2018 |
Hagenmuller, David ; Schutz, Stefan ; Schachenmayer, Johannes ; Genes, Claudiu ; Pupillo, Guido Cavity-assisted mesoscopic transport of fermions: Coherent and dissipative dynamics Journal Article In: PHYSICAL REVIEW B, 97 (20), 2018, ISSN: 2469-9950. @article{hagenmuller_cavity-assisted_2018, title = {Cavity-assisted mesoscopic transport of fermions: Coherent and dissipative dynamics}, author = {Hagenmuller, David and Schutz, Stefan and Schachenmayer, Johannes and Genes, Claudiu and Pupillo, Guido}, doi = {10.1103/PhysRevB.97.205303}, issn = {2469-9950}, year = {2018}, date = {2018-05-01}, journal = {PHYSICAL REVIEW B}, volume = {97}, number = {20}, abstract = {We study the interplay between charge transport and light-matter interactions in a confined geometry by considering an open, mesoscopic chain of two-orbital systems resonantly coupled to a single bosonic mode close to its vacuum state. We introduce and benchmark different methods based on self-consistent solutions of nonequilibrium Green's functions and numerical simulations of the quantum master equation, and derive both analytical and numerical results. It is shown that in the dissipative regime where the cavity photon decay rate is the largest parameter, the light-matter coupling is responsible for a steady-state current enhancement scaling with the cooperativity parameter. We further identify different regimes of interest depending on the ratio between the cavity decay rate and the electronic bandwidth. Considering the situation where the lower band has a vanishing bandwidth, we show that for a high-finesse cavity, the properties of the resonant Bloch state in the upper band are transferred to the lower one, giving rise to a delocalized state along the chain. Conversely, in the dissipative regime with low-cavity quality factors, we find that the current enhancement is due to a collective decay of populations from the upper to the lower band.}, keywords = {}, pubstate = {published}, tppubtype = {article} } We study the interplay between charge transport and light-matter interactions in a confined geometry by considering an open, mesoscopic chain of two-orbital systems resonantly coupled to a single bosonic mode close to its vacuum state. We introduce and benchmark different methods based on self-consistent solutions of nonequilibrium Green's functions and numerical simulations of the quantum master equation, and derive both analytical and numerical results. It is shown that in the dissipative regime where the cavity photon decay rate is the largest parameter, the light-matter coupling is responsible for a steady-state current enhancement scaling with the cooperativity parameter. We further identify different regimes of interest depending on the ratio between the cavity decay rate and the electronic bandwidth. Considering the situation where the lower band has a vanishing bandwidth, we show that for a high-finesse cavity, the properties of the resonant Bloch state in the upper band are transferred to the lower one, giving rise to a delocalized state along the chain. Conversely, in the dissipative regime with low-cavity quality factors, we find that the current enhancement is due to a collective decay of populations from the upper to the lower band. |
Giglio, Valentina ; Varela-Aramburu, Silvia ; Travaglini, Leana ; Fiorini, Federica ; Seeberger, Peter H; Maggini, Laura ; De Cola, Luisa Reshaping silica particles: Mesoporous nanodiscs for bimodal delivery and improved cellular uptake Journal Article In: CHEMICAL ENGINEERING JOURNAL, 340 (SI), pp. 148–154, 2018, ISSN: 1385-8947. @article{giglio_reshaping_2018, title = {Reshaping silica particles: Mesoporous nanodiscs for bimodal delivery and improved cellular uptake}, author = {Giglio, Valentina and Varela-Aramburu, Silvia and Travaglini, Leana and Fiorini, Federica and Seeberger, Peter H. and Maggini, Laura and De Cola, Luisa}, doi = {10.1016/j.cej.2018.01.059}, issn = {1385-8947}, year = {2018}, date = {2018-05-01}, journal = {CHEMICAL ENGINEERING JOURNAL}, volume = {340}, number = {SI}, pages = {148--154}, abstract = {The role played by the shape of mesoporous silica nanoparticles has been investigated for intra-and extracellular delivery. Specifically, we have developed the bottom-up synthesis of flat disc-shaped mesoporous silica nanoparticles, the Nanodiscs (NDs). Due to their peculiar shape and large porous system, NDs present a higher cellular uptake than commonly investigated spherical mesoporous nanoparticles. Moreover, NDs are able to efficiently perform exhaustive delivery of their therapeutic cargo when loaded with the anticancer drug Doxorubicin and administered in vitro to cancerous HeLa cells. Thanks to their aspect ratio, NDs can also be readily assembled into well-organized monolayers to be employed in HeLa cells adhesion experiments upon preliminary functionalization with a specific targeting ligand. In these conditions NDs are able to deliver a hydrophobic dye to adhered cells via the highly accessible vertically aligned pores and their flat surface that ensures optimal cell contact. This initial investigation on the performance of NDs in both intra- and extracellular delivery activities suggests the great potential of these particles.}, keywords = {}, pubstate = {published}, tppubtype = {article} } The role played by the shape of mesoporous silica nanoparticles has been investigated for intra-and extracellular delivery. Specifically, we have developed the bottom-up synthesis of flat disc-shaped mesoporous silica nanoparticles, the Nanodiscs (NDs). Due to their peculiar shape and large porous system, NDs present a higher cellular uptake than commonly investigated spherical mesoporous nanoparticles. Moreover, NDs are able to efficiently perform exhaustive delivery of their therapeutic cargo when loaded with the anticancer drug Doxorubicin and administered in vitro to cancerous HeLa cells. Thanks to their aspect ratio, NDs can also be readily assembled into well-organized monolayers to be employed in HeLa cells adhesion experiments upon preliminary functionalization with a specific targeting ligand. In these conditions NDs are able to deliver a hydrophobic dye to adhered cells via the highly accessible vertically aligned pores and their flat surface that ensures optimal cell contact. This initial investigation on the performance of NDs in both intra- and extracellular delivery activities suggests the great potential of these particles. |
Dhez, Anne-Chloe ; Benedetti, Elisabetta ; Antonosante, Andrea ; Panella, Gloria ; Ranieri, Brigida ; Florio, Tiziana M; Cristiano, Loredana ; Angelucci, Francesco ; Giansanti, Francesco ; Di Leandro, Luana ; d'Angelo , Michele ; Melone, Marina ; De Cola, Antonella ; Federici, Luca ; Galzio, Renato ; Cascone, Ilaria ; Raineri, Fabio ; Cimini, Annamaria ; Courty, Jose ; Giordano, Antonio ; Ippoliti, Rodolfo Targeted therapy of human glioblastoma via delivery of a toxin through a peptide directed to cell surface nucleolin Journal Article In: JOURNAL OF CELLULAR PHYSIOLOGY, 233 (5), pp. 4091–4105, 2018, ISSN: 0021-9541. @article{dhez_targeted_2018, title = {Targeted therapy of human glioblastoma via delivery of a toxin through a peptide directed to cell surface nucleolin}, author = {Dhez, Anne-Chloe and Benedetti, Elisabetta and Antonosante, Andrea and Panella, Gloria and Ranieri, Brigida and Florio, Tiziana M. and Cristiano, Loredana and Angelucci, Francesco and Giansanti, Francesco and Di Leandro, Luana and d'Angelo, Michele and Melone, Marina and De Cola, Antonella and Federici, Luca and Galzio, Renato and Cascone, Ilaria and Raineri, Fabio and Cimini, Annamaria and Courty, Jose and Giordano, Antonio and Ippoliti, Rodolfo}, doi = {10.1002/jcp.26205}, issn = {0021-9541}, year = {2018}, date = {2018-05-01}, journal = {JOURNAL OF CELLULAR PHYSIOLOGY}, volume = {233}, number = {5}, pages = {4091--4105}, abstract = {Targeted anticancer therapies demand discovery of new cellular targets to be exploited for the delivery of toxic molecules and drugs. In this perspective, in the last few years, nucleolin has been identified as an interesting surface marker to be used for the therapy of glioblastoma. In this study, we investigated whether a synthetic antagonist of cell-surface nucleolin known as N6L, previously reported to decrease both tumor growth and tumor angiogenesis in several cancer cell lines, including glioblastoma cells, as well as endothelial cells proliferation, could be exploited to deliver a protein toxin (saporin) to glioblastoma cells. The pseudopeptide N6L cross-linked to saporin-S6 induced internalization of the toxin inside glioblastoma cancer cells. Our results in vitro demonstrated the effectiveness of this conjugate in inducing cell death, with an ID50 four orders of magnitude lower than that observed for free N6L. Furthermore, the preliminary in vivo study demonstrated efficiency in reducing the tumor mass in an orthotopic mouse model of glioblastoma.}, keywords = {}, pubstate = {published}, tppubtype = {article} } Targeted anticancer therapies demand discovery of new cellular targets to be exploited for the delivery of toxic molecules and drugs. In this perspective, in the last few years, nucleolin has been identified as an interesting surface marker to be used for the therapy of glioblastoma. In this study, we investigated whether a synthetic antagonist of cell-surface nucleolin known as N6L, previously reported to decrease both tumor growth and tumor angiogenesis in several cancer cell lines, including glioblastoma cells, as well as endothelial cells proliferation, could be exploited to deliver a protein toxin (saporin) to glioblastoma cells. The pseudopeptide N6L cross-linked to saporin-S6 induced internalization of the toxin inside glioblastoma cancer cells. Our results in vitro demonstrated the effectiveness of this conjugate in inducing cell death, with an ID50 four orders of magnitude lower than that observed for free N6L. Furthermore, the preliminary in vivo study demonstrated efficiency in reducing the tumor mass in an orthotopic mouse model of glioblastoma. |
Pakulski, Dawid ; Czepa, Wlodzimierz ; Witomska, Samanta ; Aliprandi, Alessandro ; Pawluc, Piotr ; Patroniak, Violetta ; Ciesielski, Artur ; Samori, Paolo Graphene oxide-branched polyethylenimine foams for efficient removal of toxic cations from water Journal Article In: JOURNAL OF MATERIALS CHEMISTRY A, 6 (20), pp. 9384–9390, 2018, ISSN: 2050-7488. @article{pakulski_graphene_2018, title = {Graphene oxide-branched polyethylenimine foams for efficient removal of toxic cations from water}, author = {Pakulski, Dawid and Czepa, Wlodzimierz and Witomska, Samanta and Aliprandi, Alessandro and Pawluc, Piotr and Patroniak, Violetta and Ciesielski, Artur and Samori, Paolo}, doi = {10.1039/c8ta01622d}, issn = {2050-7488}, year = {2018}, date = {2018-05-01}, journal = {JOURNAL OF MATERIALS CHEMISTRY A}, volume = {6}, number = {20}, pages = {9384--9390}, abstract = {Highly porous foams based on graphene oxide functionalized with polyethylenimine are generated and used with unprecedented efficiency for adsorbing heavy metal ions. A multiscale analysis of the GO-BPEI nanocomposite provided evidence for the covalent grafting of BPEI on GO and the formation of low crystalline porous foams. The uptake experiments revealed that the GO-BPEI's adsorption of toxic cations is strongly dependent on the pH in range from 2 to 10, as a result of the different interactions at the supramolecular level between the metal ions and the GO-BPEI foam. The maximum uptake capacities for Cu(ii), Cd(ii) and Pb(ii) are achieved at pH = 5 and exhibit values as high as 1096, 2051 and 3390 mg g(-1), respectively, being ca. over 20 times greater than standard sorbents like activated carbon. The GO-BPEI composite can be easily regenerated as proven by performing adsorption cycles. Also, the thermodynamic parameters including standard Gibbs free energy (G(o)), the enthalpy change (H-o) and entropy change (S-o) revealed the exothermic and spontaneous nature of the adsorption process.}, keywords = {}, pubstate = {published}, tppubtype = {article} } Highly porous foams based on graphene oxide functionalized with polyethylenimine are generated and used with unprecedented efficiency for adsorbing heavy metal ions. A multiscale analysis of the GO-BPEI nanocomposite provided evidence for the covalent grafting of BPEI on GO and the formation of low crystalline porous foams. The uptake experiments revealed that the GO-BPEI's adsorption of toxic cations is strongly dependent on the pH in range from 2 to 10, as a result of the different interactions at the supramolecular level between the metal ions and the GO-BPEI foam. The maximum uptake capacities for Cu(ii), Cd(ii) and Pb(ii) are achieved at pH = 5 and exhibit values as high as 1096, 2051 and 3390 mg g(-1), respectively, being ca. over 20 times greater than standard sorbents like activated carbon. The GO-BPEI composite can be easily regenerated as proven by performing adsorption cycles. Also, the thermodynamic parameters including standard Gibbs free energy (G(o)), the enthalpy change (H-o) and entropy change (S-o) revealed the exothermic and spontaneous nature of the adsorption process. |
Gobbi, Marco ; Orgiu, Emanuele ; Samori, Paolo When 2D Materials Meet Molecules: Opportunities and Challenges of Hybrid Organic/Inorganic van der Waals Heterostructures Journal Article In: ADVANCED MATERIALS, 30 (18), 2018, ISSN: 0935-9648. @article{gobbi_when_2018, title = {When 2D Materials Meet Molecules: Opportunities and Challenges of Hybrid Organic/Inorganic van der Waals Heterostructures}, author = {Gobbi, Marco and Orgiu, Emanuele and Samori, Paolo}, doi = {10.1002/adma.201706103}, issn = {0935-9648}, year = {2018}, date = {2018-05-01}, journal = {ADVANCED MATERIALS}, volume = {30}, number = {18}, abstract = {van der Waals heterostructures, composed of vertically stacked inorganic 2D materials, represent an ideal platform to demonstrate novel device architectures and to fabricate on-demand materials. The incorporation of organic molecules within these systems holds an immense potential, since, while nature offers a finite number of 2D materials, an almost unlimited variety of molecules can be designed and synthesized with predictable functionalities. The possibilities offered by systems in which continuous molecular layers are interfaced with inorganic 2D materials to form hybrid organic/inorganic van der Waals heterostructures are emphasized. Similar to their inorganic counterpart, the hybrid structures have been exploited to put forward novel device architectures, such as antiambipolar transistors and barristors. Moreover, specific molecular groups can be employed to modify intrinsic properties and confer new capabilities to 2D materials. In particular, it is highlighted how molecular self-assembly at the surface of 2D materials can be mastered to achieve precise control over position and density of (molecular) functional groups, paving the way for a new class of hybrid functional materials whose final properties can be selected by careful molecular design.}, keywords = {}, pubstate = {published}, tppubtype = {article} } van der Waals heterostructures, composed of vertically stacked inorganic 2D materials, represent an ideal platform to demonstrate novel device architectures and to fabricate on-demand materials. The incorporation of organic molecules within these systems holds an immense potential, since, while nature offers a finite number of 2D materials, an almost unlimited variety of molecules can be designed and synthesized with predictable functionalities. The possibilities offered by systems in which continuous molecular layers are interfaced with inorganic 2D materials to form hybrid organic/inorganic van der Waals heterostructures are emphasized. Similar to their inorganic counterpart, the hybrid structures have been exploited to put forward novel device architectures, such as antiambipolar transistors and barristors. Moreover, specific molecular groups can be employed to modify intrinsic properties and confer new capabilities to 2D materials. In particular, it is highlighted how molecular self-assembly at the surface of 2D materials can be mastered to achieve precise control over position and density of (molecular) functional groups, paving the way for a new class of hybrid functional materials whose final properties can be selected by careful molecular design. |
Zhang, De-Wen ; Papaioannou, Nikolaos ; David, Naomi Michelle ; Luo, Hui ; Gao, Hui ; Tanase, Liviu Cristian ; Degousee, Thibault ; Samori, Paolo ; Sapelkin, Andrei ; Fenwick, Oliver ; Titirici, Maria-Magdalena ; Krause, Steffi Photoelectrochemical response of carbon dots (CDs) derived from chitosan and their use in electrochemical imaging Journal Article In: MATERIALS HORIZONS, 5 (3), pp. 423–428, 2018, ISSN: 2051-6347. @article{zhang_photoelectrochemical_2018, title = {Photoelectrochemical response of carbon dots (CDs) derived from chitosan and their use in electrochemical imaging}, author = {Zhang, De-Wen and Papaioannou, Nikolaos and David, Naomi Michelle and Luo, Hui and Gao, Hui and Tanase, Liviu Cristian and Degousee, Thibault and Samori, Paolo and Sapelkin, Andrei and Fenwick, Oliver and Titirici, Maria-Magdalena and Krause, Steffi}, doi = {10.1039/c7mh00784a}, issn = {2051-6347}, year = {2018}, date = {2018-05-01}, journal = {MATERIALS HORIZONS}, volume = {5}, number = {3}, pages = {423--428}, abstract = {We report a direct photoelectrochemical response from low cost carbon dots (CDs) prepared from chitosan via a solvothermal method. The carbon dots were covalently linked to an indium tin oxide (ITO) surface through a self-assembled silane monolayer. We attribute the photocurrent of the ITO-silane-CD surface to a photogenerated electron-transfer process by CDs under illumination with a wavelength of 420 nm to 450 nm. The self-assembled monolayer of CDs was used for ac-photocurrent imaging of the surface with micron scale lateral resolution. This discovery opens up new applications for CDs as biocompatible, light-addressable electrochemical sensors in bioanalytical and bioimaging applications.}, keywords = {}, pubstate = {published}, tppubtype = {article} } We report a direct photoelectrochemical response from low cost carbon dots (CDs) prepared from chitosan via a solvothermal method. The carbon dots were covalently linked to an indium tin oxide (ITO) surface through a self-assembled silane monolayer. We attribute the photocurrent of the ITO-silane-CD surface to a photogenerated electron-transfer process by CDs under illumination with a wavelength of 420 nm to 450 nm. The self-assembled monolayer of CDs was used for ac-photocurrent imaging of the surface with micron scale lateral resolution. This discovery opens up new applications for CDs as biocompatible, light-addressable electrochemical sensors in bioanalytical and bioimaging applications. |
