract = {This report describes photoluminescence studies of copper-containing [2]pseudorotaxanes that mimic elements of functioning molecular machines. Excitation with visible light induces a formal oxidation of the metal center and simulates an actuation process. In all four [2] pseudorotaxanes studied, the ring ligand is the same, but the thread ligand is variable, namely 2,9-di(anisol-4-yl)-1,10-phenanthroline (dap), 6,6'-di(anisol-4-yl)-2,2'-bipyridine (o-dabipy), 5,5'-di(anisol-4-yl)-2,2'-bipyridine (m-dabipy), or 8,8'-di(anisol-4-yl)-3,3'-bi-isoquinoline (dabiiq). The absorbance bandshapes suggest that aryl substituents extending from the core ligands engage in stacking interactions and induce a partially flattened structure in the ground state. More severe flattening occurs in the excited state and precludes the observation of emission if inter-ligand steric forces do not limit the distortion. Thus, the [2] pseudorotaxanes containing dap or o-dabipy as the thread ligand exhibit uncorrected emission maxima at around 720 nm in room-temperature dichloromethane, while the less constrained analogues, containing dabiiq or m-dabipy, are not emissive in fluid solution and barely exhibit a signal in rigid media. In dichloromethane, the luminescence quantum yields of the dap- and o-dabipy-containing systems are 6 x 10(-4) and 4 x 10(-4), and the excited-state lifetimes are 98 ns and 90 ns, respectively.}, keywords = {}, pubstate = {published}, tppubtype = {article} } This report describes photoluminescence studies of copper-containing [2]pseudorotaxanes that mimic elements of functioning molecular machines. Excitation with visible light induces a formal oxidation of the metal center and simulates an actuation process. In all four [2] pseudorotaxanes studied, the ring ligand is the same, but the thread ligand is variable, namely 2,9-di(anisol-4-yl)-1,10-phenanthroline (dap), 6,6'-di(anisol-4-yl)-2,2'-bipyridine (o-dabipy), 5,5'-di(anisol-4-yl)-2,2'-bipyridine (m-dabipy), or 8,8'-di(anisol-4-yl)-3,3'-bi-isoquinoline (dabiiq). The absorbance bandshapes suggest that aryl substituents extending from the core ligands engage in stacking interactions and induce a partially flattened structure in the ground state. More severe flattening occurs in the excited state and precludes the observation of emission if inter-ligand steric forces do not limit the distortion. Thus, the [2] pseudorotaxanes containing dap or o-dabipy as the thread ligand exhibit uncorrected emission maxima at around 720 nm in room-temperature dichloromethane, while the less constrained analogues, containing dabiiq or m-dabipy, are not emissive in fluid solution and barely exhibit a signal in rigid media. In dichloromethane, the luminescence quantum yields of the dap- and o-dabipy-containing systems are 6 x 10(-4) and 4 x 10(-4), and the excited-state lifetimes are 98 ns and 90 ns, respectively. |
Winssinger, Nicolas Translating instructions into function by nucleic acid programmed self-assembly Journal Article In: ACTUALITE CHIMIQUE, (348-49), pp. 42–48, 2011, ISSN: 0151-9093. @article{winssinger_translating_2011, title = {Translating instructions into function by nucleic acid programmed self-assembly}, author = {Winssinger, Nicolas}, issn = {0151-9093}, year = {2011}, date = {2011-02-01}, journal = {ACTUALITE CHIMIQUE}, number = {348-49}, pages = {42--48}, abstract = {The predictable nature of nucleic acid hybridization offers a simple platform to program assemblies with emerging function. This review will highlight some examples from our laboratory towards the use of this concept in chemical biology. These developments capitalize on peptide nucleic acids (PNAs), a functional analogue of natural oligonucleotides to program assemblies. In the first example, hybridization is used to organize mixtures of molecules tagged with PNAs into a microarray format; in the second example, the PNA tags are used to program the dimerization of ligands onto a nucleic acid template which translates into enhanced affinity for a biomolecule; in the third one, hybridization is used to program a reaction by aligning reactive functional groups and translated into a fluorescent signal. While these examples are only a prelude in translating instructions into a function, we hope that they can be the basis of more complex network and inspire further developments in the broader context of system chemistry.}, keywords = {}, pubstate = {published}, tppubtype = {article} } The predictable nature of nucleic acid hybridization offers a simple platform to program assemblies with emerging function. This review will highlight some examples from our laboratory towards the use of this concept in chemical biology. These developments capitalize on peptide nucleic acids (PNAs), a functional analogue of natural oligonucleotides to program assemblies. In the first example, hybridization is used to organize mixtures of molecules tagged with PNAs into a microarray format; in the second example, the PNA tags are used to program the dimerization of ligands onto a nucleic acid template which translates into enhanced affinity for a biomolecule; in the third one, hybridization is used to program a reaction by aligning reactive functional groups and translated into a fluorescent signal. While these examples are only a prelude in translating instructions into a function, we hope that they can be the basis of more complex network and inspire further developments in the broader context of system chemistry. |
Aouani, Heykel ; Mahboub, Oussama ; Bonod, Nicolas ; Devaux, Eloise ; Popov, Evgeny ; Rigneault, Herve ; Ebbesen, Thomas W; Wenger, Jerome Bright Unidirectional Fluorescence Emission of Molecules in a Nanoaperture with Plasmonic Corrugations Journal Article In: NANO LETTERS, 11 (2), pp. 637–644, 2011, ISSN: 1530-6984. @article{aouani_bright_2011, title = {Bright Unidirectional Fluorescence Emission of Molecules in a Nanoaperture with Plasmonic Corrugations}, author = {Aouani, Heykel and Mahboub, Oussama and Bonod, Nicolas and Devaux, Eloise and Popov, Evgeny and Rigneault, Herve and Ebbesen, Thomas W. and Wenger, Jerome}, doi = {10.1021/nl103738d}, issn = {1530-6984}, year = {2011}, date = {2011-02-01}, journal = {NANO LETTERS}, volume = {11}, number = {2}, pages = {637--644}, abstract = {Controlling the fluorescence emission from nanoscale quantum emitters is a key element for a wide range of applications,; from efficient analytical sensing to quantum information processing. Enhancing the fluorescence intensity and narrowing the emission directivity are both essential features to achieve a full control of fluorescence, yet this is rarely obtained simultaneously with optical nanoantennas. Here we report that gold nanoapertures surrounded by periodic corrugations transform standard fluorescent molecules into bright unidirectional sources. We obtain enhancement factors of the fluorescence count rate per molecule up to 120 fold simultaneously with a directional emission of the fluorescence into a narrow angular cone in the direction normal to the sample plane. The bright emission and,wow directionality enable the detection of single molecules with a low numerical aperture objective, and improve the effectiveness of fluorescence based applications. We thoroughly quantify the increased light-matter coupling as well as the radiation pattern intensity. These results are highly relevant for the development of single molecule sensing, single-photon sources, and light emitting devices.}, keywords = {}, pubstate = {published}, tppubtype = {article} } Controlling the fluorescence emission from nanoscale quantum emitters is a key element for a wide range of applications,; from efficient analytical sensing to quantum information processing. Enhancing the fluorescence intensity and narrowing the emission directivity are both essential features to achieve a full control of fluorescence, yet this is rarely obtained simultaneously with optical nanoantennas. Here we report that gold nanoapertures surrounded by periodic corrugations transform standard fluorescent molecules into bright unidirectional sources. We obtain enhancement factors of the fluorescence count rate per molecule up to 120 fold simultaneously with a directional emission of the fluorescence into a narrow angular cone in the direction normal to the sample plane. The bright emission and,wow directionality enable the detection of single molecules with a low numerical aperture objective, and improve the effectiveness of fluorescence based applications. We thoroughly quantify the increased light-matter coupling as well as the radiation pattern intensity. These results are highly relevant for the development of single molecule sensing, single-photon sources, and light emitting devices. |
Cadeddu, Andrea ; Ciesielski, Artur ; El Malah, Tamer ; Hecht, Stefan ; Samori, Paolo Modulating the self-assembly of rigid “clicked” dendrimers at the solid-liquid interface by tuning non-covalent interactions between side groups Journal Article In: CHEMICAL COMMUNICATIONS, 47 (38), pp. 10578–10580, 2011, ISSN: 1359-7345. @article{cadeddu_modulating_2011, title = {Modulating the self-assembly of rigid “clicked” dendrimers at the solid-liquid interface by tuning non-covalent interactions between side groups}, author = {Cadeddu, Andrea and Ciesielski, Artur and El Malah, Tamer and Hecht, Stefan and Samori, Paolo}, doi = {10.1039/c1cc13099d}, issn = {1359-7345}, year = {2011}, date = {2011-01-01}, journal = {CHEMICAL COMMUNICATIONS}, volume = {47}, number = {38}, pages = {10578--10580}, abstract = {First generation poly(triazole-phenylene) dendrimers equipped with peripheral alkyl or carboxylic acid groups to engage in van der Waals and hydrogen-bonding interactions, respectively, assemble into distinct two-dimensional nano-structures at the solid-liquid interface as revealed by high resolution STM investigations.}, keywords = {}, pubstate = {published}, tppubtype = {article} } First generation poly(triazole-phenylene) dendrimers equipped with peripheral alkyl or carboxylic acid groups to engage in van der Waals and hydrogen-bonding interactions, respectively, assemble into distinct two-dimensional nano-structures at the solid-liquid interface as revealed by high resolution STM investigations. |
