2018 |
Jorge Leira-Iglesias Alessandra Tassoni, Takuji Adachi Michael Stich Thomas Hermans M Oscillations, travelling fronts and patterns in a supramolecular system Article de journal Dans: 2018, ISSN: 1748-3387, 1748-3395. @article{Hermans2018, title = {Oscillations, travelling fronts and patterns in a supramolecular system}, author = {Jorge Leira-Iglesias, Alessandra Tassoni, Takuji Adachi, Michael Stich,Thomas M. Hermans}, editor = {Nature Nanotechnology}, url = {http://www.nature.com/articles/s41565-018-0270-4}, doi = {10.1038/s41565-018-0270-4}, issn = {1748-3387, 1748-3395}, year = {2018}, date = {2018-10-15}, abstract = {Supramolecular polymers, such as microtubules, operate under non-equilibrium conditions to drive crucial functions in cells, such as motility, division and organelle transport1. In vivo and in vitro size oscillations of individual microtubules2,3 (dynamic instabilities) and collective oscillations4 have been observed. In addition, dynamic spatial structures, like waves and polygons, can form in non-stirred systems5. Here we describe an artificial supramolecular polymer made of a perylene diimide derivative that displays oscillations, travelling fronts and centimetre-scale self-organized patterns when pushed far from equilibrium by chemical fuels. Oscillations arise from a positive feedback due to nucleation–elongation–fragmentation, and a negative feedback due to size-dependent depolymerization. Travelling fronts and patterns form due to self-assembly induced density differences that cause system-wide convection. In our system, the species responsible for the nonlinear dynamics and those that self-assemble are one and the same. In contrast, other reported oscillating assemblies formed by vesicles6, micelles7 or particles8 rely on the combination of a known chemical oscillator and a stimuli-responsive system, either by communication through the solvent (for example, by changing pH7,8,9), or by anchoring one of the species covalently (for example, a Belousov–Zhabotinsky catalyst6,10). The design of self-oscillating supramolecular polymers and large-scale dissipative structures brings us closer to the creation of more life-like materials11 that respond to external stimuli similarly to living cells, or to creating artificial autonomous chemical robots12.}, keywords = {}, pubstate = {published}, tppubtype = {article} } Supramolecular polymers, such as microtubules, operate under non-equilibrium conditions to drive crucial functions in cells, such as motility, division and organelle transport1. In vivo and in vitro size oscillations of individual microtubules2,3 (dynamic instabilities) and collective oscillations4 have been observed. In addition, dynamic spatial structures, like waves and polygons, can form in non-stirred systems5. Here we describe an artificial supramolecular polymer made of a perylene diimide derivative that displays oscillations, travelling fronts and centimetre-scale self-organized patterns when pushed far from equilibrium by chemical fuels. Oscillations arise from a positive feedback due to nucleation–elongation–fragmentation, and a negative feedback due to size-dependent depolymerization. Travelling fronts and patterns form due to self-assembly induced density differences that cause system-wide convection. In our system, the species responsible for the nonlinear dynamics and those that self-assemble are one and the same. In contrast, other reported oscillating assemblies formed by vesicles6, micelles7 or particles8 rely on the combination of a known chemical oscillator and a stimuli-responsive system, either by communication through the solvent (for example, by changing pH7,8,9), or by anchoring one of the species covalently (for example, a Belousov–Zhabotinsky catalyst6,10). The design of self-oscillating supramolecular polymers and large-scale dissipative structures brings us closer to the creation of more life-like materials11 that respond to external stimuli similarly to living cells, or to creating artificial autonomous chemical robots12. |
Uzunov, N M; Melendez-Alafort, L; Bello, M; Cicoria, G; Zagni, F; De Nardo, L; Selva, A; Mou, L; Rossi-Alvarez, C; Pupillo, G; Di Domenico, G; Uccelli, L; Boschi, A; Groppi, F; Salvini, A; Taibi, A; Duatti, A; Martini, P; Pasquali, M; Loriggiola, M; Marengo, M; Strada, L; Manenti, S; Rosato, A; Esposito, J Radioisotopic purity and imaging properties of cyclotron-produced Tc-99m using direct Mo-100(p,2n) reaction Article de journal Dans: PHYSICS IN MEDICINE AND BIOLOGY, 63 (18), 2018, ISSN: 0031-9155. @article{uzunov_radioisotopic_2018, title = {Radioisotopic purity and imaging properties of cyclotron-produced Tc-99m using direct Mo-100(p,2n) reaction}, author = {Uzunov, N. M. and Melendez-Alafort, L. and Bello, M. and Cicoria, G. and Zagni, F. and De Nardo, L. and Selva, A. and Mou, L. and Rossi-Alvarez, C. and Pupillo, G. and Di Domenico, G. and Uccelli, L. and Boschi, A. and Groppi, F. and Salvini, A. and Taibi, A. and Duatti, A. and Martini, P. and Pasquali, M. and Loriggiola, M. and Marengo, M. and Strada, L. and Manenti, S. and Rosato, A. and Esposito, J.}, doi = {10.1088/1361-6560/aadc88}, issn = {0031-9155}, year = {2018}, date = {2018-09-01}, journal = {PHYSICS IN MEDICINE AND BIOLOGY}, volume = {63}, number = {18}, keywords = {}, pubstate = {published}, tppubtype = {article} } |
Gobbi, Marco ; Bonacchi, Sara ; Lian, Jian X; Vercouter, Alexandre ; Bertolazzi, Simone ; Zyska, Bjoern ; Timpel, Melanie ; Tatti, Roberta ; Olivier, Yoann ; Hecht, Stefan ; Nardi, Marco V; Beljonne, David ; Orgiu, Emanuele ; Samori, Paolo Collective molecular switching in hybrid superlattices for light-modulated two-dimensional electronics (vol 9, 3689, 2018) Article de journal Dans: NATURE COMMUNICATIONS, 9 , 2018, ISSN: 2041-1723. @article{gobbi_collective_2018-1, title = {Collective molecular switching in hybrid superlattices for light-modulated two-dimensional electronics (vol 9, 3689, 2018)}, author = {Gobbi, Marco and Bonacchi, Sara and Lian, Jian X. and Vercouter, Alexandre and Bertolazzi, Simone and Zyska, Bjoern and Timpel, Melanie and Tatti, Roberta and Olivier, Yoann and Hecht, Stefan and Nardi, Marco V. and Beljonne, David and Orgiu, Emanuele and Samori, Paolo}, doi = {10.1038/s41467-018-05541-6}, issn = {2041-1723}, year = {2018}, date = {2018-09-01}, journal = {NATURE COMMUNICATIONS}, volume = {9}, keywords = {}, pubstate = {published}, tppubtype = {article} } |
Bertolazzi, Simone ; Gobbi, Marco ; Zhao, Yuda ; Backes, Claudia ; Samori, Paolo Molecular chemistry approaches for tuning the properties of two-dimensional transition metal dichalcogenides Article de journal Dans: CHEMICAL SOCIETY REVIEWS, 47 (17), p. 6845–6888, 2018, ISSN: 0306-0012. @article{bertolazzi_molecular_2018, title = {Molecular chemistry approaches for tuning the properties of two-dimensional transition metal dichalcogenides}, author = {Bertolazzi, Simone and Gobbi, Marco and Zhao, Yuda and Backes, Claudia and Samori, Paolo}, doi = {10.1039/c8cs00169c}, issn = {0306-0012}, year = {2018}, date = {2018-09-01}, journal = {CHEMICAL SOCIETY REVIEWS}, volume = {47}, number = {17}, pages = {6845--6888}, keywords = {}, pubstate = {published}, tppubtype = {article} } |