Leydecker, Tim ; Eredia, Matilde ; Liscio, Fabiola ; Milita, Silvia ; Melinte, Georgian ; Ersen, Ovidiu ; Sommer, Michael ; Ciesielski, Artur ; Samori, Paolo Graphene exfoliation in the presence of semiconducting polymers for improved film homogeneity and electrical performances Journal Article In: CARBON, 130 , pp. 495–502, 2018, ISSN: 0008-6223. @article{leydecker_graphene_2018, title = {Graphene exfoliation in the presence of semiconducting polymers for improved film homogeneity and electrical performances}, author = {Leydecker, Tim and Eredia, Matilde and Liscio, Fabiola and Milita, Silvia and Melinte, Georgian and Ersen, Ovidiu and Sommer, Michael and Ciesielski, Artur and Samori, Paolo}, doi = {10.1016/j.carbon.2018.01.042}, issn = {0008-6223}, year = {2018}, date = {2018-04-01}, journal = {CARBON}, volume = {130}, pages = {495--502}, abstract = {We report on the production of hybrid graphene/semiconducting polymer films in one step procedure by making use of ultrasound-assisted liquid-phase exfoliation of graphite powder in the presence of pi-conjugated polymers, i.e. poly(3-hexylthiophene) (P3HT) or poly[4-(4,4-dihexadecyl-4H-cyclopenta[1,2-b: 5,4-b'] dithiophen-2-yl)-alt-[1,2,5] thiadiazolo-[3,4-c] pyridine] (PCDTPT). The polymers were chosen in view of their different propensity to form crystalline structures, their decoration with alkyl chains that are known to possess high affinity for the basal plane of graphene, the energy levels of their frontier orbitals which are extremely similar to the work function of graphene, and their high electrical performance when integrated in field-effect transistors (FETs). The polymers act as a dispersion-stabilizing agent and prevent the re-aggregation of the exfoliated graphene flakes, ultimately enabling the production of homogeneous bi-component dispersions. The electrical characterization of few-layer graphene/PCDTPT hybrids, when integrated as active layer in bottom-contact bottom-gate FETs, revealed an increase of the field-effect mobility compared to the p-conjugated-based pristine devices, a result which can be attributed to the joint effect of the few-layer graphene sheets and semiconducting polymers improving the charge-transport in the channel of the field-effect transistor. In particular, few-layer graphene/PCDTPT films displayed a 30-fold increase of PCDTPT's mobility if compared to pristine polymer samples. Such findings represent a step forward towards the optimization of graphene exfoliation and processing into electronic devices, as well as towards improved electrical performance in organic-based field-effect transistors. (c) 2018 Elsevier Ltd. All rights reserved.}, keywords = {}, pubstate = {published}, tppubtype = {article} } We report on the production of hybrid graphene/semiconducting polymer films in one step procedure by making use of ultrasound-assisted liquid-phase exfoliation of graphite powder in the presence of pi-conjugated polymers, i.e. poly(3-hexylthiophene) (P3HT) or poly[4-(4,4-dihexadecyl-4H-cyclopenta[1,2-b: 5,4-b'] dithiophen-2-yl)-alt-[1,2,5] thiadiazolo-[3,4-c] pyridine] (PCDTPT). The polymers were chosen in view of their different propensity to form crystalline structures, their decoration with alkyl chains that are known to possess high affinity for the basal plane of graphene, the energy levels of their frontier orbitals which are extremely similar to the work function of graphene, and their high electrical performance when integrated in field-effect transistors (FETs). The polymers act as a dispersion-stabilizing agent and prevent the re-aggregation of the exfoliated graphene flakes, ultimately enabling the production of homogeneous bi-component dispersions. The electrical characterization of few-layer graphene/PCDTPT hybrids, when integrated as active layer in bottom-contact bottom-gate FETs, revealed an increase of the field-effect mobility compared to the p-conjugated-based pristine devices, a result which can be attributed to the joint effect of the few-layer graphene sheets and semiconducting polymers improving the charge-transport in the channel of the field-effect transistor. In particular, few-layer graphene/PCDTPT films displayed a 30-fold increase of PCDTPT's mobility if compared to pristine polymer samples. Such findings represent a step forward towards the optimization of graphene exfoliation and processing into electronic devices, as well as towards improved electrical performance in organic-based field-effect transistors. (c) 2018 Elsevier Ltd. All rights reserved. |
Chervy, Thibault ; Azzini, Stefano ; Lorchat, Etienne ; Wang, Shaojun ; Gorodetski, Yuri ; Hutchison, James A; Berciaud, Stephane ; Ebbesen, Thomas W; Genet, Cyriaque Room Temperature Chiral Coupling of Valley Excitons with Spin-Momentum Locked Surface Plasmons Journal Article In: ACS PHOTONICS, 5 (4), pp. 1281–1287, 2018, ISSN: 2330-4022. @article{chervy_room_2018, title = {Room Temperature Chiral Coupling of Valley Excitons with Spin-Momentum Locked Surface Plasmons}, author = {Chervy, Thibault and Azzini, Stefano and Lorchat, Etienne and Wang, Shaojun and Gorodetski, Yuri and Hutchison, James A. and Berciaud, Stephane and Ebbesen, Thomas W. and Genet, Cyriaque}, doi = {10.1021/acsphotonics.7b01032}, issn = {2330-4022}, year = {2018}, date = {2018-04-01}, journal = {ACS PHOTONICS}, volume = {5}, number = {4}, pages = {1281--1287}, abstract = {We demonstrate room temperature chiral coupling of valley excitons in a transition metal dichalcogenide monolayer with spin momentum locked surface plasmons. At the onset of the strong coupling regime, we measure spin-selective excitation of directional flows of polaritons. Operating under such conditions, our platform yields surprisingly robust intervalley contrasts (ca. 40%) and coherence (ca. 5-8%) as opposed to their total absence for the uncoupled valley excitons at room temperature. These results open rich possibilities, easy to implement, in the context of chiral optical networks.}, keywords = {}, pubstate = {published}, tppubtype = {article} } We demonstrate room temperature chiral coupling of valley excitons in a transition metal dichalcogenide monolayer with spin momentum locked surface plasmons. At the onset of the strong coupling regime, we measure spin-selective excitation of directional flows of polaritons. Operating under such conditions, our platform yields surprisingly robust intervalley contrasts (ca. 40%) and coherence (ca. 5-8%) as opposed to their total absence for the uncoupled valley excitons at room temperature. These results open rich possibilities, easy to implement, in the context of chiral optical networks. |
Gu, Ruirui ; Flidrova, Karolina ; Lehn, Jean-Marie Dynamic Covalent Metathesis in the C=C/C=N Exchange between Knoevenagel Compounds and Imines Journal Article In: JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 140 (16), pp. 5560–5568, 2018, ISSN: 0002-7863. @article{gu_dynamic_2018, title = {Dynamic Covalent Metathesis in the C=C/C=N Exchange between Knoevenagel Compounds and Imines}, author = {Gu, Ruirui and Flidrova, Karolina and Lehn, Jean-Marie}, doi = {10.1021/jacs.8b01849}, issn = {0002-7863}, year = {2018}, date = {2018-04-01}, journal = {JOURNAL OF THE AMERICAN CHEMICAL SOCIETY}, volume = {140}, number = {16}, pages = {5560--5568}, abstract = {Fast and reversible dynamic covalent C=C/C=N exchange takes place without catalyst in nonpolar solvents between barbiturate-derived Knoevenagel (Kn) compounds and imines. A detailed study of the reaction indicates that it proceeds by an associative organo-metathesis mechanism involving the formation of a four-membered ring azetidine intermediate by addition of the imine C=N group to the C=C bond of the Kn compound. This intermediate could be generated cleanly and stabilized at low temperature by condensation of the o,p-dinitrophenyl Kn derivative with the cyclic imine 1-azacyclohexene. It was characterized by extensive NMR and mass spectrometric studies. The process described represents a genuine dynamic covalent organo-metathesis through a four-membered ring adduct as intermediate. It paves the way for the exploration of a wide set of dynamic systems involving (strongly) polarized C=C bonds and various imines, extending also into covalent dynamic polymers and polymolecular assemblies.}, keywords = {}, pubstate = {published}, tppubtype = {article} } Fast and reversible dynamic covalent C=C/C=N exchange takes place without catalyst in nonpolar solvents between barbiturate-derived Knoevenagel (Kn) compounds and imines. A detailed study of the reaction indicates that it proceeds by an associative organo-metathesis mechanism involving the formation of a four-membered ring azetidine intermediate by addition of the imine C=N group to the C=C bond of the Kn compound. This intermediate could be generated cleanly and stabilized at low temperature by condensation of the o,p-dinitrophenyl Kn derivative with the cyclic imine 1-azacyclohexene. It was characterized by extensive NMR and mass spectrometric studies. The process described represents a genuine dynamic covalent organo-metathesis through a four-membered ring adduct as intermediate. It paves the way for the exploration of a wide set of dynamic systems involving (strongly) polarized C=C bonds and various imines, extending also into covalent dynamic polymers and polymolecular assemblies. |
Pupillo, Guido Modifying conductivity and material properties of molecular ensembles under light-matter strong coupling Journal Article In: ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY, 255 , 2018, ISSN: 0065-7727. @article{pupillo_modifying_2018, title = {Modifying conductivity and material properties of molecular ensembles under light-matter strong coupling}, author = {Pupillo, Guido}, issn = {0065-7727}, year = {2018}, date = {2018-03-01}, journal = {ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY}, volume = {255}, keywords = {}, pubstate = {published}, tppubtype = {article} } |
Galanti, Agostino ; Biellmann, Thomas ; Wytko, Jennifer ; Boixel, Julien ; Guerchais, Veronique ; Samori, Paolo ; Weiss, Jean Photo-inks based on porphyrins and diarylethenes (DAEs) Journal Article In: ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY, 255 , 2018, ISSN: 0065-7727. @article{galanti_photo-inks_2018, title = {Photo-inks based on porphyrins and diarylethenes (DAEs)}, author = {Galanti, Agostino and Biellmann, Thomas and Wytko, Jennifer and Boixel, Julien and Guerchais, Veronique and Samori, Paolo and Weiss, Jean}, issn = {0065-7727}, year = {2018}, date = {2018-03-01}, journal = {ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY}, volume = {255}, keywords = {}, pubstate = {published}, tppubtype = {article} } |
Janica, Iwona ; Patroniak, Violetta ; Samori, Paolo ; Ciesielski, Artur Imine-Based Architectures at Surfaces and Interfaces: FromSelf-Assembly to Dynamic Covalent Chemistry in 2D Journal Article In: CHEMISTRY-AN ASIAN JOURNAL, 13 (5), pp. 465–481, 2018, ISSN: 1861-4728. @article{janica_imine-based_2018, title = {Imine-Based Architectures at Surfaces and Interfaces: FromSelf-Assembly to Dynamic Covalent Chemistry in 2D}, author = {Janica, Iwona and Patroniak, Violetta and Samori, Paolo and Ciesielski, Artur}, doi = {10.1002/asia.201701629}, issn = {1861-4728}, year = {2018}, date = {2018-03-01}, journal = {CHEMISTRY-AN ASIAN JOURNAL}, volume = {13}, number = {5}, pages = {465--481}, abstract = {Within the last two decades, dynamic covalent chemistry (DCC) has emerged as an efficient and versatile strategy for the design and synthesis of complex molecular systems in solution. While early examples of supramolecularly assisted covalent synthesis at surfaces relied strongly on kinetically controlled reactions for post-assembly covalent modification, the DCC method takes advantage of the reversible nature of bond formation and allows the generation of the new covalently bonded structures under thermodynamic control. These structurally complex architectures obtained by means of DCC protocols offer a wealth of solutions and opportunities in the generation of new complex materials that possess sophisticated properties. In this focus review we examine the formation of covalently bonded imine-based discrete nanostructures as well as one-dimensional (1D) polymers and two-dimensional (2D) covalent organic frameworks (COFs) physisorbed on solid substrates under various experimental conditions, for example, under ultra-high vacuum (UHV) or at the solid-liquid interface. Scanning tunneling microscopy (STM) was used to gain insight, with a sub-nanometer resolution, into the structure and properties of those complex nanopatterns.}, keywords = {}, pubstate = {published}, tppubtype = {article} } Within the last two decades, dynamic covalent chemistry (DCC) has emerged as an efficient and versatile strategy for the design and synthesis of complex molecular systems in solution. While early examples of supramolecularly assisted covalent synthesis at surfaces relied strongly on kinetically controlled reactions for post-assembly covalent modification, the DCC method takes advantage of the reversible nature of bond formation and allows the generation of the new covalently bonded structures under thermodynamic control. These structurally complex architectures obtained by means of DCC protocols offer a wealth of solutions and opportunities in the generation of new complex materials that possess sophisticated properties. In this focus review we examine the formation of covalently bonded imine-based discrete nanostructures as well as one-dimensional (1D) polymers and two-dimensional (2D) covalent organic frameworks (COFs) physisorbed on solid substrates under various experimental conditions, for example, under ultra-high vacuum (UHV) or at the solid-liquid interface. Scanning tunneling microscopy (STM) was used to gain insight, with a sub-nanometer resolution, into the structure and properties of those complex nanopatterns. |
Ovchinnikov, Victor ; Louveau, Joy E; Barton, John P; Karplus, Martin ; Chakraborty, Arup K Role of framework mutations and antibody flexibility in the evolution of broadly neutralizing antibodies Journal Article In: ELIFE, 7 , 2018, ISSN: 2050-084X. @article{ovchinnikov_role_2018, title = {Role of framework mutations and antibody flexibility in the evolution of broadly neutralizing antibodies}, author = {Ovchinnikov, Victor and Louveau, Joy E. and Barton, John P. and Karplus, Martin and Chakraborty, Arup K.}, doi = {10.7554/eLife.33038}, issn = {2050-084X}, year = {2018}, date = {2018-02-01}, journal = {ELIFE}, volume = {7}, abstract = {Eliciting antibodies that are cross reactive with surface proteins of diverse strains of highly mutable pathogens (e.g., HIV, influenza) could be key for developing effective universal vaccines. Mutations in the framework regions of such broadly neutralizing antibodies (bnAbs) have been reported to play a role in determining their properties. We used molecular dynamics simulations and models of affinity maturation to study specific bnAbs against HIV. Our results suggest that there are different classes of evolutionary lineages for the bnAbs. If germline B cells that initiate affinity maturation have high affinity for the conserved residues of the targeted epitope, framework mutations increase antibody rigidity as affinity maturation progresses to evolve bnAbs. If the germline B cells exhibit weak/moderate affinity for conserved residues, an initial increase in flexibility via framework mutations may be required for the evolution of bnAbs. Subsequent mutations that increase rigidity result in highly potent bnAbs. Implications of our results for immunogen design are discussed.}, keywords = {}, pubstate = {published}, tppubtype = {article} } Eliciting antibodies that are cross reactive with surface proteins of diverse strains of highly mutable pathogens (e.g., HIV, influenza) could be key for developing effective universal vaccines. Mutations in the framework regions of such broadly neutralizing antibodies (bnAbs) have been reported to play a role in determining their properties. We used molecular dynamics simulations and models of affinity maturation to study specific bnAbs against HIV. Our results suggest that there are different classes of evolutionary lineages for the bnAbs. If germline B cells that initiate affinity maturation have high affinity for the conserved residues of the targeted epitope, framework mutations increase antibody rigidity as affinity maturation progresses to evolve bnAbs. If the germline B cells exhibit weak/moderate affinity for conserved residues, an initial increase in flexibility via framework mutations may be required for the evolution of bnAbs. Subsequent mutations that increase rigidity result in highly potent bnAbs. Implications of our results for immunogen design are discussed. |
