2019 |
Zhao, Yuda; Bertolazzi, Simone; Samorì, Paolo A Universal Approach toward Light-Responsive Two-Dimensional Electronics: Chemically Tailored Hybrid van der Waals Heterostructures Journal Article In: ACS Nano 2019, 13 (4), pp. 4814-4825, 2019. @article{Zhao2019, title = {A Universal Approach toward Light-Responsive Two-Dimensional Electronics: Chemically Tailored Hybrid van der Waals Heterostructures}, author = {Yuda Zhao and Simone Bertolazzi and Paolo Samorì}, editor = {2019 American Chemical Society}, url = {https://pubs.acs.org/doi/pdf/10.1021/acsnano.9b01716}, doi = {10.1021/acsnano.9b01716}, year = {2019}, date = {2019-03-27}, journal = {ACS Nano 2019}, volume = {13}, number = {4}, pages = {4814-4825}, abstract = {Stimuli-responsive hybrid van der Waals heterostructures (vdWHs), composed of organic molecular switches superimposed on inorganic 2D materials (2DMs), can combine the outstanding physical properties of the latter components with the virtually infinite variety of tunable functionality of molecules, thereby offering an efficient protocol for the development of high-performance multifunctional materials and devices. The use of light as a remote control to modulate the properties of semiconducting 2DMs when interfaced with photochromic molecules suffers from both the limitation associated with the persistent photoconductivity characterizing the 2DMs and the finite thermal stability of the photochromic molecule in its different states. Here, we have devised a universal approach toward the fabrication of optically switchable electronic devices comprising a few nanometers thick azobenzene (AZO) layer physisorbed on 2D semiconductors supported on a trap-free polymer dielectric. The joint effect of the improved 2D/dielectric interface, the molecule’s light-modulated dipolar doping, and the high thermal stability of cis-AZO offers the highest control over the reversible and efficient charge carrier tuning in 2D semiconductors with a preserved high performance in 2D field-effect transistors, as quantified in terms of carrier mobility and Ion/Ioff ratio. The device has the potential to operate as an optical memory with four current levels and long retention time (>15 h). Furthermore, by using a CMOS-compatible micropatterning process, the photoswitchable resistor–diode transition has been achieved on hybrid lateral heterojunction devices. Our approach is of general applicability toward the generation of high-performance hybrid vdWHs for the emergence of functional and responsive devices.}, keywords = {}, pubstate = {published}, tppubtype = {article} } Stimuli-responsive hybrid van der Waals heterostructures (vdWHs), composed of organic molecular switches superimposed on inorganic 2D materials (2DMs), can combine the outstanding physical properties of the latter components with the virtually infinite variety of tunable functionality of molecules, thereby offering an efficient protocol for the development of high-performance multifunctional materials and devices. The use of light as a remote control to modulate the properties of semiconducting 2DMs when interfaced with photochromic molecules suffers from both the limitation associated with the persistent photoconductivity characterizing the 2DMs and the finite thermal stability of the photochromic molecule in its different states. Here, we have devised a universal approach toward the fabrication of optically switchable electronic devices comprising a few nanometers thick azobenzene (AZO) layer physisorbed on 2D semiconductors supported on a trap-free polymer dielectric. The joint effect of the improved 2D/dielectric interface, the molecule’s light-modulated dipolar doping, and the high thermal stability of cis-AZO offers the highest control over the reversible and efficient charge carrier tuning in 2D semiconductors with a preserved high performance in 2D field-effect transistors, as quantified in terms of carrier mobility and Ion/Ioff ratio. The device has the potential to operate as an optical memory with four current levels and long retention time (>15 h). Furthermore, by using a CMOS-compatible micropatterning process, the photoswitchable resistor–diode transition has been achieved on hybrid lateral heterojunction devices. Our approach is of general applicability toward the generation of high-performance hybrid vdWHs for the emergence of functional and responsive devices. |
Darmawan, Noviyan ; Sambri, Letizia ; Daniliuc, Constantin G; De Cola, Luisa Blue-emitting bolaamphiphilic zwitterionic iridium(iii) complex Journal Article In: DALTON TRANSACTIONS, 48 (11), pp. 3664-3670 , 2019. @article{Darmawan2019, title = {Blue-emitting bolaamphiphilic zwitterionic iridium(iii) complex}, author = {Darmawan, Noviyan and Sambri, Letizia and Daniliuc, Constantin G. and De Cola, Luisa}, editor = {DALTON TRANSACTIONS}, doi = {10.1039/c8dt04833a}, year = {2019}, date = {2019-03-21}, journal = {DALTON TRANSACTIONS}, volume = {48}, number = {11}, pages = {3664-3670 }, abstract = {Aggregation induced emission is a very interesting phenomenon that recently has attracted a lot of interest. Most of the examples deal with organic molecules or flat metal complexes. Here we demonstrate that, by design, even iridium compounds can display this process without shifting the emission energy. In order to enhance the aggregation properties we have focussed on amphiphilic complexes. We report the synthesis and photophysical characterisation of a blue-emitting bolaamphiphilic zwitterionic Ir(III) complex and an analogous cationic amphiphilic compound, used as a reference. The bolaamphiphile exhibited blue (lambda(max) = 450 nm) emission in dilute, deaerated solution with a photoluminescence quantum yield (PLQY) of 22%, similar to the related cationic amphiphilic complex. The bolaamphiphile displayed significant emission enhancement in the solid state, with an emission quantum yield that reach 52%. Interestingly, the emission of the cationic analogue suffers from aggregation quenching in the solid state, (PLQY = 3%) as is common for these type of complexes. A correlation between the photophysical data and the arrangement in the solid state is discussed.}, keywords = {}, pubstate = {published}, tppubtype = {article} } Aggregation induced emission is a very interesting phenomenon that recently has attracted a lot of interest. Most of the examples deal with organic molecules or flat metal complexes. Here we demonstrate that, by design, even iridium compounds can display this process without shifting the emission energy. In order to enhance the aggregation properties we have focussed on amphiphilic complexes. We report the synthesis and photophysical characterisation of a blue-emitting bolaamphiphilic zwitterionic Ir(III) complex and an analogous cationic amphiphilic compound, used as a reference. The bolaamphiphile exhibited blue (lambda(max) = 450 nm) emission in dilute, deaerated solution with a photoluminescence quantum yield (PLQY) of 22%, similar to the related cationic amphiphilic complex. The bolaamphiphile displayed significant emission enhancement in the solid state, with an emission quantum yield that reach 52%. Interestingly, the emission of the cationic analogue suffers from aggregation quenching in the solid state, (PLQY = 3%) as is common for these type of complexes. A correlation between the photophysical data and the arrangement in the solid state is discussed. |
Hagenmüller, David; Schachenmayer, Johannes; Genet, Cyriaque; Ebbesen, Thomas W; Pupillo, Guido Enhancement of the Electron−Phonon Scattering Induced by Intrinsic Surface Plasmon−Phonon Polaritons Journal Article In: ACS Photonics 2019, 6 (4), pp 1073–1081, 6 (4), pp. 1073-1081, 2019. @article{Hagenmüller2019, title = {Enhancement of the Electron−Phonon Scattering Induced by Intrinsic Surface Plasmon−Phonon Polaritons}, author = {David Hagenmüller and Johannes Schachenmayer and Cyriaque Genet and Thomas W. Ebbesen and Guido Pupillo}, editor = {Copyright © 2019 American Chemical Society }, doi = {10.1021/acsphotonics.9b00268}, year = {2019}, date = {2019-03-17}, journal = {ACS Photonics 2019, 6 (4), pp 1073–1081}, volume = {6}, number = {4}, pages = {1073-1081}, abstract = {We investigate light−matter coupling in metallic crystals where plasmons coexist with phonons exhibiting large oscillator strength. We demonstrate theoretically that this coexistence can lead to strong light−matter interactions without external resonators. When the frequencies of plasmons and phonons are comparable, hybridization of these collective matter modes occurs in the crystal. We show that the coupling of these modes to photonic degrees of freedom gives rise to intrinsic surface plasmon−phonon polaritons, which offer the unique possibility to control the phonon properties by tuning the electron density and the crystal thickness. In particular, dressed phonons with reduced frequency and large wave vectors arise in the case of quasi-2D crystals, which could lead to large enhancements of the electron−phonon scattering in the vibrational ultrastrong coupling regime. This suggests that photons can play a key role in determining the quantum properties of certain materials. A nonperturbative self-consistent Hamiltonian method is presented that is valid for arbitrarily large coupling strengths.}, keywords = {}, pubstate = {published}, tppubtype = {article} } We investigate light−matter coupling in metallic crystals where plasmons coexist with phonons exhibiting large oscillator strength. We demonstrate theoretically that this coexistence can lead to strong light−matter interactions without external resonators. When the frequencies of plasmons and phonons are comparable, hybridization of these collective matter modes occurs in the crystal. We show that the coupling of these modes to photonic degrees of freedom gives rise to intrinsic surface plasmon−phonon polaritons, which offer the unique possibility to control the phonon properties by tuning the electron density and the crystal thickness. In particular, dressed phonons with reduced frequency and large wave vectors arise in the case of quasi-2D crystals, which could lead to large enhancements of the electron−phonon scattering in the vibrational ultrastrong coupling regime. This suggests that photons can play a key role in determining the quantum properties of certain materials. A nonperturbative self-consistent Hamiltonian method is presented that is valid for arbitrarily large coupling strengths. |