Verduci, Tindara ; Chaumy, Guillaume ; Dayen, Jean-Francois ; Leclerc, Nicolas ; Devaux, Eloise ; Stoeckel, Marc-Antoine ; Orgiu, Emanuele ; Samori, Paolo ; Doudin, Bernard Current crowding issues on nanoscale planar organic transistors for spintronic applications Article de journal Dans: NANOTECHNOLOGY, 29 (36), 2018, ISSN: 0957-4484. @article{verduci_current_2018, title = {Current crowding issues on nanoscale planar organic transistors for spintronic applications}, author = {Verduci, Tindara and Chaumy, Guillaume and Dayen, Jean-Francois and Leclerc, Nicolas and Devaux, Eloise and Stoeckel, Marc-Antoine and Orgiu, Emanuele and Samori, Paolo and Doudin, Bernard}, doi = {10.1088/1361-6528/aacc22}, issn = {0957-4484}, year = {2018}, date = {2018-09-01}, journal = {NANOTECHNOLOGY}, volume = {29}, number = {36}, keywords = {}, pubstate = {published}, tppubtype = {article} } |
Richmond, Edward ; Yi, Jing ; Vukovic, Vuk D; Sajadi, Fatima ; Rowley, Christopher N; Moran, Joseph Ring-opening hydroarylation of monosubstituted cyclopropanes enabled by hexafluoroisopropanol Article de journal Dans: CHEMICAL SCIENCE, 9 (30), p. 6411–6416, 2018, ISSN: 2041-6520. @article{richmond_ring-opening_2018, title = {Ring-opening hydroarylation of monosubstituted cyclopropanes enabled by hexafluoroisopropanol}, author = {Richmond, Edward and Yi, Jing and Vukovic, Vuk D. and Sajadi, Fatima and Rowley, Christopher N. and Moran, Joseph}, doi = {10.1039/c8sc02126k}, issn = {2041-6520}, year = {2018}, date = {2018-08-01}, journal = {CHEMICAL SCIENCE}, volume = {9}, number = {30}, pages = {6411--6416}, keywords = {}, pubstate = {published}, tppubtype = {article} } |
El Garah, Mohamed ; Cook, Timothy R; Sepehrpour, Hajar ; Ciesielski, Artur ; Stang, Peter J; Samori, Paolo Concentration-dependent supramolecular patterns of C-3 and C-2 symmetric molecules at the solid/liquid interface Article de journal Dans: COLLOIDS AND SURFACES B-BIOINTERFACES, 168 , p. 211–216, 2018, ISSN: 0927-7765. @article{el_garah_concentration-dependent_2018, title = {Concentration-dependent supramolecular patterns of C-3 and C-2 symmetric molecules at the solid/liquid interface}, author = {El Garah, Mohamed and Cook, Timothy R. and Sepehrpour, Hajar and Ciesielski, Artur and Stang, Peter J. and Samori, Paolo}, doi = {10.1016/j.colsurfb.2017.11.065}, issn = {0927-7765}, year = {2018}, date = {2018-08-01}, journal = {COLLOIDS AND SURFACES B-BIOINTERFACES}, volume = {168}, pages = {211--216}, keywords = {}, pubstate = {published}, tppubtype = {article} } |
Atoini, Youssef ; Prasetyanto, Eko Adi ; Chen, Pengkun ; Silvestrini, Simone ; Harrowfield, Jack ; De Cola, Luisa Luminescence of Amphiphilic Pt-II Complexes Controlled by Confinement Article de journal Dans: CHEMISTRY-A EUROPEAN JOURNAL, 24 (46), p. 12054–12060, 2018, ISSN: 0947-6539. @article{atoini_luminescence_2018, title = {Luminescence of Amphiphilic Pt-II Complexes Controlled by Confinement}, author = {Atoini, Youssef and Prasetyanto, Eko Adi and Chen, Pengkun and Silvestrini, Simone and Harrowfield, Jack and De Cola, Luisa}, doi = {10.1002/chem.201802743}, issn = {0947-6539}, year = {2018}, date = {2018-08-01}, journal = {CHEMISTRY-A EUROPEAN JOURNAL}, volume = {24}, number = {46}, pages = {12054--12060}, keywords = {}, pubstate = {published}, tppubtype = {article} } |
Mengozzi, Luca ; El Garah, Mohamed ; Gualandi, Andrea ; Iurlo, Matteo ; Fiorani, Andrea ; Ciesielski, Artur ; Marcaccio, Massimo ; Paolucci, Francesco ; Samori, Paolo ; Cozzi, Pier Giorgio Phenoxyaluminum(salophen) Scaffolds: Synthesis, Electrochemical Properties, and Self-Assembly at Surfaces of Multifunctional Systems Article de journal Dans: CHEMISTRY-A EUROPEAN JOURNAL, 24 (46), p. 11954–11960, 2018, ISSN: 0947-6539. @article{mengozzi_phenoxyaluminumsalophen_2018, title = {Phenoxyaluminum(salophen) Scaffolds: Synthesis, Electrochemical Properties, and Self-Assembly at Surfaces of Multifunctional Systems}, author = {Mengozzi, Luca and El Garah, Mohamed and Gualandi, Andrea and Iurlo, Matteo and Fiorani, Andrea and Ciesielski, Artur and Marcaccio, Massimo and Paolucci, Francesco and Samori, Paolo and Cozzi, Pier Giorgio}, doi = {10.1002/chem.201801118}, issn = {0947-6539}, year = {2018}, date = {2018-08-01}, journal = {CHEMISTRY-A EUROPEAN JOURNAL}, volume = {24}, number = {46}, pages = {11954--11960}, keywords = {}, pubstate = {published}, tppubtype = {article} } |
Ovchinnikov, Victor ; Stone, Tracy A; Deber, Charles M; Karplus, Martin Structure of the EmrE multidrug transporter and its use for inhibitor peptide design Article de journal Dans: PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA, 115 (34), p. E7932–E7941, 2018, ISSN: 0027-8424. @article{ovchinnikov_structure_2018, title = {Structure of the EmrE multidrug transporter and its use for inhibitor peptide design}, author = {Ovchinnikov, Victor and Stone, Tracy A. and Deber, Charles M. and Karplus, Martin}, doi = {10.1073/pnas.1802177115}, issn = {0027-8424}, year = {2018}, date = {2018-08-01}, journal = {PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA}, volume = {115}, number = {34}, pages = {E7932--E7941}, keywords = {}, pubstate = {published}, tppubtype = {article} } |
Spitzer, Daniel ; Marichez, Vincent ; Formon, Georges J M; Besenius, Pol ; Hermans, Thomas M Surface-Assisted Self-Assembly of a Hydrogel by Proton Diffusion Article de journal Dans: ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 57 (35), p. 11349–11353, 2018, ISSN: 1433-7851. @article{spitzer_surface-assisted_2018, title = {Surface-Assisted Self-Assembly of a Hydrogel by Proton Diffusion}, author = {Spitzer, Daniel and Marichez, Vincent and Formon, Georges J. M. and Besenius, Pol and Hermans, Thomas M.}, doi = {10.1002/anie.201806668}, issn = {1433-7851}, year = {2018}, date = {2018-08-01}, journal = {ANGEWANDTE CHEMIE-INTERNATIONAL EDITION}, volume = {57}, number = {35}, pages = {11349--11353}, keywords = {}, pubstate = {published}, tppubtype = {article} } |
Naydenov, Borislav ; Torsney, Samuel ; Bonilla, Alejandro Santana ; El Garah, Mohamed ; Ciesielski, Artur ; Gualandi, Andrea ; Mengozzi, Luca ; Cozzi, Pier Giorgio ; Gutierrez, Rafael ; Samori, Paolo ; Cuniberti, Gianaurelio ; Boland, John J Self-Assembled Two-Dimensional Supramolecular Networks Characterized by Scanning Tunneling Microscopy and Spectroscopy in Air and under Vacuum Article de journal Dans: LANGMUIR, 34 (26), p. 7698–7707, 2018, ISSN: 0743-7463. @article{naydenov_self-assembled_2018, title = {Self-Assembled Two-Dimensional Supramolecular Networks Characterized by Scanning Tunneling Microscopy and Spectroscopy in Air and under Vacuum}, author = {Naydenov, Borislav and Torsney, Samuel and Bonilla, Alejandro Santana and El Garah, Mohamed and Ciesielski, Artur and Gualandi, Andrea and Mengozzi, Luca and Cozzi, Pier Giorgio and Gutierrez, Rafael and Samori, Paolo and Cuniberti, Gianaurelio and Boland, John J.}, doi = {10.1021/acs.langmuir.8b01374}, issn = {0743-7463}, year = {2018}, date = {2018-07-01}, journal = {LANGMUIR}, volume = {34}, number = {26}, pages = {7698--7707}, keywords = {}, pubstate = {published}, tppubtype = {article} } |