Richmond, Edward ; Vukovic, Vuk D; Moran, Joseph Nucleophilic Ring Opening of Donor-Acceptor Cyclopropanes Catalyzed by a Bronsted Acid in Hexafluoroisopropanol Journal Article In: ORGANIC LETTERS, 20 (3), pp. 574–577, 2018, ISSN: 1523-7060. @article{richmond_nucleophilic_2018, title = {Nucleophilic Ring Opening of Donor-Acceptor Cyclopropanes Catalyzed by a Bronsted Acid in Hexafluoroisopropanol}, author = {Richmond, Edward and Vukovic, Vuk D. and Moran, Joseph}, doi = {10.1021/acs.orglett.7b03688}, issn = {1523-7060}, year = {2018}, date = {2018-02-01}, journal = {ORGANIC LETTERS}, volume = {20}, number = {3}, pages = {574--577}, abstract = {A general, Bronsted acid catalyzed method for the room temperature, nucleophilic ring opening of donor acceptor cyclopropanes in fluorinated alcohol solvent, HFIP, is described. Salient features of this method include an expanded cydopropane scope, including those bearing single keto-acceptor groups and those bearing electron-deficient aryl groups. Notably, the catalytic system proved amenable to a wide range of nucleophiles including, arenes, indoles, azides, diketones, and alcohols.}, keywords = {}, pubstate = {published}, tppubtype = {article} } A general, Bronsted acid catalyzed method for the room temperature, nucleophilic ring opening of donor acceptor cyclopropanes in fluorinated alcohol solvent, HFIP, is described. Salient features of this method include an expanded cydopropane scope, including those bearing single keto-acceptor groups and those bearing electron-deficient aryl groups. Notably, the catalytic system proved amenable to a wide range of nucleophiles including, arenes, indoles, azides, diketones, and alcohols. |
Richmond, Edward ; Moran, Joseph Recent Advances in Nickel Catalysis Enabled by Stoichiometric Metallic Reducing Agents Journal Article In: SYNTHESIS-STUTTGART, 50 (3), pp. 499–513, 2018, ISSN: 0039-7881. @article{richmond_recent_2018, title = {Recent Advances in Nickel Catalysis Enabled by Stoichiometric Metallic Reducing Agents}, author = {Richmond, Edward and Moran, Joseph}, doi = {10.1055/s-0036-1591853}, issn = {0039-7881}, year = {2018}, date = {2018-02-01}, journal = {SYNTHESIS-STUTTGART}, volume = {50}, number = {3}, pages = {499--513}, abstract = {This short review describes recent advances in the field of nickel catalysis, specifically transformations employing stable Ni(II) precatalysts that are activated in situ with the use of stoichiometric metallic reducing agents. The article seeks to summarise the field, highlighting key studies and discussing mechanistic facets. The review closes with an eye on future directions in redox-enabled nickel catalysis. 1 Introduction 2 Nickel Catalysis Enabled by Metallic Reducing Agents 3 Reductive Cross-Coupling 4 Reductive Carboxylation and Acylation-type reactions 5 Miscellaneous Reactivity 6 Perspectives and Future Directions}, keywords = {}, pubstate = {published}, tppubtype = {article} } This short review describes recent advances in the field of nickel catalysis, specifically transformations employing stable Ni(II) precatalysts that are activated in situ with the use of stoichiometric metallic reducing agents. The article seeks to summarise the field, highlighting key studies and discussing mechanistic facets. The review closes with an eye on future directions in redox-enabled nickel catalysis. 1 Introduction 2 Nickel Catalysis Enabled by Metallic Reducing Agents 3 Reductive Cross-Coupling 4 Reductive Carboxylation and Acylation-type reactions 5 Miscellaneous Reactivity 6 Perspectives and Future Directions |
Sinn, Stephan ; Yang, Liulin ; Biedermann, Frank ; Wang, Di ; Kuebel, Christian ; Cornelissen, Jeroen J L M; De Cola, Luisa Templated Formation of Luminescent Virus-like Particles by Tailor-Made Pt(II) Amphiphiles Journal Article In: JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 140 (6), pp. 2355–2362, 2018, ISSN: 0002-7863. @article{sinn_templated_2018, title = {Templated Formation of Luminescent Virus-like Particles by Tailor-Made Pt(II) Amphiphiles}, author = {Sinn, Stephan and Yang, Liulin and Biedermann, Frank and Wang, Di and Kuebel, Christian and Cornelissen, Jeroen J. L. M. and De Cola, Luisa}, doi = {10.1021/jacs.7b12447}, issn = {0002-7863}, year = {2018}, date = {2018-02-01}, journal = {JOURNAL OF THE AMERICAN CHEMICAL SOCIETY}, volume = {140}, number = {6}, pages = {2355--2362}, abstract = {Virus-like particles (VLPs) have been created from luminescent Pt(II) complex amphiphiles, able to form supramolecular structures in water solutions, that can be encapsulated or act as templates of cowpea chlorotic mottle virus capsid proteins. By virtue of a bottom-up molecular design, icosahedral and nonicosahedral (rod-like) VLPs have been constructed through diverse pathways, and a relationship between the molecular structure of the complexes and the shape and size of the VLPs has been observed. A deep insight into the mechanism for the templated formation of the differently shaped VLPs was achieved, by electron microscopy measurements (TEM and STEM) and bulk analysis (FPLC, DLS, photophysical investigations). Interestingly, the obtained VLPs can be visualized by their intense emission at room temperature, generated by the self-assembly of the Pt(II) complexes. The encapsulation of the luminescent species is further verified by their higher emission quantum yields inside the VLPs, which is due to the confinement effect of the protein cage. These hybrid materials demonstrate the potential of tailor-made supramolecular systems able to control the assembly of biological building blocks.}, keywords = {}, pubstate = {published}, tppubtype = {article} } Virus-like particles (VLPs) have been created from luminescent Pt(II) complex amphiphiles, able to form supramolecular structures in water solutions, that can be encapsulated or act as templates of cowpea chlorotic mottle virus capsid proteins. By virtue of a bottom-up molecular design, icosahedral and nonicosahedral (rod-like) VLPs have been constructed through diverse pathways, and a relationship between the molecular structure of the complexes and the shape and size of the VLPs has been observed. A deep insight into the mechanism for the templated formation of the differently shaped VLPs was achieved, by electron microscopy measurements (TEM and STEM) and bulk analysis (FPLC, DLS, photophysical investigations). Interestingly, the obtained VLPs can be visualized by their intense emission at room temperature, generated by the self-assembly of the Pt(II) complexes. The encapsulation of the luminescent species is further verified by their higher emission quantum yields inside the VLPs, which is due to the confinement effect of the protein cage. These hybrid materials demonstrate the potential of tailor-made supramolecular systems able to control the assembly of biological building blocks. |
Donato, Loic ; Atoini, Youssef ; Prasetyanto, Eko Adi ; Chen, Pengkun ; Rosticher, Celine ; Bizzarri, Claudia ; Rissanen, Kari ; De Cola, Luisa Selective Encapsulation and Enhancement of the Emission Properties of a Luminescent Cu(I) Complex in Mesoporous Silica Journal Article In: HELVETICA CHIMICA ACTA, 101 (2), 2018, ISSN: 0018-019X. @article{donato_selective_2018, title = {Selective Encapsulation and Enhancement of the Emission Properties of a Luminescent Cu(I) Complex in Mesoporous Silica}, author = {Donato, Loic and Atoini, Youssef and Prasetyanto, Eko Adi and Chen, Pengkun and Rosticher, Celine and Bizzarri, Claudia and Rissanen, Kari and De Cola, Luisa}, doi = {10.1002/hlca.201700273}, issn = {0018-019X}, year = {2018}, date = {2018-02-01}, journal = {HELVETICA CHIMICA ACTA}, volume = {101}, number = {2}, abstract = {We describe a synthetic approach to prepare new luminescent silica-based materials through the encapsulation of a neutral copper(I) complex inside the pores of mesoporous silica nanoparticles (MSN). The copper(I) complex is present, in the solid state, as two polymorphs, blue and yellow emissive, and in solution it shows a pale yellow color that is also mirrored by an emission in the yellow-orange region of the electromagnetic spectrum. The X-ray structures of single crystals have been obtained for both polymorphs. The complex encapsulation in MSN is achieved by its entrapment inside micelles followed by condensation of the silica source. Interestingly, the entrapment leads to the isolation of only one species. Indeed, the compound inside the MSN exhibits remarkable photophysical properties, showing an intense blue emission in solution and in the solid state. Powder X-ray diffraction of the hybrid materials proves that the complex entrapped in MSN is indeed the blue polymorph. The confinement provides not only a method to isolate only one form of the complex, but also a certain rigidity, more stability of the system by protection of the complex from undesirable oxidation, leading to a highly emissive material possessing a photoluminescence quantum yield of 65%.}, keywords = {}, pubstate = {published}, tppubtype = {article} } We describe a synthetic approach to prepare new luminescent silica-based materials through the encapsulation of a neutral copper(I) complex inside the pores of mesoporous silica nanoparticles (MSN). The copper(I) complex is present, in the solid state, as two polymorphs, blue and yellow emissive, and in solution it shows a pale yellow color that is also mirrored by an emission in the yellow-orange region of the electromagnetic spectrum. The X-ray structures of single crystals have been obtained for both polymorphs. The complex encapsulation in MSN is achieved by its entrapment inside micelles followed by condensation of the silica source. Interestingly, the entrapment leads to the isolation of only one species. Indeed, the compound inside the MSN exhibits remarkable photophysical properties, showing an intense blue emission in solution and in the solid state. Powder X-ray diffraction of the hybrid materials proves that the complex entrapped in MSN is indeed the blue polymorph. The confinement provides not only a method to isolate only one form of the complex, but also a certain rigidity, more stability of the system by protection of the complex from undesirable oxidation, leading to a highly emissive material possessing a photoluminescence quantum yield of 65%. |
Mohankumar, Meera ; Holler, Michel ; Meichsner, Eric ; Nierengarten, Jean-Francois ; Niess, Frederic ; Sauvage, Jean-Pierre ; Delavaux-Nicot, Beatrice ; Leoni, Enrico ; Monti, Filippo ; Malicka, Joanna M; Cocchi, Massimo ; Bandini, Elisa ; Armaroli, Nicola Heteroleptic Copper(I) Pseudorotaxanes Incorporating Macrocyclic Phenanthroline Ligands of Different Sizes Journal Article In: JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 140 (6), pp. 2336–2347, 2018, ISSN: 0002-7863. @article{mohankumar_heteroleptic_2018, title = {Heteroleptic Copper(I) Pseudorotaxanes Incorporating Macrocyclic Phenanthroline Ligands of Different Sizes}, author = {Mohankumar, Meera and Holler, Michel and Meichsner, Eric and Nierengarten, Jean-Francois and Niess, Frederic and Sauvage, Jean-Pierre and Delavaux-Nicot, Beatrice and Leoni, Enrico and Monti, Filippo and Malicka, Joanna M. and Cocchi, Massimo and Bandini, Elisa and Armaroli, Nicola}, doi = {10.1021/jacs.7b12671}, issn = {0002-7863}, year = {2018}, date = {2018-02-01}, journal = {JOURNAL OF THE AMERICAN CHEMICAL SOCIETY}, volume = {140}, number = {6}, pages = {2336--2347}, abstract = {A series of copper(I) pseudorotaxanes has been prepared from bis[2-(diphenylphosphino)phenyl] ether (POP) and macrocyclic phenanthroline ligands with different ring sizes (m30, m37, and m42). Variable-temperature studies carried out on the resulting [Cu(mXX)(POP)](+) (mXX = m30, m37, and m42) derivatives have revealed a dynamic conformational equilibrium due to the folding of the macrocyclic ligand. The absorption and luminescence properties of the pseudorotaxanes have been investigated in CH2Cl2. They exhibit metal-to-ligand charge-transfer emission with photoluminescence quantum yields (PLQYs) in the range 20-30%. The smallest system [Cu(m30)(POP)](+) shows minimal differences in spectral shape and position compared to its analogues, suggesting a slightly distorted coordination environment. PLQY is substantially enhanced in poly(methyl methacrylate) films (similar to 40-45%). The study of emission spectra and excited-state lifetimes in powder samples as a function of temperature (78-338 K) reveals thermally activated delayed fluorescence, with sizable differences in the singlet-triplet energy gap compared to the reference compound [Cu(dmp)(POP)](+) (dmp = 2,9-dimethyl-1,10-phenanthroline) and within the pseudorotaxane series. The system with the largest ring ([Cu(m42)(POP)](+)) has been tested as emissive material in OLEDs and affords bright green devices with higher luminance and greater stability compared to [Cu(dmp)(POP)](+), which lacks the macrocyclic ring. This highlights the importance of structural factors in the stability of electroluminescent devices based on Cu(I) materials.}, keywords = {}, pubstate = {published}, tppubtype = {article} } A series of copper(I) pseudorotaxanes has been prepared from bis[2-(diphenylphosphino)phenyl] ether (POP) and macrocyclic phenanthroline ligands with different ring sizes (m30, m37, and m42). Variable-temperature studies carried out on the resulting [Cu(mXX)(POP)](+) (mXX = m30, m37, and m42) derivatives have revealed a dynamic conformational equilibrium due to the folding of the macrocyclic ligand. The absorption and luminescence properties of the pseudorotaxanes have been investigated in CH2Cl2. They exhibit metal-to-ligand charge-transfer emission with photoluminescence quantum yields (PLQYs) in the range 20-30%. The smallest system [Cu(m30)(POP)](+) shows minimal differences in spectral shape and position compared to its analogues, suggesting a slightly distorted coordination environment. PLQY is substantially enhanced in poly(methyl methacrylate) films (similar to 40-45%). The study of emission spectra and excited-state lifetimes in powder samples as a function of temperature (78-338 K) reveals thermally activated delayed fluorescence, with sizable differences in the singlet-triplet energy gap compared to the reference compound [Cu(dmp)(POP)](+) (dmp = 2,9-dimethyl-1,10-phenanthroline) and within the pseudorotaxane series. The system with the largest ring ([Cu(m42)(POP)](+)) has been tested as emissive material in OLEDs and affords bright green devices with higher luminance and greater stability compared to [Cu(dmp)(POP)](+), which lacks the macrocyclic ring. This highlights the importance of structural factors in the stability of electroluminescent devices based on Cu(I) materials. |
Biellmann, Thomas ; Galanti, Agostino ; Boixel, Julien ; Wytko, Jennifer A; Guerchais, Veronique ; Samori, Paolo ; Weiss, Jean Fluorescence Commutation and Surface Photopatterning with Porphyrin Tetradithienylethene Switches Journal Article In: CHEMISTRY-A EUROPEAN JOURNAL, 24 (7), pp. 1631–1639, 2018, ISSN: 0947-6539. @article{biellmann_fluorescence_2018, title = {Fluorescence Commutation and Surface Photopatterning with Porphyrin Tetradithienylethene Switches}, author = {Biellmann, Thomas and Galanti, Agostino and Boixel, Julien and Wytko, Jennifer A. and Guerchais, Veronique and Samori, Paolo and Weiss, Jean}, doi = {10.1002/chem.201704222}, issn = {0947-6539}, year = {2018}, date = {2018-02-01}, journal = {CHEMISTRY-A EUROPEAN JOURNAL}, volume = {24}, number = {7}, pages = {1631--1639}, abstract = {Four tetradithienylethene (DTE) substituted porphyrins, the free base 1H(2), and three metal derivatives (1Zn, 1Co, 1Ni), were synthesized and studied. These dyads, for which the DTE units are connected to the porphyrin's meso positions via a meta-phenyl spacer, exhibit reversible photochromic properties in all cases, with conversion to the photostationary state (PSS) up to 88%, as confirmed by absorption and NMR spectroscopies. Compounds1H(2) and 1Zn are fluorescent in solution and display a red emission. Upon irradiation with UV light to trigger the closing of the DTEs, the fluorescence of both the free base and zinc porphyrin was very efficiently quenched in solution. The reversible, photo-switching of luminescence was retained in a tetra-DTE free-base porphyrin-doped polystyrene film, for which photo-patterning was demonstrated by confocal scanning microscopy. The tunable fluorescent properties of this multi-DTE framework render this compound of interest as a photo-rewritable fluorescent ink.}, keywords = {}, pubstate = {published}, tppubtype = {article} } Four tetradithienylethene (DTE) substituted porphyrins, the free base 1H(2), and three metal derivatives (1Zn, 1Co, 1Ni), were synthesized and studied. These dyads, for which the DTE units are connected to the porphyrin's meso positions via a meta-phenyl spacer, exhibit reversible photochromic properties in all cases, with conversion to the photostationary state (PSS) up to 88%, as confirmed by absorption and NMR spectroscopies. Compounds1H(2) and 1Zn are fluorescent in solution and display a red emission. Upon irradiation with UV light to trigger the closing of the DTEs, the fluorescence of both the free base and zinc porphyrin was very efficiently quenched in solution. The reversible, photo-switching of luminescence was retained in a tetra-DTE free-base porphyrin-doped polystyrene film, for which photo-patterning was demonstrated by confocal scanning microscopy. The tunable fluorescent properties of this multi-DTE framework render this compound of interest as a photo-rewritable fluorescent ink. |