Ciesielski, Artur ; Colella, Silvia ; Zalewski, Leszek ; Bruchmann, Bernd ; Samori, Paolo Nanopatterning the graphite surface with ordered macrocyclic or ribbon-like assemblies of isocytosine derivatives: an STM study Journal Article In: CRYSTENGCOMM, 13 (18), pp. 5535–5537, 2011, ISSN: 1466-8033. @article{ciesielski_nanopatterning_2011, title = {Nanopatterning the graphite surface with ordered macrocyclic or ribbon-like assemblies of isocytosine derivatives: an STM study}, author = {Ciesielski, Artur and Colella, Silvia and Zalewski, Leszek and Bruchmann, Bernd and Samori, Paolo}, doi = {10.1039/c1ce05521f}, issn = {1466-8033}, year = {2011}, date = {2011-01-01}, journal = {CRYSTENGCOMM}, volume = {13}, number = {18}, pages = {5535--5537}, abstract = {STM studies of the self-assembly at the solid-liquid interface of substituted isocytosine derivatives exposing side groups featuring different steric hindrance revealed the formation of distinct crystalline nanopatterns.}, keywords = {}, pubstate = {published}, tppubtype = {article} } STM studies of the self-assembly at the solid-liquid interface of substituted isocytosine derivatives exposing side groups featuring different steric hindrance revealed the formation of distinct crystalline nanopatterns. |
Savage, Rebecca C; Mativetsky, Jeffrey M; Orgiu, Emanuele ; Palma, Matteo ; Gbabode, Gabin ; Geerts, Yves H; Samori, P Integration of self-assembled discotic-based fibres into field-effect transistors: a comparison of preparation approaches Journal Article In: JOURNAL OF MATERIALS CHEMISTRY, 21 (1), pp. 206–213, 2011, ISSN: 0959-9428. @article{savage_integration_2011, title = {Integration of self-assembled discotic-based fibres into field-effect transistors: a comparison of preparation approaches}, author = {Savage, Rebecca C. and Mativetsky, Jeffrey M. and Orgiu, Emanuele and Palma, Matteo and Gbabode, Gabin and Geerts, Yves H. and Samori, P.}, doi = {10.1039/c0jm01754j}, issn = {0959-9428}, year = {2011}, date = {2011-01-01}, journal = {JOURNAL OF MATERIALS CHEMISTRY}, volume = {21}, number = {1}, pages = {206--213}, abstract = {The role played by the preparation method upon the morphological and electrical properties of alkyl substituted thio-triphenylene-based self-assembled fibres is explored by comparing two processing approaches, termed solvent vapour annealing (SVA) and solvent induced precipitation (SIP). Both approaches led to fibres having widths of several hundred nanometres and lengths of tens of micrometres. SVA formed isolated fibres which were tens of nanometres high, flat, and tapered at the ends. Conversely, SIP fibres exhibited nearly matching heights and widths, but organized into bundles. Despite these morphological differences, the same intermolecular packing is found by XRD in each type of structure, albeit with differing degrees of long-range order. The fibres were integrated into bottom-gate bottom-contact field-effect transistors. The density and configuration of the fibres with respect to the electrodes and gate dielectric were found to play an important role in the transport properties. SIP devices yielded the highest mobilities compared to SVA and spin-coated devices, largely owing to their high degree of internal order and the possibility to achieve high fibre densities within the transistor channel.}, keywords = {}, pubstate = {published}, tppubtype = {article} } The role played by the preparation method upon the morphological and electrical properties of alkyl substituted thio-triphenylene-based self-assembled fibres is explored by comparing two processing approaches, termed solvent vapour annealing (SVA) and solvent induced precipitation (SIP). Both approaches led to fibres having widths of several hundred nanometres and lengths of tens of micrometres. SVA formed isolated fibres which were tens of nanometres high, flat, and tapered at the ends. Conversely, SIP fibres exhibited nearly matching heights and widths, but organized into bundles. Despite these morphological differences, the same intermolecular packing is found by XRD in each type of structure, albeit with differing degrees of long-range order. The fibres were integrated into bottom-gate bottom-contact field-effect transistors. The density and configuration of the fibres with respect to the electrodes and gate dielectric were found to play an important role in the transport properties. SIP devices yielded the highest mobilities compared to SVA and spin-coated devices, largely owing to their high degree of internal order and the possibility to achieve high fibre densities within the transistor channel. |
Liscio, Andrea ; Veronese, Giulio Paolo ; Treossi, Emanuele ; Suriano, Francesco ; Rossella, Francesco ; Bellani, Vittorio ; Rizzoli, Rita ; Samori, Paolo ; Palermo, Vincenzo Charge transport in graphene-polythiophene blends as studied by Kelvin Probe Force Microscopy and transistor characterization Journal Article In: JOURNAL OF MATERIALS CHEMISTRY, 21 (9), pp. 2924–2931, 2011, ISSN: 0959-9428. @article{liscio_charge_2011, title = {Charge transport in graphene-polythiophene blends as studied by Kelvin Probe Force Microscopy and transistor characterization}, author = {Liscio, Andrea and Veronese, Giulio Paolo and Treossi, Emanuele and Suriano, Francesco and Rossella, Francesco and Bellani, Vittorio and Rizzoli, Rita and Samori, Paolo and Palermo, Vincenzo}, doi = {10.1039/c0jm02940h}, issn = {0959-9428}, year = {2011}, date = {2011-01-01}, journal = {JOURNAL OF MATERIALS CHEMISTRY}, volume = {21}, number = {9}, pages = {2924--2931}, abstract = {Blends of reduced graphene oxide (RGO) and poly(3-hexylthiophene) (P3HT) are used as the active layer of field-effect transistors (FETs). By using sequential deposition of the two components, the density of RGO sheets can be tuned linearly, thereby modulating their contribution to the charge transport in the transistors, and the onset of charge percolation. The surface potential of RGO, P3HT and source-drain contacts is measured on the nanometric scale with Kelvin Probe Force Microscopy (KPFM), and correlated with the macroscopic performance of the FETs. KPFM is also used to monitor the potential decay along the channel in the working FETs.}, keywords = {}, pubstate = {published}, tppubtype = {article} } Blends of reduced graphene oxide (RGO) and poly(3-hexylthiophene) (P3HT) are used as the active layer of field-effect transistors (FETs). By using sequential deposition of the two components, the density of RGO sheets can be tuned linearly, thereby modulating their contribution to the charge transport in the transistors, and the onset of charge percolation. The surface potential of RGO, P3HT and source-drain contacts is measured on the nanometric scale with Kelvin Probe Force Microscopy (KPFM), and correlated with the macroscopic performance of the FETs. KPFM is also used to monitor the potential decay along the channel in the working FETs. |
Singh, Prabhpreet ; Samori, Cristian ; Toma, Francesca Maria ; Bussy, Cyrill ; Nunes, Antonio ; Al-Jamal, Khuloud T; Menard-Moyon, Cecilia ; Prato, Maurizio ; Kostarelos, Kostas ; Bianco, Alberto Polyamine functionalized carbon nanotubes: synthesis, characterization, cytotoxicity and siRNA binding Journal Article In: JOURNAL OF MATERIALS CHEMISTRY, 21 (13), pp. 4850–4860, 2011, ISSN: 0959-9428. @article{singh_polyamine_2011, title = {Polyamine functionalized carbon nanotubes: synthesis, characterization, cytotoxicity and siRNA binding}, author = {Singh, Prabhpreet and Samori, Cristian and Toma, Francesca Maria and Bussy, Cyrill and Nunes, Antonio and Al-Jamal, Khuloud T. and Menard-Moyon, Cecilia and Prato, Maurizio and Kostarelos, Kostas and Bianco, Alberto}, doi = {10.1039/c0jm04064a}, issn = {0959-9428}, year = {2011}, date = {2011-01-01}, journal = {JOURNAL OF MATERIALS CHEMISTRY}, volume = {21}, number = {13}, pages = {4850--4860}, abstract = {In this work we have synthesized a new series of cationic carbon nanotubes (CNTs) for siRNA binding. Both single- and multi-walled CNTs have been modified by addition or amidation reaction with short linear polyamine chains including putrescine, spermidine and spermine. All the new conjugates have been characterized with several spectroscopic and microscopic techniques. Their cytotoxic effects have been assessed on human lung carcinoma cell line. Finally, we have analyzed their capacity to bind siRNA towards the development of new carriers for gene silencing applications. The dispersibility properties and the capacity to complex siRNA of the different conjugates were found to be strongly dependent on the position of the functional groups on CNTs (i.e. mainly at the tips following the amidation reaction or on the sidewalls by direct C-C addition).}, keywords = {}, pubstate = {published}, tppubtype = {article} } In this work we have synthesized a new series of cationic carbon nanotubes (CNTs) for siRNA binding. Both single- and multi-walled CNTs have been modified by addition or amidation reaction with short linear polyamine chains including putrescine, spermidine and spermine. All the new conjugates have been characterized with several spectroscopic and microscopic techniques. Their cytotoxic effects have been assessed on human lung carcinoma cell line. Finally, we have analyzed their capacity to bind siRNA towards the development of new carriers for gene silencing applications. The dispersibility properties and the capacity to complex siRNA of the different conjugates were found to be strongly dependent on the position of the functional groups on CNTs (i.e. mainly at the tips following the amidation reaction or on the sidewalls by direct C-C addition). |