Dhers, Sebastien ; Mondal, Abhishake ; Aguila, David ; Ramirez, Juan ; Vela, Sergi ; Dechambenoit, Pierre ; Rouzieres, Mathieu ; Nitschke, Jonathan R; Clerac, Rodolphe ; Lehn, Jean-Marie Spin State Chemistry: Modulation of Ligand pK(a) by Spin State Switching in a [2x2] Iron(II) Grid-Type Complex Article de journal Dans: JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 140 (26), p. 8218–8227, 2018, ISSN: 0002-7863. @article{dhers_spin_2018, title = {Spin State Chemistry: Modulation of Ligand pK(a) by Spin State Switching in a [2x2] Iron(II) Grid-Type Complex}, author = {Dhers, Sebastien and Mondal, Abhishake and Aguila, David and Ramirez, Juan and Vela, Sergi and Dechambenoit, Pierre and Rouzieres, Mathieu and Nitschke, Jonathan R. and Clerac, Rodolphe and Lehn, Jean-Marie}, doi = {10.1021/jacs.8b03735}, issn = {0002-7863}, year = {2018}, date = {2018-07-01}, journal = {JOURNAL OF THE AMERICAN CHEMICAL SOCIETY}, volume = {140}, number = {26}, pages = {8218--8227}, keywords = {}, pubstate = {published}, tppubtype = {article} } |
Boehringer, Regis ; Kieffer, Bruno ; Torbeev, Vladimir Total chemical synthesis and biophysical properties of a designed soluble 24 kDa amyloid analogue Article de journal Dans: CHEMICAL SCIENCE, 9 (25), p. 5594–5599, 2018, ISSN: 2041-6520. @article{boehringer_total_2018, title = {Total chemical synthesis and biophysical properties of a designed soluble 24 kDa amyloid analogue}, author = {Boehringer, Regis and Kieffer, Bruno and Torbeev, Vladimir}, doi = {10.1039/c8sc01790e}, issn = {2041-6520}, year = {2018}, date = {2018-07-01}, journal = {CHEMICAL SCIENCE}, volume = {9}, number = {25}, pages = {5594--5599}, keywords = {}, pubstate = {published}, tppubtype = {article} } |
Anichini, Cosimo ; Czepa, Wlodzimierz ; Pakulski, Dawid ; Aliprandi, Alessandro ; Ciesielski, Artur ; Samori, Paolo Chemical sensing with 2D materials Article de journal Dans: CHEMICAL SOCIETY REVIEWS, 47 (13), p. 4860–4908, 2018, ISSN: 0306-0012. @article{anichini_chemical_2018, title = {Chemical sensing with 2D materials}, author = {Anichini, Cosimo and Czepa, Wlodzimierz and Pakulski, Dawid and Aliprandi, Alessandro and Ciesielski, Artur and Samori, Paolo}, doi = {10.1039/c8cs00417j}, issn = {0306-0012}, year = {2018}, date = {2018-07-01}, journal = {CHEMICAL SOCIETY REVIEWS}, volume = {47}, number = {13}, pages = {4860--4908}, keywords = {}, pubstate = {published}, tppubtype = {article} } |
Samori, Paolo ; Biscarini, Fabio Nanomaterials properties tuned by their environment: integrating supramolecular concepts into sensing devices Article de journal Dans: CHEMICAL SOCIETY REVIEWS, 47 (13), p. 4675–4676, 2018, ISSN: 0306-0012. @article{samori_nanomaterials_2018, title = {Nanomaterials properties tuned by their environment: integrating supramolecular concepts into sensing devices}, author = {Samori, Paolo and Biscarini, Fabio}, doi = {10.1039/c8cs90066c}, issn = {0306-0012}, year = {2018}, date = {2018-07-01}, journal = {CHEMICAL SOCIETY REVIEWS}, volume = {47}, number = {13}, pages = {4675--4676}, keywords = {}, pubstate = {published}, tppubtype = {article} } |
Gobbi, Marco ; Bonacchi, Sara ; Lian, Jian X; Vercouter, Alexandre ; Bertolazzi, Simone ; Zyska, Bjoern ; Timpel, Melanie ; Tatti, Roberta ; Olivier, Yoann ; Hecht, Stefan ; Nardi, Marco V; Beljonne, David ; Orgiu, Emanuele ; Samori, Paolo Collective molecular switching in hybrid superlattices for light-modulated two-dimensional electronics Article de journal Dans: NATURE COMMUNICATIONS, 9 , 2018, ISSN: 2041-1723. @article{gobbi_collective_2018, title = {Collective molecular switching in hybrid superlattices for light-modulated two-dimensional electronics}, author = {Gobbi, Marco and Bonacchi, Sara and Lian, Jian X. and Vercouter, Alexandre and Bertolazzi, Simone and Zyska, Bjoern and Timpel, Melanie and Tatti, Roberta and Olivier, Yoann and Hecht, Stefan and Nardi, Marco V. and Beljonne, David and Orgiu, Emanuele and Samori, Paolo}, doi = {10.1038/s41467-018-04932-z}, issn = {2041-1723}, year = {2018}, date = {2018-07-01}, journal = {NATURE COMMUNICATIONS}, volume = {9}, keywords = {}, pubstate = {published}, tppubtype = {article} } |
El Hage, Krystel ; Hedin, Florent ; Gupta, Prashant K; Meuwly, Markus ; Karplus, Martin Valid molecular dynamics simulations of human hemoglobin require a surprisingly large box size Article de journal Dans: ELIFE, 7 , 2018, ISSN: 2050-084X. @article{el_hage_valid_2018, title = {Valid molecular dynamics simulations of human hemoglobin require a surprisingly large box size}, author = {El Hage, Krystel and Hedin, Florent and Gupta, Prashant K. and Meuwly, Markus and Karplus, Martin}, doi = {10.7554/eLife.35560}, issn = {2050-084X}, year = {2018}, date = {2018-07-01}, journal = {ELIFE}, volume = {7}, keywords = {}, pubstate = {published}, tppubtype = {article} } |
Zhang, Lei ; Pasthukova, Nadiia ; Yao, Yifan ; Zhong, Xiaolan ; Pavlica, Egon ; Bratina, Gvido ; Orgiu, Emanuele ; Samori, Paolo Self-Suspended Nanomesh Scaffold for Ultrafast Flexible Photodetectors Based on Organic Semiconducting Crystals Article de journal Dans: ADVANCED MATERIALS, 30 (28), 2018, ISSN: 0935-9648. @article{zhang_self-suspended_2018, title = {Self-Suspended Nanomesh Scaffold for Ultrafast Flexible Photodetectors Based on Organic Semiconducting Crystals}, author = {Zhang, Lei and Pasthukova, Nadiia and Yao, Yifan and Zhong, Xiaolan and Pavlica, Egon and Bratina, Gvido and Orgiu, Emanuele and Samori, Paolo}, doi = {10.1002/adma.201801181}, issn = {0935-9648}, year = {2018}, date = {2018-07-01}, journal = {ADVANCED MATERIALS}, volume = {30}, number = {28}, keywords = {}, pubstate = {published}, tppubtype = {article} } |
Trolez, Yann ; Finke, Aaron D; Silvestri, Fabio ; Monti, Filippo ; Ventura, Barbara ; Boudon, Corinne ; Gisselbrecht, Jean-Paul ; Schweizer, Bernd W; Sauvage, Jean-Pierre ; Armaroli, Nicola ; Diederich, Francois Unconventional Synthesis of a Cu-I Rotaxane with a Superacceptor Stopper: Ultrafast Excited-State Dynamics and Near-Infrared Luminescence Article de journal Dans: CHEMISTRY-A EUROPEAN JOURNAL, 24 (41), p. 10422–10433, 2018, ISSN: 0947-6539. @article{trolez_unconventional_2018, title = {Unconventional Synthesis of a Cu-I Rotaxane with a Superacceptor Stopper: Ultrafast Excited-State Dynamics and Near-Infrared Luminescence}, author = {Trolez, Yann and Finke, Aaron D. and Silvestri, Fabio and Monti, Filippo and Ventura, Barbara and Boudon, Corinne and Gisselbrecht, Jean-Paul and Schweizer, W. Bernd and Sauvage, Jean-Pierre and Armaroli, Nicola and Diederich, Francois}, doi = {10.1002/chem.201801161}, issn = {0947-6539}, year = {2018}, date = {2018-07-01}, journal = {CHEMISTRY-A EUROPEAN JOURNAL}, volume = {24}, number = {41}, pages = {10422--10433}, keywords = {}, pubstate = {published}, tppubtype = {article} } |
Drozdz, Wojciech ; Walczak, Anna ; Bessin, Yannick ; Gervais, Virginie ; Cao, Xiao-Yu ; Lehn, Jean-Marie ; Ulrich, Sebastien ; Stefankiewicz, Artur R Multivalent Metallosupramolecular Assemblies as Effective DNA Binding Agents Article de journal Dans: CHEMISTRY-A EUROPEAN JOURNAL, 24 (42), p. 10802–10811, 2018, ISSN: 0947-6539. @article{drozdz_multivalent_2018, title = {Multivalent Metallosupramolecular Assemblies as Effective DNA Binding Agents}, author = {Drozdz, Wojciech and Walczak, Anna and Bessin, Yannick and Gervais, Virginie and Cao, Xiao-Yu and Lehn, Jean-Marie and Ulrich, Sebastien and Stefankiewicz, Artur R.}, doi = {10.1002/chem.201801552}, issn = {0947-6539}, year = {2018}, date = {2018-07-01}, journal = {CHEMISTRY-A EUROPEAN JOURNAL}, volume = {24}, number = {42}, pages = {10802--10811}, keywords = {}, pubstate = {published}, tppubtype = {article} } |