Lehn, Jean-Marie Beyond Chemical Synthesis: Self-Organization⁈ Journal Article In: ISRAEL JOURNAL OF CHEMISTRY, 58 (1-2, SI), pp. 136–141, 2018, ISSN: 0021-2148. @article{lehn_beyond_2018, title = {Beyond Chemical Synthesis: Self-Organization⁈}, author = {Lehn, Jean-Marie}, doi = {10.1002/ijch.201800010}, issn = {0021-2148}, year = {2018}, date = {2018-02-01}, journal = {ISRAEL JOURNAL OF CHEMISTRY}, volume = {58}, number = {1-2, SI}, pages = {136--141}, abstract = {The present text presents briefly some general considerations on the steps from molecular synthesis to the development of chemistry beyond the molecule, towards mastering progressively the processes underlying the generation of complex matter by self-organization.}, keywords = {}, pubstate = {published}, tppubtype = {article} } The present text presents briefly some general considerations on the steps from molecular synthesis to the development of chemistry beyond the molecule, towards mastering progressively the processes underlying the generation of complex matter by self-organization. |
Drozdz, Wojciech ; Bessin, Yannick ; Gervais, Virginie ; Cao, Xiao-Yu ; Lehn, Jean-Marie ; Stefankiewicz, Artur R; Ulrich, Sebastien Switching Multivalent DNA Complexation using Metal-Controlled Cationic Supramolecular Self-Assemblies Journal Article In: CHEMISTRY-A EUROPEAN JOURNAL, 24 (7), pp. 1518–1521, 2018, ISSN: 0947-6539. @article{drozdz_switching_2018, title = {Switching Multivalent DNA Complexation using Metal-Controlled Cationic Supramolecular Self-Assemblies}, author = {Drozdz, Wojciech and Bessin, Yannick and Gervais, Virginie and Cao, Xiao-Yu and Lehn, Jean-Marie and Stefankiewicz, Artur R. and Ulrich, Sebastien}, doi = {10.1002/chem.201705630}, issn = {0947-6539}, year = {2018}, date = {2018-02-01}, journal = {CHEMISTRY-A EUROPEAN JOURNAL}, volume = {24}, number = {7}, pages = {1518--1521}, abstract = {We provide a proof-of-principle that coordination chemistry drives the in situ self-assembly of an inactive ligand into a multivalent cluster capable of effectively complexing DNA. We show that metal coordination and scavenging can be used to switch the multivalency of the system. Thus, controlled DNA complexation and decomplexation could be achieved.}, keywords = {}, pubstate = {published}, tppubtype = {article} } We provide a proof-of-principle that coordination chemistry drives the in situ self-assembly of an inactive ligand into a multivalent cluster capable of effectively complexing DNA. We show that metal coordination and scavenging can be used to switch the multivalency of the system. Thus, controlled DNA complexation and decomplexation could be achieved. |
Ohmori, Kenji ; Pupillo, Guido ; Thywissen, Joseph H; Weidemuller, Matthias Special issue on addressing many-body problems with cold atoms and molecules Journal Article In: JOURNAL OF PHYSICS B-ATOMIC MOLECULAR AND OPTICAL PHYSICS, 51 (2), 2018, ISSN: 0953-4075. @article{ohmori_special_2018, title = {Special issue on addressing many-body problems with cold atoms and molecules}, author = {Ohmori, Kenji and Pupillo, Guido and Thywissen, Joseph H. and Weidemuller, Matthias}, doi = {10.1088/1361-6455/aa9d13}, issn = {0953-4075}, year = {2018}, date = {2018-01-01}, journal = {JOURNAL OF PHYSICS B-ATOMIC MOLECULAR AND OPTICAL PHYSICS}, volume = {51}, number = {2}, keywords = {}, pubstate = {published}, tppubtype = {article} } |
Vilaca, Natalia ; Totovao, Ricardo ; Prasetyanto, Eko Adi ; Miranda-Goncalves, Vera ; Morais-Santos, Filipa ; Fernandes, Rui ; Figueiredo, Francisco ; Banobre-Lopez, Manuel ; Fonseca, Antonio M; De Cola, Luisa ; Baltazar, Fatima ; Neves, Isabel C Internalization studies on zeolite nanoparticles using human cells Journal Article In: JOURNAL OF MATERIALS CHEMISTRY B, 6 (3), pp. 469–476, 2018, ISSN: 2050-750X. @article{vilaca_internalization_2018, title = {Internalization studies on zeolite nanoparticles using human cells}, author = {Vilaca, Natalia and Totovao, Ricardo and Prasetyanto, Eko Adi and Miranda-Goncalves, Vera and Morais-Santos, Filipa and Fernandes, Rui and Figueiredo, Francisco and Banobre-Lopez, Manuel and Fonseca, Antonio M. and De Cola, Luisa and Baltazar, Fatima and Neves, Isabel C.}, doi = {10.1039/c7tb02534c}, issn = {2050-750X}, year = {2018}, date = {2018-01-01}, journal = {JOURNAL OF MATERIALS CHEMISTRY B}, volume = {6}, number = {3}, pages = {469--476}, abstract = {Zeolites are crystalline porous materials with a regular framework which have non-toxic effects on a variety of human cell lines and have been explored for cell imaging and drug delivery. Understanding the interaction between zeolite nanoparticles and cells is imperative for improving their potentialities, since the process of internalization of these particles is still poorly understood. In this study, the intracellular trafficking and internalization kinetics of zeolite L into breast cancer cells and normal epithelial mammary cells were analysed using scanning electron microscopy (SEM), confocal microscopy and transmission electron microscopy (TEM). We also studied the involvement of endocytic pathways using two pharmacological inhibitors, chlorpromazine and dynasore. Zeolite nanoparticles were taken up by both cell types and the cellular uptake was fast, and started immediately after 5 min of incubation. Interestingly, the uptake was dependent on the cell type since in breast cancer cells it was faster and more efficient, with a higher number of nanoparticles being internalized by cancer cells over time, compared to that in the epithelial mammary cells. TEM results showed that the internalized nanoparticles were mainly localized in the cell vacuoles. The data obtained upon using endocytic pharmacological inhibitors suggest that the zeolite L uptake is mediated by caveolin.}, keywords = {}, pubstate = {published}, tppubtype = {article} } Zeolites are crystalline porous materials with a regular framework which have non-toxic effects on a variety of human cell lines and have been explored for cell imaging and drug delivery. Understanding the interaction between zeolite nanoparticles and cells is imperative for improving their potentialities, since the process of internalization of these particles is still poorly understood. In this study, the intracellular trafficking and internalization kinetics of zeolite L into breast cancer cells and normal epithelial mammary cells were analysed using scanning electron microscopy (SEM), confocal microscopy and transmission electron microscopy (TEM). We also studied the involvement of endocytic pathways using two pharmacological inhibitors, chlorpromazine and dynasore. Zeolite nanoparticles were taken up by both cell types and the cellular uptake was fast, and started immediately after 5 min of incubation. Interestingly, the uptake was dependent on the cell type since in breast cancer cells it was faster and more efficient, with a higher number of nanoparticles being internalized by cancer cells over time, compared to that in the epithelial mammary cells. TEM results showed that the internalized nanoparticles were mainly localized in the cell vacuoles. The data obtained upon using endocytic pharmacological inhibitors suggest that the zeolite L uptake is mediated by caveolin. |
Biedermann, Frank ; De Cola, Luisa Porous supramolecular materials: the importance of emptiness Journal Article In: SUPRAMOLECULAR CHEMISTRY, 30 (3), pp. 166–168, 2018, ISSN: 1061-0278. @article{biedermann_porous_2018, title = {Porous supramolecular materials: the importance of emptiness}, author = {Biedermann, Frank and De Cola, Luisa}, doi = {10.1080/10610278.2017.1412015}, issn = {1061-0278}, year = {2018}, date = {2018-01-01}, journal = {SUPRAMOLECULAR CHEMISTRY}, volume = {30}, number = {3}, pages = {166--168}, keywords = {}, pubstate = {published}, tppubtype = {article} } |
De Cola, A; Franceschini, M; Di Matteo, A; Colotti, G; Celani, R; Clemente, E; Ippoliti, R; Cimini, A M; Dhez, A C; Vallee, B; Raineri, F; Cascone, I; Destouches, D; De Laurenzi, V; Courty, J; Federici, L N6L pseudopeptide interferes with nucleophosmin protein-protein interactions and sensitizes leukemic cells to chemotherapy Journal Article In: CANCER LETTERS, 412 , pp. 272–282, 2018, ISSN: 0304-3835. @article{de_cola_n6l_2018, title = {N6L pseudopeptide interferes with nucleophosmin protein-protein interactions and sensitizes leukemic cells to chemotherapy}, author = {De Cola, A. and Franceschini, M. and Di Matteo, A. and Colotti, G. and Celani, R. and Clemente, E. and Ippoliti, R. and Cimini, A. M. and Dhez, A. C. and Vallee, B. and Raineri, F. and Cascone, I. and Destouches, D. and De Laurenzi, V. and Courty, J. and Federici, L.}, doi = {10.1016/j.canlet.2017.10.038}, issn = {0304-3835}, year = {2018}, date = {2018-01-01}, journal = {CANCER LETTERS}, volume = {412}, pages = {272--282}, abstract = {NPM1 is a multifunctional nucleolar protein implicated in several processes such as ribosome maturation and export, DNA damage response and apoptotic response to stress stimuli. The NPMI gene is involved in human tumorigenesis and is found mutated in one third of acute myeloid leukemia patients, leading to the aberrant cytoplasmic localization of NPM1. Recent studies indicated that the N6L multivalent pseudopeptide, a synthetic ligand of cell surface nucleolin, is also able to bind NPM1 with high affinity. N6L inhibits cell growth with different mechanisms and represents a good candidate as a novel anticancer drug for a number of malignancies of different histological origin. In this study we investigated whether N6L treatment could drive antitumor effect in acute myeloid leukemia cell lines. We found that N6L binds NPM1 at the N-terminal domain, co-localizes with cytoplasmic, mutated NPM1, and interferes with its protein-protein associations. N6L toxicity appears to be p53 dependent but interestingly, the leukemic cell line harbouring the mutated form of NPM1 is more resistant to treatment, suggesting that NPM1 cytoplasmic delocalization confers protection from p53 activation. Moreover, we show that N6L sensitizes AML cells to doxorubicin and cytarabine treatment. These studies suggest that N6L may be a promising option in combination therapies for acute myeloid leukemia treatment. (C) 2017 The Authors. Published by Elsevier B.V.}, keywords = {}, pubstate = {published}, tppubtype = {article} } NPM1 is a multifunctional nucleolar protein implicated in several processes such as ribosome maturation and export, DNA damage response and apoptotic response to stress stimuli. The NPMI gene is involved in human tumorigenesis and is found mutated in one third of acute myeloid leukemia patients, leading to the aberrant cytoplasmic localization of NPM1. Recent studies indicated that the N6L multivalent pseudopeptide, a synthetic ligand of cell surface nucleolin, is also able to bind NPM1 with high affinity. N6L inhibits cell growth with different mechanisms and represents a good candidate as a novel anticancer drug for a number of malignancies of different histological origin. In this study we investigated whether N6L treatment could drive antitumor effect in acute myeloid leukemia cell lines. We found that N6L binds NPM1 at the N-terminal domain, co-localizes with cytoplasmic, mutated NPM1, and interferes with its protein-protein associations. N6L toxicity appears to be p53 dependent but interestingly, the leukemic cell line harbouring the mutated form of NPM1 is more resistant to treatment, suggesting that NPM1 cytoplasmic delocalization confers protection from p53 activation. Moreover, we show that N6L sensitizes AML cells to doxorubicin and cytarabine treatment. These studies suggest that N6L may be a promising option in combination therapies for acute myeloid leukemia treatment. (C) 2017 The Authors. Published by Elsevier B.V. |
Okada, Daichi ; Azzin, Stefano ; Nishioka, Hiroki ; Ichimura, Anna ; Tsuji, Hayato ; Nakamura, Eiichi ; Sasaki, Fumio ; Genet, Cyriaque ; Ebbesen, Thomas W; Yamamoto, Yohei pi-Electronic Co-crystal Microcavities with Selective Vibronic-Mode Light Amplification: Toward Forster Resonance Energy Transfer Lasing Journal Article In: NANO LETTERS, 18 (7), pp. 4396–4402, 2018, ISSN: 1530-6984. @article{okada_pi-electronic_2018, title = {pi-Electronic Co-crystal Microcavities with Selective Vibronic-Mode Light Amplification: Toward Forster Resonance Energy Transfer Lasing}, author = {Okada, Daichi and Azzin, Stefano and Nishioka, Hiroki and Ichimura, Anna and Tsuji, Hayato and Nakamura, Eiichi and Sasaki, Fumio and Genet, Cyriaque and Ebbesen, Thomas W. and Yamamoto, Yohei}, doi = {10.1021/acs.nanolett.8b01442}, issn = {1530-6984}, year = {2018}, date = {2018-01-01}, journal = {NANO LETTERS}, volume = {18}, number = {7}, pages = {4396--4402}, keywords = {}, pubstate = {published}, tppubtype = {article} } |
Lichosyt, Dawid ; Wasilek, Sylwia ; Dydio, Pawel ; Jurczak, Janusz The Influence of Binding Site Geometry on Anion-Binding Selectivity: A Case Study of Macrocyclic Receptors Built on the Azulene Skeleton Journal Article In: CHEMISTRY-A EUROPEAN JOURNAL, 24 (45), pp. 11683–11692, 2018, ISSN: 0947-6539. @article{lichosyt_influence_2018, title = {The Influence of Binding Site Geometry on Anion-Binding Selectivity: A Case Study of Macrocyclic Receptors Built on the Azulene Skeleton}, author = {Lichosyt, Dawid and Wasilek, Sylwia and Dydio, Pawel and Jurczak, Janusz}, doi = {10.1002/chem.201801460}, issn = {0947-6539}, year = {2018}, date = {2018-01-01}, journal = {CHEMISTRY-A EUROPEAN JOURNAL}, volume = {24}, number = {45}, pages = {11683--11692}, keywords = {}, pubstate = {published}, tppubtype = {article} } |
Bonardi, S; Le Guern, A S; Savin, C; Pupillo, G; Bolzoni, L; Cavalca, M; Pongolini, S Detection, virulence and antimicrobial resistance of Yersinia enterocolitica in bulk tank milk in Italy Journal Article In: INTERNATIONAL DAIRY JOURNAL, 84 , pp. 46–53, 2018, ISSN: 0958-6946. @article{bonardi_detection_2018, title = {Detection, virulence and antimicrobial resistance of Yersinia enterocolitica in bulk tank milk in Italy}, author = {Bonardi, S. and Le Guern, A. S. and Savin, C. and Pupillo, G. and Bolzoni, L. and Cavalca, M. and Pongolini, S.}, doi = {10.1016/j.idairyj.2018.04.003}, issn = {0958-6946}, year = {2018}, date = {2018-01-01}, journal = {INTERNATIONAL DAIRY JOURNAL}, volume = {84}, pages = {46--53}, keywords = {}, pubstate = {published}, tppubtype = {article} } |
Chervy, Thibault ; Thomas, Anoop ; Akiki, Elias ; Vergauwe, Robrecht M A; Shalabney, Atef ; George, Jino ; Devaux, Eloise ; Hutchison, James A; Genet, Cyriaque ; Ebbesen, Thomas W Vibro-Polaritonic IR Emission in the Strong Coupling Regime Journal Article In: ACS PHOTONICS, 5 (1, SI), pp. 217–224, 2018, ISSN: 2330-4022. @article{chervy_vibro-polaritonic_2018, title = {Vibro-Polaritonic IR Emission in the Strong Coupling Regime}, author = {Chervy, Thibault and Thomas, Anoop and Akiki, Elias and Vergauwe, Robrecht M. A. and Shalabney, Atef and George, Jino and Devaux, Eloise and Hutchison, James A. and Genet, Cyriaque and Ebbesen, Thomas W.}, doi = {10.1021/acsphotonics.7b00677}, issn = {2330-4022}, year = {2018}, date = {2018-01-01}, journal = {ACS PHOTONICS}, volume = {5}, number = {1, SI}, pages = {217--224}, abstract = {The strong coupling regime of light matter interaction has recently been extended to IR active molecular vibrations coupled to microcavities, resulting in the formation of so-called vibro-polaritonic states. Here we demonstrate the emissivity of such hybrid states. Using thermal excitation, we achieve polaritonic IR emission from a strongly coupled polymer. Thermal excitation of vibro-polaritons, thus, constitutes an original way of establishing sizable excited states populations in strongly coupled systems and opens new routes to the study of interacting vibro-polaritons.}, keywords = {}, pubstate = {published}, tppubtype = {article} } The strong coupling regime of light matter interaction has recently been extended to IR active molecular vibrations coupled to microcavities, resulting in the formation of so-called vibro-polaritonic states. Here we demonstrate the emissivity of such hybrid states. Using thermal excitation, we achieve polaritonic IR emission from a strongly coupled polymer. Thermal excitation of vibro-polaritons, thus, constitutes an original way of establishing sizable excited states populations in strongly coupled systems and opens new routes to the study of interacting vibro-polaritons. |
Bahsoun, Hadi ; Chervy, Thibault ; Thomas, Anoop ; Borjesson, Karl ; Hertzog, Manuel ; George, Jino ; Devaux, Eloise ; Genet, Cyriaque ; Hutchison, James A; Ebbesen, Thomas W Electronic Light-Matter Strong Coupling in Nanofluidic Fabry-Perot Cavities Journal Article In: ACS PHOTONICS, 5 (1, SI), pp. 225–232, 2018, ISSN: 2330-4022. @article{bahsoun_electronic_2018, title = {Electronic Light-Matter Strong Coupling in Nanofluidic Fabry-Perot Cavities}, author = {Bahsoun, Hadi and Chervy, Thibault and Thomas, Anoop and Borjesson, Karl and Hertzog, Manuel and George, Jino and Devaux, Eloise and Genet, Cyriaque and Hutchison, James A. and Ebbesen, Thomas W.}, doi = {10.1021/acsphotonics.7b00679}, issn = {2330-4022}, year = {2018}, date = {2018-01-01}, journal = {ACS PHOTONICS}, volume = {5}, number = {1, SI}, pages = {225--232}, abstract = {Electronic light-matter strong coupling has been limited to solid molecular films due to the challenge of preparing optical cavities with nanoscale dimensions. Here we report a technique to fabricate such Fabry-Perot nanocavities in which solutions can be introduced such that light molecule interactions can be studied at will in the liquid phase. We illustrate the versatility of these cavities by studying the emission properties of Chlorin e6 solutions in both the weak and strong coupling regimes as a function of cavity detuning. Liquid nanocavities will broaden the investigation of strong coupling to many solution-based molecular processes.}, keywords = {}, pubstate = {published}, tppubtype = {article} } Electronic light-matter strong coupling has been limited to solid molecular films due to the challenge of preparing optical cavities with nanoscale dimensions. Here we report a technique to fabricate such Fabry-Perot nanocavities in which solutions can be introduced such that light molecule interactions can be studied at will in the liquid phase. We illustrate the versatility of these cavities by studying the emission properties of Chlorin e6 solutions in both the weak and strong coupling regimes as a function of cavity detuning. Liquid nanocavities will broaden the investigation of strong coupling to many solution-based molecular processes. |