Bertolazzi, S; Bondavalli, P; Roche, S; San, T; Choi, S -Y; Colombo, L; Bonaccorso, F; Samorì, P Nonvolatile Memories Based on Graphene and Related 2D Materials Journal Article In: Advanced Materials, 31 (Issue 10), pp. 1806663, 2019. @article{Bertolazzi2019, title = {Nonvolatile Memories Based on Graphene and Related 2D Materials}, author = {S. Bertolazzi and P. Bondavalli and S. Roche and T. San and S.-Y. Choi and L. Colombo and F. Bonaccorso and P. Samorì}, editor = {Wiley Online Library}, url = {https://onlinelibrary.wiley.com/doi/abs/10.1002/adma.201806663}, doi = {10.1002/adma.201806663}, year = {2019}, date = {2019-03-08}, journal = {Advanced Materials}, volume = {31}, number = {Issue 10}, pages = {1806663}, abstract = {The pervasiveness of information technologies is generating an impressive amount of data, which need to be accessed very quickly. Nonvolatile memories (NVMs) are making inroads into high‐capacity storage to replace hard disk drives, fuelling the expansion of the global storage memory market. As silicon‐based flash memories are approaching their fundamental limit, vertical stacking of multiple memory cell layers, innovative device concepts, and novel materials are being investigated. In this context, emerging 2D materials, such as graphene, transition metal dichalcogenides, and black phosphorous, offer a host of physical and chemical properties, which could both improve existing memory technologies and enable the next generation of low‐cost, flexible, and wearable storage devices. Herein, an overview of graphene and related 2D materials (GRMs) in different types of NVM cells is provided, including resistive random‐access, flash, magnetic and phase‐change memories. The physical and chemical mechanisms underlying the switching of GRM‐based memory devices studied in the last decade are discussed. Although at this stage most of the proof‐of‐concept devices investigated do not compete with state‐of‐the‐art devices, a number of promising technological advancements have emerged. Here, the most relevant material properties and device structures are analyzed, emphasizing opportunities and challenges toward the realization of practical NVM devices.}, keywords = {}, pubstate = {published}, tppubtype = {article} } The pervasiveness of information technologies is generating an impressive amount of data, which need to be accessed very quickly. Nonvolatile memories (NVMs) are making inroads into high‐capacity storage to replace hard disk drives, fuelling the expansion of the global storage memory market. As silicon‐based flash memories are approaching their fundamental limit, vertical stacking of multiple memory cell layers, innovative device concepts, and novel materials are being investigated. In this context, emerging 2D materials, such as graphene, transition metal dichalcogenides, and black phosphorous, offer a host of physical and chemical properties, which could both improve existing memory technologies and enable the next generation of low‐cost, flexible, and wearable storage devices. Herein, an overview of graphene and related 2D materials (GRMs) in different types of NVM cells is provided, including resistive random‐access, flash, magnetic and phase‐change memories. The physical and chemical mechanisms underlying the switching of GRM‐based memory devices studied in the last decade are discussed. Although at this stage most of the proof‐of‐concept devices investigated do not compete with state‐of‐the‐art devices, a number of promising technological advancements have emerged. Here, the most relevant material properties and device structures are analyzed, emphasizing opportunities and challenges toward the realization of practical NVM devices. |
Schnoering, Gabriel; Rosales-Cabara, Yoseline; Wendehenne, Hugo; Canaguier-Durand, Antoine; Genet, Cyriaque Thermally Limited Force Microscopy on Optically Trapped Single Metallic Nanoparticles Journal Article In: PHYSICAL REVIEW APPLIED , 11 ( 034023), 2019. @article{Schnoering2019, title = {Thermally Limited Force Microscopy on Optically Trapped Single Metallic Nanoparticles}, author = {Gabriel Schnoering and Yoseline Rosales-Cabara and Hugo Wendehenne and Antoine Canaguier-Durand and Cyriaque Genet}, editor = {© 2019 American Physical Society}, doi = {DOI: 10.1103/PhysRevApplied.11.034023}, year = {2019}, date = {2019-03-08}, journal = {PHYSICAL REVIEW APPLIED }, volume = {11}, number = { 034023}, abstract = {We propose and evaluate a new type of optical force microscope based on a standing-wave optical trap. Our microscope, calibrated in situ and operating in a dynamic mode, is able to trap, without heating, a single metallic nanoparticle of 150 nm that acts as a highly sensitive probe for external radiation pressure. An Allan-deviation-based stability analysis of the setup yields an optimal 0.1-Hz measurement bandwidth over which the microscope is thermally limited. Over this bandwidth, and with a genuine sine-wave external drive, we demonstrate an optical force resolution down to 3 fN in water at room temperature with a dynamical range for force detection that covers almost 2 orders of magnitude. This resolution is reached in both the confined regime and the freely diffusing regime of the optical trap. In the latter, we measure induced displacements of 10−11 m on the trapped nanoparticle spatially confined within less than 25 nm along the optical axis.}, keywords = {}, pubstate = {published}, tppubtype = {article} } We propose and evaluate a new type of optical force microscope based on a standing-wave optical trap. Our microscope, calibrated in situ and operating in a dynamic mode, is able to trap, without heating, a single metallic nanoparticle of 150 nm that acts as a highly sensitive probe for external radiation pressure. An Allan-deviation-based stability analysis of the setup yields an optimal 0.1-Hz measurement bandwidth over which the microscope is thermally limited. Over this bandwidth, and with a genuine sine-wave external drive, we demonstrate an optical force resolution down to 3 fN in water at room temperature with a dynamical range for force detection that covers almost 2 orders of magnitude. This resolution is reached in both the confined regime and the freely diffusing regime of the optical trap. In the latter, we measure induced displacements of 10−11 m on the trapped nanoparticle spatially confined within less than 25 nm along the optical axis. |
K, Muchowska; E, Chevallot-Beroux; J, Moran Recreating ancient metabolic pathways before enzymes. Journal Article In: Bioorganic & Medicinal Chemistry, 2019. @article{K2019, title = {Recreating ancient metabolic pathways before enzymes.}, author = {Muchowska K and Chevallot-Beroux E and Moran J}, editor = {Copyright © 2019. Published by Elsevier Ltd}, url = {https://www.sciencedirect.com/science/article/pii/S0968089619300033?via%3Dihub}, doi = {10.1016/j.bmc.2019.03.012}, year = {2019}, date = {2019-03-07}, journal = {Bioorganic & Medicinal Chemistry}, abstract = {The biochemistry of all living organisms uses complex, enzyme-catalyzed metabolic reaction networks. Yet, at life's origins, enzymes had not yet evolved. Therefore, it has been postulated that non-enzymatic metabolic pathways predated their enzymatic counterparts. In this account article, we describe our recent work to evaluate whether two ancient carbon fixation pathways, the rTCA (reductive tricarboxylic acid) cycle and the reductive AcCoA (Wood-Ljungdahl) pathway, could have operated without enzymes and therefore have originated as prebiotic chemistry. We also describe the discovery of an Fe2+-promoted complex reaction network that may represent a prebiotic predecessor to the TCA and glyoxylate cycles. The collective results support the idea that most central metabolic pathways could have roots in prebiotic chemistry.}, keywords = {}, pubstate = {published}, tppubtype = {article} } The biochemistry of all living organisms uses complex, enzyme-catalyzed metabolic reaction networks. Yet, at life's origins, enzymes had not yet evolved. Therefore, it has been postulated that non-enzymatic metabolic pathways predated their enzymatic counterparts. In this account article, we describe our recent work to evaluate whether two ancient carbon fixation pathways, the rTCA (reductive tricarboxylic acid) cycle and the reductive AcCoA (Wood-Ljungdahl) pathway, could have operated without enzymes and therefore have originated as prebiotic chemistry. We also describe the discovery of an Fe2+-promoted complex reaction network that may represent a prebiotic predecessor to the TCA and glyoxylate cycles. The collective results support the idea that most central metabolic pathways could have roots in prebiotic chemistry. |