Kovaricek, Petr ; Cebecauer, Marek ; Neburkova, Jitka ; Barton, Jan ; Fridrichova, Michaela ; Drogowska, Karolina A; Cigler, Petr ; Lehn, Jean-Marie ; Kalbac, Martin Proton-Gradient-Driven Oriented Motion of Nanodiamonds Grafted to Graphene by Dynamic Covalent Bonds Article de journal Dans: ACS NANO, 12 (7), p. 7141–7147, 2018, ISSN: 1936-0851. @article{kovaricek_proton-gradient-driven_2018, title = {Proton-Gradient-Driven Oriented Motion of Nanodiamonds Grafted to Graphene by Dynamic Covalent Bonds}, author = {Kovaricek, Petr and Cebecauer, Marek and Neburkova, Jitka and Barton, Jan and Fridrichova, Michaela and Drogowska, Karolina A. and Cigler, Petr and Lehn, Jean-Marie and Kalbac, Martin}, doi = {10.1021/acsnano.8b03015}, issn = {1936-0851}, year = {2018}, date = {2018-07-01}, journal = {ACS NANO}, volume = {12}, number = {7}, pages = {7141--7147}, abstract = {Manipulating nanoscopic objects by external stimuli is the cornerstone of nanoscience. Here, we report the implementation of dynamic covalent chemistry in the reversible binding and directional motion of fluorescent nanodiamond particles at a functionalized graphene surface via imine linkages. The dynamic connections allow for controlling the formation and rupture of these linkages by external stimuli. By introduction of pH gradients, the nanoparticles are driven to move along the gradient due to the different rates of the imine condensation and hydrolysis in the two environments. The multivalent nature of the particle-to-surface connection ensures that particles remain attached to the surface, whereas its dynamic character allows for exchange reaction, thus leading to displacement yet bound behavior in two-dimensional space. These results open a pathway for thermodynamically controlled manipulation of objects on the nanoscale.}, keywords = {}, pubstate = {published}, tppubtype = {article} } Manipulating nanoscopic objects by external stimuli is the cornerstone of nanoscience. Here, we report the implementation of dynamic covalent chemistry in the reversible binding and directional motion of fluorescent nanodiamond particles at a functionalized graphene surface via imine linkages. The dynamic connections allow for controlling the formation and rupture of these linkages by external stimuli. By introduction of pH gradients, the nanoparticles are driven to move along the gradient due to the different rates of the imine condensation and hydrolysis in the two environments. The multivalent nature of the particle-to-surface connection ensures that particles remain attached to the surface, whereas its dynamic character allows for exchange reaction, thus leading to displacement yet bound behavior in two-dimensional space. These results open a pathway for thermodynamically controlled manipulation of objects on the nanoscale. |
Graf, Ernest ; Harrowfield, Jack ; Kintzinger, Jean-Pierre ; Lehn, Jean-Marie ; Le Moigne, Jacques ; Rissanen, Kari Protonation of a Spherical Macrotricyclic Tetramine: Water Inclusion, Allosteric Effect, and Cooperativity Article de journal Dans: CHEMPLUSCHEM, 83 (7, SI), p. 605–611, 2018, ISSN: 2192-6506. @article{graf_protonation_2018, title = {Protonation of a Spherical Macrotricyclic Tetramine: Water Inclusion, Allosteric Effect, and Cooperativity}, author = {Graf, Ernest and Harrowfield, Jack and Kintzinger, Jean-Pierre and Lehn, Jean-Marie and Le Moigne, Jacques and Rissanen, Kari}, doi = {10.1002/cplu.201700557}, issn = {2192-6506}, year = {2018}, date = {2018-07-01}, journal = {CHEMPLUSCHEM}, volume = {83}, number = {7, SI}, pages = {605--611}, abstract = {The spherical macrotricyclic cryptand tetramine “C24” (1) displays remarkable protonation behaviour. It undergoes protonation in four successive steps for which pK(a) values of 11.17 +/- 0.05, 10.28 +/- 0.04, 6.00 +/- 0.06 and 3.08 +/- 0.08 have been determined at 298 K. The unusually close values for the first two protonations provide evidence for the encapsulation of a water molecule serving as effector for the second protonation, which is consistent with earlier observations that the exchange of protons bound in the diprotonated species with solvent protons is unusually slow and that O-17 NMR spectra show the presence of an oxygen centre in the same species quite distinct from that of solvent water. Encapsulation of water is also observed in the solid state in the picrate salt of the triprotonated form of 1 and has been characterised by means of X-ray structural determination.}, keywords = {}, pubstate = {published}, tppubtype = {article} } The spherical macrotricyclic cryptand tetramine “C24” (1) displays remarkable protonation behaviour. It undergoes protonation in four successive steps for which pK(a) values of 11.17 +/- 0.05, 10.28 +/- 0.04, 6.00 +/- 0.06 and 3.08 +/- 0.08 have been determined at 298 K. The unusually close values for the first two protonations provide evidence for the encapsulation of a water molecule serving as effector for the second protonation, which is consistent with earlier observations that the exchange of protons bound in the diprotonated species with solvent protons is unusually slow and that O-17 NMR spectra show the presence of an oxygen centre in the same species quite distinct from that of solvent water. Encapsulation of water is also observed in the solid state in the picrate salt of the triprotonated form of 1 and has been characterised by means of X-ray structural determination. |
Schuettpelz, Eric ; Rouhan, Germinal ; Pryer, Kathleen M; Rothfels, Carl J; Prado, Jefferson ; Sundue, Michael A; Windham, Michael D; Moran, Robbin C; Smith, Alan R Are there too many fern genera? Article de journal Dans: TAXON, 67 (3), p. 473–480, 2018, ISSN: 0040-0262. @article{schuettpelz_are_2018, title = {Are there too many fern genera?}, author = {Schuettpelz, Eric and Rouhan, Germinal and Pryer, Kathleen M. and Rothfels, Carl J. and Prado, Jefferson and Sundue, Michael A. and Windham, Michael D. and Moran, Robbin C. and Smith, Alan R.}, doi = {10.12705/673.1}, issn = {0040-0262}, year = {2018}, date = {2018-06-01}, journal = {TAXON}, volume = {67}, number = {3}, pages = {473--480}, keywords = {}, pubstate = {published}, tppubtype = {article} } |
Varma, Sreejith J; Muchowska, Kamila B; Chatelain, Paul ; Moran, Joseph Native iron reduces CO2 to intermediates and end-products of the acetyl-CoA pathway Article de journal Dans: NATURE ECOLOGY & EVOLUTION, 2 (6), p. 1019+, 2018, ISSN: 2397-334X. @article{varma_native_2018, title = {Native iron reduces CO2 to intermediates and end-products of the acetyl-CoA pathway}, author = {Varma, Sreejith J. and Muchowska, Kamila B. and Chatelain, Paul and Moran, Joseph}, doi = {10.1038/s41559-018-0542-2}, issn = {2397-334X}, year = {2018}, date = {2018-06-01}, journal = {NATURE ECOLOGY & EVOLUTION}, volume = {2}, number = {6}, pages = {1019+}, abstract = {Autotrophic theories for the origin of life propose that CO(2 )was the carbon source for primordial biosynthesis. Among the six known CO2 fixation pathways in nature, the acetyl-CoA (AcCoA; or Wood-Ljungdahl) pathway is the most ancient, and relies on transition metals for catalysis. Modern microbes that use the AcCoA pathway typically fix CO2 with electrons from H-2, which requires complex flavin-based electron bifurcation. This presents a paradox: how could primitive metabolic systems have fixed CO2 before the origin of proteins? Here, we show that native transition metals (Fe-0, Ni-0 and Co-0) selectively reduce CO2 to acetate and pyruvate-the intermediates and end-products of the AcCoA pathway-in near millimolar concentrations in water over hours to days using 1-40 bar CO2 and at temperatures from 30 to 100 degrees C. Geochemical CO2 fixation from native metals could have supplied critical C-2 and C-3 metabolites before the emergence of enzymes.