Ayme, Jean-Francois ; Lehn, Jean-Marie From Coordination Chemistry to Adaptive Chemistry Incollection In: {VanEldik, R; Puchta, R} (Ed.): ADVANCES IN INORGANIC CHEMISTRY, VOL 71: SUPRAMOLECULAR CHEMISTRY, 71 , pp. 3–78, 2018, ISBN: 978-0-12-815109-9. @incollection{ayme_coordination_2018, title = {From Coordination Chemistry to Adaptive Chemistry}, author = {Ayme, Jean-Francois and Lehn, Jean-Marie}, editor = {{VanEldik, R and Puchta, R}}, doi = {10.1016/bs.adioch.2017.11.009}, isbn = {978-0-12-815109-9}, year = {2018}, date = {2018-01-01}, booktitle = {ADVANCES IN INORGANIC CHEMISTRY, VOL 71: SUPRAMOLECULAR CHEMISTRY}, volume = {71}, pages = {3--78}, series = {Advances in Inorganic Chemistry}, abstract = {The object of chemistry has steadily evolved from discrete molecules to discrete numbers of assembled molecules and finally to networks of constitutional dynamic molecules, introducing the notion of adaptive chemistry. Inorganic coordination chemistry has been at the heart of this evolution with the metamorphosis of metal cations from coordination centers to templates to effectors. This chapter retraces 25 years of advances in metallosupramolecular chemistry by covering the birth and evolution of emblematic concepts such as the concepts of self-organization, self-sorting, constitutional dynamic chemistry, adaptive chemistry, and constitutional dynamic network. Additionally, some key metallosupramolecular structures such as helicates and grids like complexes, cages, and dynamers will be discussed alongside the implementation of motional dynamics in metallosupramolecular chemistry.}, keywords = {}, pubstate = {published}, tppubtype = {incollection} } The object of chemistry has steadily evolved from discrete molecules to discrete numbers of assembled molecules and finally to networks of constitutional dynamic molecules, introducing the notion of adaptive chemistry. Inorganic coordination chemistry has been at the heart of this evolution with the metamorphosis of metal cations from coordination centers to templates to effectors. This chapter retraces 25 years of advances in metallosupramolecular chemistry by covering the birth and evolution of emblematic concepts such as the concepts of self-organization, self-sorting, constitutional dynamic chemistry, adaptive chemistry, and constitutional dynamic network. Additionally, some key metallosupramolecular structures such as helicates and grids like complexes, cages, and dynamers will be discussed alongside the implementation of motional dynamics in metallosupramolecular chemistry. |
2017 |
Hertzog, Manuel ; Rudquist, Per ; Hutchison, James A; George, Jino ; Ebbesen, Thomas W; Borjesson, Karl Voltage-Controlled Switching of Strong Light-Matter Interactions using Liquid Crystals Journal Article In: CHEMISTRY-A EUROPEAN JOURNAL, 23 (72), pp. 18166–18170, 2017, ISSN: 0947-6539. @article{hertzog_voltage-controlled_2017, title = {Voltage-Controlled Switching of Strong Light-Matter Interactions using Liquid Crystals}, author = {Hertzog, Manuel and Rudquist, Per and Hutchison, James A. and George, Jino and Ebbesen, Thomas W. and Borjesson, Karl}, doi = {10.1002/chem.201705461}, issn = {0947-6539}, year = {2017}, date = {2017-12-01}, journal = {CHEMISTRY-A EUROPEAN JOURNAL}, volume = {23}, number = {72}, pages = {18166--18170}, abstract = {textbackslashtextbackslashtextbackslashtextbackslash We experimentally demonstrate a fine control over the coupling strength of vibrational light-matter hybrid states by controlling the orientation of a nematic liquid crystal. Through an external voltage, the liquid crystal is seamlessly switched between two orthogonal directions. Using these features, for the first time, we demonstrate electrical switching and increased Rabi splitting through transition dipole moment alignment. The C-N-str vibration on the liquid crystal molecule is coupled to a cavity mode, and FT-IR is used to probe the formed vibropolaritonic states. A switching ratio of the Rabi splitting of 1.78 is demonstrated between the parallel and the perpendicular orientation. Furthermore, the orientational order increases the Rabi splitting by 41% as compared to an isotropic liquid. Finally, by examining the influence of molecular alignment on the Rabi splitting, the scalar product used in theoretical modeling between light and matter in the strong coupling regime is verified.}, keywords = {}, pubstate = {published}, tppubtype = {article} } textbackslashtextbackslashtextbackslashtextbackslash We experimentally demonstrate a fine control over the coupling strength of vibrational light-matter hybrid states by controlling the orientation of a nematic liquid crystal. Through an external voltage, the liquid crystal is seamlessly switched between two orthogonal directions. Using these features, for the first time, we demonstrate electrical switching and increased Rabi splitting through transition dipole moment alignment. The C-N-str vibration on the liquid crystal molecule is coupled to a cavity mode, and FT-IR is used to probe the formed vibropolaritonic states. A switching ratio of the Rabi splitting of 1.78 is demonstrated between the parallel and the perpendicular orientation. Furthermore, the orientational order increases the Rabi splitting by 41% as compared to an isotropic liquid. Finally, by examining the influence of molecular alignment on the Rabi splitting, the scalar product used in theoretical modeling between light and matter in the strong coupling regime is verified. |
Yue, Liang ; Wang, Shan ; Cecconello, Alessandro ; Lehn, Jean-Marie ; Willner, Itamar Orthogonal Operation of Constitutional Dynamic Networks Consisting of DNA-Tweezer Machines Journal Article In: ACS NANO, 11 (12), pp. 12027–12036, 2017, ISSN: 1936-0851. @article{yue_orthogonal_2017, title = {Orthogonal Operation of Constitutional Dynamic Networks Consisting of DNA-Tweezer Machines}, author = {Yue, Liang and Wang, Shan and Cecconello, Alessandro and Lehn, Jean-Marie and Willner, Itamar}, doi = {10.1021/acsnano.7b04557}, issn = {1936-0851}, year = {2017}, date = {2017-12-01}, journal = {ACS NANO}, volume = {11}, number = {12}, pages = {12027--12036}, abstract = {Overexpression or down-regulation of cellular processes are often controlled by dynamic chemical networks. Bioinspired by nature, we introduce constitutional dynamic networks (CDNs) as systems that emulate the principle of the nature processes. The CDNs comprise dynamically interconvertible equilibrated constituents that respond to external triggers by adapting the composition of the dynamic mixture to the energetic stabilization of the constituents. We introduce a nucleic acid-based CDN that includes four interconvertible and mechanically triggered tweezers, AA', BB', AB' and BA', existing in closed, closed, open, and open configurations, respectively. By subjecting the CDN to auxiliary triggers, the guided stabilization of one of the network constituents dictates the dynamic reconfiguration of the structures of the tweezers constituents. The orthogonal and reversible operations of the CDN DNA tweezers are demonstrated, using T-A center dot T triplex or K+-stabilized G-quadruplex as structural motifs that control the stabilities of the constituents. The implications of the study rest on the possible applications of input-guided CDN assemblies for sensing, logic gate operations, and programmed activation of molecular machines.}, keywords = {}, pubstate = {published}, tppubtype = {article} } Overexpression or down-regulation of cellular processes are often controlled by dynamic chemical networks. Bioinspired by nature, we introduce constitutional dynamic networks (CDNs) as systems that emulate the principle of the nature processes. The CDNs comprise dynamically interconvertible equilibrated constituents that respond to external triggers by adapting the composition of the dynamic mixture to the energetic stabilization of the constituents. We introduce a nucleic acid-based CDN that includes four interconvertible and mechanically triggered tweezers, AA', BB', AB' and BA', existing in closed, closed, open, and open configurations, respectively. By subjecting the CDN to auxiliary triggers, the guided stabilization of one of the network constituents dictates the dynamic reconfiguration of the structures of the tweezers constituents. The orthogonal and reversible operations of the CDN DNA tweezers are demonstrated, using T-A center dot T triplex or K+-stabilized G-quadruplex as structural motifs that control the stabilities of the constituents. The implications of the study rest on the possible applications of input-guided CDN assemblies for sensing, logic gate operations, and programmed activation of molecular machines. |
Hwang, Wonmuk ; Lang, Matthew J; Karplus, Martin Kinesin motility is driven by subdomain dynamics Journal Article In: ELIFE, 6 , 2017, ISSN: 2050-084X. @article{hwang_kinesin_2017, title = {Kinesin motility is driven by subdomain dynamics}, author = {Hwang, Wonmuk and Lang, Matthew J. and Karplus, Martin}, doi = {10.7554/eLife.28948}, issn = {2050-084X}, year = {2017}, date = {2017-11-01}, journal = {ELIFE}, volume = {6}, abstract = {The microtubule (MT)-associated motor protein kinesin utilizes its conserved ATPase head to achieve diverse motility characteristics. Despite considerable knowledge about how its ATPase activity and MT binding are coupled to the motility cycle, the atomic mechanism of the core events remain to be found. To obtain insights into the mechanism, we performed 38.5 microseconds of all-atom molecular dynamics simulations of kinesin-MT complexes in different nucleotide states. Local subdomain dynamics were found to be essential for nucleotide processing. Catalytic water molecules are dynamically organized by the switch domains of the nucleotide binding pocket while ATP is torsionally strained. Hydrolysis products are `pulled' by switch-I, and a new ATP is `captured' by a concerted motion of the alpha O/L5/switch-I trio. The dynamic and wet kinesin-MT interface is tuned for rapid interactions while maintaining specificity. The proposed mechanism provides the flexibility necessary for walking in the crowded cellular environment.}, keywords = {}, pubstate = {published}, tppubtype = {article} } The microtubule (MT)-associated motor protein kinesin utilizes its conserved ATPase head to achieve diverse motility characteristics. Despite considerable knowledge about how its ATPase activity and MT binding are coupled to the motility cycle, the atomic mechanism of the core events remain to be found. To obtain insights into the mechanism, we performed 38.5 microseconds of all-atom molecular dynamics simulations of kinesin-MT complexes in different nucleotide states. Local subdomain dynamics were found to be essential for nucleotide processing. Catalytic water molecules are dynamically organized by the switch domains of the nucleotide binding pocket while ATP is torsionally strained. Hydrolysis products are `pulled' by switch-I, and a new ATP is `captured' by a concerted motion of the alpha O/L5/switch-I trio. The dynamic and wet kinesin-MT interface is tuned for rapid interactions while maintaining specificity. The proposed mechanism provides the flexibility necessary for walking in the crowded cellular environment. |
Muchowska, Kamila B; Varma, Sreejith J; Chevallot-Beroux, Elodie ; Lethuillier-Karl, Lucas ; Li, Guang ; Moran, Joseph Metals promote sequences of the reverse Krebs cycle Journal Article In: NATURE ECOLOGY & EVOLUTION, 1 (11), pp. 1716–1721, 2017, ISSN: 2397-334X. @article{muchowska_metals_2017, title = {Metals promote sequences of the reverse Krebs cycle}, author = {Muchowska, Kamila B. and Varma, Sreejith J. and Chevallot-Beroux, Elodie and Lethuillier-Karl, Lucas and Li, Guang and Moran, Joseph}, doi = {10.1038/s41559-017-0311-7}, issn = {2397-334X}, year = {2017}, date = {2017-11-01}, journal = {NATURE ECOLOGY & EVOLUTION}, volume = {1}, number = {11}, pages = {1716--1721}, abstract = {The reverse tricarboxylic acid(rTCA) cycle (also known as the reverse Krebs cycle) is a central anabolic biochemical pathway whose origins are proposed to trace back to geochemistry, long before the advent of enzymes, RNA or cells, and whose imprint remains intimately embedded in the structure of core metabolism. If it existed, a primordial version of the rTCA cycle would necessarily have been catalysed by naturally occurring minerals at the earliest stage of the transition from geochemistry to biochemistry. Here, we report non-enzymatic promotion of multiple reactions of the rTCA cycle in consecutive sequence, whereby 6 of its 11 reactions were promoted by Zn2+, Cr(3+)and Fe-0 in an acidic aqueous solution. Two distinct three-reaction sequences were achieved under a common set of conditions. Selectivity was observed for reduction reactions producing rTCA cycle intermediates compared with those leading off-cycle. Reductive amination of ketoacids to furnish amino acids was observed under similar conditions. The emerging reaction network supports the feasibility of primitive anabolism in an acidic, metal-rich reducing environment.}, keywords = {}, pubstate = {published}, tppubtype = {article} } The reverse tricarboxylic acid(rTCA) cycle (also known as the reverse Krebs cycle) is a central anabolic biochemical pathway whose origins are proposed to trace back to geochemistry, long before the advent of enzymes, RNA or cells, and whose imprint remains intimately embedded in the structure of core metabolism. If it existed, a primordial version of the rTCA cycle would necessarily have been catalysed by naturally occurring minerals at the earliest stage of the transition from geochemistry to biochemistry. Here, we report non-enzymatic promotion of multiple reactions of the rTCA cycle in consecutive sequence, whereby 6 of its 11 reactions were promoted by Zn2+, Cr(3+)and Fe-0 in an acidic aqueous solution. Two distinct three-reaction sequences were achieved under a common set of conditions. Selectivity was observed for reduction reactions producing rTCA cycle intermediates compared with those leading off-cycle. Reductive amination of ketoacids to furnish amino acids was observed under similar conditions. The emerging reaction network supports the feasibility of primitive anabolism in an acidic, metal-rich reducing environment. |
Hagenmueller, David ; Schachenmayer, Johannes ; Schutz, Stefan ; Genes, Claudiu ; Pupillo, Guido Cavity-Enhanced Transport of Charge Journal Article In: PHYSICAL REVIEW LETTERS, 119 (22), 2017, ISSN: 0031-9007. @article{hagenmueller_cavity-enhanced_2017, title = {Cavity-Enhanced Transport of Charge}, author = {Hagenmueller, David and Schachenmayer, Johannes and Schutz, Stefan and Genes, Claudiu and Pupillo, Guido}, doi = {10.1103/PhysRevLett.119.223601}, issn = {0031-9007}, year = {2017}, date = {2017-11-01}, journal = {PHYSICAL REVIEW LETTERS}, volume = {119}, number = {22}, abstract = {We theoretically investigate charge transport through electronic bands of a mesoscopic one-dimensional system, where interband transitions are coupled to a confined cavity mode, initially prepared close to its vacuum. This coupling leads to light-matter hybridization where the dressed fermionic bands interact via absorption and emission of dressed cavity photons. Using a self-consistent nonequilibrium Green's function method, we compute electronic transmissions and cavity photon spectra and demonstrate how light-matter coupling can lead to an enhancement of charge conductivity in the steady state. We find that depending on cavity loss rate, electronic bandwidth, and coupling strength, the dynamics involves either an individual or a collective response of Bloch states, and we explain how this affects the current enhancement. We show that the charge conductivity enhancement can reach orders of magnitudes under experimentally relevant conditions.}, keywords = {}, pubstate = {published}, tppubtype = {article} } We theoretically investigate charge transport through electronic bands of a mesoscopic one-dimensional system, where interband transitions are coupled to a confined cavity mode, initially prepared close to its vacuum. This coupling leads to light-matter hybridization where the dressed fermionic bands interact via absorption and emission of dressed cavity photons. Using a self-consistent nonequilibrium Green's function method, we compute electronic transmissions and cavity photon spectra and demonstrate how light-matter coupling can lead to an enhancement of charge conductivity in the steady state. We find that depending on cavity loss rate, electronic bandwidth, and coupling strength, the dynamics involves either an individual or a collective response of Bloch states, and we explain how this affects the current enhancement. We show that the charge conductivity enhancement can reach orders of magnitudes under experimentally relevant conditions. |