Ciesielski, Artur ; Samori, Paolo Supramolecular assembly/reassembly processes: molecular motors and dynamers operating at surfaces Journal Article In: NANOSCALE, 3 (4), pp. 1397–1410, 2011, ISSN: 2040-3364. @article{ciesielski_supramolecular_2011, title = {Supramolecular assembly/reassembly processes: molecular motors and dynamers operating at surfaces}, author = {Ciesielski, Artur and Samori, Paolo}, doi = {10.1039/c0nr00914h}, issn = {2040-3364}, year = {2011}, date = {2011-01-01}, journal = {NANOSCALE}, volume = {3}, number = {4}, pages = {1397--1410}, abstract = {Among the many significant advances within the field of supramolecular chemistry over the past decades, the development of the so-called “dynamers” features a direct relevance to materials science. Defined as “combinatorial dynamic polymers”, dynamers are constitutional dynamic systems and materials resulting from the application of the principles of supramolecular chemistry to polymer science. Like supramolecular materials in general, dynamers are reversible dynamic multifunctional architectures, capable of modifying their constitution by exchanging, recombining, incorporating components. They may exhibit a variety of novel properties and behave as adaptive materials. In this review we focus on the design of responsive switchable monolayers, i.e. monolayers capable to undergo significant changes in their physical or chemical properties as a result of external stimuli. Scanning tunneling microscopy studies provide direct evidence with a sub-nanometre resolution, on the formation and dynamic response of these self-assembled systems featuring controlled geometries and properties.}, keywords = {}, pubstate = {published}, tppubtype = {article} } Among the many significant advances within the field of supramolecular chemistry over the past decades, the development of the so-called “dynamers” features a direct relevance to materials science. Defined as “combinatorial dynamic polymers”, dynamers are constitutional dynamic systems and materials resulting from the application of the principles of supramolecular chemistry to polymer science. Like supramolecular materials in general, dynamers are reversible dynamic multifunctional architectures, capable of modifying their constitution by exchanging, recombining, incorporating components. They may exhibit a variety of novel properties and behave as adaptive materials. In this review we focus on the design of responsive switchable monolayers, i.e. monolayers capable to undergo significant changes in their physical or chemical properties as a result of external stimuli. Scanning tunneling microscopy studies provide direct evidence with a sub-nanometre resolution, on the formation and dynamic response of these self-assembled systems featuring controlled geometries and properties. |
Ciesielski, Artur ; Cadeddu, Andrea ; Palma, Carlos-Andres ; Gorczynski, Adam ; Patroniak, Violetta ; Cecchini, Marco ; Samori, Paolo Self-templating 2D supramolecular networks: a new avenue to reach control over a bilayer formation Journal Article In: NANOSCALE, 3 (10), pp. 4125–4129, 2011, ISSN: 2040-3364. @article{ciesielski_self-templating_2011, title = {Self-templating 2D supramolecular networks: a new avenue to reach control over a bilayer formation}, author = {Ciesielski, Artur and Cadeddu, Andrea and Palma, Carlos-Andres and Gorczynski, Adam and Patroniak, Violetta and Cecchini, Marco and Samori, Paolo}, doi = {10.1039/c1nr10485c}, issn = {2040-3364}, year = {2011}, date = {2011-01-01}, journal = {NANOSCALE}, volume = {3}, number = {10}, pages = {4125--4129}, abstract = {One of the greatest challenges in 2D self-assembly at interfaces is the ability to grow spatially controlled supramolecular motifs in the third dimension, exploiting the surface as a template. In this manuscript a concentration-dependent study by scanning tunneling microscopy at the solid-liquid interface, corroborated by Molecular Dynamics (MD) simulations, reveals the controlled generation of mono- or bilayer self-assembled Kagome networks based on a fully planar tetracarboxylic acid derivative. By programming the backbone of the molecular building blocks, we present a strategy to gain spatial control over the adlayer structure by conferring self-templating capacity to the 2D self-assembled network.}, keywords = {}, pubstate = {published}, tppubtype = {article} } One of the greatest challenges in 2D self-assembly at interfaces is the ability to grow spatially controlled supramolecular motifs in the third dimension, exploiting the surface as a template. In this manuscript a concentration-dependent study by scanning tunneling microscopy at the solid-liquid interface, corroborated by Molecular Dynamics (MD) simulations, reveals the controlled generation of mono- or bilayer self-assembled Kagome networks based on a fully planar tetracarboxylic acid derivative. By programming the backbone of the molecular building blocks, we present a strategy to gain spatial control over the adlayer structure by conferring self-templating capacity to the 2D self-assembled network. |
Crivillers, N; Liscio, A; Di Stasio, F; Van Dyck, C; Osella, S; Cornil, D; Mian, S; Lazzerini, G M; Fenwick, O; Orgiu, E; Reinders, F; Braun, S; Fahlman, M; Mayor, M; Cornil, J; Palermo, V; Cacialli, F; Samori, P Photoinduced work function changes by isomerization of a densely packed azobenzene-based SAM on Au: a joint experimental and theoretical study Journal Article In: PHYSICAL CHEMISTRY CHEMICAL PHYSICS, 13 (32), pp. 14302–14310, 2011, ISSN: 1463-9076. @article{crivillers_photoinduced_2011, title = {Photoinduced work function changes by isomerization of a densely packed azobenzene-based SAM on Au: a joint experimental and theoretical study}, author = {Crivillers, N. and Liscio, A. and Di Stasio, F. and Van Dyck, C. and Osella, S. and Cornil, D. and Mian, S. and Lazzerini, G. M. and Fenwick, O. and Orgiu, E. and Reinders, F. and Braun, S. and Fahlman, M. and Mayor, M. and Cornil, J. and Palermo, V. and Cacialli, F. and Samori, P.}, doi = {10.1039/c1cp20851a}, issn = {1463-9076}, year = {2011}, date = {2011-01-01}, journal = {PHYSICAL CHEMISTRY CHEMICAL PHYSICS}, volume = {13}, number = {32}, pages = {14302--14310}, abstract = {Responsive monolayers are key building blocks for future applications in organic and molecular electronics in particular because they hold potential for tuning the physico-chemical properties of interfaces, including their energetics. Here we study a photochromic SAM based on a conjugated azobenzene derivative and its influence on the gold work function (Phi(Au)) when chemisorbed on its surface. In particular we show that the Phi(Au) can be modulated with external stimuli by controlling the azobenzene trans/cis isomerization process. This phenomenon is characterized experimentally by four different techniques, kelvin probe, kelvin probe force microscopy, electroabsorption spectroscopy and ultraviolet photoelectron spectroscopy. The use of different techniques implies exposing the SAM to different measurement conditions and different preparation methods, which, remarkably, do not alter the observed work function change (Phi(trans)-Phi(cis)). Theoretical calculations provided a complementary insight crucial to attain a deeper knowledge on the origin of the work function photo-modulation.}, keywords = {}, pubstate = {published}, tppubtype = {article} } Responsive monolayers are key building blocks for future applications in organic and molecular electronics in particular because they hold potential for tuning the physico-chemical properties of interfaces, including their energetics. Here we study a photochromic SAM based on a conjugated azobenzene derivative and its influence on the gold work function (Phi(Au)) when chemisorbed on its surface. In particular we show that the Phi(Au) can be modulated with external stimuli by controlling the azobenzene trans/cis isomerization process. This phenomenon is characterized experimentally by four different techniques, kelvin probe, kelvin probe force microscopy, electroabsorption spectroscopy and ultraviolet photoelectron spectroscopy. The use of different techniques implies exposing the SAM to different measurement conditions and different preparation methods, which, remarkably, do not alter the observed work function change (Phi(trans)-Phi(cis)). Theoretical calculations provided a complementary insight crucial to attain a deeper knowledge on the origin of the work function photo-modulation. |