}, keywords = {}, pubstate = {published}, tppubtype = {article} } Autotrophic theories for the origin of life propose that CO(2 )was the carbon source for primordial biosynthesis. Among the six known CO2 fixation pathways in nature, the acetyl-CoA (AcCoA; or Wood-Ljungdahl) pathway is the most ancient, and relies on transition metals for catalysis. Modern microbes that use the AcCoA pathway typically fix CO2 with electrons from H-2, which requires complex flavin-based electron bifurcation. This presents a paradox: how could primitive metabolic systems have fixed CO2 before the origin of proteins? Here, we show that native transition metals (Fe-0, Ni-0 and Co-0) selectively reduce CO2 to acetate and pyruvate-the intermediates and end-products of the AcCoA pathway-in near millimolar concentrations in water over hours to days using 1-40 bar CO2 and at temperatures from 30 to 100 degrees C. Geochemical CO2 fixation from native metals could have supplied critical C-2 and C-3 metabolites before the emergence of enzymes. |
Travaglini, Leana ; De Cola, Luisa Morphology Control of Mesoporous Silica Particles Using Bile Acids as Cosurfactants Article de journal Dans: CHEMISTRY OF MATERIALS, 30 (12), p. 4168–4175, 2018, ISSN: 0897-4756. @article{travaglini_morphology_2018, title = {Morphology Control of Mesoporous Silica Particles Using Bile Acids as Cosurfactants}, author = {Travaglini, Leana and De Cola, Luisa}, doi = {10.1021/acs.chemmater.8b01873}, issn = {0897-4756}, year = {2018}, date = {2018-06-01}, journal = {CHEMISTRY OF MATERIALS}, volume = {30}, number = {12}, pages = {4168--4175}, abstract = {Morphology control and tuning of nanomaterials are crucial to determine their properties and applications. Solutions based on different synthetic methodologies have been proposed, and in general they required variation of several parameters. Here, a new facile and cost-effective bottom-up strategy to control the morphology of mesoporous silica particles is presented. Specifically, catanionic templating systems composed of bile acids and CTAB enable the production of submicrometer MCM-41 particles of various shapes, high porosity, and remarkable features. The variation of a single component, the bile acid, leads to the preparation of particles with different morphologies. For instance, small (textbackslashtextbackslashtextless500 nm) well-separated hexagonal platelets and twisted rods, with tunable aspect ratio and chiral pore channels, were prepared. Experiments aimed at elucidating the role of the bile acids showed that the control of shape is due to the specific interactions between bile acids and CTAB.}, keywords = {}, pubstate = {published}, tppubtype = {article} } Morphology control and tuning of nanomaterials are crucial to determine their properties and applications. Solutions based on different synthetic methodologies have been proposed, and in general they required variation of several parameters. Here, a new facile and cost-effective bottom-up strategy to control the morphology of mesoporous silica particles is presented. Specifically, catanionic templating systems composed of bile acids and CTAB enable the production of submicrometer MCM-41 particles of various shapes, high porosity, and remarkable features. The variation of a single component, the bile acid, leads to the preparation of particles with different morphologies. For instance, small (textbackslashtextbackslashtextless500 nm) well-separated hexagonal platelets and twisted rods, with tunable aspect ratio and chiral pore channels, were prepared. Experiments aimed at elucidating the role of the bile acids showed that the control of shape is due to the specific interactions between bile acids and CTAB. |
Rizzi, Vito ; Fiorini, Federica ; Lamanna, Giuseppe ; Gubitosa, Jennifer ; Prasetyanto, Eko Adi ; Fini, Paola ; Fanelli, Fiorenza ; Nacci, Angelo ; De Cola, Luisa ; Cosma, Pinalysa Polyamidoamine-Based Hydrogel for Removal of Blue and Red Dyes from Wastewater Article de journal Dans: ADVANCED SUSTAINABLE SYSTEMS, 2 (6), 2018, ISSN: 2366-7486. @article{rizzi_polyamidoamine-based_2018, title = {Polyamidoamine-Based Hydrogel for Removal of Blue and Red Dyes from Wastewater}, author = {Rizzi, Vito and Fiorini, Federica and Lamanna, Giuseppe and Gubitosa, Jennifer and Prasetyanto, Eko Adi and Fini, Paola and Fanelli, Fiorenza and Nacci, Angelo and De Cola, Luisa and Cosma, Pinalysa}, doi = {10.1002/adsu.201700146}, issn = {2366-7486}, year = {2018}, date = {2018-06-01}, journal = {ADVANCED SUSTAINABLE SYSTEMS}, volume = {2}, number = {6}, abstract = {One of the major problems related to the use of dyes in industrial applications is their elimination from the water or soil and eventually their recovery and reutilization. In this context, a new biocompatible material, previously considered suitable for biomedical applications, is presented for the first time, as an innovative adsorbent material for wastewater treatment. A polyamidoamine-based hydrogel, prepared by Michael-type polyaddition in water, is used for efficiently adsorbing two anionic toxic textile dyes from aqueous solutions. Several parameters affecting the adsorption process, such as the pH of solutions containing dyes, the amount of hydrogel and dyes, and the effect of temperature, are investigated. Moreover, the hydrogel dehydration and swollen conditions by using dye water solution are studied by Thermo-Gravimetry (TG) and Differential Scanning Calorimetry (DSC) analyses, finding that the dehydration temperature plays a relevant role in determining the subsequent adsorbing behavior. The material characterization shows that the adsorption process can be attributed to a combination of electrostatic attraction and intermolecular interactions between hydrogel functional groups and the dye molecules. Visible absorption spectroscopy and Fourier Transform InfraRed-Attenuated Total Reflectance (FTIR-ATR) support the findings. The kinetics of the dye adsorption process are also evaluated, together with the adsorption isotherms.}, keywords = {}, pubstate = {published}, tppubtype = {article} } One of the major problems related to the use of dyes in industrial applications is their elimination from the water or soil and eventually their recovery and reutilization. In this context, a new biocompatible material, previously considered suitable for biomedical applications, is presented for the first time, as an innovative adsorbent material for wastewater treatment. A polyamidoamine-based hydrogel, prepared by Michael-type polyaddition in water, is used for efficiently adsorbing two anionic toxic textile dyes from aqueous solutions. Several parameters affecting the adsorption process, such as the pH of solutions containing dyes, the amount of hydrogel and dyes, and the effect of temperature, are investigated. Moreover, the hydrogel dehydration and swollen conditions by using dye water solution are studied by Thermo-Gravimetry (TG) and Differential Scanning Calorimetry (DSC) analyses, finding that the dehydration temperature plays a relevant role in determining the subsequent adsorbing behavior. The material characterization shows that the adsorption process can be attributed to a combination of electrostatic attraction and intermolecular interactions between hydrogel functional groups and the dye molecules. Visible absorption spectroscopy and Fourier Transform InfraRed-Attenuated Total Reflectance (FTIR-ATR) support the findings. The kinetics of the dye adsorption process are also evaluated, together with the adsorption isotherms. |