Aliprandi, Alessandro ; Pakulski, Dawid ; Ciesielski, Artur ; Samori, Paolo Punctured Two-Dimensional Sheets for Harvesting Blue Energy Journal Article In: ACS NANO, 11 (11), pp. 10654–10658, 2017, ISSN: 1936-0851. @article{aliprandi_punctured_2017, title = {Punctured Two-Dimensional Sheets for Harvesting Blue Energy}, author = {Aliprandi, Alessandro and Pakulski, Dawid and Ciesielski, Artur and Samori, Paolo}, doi = {10.1021/acsnano.7b06657}, issn = {1936-0851}, year = {2017}, date = {2017-11-01}, journal = {ACS NANO}, volume = {11}, number = {11}, pages = {10654--10658}, abstract = {The challenges of global climate change and the world's growing demand for energy have brought the need for new renewable energy sources to the top of the international community's agenda. We have known for many centuries that energy is released upon mixing seawater and freshwater, yet it was just a few decades ago that it became clear how this energy can be converted into electricity instead of heat. As a result, the blue energy rush has raised and set new strategies in different science and technology sectors, leading to the construction of a new generation of plants and other technological investments. Among many approaches, pressure retarded osmosis has emerged as a promising method to collect the largest amount of produced blue energy. In this Perspective, we highlight the advances in the development of ultrathin membranes based on two-dimensional materials. We discuss the most relevant synthetic methods devised to generate atomically thin membranes for pressure-retarded osmosis and retarded electrodialysis applications, and we provide some critical views on the greatest challenges in this thrilling research area.}, keywords = {}, pubstate = {published}, tppubtype = {article} } The challenges of global climate change and the world's growing demand for energy have brought the need for new renewable energy sources to the top of the international community's agenda. We have known for many centuries that energy is released upon mixing seawater and freshwater, yet it was just a few decades ago that it became clear how this energy can be converted into electricity instead of heat. As a result, the blue energy rush has raised and set new strategies in different science and technology sectors, leading to the construction of a new generation of plants and other technological investments. Among many approaches, pressure retarded osmosis has emerged as a promising method to collect the largest amount of produced blue energy. In this Perspective, we highlight the advances in the development of ultrathin membranes based on two-dimensional materials. We discuss the most relevant synthetic methods devised to generate atomically thin membranes for pressure-retarded osmosis and retarded electrodialysis applications, and we provide some critical views on the greatest challenges in this thrilling research area. |
Cao, Yihai ; Clavien, Pierre-Alain ; Humar, Bostjan ; Lehn, Jean-Marie ; He, Yuanzheng ; Rajpoot, Nasir ; Canc, Editorial Off Chinese Journal The 150 most important questions in cancer research and clinical oncology series: questions 76-85 Journal Article In: CHINESE JOURNAL OF CANCER, 36 , pp. 1–6, 2017, ISSN: 1000-467X. @article{cao_150_2017, title = {The 150 most important questions in cancer research and clinical oncology series: questions 76-85}, author = {Cao, Yihai and Clavien, Pierre-Alain and Humar, Bostjan and Lehn, Jean-Marie and He, Yuanzheng and Rajpoot, Nasir and Canc, Editorial Off Chinese Journal}, doi = {10.1186/s40880-017-0259-7}, issn = {1000-467X}, year = {2017}, date = {2017-11-01}, journal = {CHINESE JOURNAL OF CANCER}, volume = {36}, pages = {1--6}, abstract = {Since the beginning of 2017, Chinese Journal of Cancer has published a series of important questions in cancer research and clinical oncology to promote cancer research and accelerate collaborations. In this article, 10 questions are presented as followed. Question 76. How to develop effective therapeutics for cancer cachexia? Question 77. How can we develop preclinical animal models to recapitulate clinical situations of cancer patients for more effective anti-cancer drug development? Question 78. How can we develop novel effective therapeutics for pancreatic cancer and hepatocellular carcinoma? Question 79. What are the true beneficial mechanisms of antiangiogenic therapy in cancer patients? Question 80. How to approach the complex mechanisms of interplay among various cellular and molecular components in the tumor microenvironment? Question 81. Can tissue oxygenation improve the efficacy of conventional chemotherapy on cancer? Question 82. Can tissue oxygenation improve the efficacy of radiotherapy on digestive system tumors including liver cancer? Question 83. Can we integrate metabolic priming into multimodal management of liver cancer? Question 84. Has the limit of anti-androgen strategy in prostate cancer treatment been reached by the new generation of anti-androgen drugs? Question 85. Can we identify individuals with early-stage cancers via analyzing their clinical and non-clinical information collected from social media, shopping history, and clinical, pathological, and molecular traces?.}, keywords = {}, pubstate = {published}, tppubtype = {article} } Since the beginning of 2017, Chinese Journal of Cancer has published a series of important questions in cancer research and clinical oncology to promote cancer research and accelerate collaborations. In this article, 10 questions are presented as followed. Question 76. How to develop effective therapeutics for cancer cachexia? Question 77. How can we develop preclinical animal models to recapitulate clinical situations of cancer patients for more effective anti-cancer drug development? Question 78. How can we develop novel effective therapeutics for pancreatic cancer and hepatocellular carcinoma? Question 79. What are the true beneficial mechanisms of antiangiogenic therapy in cancer patients? Question 80. How to approach the complex mechanisms of interplay among various cellular and molecular components in the tumor microenvironment? Question 81. Can tissue oxygenation improve the efficacy of conventional chemotherapy on cancer? Question 82. Can tissue oxygenation improve the efficacy of radiotherapy on digestive system tumors including liver cancer? Question 83. Can we integrate metabolic priming into multimodal management of liver cancer? Question 84. Has the limit of anti-androgen strategy in prostate cancer treatment been reached by the new generation of anti-androgen drugs? Question 85. Can we identify individuals with early-stage cancers via analyzing their clinical and non-clinical information collected from social media, shopping history, and clinical, pathological, and molecular traces?. |
Limani, Perparim ; Linecker, Michael ; Schneider, Marcel A; Kron, Philipp ; Tschuor, Christoph ; Kachaylo, Ekaterina ; Ungethuem, Udo ; Nicolau, Claude ; Lehn, Jean-Marie ; Graf, Rolf ; Humar, Bostjan ; Clavien, Pierre-Alain The Allosteric Hemoglobin Effector ITPP Inhibits Metastatic Colon Cancer in Mice Journal Article In: ANNALS OF SURGERY, 266 (5), pp. 746–753, 2017, ISSN: 0003-4932. @article{limani_allosteric_2017, title = {The Allosteric Hemoglobin Effector ITPP Inhibits Metastatic Colon Cancer in Mice}, author = {Limani, Perparim and Linecker, Michael and Schneider, Marcel A. and Kron, Philipp and Tschuor, Christoph and Kachaylo, Ekaterina and Ungethuem, Udo and Nicolau, Claude and Lehn, Jean-Marie and Graf, Rolf and Humar, Bostjan and Clavien, Pierre-Alain}, doi = {10.1097/SLA.0000000000002431}, issn = {0003-4932}, year = {2017}, date = {2017-11-01}, journal = {ANNALS OF SURGERY}, volume = {266}, number = {5}, pages = {746--753}, abstract = {Objective: To test the effects of enhanced intracellular oxygen contents on the metastatic potential of colon cancer. Background: Colorectal cancer is the commonest gastrointestinal carcinoma. Distant metastases occur in half of patients and are responsible for most cancer-related deaths. Tumor hypoxia is central to the pathogenesis of metastases. Myo-Inositoltrispyrophosphate (ITPP), a nontoxic, antihypoxic compound, has recently shown significant benefits in experimental cancer, particularly when combined with standard chemotherapy. Whether ITPP protects from distant metastases in primary colon cancer is unknown. Methods: ITPP alone or combined with FOLFOX was tested in a mouse model with cecal implantation of green fluorescent protein-labeled syngeneic colorectal cancer cells. Tumor development was monitored through longitudinal magnetic resonance imaging-based morphometric analysis and survival. Established serum markers of tumor spread were measured serially and circulating tumor cells were detected via fluorescence measurements. Results: ITPP significantly reduced the occurrence of metastases as well as other indicators of tumor aggressiveness. Less circulating tumor cells along with reduction in malignant serum markers (osteopontin, Cxcl12) were noted. The ITPP benefits also affected the primary cancer site. Importantly, animals treated with ITPP had a significant survival benefit compared with respective controls, while a combination of FOLFOX with ITPP conferred the maximum benefits, including dramatic improvements in survival (mean 86 vs 188 d). Conclusions: Restoring oxygen in metastatic colon cancer through ITPP inhibits tumor spread and markedly improves animal survival; an effect that is enhanced through the application of subsequent chemotherapy. These promising novel findings call for a clinical trial on ITPP in patients with colorectal cancer, which is under way.}, keywords = {}, pubstate = {published}, tppubtype = {article} } Objective: To test the effects of enhanced intracellular oxygen contents on the metastatic potential of colon cancer. Background: Colorectal cancer is the commonest gastrointestinal carcinoma. Distant metastases occur in half of patients and are responsible for most cancer-related deaths. Tumor hypoxia is central to the pathogenesis of metastases. Myo-Inositoltrispyrophosphate (ITPP), a nontoxic, antihypoxic compound, has recently shown significant benefits in experimental cancer, particularly when combined with standard chemotherapy. Whether ITPP protects from distant metastases in primary colon cancer is unknown. Methods: ITPP alone or combined with FOLFOX was tested in a mouse model with cecal implantation of green fluorescent protein-labeled syngeneic colorectal cancer cells. Tumor development was monitored through longitudinal magnetic resonance imaging-based morphometric analysis and survival. Established serum markers of tumor spread were measured serially and circulating tumor cells were detected via fluorescence measurements. Results: ITPP significantly reduced the occurrence of metastases as well as other indicators of tumor aggressiveness. Less circulating tumor cells along with reduction in malignant serum markers (osteopontin, Cxcl12) were noted. The ITPP benefits also affected the primary cancer site. Importantly, animals treated with ITPP had a significant survival benefit compared with respective controls, while a combination of FOLFOX with ITPP conferred the maximum benefits, including dramatic improvements in survival (mean 86 vs 188 d). Conclusions: Restoring oxygen in metastatic colon cancer through ITPP inhibits tumor spread and markedly improves animal survival; an effect that is enhanced through the application of subsequent chemotherapy. These promising novel findings call for a clinical trial on ITPP in patients with colorectal cancer, which is under way. |
Carmona-Vargas, Christian C; Vaquiro, Ingri Y; Jaramillo-Gomez, Luz M; Lehn, Jean-Marie ; Chaur, Manuel N Grid-type complexes of M2+ (M = Co, Ni, and Zn) with highly soluble bis (hydrazone)thiopyrimidine-based ligands: Spectroscopy and electrochemical properties Journal Article In: INORGANICA CHIMICA ACTA, 468 , pp. 131–139, 2017, ISSN: 0020-1693. @article{carmona-vargas_grid-type_2017, title = {Grid-type complexes of M2+ (M = Co, Ni, and Zn) with highly soluble bis (hydrazone)thiopyrimidine-based ligands: Spectroscopy and electrochemical properties}, author = {Carmona-Vargas, Christian C. and Vaquiro, Ingri Y. and Jaramillo-Gomez, Luz M. and Lehn, Jean-Marie and Chaur, Manuel N.}, doi = {10.1016/j.ica.2017.05.002}, issn = {0020-1693}, year = {2017}, date = {2017-11-01}, journal = {INORGANICA CHIMICA ACTA}, volume = {468}, pages = {131--139}, abstract = {Herein we present the syntheses of two types of two-site symmetric bis(hydrazone) ligands (1 and 2) which contain two tridentate subunits suitable for metal ion complexation, with remarkable solubility in most organic solvents, contrary to other pyrimidine-based bis(hydrazones) used for the preparation of metallogrids. As expected, compounds 1 and 2 exhibit conformational changes when coordinated metal ions (Zn2+, Ni2+, Co2+) through the two terpyridine-like sites leading to the metal complexes 1ac and 2a-c. The absorption spectra and redox properties of ligands 1 and 2 and of the metal complexes 1a-c and 2a-c were studied. Compounds 1 and 2 exhibit absorption spectra dominated by intense p-p/ bands in the UV region, while the absorption spectra of the metal complexes 1a-c and 2a-c show intense bands in the UV region, due to the spin-allowed ligand-centred (LC) transitions, and in the visible region, due to spin-allowed metal-to-ligand charge transfer (MLCT) transitions. Cyclic voltammetry and square wave voltammetry were carried out in order to establish the relevance of the complexation, and the grid formation in the redox potentials of the ligands 1 and 2. (C) 2017 Elsevier B.V. All rights reserved.}, keywords = {}, pubstate = {published}, tppubtype = {article} } Herein we present the syntheses of two types of two-site symmetric bis(hydrazone) ligands (1 and 2) which contain two tridentate subunits suitable for metal ion complexation, with remarkable solubility in most organic solvents, contrary to other pyrimidine-based bis(hydrazones) used for the preparation of metallogrids. As expected, compounds 1 and 2 exhibit conformational changes when coordinated metal ions (Zn2+, Ni2+, Co2+) through the two terpyridine-like sites leading to the metal complexes 1ac and 2a-c. The absorption spectra and redox properties of ligands 1 and 2 and of the metal complexes 1a-c and 2a-c were studied. Compounds 1 and 2 exhibit absorption spectra dominated by intense p-p/ bands in the UV region, while the absorption spectra of the metal complexes 1a-c and 2a-c show intense bands in the UV region, due to the spin-allowed ligand-centred (LC) transitions, and in the visible region, due to spin-allowed metal-to-ligand charge transfer (MLCT) transitions. Cyclic voltammetry and square wave voltammetry were carried out in order to establish the relevance of the complexation, and the grid formation in the redox potentials of the ligands 1 and 2. (C) 2017 Elsevier B.V. All rights reserved. |
Klein, Mason ; Krivov, Sergei V; Ferrer, Anggie J; Luo, Linjiao ; Samuel, Aravinthan D T; Karplus, Martin Exploratory search during directed navigation in C. elegans and Drosophila larva Journal Article In: ELIFE, 6 , 2017, ISSN: 2050-084X. @article{klein_exploratory_2017, title = {Exploratory search during directed navigation in C. elegans and Drosophila larva}, author = {Klein, Mason and Krivov, Sergei V. and Ferrer, Anggie J. and Luo, Linjiao and Samuel, Aravinthan D. T. and Karplus, Martin}, doi = {10.7554/eLife.30503}, issn = {2050-084X}, year = {2017}, date = {2017-10-01}, journal = {ELIFE}, volume = {6}, abstract = {Many organisms from bacteria to nematodes to insect larvae navigate their environments by biasing random movements. In these organisms, navigation in isotropic environments can be characterized as an essentially diffusive and undirected process. In stimulus gradients, movement decisions are biased to drive directed navigation toward favorable environments. How does directed navigation in a gradient modulate random exploration either parallel or orthogonal to the gradient? Here, we introduce methods originally used for analyzing protein folding trajectories to study the trajectories of the nematode Caenorhabditis elegans and the Drosophila larva in isotropic environments, as well as in thermal and chemical gradients. We find that the statistics of random exploration in any direction are little affected by directed movement along a stimulus gradient. A key constraint on the behavioral strategies of these organisms appears to be the preservation of their capacity to continuously explore their environments in all directions even while moving toward favorable conditions.}, keywords = {}, pubstate = {published}, tppubtype = {article} } Many organisms from bacteria to nematodes to insect larvae navigate their environments by biasing random movements. In these organisms, navigation in isotropic environments can be characterized as an essentially diffusive and undirected process. In stimulus gradients, movement decisions are biased to drive directed navigation toward favorable environments. How does directed navigation in a gradient modulate random exploration either parallel or orthogonal to the gradient? Here, we introduce methods originally used for analyzing protein folding trajectories to study the trajectories of the nematode Caenorhabditis elegans and the Drosophila larva in isotropic environments, as well as in thermal and chemical gradients. We find that the statistics of random exploration in any direction are little affected by directed movement along a stimulus gradient. A key constraint on the behavioral strategies of these organisms appears to be the preservation of their capacity to continuously explore their environments in all directions even while moving toward favorable conditions. |