Fylaktakidou, Konstantina C; Duarte, Carolina D; Koumbis, Alexandros E; Nicolau, Claude ; Lehn, Jean-Marie Polyphosphates and Pyrophosphates of Hexopyranoses as Allosteric Effectors of Human Hemoglobin: Synthesis, Molecular Recognition, and Effect on Oxygen Release Journal Article In: CHEMMEDCHEM, 6 (1), pp. 153–168, 2011, ISSN: 1860-7179. @article{fylaktakidou_polyphosphates_2011-1, title = {Polyphosphates and Pyrophosphates of Hexopyranoses as Allosteric Effectors of Human Hemoglobin: Synthesis, Molecular Recognition, and Effect on Oxygen Release}, author = {Fylaktakidou, Konstantina C. and Duarte, Carolina D. and Koumbis, Alexandros E. and Nicolau, Claude and Lehn, Jean-Marie}, doi = {10.1002/cmdc.201000366}, issn = {1860-7179}, year = {2011}, date = {2011-01-01}, journal = {CHEMMEDCHEM}, volume = {6}, number = {1}, pages = {153--168}, abstract = {Polyphosphorylated and perphosphorylated hexopyranose monosaccharides and disaccharides were synthesized from parent or partially protected carbohydrates as potential allosteric effectors of hemoglobin. A study toward the construction of seven- and eight-membered cyclic pyrophosphates was also performed on the sugars which had the proper orientation, protection, and number of phosphates. All final compounds were tested for their efficiency on oxygen release from human hemoglobin. Several compounds presented higher potency than myo-inositol hexakisphosphate, which is the most efficient of the known allosteric effectors of hemoglobin. Structure-activity relationships were analyzed. The affinity and efficiency depend on the number of phosphates attached to the carbohydrate skeleton and are related primarily to the number of negative charges present. Other effects operate, but play a lesser role.}, keywords = {}, pubstate = {published}, tppubtype = {article} } Polyphosphorylated and perphosphorylated hexopyranose monosaccharides and disaccharides were synthesized from parent or partially protected carbohydrates as potential allosteric effectors of hemoglobin. A study toward the construction of seven- and eight-membered cyclic pyrophosphates was also performed on the sugars which had the proper orientation, protection, and number of phosphates. All final compounds were tested for their efficiency on oxygen release from human hemoglobin. Several compounds presented higher potency than myo-inositol hexakisphosphate, which is the most efficient of the known allosteric effectors of hemoglobin. Structure-activity relationships were analyzed. The affinity and efficiency depend on the number of phosphates attached to the carbohydrate skeleton and are related primarily to the number of negative charges present. Other effects operate, but play a lesser role. |
Koumbis, Alexandros E; Duarte, Carolina D; Nicolau, Claude ; Lehn, Jean-Marie Tetrakisphosphates and Bispyrophosphates of myo-Inositol Derivatives as Allosteric Effectors of Human Hemoglobin: Synthesis, Molecular Recognition, and Oxygen Release Journal Article In: CHEMMEDCHEM, 6 (1), pp. 169–180, 2011, ISSN: 1860-7179. @article{koumbis_tetrakisphosphates_2011, title = {Tetrakisphosphates and Bispyrophosphates of myo-Inositol Derivatives as Allosteric Effectors of Human Hemoglobin: Synthesis, Molecular Recognition, and Oxygen Release}, author = {Koumbis, Alexandros E. and Duarte, Carolina D. and Nicolau, Claude and Lehn, Jean-Marie}, doi = {10.1002/cmdc.201000421}, issn = {1860-7179}, year = {2011}, date = {2011-01-01}, journal = {CHEMMEDCHEM}, volume = {6}, number = {1}, pages = {169--180}, abstract = {Various 2,5- and 1,4-substituted and unsubstituted myo-inositol tetrakisphosphates and bispyrophosphates were prepared following a general synthetic pathway. All final compounds were tested for their capability to induce oxygen release from human hemoglobin. Most of these proved to be efficient allosteric effectors, with similar affinities for hemoglobin to that of myo-inositol hexakisphosphate, which is one of the best known allosteric effectors of hemoglobin. The efficacy was found to be higher for free phosphates than pyrophosphates. As allosteric Hb effectors, these compounds enable enhanced oxygen release. These effects increase with the strength of Hb binding and correspond primarily to electrostatic interactions. Stereochemical and steric factors also play a significant but secondary role in molecular recognition. In view of the central role played by hypoxia in numerous types of diseases, the exploration of myo-inositol phosphate derivatives represents an important avenue in the search for substances which act on the oxygenation status of tissues and may have significant potential in the discovery and development of novel drug candidates.}, keywords = {}, pubstate = {published}, tppubtype = {article} } Various 2,5- and 1,4-substituted and unsubstituted myo-inositol tetrakisphosphates and bispyrophosphates were prepared following a general synthetic pathway. All final compounds were tested for their capability to induce oxygen release from human hemoglobin. Most of these proved to be efficient allosteric effectors, with similar affinities for hemoglobin to that of myo-inositol hexakisphosphate, which is one of the best known allosteric effectors of hemoglobin. The efficacy was found to be higher for free phosphates than pyrophosphates. As allosteric Hb effectors, these compounds enable enhanced oxygen release. These effects increase with the strength of Hb binding and correspond primarily to electrostatic interactions. Stereochemical and steric factors also play a significant but secondary role in molecular recognition. In view of the central role played by hypoxia in numerous types of diseases, the exploration of myo-inositol phosphate derivatives represents an important avenue in the search for substances which act on the oxygenation status of tissues and may have significant potential in the discovery and development of novel drug candidates. |
Parizel, Nathalie ; Ramirez, Juan ; Burg, Christophe ; Choua, Sylvie ; Bernard, Maxime ; Gambarelli, Serge ; Maurel, Vincent ; Brelot, Lydia ; Lehn, Jean-Marie ; Turek, Philippe ; Stadler, Adrian-Mihail Modulation of self-assembly and magnetism of Cu(II) grids in solution Journal Article In: CHEMICAL COMMUNICATIONS, 47 (39), pp. 10951–10953, 2011, ISSN: 1359-7345. @article{parizel_modulation_2011, title = {Modulation of self-assembly and magnetism of Cu(II) grids in solution}, author = {Parizel, Nathalie and Ramirez, Juan and Burg, Christophe and Choua, Sylvie and Bernard, Maxime and Gambarelli, Serge and Maurel, Vincent and Brelot, Lydia and Lehn, Jean-Marie and Turek, Philippe and Stadler, Adrian-Mihail}, doi = {10.1039/c0cc01612h}, issn = {1359-7345}, year = {2011}, date = {2011-01-01}, journal = {CHEMICAL COMMUNICATIONS}, volume = {47}, number = {39}, pages = {10951--10953}, abstract = {Depending on the Cu(II)/ligand molar ratio, a pyrimidine-based ligand generates a tetranuclear grid (1/1) or a dinuclear stick (2/1). EPR, MS and visible spectroscopy studies suggest that dilution produces partial dissociation of the grid in solution. Replacement of 2-H-pyrimidine by a 2-phenyl-triazine unit prevents the dissociation of the grid. All these factors influence the magnetic properties of the architectures herein involved.}, keywords = {}, pubstate = {published}, tppubtype = {article} } Depending on the Cu(II)/ligand molar ratio, a pyrimidine-based ligand generates a tetranuclear grid (1/1) or a dinuclear stick (2/1). EPR, MS and visible spectroscopy studies suggest that dilution produces partial dissociation of the grid in solution. Replacement of 2-H-pyrimidine by a 2-phenyl-triazine unit prevents the dissociation of the grid. All these factors influence the magnetic properties of the architectures herein involved. |
Chaur, Manuel N; Collado, Daniel ; Lehn, Jean-Marie Configurational and Constitutional Information Storage: Multiple Dynamics in Systems Based on Pyridyl and Acyl Hydrazones Journal Article In: CHEMISTRY-A EUROPEAN JOURNAL, 17 (1), pp. 248–258, 2011, ISSN: 0947-6539. @article{chaur_configurational_2011, title = {Configurational and Constitutional Information Storage: Multiple Dynamics in Systems Based on Pyridyl and Acyl Hydrazones}, author = {Chaur, Manuel N. and Collado, Daniel and Lehn, Jean-Marie}, doi = {10.1002/chem.201002308}, issn = {0947-6539}, year = {2011}, date = {2011-01-01}, journal = {CHEMISTRY-A EUROPEAN JOURNAL}, volume = {17}, number = {1}, pages = {248--258}, abstract = {The C=N group of hydrazones can undergo E/Z isomerization both photochemically and thermally, allowing the generation of a closed process that can be tuned by either of these two physical stimuli. On the other hand, hydrazine-exchange reactions enable a constitutional change in a given hydrazone. The two classes of processes: 1) configurational (physically stimulated) and 2) constitutional (chemically stimulated) give access to short-term and long-term information storage, respectively. Such transformations are reported herein for two hydrazones (bis-pyridyl hydrazone and 2-pyridinecarboxaldehyde phenylhydrazone) that undergo a closed, chemically or physically driven process, and, in addition, can be locked or unlocked at will by metal-ion coordination or removal. These features also extend to acyl hydrazones derived from 2-pyridinecarboxaldehyde. Similarly to the terpydine-like hydrazones, such acyl hydrazones can undergo both constitutional and configurational changes, as well as metal-ion coordination. All these types of hydrazones represent dynamic systems capable of acting as multiple state molecular devices, in which the presence of coordination sites furthermore allows the metal ion-controlled locking and unlocking of the interconversion of the different states.}, keywords = {}, pubstate = {published}, tppubtype = {article} } The C=N group of hydrazones can undergo E/Z isomerization both photochemically and thermally, allowing the generation of a closed process that can be tuned by either of these two physical stimuli. On the other hand, hydrazine-exchange reactions enable a constitutional change in a given hydrazone. The two classes of processes: 1) configurational (physically stimulated) and 2) constitutional (chemically stimulated) give access to short-term and long-term information storage, respectively. Such transformations are reported herein for two hydrazones (bis-pyridyl hydrazone and 2-pyridinecarboxaldehyde phenylhydrazone) that undergo a closed, chemically or physically driven process, and, in addition, can be locked or unlocked at will by metal-ion coordination or removal. These features also extend to acyl hydrazones derived from 2-pyridinecarboxaldehyde. Similarly to the terpydine-like hydrazones, such acyl hydrazones can undergo both constitutional and configurational changes, as well as metal-ion coordination. All these types of hydrazones represent dynamic systems capable of acting as multiple state molecular devices, in which the presence of coordination sites furthermore allows the metal ion-controlled locking and unlocking of the interconversion of the different states. |