Krystek, M; Pakulski, D; Patroniak, V; Górski, M; Szojda, L; Ciesielski, A; Samorì, P High‐Performance Graphene‐Based Cementitious Composites Journal Article In: ADVANCED SCIENCE, 6 (1801195), 2019. @article{Krystek2019, title = {High‐Performance Graphene‐Based Cementitious Composites}, author = {M. Krystek and D. Pakulski and V. Patroniak and M. Górski and L. Szojda and A. Ciesielski and P. Samorì}, editor = {Wiley Online Library }, url = { https://doi.org/10.1002/advs.201801195}, doi = {10.1002/advs.201801195}, year = {2019}, date = {2019-03-07}, journal = {ADVANCED SCIENCE}, volume = {6}, number = {1801195}, abstract = {This study reports on the development of a cementitious composite incorporating electrochemically exfoliated graphene (EEG). This hybrid functional material features significantly enhanced microstructure and mechanical properties, as well as unaffected workability; thus, it outperforms previously reported cementitious composites containing graphene derivatives. The manufacturing of the composite relies on a simple and efficient method that enables the uniform dispersion of EEG within cement matrix in the absence of surfactants. Different from graphene oxide, EEG is found to not agglomerate in cement alkaline environment, thereby not affecting the fluidity of cementitious composites. The addition of 0.05 wt% graphene content to ordinary Portland cement results in an increase up to 79%, 8%, and 9% for the tensile strength, compressive strength, and Young's modulus, respectively. Remarkably, it is found that the addition of EEG promotes the hydration reaction of both alite and belite, thus leading to the formation of a large fraction of 3CaO·2SiO2·3H2O (C‐S‐H) phase. These findings represent a major step forward toward the practical application of nanomaterials in civil engineering.}, keywords = {}, pubstate = {published}, tppubtype = {article} } This study reports on the development of a cementitious composite incorporating electrochemically exfoliated graphene (EEG). This hybrid functional material features significantly enhanced microstructure and mechanical properties, as well as unaffected workability; thus, it outperforms previously reported cementitious composites containing graphene derivatives. The manufacturing of the composite relies on a simple and efficient method that enables the uniform dispersion of EEG within cement matrix in the absence of surfactants. Different from graphene oxide, EEG is found to not agglomerate in cement alkaline environment, thereby not affecting the fluidity of cementitious composites. The addition of 0.05 wt% graphene content to ordinary Portland cement results in an increase up to 79%, 8%, and 9% for the tensile strength, compressive strength, and Young's modulus, respectively. Remarkably, it is found that the addition of EEG promotes the hydration reaction of both alite and belite, thus leading to the formation of a large fraction of 3CaO·2SiO2·3H2O (C‐S‐H) phase. These findings represent a major step forward toward the practical application of nanomaterials in civil engineering. |
Hou, Lili; Zhang, Xiaoyan; Cotella, Giovanni F; Carnicella, Giuseppe; Herder, Martin; Schmidt, Bernd M; Pätzel, Michael; andFranco Cacialli, Stefan Hecht; Samorì, Paolo Optically switchable organic light-emitting transistors Journal Article In: Nature Nanotechnology, 14 , pp. 347-353, 2019. @article{Hou2019b, title = {Optically switchable organic light-emitting transistors}, author = {Lili Hou and Xiaoyan Zhang and Giovanni F Cotella and Giuseppe Carnicella and Martin Herder and Bernd M Schmidt and Michael Pätzel and Stefan Hecht andFranco Cacialli and Paolo Samorì }, editor = {Nature}, url = {https://www.nature.com/articles/s41565-019-0370-9}, doi = {10.1038/s41565-019-0370-9}, year = {2019}, date = {2019-02-18}, journal = {Nature Nanotechnology}, volume = {14}, pages = {347-353}, abstract = {Organic light-emitting transistors are pivotal components for emerging opto- and nanoelectronics applications, such as logic circuitries and smart displays. Within this technology sector, the integration of multiple functionalities in a single electronic device remains the key challenge. Here we show optically switchable organic light-emitting transistors fabricated through a judicious combination of light-emitting semiconductors and photochromic molecules. Irradiation of the solution-processed films at selected wavelengths enables the efficient and reversible tuning of charge transport and electroluminescence simultaneously, with a high degree of modulation (on/off ratios up to 500) in the three primary colours. Different emitting patterns can be written and erased through a non-invasive and mask-free process, on a length scale of a few micrometres in a single device, thereby rendering this technology potentially promising for optically gated highly integrated full-colour displays and active optical memory.}, keywords = {}, pubstate = {published}, tppubtype = {article} } Organic light-emitting transistors are pivotal components for emerging opto- and nanoelectronics applications, such as logic circuitries and smart displays. Within this technology sector, the integration of multiple functionalities in a single electronic device remains the key challenge. Here we show optically switchable organic light-emitting transistors fabricated through a judicious combination of light-emitting semiconductors and photochromic molecules. Irradiation of the solution-processed films at selected wavelengths enables the efficient and reversible tuning of charge transport and electroluminescence simultaneously, with a high degree of modulation (on/off ratios up to 500) in the three primary colours. Different emitting patterns can be written and erased through a non-invasive and mask-free process, on a length scale of a few micrometres in a single device, thereby rendering this technology potentially promising for optically gated highly integrated full-colour displays and active optical memory. |
Chevallot-Beroux, Elodie; Ako, Ayuk M; Schmitt, Wolfgang; Twamley, Brendan; Moran, Joseph; Corinne, Boudon; Ruhlmannc, Laurent; Mameri, Samir Synthesis of new Mn19 analogues and their structural, electrochemical and catalytic properties Journal Article In: Dalton Transactions, (15), 2019. @article{Chevallot-Beroux2019, title = {Synthesis of new Mn19 analogues and their structural, electrochemical and catalytic properties }, author = { Elodie Chevallot-Beroux and Ayuk M. Ako and Wolfgang Schmitt and Brendan Twamley and Joseph Moran and Boudon Corinne and Laurent Ruhlmannc and Samir Mameri}, editor = {Royal Society of Chemistry}, doi = {10.1039/C8DT04807J}, year = {2019}, date = {2019-02-13}, journal = {Dalton Transactions}, number = {15}, abstract = {We report the synthesis and structural characterisation of new Mn19 and Mn18M analogues, [MnIII12MnII7(μ4-O)8(μ3-OCH3)2(μ3-Br)6(HLMe)12(MeOH)6]Br2 (2) and [MnIII12MnII6Sr(μ4-O8(μ3-Cl)8(HLMe)12(MeCN)6]Cl2 cluster (3), where H3LMe is 2,6-bis(hydroxymethyl)-p-cresol. The electrochemistry of 2 and 3 has been investigated and their activity as catalysts in the oxidation of benzyl alcohol has been evaluated. Selective oxidation of benzyl alcohol to benzaldehyde by O2 was achieved using 1 mol% of catalyst with conversions of 74% (2) and 60% (3) at 140 °C using TEMPO as a co-catalyst. No partial conversion of benzaldehyde to benzoic acid was observed. The results obtained revealed that different operative parameters – such as catalyst loading, temperature, time, solvent and the presence of molecular oxygen – played an important role in the selective oxidation of benzyl alcohol.}, keywords = {}, pubstate = {published}, tppubtype = {article} } We report the synthesis and structural characterisation of new Mn19 and Mn18M analogues, [MnIII12MnII7(μ4-O)8(μ3-OCH3)2(μ3-Br)6(HLMe)12(MeOH)6]Br2 (2) and [MnIII12MnII6Sr(μ4-O8(μ3-Cl)8(HLMe)12(MeCN)6]Cl2 cluster (3), where H3LMe is 2,6-bis(hydroxymethyl)-p-cresol. The electrochemistry of 2 and 3 has been investigated and their activity as catalysts in the oxidation of benzyl alcohol has been evaluated. Selective oxidation of benzyl alcohol to benzaldehyde by O2 was achieved using 1 mol% of catalyst with conversions of 74% (2) and 60% (3) at 140 °C using TEMPO as a co-catalyst. No partial conversion of benzaldehyde to benzoic acid was observed. The results obtained revealed that different operative parameters – such as catalyst loading, temperature, time, solvent and the presence of molecular oxygen – played an important role in the selective oxidation of benzyl alcohol. |