Yao, Yifan ; Zhang, Lei ; Leydecker, Tim ; Samori, Paolo Direct Photolithography on Molecular Crystals for High Performance Organic Optoelectronic Devices Article de journal Dans: JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 140 (22), p. 6984–6990, 2018, ISSN: 0002-7863. @article{yao_direct_2018, title = {Direct Photolithography on Molecular Crystals for High Performance Organic Optoelectronic Devices}, author = {Yao, Yifan and Zhang, Lei and Leydecker, Tim and Samori, Paolo}, doi = {10.1021/jacs.8b03526}, issn = {0002-7863}, year = {2018}, date = {2018-06-01}, journal = {JOURNAL OF THE AMERICAN CHEMICAL SOCIETY}, volume = {140}, number = {22}, pages = {6984--6990}, abstract = {Organic crystals are generated via the bottom up self-assembly of molecular building blocks which are held together through weak noncovalent interactions. Although they revealed extraordinary charge transport characteristics, their labile nature represents a major drawback toward their integration in optoelectronic devices when the use of sophisticated patterning techniques is required. Here we have devised a radically new method to enable the use of photolithography directly on molecular crystals, with a spatial resolution below 300 nm, thereby allowing the precise wiring up of multiple crystals on demand. Two archetypal organic crystals, i.e., p-type 2,7-diphenyl[1]benzothieno[3,2-b][1]benzothiophene (Dph-BTBT) nanoflakes and n-type N,N'-dioctyl-3,4,9,10-perylenedicarboximide (PTCDI-C8) nanowires, have been exploited as active materials to realize high-performance top contact organic field-effect transistors (OFETs), inverter and p-n heterojunction photovoltaic devices supported on plastic substrate. The compatibility of our direct photolithography technique with organic molecular crystals is key for exploiting the full potential of organic electronics for sophisticated large-area devices and logic circuitries, thus paving the way toward novel applications in plastic (opto)electronics.}, keywords = {}, pubstate = {published}, tppubtype = {article} } Organic crystals are generated via the bottom up self-assembly of molecular building blocks which are held together through weak noncovalent interactions. Although they revealed extraordinary charge transport characteristics, their labile nature represents a major drawback toward their integration in optoelectronic devices when the use of sophisticated patterning techniques is required. Here we have devised a radically new method to enable the use of photolithography directly on molecular crystals, with a spatial resolution below 300 nm, thereby allowing the precise wiring up of multiple crystals on demand. Two archetypal organic crystals, i.e., p-type 2,7-diphenyl[1]benzothieno[3,2-b][1]benzothiophene (Dph-BTBT) nanoflakes and n-type N,N'-dioctyl-3,4,9,10-perylenedicarboximide (PTCDI-C8) nanowires, have been exploited as active materials to realize high-performance top contact organic field-effect transistors (OFETs), inverter and p-n heterojunction photovoltaic devices supported on plastic substrate. The compatibility of our direct photolithography technique with organic molecular crystals is key for exploiting the full potential of organic electronics for sophisticated large-area devices and logic circuitries, thus paving the way toward novel applications in plastic (opto)electronics. |
Thomas, Anoop ; Chervy, Thibault ; Azzini, Stefano ; Li, Minghao ; George, Jino ; Genet, Cyriaque ; Ebbesen, Thomas W Mueller Polarimetry of Chiral Supramolecular Assembly Article de journal Dans: JOURNAL OF PHYSICAL CHEMISTRY C, 122 (25, SI), p. 14205–14212, 2018, ISSN: 1932-7447. @article{thomas_mueller_2018, title = {Mueller Polarimetry of Chiral Supramolecular Assembly}, author = {Thomas, Anoop and Chervy, Thibault and Azzini, Stefano and Li, Minghao and George, Jino and Genet, Cyriaque and Ebbesen, Thomas W.}, doi = {10.1021/acs.jpcc.8b01867}, issn = {1932-7447}, year = {2018}, date = {2018-06-01}, journal = {JOURNAL OF PHYSICAL CHEMISTRY C}, volume = {122}, number = {25, SI}, pages = {14205--14212}, abstract = {Supramolecular organizations of achiral molecules are known to undergo spontaneous mirror symmetry breaking, materializing chiral macroscopic structures with enantiomeric excess. Using Mueller polarimetry, we show that the hierarchy at play in the self-assembly of an achiral amphiphilic cyanine molecule, C8O3, can be encoded in a hierarchical evolution of the states of polarization of a light beam interacting with the self-assembly. We propose a methodology to monitor the formation, growth and bundling of supramolecular assemblies in solution by tracing, at each stage of assembly, the circular and linear dichroisms together with degree of depolarization. This systematic polarization monitoring of the self assembly allows us to investigate the various stages of the chiral nucleation process. In particular, we reveal that mirror symmetry breaking is driven, at the earliest stage of the self-assembly, by hydrophobic forces. Chiral excitons are then formed in tubular J-aggregates by a secondary nucleation, before an amplification of the chiral signal is observed in the final stage of assembly, corresponding to exciton coupling aided by the bundling of the tubular aggregates.}, keywords = {}, pubstate = {published}, tppubtype = {article} } Supramolecular organizations of achiral molecules are known to undergo spontaneous mirror symmetry breaking, materializing chiral macroscopic structures with enantiomeric excess. Using Mueller polarimetry, we show that the hierarchy at play in the self-assembly of an achiral amphiphilic cyanine molecule, C8O3, can be encoded in a hierarchical evolution of the states of polarization of a light beam interacting with the self-assembly. We propose a methodology to monitor the formation, growth and bundling of supramolecular assemblies in solution by tracing, at each stage of assembly, the circular and linear dichroisms together with degree of depolarization. This systematic polarization monitoring of the self assembly allows us to investigate the various stages of the chiral nucleation process. In particular, we reveal that mirror symmetry breaking is driven, at the earliest stage of the self-assembly, by hydrophobic forces. Chiral excitons are then formed in tubular J-aggregates by a secondary nucleation, before an amplification of the chiral signal is observed in the final stage of assembly, corresponding to exciton coupling aided by the bundling of the tubular aggregates. |