Brelot, Lydia ; Cao, Xiao-yu ; Harrowfield, Jack ; Lehn, Jean-Marie ; Rissanen, Kari ; Russo, Luca A new hydrogen bonding motif involved in self-recognition in the solid state by functionalised macrocycles Journal Article In: CRYSTENGCOMM, 13 (7), pp. 2346–2349, 2011, ISSN: 1466-8033. @article{brelot_new_2011, title = {A new hydrogen bonding motif involved in self-recognition in the solid state by functionalised macrocycles}, author = {Brelot, Lydia and Cao, Xiao-yu and Harrowfield, Jack and Lehn, Jean-Marie and Rissanen, Kari and Russo, Luca}, doi = {10.1039/c0ce00814a}, issn = {1466-8033}, year = {2011}, date = {2011-01-01}, journal = {CRYSTENGCOMM}, volume = {13}, number = {7}, pages = {2346--2349}, abstract = {Self-recognition within the crystal lattices of three functionalised macrocycles results in the formation of arrays of remarkably similar hermaphroditic pairs of macrocycles. In the case of two of the macrocycles containing acylhydrazine substituents, a hitherto unknown recognition pattern is found in the interaction of the hydrazine moiety with crown-ether oxygen atoms.}, keywords = {}, pubstate = {published}, tppubtype = {article} } Self-recognition within the crystal lattices of three functionalised macrocycles results in the formation of arrays of remarkably similar hermaphroditic pairs of macrocycles. In the case of two of the macrocycles containing acylhydrazine substituents, a hitherto unknown recognition pattern is found in the interaction of the hydrazine moiety with crown-ether oxygen atoms. |
Stefankiewicz, Artur R; Harrowfield, Jack ; Madalan, Augustin ; Rissanen, Kari ; Sobolev, Alexandre N; Lehn, Jean-Marie Structural and metallo selectivity in the assembly of [2 x 2] grid-type metallosupramolecular species: Mechanisms and kinetic control Journal Article In: DALTON TRANSACTIONS, 40 (45), pp. 12320–12332, 2011, ISSN: 1477-9226. @article{stefankiewicz_structural_2011, title = {Structural and metallo selectivity in the assembly of [2 x 2] grid-type metallosupramolecular species: Mechanisms and kinetic control}, author = {Stefankiewicz, Artur R. and Harrowfield, Jack and Madalan, Augustin and Rissanen, Kari and Sobolev, Alexandre N. and Lehn, Jean-Marie}, doi = {10.1039/c1dt11226k}, issn = {1477-9226}, year = {2011}, date = {2011-01-01}, journal = {DALTON TRANSACTIONS}, volume = {40}, number = {45}, pages = {12320--12332}, abstract = {An unsymmetrical bis(tridentate) ligand LH in which one binding site can be readily deprotonated forms a kinetically inert [Co(III)L-2](+) complex which can be used as a “corner” species for the “Coupe du Roi” assembly of trans, trans-[Co2M2L4](6+) metallogrids (M = Fe(II), Co(II), Cu(II), Zn(II)). In the mixed Co(III)/Co(II) species, the oxidation states appear to be localised. In solution, the ligand LH forms octacationic, homometallic [2 x 2] grids with the individual labile metal ions Fe(II), Co(II), Cu(II), Zn(II), seemingly as mixtures of all possible isomers arising from the unsymmetrical nature of the ligand. In the solid state, however, [Zn4L4](CF3SO3)(8)center dot 4CH(3)CN crystallises as a single species where the cation has S-4 symmetry. This stereoselectivity in the crystalline lattice is associated with interactions between the cation and triflate anions which can again be analysed in terms of the Coupe du Roi concept.}, keywords = {}, pubstate = {published}, tppubtype = {article} } An unsymmetrical bis(tridentate) ligand LH in which one binding site can be readily deprotonated forms a kinetically inert [Co(III)L-2](+) complex which can be used as a “corner” species for the “Coupe du Roi” assembly of trans, trans-[Co2M2L4](6+) metallogrids (M = Fe(II), Co(II), Cu(II), Zn(II)). In the mixed Co(III)/Co(II) species, the oxidation states appear to be localised. In solution, the ligand LH forms octacationic, homometallic [2 x 2] grids with the individual labile metal ions Fe(II), Co(II), Cu(II), Zn(II), seemingly as mixtures of all possible isomers arising from the unsymmetrical nature of the ligand. In the solid state, however, [Zn4L4](CF3SO3)(8)center dot 4CH(3)CN crystallises as a single species where the cation has S-4 symmetry. This stereoselectivity in the crystalline lattice is associated with interactions between the cation and triflate anions which can again be analysed in terms of the Coupe du Roi concept. |
Buchs (Nee Levrand), Barbara ; Fieber, Wolfgang ; Vigouroux-Elie, Florence ; Sreenivasachary, Nampally ; Lehn, Jean-Marie ; Herrmann, Andreas Release of bioactive volatiles from supramolecular hydrogels: influence of reversible acylhydrazone formation on gel stability and volatile compound evaporation Journal Article In: ORGANIC & BIOMOLECULAR CHEMISTRY, 9 (8), pp. 2906–2919, 2011, ISSN: 1477-0520. @article{buchs_nee_levrand_release_2011, title = {Release of bioactive volatiles from supramolecular hydrogels: influence of reversible acylhydrazone formation on gel stability and volatile compound evaporation}, author = {Buchs (Nee Levrand), Barbara and Fieber, Wolfgang and Vigouroux-Elie, Florence and Sreenivasachary, Nampally and Lehn, Jean-Marie and Herrmann, Andreas}, doi = {10.1039/c0ob01139h}, issn = {1477-0520}, year = {2011}, date = {2011-01-01}, journal = {ORGANIC & BIOMOLECULAR CHEMISTRY}, volume = {9}, number = {8}, pages = {2906--2919}, abstract = {In the presence of alkali metal cations, guanosine-5'-hydrazide (1) forms stable supramolecular hydrogels by selective self-assembly into a G-quartet structure. Besides being physically trapped inside the gel structure, biologically active aldehydes or ketones can also reversibly react with the free hydrazide functions at the periphery of the G-quartet to form acylhydrazones. This particularity makes the hydrogels interesting as delivery systems for the slow release of bioactive carbonyl derivatives. Hydrogels formed from 1 were found to be significantly more stable than those obtained from guanosine. Both physical inclusion of bioactive volatiles and reversible hydrazone formation could be demonstrated by indirect methods. Gel stabilities were measured by oscillating disk rheology measurements, which showed that thermodynamic equilibration of the gel is slow and requires several cooling and heating cycles. Furthermore, combining the rheology data with dynamic headspace analysis of fragrance evaporation suggested that reversible hydrazone formation of some carbonyl compounds influences the release of volatiles, whereas the absolute stability of the gel seemed to have no influence on the evaporation rates.}, keywords = {}, pubstate = {published}, tppubtype = {article} } In the presence of alkali metal cations, guanosine-5'-hydrazide (1) forms stable supramolecular hydrogels by selective self-assembly into a G-quartet structure. Besides being physically trapped inside the gel structure, biologically active aldehydes or ketones can also reversibly react with the free hydrazide functions at the periphery of the G-quartet to form acylhydrazones. This particularity makes the hydrogels interesting as delivery systems for the slow release of bioactive carbonyl derivatives. Hydrogels formed from 1 were found to be significantly more stable than those obtained from guanosine. Both physical inclusion of bioactive volatiles and reversible hydrazone formation could be demonstrated by indirect methods. Gel stabilities were measured by oscillating disk rheology measurements, which showed that thermodynamic equilibration of the gel is slow and requires several cooling and heating cycles. Furthermore, combining the rheology data with dynamic headspace analysis of fragrance evaporation suggested that reversible hydrazone formation of some carbonyl compounds influences the release of volatiles, whereas the absolute stability of the gel seemed to have no influence on the evaporation rates. |