Thomas, A; Lethuillier-Karl, L; K. Nagarajan, Vergauwe R M A; George, J; Chervy, T; Shalabney, A; Devaux, E; Genet, C; nd Ebbesen, Morana J T W Tilting a ground-state reactivity landscape by vibrational strong coupling Journal Article In: Science, 363 (6427), pp. 615-619, 2019. @article{Thomas2019, title = {Tilting a ground-state reactivity landscape by vibrational strong coupling}, author = {A. Thomas and L. Lethuillier-Karl and K. Nagarajan, R. M. A. Vergauwe and J. George and T. Chervy and A. Shalabney and E. Devaux and C. Genet and J. Morana nd T. W. Ebbesen}, url = {https://science.sciencemag.org/content/363/6427/615.abstract}, doi = {10.1126/science.aau7742 }, year = {2019}, date = {2019-02-08}, journal = {Science}, volume = {363}, number = {6427}, pages = {615-619}, abstract = {Many chemical methods have been developed to favor a particular product in transformations of compounds that have two or more reactive sites. We explored a different approach to site selectivity using vibrational strong coupling (VSC) between a reactant and the vacuum field of a microfluidic optical cavity. Specifically, we studied the reactivity of a compound bearing two possible silyl bond cleavage sites—Si–C and Si–O, respectively—as a function of VSC of three distinct vibrational modes in the dark. The results show that VSC can indeed tilt the reactivity landscape to favor one product over the other. Thermodynamic parameters reveal the presence of a large activation barrier and substantial changes to the activation entropy, confirming the modified chemical landscape under strong coupling.}, keywords = {}, pubstate = {published}, tppubtype = {article} } Many chemical methods have been developed to favor a particular product in transformations of compounds that have two or more reactive sites. We explored a different approach to site selectivity using vibrational strong coupling (VSC) between a reactant and the vacuum field of a microfluidic optical cavity. Specifically, we studied the reactivity of a compound bearing two possible silyl bond cleavage sites—Si–C and Si–O, respectively—as a function of VSC of three distinct vibrational modes in the dark. The results show that VSC can indeed tilt the reactivity landscape to favor one product over the other. Thermodynamic parameters reveal the presence of a large activation barrier and substantial changes to the activation entropy, confirming the modified chemical landscape under strong coupling. |
Li, S L; Zhang, L; Zhong, X; Gobbi, M; Bertolazzi, S; Guo, W; Wu, B; Liu, Y; Xu, N; Niu, W; Hao, Y; Orgiu, E; Samori, P Nano-Subsidence-Assisted Precise Integration of Patterned Two-Dimensional Materials for High-Performance Photodetector Arrays Journal Article In: ACS Nano, 13 (2), pp. 2654–2662, 2019. @article{Li2019, title = {Nano-Subsidence-Assisted Precise Integration of Patterned Two-Dimensional Materials for High-Performance Photodetector Arrays}, author = {S.L. Li and L. Zhang and X. Zhong and M. Gobbi and S. Bertolazzi and W. Guo and B. Wu and Y. Liu and N. Xu and W. Niu and Y. Hao and E. Orgiu and P. Samori}, editor = {ASC Publications}, url = {https://pubs.acs.org/doi/10.1021/acsnano.9b00889}, doi = {10.1021/acsnano.9b00889}, year = {2019}, date = {2019-02-07}, journal = {ACS Nano}, volume = {13}, number = {2}, pages = {2654–2662}, abstract = {The spatially precise integration of arrays of micropatterned two-dimensional (2D) crystals onto three-dimensionally structured Si/SiO2 substrates represents an attractive, low-cost system-on-chip strategy toward the realization of extended functions in silicon microelectronics. However, the reliable integration of such atomically thin arrays on planar patterned surfaces has proven challenging due to their poor adhesion to underlying substrates, as ruled by weak van der Waals interactions. Here, we report on an integration method utilizing the flexibility of the atomically thin crystals and their physical subsidence in liquids, which enables the reliable fabrication of the micropatterned 2D materials/Si arrays. Our photodiode devices display peak sensitivity as high as 0.35 A/W and external quantum efficiency (EQE) of ∼90%. The nano-subsidence technique represents a viable path to on-chip integration of 2D crystals onto silicon for advanced microelectronics.}, keywords = {}, pubstate = {published}, tppubtype = {article} } The spatially precise integration of arrays of micropatterned two-dimensional (2D) crystals onto three-dimensionally structured Si/SiO2 substrates represents an attractive, low-cost system-on-chip strategy toward the realization of extended functions in silicon microelectronics. However, the reliable integration of such atomically thin arrays on planar patterned surfaces has proven challenging due to their poor adhesion to underlying substrates, as ruled by weak van der Waals interactions. Here, we report on an integration method utilizing the flexibility of the atomically thin crystals and their physical subsidence in liquids, which enables the reliable fabrication of the micropatterned 2D materials/Si arrays. Our photodiode devices display peak sensitivity as high as 0.35 A/W and external quantum efficiency (EQE) of ∼90%. The nano-subsidence technique represents a viable path to on-chip integration of 2D crystals onto silicon for advanced microelectronics. |
D. Pakulski A. Gorczyński, Czepa Liu Ortolani Morandi Patroniak Ciesielski Samorì W Z L V V A P Novel Keplerate type polyoxometalate-surfactant-graphene hybrids as advanced electrode materials for supercapacitors Journal Article In: Energy Storage Materials, 17 (February 2019), pp. p 186-193, 2019. @article{Pakulski2018, title = {Novel Keplerate type polyoxometalate-surfactant-graphene hybrids as advanced electrode materials for supercapacitors}, author = {D. Pakulski, A. Gorczyński, W. Czepa, Z. Liu, L. Ortolani, V. Morandi, V. Patroniak, A. Ciesielski, P. Samorì}, editor = {ELSEVIER}, url = {https://doi.org/10.1016/j.ensm.2018.11.012}, year = {2019}, date = {2019-02-01}, journal = {Energy Storage Materials}, volume = {17}, number = {February 2019}, pages = {p 186-193}, abstract = {The development of novel materials for enhanced electrochemical energy storage applications, in particular for the fabrication of supercapacitors (SCs) displaying increased properties, is a milestone of both fundamental and technological relevance. Among nanostructured materials, polyoxometalates (POMs) combined with various carbon-based nanostructures represent a very promising class of hybrid systems for energy storage, yet, guidelines for their rational design and synthesis leading to high-performance SCs is still lacking. Here, we have produced a novel hybrid architecture based on Keplerate type POM (Mo132) functionalized with dodecyltrimethylammonium bromide (DTAB), which upon mixing with electrochemically exfoliated graphene (EEG) nanosheets results in the formation of porous 3D superstructures. Mo132-DTAB-EEG combines the redox activity of POMs and high electrical conductivity of graphene, all synergically mediated by the surfactant-assisted porosity enhancement, to form new electrode materials for SCs. Cyclic voltammetry and galvanostatic charge/discharge electrochemical studies on Mo132-DTAB-EEG performed in aqueous H2SO4 electrolyte revealed that the unique combination of these three components yields highly efficient energy storage materials. In particular, our highly porous hybrids system exhibits high specific capacitance of 65 F g−1 (93 F cm−3, 93mFcm−2) combined with excellent stability (99% of specific capacitance retained) after 5000 charge/discharge cycles at different current densities, overall displaying significantly improved performance compared to pristine electrochemically exfoliated graphene material. Strong non-covalent interactions between Keplerate type polyoxometalate Mo132-DTAB and graphene surface offer higher stability compared to other hybrid POM/carbon-based systems, and unique electrical properties of the multicomponent structure, thereby paving the way towards the development of novel, and potentially multifunctional, POM-based architectures to be exploited as SC electrode materials.}, keywords = {}, pubstate = {published}, tppubtype = {article} } The development of novel materials for enhanced electrochemical energy storage applications, in particular for the fabrication of supercapacitors (SCs) displaying increased properties, is a milestone of both fundamental and technological relevance. Among nanostructured materials, polyoxometalates (POMs) combined with various carbon-based nanostructures represent a very promising class of hybrid systems for energy storage, yet, guidelines for their rational design and synthesis leading to high-performance SCs is still lacking. Here, we have produced a novel hybrid architecture based on Keplerate type POM (Mo132) functionalized with dodecyltrimethylammonium bromide (DTAB), which upon mixing with electrochemically exfoliated graphene (EEG) nanosheets results in the formation of porous 3D superstructures. Mo132-DTAB-EEG combines the redox activity of POMs and high electrical conductivity of graphene, all synergically mediated by the surfactant-assisted porosity enhancement, to form new electrode materials for SCs. Cyclic voltammetry and galvanostatic charge/discharge electrochemical studies on Mo132-DTAB-EEG performed in aqueous H2SO4 electrolyte revealed that the unique combination of these three components yields highly efficient energy storage materials. In particular, our highly porous hybrids system exhibits high specific capacitance of 65 F g−1 (93 F cm−3, 93mFcm−2) combined with excellent stability (99% of specific capacitance retained) after 5000 charge/discharge cycles at different current densities, overall displaying significantly improved performance compared to pristine electrochemically exfoliated graphene material. Strong non-covalent interactions between Keplerate type polyoxometalate Mo132-DTAB and graphene surface offer higher stability compared to other hybrid POM/carbon-based systems, and unique electrical properties of the multicomponent structure, thereby paving the way towards the development of novel, and potentially multifunctional, POM-based architectures to be exploited as SC electrode materials. |