Carrara, Serena ; Aliprandi, Alessandro ; Hogan, Conor F; De Cola, Luisa Aggregation-Induced Electrochemiluminescence of Platinum(II) Complexes Journal Article In: JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 139 (41), pp. 14605–14610, 2017, ISSN: 0002-7863. @article{carrara_aggregation-induced_2017, title = {Aggregation-Induced Electrochemiluminescence of Platinum(II) Complexes}, author = {Carrara, Serena and Aliprandi, Alessandro and Hogan, Conor F. and De Cola, Luisa}, doi = {10.1021/jacs.7b07710}, issn = {0002-7863}, year = {2017}, date = {2017-10-01}, journal = {JOURNAL OF THE AMERICAN CHEMICAL SOCIETY}, volume = {139}, number = {41}, pages = {14605--14610}, abstract = {We report the electrochemiluminescence properties of square-planar Pt(II) complexes that result from the formation of supramolecular nanostructures. We define this new phenomenon as aggregation-induced electrochemiluminescence (AIECL). In this system, self-assembly changes the HOMO and LUMO energies, making their population accessible via ECL pathways and leading to the generation of the luminescent excited state. Significantly, the emission from the self-assembled system is the first example of electrochemiluminescence (ECL) of Pt(II) complexes in aqueous solution having higher efficiency than the standard, Ru(bpy)(3)(2+). The finding can lead to a new generation of bright emitters that can be used as ECL labels.}, keywords = {}, pubstate = {published}, tppubtype = {article} } We report the electrochemiluminescence properties of square-planar Pt(II) complexes that result from the formation of supramolecular nanostructures. We define this new phenomenon as aggregation-induced electrochemiluminescence (AIECL). In this system, self-assembly changes the HOMO and LUMO energies, making their population accessible via ECL pathways and leading to the generation of the luminescent excited state. Significantly, the emission from the self-assembled system is the first example of electrochemiluminescence (ECL) of Pt(II) complexes in aqueous solution having higher efficiency than the standard, Ru(bpy)(3)(2+). The finding can lead to a new generation of bright emitters that can be used as ECL labels. |
Martin, Nicolas E; Malik, Siddharth ; Calimet, Nicolas ; Changeux, Jean-Pierre ; Cecchini, Marco Un-gating and allosteric modulation of a pentameric ligand-gated ion channel captured by molecular dynamics Journal Article In: PLOS COMPUTATIONAL BIOLOGY, 13 (10), 2017, ISSN: 1553-734X. @article{martin_-gating_2017, title = {Un-gating and allosteric modulation of a pentameric ligand-gated ion channel captured by molecular dynamics}, author = {Martin, Nicolas E. and Malik, Siddharth and Calimet, Nicolas and Changeux, Jean-Pierre and Cecchini, Marco}, doi = {10.1371/journal.pcbi.1005784}, issn = {1553-734X}, year = {2017}, date = {2017-10-01}, journal = {PLOS COMPUTATIONAL BIOLOGY}, volume = {13}, number = {10}, abstract = {Pentameric ligand-gated ion channels (pLGICs) mediate intercellular communication at synapses through the opening of an ion pore in response to the binding of a neurotransmitter. Despite the increasing availability of high-resolution structures of pLGICs, a detailed understanding of the functional isomerization from closed to open (gating) and back is currently missing. Here, we provide the first atomistic description of the transition from open to closed (un-gating) in the glutamate-gated chloride channel (GluCl) from Caenorhabditis Elegans. Starting with the active-state structure solved in complex with the neurotransmitter L-glutamate and the positive allosteric modulator (PAM) ivermectin, we analyze the spontaneous relaxation of the channel upon removal of ivermectin by explicit solvent/membrane Molecular Dynamics (MD) simulations. The mu s-long trajectories support the conclusion that ion-channel deactivation is mediated by two distinct quaternary transitions, i.e. a global receptor twisting followed by the radial expansion (or blooming) of the extracellular domain. At variance with previous models, we show that pore closing is exclusively regulated by the global twisting, which controls the position of the beta 1-beta 2 loop relative to the M2-M3 loop at the EC/TM domain interface. Additional simulations with L-glutamate restrained to the crystallographic binding mode and ivermectin removed indicate that the same twisting isomerization is regulated by agonist binding at the orthosteric site. These results provide a structural model for gating in pLGICs and suggest a plausible mechanism for the pharmacological action of PAMs in this neurotransmitter receptor family. The simulated un-gating converges to the X-ray structure of GluCl resting state both globally and locally, demonstrating the predictive character of state-of-art MD simulations.}, keywords = {}, pubstate = {published}, tppubtype = {article} } Pentameric ligand-gated ion channels (pLGICs) mediate intercellular communication at synapses through the opening of an ion pore in response to the binding of a neurotransmitter. Despite the increasing availability of high-resolution structures of pLGICs, a detailed understanding of the functional isomerization from closed to open (gating) and back is currently missing. Here, we provide the first atomistic description of the transition from open to closed (un-gating) in the glutamate-gated chloride channel (GluCl) from Caenorhabditis Elegans. Starting with the active-state structure solved in complex with the neurotransmitter L-glutamate and the positive allosteric modulator (PAM) ivermectin, we analyze the spontaneous relaxation of the channel upon removal of ivermectin by explicit solvent/membrane Molecular Dynamics (MD) simulations. The mu s-long trajectories support the conclusion that ion-channel deactivation is mediated by two distinct quaternary transitions, i.e. a global receptor twisting followed by the radial expansion (or blooming) of the extracellular domain. At variance with previous models, we show that pore closing is exclusively regulated by the global twisting, which controls the position of the beta 1-beta 2 loop relative to the M2-M3 loop at the EC/TM domain interface. Additional simulations with L-glutamate restrained to the crystallographic binding mode and ivermectin removed indicate that the same twisting isomerization is regulated by agonist binding at the orthosteric site. These results provide a structural model for gating in pLGICs and suggest a plausible mechanism for the pharmacological action of PAMs in this neurotransmitter receptor family. The simulated un-gating converges to the X-ray structure of GluCl resting state both globally and locally, demonstrating the predictive character of state-of-art MD simulations. |
Zhang, Lei ; Li, Songlin ; Squillaci, Marco A; Zhong, Xiaolan ; Yao, Yifan ; Orgiu, Emanuele ; Samori, Paolo Supramolecular Self-Assembly in a Sub-micrometer Electrodic Cavity: Fabrication of Heat-Reversible pi-Gel Memristor Journal Article In: JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 139 (41), pp. 14406–14411, 2017, ISSN: 0002-7863. @article{zhang_supramolecular_2017, title = {Supramolecular Self-Assembly in a Sub-micrometer Electrodic Cavity: Fabrication of Heat-Reversible pi-Gel Memristor}, author = {Zhang, Lei and Li, Songlin and Squillaci, Marco A. and Zhong, Xiaolan and Yao, Yifan and Orgiu, Emanuele and Samori, Paolo}, doi = {10.1021/jacs.7b04347}, issn = {0002-7863}, year = {2017}, date = {2017-10-01}, journal = {JOURNAL OF THE AMERICAN CHEMICAL SOCIETY}, volume = {139}, number = {41}, pages = {14406--14411}, abstract = {The use of biomimetic approaches toward, the production of nonsolid yet functional architectures holds potential for the emergence of novel device concepts. Gels, in particular those obtained via self-assembly of pi-conjugated molecules, are dynamic materials possessing unique (opto)electronic properties. Their adaptive nature imparts unprecedented responsivity to various stimuli. Hitherto, a viable device platform to electrically probe in situ a sol-gel transition is still lacking. Here we describe the fabrication of a sub-micrometer electrodic cavity, which enables low-voltage electrical operation of pi-gels. Thanks to the in situ stiprarnolecular self-assembly of the pi-gelator occurring within: the cavity, we conceived a novel gel based memristor whose sol-gel transition is reversible and can be controlled via heating and de bias. This work opens perspectives toward the fabrication of a novel generation of nonsolid multiresponsive devices.}, keywords = {}, pubstate = {published}, tppubtype = {article} } The use of biomimetic approaches toward, the production of nonsolid yet functional architectures holds potential for the emergence of novel device concepts. Gels, in particular those obtained via self-assembly of pi-conjugated molecules, are dynamic materials possessing unique (opto)electronic properties. Their adaptive nature imparts unprecedented responsivity to various stimuli. Hitherto, a viable device platform to electrically probe in situ a sol-gel transition is still lacking. Here we describe the fabrication of a sub-micrometer electrodic cavity, which enables low-voltage electrical operation of pi-gels. Thanks to the in situ stiprarnolecular self-assembly of the pi-gelator occurring within: the cavity, we conceived a novel gel based memristor whose sol-gel transition is reversible and can be controlled via heating and de bias. This work opens perspectives toward the fabrication of a novel generation of nonsolid multiresponsive devices. |
Stoeckel, Marc-Antoine ; Gobbi, Marco ; Bonacchi, Sara ; Liscio, Fabiola ; Ferlauto, Laura ; Orgiu, Emanuele ; Samori, Paolo Reversible, Fast, and Wide-Range Oxygen Sensor Based on Nanostructured Organometal Halide Perovskite Journal Article In: ADVANCED MATERIALS, 29 (38), 2017, ISSN: 0935-9648. @article{stoeckel_reversible_2017, title = {Reversible, Fast, and Wide-Range Oxygen Sensor Based on Nanostructured Organometal Halide Perovskite}, author = {Stoeckel, Marc-Antoine and Gobbi, Marco and Bonacchi, Sara and Liscio, Fabiola and Ferlauto, Laura and Orgiu, Emanuele and Samori, Paolo}, doi = {10.1002/adma.201702469}, issn = {0935-9648}, year = {2017}, date = {2017-10-01}, journal = {ADVANCED MATERIALS}, volume = {29}, number = {38}, abstract = {Nanostructured materials characterized by high surface-volume ratio hold the promise to constitute the active materials for next-generation sensors. Solution-processed hybrid organohalide perovskites, which have been extensively used in the last few years for optoelectronic applications, are characterized by a self-assembled nanostructured morphology, which makes them an ideal candidate for gas sensing. Hitherto, detailed studies of the dependence of their electrical characteristics on the environmental atmosphere have not been performed, and even the effect of a ubiquitous gas such as O-2 has been widely overlooked. Here, the electrical response of organohalide perovskites to oxygen is studied. Surprisingly, a colossal increase (3000-fold) in the resistance of perovskite-based lateral devices is found when measured in a full oxygen atmosphere, which is ascribed to a trap healing mechanism originating from an O-2-mediated iodine vacancies filling. A variation as small as 70 ppm in the oxygen concentration can be detected. The effect is fast (textbackslashtextbackslashtextless400 ms) and fully reversible, making organohalide perovskites ideal active materials for oxygen sensing. The effect of oxygen on the electrical characteristics of organohalide perovskites must be taken into deep consideration for the design and optimization of any other perovskite-based (opto-) electronic device working in ambient conditions.}, keywords = {}, pubstate = {published}, tppubtype = {article} } Nanostructured materials characterized by high surface-volume ratio hold the promise to constitute the active materials for next-generation sensors. Solution-processed hybrid organohalide perovskites, which have been extensively used in the last few years for optoelectronic applications, are characterized by a self-assembled nanostructured morphology, which makes them an ideal candidate for gas sensing. Hitherto, detailed studies of the dependence of their electrical characteristics on the environmental atmosphere have not been performed, and even the effect of a ubiquitous gas such as O-2 has been widely overlooked. Here, the electrical response of organohalide perovskites to oxygen is studied. Surprisingly, a colossal increase (3000-fold) in the resistance of perovskite-based lateral devices is found when measured in a full oxygen atmosphere, which is ascribed to a trap healing mechanism originating from an O-2-mediated iodine vacancies filling. A variation as small as 70 ppm in the oxygen concentration can be detected. The effect is fast (textbackslashtextbackslashtextless400 ms) and fully reversible, making organohalide perovskites ideal active materials for oxygen sensing. The effect of oxygen on the electrical characteristics of organohalide perovskites must be taken into deep consideration for the design and optimization of any other perovskite-based (opto-) electronic device working in ambient conditions. |
Liang, Chunshuang ; Kulchat, Sirinan ; Jiang, Shimei ; Lehn, Jean-Marie Gelation-driven selection in dynamic covalent C=C/C=N exchange Journal Article In: CHEMICAL SCIENCE, 8 (10), pp. 6822–6828, 2017, ISSN: 2041-6520. @article{liang_gelation-driven_2017, title = {Gelation-driven selection in dynamic covalent C=C/C=N exchange}, author = {Liang, Chunshuang and Kulchat, Sirinan and Jiang, Shimei and Lehn, Jean-Marie}, doi = {10.1039/c7sc02827j}, issn = {2041-6520}, year = {2017}, date = {2017-10-01}, journal = {CHEMICAL SCIENCE}, volume = {8}, number = {10}, pages = {6822--6828}, abstract = {Knoevenagel barbiturate derivatives bearing long alkyl chains were proven to form organogels in suitable solvents based on supramolecular interactions. Their reaction with imines allows for component exchange through C=C/C=N recombination. The effect of various parameters (solvents, chain length, and temperature) on the C=C/C=N exchange reaction has been studied. Mixing Knoevenagel compound K and imine I-16 in a 1 : 1 ratio generated a constitutional dynamic library containing the four constituents K, I-16, K'-16, and I'. The reversible exchange reaction was monitored by H-1-NMR, showing marked changes in the fractions of the four constituents on sol-gel interconversion as a function of temperature. The library composition changed from statistical distribution of the four constituents in the sol state to selective amplification of the gel forming K'-16 constituent together with that of its agonist I'. The process amounts to self-organization driven component selection in a constitutional dynamic organogel system undergoing gelation. This process displays up-regulation of the gel-forming constituent by component redistribution through reversible covalent connections.}, keywords = {}, pubstate = {published}, tppubtype = {article} } Knoevenagel barbiturate derivatives bearing long alkyl chains were proven to form organogels in suitable solvents based on supramolecular interactions. Their reaction with imines allows for component exchange through C=C/C=N recombination. The effect of various parameters (solvents, chain length, and temperature) on the C=C/C=N exchange reaction has been studied. Mixing Knoevenagel compound K and imine I-16 in a 1 : 1 ratio generated a constitutional dynamic library containing the four constituents K, I-16, K'-16, and I'. The reversible exchange reaction was monitored by H-1-NMR, showing marked changes in the fractions of the four constituents on sol-gel interconversion as a function of temperature. The library composition changed from statistical distribution of the four constituents in the sol state to selective amplification of the gel forming K'-16 constituent together with that of its agonist I'. The process amounts to self-organization driven component selection in a constitutional dynamic organogel system undergoing gelation. This process displays up-regulation of the gel-forming constituent by component redistribution through reversible covalent connections. |
Sandor, Nora ; Gonzalez-Ferez, Rosario ; Julienne, Paul S; Pupillo, Guido Rydberg optical Feshbach resonances in cold gases Journal Article In: PHYSICAL REVIEW A, 96 (3), 2017, ISSN: 2469-9926. @article{sandor_rydberg_2017, title = {Rydberg optical Feshbach resonances in cold gases}, author = {Sandor, Nora and Gonzalez-Ferez, Rosario and Julienne, Paul S. and Pupillo, Guido}, doi = {10.1103/PhysRevA.96.032719}, issn = {2469-9926}, year = {2017}, date = {2017-09-01}, journal = {PHYSICAL REVIEW A}, volume = {96}, number = {3}, abstract = {We propose a scheme to efficiently tune the scattering length of two colliding ground-state atoms by offresonantly coupling the scattering state to an excited Rydberg molecular state using laser light. For the s-wave scattering of two colliding 87Rb atoms, we demonstrate that the effective optical length and pole strength of this Rydberg optical Feshbach resonance can be tuned over several orders of magnitude, while incoherent processes and losses are minimized. Given the ubiquity of Rydberg molecular states, this technique should be generally applicable to homonuclear atomic pairs as well as to atomic mixtures with s-wave (or even p-wave) scattering.}, keywords = {}, pubstate = {published}, tppubtype = {article} } We propose a scheme to efficiently tune the scattering length of two colliding ground-state atoms by offresonantly coupling the scattering state to an excited Rydberg molecular state using laser light. For the s-wave scattering of two colliding 87Rb atoms, we demonstrate that the effective optical length and pole strength of this Rydberg optical Feshbach resonance can be tuned over several orders of magnitude, while incoherent processes and losses are minimized. Given the ubiquity of Rydberg molecular states, this technique should be generally applicable to homonuclear atomic pairs as well as to atomic mixtures with s-wave (or even p-wave) scattering. |