Delanoe-Ayari, Helene ; Brevier, Julien ; Riveline, Daniel Scaling concepts in cell physics: paradigms for cell adhesion Journal Article In: SOFT MATTER, 7 (3), pp. 824–829, 2011, ISSN: 1744-683X. @article{delanoe-ayari_scaling_2011, title = {Scaling concepts in cell physics: paradigms for cell adhesion}, author = {Delanoe-Ayari, Helene and Brevier, Julien and Riveline, Daniel}, doi = {10.1039/c0sm00293c}, issn = {1744-683X}, year = {2011}, date = {2011-01-01}, journal = {SOFT MATTER}, volume = {7}, number = {3}, pages = {824--829}, abstract = {Shapes and lengths are treated differently in cell biology and in physics. In cell biology, morphology is considered a powerful read-out for estimating protein activities and for classifying pathways. Spatial features are often viewed as binary signals, on or off, active or non-active. In contrast, in condensed matter physics, spatial dimensions are generally derived quantitatively with scaling relations using the mechanical properties of matter. This powerful approach allows predicting scales in new experiments. Here, we applied such a type of scaling method for specific organelles in cells: the cell adhesion structures. We show that simple relations allow one to derive measured lengths in a variety of situations and proteic complexes; if the molecular detail is not at play in such an approach, the mesoscopic equations allow one to quantitatively match the experimental observations. Based on these relations, we also predict simple rules for varying lengths of contacts and distances between contacts in future experiments.}, keywords = {}, pubstate = {published}, tppubtype = {article} } Shapes and lengths are treated differently in cell biology and in physics. In cell biology, morphology is considered a powerful read-out for estimating protein activities and for classifying pathways. Spatial features are often viewed as binary signals, on or off, active or non-active. In contrast, in condensed matter physics, spatial dimensions are generally derived quantitatively with scaling relations using the mechanical properties of matter. This powerful approach allows predicting scales in new experiments. Here, we applied such a type of scaling method for specific organelles in cells: the cell adhesion structures. We show that simple relations allow one to derive measured lengths in a variety of situations and proteic complexes; if the molecular detail is not at play in such an approach, the mesoscopic equations allow one to quantitatively match the experimental observations. Based on these relations, we also predict simple rules for varying lengths of contacts and distances between contacts in future experiments. |
Kruse, Karsten ; Riveline, Daniel SPONTANEOUS MECHANICAL OSCILLATIONS: IMPLICATIONS FOR DEVELOPING ORGANISMS Incollection In: {Labouesse, M} (Ed.): FORCES AND TENSION IN DEVELOPMENT, 95 , pp. 67–91, 2011, ISBN: 978-0-12-385065-2. @incollection{kruse_spontaneous_2011, title = {SPONTANEOUS MECHANICAL OSCILLATIONS: IMPLICATIONS FOR DEVELOPING ORGANISMS}, author = {Kruse, Karsten and Riveline, Daniel}, editor = {{Labouesse, M}}, doi = {10.1016/B978-0-12-385065-2.00003-7}, isbn = {978-0-12-385065-2}, year = {2011}, date = {2011-01-01}, booktitle = {FORCES AND TENSION IN DEVELOPMENT}, volume = {95}, pages = {67--91}, series = {Current Topics in Developmental Biology}, abstract = {Major transformations of cells during embryonic development are traditionally associated with the activation or inhibition of genes and with protein modifications. The contributions of mechanical properties intrinsic to the matter an organism is made of, however, are often overlooked. The emerging field “physics of living matter” is addressing active material properties of the cytoskeleton and tissues like the spontaneous generation of stress, which may lead to shape changes and tissue flows, and their implications for embryonic development. Here, we discuss spontaneous mechanical oscillations to present some basic elements for understanding this physics, and we illustrate its application to developing embryos. We highlight the role of state diagrams to quantitatively probe the significance of the corresponding physical concepts for understanding development.}, keywords = {}, pubstate = {published}, tppubtype = {incollection} } Major transformations of cells during embryonic development are traditionally associated with the activation or inhibition of genes and with protein modifications. The contributions of mechanical properties intrinsic to the matter an organism is made of, however, are often overlooked. The emerging field “physics of living matter” is addressing active material properties of the cytoskeleton and tissues like the spontaneous generation of stress, which may lead to shape changes and tissue flows, and their implications for embryonic development. Here, we discuss spontaneous mechanical oscillations to present some basic elements for understanding this physics, and we illustrate its application to developing embryos. We highlight the role of state diagrams to quantitatively probe the significance of the corresponding physical concepts for understanding development. |
Beyler, Maryline ; Heitz, Valerie ; Sauvage, Jean-Pierre A noncovalently assembled porphyrinic catenane consisting of two interlocking [43]-membered rings Journal Article In: NEW JOURNAL OF CHEMISTRY, 35 (8), pp. 1751–1757, 2011, ISSN: 1144-0546. @article{beyler_noncovalently_2011, title = {A noncovalently assembled porphyrinic catenane consisting of two interlocking [43]-membered rings}, author = {Beyler, Maryline and Heitz, Valerie and Sauvage, Jean-Pierre}, doi = {10.1039/c1nj20294d}, issn = {1144-0546}, year = {2011}, date = {2011-01-01}, journal = {NEW JOURNAL OF CHEMISTRY}, volume = {35}, number = {8}, pages = {1751--1757}, abstract = {A new macrocycle and the corresponding [2]catenane were prepared quantitatively from relatively large organic fragments using coordination chemistry bonds only (Zn-N bonds for the ring and Cu-N bonds for the catenane). The two constitutive macrorings of the [2]catenane are 43-membered rings. The organic components consist of a bis-Zn porphyrin and a 1,10-phenanthroline derivative, both fragments being significantly larger than those previously used for making related compounds. The catenane was assembled in two steps from a bis-Zn porphyrin and a 2,9-di(4 `'-pyridyl-4'-phenyl)-1,10-phenanthroline. In a first step the entwined copper(I) complex of the phenanthroline derivative was formed via Cu(I)-N interactions. Subsequently, a double ring closing reaction was performed by coordination of two equivalents of bis-Zn porphyrin to the entwined copper(I) complex. The tetraporphyrinic [2]catenane was thus obtained thanks to the formation of four Zn(II)-pyridine bonds. It has a high association constant, 4 x 10(10) M-2, due to the good geometrical fit between the constituents.}, keywords = {}, pubstate = {published}, tppubtype = {article} } A new macrocycle and the corresponding [2]catenane were prepared quantitatively from relatively large organic fragments using coordination chemistry bonds only (Zn-N bonds for the ring and Cu-N bonds for the catenane). The two constitutive macrorings of the [2]catenane are 43-membered rings. The organic components consist of a bis-Zn porphyrin and a 1,10-phenanthroline derivative, both fragments being significantly larger than those previously used for making related compounds. The catenane was assembled in two steps from a bis-Zn porphyrin and a 2,9-di(4 `'-pyridyl-4'-phenyl)-1,10-phenanthroline. In a first step the entwined copper(I) complex of the phenanthroline derivative was formed via Cu(I)-N interactions. Subsequently, a double ring closing reaction was performed by coordination of two equivalents of bis-Zn porphyrin to the entwined copper(I) complex. The tetraporphyrinic [2]catenane was thus obtained thanks to the formation of four Zn(II)-pyridine bonds. It has a high association constant, 4 x 10(10) M-2, due to the good geometrical fit between the constituents. |
Durola, Fabien ; Lux, Jacques ; Sauvage, Jean-Pierre ; Wenger, Oliver S Bigger, better, faster: molecular shuttles with sterically non-hindering biisoquinoline chelates Journal Article In: SUPRAMOLECULAR CHEMISTRY, 23 (1-2, SI), pp. 42–52, 2011, ISSN: 1061-0278. @article{durola_bigger_2011, title = {Bigger, better, faster: molecular shuttles with sterically non-hindering biisoquinoline chelates}, author = {Durola, Fabien and Lux, Jacques and Sauvage, Jean-Pierre and Wenger, Oliver S.}, doi = {10.1080/10610278.2010.510189}, issn = {1061-0278}, year = {2011}, date = {2011-01-01}, journal = {SUPRAMOLECULAR CHEMISTRY}, volume = {23}, number = {1-2, SI}, pages = {42--52}, abstract = {In the past, a variety of mechanically interlocked systems such as catenanes and rotaxanes were constructed on the basis of Cu(I) coordination chemistry and endocyclic 1,10-phenanthroline ligands. This review reports on the coordination chemistry of a new family of endocyclic bidentate chelators that are sterically non-hindering, namely 8,8'-diaryl-substituted 3,3'-biisoquinolines. These ligands allow the construction of new multi-component assemblies that are inaccessible with the previously investigated 1,10-phenanthrolines. On the one hand, the sterically non-hindering nature of the new endocyclic chelators makes three-component entanglements around octahedral metal centres such as iron(II), cobalt(II) and ruthenium(II) readily possible. On the other hand, it permits the construction of copper-based molecular shuttles that exhibit shuttling kinetics that excels over those of previously investigated analogous systems with 1,10-phenanthrolines. Thus, within this class of molecular machines, a bigger chelator leads to faster molecular movement, i.e. to a better performance of the molecular machine.}, keywords = {}, pubstate = {published}, tppubtype = {article} } In the past, a variety of mechanically interlocked systems such as catenanes and rotaxanes were constructed on the basis of Cu(I) coordination chemistry and endocyclic 1,10-phenanthroline ligands. This review reports on the coordination chemistry of a new family of endocyclic bidentate chelators that are sterically non-hindering, namely 8,8'-diaryl-substituted 3,3'-biisoquinolines. These ligands allow the construction of new multi-component assemblies that are inaccessible with the previously investigated 1,10-phenanthrolines. On the one hand, the sterically non-hindering nature of the new endocyclic chelators makes three-component entanglements around octahedral metal centres such as iron(II), cobalt(II) and ruthenium(II) readily possible. On the other hand, it permits the construction of copper-based molecular shuttles that exhibit shuttling kinetics that excels over those of previously investigated analogous systems with 1,10-phenanthrolines. Thus, within this class of molecular machines, a bigger chelator leads to faster molecular movement, i.e. to a better performance of the molecular machine. |