Lichosyt, D; Zhang, Y; Hurej, K; Dydio, P Catalytic Transition Metal Systems for Functionalization of Unreactive Sites of Molecules Journal Article In: Nature Catalysis, 2 , pp. 114-122, 2019. @article{Lichosyt2019, title = {Catalytic Transition Metal Systems for Functionalization of Unreactive Sites of Molecules}, author = {Lichosyt, D. and Zhang, Y. and Hurej, K. and Dydio, P.}, editor = {Nature}, url = {https://www.nature.com/articles/s41929-018-0207-1}, year = {2019}, date = {2019-01-29}, journal = {Nature Catalysis}, volume = {2}, pages = {114-122}, abstract = {Catalytic reactions occur readily at the sites of starting materials that are both innately reactive and sterically accessible, or that are predisposed by a functional group amenable to direct a catalyst. However, selective reactions at unbiased sites of substrates remain challenging and typically require additional preactivation steps or the use of highly reactive reagents. Here we report dual-catalytic transition metal systems that merge a reversible activation cycle with a functionalization cycle, which together enable the functionalization of substrates at their inherently unreactive sites. By engaging the Ru- or Fe-catalysed equilibrium between an alcohol and an aldehyde, methods for Pd-catalysed β-arylation of aliphatic alcohols and Rh-catalysed γ-hydroarylation of allylic alcohols were developed. The mild conditions, functional group tolerance and broad scope (81 examples) demonstrate the synthetic applicability of the dual-catalytic systems. This work highlights the potential of the multicatalytic approach to address challenging transformations to circumvent multistep procedures and the use of highly reactive reagents in organic synthesis.}, keywords = {}, pubstate = {published}, tppubtype = {article} } Catalytic reactions occur readily at the sites of starting materials that are both innately reactive and sterically accessible, or that are predisposed by a functional group amenable to direct a catalyst. However, selective reactions at unbiased sites of substrates remain challenging and typically require additional preactivation steps or the use of highly reactive reagents. Here we report dual-catalytic transition metal systems that merge a reversible activation cycle with a functionalization cycle, which together enable the functionalization of substrates at their inherently unreactive sites. By engaging the Ru- or Fe-catalysed equilibrium between an alcohol and an aldehyde, methods for Pd-catalysed β-arylation of aliphatic alcohols and Rh-catalysed γ-hydroarylation of allylic alcohols were developed. The mild conditions, functional group tolerance and broad scope (81 examples) demonstrate the synthetic applicability of the dual-catalytic systems. This work highlights the potential of the multicatalytic approach to address challenging transformations to circumvent multistep procedures and the use of highly reactive reagents in organic synthesis. |
Ye Wang Amine Slassi, Marc-Antoine Stoeckel Simone Bertolazzi Jerôme Cornil David Beljonne Paolo Samorì Doping of Monolayer Transition-Metal Dichalcogenides via Physisorption of Aromatic Solvent Molecules Journal Article In: J. Phys. Chem. Lett, 10 (3), pp. 540-547, 2019. @article{Wang2019, title = {Doping of Monolayer Transition-Metal Dichalcogenides via Physisorption of Aromatic Solvent Molecules}, author = {Ye Wang, Amine Slassi, Marc-Antoine Stoeckel, Simone Bertolazzi, Jerôme Cornil, David Beljonne , Paolo Samorì}, editor = {Copyright © 2019 American Chemical Society }, url = {https://pubs.acs.org/doi/10.1021/acs.jpclett.8b03697}, doi = {10.1021/acs.jpclett.8b03697}, year = {2019}, date = {2019-01-16}, journal = {J. Phys. Chem. Lett}, volume = {10}, number = {3}, pages = {540-547}, abstract = {Two-dimensional (2D) transition-metal dichalcogenides (TMDs) recently emerged as novel materials displaying a wide variety of physicochemical properties that render them unique scaffolds for high-performance (opto)electronics. The controlled physisorption of molecules on the TMD surface is a viable approach for tuning their optical and electronic properties. Solvents, made of small aromatic molecules, are frequently employed for the cleaning of the 2D materials or as a “dispersant” for their chemical functionalization with larger (macro)molecules, without considering their potential key effect in locally modifying the characteristics of 2D materials. In this work, we demonstrate how the electronic and optical properties of a mechanically exfoliated monolayer of MoS2 and WSe2 are modified when physically interacting with small aromatic molecules of common solvents. Low-temperature photoluminescence (PL) spectra recorded at 78 K revealed that physisorbed benzene derivatives could modulate the charge carrier density in monolayer TMDs, hence affecting the switching between a neutral exciton and trion (charged exciton). By combining experimental evidence with density functional theory calculations, we confirm that charge-transfer doping on TMDs depends not only on the difference in chemical potential between molecules and 2D materials but also on the thermodynamic stability of physisorption. Our results provide unambiguous evidences of the great potential of optical and electrical tuning of monolayer MoS2 and WSe2 by physisorption of small aromatic solvent molecules, which is highly relevant for both fundamental studies and device application purposes.}, keywords = {}, pubstate = {published}, tppubtype = {article} } Two-dimensional (2D) transition-metal dichalcogenides (TMDs) recently emerged as novel materials displaying a wide variety of physicochemical properties that render them unique scaffolds for high-performance (opto)electronics. The controlled physisorption of molecules on the TMD surface is a viable approach for tuning their optical and electronic properties. Solvents, made of small aromatic molecules, are frequently employed for the cleaning of the 2D materials or as a “dispersant” for their chemical functionalization with larger (macro)molecules, without considering their potential key effect in locally modifying the characteristics of 2D materials. In this work, we demonstrate how the electronic and optical properties of a mechanically exfoliated monolayer of MoS2 and WSe2 are modified when physically interacting with small aromatic molecules of common solvents. Low-temperature photoluminescence (PL) spectra recorded at 78 K revealed that physisorbed benzene derivatives could modulate the charge carrier density in monolayer TMDs, hence affecting the switching between a neutral exciton and trion (charged exciton). By combining experimental evidence with density functional theory calculations, we confirm that charge-transfer doping on TMDs depends not only on the difference in chemical potential between molecules and 2D materials but also on the thermodynamic stability of physisorption. Our results provide unambiguous evidences of the great potential of optical and electrical tuning of monolayer MoS2 and WSe2 by physisorption of small aromatic solvent molecules, which is highly relevant for both fundamental studies and device application purposes. |