Herder, Martin ; Lehn, Jean-Marie The Photodynamic Covalent Bond: Sensitized Alkoxyamines as a Tool To Shift Reaction Networks Out-of-Equilibrium Using Light Energy Article de journal Dans: JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 140 (24), p. 7647–7657, 2018, ISSN: 0002-7863. @article{herder_photodynamic_2018, title = {The Photodynamic Covalent Bond: Sensitized Alkoxyamines as a Tool To Shift Reaction Networks Out-of-Equilibrium Using Light Energy}, author = {Herder, Martin and Lehn, Jean-Marie}, doi = {10.1021/jacs.8b03633}, issn = {0002-7863}, year = {2018}, date = {2018-06-01}, journal = {JOURNAL OF THE AMERICAN CHEMICAL SOCIETY}, volume = {140}, number = {24}, pages = {7647--7657}, abstract = {We implement sensitized alkoxyamines as “photodynamic covalent bonds”-bonds that, while being stable in the dark at ambient temperatures, upon photoexcitation efficiently dissociate and recombine to the bound state in a fast thermal reaction. This type of bond allows for the photochemically induced exchange of molecular building blocks and resulting constitutional variation within dynamic reaction networks. To this end, alkoxyamines are coupled to a xanthone unit as triplet sensitizer enabling their reversible photodissociation into two radical species. By studying the photochemical properties of three generations of sensitized alkoxyamines it became clear that the nature and efficiency of triplet energy transfer from the sensitizer to the alkoxyamine bond as well as the reversibility of photodissociation crucially depends on the structure of the nitroxide terminus. By employing the thus designed photodynamic covalent bonding motif, we demonstrate how to use light energy to shift a dynamic covalent reaction network away from its thermodynamic minimum into a photostationary state. The network could be repeatedly switched between its minimum and kinetically trapped out-of-equilibrium state by thermal scrambling and selective photoactivation of sensitized alkoxyamines, respectively.}, keywords = {}, pubstate = {published}, tppubtype = {article} } We implement sensitized alkoxyamines as “photodynamic covalent bonds”-bonds that, while being stable in the dark at ambient temperatures, upon photoexcitation efficiently dissociate and recombine to the bound state in a fast thermal reaction. This type of bond allows for the photochemically induced exchange of molecular building blocks and resulting constitutional variation within dynamic reaction networks. To this end, alkoxyamines are coupled to a xanthone unit as triplet sensitizer enabling their reversible photodissociation into two radical species. By studying the photochemical properties of three generations of sensitized alkoxyamines it became clear that the nature and efficiency of triplet energy transfer from the sensitizer to the alkoxyamine bond as well as the reversibility of photodissociation crucially depends on the structure of the nitroxide terminus. By employing the thus designed photodynamic covalent bonding motif, we demonstrate how to use light energy to shift a dynamic covalent reaction network away from its thermodynamic minimum into a photostationary state. The network could be repeatedly switched between its minimum and kinetically trapped out-of-equilibrium state by thermal scrambling and selective photoactivation of sensitized alkoxyamines, respectively. |
Hagenmuller, David ; Schutz, Stefan ; Schachenmayer, Johannes ; Genes, Claudiu ; Pupillo, Guido Cavity-assisted mesoscopic transport of fermions: Coherent and dissipative dynamics Article de journal Dans: 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 Article de journal Dans: CHEMICAL ENGINEERING JOURNAL, 340 (SI), p. 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 Article de journal Dans: JOURNAL OF CELLULAR PHYSIOLOGY, 233 (5), p. 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 Article de journal Dans: JOURNAL OF MATERIALS CHEMISTRY A, 6 (20), p. 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 Article de journal Dans: 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 Article de journal Dans: MATERIALS HORIZONS, 5 (3), p. 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 Article de journal Dans: CARBON, 130 , p. 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 Article de journal Dans: ACS PHOTONICS, 5 (4), p. 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 Article de journal Dans: JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 140 (16), p. 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 Article de journal Dans: 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) Article de journal Dans: 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 Article de journal Dans: CHEMISTRY-AN ASIAN JOURNAL, 13 (5), p. 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 Article de journal Dans: 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 Article de journal Dans: ORGANIC LETTERS, 20 (3), p. 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 Article de journal Dans: SYNTHESIS-STUTTGART, 50 (3), p. 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 Article de journal Dans: JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 140 (6), p. 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 Article de journal Dans: 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 Article de journal Dans: JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 140 (6), p. 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 Article de journal Dans: CHEMISTRY-A EUROPEAN JOURNAL, 24 (7), p. 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⁈ Article de journal Dans: ISRAEL JOURNAL OF CHEMISTRY, 58 (1-2, SI), p. 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. |
Publications (FR)
2018 |
Oscillations, travelling fronts and patterns in a supramolecular system Article de journal Dans: 2018, ISSN: 1748-3387, 1748-3395. |
Radioisotopic purity and imaging properties of cyclotron-produced Tc-99m using direct Mo-100(p,2n) reaction Article de journal Dans: PHYSICS IN MEDICINE AND BIOLOGY, 63 (18), 2018, ISSN: 0031-9155. |
Collective molecular switching in hybrid superlattices for light-modulated two-dimensional electronics (vol 9, 3689, 2018) Article de journal Dans: NATURE COMMUNICATIONS, 9 , 2018, ISSN: 2041-1723. |
Molecular chemistry approaches for tuning the properties of two-dimensional transition metal dichalcogenides Article de journal Dans: CHEMICAL SOCIETY REVIEWS, 47 (17), p. 6845–6888, 2018, ISSN: 0306-0012. |
Current crowding issues on nanoscale planar organic transistors for spintronic applications Article de journal Dans: NANOTECHNOLOGY, 29 (36), 2018, ISSN: 0957-4484. |
Ring-opening hydroarylation of monosubstituted cyclopropanes enabled by hexafluoroisopropanol Article de journal Dans: CHEMICAL SCIENCE, 9 (30), p. 6411–6416, 2018, ISSN: 2041-6520. |
Concentration-dependent supramolecular patterns of C-3 and C-2 symmetric molecules at the solid/liquid interface Article de journal Dans: COLLOIDS AND SURFACES B-BIOINTERFACES, 168 , p. 211–216, 2018, ISSN: 0927-7765. |
Luminescence of Amphiphilic Pt-II Complexes Controlled by Confinement Article de journal Dans: CHEMISTRY-A EUROPEAN JOURNAL, 24 (46), p. 12054–12060, 2018, ISSN: 0947-6539. |
Phenoxyaluminum(salophen) Scaffolds: Synthesis, Electrochemical Properties, and Self-Assembly at Surfaces of Multifunctional Systems Article de journal Dans: CHEMISTRY-A EUROPEAN JOURNAL, 24 (46), p. 11954–11960, 2018, ISSN: 0947-6539. |
Structure of the EmrE multidrug transporter and its use for inhibitor peptide design Article de journal Dans: PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA, 115 (34), p. E7932–E7941, 2018, ISSN: 0027-8424. |
Surface-Assisted Self-Assembly of a Hydrogel by Proton Diffusion Article de journal Dans: ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 57 (35), p. 11349–11353, 2018, ISSN: 1433-7851. |