Boyle, Megan M; Forgan, Ross S; Friedman, Douglas C; Gassensmith, Jeremiah J; Smaldone, Ronald A; Stoddart, Fraser J; Sauvage, Jean-Pierre Donor-acceptor molecular figures-of-eight Journal Article In: CHEMICAL COMMUNICATIONS, 47 (43), pp. 11870–11872, 2011, ISSN: 1359-7345. @article{boyle_donor-acceptor_2011, title = {Donor-acceptor molecular figures-of-eight}, author = {Boyle, Megan M. and Forgan, Ross S. and Friedman, Douglas C. and Gassensmith, Jeremiah J. and Smaldone, Ronald A. and Stoddart, J. Fraser and Sauvage, Jean-Pierre}, doi = {10.1039/c1cc15333a}, issn = {1359-7345}, year = {2011}, date = {2011-01-01}, journal = {CHEMICAL COMMUNICATIONS}, volume = {47}, number = {43}, pages = {11870--11872}, abstract = {The intermolecular template-directed synthesis, separation and characterisation of two constitutional isomers that are self-complexing donor-acceptor [1] rotaxanes has been achieved by click chemistry, starting from a pi-electron deficient tetracationic cyclophane containing two azide functions and a pi-electron rich 1,5-dioxynaphthalene-containing polyether chain terminated by propargyl groups.}, keywords = {}, pubstate = {published}, tppubtype = {article} } The intermolecular template-directed synthesis, separation and characterisation of two constitutional isomers that are self-complexing donor-acceptor [1] rotaxanes has been achieved by click chemistry, starting from a pi-electron deficient tetracationic cyclophane containing two azide functions and a pi-electron rich 1,5-dioxynaphthalene-containing polyether chain terminated by propargyl groups. |
Huang, Kuo-Ting ; Gorska, Katarzyna ; Alvarez, Susana ; Barluenga, Sofia ; Winssinger, Nicolas Combinatorial Self-Assembly of Glycan Fragments into Microarrays Journal Article In: CHEMBIOCHEM, 12 (1), pp. 56–60, 2011, ISSN: 1439-4227. @article{huang_combinatorial_2011, title = {Combinatorial Self-Assembly of Glycan Fragments into Microarrays}, author = {Huang, Kuo-Ting and Gorska, Katarzyna and Alvarez, Susana and Barluenga, Sofia and Winssinger, Nicolas}, doi = {10.1002/cbic.201000567}, issn = {1439-4227}, year = {2011}, date = {2011-01-01}, journal = {CHEMBIOCHEM}, volume = {12}, number = {1}, pages = {56--60}, keywords = {}, pubstate = {published}, tppubtype = {article} } |
Collin, Jean-Paul ; Durot, Stephanie ; Keller, Michel ; Sauvage, Jean-Pierre ; Trolez, Yann ; Cetina, Mario ; Rissanen, Kari Synthesis of [5]Rotaxanes Containing Bi- and Tridentate Coordination Sites in the Axis Journal Article In: CHEMISTRY-A EUROPEAN JOURNAL, 17 (3), pp. 947–957, 2011, ISSN: 0947-6539. @article{collin_synthesis_2011, title = {Synthesis of [5]Rotaxanes Containing Bi- and Tridentate Coordination Sites in the Axis}, author = {Collin, Jean-Paul and Durot, Stephanie and Keller, Michel and Sauvage, Jean-Pierre and Trolez, Yann and Cetina, Mario and Rissanen, Kari}, doi = {10.1002/chem.201002220}, issn = {0947-6539}, year = {2011}, date = {2011-01-01}, journal = {CHEMISTRY-A EUROPEAN JOURNAL}, volume = {17}, number = {3}, pages = {947--957}, abstract = {A new example of a linear [5]rotaxane has been synthesized by using the traditional “gathering-and-threading” approach but based on an unusual axle incorporating a symmetrical bis(bidentate) chelating fragment built on a 4,7-phenanthroline core. The stoppering reaction is particularly noteworthy since, instead of using a trivial bulky stopper as precursor to the blocking group, two semistoppered copper-complexed [2]pseudorotaxanes (namely [2]semirotaxanes) are used, which leads to the desired [5]rotaxane in good yield. The efficiency of the method relies on the use of “click” chemistry, with its very mild conditions, and on the protection by a transition-metal (copper(I)) of the various coordinating groups present in the fragments to be interconnected (terpy and bidentate chelating groups), thus inhibiting potential detrimental side reactions during the copper-catalyzed stoppering reaction. Since the external fragments and the central core of the system contain tri- and bidentate chelating units, respectively, the axle of the final [5]rotaxane incorporates two types of coordinating units: two external terpy groups (terpy: 2,2':6',2 `'-terpyridine) and two central bidentate ligands. Such a situation enables the system to tidy two different metals centers, and to localize them in a priori well-defined positions. This is what was observed when mixing the free ligand with a mixture of Zn2+ and Li+: the zinc(II) ions were unambiguously shown to occupy the external sites, whereas the Li+ cations were found in the central part of the [5]rotaxane. An X-ray diffraction study carried out on a [3]pseudorotaxane, the axis of which is similar to the central part of the [5]rotaxane axle, demonstrates that Zn2+ is clearly five-coordinate, the fifth ligand being a counterion, even when the coordination site of the pseudorotaxane is designed for four-coordinate metals, which is in marked contrast with copper(I) or Li+.}, keywords = {}, pubstate = {published}, tppubtype = {article} } A new example of a linear [5]rotaxane has been synthesized by using the traditional “gathering-and-threading” approach but based on an unusual axle incorporating a symmetrical bis(bidentate) chelating fragment built on a 4,7-phenanthroline core. The stoppering reaction is particularly noteworthy since, instead of using a trivial bulky stopper as precursor to the blocking group, two semistoppered copper-complexed [2]pseudorotaxanes (namely [2]semirotaxanes) are used, which leads to the desired [5]rotaxane in good yield. The efficiency of the method relies on the use of “click” chemistry, with its very mild conditions, and on the protection by a transition-metal (copper(I)) of the various coordinating groups present in the fragments to be interconnected (terpy and bidentate chelating groups), thus inhibiting potential detrimental side reactions during the copper-catalyzed stoppering reaction. Since the external fragments and the central core of the system contain tri- and bidentate chelating units, respectively, the axle of the final [5]rotaxane incorporates two types of coordinating units: two external terpy groups (terpy: 2,2':6',2 `'-terpyridine) and two central bidentate ligands. Such a situation enables the system to tidy two different metals centers, and to localize them in a priori well-defined positions. This is what was observed when mixing the free ligand with a mixture of Zn2+ and Li+: the zinc(II) ions were unambiguously shown to occupy the external sites, whereas the Li+ cations were found in the central part of the [5]rotaxane. An X-ray diffraction study carried out on a [3]pseudorotaxane, the axis of which is similar to the central part of the [5]rotaxane axle, demonstrates that Zn2+ is clearly five-coordinate, the fifth ligand being a counterion, even when the coordination site of the pseudorotaxane is designed for four-coordinate metals, which is in marked contrast with copper(I) or Li+. |
Collin, Jean-Paul ; Durot, Stephanie ; Sauvage, Jean-Pierre ; Trolez, Yann Synthesis of [2]-, [3]-, and [4]rotaxanes whose axis contains two bidentate and two tridentate chelates Journal Article In: NEW JOURNAL OF CHEMISTRY, 35 (10), pp. 2009–2012, 2011, ISSN: 1144-0546. @article{collin_synthesis_2011-1, title = {Synthesis of [2]-, [3]-, and [4]rotaxanes whose axis contains two bidentate and two tridentate chelates}, author = {Collin, Jean-Paul and Durot, Stephanie and Sauvage, Jean-Pierre and Trolez, Yann}, doi = {10.1039/c1nj20213h}, issn = {1144-0546}, year = {2011}, date = {2011-01-01}, journal = {NEW JOURNAL OF CHEMISTRY}, volume = {35}, number = {10}, pages = {2009--2012}, abstract = {A [3]rotaxane consisting of two 30-membered rings threaded by a symmetrical filament-like fragment was synthesized thanks to the copper(I)-template effect. The filament incorporates two tridentate coordinating units and two bidentate chelating groups. In addition to the [3]rotaxane, two homologous compounds were isolated in very significant yields: the corresponding [2]- and [4]-rotaxanes containing the same thread as the [3]rotaxane and encompassing one or three rings respectively.}, keywords = {}, pubstate = {published}, tppubtype = {article} } A [3]rotaxane consisting of two 30-membered rings threaded by a symmetrical filament-like fragment was synthesized thanks to the copper(I)-template effect. The filament incorporates two tridentate coordinating units and two bidentate chelating groups. In addition to the [3]rotaxane, two homologous compounds were isolated in very significant yields: the corresponding [2]- and [4]-rotaxanes containing the same thread as the [3]rotaxane and encompassing one or three rings respectively. |
Publications
2011 |
Blueprinting macromolecular electronics Journal Article In: NATURE CHEMISTRY, 3 (6), pp. 431–436, 2011, ISSN: 1755-4330. |
Determining the Conformational Change that Accompanies Donor-Acceptor Distance Fluctuations: An Umbrella Sampling Analysis Journal Article In: JOURNAL OF PHYSICAL CHEMISTRY B, 115 (24), pp. 7991–7995, 2011, ISSN: 1520-6106. |