Witomska Samanta Liu Zhaoyang, Czepa Wlodzimierz Aliprandi Alessandro Pakulski Dawid Pawluc Piotr Ciesielski Artur Samori Paolo Graphene Oxide Hybrid with Sulfur–Nitrogen Polymer for High-Performance Pseudocapacitors Journal Article In: J. Am. Chem. Soc., 141 (1), pp. 482-487, 2019. @article{, title = {Graphene Oxide Hybrid with Sulfur–Nitrogen Polymer for High-Performance Pseudocapacitors}, author = {Witomska Samanta , Liu Zhaoyang , Czepa, Wlodzimierz , Aliprandi, Alessandro , Pakulski, Dawid , Pawluc, Piotr , Ciesielski, Artur , Samori Paolo ,}, editor = {Copyright © 2019 American Chemical Society}, url = {https://pubs.acs.org/doi/10.1021/jacs.8b11181}, doi = {10.1021/jacs.8b11181}, year = {2019}, date = {2019-01-09}, journal = {J. Am. Chem. Soc.}, volume = {141}, number = {1}, pages = {482-487}, abstract = {Toward the introduction of fast faradaic pseudocapacitive behavior and the increase of the specific capacitance of carbon-based electrodes, we covalently functionalized graphene oxide with a redox active thiourea-formaldehyde polymer, yielding a multifunctional hybrid system. The multiscale physical and chemical characterization of the novel 3-dimensional hybrid revealed high material porosity with high specific surface area (402 m2 g–1) and homogeneous element distribution. The presence of multiple functional groups comprising sulfur, nitrogen, and oxygen provide additional contribution of Faradaic redox reaction in supercapacity performance, leading to a high effective electrochemical pseudocapacitance. Significantly, our graphene-based 3-dimensional thiourea-formaldehyde hybrid exhibited specific capacitance as high as 400 F g–1, areal capacitance of 160 mF cm–2, and an energy density of 11.1 mWh cm–3 at scan rate of 1 mV s–1 with great capacitance retention (100%) after 5000 cycles at scan rate of 100 mV s–}, keywords = {}, pubstate = {published}, tppubtype = {article} } Toward the introduction of fast faradaic pseudocapacitive behavior and the increase of the specific capacitance of carbon-based electrodes, we covalently functionalized graphene oxide with a redox active thiourea-formaldehyde polymer, yielding a multifunctional hybrid system. The multiscale physical and chemical characterization of the novel 3-dimensional hybrid revealed high material porosity with high specific surface area (402 m2 g–1) and homogeneous element distribution. The presence of multiple functional groups comprising sulfur, nitrogen, and oxygen provide additional contribution of Faradaic redox reaction in supercapacity performance, leading to a high effective electrochemical pseudocapacitance. Significantly, our graphene-based 3-dimensional thiourea-formaldehyde hybrid exhibited specific capacitance as high as 400 F g–1, areal capacitance of 160 mF cm–2, and an energy density of 11.1 mWh cm–3 at scan rate of 1 mV s–1 with great capacitance retention (100%) after 5000 cycles at scan rate of 100 mV s– |
Chang-Bo Huang; Samanta, Witomska; Alessandro Aliprandi; Marc-Antoine Stoeckel; Massimo Bonini; Artur Ciesielski* & Paolo Samorì* Molecule–Graphene Hybrid Materials with Tunable Mechanoresponse: Highly Sensitive Pressure Sensors for Health Monitoring Journal Article In: Advanced Materials, 31(1), 1804600, 2019. @article{Huang2018, title = {Molecule–Graphene Hybrid Materials with Tunable Mechanoresponse: Highly Sensitive Pressure Sensors for Health Monitoring}, author = {Chang-Bo Huang; Samanta, Witomska; Alessandro Aliprandi; Marc-Antoine Stoeckel; Massimo Bonini; Artur Ciesielski* & Paolo Samorì*}, editor = {Wiley Online Library }, url = {https://onlinelibrary.wiley.com/doi/abs/10.1002/adma.201804600}, doi = {10.1002/adma.201804600}, year = {2019}, date = {2019-01-04}, journal = {Advanced Materials, 31(1), 1804600}, abstract = {The development of pressure sensors is crucial for the implementation of electronic skins and for health monitoring integrated into novel wearable devices. Tremendous effort is devoted toward improving their sensitivity, e.g., by employing microstructured electrodes or active materials through cumbersome processes. Here, a radically new type of piezoresistive pressure sensor based on a millefeuille‐like architecture of reduced graphene oxide (rGO) intercalated by covalently tethered molecular pillars holding on‐demand mechanical properties are fabricated. By applying a tiny pressure to the multilayer structure, the electron tunnelling ruling the charge transport between successive rGO sheets yields a colossal decrease in the material's electrical resistance. Significantly, the intrinsic rigidity of the molecular pillars employed enables the fine‐tuning of the sensor's sensitivity, reaching sensitivities as high as 0.82 kPa−1 in the low pressure region (0–0.6 kPa), with short response times (≈24 ms) and detection limit (7 Pa). The pressure sensors enable efficient heartbeat monitoring and can be easily transformed into a matrix capable of providing a 3D map of the pressure exerted by different objects. }, keywords = {}, pubstate = {published}, tppubtype = {article} } The development of pressure sensors is crucial for the implementation of electronic skins and for health monitoring integrated into novel wearable devices. Tremendous effort is devoted toward improving their sensitivity, e.g., by employing microstructured electrodes or active materials through cumbersome processes. Here, a radically new type of piezoresistive pressure sensor based on a millefeuille‐like architecture of reduced graphene oxide (rGO) intercalated by covalently tethered molecular pillars holding on‐demand mechanical properties are fabricated. By applying a tiny pressure to the multilayer structure, the electron tunnelling ruling the charge transport between successive rGO sheets yields a colossal decrease in the material's electrical resistance. Significantly, the intrinsic rigidity of the molecular pillars employed enables the fine‐tuning of the sensor's sensitivity, reaching sensitivities as high as 0.82 kPa−1 in the low pressure region (0–0.6 kPa), with short response times (≈24 ms) and detection limit (7 Pa). The pressure sensors enable efficient heartbeat monitoring and can be easily transformed into a matrix capable of providing a 3D map of the pressure exerted by different objects. |
Rizzi, Vito ; Prasetyanto, Eko Adi ; Chen, Pengkun ; Gubitosa, Jennifer ; Fini, Paola ; Agostiano, Angela ; De Cola, Luisa ; Cosma, Pinalysa "Amino grafted MCM-41 as highly efficient and reversible ecofriendly adsorbent material for the Direct Blue removal from wastewater" Journal Article In: JOURNAL OF MOLECULAR LIQUIDS, 273 , pp. 435-446 , 2019. @article{Rizzi2019, title = {"Amino grafted MCM-41 as highly efficient and reversible ecofriendly adsorbent material for the Direct Blue removal from wastewater"}, author = {Rizzi, Vito and Prasetyanto, Eko Adi and Chen, Pengkun and Gubitosa, Jennifer and Fini, Paola and Agostiano, Angela and De Cola, Luisa and Cosma, Pinalysa}, editor = {JOURNAL OF MOLECULAR LIQUIDS}, doi = {10.1016/j.molliq.2018.10.060}, year = {2019}, date = {2019-01-01}, journal = {JOURNAL OF MOLECULAR LIQUIDS}, volume = { 273}, pages = {435-446 }, abstract = {The very high adsorption efficiency of Direct Blue (DB), an anionic toxic azo dye, onto amino grafted mesoporous silica nanoparticles (MCM-41), was studied in this paper, for possible industrial applications. Interesting challenges and advances are proposed in this field, presenting an adsorbent able to efficiently and rapidly remove the anionic dye from water. The important added value of this work regards the system recycle, which allows both the DB and adsorbent material recover, with a global reduction of the environmental impact, in the viewpoint of the green economy. Indeed, this paper is the first example of very fast removal and recycle of great amounts of DB with adsorbent materials characterized by impressive adsorption/desorption capacities, at least of around 300 mg/g for each adsorption cycle, potentially increasable by performing consecutive cycles of DB adsorption/desorption. In detail, the MCM-41 amino functionalization (MCM-41-NH2) was obtained after (MCM-41-POST) and during (MCM-41-PRE) the synthesis of MCM-41, obtaining materials with different behavior towards the DB adsorption. The MCM-41-NH2 surface features and porous structure, before and after the dye adsorption, were carefully characterized. Considering the adsorption process, for investigating the nature of the DB/MCM-41-NH2 interaction, several parameters were studied: the contact time, the DB solutions pH values, adsorbent material and dye amount, with the additional analysis of how the adsorption process was influenced by the presence of electrolytes. The isotherms of adsorption were also considered. Although MCM-41-PRE exhibited a higher affinity towards DB molecules, the MCM-41-POST were able to rapidly desorb it, thus recycling both DB and the adsorbent material. (C) 2018 Elsevier B.V. All rights reserved.}, keywords = {}, pubstate = {published}, tppubtype = {article} } The very high adsorption efficiency of Direct Blue (DB), an anionic toxic azo dye, onto amino grafted mesoporous silica nanoparticles (MCM-41), was studied in this paper, for possible industrial applications. Interesting challenges and advances are proposed in this field, presenting an adsorbent able to efficiently and rapidly remove the anionic dye from water. The important added value of this work regards the system recycle, which allows both the DB and adsorbent material recover, with a global reduction of the environmental impact, in the viewpoint of the green economy. Indeed, this paper is the first example of very fast removal and recycle of great amounts of DB with adsorbent materials characterized by impressive adsorption/desorption capacities, at least of around 300 mg/g for each adsorption cycle, potentially increasable by performing consecutive cycles of DB adsorption/desorption. In detail, the MCM-41 amino functionalization (MCM-41-NH2) was obtained after (MCM-41-POST) and during (MCM-41-PRE) the synthesis of MCM-41, obtaining materials with different behavior towards the DB adsorption. The MCM-41-NH2 surface features and porous structure, before and after the dye adsorption, were carefully characterized. Considering the adsorption process, for investigating the nature of the DB/MCM-41-NH2 interaction, several parameters were studied: the contact time, the DB solutions pH values, adsorbent material and dye amount, with the additional analysis of how the adsorption process was influenced by the presence of electrolytes. The isotherms of adsorption were also considered. Although MCM-41-PRE exhibited a higher affinity towards DB molecules, the MCM-41-POST were able to rapidly desorb it, thus recycling both DB and the adsorbent material. (C) 2018 Elsevier B.V. All rights reserved. |