Self-Assembled Two-Dimensional Supramolecular Networks Characterized by Scanning Tunneling Microscopy and Spectroscopy in Air and under Vacuum Article de journal Dans: LANGMUIR, 34 (26), p. 7698–7707, 2018, ISSN: 0743-7463. |
Spin State Chemistry: Modulation of Ligand pK(a) by Spin State Switching in a [2x2] Iron(II) Grid-Type Complex Article de journal Dans: JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 140 (26), p. 8218–8227, 2018, ISSN: 0002-7863. |
Total chemical synthesis and biophysical properties of a designed soluble 24 kDa amyloid analogue Article de journal Dans: CHEMICAL SCIENCE, 9 (25), p. 5594–5599, 2018, ISSN: 2041-6520. |
Chemical sensing with 2D materials Article de journal Dans: CHEMICAL SOCIETY REVIEWS, 47 (13), p. 4860–4908, 2018, ISSN: 0306-0012. |
Nanomaterials properties tuned by their environment: integrating supramolecular concepts into sensing devices Article de journal Dans: CHEMICAL SOCIETY REVIEWS, 47 (13), p. 4675–4676, 2018, ISSN: 0306-0012. |
Collective molecular switching in hybrid superlattices for light-modulated two-dimensional electronics Article de journal Dans: NATURE COMMUNICATIONS, 9 , 2018, ISSN: 2041-1723. |
Valid molecular dynamics simulations of human hemoglobin require a surprisingly large box size Article de journal Dans: ELIFE, 7 , 2018, ISSN: 2050-084X. |
Self-Suspended Nanomesh Scaffold for Ultrafast Flexible Photodetectors Based on Organic Semiconducting Crystals Article de journal Dans: ADVANCED MATERIALS, 30 (28), 2018, ISSN: 0935-9648. |
Unconventional Synthesis of a Cu-I Rotaxane with a Superacceptor Stopper: Ultrafast Excited-State Dynamics and Near-Infrared Luminescence Article de journal Dans: CHEMISTRY-A EUROPEAN JOURNAL, 24 (41), p. 10422–10433, 2018, ISSN: 0947-6539. |
Multivalent Metallosupramolecular Assemblies as Effective DNA Binding Agents Article de journal Dans: CHEMISTRY-A EUROPEAN JOURNAL, 24 (42), p. 10802–10811, 2018, ISSN: 0947-6539. |
Proton-Gradient-Driven Oriented Motion of Nanodiamonds Grafted to Graphene by Dynamic Covalent Bonds Article de journal Dans: ACS NANO, 12 (7), p. 7141–7147, 2018, ISSN: 1936-0851. |
Protonation of a Spherical Macrotricyclic Tetramine: Water Inclusion, Allosteric Effect, and Cooperativity Article de journal Dans: CHEMPLUSCHEM, 83 (7, SI), p. 605–611, 2018, ISSN: 2192-6506. |
Are there too many fern genera? Article de journal Dans: TAXON, 67 (3), p. 473–480, 2018, ISSN: 0040-0262. |
Native iron reduces CO2 to intermediates and end-products of the acetyl-CoA pathway Article de journal Dans: NATURE ECOLOGY & EVOLUTION, 2 (6), p. 1019+, 2018, ISSN: 2397-334X. |
Morphology Control of Mesoporous Silica Particles Using Bile Acids as Cosurfactants Article de journal Dans: CHEMISTRY OF MATERIALS, 30 (12), p. 4168–4175, 2018, ISSN: 0897-4756. |
Polyamidoamine-Based Hydrogel for Removal of Blue and Red Dyes from Wastewater Article de journal Dans: ADVANCED SUSTAINABLE SYSTEMS, 2 (6), 2018, ISSN: 2366-7486. |
Direct Photolithography on Molecular Crystals for High Performance Organic Optoelectronic Devices Article de journal Dans: JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 140 (22), p. 6984–6990, 2018, ISSN: 0002-7863. |
Mueller Polarimetry of Chiral Supramolecular Assembly Article de journal Dans: JOURNAL OF PHYSICAL CHEMISTRY C, 122 (25, SI), p. 14205–14212, 2018, ISSN: 1932-7447. |
The Photodynamic Covalent Bond: Sensitized Alkoxyamines as a Tool To Shift Reaction Networks Out-of-Equilibrium Using Light Energy Article de journal Dans: JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 140 (24), p. 7647–7657, 2018, ISSN: 0002-7863. |
Cavity-assisted mesoscopic transport of fermions: Coherent and dissipative dynamics Article de journal Dans: PHYSICAL REVIEW B, 97 (20), 2018, ISSN: 2469-9950. |
Reshaping silica particles: Mesoporous nanodiscs for bimodal delivery and improved cellular uptake Article de journal Dans: CHEMICAL ENGINEERING JOURNAL, 340 (SI), p. 148–154, 2018, ISSN: 1385-8947. |
Targeted therapy of human glioblastoma via delivery of a toxin through a peptide directed to cell surface nucleolin Article de journal Dans: JOURNAL OF CELLULAR PHYSIOLOGY, 233 (5), p. 4091–4105, 2018, ISSN: 0021-9541. |
Graphene oxide-branched polyethylenimine foams for efficient removal of toxic cations from water Article de journal Dans: JOURNAL OF MATERIALS CHEMISTRY A, 6 (20), p. 9384–9390, 2018, ISSN: 2050-7488. |
When 2D Materials Meet Molecules: Opportunities and Challenges of Hybrid Organic/Inorganic van der Waals Heterostructures Article de journal Dans: ADVANCED MATERIALS, 30 (18), 2018, ISSN: 0935-9648. |
Photoelectrochemical response of carbon dots (CDs) derived from chitosan and their use in electrochemical imaging Article de journal Dans: MATERIALS HORIZONS, 5 (3), p. 423–428, 2018, ISSN: 2051-6347. |
Graphene exfoliation in the presence of semiconducting polymers for improved film homogeneity and electrical performances Article de journal Dans: CARBON, 130 , p. 495–502, 2018, ISSN: 0008-6223. |
Room Temperature Chiral Coupling of Valley Excitons with Spin-Momentum Locked Surface Plasmons Article de journal Dans: ACS PHOTONICS, 5 (4), p. 1281–1287, 2018, ISSN: 2330-4022. |
Dynamic Covalent Metathesis in the C=C/C=N Exchange between Knoevenagel Compounds and Imines Article de journal Dans: JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 140 (16), p. 5560–5568, 2018, ISSN: 0002-7863. |
Modifying conductivity and material properties of molecular ensembles under light-matter strong coupling Article de journal Dans: ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY, 255 , 2018, ISSN: 0065-7727. |
Photo-inks based on porphyrins and diarylethenes (DAEs) Article de journal Dans: 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 Article de journal Dans: CHEMISTRY-AN ASIAN JOURNAL, 13 (5), p. 465–481, 2018, ISSN: 1861-4728. |
Role of framework mutations and antibody flexibility in the evolution of broadly neutralizing antibodies Article de journal Dans: ELIFE, 7 , 2018, ISSN: 2050-084X. |
Nucleophilic Ring Opening of Donor-Acceptor Cyclopropanes Catalyzed by a Bronsted Acid in Hexafluoroisopropanol Article de journal Dans: ORGANIC LETTERS, 20 (3), p. 574–577, 2018, ISSN: 1523-7060. |
Recent Advances in Nickel Catalysis Enabled by Stoichiometric Metallic Reducing Agents Article de journal Dans: SYNTHESIS-STUTTGART, 50 (3), p. 499–513, 2018, ISSN: 0039-7881. |
Templated Formation of Luminescent Virus-like Particles by Tailor-Made Pt(II) Amphiphiles Article de journal Dans: JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 140 (6), p. 2355–2362, 2018, ISSN: 0002-7863. |
Selective Encapsulation and Enhancement of the Emission Properties of a Luminescent Cu(I) Complex in Mesoporous Silica Article de journal Dans: HELVETICA CHIMICA ACTA, 101 (2), 2018, ISSN: 0018-019X. |
Heteroleptic Copper(I) Pseudorotaxanes Incorporating Macrocyclic Phenanthroline Ligands of Different Sizes Article de journal Dans: JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 140 (6), p. 2336–2347, 2018, ISSN: 0002-7863. |
Fluorescence Commutation and Surface Photopatterning with Porphyrin Tetradithienylethene Switches Article de journal Dans: CHEMISTRY-A EUROPEAN JOURNAL, 24 (7), p. 1631–1639, 2018, ISSN: 0947-6539. |
Beyond Chemical Synthesis: Self-Organization⁈ Article de journal Dans: ISRAEL JOURNAL OF CHEMISTRY, 58 (1-2, SI), p. 136–141, 2018, ISSN: 0021-2148. |