Field enhancement and extraordinary optical transmission by tapered periodic slits in gold films Journal Article In: NEW JOURNAL OF PHYSICS, 13 , 2011, ISSN: 1367-2630. |
Plasmonic Antennas for Directional Sorting of Fluorescence Emission Journal Article In: NANO LETTERS, 11 (6), pp. 2400–2406, 2011, ISSN: 1530-6984. |
H-Bonding Tuned Self-Assembly of Phenylene-Thiophene-Thiophene-Phenylene Derivatives at Surfaces: Structural and Electrical Studies Journal Article In: JOURNAL OF PHYSICAL CHEMISTRY C, 115 (19), pp. 9753–9759, 2011, ISSN: 1932-7447. |
Transition-Metal-Complexed Cyclic [3]- and [4]Pseudorotaxanes Containing Rigid Ring-and-Filament Conjugates: Synthesis and Solution Studies Journal Article In: CHEMISTRY-A EUROPEAN JOURNAL, 17 (19), pp. 5404–5414, 2011, ISSN: 0947-6539. |
Intercalation of Tetrathiafulvalene between the Two Plates of a Copper(I)-Complexed [4]Rotaxane Journal Article In: EUROPEAN JOURNAL OF ORGANIC CHEMISTRY, (13), pp. 2413–2416, 2011, ISSN: 1434-193X. |
Mechanisms for extraordinary optical transmission through bull's eye structures Journal Article In: OPTICS EXPRESS, 19 (11), pp. 10429–10442, 2011, ISSN: 1094-4087. |
Reversible Switching of Ultrastrong Light-Molecule Coupling Journal Article In: PHYSICAL REVIEW LETTERS, 106 (19), 2011, ISSN: 0031-9007. |
Mastering Self-Organization of Functional Materials at Different Length Scale Journal Article In: ADVANCED FUNCTIONAL MATERIALS, 21 (7, SI), pp. 1210–1211, 2011, ISSN: 1616-301X. |
Non-conventional Processing and Post-processing Methods for the Nanostructuring of Conjugated Materials for Organic Electronics Journal Article In: ADVANCED FUNCTIONAL MATERIALS, 21 (7, SI), pp. 1279–1295, 2011, ISSN: 1616-301X. |
Unsuspected pathway of the allosteric transition in hemoglobin Journal Article In: PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA, 108 (14), pp. 5608–5613, 2011, ISSN: 0027-8424. |
Beyond synthesis: Self-organization Journal Article In: COMPTES RENDUS CHIMIE, 14 (4), pp. 348–361, 2011, ISSN: 1631-0748. |
Controlled Supramolecular Oligomerization of C-3-Symmetrical Molecules in Water: The Impact of Hydrophobic Shielding Journal Article In: CHEMISTRY-A EUROPEAN JOURNAL, 17 (18), pp. 5193–5203, 2011, ISSN: 0947-6539. |
New generation of amino coumarin methyl sulfonate-based fluorogenic substrates for amidase assays in droplet-based microfluidic applications Journal Article In: Analytical Chemistry, 83 (8), pp. 2852–2857, 2011, ISSN: 1520-6882. |
Optical Modulation of the Charge Injection in an Organic Field-Effect Transistor Based on Photochromic Self-Assembled-Monolayer-Functionalized Electrodes Journal Article In: ADVANCED MATERIALS, 23 (12), pp. 1447–1452, 2011, ISSN: 0935-9648. |
Self-Assembled Conjugated Thiophene-Based Rotaxane Architectures: Structural, Computational, and Spectroscopic Insights into Molecular Aggregation Journal Article In: ADVANCED FUNCTIONAL MATERIALS, 21 (5), pp. 834–844, 2011, ISSN: 1616-301X. |
Local Surface Potential of pi-Conjugated Nanostructures by Kelvin Probe Force Microscopy: Effect of the Sampling Depth Journal Article In: SMALL, 7 (5), pp. 634–639, 2011, ISSN: 1613-6810. |
Myo-InositolTrisPyroPhosphate Treatment Leads to HIF-1 alpha Suppression and Eradication of Early Hepatoma Tumors in Rats Journal Article In: CHEMBIOCHEM, 12 (5), pp. 777–783, 2011, ISSN: 1439-4227. |
Cysteine Mapping in Conformationally Distinct Kinase Nucleotide Binding Sites: Application to the Design of Selective Covalent Inhibitors Journal Article In: JOURNAL OF MEDICINAL CHEMISTRY, 54 (5), pp. 1347–1355, 2011, ISSN: 0022-2623. |
Rigid Dimers Formed through Strong Interdigitated Ħ-Bonds Yield Compact 1D Supramolecular Helical Polymers Journal Article In: SMALL, 7 (3), pp. 342–350, 2011, ISSN: 1613-6810. |
Free energy of conformational transition paths in biomolecules: The string method and its application to myosin VI Journal Article In: JOURNAL OF CHEMICAL PHYSICS, 134 (8), 2011, ISSN: 0021-9606. |
Reversible Aminal Formation: Controlling the Evaporation of Bioactive Volatiles by Dynamic Combinatorial/Covalent Chemistry Journal Article In: EUROPEAN JOURNAL OF ORGANIC CHEMISTRY, (4), pp. 681–695, 2011, ISSN: 1434-193X. |
A new terrestrial vertebrate site just after the Paleocene-Eocene boundary in the Mortemer Formation of Upper Normandy, France Journal Article In: COMPTES RENDUS PALEVOL, 10 (1), pp. 11–20, 2011, ISSN: 1631-0683. |
Luminescence studies of copper(I)-containing [2]pseudorotaxanes Journal Article In: CANADIAN JOURNAL OF CHEMISTRY, 89 (2), pp. 98–103, 2011, ISSN: 0008-4042. |
Translating instructions into function by nucleic acid programmed self-assembly Journal Article In: ACTUALITE CHIMIQUE, (348-49), pp. 42–48, 2011, ISSN: 0151-9093. |
Bright Unidirectional Fluorescence Emission of Molecules in a Nanoaperture with Plasmonic Corrugations Journal Article In: NANO LETTERS, 11 (2), pp. 637–644, 2011, ISSN: 1530-6984. |
Modulating the self-assembly of rigid “clicked” dendrimers at the solid-liquid interface by tuning non-covalent interactions between side groups Journal Article In: CHEMICAL COMMUNICATIONS, 47 (38), pp. 10578–10580, 2011, ISSN: 1359-7345. |
Nanopatterning the graphite surface with ordered macrocyclic or ribbon-like assemblies of isocytosine derivatives: an STM study Journal Article In: CRYSTENGCOMM, 13 (18), pp. 5535–5537, 2011, ISSN: 1466-8033. |
Integration of self-assembled discotic-based fibres into field-effect transistors: a comparison of preparation approaches Journal Article In: JOURNAL OF MATERIALS CHEMISTRY, 21 (1), pp. 206–213, 2011, ISSN: 0959-9428. |
Charge transport in graphene-polythiophene blends as studied by Kelvin Probe Force Microscopy and transistor characterization Journal Article In: JOURNAL OF MATERIALS CHEMISTRY, 21 (9), pp. 2924–2931, 2011, ISSN: 0959-9428. |
Polyamine functionalized carbon nanotubes: synthesis, characterization, cytotoxicity and siRNA binding Journal Article In: JOURNAL OF MATERIALS CHEMISTRY, 21 (13), pp. 4850–4860, 2011, ISSN: 0959-9428. |
Supramolecular assembly/reassembly processes: molecular motors and dynamers operating at surfaces Journal Article In: NANOSCALE, 3 (4), pp. 1397–1410, 2011, ISSN: 2040-3364. |
Self-templating 2D supramolecular networks: a new avenue to reach control over a bilayer formation Journal Article In: NANOSCALE, 3 (10), pp. 4125–4129, 2011, ISSN: 2040-3364. |
Photoinduced work function changes by isomerization of a densely packed azobenzene-based SAM on Au: a joint experimental and theoretical study Journal Article In: PHYSICAL CHEMISTRY CHEMICAL PHYSICS, 13 (32), pp. 14302–14310, 2011, ISSN: 1463-9076. |
Polyphosphates and Pyrophosphates of Hexopyranoses as Allosteric Effectors of Human Hemoglobin: Synthesis, Molecular Recognition, and Effect on Oxygen Release Journal Article In: CHEMMEDCHEM, 6 (1), pp. 153–168, 2011, ISSN: 1860-7179. |
Tetrakisphosphates and Bispyrophosphates of myo-Inositol Derivatives as Allosteric Effectors of Human Hemoglobin: Synthesis, Molecular Recognition, and Oxygen Release Journal Article In: CHEMMEDCHEM, 6 (1), pp. 169–180, 2011, ISSN: 1860-7179. |
Modulation of self-assembly and magnetism of Cu(II) grids in solution Journal Article In: CHEMICAL COMMUNICATIONS, 47 (39), pp. 10951–10953, 2011, ISSN: 1359-7345. |
Configurational and Constitutional Information Storage: Multiple Dynamics in Systems Based on Pyridyl and Acyl Hydrazones Journal Article In: CHEMISTRY-A EUROPEAN JOURNAL, 17 (1), pp. 248–258, 2011, ISSN: 0947-6539. |
A new hydrogen bonding motif involved in self-recognition in the solid state by functionalised macrocycles Journal Article In: CRYSTENGCOMM, 13 (7), pp. 2346–2349, 2011, ISSN: 1466-8033. |
Structural and metallo selectivity in the assembly of [2 x 2] grid-type metallosupramolecular species: Mechanisms and kinetic control Journal Article In: DALTON TRANSACTIONS, 40 (45), pp. 12320–12332, 2011, ISSN: 1477-9226. |
Release of bioactive volatiles from supramolecular hydrogels: influence of reversible acylhydrazone formation on gel stability and volatile compound evaporation Journal Article In: ORGANIC & BIOMOLECULAR CHEMISTRY, 9 (8), pp. 2906–2919, 2011, ISSN: 1477-0520. |
Scaling concepts in cell physics: paradigms for cell adhesion Journal Article In: SOFT MATTER, 7 (3), pp. 824–829, 2011, ISSN: 1744-683X. |
SPONTANEOUS MECHANICAL OSCILLATIONS: IMPLICATIONS FOR DEVELOPING ORGANISMS Incollection In: {Labouesse, M} (Ed.): FORCES AND TENSION IN DEVELOPMENT, 95 , pp. 67–91, 2011, ISBN: 978-0-12-385065-2. |
A noncovalently assembled porphyrinic catenane consisting of two interlocking [43]-membered rings Journal Article In: NEW JOURNAL OF CHEMISTRY, 35 (8), pp. 1751–1757, 2011, ISSN: 1144-0546. |
Bigger, better, faster: molecular shuttles with sterically non-hindering biisoquinoline chelates Journal Article In: SUPRAMOLECULAR CHEMISTRY, 23 (1-2, SI), pp. 42–52, 2011, ISSN: 1061-0278. |
Donor-acceptor molecular figures-of-eight Journal Article In: CHEMICAL COMMUNICATIONS, 47 (43), pp. 11870–11872, 2011, ISSN: 1359-7345. |
Combinatorial Self-Assembly of Glycan Fragments into Microarrays Journal Article In: CHEMBIOCHEM, 12 (1), pp. 56–60, 2011, ISSN: 1439-4227. |
Synthesis of [5]Rotaxanes Containing Bi- and Tridentate Coordination Sites in the Axis Journal Article In: CHEMISTRY-A EUROPEAN JOURNAL, 17 (3), pp. 947–957, 2011, ISSN: 0947-6539. |
Synthesis of [2]-, [3]-, and [4]rotaxanes whose axis contains two bidentate and two tridentate chelates Journal Article In: NEW JOURNAL OF CHEMISTRY, 35 (10), pp. 2009–2012, 2011, ISSN: 1144-0546. |