Travaglini, Leana ; Picchetti, Pierre ; Totovao, Ricardo ; Prasetyanto, Eko Adi ; De Cola, Luisa "Highly degradable imine-doped mesoporous silica particles" Journal Article In: MATERIALS CHEMISTRY FRONTIERS, 3 (1), pp. 111-119 , 2019. @article{Travaglini2019b, title = {"Highly degradable imine-doped mesoporous silica particles"}, author = {Travaglini, Leana and Picchetti, Pierre and Totovao, Ricardo and Prasetyanto, Eko Adi and De Cola, Luisa}, editor = {MATERIALS CHEMISTRY FRONTIERS}, doi = {10.1039/c8qm00438b}, year = {2019}, date = {2019-01-01}, journal = {MATERIALS CHEMISTRY FRONTIERS}, volume = {3}, number = {1}, pages = {111-119 }, abstract = {The degradation of mesoporous silica particles (MSPs) in water is a key aspect that boosts their use especially in bio-related fields. Although MSP degradation in aqueous media has been proven, big efforts have been devoted to tuning silica dissolution in order to obtain functional materials whose degradation can be finely controlled and enhanced, to tackle the issue of bioaccumulation. In particular, the introduction of stimuli-responsive functional groups into the silica framework was proven to be a successful strategy. Yet, the fast dissolution of silica particles in aqueous media in the absence of external stimuli has to be fully addressed. In this context, we reported herein the preparation and thorough characterisation of MSPs containing imine groups embedded within the silica framework (Im-MSPs). Particles with different contents of imine groups have been investigated in order to assess the effect on the physicochemical properties and the Im-MSPs showed fast degradation in both acidic and neutral aqueous solutions, at a rate that depended on the pH value. Of special interest is their fast degradation at acidic pH, where instead MSPs are normally more stable. The described results unveil the potential of these particles in applications that require a fast degradation in aqueous media.}, keywords = {}, pubstate = {published}, tppubtype = {article} } The degradation of mesoporous silica particles (MSPs) in water is a key aspect that boosts their use especially in bio-related fields. Although MSP degradation in aqueous media has been proven, big efforts have been devoted to tuning silica dissolution in order to obtain functional materials whose degradation can be finely controlled and enhanced, to tackle the issue of bioaccumulation. In particular, the introduction of stimuli-responsive functional groups into the silica framework was proven to be a successful strategy. Yet, the fast dissolution of silica particles in aqueous media in the absence of external stimuli has to be fully addressed. In this context, we reported herein the preparation and thorough characterisation of MSPs containing imine groups embedded within the silica framework (Im-MSPs). Particles with different contents of imine groups have been investigated in order to assess the effect on the physicochemical properties and the Im-MSPs showed fast degradation in both acidic and neutral aqueous solutions, at a rate that depended on the pH value. Of special interest is their fast degradation at acidic pH, where instead MSPs are normally more stable. The described results unveil the potential of these particles in applications that require a fast degradation in aqueous media. |
2018 |
Agostino Galanti; Valentin, Diez-Cabanes; Jasmin Santoro; Michal Valášek; Andrea Minoia; Marcel Mayor; Jérôme Cornil; Paolo Samorì; Electronic Decoupling in C3-Symmetrical Light-Responsive Tris(Azobenzene) Scaffolds: Self-Assembly and Multiphotochromism Journal Article In: J. Am. Chem. Soc., 2018, 140 (47), 16062–16070, 2018. @article{Galanti2018, title = {Electronic Decoupling in C3-Symmetrical Light-Responsive Tris(Azobenzene) Scaffolds: Self-Assembly and Multiphotochromism}, author = {Agostino, Galanti; Valentin, Diez-Cabanes; Jasmin, Santoro; Michal, Valášek; Andrea, Minoia; Marcel, Mayor; Jérôme, Cornil; Paolo, Samorì;}, editor = {ACS Publcation}, url = {https://pubs.acs.org/doi/10.1021/jacs.8b06324}, doi = {10.1021/jacs.8b06324}, year = {2018}, date = {2018-10-31}, journal = {J. Am. Chem. Soc., 2018, 140 (47), 16062–16070}, abstract = {We report the synthesis of a novel C3-symmetrical multiphotochromic molecule bearing three azobenzene units at positions 1, 3, 5 of the central phenyl ring. The unique geometrical design of such a rigid scaffold enables the electronic decoupling of the azobenzene moieties to guarantee their simultaneous isomerization. Photoswitching of all azobenzenes in solution was demonstrated by means of UV–vis absorption spectroscopy and high performance liquid chromatography (HPLC) analysis. Scanning tunneling microscopy investigations at the solid–liquid interface, corroborated by molecular modeling, made it possible to unravel the dynamic self-assembly of such systems into ordered supramolecular architectures, by visualizing and identifying the patterns resulting from three different isomers, thereby demonstrating that the multiphotochromism is retained when the molecules are confined in two dimensions.}, keywords = {}, pubstate = {published}, tppubtype = {article} } We report the synthesis of a novel C3-symmetrical multiphotochromic molecule bearing three azobenzene units at positions 1, 3, 5 of the central phenyl ring. The unique geometrical design of such a rigid scaffold enables the electronic decoupling of the azobenzene moieties to guarantee their simultaneous isomerization. Photoswitching of all azobenzenes in solution was demonstrated by means of UV–vis absorption spectroscopy and high performance liquid chromatography (HPLC) analysis. Scanning tunneling microscopy investigations at the solid–liquid interface, corroborated by molecular modeling, made it possible to unravel the dynamic self-assembly of such systems into ordered supramolecular architectures, by visualizing and identifying the patterns resulting from three different isomers, thereby demonstrating that the multiphotochromism is retained when the molecules are confined in two dimensions. |
Jorge Leira-Iglesias Alessandra Tassoni, Takuji Adachi Michael Stich Thomas Hermans M Oscillations, travelling fronts and patterns in a supramolecular system Journal Article In: 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. |
Aliprandi, Alessandro; Marco, Brian Di N; Cola, Luisa De "Transition metal complexes in ECL: diagnostics and biosensing" Journal Article In: Photochemistry, 46 , pp. 319–351, 2018, ISBN: 978-1-78801-336-9. @article{Aliprandi2018, title = {"Transition metal complexes in ECL: diagnostics and biosensing"}, author = {Alessandro Aliprandi and Brian N. Di Marco and Luisa De Cola}, editor = {Photochemistry}, url = {https://doi.org/10.1039/9781788013598-00319}, isbn = { 978-1-78801-336-9}, year = {2018}, date = {2018-09-03}, journal = {Photochemistry}, volume = {46}, pages = {319–351}, keywords = {}, pubstate = {published}, tppubtype = {article} } |
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 Journal Article In: 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) Journal Article In: 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 Journal Article In: CHEMICAL SOCIETY REVIEWS, 47 (17), pp. 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 Journal Article In: 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 Journal Article In: CHEMICAL SCIENCE, 9 (30), pp. 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 Journal Article In: COLLOIDS AND SURFACES B-BIOINTERFACES, 168 , pp. 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 Journal Article In: CHEMISTRY-A EUROPEAN JOURNAL, 24 (46), pp. 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 Journal Article In: CHEMISTRY-A EUROPEAN JOURNAL, 24 (46), pp. 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 Journal Article In: PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA, 115 (34), pp. 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 Journal Article In: ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 57 (35), pp. 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 Journal Article In: LANGMUIR, 34 (26), pp. 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 Journal Article In: JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 140 (26), pp. 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 Journal Article In: CHEMICAL SCIENCE, 9 (25), pp. 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 Journal Article In: CHEMICAL SOCIETY REVIEWS, 47 (13), pp. 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 Journal Article In: CHEMICAL SOCIETY REVIEWS, 47 (13), pp. 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 Journal Article In: 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 Journal Article In: 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 Journal Article In: 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 Journal Article In: CHEMISTRY-A EUROPEAN JOURNAL, 24 (41), pp. 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 Journal Article In: CHEMISTRY-A EUROPEAN JOURNAL, 24 (42), pp. 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 Journal Article In: ACS NANO, 12 (7), pp. 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 Journal Article In: CHEMPLUSCHEM, 83 (7, SI), pp. 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? Journal Article In: TAXON, 67 (3), pp. 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 Journal Article In: NATURE ECOLOGY & EVOLUTION, 2 (6), pp. 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 Journal Article In: CHEMISTRY OF MATERIALS, 30 (12), pp. 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 Journal Article In: 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 Journal Article In: JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 140 (22), pp. 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 Journal Article In: JOURNAL OF PHYSICAL CHEMISTRY C, 122 (25, SI), pp. 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 Journal Article In: JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 140 (24), pp. 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. |