Robinson, Matthew E; Nazemi, Ali ; Lunn, David J; Hayward, Dominic W; Boott, Charlotte E; Hsiao, Ming-Siao ; Harniman, Robert L; Davis, Sean A; Whittell, George R; Richardson, Robert M; De Cola, Luisa ; Manners, Ian Dimensional Control and Morphological Transformations of Supramolecular Polymeric Nanofibers Based on Cofacially-Stacked Planar Amphiphilic Platinum(II) Complexes Journal Article In: ACS NANO, 11 (9), pp. 9162–9175, 2017, ISSN: 1936-0851. @article{robinson_dimensional_2017, title = {Dimensional Control and Morphological Transformations of Supramolecular Polymeric Nanofibers Based on Cofacially-Stacked Planar Amphiphilic Platinum(II) Complexes}, author = {Robinson, Matthew E. and Nazemi, Ali and Lunn, David J. and Hayward, Dominic W. and Boott, Charlotte E. and Hsiao, Ming-Siao and Harniman, Robert L. and Davis, Sean A. and Whittell, George R. and Richardson, Robert M. and De Cola, Luisa and Manners, Ian}, doi = {10.1021/acsnano.7b04069}, issn = {1936-0851}, year = {2017}, date = {2017-09-01}, journal = {ACS NANO}, volume = {11}, number = {9}, pages = {9162--9175}, abstract = {Square-planar platinum(II) complexes often stack cofacially to yield supramolecular fiber-like structures with interesting photophysical properties. However, control over fiber dimensions and the resulting colloidal stability is limited. We report the self-assembly of amphiphilic Pt(II) complexes with solubilizing ancillary ligands based on polyethylene glycol [PEG(n), where n = 16, 12, 7]. The complex with the longest solubilizing PEG ligand, Pt-PEG(16), self-assembled to form polydisperse one-dimensional (1D) nanofibers (diameters textbackslashtextbackslashtextless5 nm). Sonication led to short seeds which, on addition of further molecularly dissolved Pt-PEG(16) complex, underwent elongation in a living supramolecular polymerization process to yield relatively uniform fibers of length up to ca. 400 nm. The fiber lengths were dependent on the Pt-PEG(16) complex to seed mass ratio in a manner analogous to a living covalent polymerization of molecular monomers. Moreover, the fiber lengths were unchanged in solution after 1 week and were therefore static with respect to interfiber exchange processes on this time scale. In contrast, similarly formed near-uniform fibers of Pt-PEG(12) exhibited dynamic behavior that led to broadening of the length distribution within 48 h. After aging for 4 weeks in solution, Pt-PEG(12) fibers partially evolved into 2D platelets. Furthermore, self-assembly of Pt-PEG(7) yielded only transient fibers which rapidly evolved into 2D platelets. On addition of further fiber-forming Pt complex (Pt-PEG(16)), the platelets formed assemblies via the growth of fibers selectively from their short edges. Our studies demonstrate that when interfiber dynamic exchange is suppressed, dimensional control and hierarchical structure formation are possible for supramolecular polymers through the use of kinetically controlled seeded growth methods.}, keywords = {}, pubstate = {published}, tppubtype = {article} } Square-planar platinum(II) complexes often stack cofacially to yield supramolecular fiber-like structures with interesting photophysical properties. However, control over fiber dimensions and the resulting colloidal stability is limited. We report the self-assembly of amphiphilic Pt(II) complexes with solubilizing ancillary ligands based on polyethylene glycol [PEG(n), where n = 16, 12, 7]. The complex with the longest solubilizing PEG ligand, Pt-PEG(16), self-assembled to form polydisperse one-dimensional (1D) nanofibers (diameters textbackslashtextbackslashtextless5 nm). Sonication led to short seeds which, on addition of further molecularly dissolved Pt-PEG(16) complex, underwent elongation in a living supramolecular polymerization process to yield relatively uniform fibers of length up to ca. 400 nm. The fiber lengths were dependent on the Pt-PEG(16) complex to seed mass ratio in a manner analogous to a living covalent polymerization of molecular monomers. Moreover, the fiber lengths were unchanged in solution after 1 week and were therefore static with respect to interfiber exchange processes on this time scale. In contrast, similarly formed near-uniform fibers of Pt-PEG(12) exhibited dynamic behavior that led to broadening of the length distribution within 48 h. After aging for 4 weeks in solution, Pt-PEG(12) fibers partially evolved into 2D platelets. Furthermore, self-assembly of Pt-PEG(7) yielded only transient fibers which rapidly evolved into 2D platelets. On addition of further fiber-forming Pt complex (Pt-PEG(16)), the platelets formed assemblies via the growth of fibers selectively from their short edges. Our studies demonstrate that when interfiber dynamic exchange is suppressed, dimensional control and hierarchical structure formation are possible for supramolecular polymers through the use of kinetically controlled seeded growth methods. |
Sorrenti, Alessandro ; Leira-Iglesias, Jorge ; Markvoort, Albert J; de Greef, Tom F A; Hermans, Thomas M Non-equilibrium supramolecular polymerization Journal Article In: CHEMICAL SOCIETY REVIEWS, 46 (18), pp. 5476–5490, 2017, ISSN: 0306-0012. @article{sorrenti_non-equilibrium_2017-1, title = {Non-equilibrium supramolecular polymerization}, author = {Sorrenti, Alessandro and Leira-Iglesias, Jorge and Markvoort, Albert J. and de Greef, Tom F. A. and Hermans, Thomas M.}, doi = {10.1039/c7cs00121e}, issn = {0306-0012}, year = {2017}, date = {2017-09-01}, journal = {CHEMICAL SOCIETY REVIEWS}, volume = {46}, number = {18}, pages = {5476--5490}, keywords = {}, pubstate = {published}, tppubtype = {article} } |
Sauvage, Jean-Pierre From Chemical Topology to Molecular Machines (Nobel Lecture) Journal Article In: ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 56 (37, SI), pp. 11080–11093, 2017, ISSN: 1433-7851. @article{sauvage_chemical_2017, title = {From Chemical Topology to Molecular Machines (Nobel Lecture)}, author = {Sauvage, Jean-Pierre}, doi = {10.1002/anie.201702992}, issn = {1433-7851}, year = {2017}, date = {2017-09-01}, journal = {ANGEWANDTE CHEMIE-INTERNATIONAL EDITION}, volume = {56}, number = {37, SI}, pages = {11080--11093}, abstract = {To a large extent, the field of “molecular machines” started after several groups were able to prepare, reasonably easily, interlocking ring compounds (named catenanes for compounds consisting of interlocking rings and rotaxanes for rings threaded by molecular filaments or axes). Important families of molecular machines not belonging to the interlocking world were also designed, prepared, and studied but, for most of them, their elaboration was more recent than that of catenanes or rotaxanes. Since the creation of interlocking ring molecules is so important in relation to the molecular machinery area, we will start with this aspect of our work. The second part will naturally be devoted to the dynamic properties of such systems and to the compounds for which motions can be directed in a controlled manner from the outside, that is, molecular machines. We will restrict our discussion to a very limited number of examples which we consider as particularly representative of the field.}, keywords = {}, pubstate = {published}, tppubtype = {article} } To a large extent, the field of “molecular machines” started after several groups were able to prepare, reasonably easily, interlocking ring compounds (named catenanes for compounds consisting of interlocking rings and rotaxanes for rings threaded by molecular filaments or axes). Important families of molecular machines not belonging to the interlocking world were also designed, prepared, and studied but, for most of them, their elaboration was more recent than that of catenanes or rotaxanes. Since the creation of interlocking ring molecules is so important in relation to the molecular machinery area, we will start with this aspect of our work. The second part will naturally be devoted to the dynamic properties of such systems and to the compounds for which motions can be directed in a controlled manner from the outside, that is, molecular machines. We will restrict our discussion to a very limited number of examples which we consider as particularly representative of the field. |
Publications
2018 |
Cavity-assisted mesoscopic transport of fermions: Coherent and dissipative dynamics Journal Article In: PHYSICAL REVIEW B, 97 (20), 2018, ISSN: 2469-9950. |
Reshaping silica particles: Mesoporous nanodiscs for bimodal delivery and improved cellular uptake Journal Article In: CHEMICAL ENGINEERING JOURNAL, 340 (SI), pp. 148–154, 2018, ISSN: 1385-8947. |
Targeted therapy of human glioblastoma via delivery of a toxin through a peptide directed to cell surface nucleolin Journal Article In: JOURNAL OF CELLULAR PHYSIOLOGY, 233 (5), pp. 4091–4105, 2018, ISSN: 0021-9541. |
Graphene oxide-branched polyethylenimine foams for efficient removal of toxic cations from water Journal Article In: JOURNAL OF MATERIALS CHEMISTRY A, 6 (20), pp. 9384–9390, 2018, ISSN: 2050-7488. |
When 2D Materials Meet Molecules: Opportunities and Challenges of Hybrid Organic/Inorganic van der Waals Heterostructures Journal Article In: ADVANCED MATERIALS, 30 (18), 2018, ISSN: 0935-9648. |
Photoelectrochemical response of carbon dots (CDs) derived from chitosan and their use in electrochemical imaging Journal Article In: MATERIALS HORIZONS, 5 (3), pp. 423–428, 2018, ISSN: 2051-6347. |
Graphene exfoliation in the presence of semiconducting polymers for improved film homogeneity and electrical performances Journal Article In: CARBON, 130 , pp. 495–502, 2018, ISSN: 0008-6223. |
Room Temperature Chiral Coupling of Valley Excitons with Spin-Momentum Locked Surface Plasmons Journal Article In: ACS PHOTONICS, 5 (4), pp. 1281–1287, 2018, ISSN: 2330-4022. |
Dynamic Covalent Metathesis in the C=C/C=N Exchange between Knoevenagel Compounds and Imines Journal Article In: JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 140 (16), pp. 5560–5568, 2018, ISSN: 0002-7863. |
Modifying conductivity and material properties of molecular ensembles under light-matter strong coupling Journal Article In: ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY, 255 , 2018, ISSN: 0065-7727. |
Photo-inks based on porphyrins and diarylethenes (DAEs) Journal Article In: ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY, 255 , 2018, ISSN: 0065-7727. |
Imine-Based Architectures at Surfaces and Interfaces: FromSelf-Assembly to Dynamic Covalent Chemistry in 2D Journal Article In: CHEMISTRY-AN ASIAN JOURNAL, 13 (5), pp. 465–481, 2018, ISSN: 1861-4728. |
Role of framework mutations and antibody flexibility in the evolution of broadly neutralizing antibodies Journal Article In: ELIFE, 7 , 2018, ISSN: 2050-084X. |
Nucleophilic Ring Opening of Donor-Acceptor Cyclopropanes Catalyzed by a Bronsted Acid in Hexafluoroisopropanol Journal Article In: ORGANIC LETTERS, 20 (3), pp. 574–577, 2018, ISSN: 1523-7060. |
Recent Advances in Nickel Catalysis Enabled by Stoichiometric Metallic Reducing Agents Journal Article In: SYNTHESIS-STUTTGART, 50 (3), pp. 499–513, 2018, ISSN: 0039-7881. |
Templated Formation of Luminescent Virus-like Particles by Tailor-Made Pt(II) Amphiphiles Journal Article In: JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 140 (6), pp. 2355–2362, 2018, ISSN: 0002-7863. |
Selective Encapsulation and Enhancement of the Emission Properties of a Luminescent Cu(I) Complex in Mesoporous Silica Journal Article In: HELVETICA CHIMICA ACTA, 101 (2), 2018, ISSN: 0018-019X. |
Heteroleptic Copper(I) Pseudorotaxanes Incorporating Macrocyclic Phenanthroline Ligands of Different Sizes Journal Article In: JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 140 (6), pp. 2336–2347, 2018, ISSN: 0002-7863. |
Fluorescence Commutation and Surface Photopatterning with Porphyrin Tetradithienylethene Switches Journal Article In: CHEMISTRY-A EUROPEAN JOURNAL, 24 (7), pp. 1631–1639, 2018, ISSN: 0947-6539. |
Beyond Chemical Synthesis: Self-Organization⁈ Journal Article In: ISRAEL JOURNAL OF CHEMISTRY, 58 (1-2, SI), pp. 136–141, 2018, ISSN: 0021-2148. |
Switching Multivalent DNA Complexation using Metal-Controlled Cationic Supramolecular Self-Assemblies Journal Article In: CHEMISTRY-A EUROPEAN JOURNAL, 24 (7), pp. 1518–1521, 2018, ISSN: 0947-6539. |
Special issue on addressing many-body problems with cold atoms and molecules Journal Article In: JOURNAL OF PHYSICS B-ATOMIC MOLECULAR AND OPTICAL PHYSICS, 51 (2), 2018, ISSN: 0953-4075. |
Internalization studies on zeolite nanoparticles using human cells Journal Article In: JOURNAL OF MATERIALS CHEMISTRY B, 6 (3), pp. 469–476, 2018, ISSN: 2050-750X. |
Porous supramolecular materials: the importance of emptiness Journal Article In: SUPRAMOLECULAR CHEMISTRY, 30 (3), pp. 166–168, 2018, ISSN: 1061-0278. |
N6L pseudopeptide interferes with nucleophosmin protein-protein interactions and sensitizes leukemic cells to chemotherapy Journal Article In: CANCER LETTERS, 412 , pp. 272–282, 2018, ISSN: 0304-3835. |
pi-Electronic Co-crystal Microcavities with Selective Vibronic-Mode Light Amplification: Toward Forster Resonance Energy Transfer Lasing Journal Article In: NANO LETTERS, 18 (7), pp. 4396–4402, 2018, ISSN: 1530-6984. |
The Influence of Binding Site Geometry on Anion-Binding Selectivity: A Case Study of Macrocyclic Receptors Built on the Azulene Skeleton Journal Article In: CHEMISTRY-A EUROPEAN JOURNAL, 24 (45), pp. 11683–11692, 2018, ISSN: 0947-6539. |
Detection, virulence and antimicrobial resistance of Yersinia enterocolitica in bulk tank milk in Italy Journal Article In: INTERNATIONAL DAIRY JOURNAL, 84 , pp. 46–53, 2018, ISSN: 0958-6946. |
Vibro-Polaritonic IR Emission in the Strong Coupling Regime Journal Article In: ACS PHOTONICS, 5 (1, SI), pp. 217–224, 2018, ISSN: 2330-4022. |
Electronic Light-Matter Strong Coupling in Nanofluidic Fabry-Perot Cavities Journal Article In: ACS PHOTONICS, 5 (1, SI), pp. 225–232, 2018, ISSN: 2330-4022. |
From Coordination Chemistry to Adaptive Chemistry Incollection In: {VanEldik, R; Puchta, R} (Ed.): ADVANCES IN INORGANIC CHEMISTRY, VOL 71: SUPRAMOLECULAR CHEMISTRY, 71 , pp. 3–78, 2018, ISBN: 978-0-12-815109-9. |
2017 |
Voltage-Controlled Switching of Strong Light-Matter Interactions using Liquid Crystals Journal Article In: CHEMISTRY-A EUROPEAN JOURNAL, 23 (72), pp. 18166–18170, 2017, ISSN: 0947-6539. |
Orthogonal Operation of Constitutional Dynamic Networks Consisting of DNA-Tweezer Machines Journal Article In: ACS NANO, 11 (12), pp. 12027–12036, 2017, ISSN: 1936-0851. |
Kinesin motility is driven by subdomain dynamics Journal Article In: ELIFE, 6 , 2017, ISSN: 2050-084X. |
Metals promote sequences of the reverse Krebs cycle Journal Article In: NATURE ECOLOGY & EVOLUTION, 1 (11), pp. 1716–1721, 2017, ISSN: 2397-334X. |
Cavity-Enhanced Transport of Charge Journal Article In: PHYSICAL REVIEW LETTERS, 119 (22), 2017, ISSN: 0031-9007. |
Punctured Two-Dimensional Sheets for Harvesting Blue Energy Journal Article In: ACS NANO, 11 (11), pp. 10654–10658, 2017, ISSN: 1936-0851. |
The 150 most important questions in cancer research and clinical oncology series: questions 76-85 Journal Article In: CHINESE JOURNAL OF CANCER, 36 , pp. 1–6, 2017, ISSN: 1000-467X. |
The Allosteric Hemoglobin Effector ITPP Inhibits Metastatic Colon Cancer in Mice Journal Article In: ANNALS OF SURGERY, 266 (5), pp. 746–753, 2017, ISSN: 0003-4932. |
Grid-type complexes of M2+ (M = Co, Ni, and Zn) with highly soluble bis (hydrazone)thiopyrimidine-based ligands: Spectroscopy and electrochemical properties Journal Article In: INORGANICA CHIMICA ACTA, 468 , pp. 131–139, 2017, ISSN: 0020-1693. |
Exploratory search during directed navigation in C. elegans and Drosophila larva Journal Article In: ELIFE, 6 , 2017, ISSN: 2050-084X. |
Aggregation-Induced Electrochemiluminescence of Platinum(II) Complexes Journal Article In: JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 139 (41), pp. 14605–14610, 2017, ISSN: 0002-7863. |
Un-gating and allosteric modulation of a pentameric ligand-gated ion channel captured by molecular dynamics Journal Article In: PLOS COMPUTATIONAL BIOLOGY, 13 (10), 2017, ISSN: 1553-734X. |
Supramolecular Self-Assembly in a Sub-micrometer Electrodic Cavity: Fabrication of Heat-Reversible pi-Gel Memristor Journal Article In: JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 139 (41), pp. 14406–14411, 2017, ISSN: 0002-7863. |
Reversible, Fast, and Wide-Range Oxygen Sensor Based on Nanostructured Organometal Halide Perovskite Journal Article In: ADVANCED MATERIALS, 29 (38), 2017, ISSN: 0935-9648. |
Gelation-driven selection in dynamic covalent C=C/C=N exchange Journal Article In: CHEMICAL SCIENCE, 8 (10), pp. 6822–6828, 2017, ISSN: 2041-6520. |
Rydberg optical Feshbach resonances in cold gases Journal Article In: PHYSICAL REVIEW A, 96 (3), 2017, ISSN: 2469-9926. |
Dimensional Control and Morphological Transformations of Supramolecular Polymeric Nanofibers Based on Cofacially-Stacked Planar Amphiphilic Platinum(II) Complexes Journal Article In: ACS NANO, 11 (9), pp. 9162–9175, 2017, ISSN: 1936-0851. |
Non-equilibrium supramolecular polymerization Journal Article In: CHEMICAL SOCIETY REVIEWS, 46 (18), pp. 5476–5490, 2017, ISSN: 0306-0012. |
From Chemical Topology to Molecular Machines (Nobel Lecture) Journal Article In: ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 56 (37, SI), pp. 11080–11093, 2017, ISSN: 1433-7851. |