Publications
2019 |
A Universal Approach toward Light-Responsive Two-Dimensional Electronics: Chemically Tailored Hybrid van der Waals Heterostructures Journal Article In: ACS Nano 2019, 13 (4), pp. 4814-4825, 2019. |
Blue-emitting bolaamphiphilic zwitterionic iridium(iii) complex Journal Article In: DALTON TRANSACTIONS, 48 (11), pp. 3664-3670 , 2019. |
Enhancement of the Electron−Phonon Scattering Induced by Intrinsic Surface Plasmon−Phonon Polaritons Journal Article In: ACS Photonics 2019, 6 (4), pp 1073–1081, 6 (4), pp. 1073-1081, 2019. |
Nonvolatile Memories Based on Graphene and Related 2D Materials Journal Article In: Advanced Materials, 31 (Issue 10), pp. 1806663, 2019. |
Thermally Limited Force Microscopy on Optically Trapped Single Metallic Nanoparticles Journal Article In: PHYSICAL REVIEW APPLIED , 11 ( 034023), 2019. |
Recreating ancient metabolic pathways before enzymes. Journal Article In: Bioorganic & Medicinal Chemistry, 2019. |
High‐Performance Graphene‐Based Cementitious Composites Journal Article In: ADVANCED SCIENCE, 6 (1801195), 2019. |
Optically switchable organic light-emitting transistors Journal Article In: Nature Nanotechnology, 14 , pp. 347-353, 2019. |
Synthesis of new Mn19 analogues and their structural, electrochemical and catalytic properties Journal Article In: Dalton Transactions, (15), 2019. |
Tilting a ground-state reactivity landscape by vibrational strong coupling Journal Article In: Science, 363 (6427), pp. 615-619, 2019. |
Nano-Subsidence-Assisted Precise Integration of Patterned Two-Dimensional Materials for High-Performance Photodetector Arrays Journal Article In: ACS Nano, 13 (2), pp. 2654–2662, 2019. |
Novel Keplerate type polyoxometalate-surfactant-graphene hybrids as advanced electrode materials for supercapacitors Journal Article In: Energy Storage Materials, 17 (February 2019), pp. p 186-193, 2019. |
Catalytic Transition Metal Systems for Functionalization of Unreactive Sites of Molecules Journal Article In: Nature Catalysis, 2 , pp. 114-122, 2019. |
Doping of Monolayer Transition-Metal Dichalcogenides via Physisorption of Aromatic Solvent Molecules Journal Article In: J. Phys. Chem. Lett, 10 (3), pp. 540-547, 2019. |
Graphene Oxide Hybrid with Sulfur–Nitrogen Polymer for High-Performance Pseudocapacitors Journal Article In: J. Am. Chem. Soc., 141 (1), pp. 482-487, 2019. |
Molecule–Graphene Hybrid Materials with Tunable Mechanoresponse: Highly Sensitive Pressure Sensors for Health Monitoring Journal Article In: Advanced Materials, 31(1), 1804600, 2019. |
"Amino grafted MCM-41 as highly efficient and reversible ecofriendly adsorbent material for the Direct Blue removal from wastewater" Journal Article In: JOURNAL OF MOLECULAR LIQUIDS, 273 , pp. 435-446 , 2019. |
"Highly degradable imine-doped mesoporous silica particles" Journal Article In: MATERIALS CHEMISTRY FRONTIERS, 3 (1), pp. 111-119 , 2019. |
2018 |
Electronic Decoupling in C3-Symmetrical Light-Responsive Tris(Azobenzene) Scaffolds: Self-Assembly and Multiphotochromism Journal Article In: J. Am. Chem. Soc., 2018, 140 (47), 16062–16070, 2018. |
Oscillations, travelling fronts and patterns in a supramolecular system Journal Article In: 2018, ISSN: 1748-3387, 1748-3395. |
"Transition metal complexes in ECL: diagnostics and biosensing" Journal Article In: Photochemistry, 46 , pp. 319–351, 2018, ISBN: 978-1-78801-336-9. |
Radioisotopic purity and imaging properties of cyclotron-produced Tc-99m using direct Mo-100(p,2n) reaction Journal Article In: 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) Journal Article In: NATURE COMMUNICATIONS, 9 , 2018, ISSN: 2041-1723. |
Molecular chemistry approaches for tuning the properties of two-dimensional transition metal dichalcogenides Journal Article In: CHEMICAL SOCIETY REVIEWS, 47 (17), pp. 6845–6888, 2018, ISSN: 0306-0012. |
Current crowding issues on nanoscale planar organic transistors for spintronic applications Journal Article In: NANOTECHNOLOGY, 29 (36), 2018, ISSN: 0957-4484. |
Ring-opening hydroarylation of monosubstituted cyclopropanes enabled by hexafluoroisopropanol Journal Article In: CHEMICAL SCIENCE, 9 (30), pp. 6411–6416, 2018, ISSN: 2041-6520. |
Concentration-dependent supramolecular patterns of C-3 and C-2 symmetric molecules at the solid/liquid interface Journal Article In: COLLOIDS AND SURFACES B-BIOINTERFACES, 168 , pp. 211–216, 2018, ISSN: 0927-7765. |
Luminescence of Amphiphilic Pt-II Complexes Controlled by Confinement Journal Article In: CHEMISTRY-A EUROPEAN JOURNAL, 24 (46), pp. 12054–12060, 2018, ISSN: 0947-6539. |
Phenoxyaluminum(salophen) Scaffolds: Synthesis, Electrochemical Properties, and Self-Assembly at Surfaces of Multifunctional Systems Journal Article In: CHEMISTRY-A EUROPEAN JOURNAL, 24 (46), pp. 11954–11960, 2018, ISSN: 0947-6539. |
Structure of the EmrE multidrug transporter and its use for inhibitor peptide design Journal Article In: PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA, 115 (34), pp. E7932–E7941, 2018, ISSN: 0027-8424. |
Surface-Assisted Self-Assembly of a Hydrogel by Proton Diffusion Journal Article In: ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 57 (35), pp. 11349–11353, 2018, ISSN: 1433-7851. |
Self-Assembled Two-Dimensional Supramolecular Networks Characterized by Scanning Tunneling Microscopy and Spectroscopy in Air and under Vacuum Journal Article In: LANGMUIR, 34 (26), pp. 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 Journal Article In: JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 140 (26), pp. 8218–8227, 2018, ISSN: 0002-7863. |
Total chemical synthesis and biophysical properties of a designed soluble 24 kDa amyloid analogue Journal Article In: CHEMICAL SCIENCE, 9 (25), pp. 5594–5599, 2018, ISSN: 2041-6520. |
Chemical sensing with 2D materials Journal Article In: CHEMICAL SOCIETY REVIEWS, 47 (13), pp. 4860–4908, 2018, ISSN: 0306-0012. |
Nanomaterials properties tuned by their environment: integrating supramolecular concepts into sensing devices Journal Article In: CHEMICAL SOCIETY REVIEWS, 47 (13), pp. 4675–4676, 2018, ISSN: 0306-0012. |
Collective molecular switching in hybrid superlattices for light-modulated two-dimensional electronics Journal Article In: NATURE COMMUNICATIONS, 9 , 2018, ISSN: 2041-1723. |
Valid molecular dynamics simulations of human hemoglobin require a surprisingly large box size Journal Article In: ELIFE, 7 , 2018, ISSN: 2050-084X. |
Self-Suspended Nanomesh Scaffold for Ultrafast Flexible Photodetectors Based on Organic Semiconducting Crystals Journal Article In: 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 Journal Article In: CHEMISTRY-A EUROPEAN JOURNAL, 24 (41), pp. 10422–10433, 2018, ISSN: 0947-6539. |
Multivalent Metallosupramolecular Assemblies as Effective DNA Binding Agents Journal Article In: CHEMISTRY-A EUROPEAN JOURNAL, 24 (42), pp. 10802–10811, 2018, ISSN: 0947-6539. |
Proton-Gradient-Driven Oriented Motion of Nanodiamonds Grafted to Graphene by Dynamic Covalent Bonds Journal Article In: ACS NANO, 12 (7), pp. 7141–7147, 2018, ISSN: 1936-0851. |
Protonation of a Spherical Macrotricyclic Tetramine: Water Inclusion, Allosteric Effect, and Cooperativity Journal Article In: CHEMPLUSCHEM, 83 (7, SI), pp. 605–611, 2018, ISSN: 2192-6506. |
Are there too many fern genera? Journal Article In: TAXON, 67 (3), pp. 473–480, 2018, ISSN: 0040-0262. |
Native iron reduces CO2 to intermediates and end-products of the acetyl-CoA pathway Journal Article In: NATURE ECOLOGY & EVOLUTION, 2 (6), pp. 1019+, 2018, ISSN: 2397-334X. |
Morphology Control of Mesoporous Silica Particles Using Bile Acids as Cosurfactants Journal Article In: CHEMISTRY OF MATERIALS, 30 (12), pp. 4168–4175, 2018, ISSN: 0897-4756. |
Polyamidoamine-Based Hydrogel for Removal of Blue and Red Dyes from Wastewater Journal Article In: ADVANCED SUSTAINABLE SYSTEMS, 2 (6), 2018, ISSN: 2366-7486. |
Direct Photolithography on Molecular Crystals for High Performance Organic Optoelectronic Devices Journal Article In: JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 140 (22), pp. 6984–6990, 2018, ISSN: 0002-7863. |
Mueller Polarimetry of Chiral Supramolecular Assembly Journal Article In: JOURNAL OF PHYSICAL CHEMISTRY C, 122 (25, SI), pp. 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 Journal Article In: JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 140 (24), pp. 7647–7657, 2018, ISSN: 0002-7863. |