Search

Your search keyword '"Yann R. Leroux"' showing total 70 results
Start Over Author "Yann R. Leroux"
70 results on '"Yann R. Leroux"'

1. A comprehensive study of tetracyanobutadiene push-pull chromophores derived from γ-pyranylidene

Author

Clotilde Philippe, Johann Melan, Alberto Barsella, Thomas Vives, Yann R. Leroux, Françoise Robin-Le Guen, Loïc Lemiègre, Denis Jacquemin, Sébastien Gauthier, and Yann Trolez

Subjects
γ-Pyranylidene, TCBD, Cycloaddition-retroelectrocyclization, Nonlinear optics, Organic chemistry, QD241-441
Abstract

A new class of push-pull 1,1,4,4-tetracyanobutadienes (TCBDs) chromophores bearing a γ-pyranylidene as a pro-aromatic donor group have been developed, characterized and studied for their electrochemical, photophysical and second-order nonlinear optical (NLO) properties. [2 ​+ ​2] Cycloaddition-retroelectrocyclizations (CA-RE) with tetracyanoethylene (TCNE) allowed the formation of new TCBDs by taking advantage of the electron-donating ability of γ-pyranylidene functional groups. The limits of the reaction between TCNE and the corresponding alkynes have been investigated, both in terms of reactivity and solubility. Electrochemical studies of pyranylidene-TCBD 1a-1j revealed two reversible reduction waves typical of TCBDs, and two oxidation waves originating from the γ-pyranylidene moiety. More complex electrochemical signals have been recorded when studying chromophores bearing multiple TCBD and/or γ-pyranylidene units. All pyranylidene-TCBDs showed panchromatic absorption properties, extending to the NIR in some cases. Changes made around the electron-withdrawing TCBD units significantly affected the ICT performance of the push-pull chromophores. Computational studies have been performed on this series of compounds to rationalize the origin of their optical properties. TD-DFT calculations confirmed that the synthesized pyranylidene-TCBDs are potential NLOphores. The second-order NLO properties of all chromophores were determined by the Electric Field-Induced Second Harmonic generation (EFISH) technique, and all systems exhibited valuable NLO properties with large μβEFISH values for purely organic compounds, up to 5700 10−48 ​esu.

Published
2023
Full Text
View/download PDF

2. Chemical Tuning of Metal Nanocatalysts Interface for ORR Electrocatalysis

Author

Quentin Lenne, Alice Mattiuzzi, Ivan Jabin, Jonathan Hamon, Yann R. Leroux, and Corinne Lagrost

Subjects
diazonium, electrocatalysis, nanoparticles, ORR, surface functionalization, Physics, QC1-999, Technology
Abstract

Abstract A series of surface‐functionalized gold nanocatalysts are synthesized. Through diazonium chemistry, calix[4]arene molecules are grafted at the gold surface. Sharing the same anchoring function and a common backbone, the calix[4]arene ligands possess distinct terminal chemical functions where the length, hydrophobic nature, and oxygen affinity are varied. Thanks to the versatility of the calix[4]arene platform, this paper only focuses on the molecular tuning of the solid/liquid interface through the change of the tail groups while electronic effects that are regulated by the anchoring function will be similar for all catalysts. Electrocatalytic tests demonstrate the influence of the tails group on the oxygen reduction reaction performances, including efficiency, selectivity, and durability. Beyond a pure geometric steric effect, it is shown that chemical properties of the ligands can effectively tune the interactions between the metallic catalyst and the electrolyte and reactants.

Published
2023
Full Text
View/download PDF

3. Strategies for the Formation of Monolayers From Diazonium Salts: Unconventional Grafting Media, Unconventional Building Blocks

Author

Alice Mattiuzzi, Quentin Lenne, Janine Carvalho Padilha, Ludovic Troian-Gautier, Yann R. Leroux, Ivan Jabin, and Corinne Lagrost

Subjects
diazonium, surface functionalization, monolayers, calixarene, ionic liquids, Chemistry, QD1-999
Abstract

Pioneered by J. Pinson and coll. in 1990s, the reductive grafting of aryldiazonium salts has become a powerful method for surface functionalization. Highly robust interfaces result from this surface attachment, resistant to heat, chemical degradation and ultrasonication. Importantly, this approach can be applied to many materials, ranging from conducting, semi-conducting, oxides to insulating substrates. In addition, either massive, flat surfaces or nanomaterials can be functionalized. The method is easy to process and fast. The grafting process involves the formation of highly reactive aryl radicals able to attack the substrate. However, the generated radicals can also react with already-grafted aryl species, leading to the formation of loosely-packed polyaryl multilayer films, typically of 10–15 nm thick. It is thus highly challenging to control the vertical extension of the deposited layer and to form well-ordered monolayers from aryldiazonium salts. In this mini review, we briefly describe the different strategies that have been developed to prepare well-ordered monolayers. We especially focus on two strategies successfully used in our laboratories, namely the use of unconventional solvents, i.e., room temperature ionic liquids (RTILs), as grafting media and the use of calixarene macrocycles by taking benefit of their pre-organized structure. These strategies give large possibilities for the structuring of interfaces with the widest choice of materials and highlight the potential of aryldiazonium grafting as a competitive alternative to self-assembled monolayers (SAMs) of alkyl thiols.

Published
2020
Full Text
View/download PDF

4. Chemical Surface Grafting of Pt Nanocatalysts for Reconciling Methanol Tolerance with Methanol Oxidation Activity

Author

Quentin Lenne, Alice Mattiuzzi, Ivan Jabin, Ludovic Troian‐Gautier, Jonathan Hamon, Yann R. Leroux, Corinne Lagrost, Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), X4C, Université libre de Bruxelles (ULB), Université Catholique de Louvain = Catholic University of Louvain (UCL), Institut des Matériaux Jean Rouxel (IMN), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Nantes université - UFR des Sciences et des Techniques (Nantes univ - UFR ST), Nantes Université - pôle Sciences et technologie, Nantes Université (Nantes Univ)-Nantes Université (Nantes Univ)-Nantes Université - pôle Sciences et technologie, Nantes Université (Nantes Univ)-Nantes Université (Nantes Univ)-Nantes Université - Ecole Polytechnique de l'Université de Nantes (Nantes Univ - EPUN), Nantes Université (Nantes Univ)-Nantes Université (Nantes Univ), This work is supported by Agence Nationale de la Recherche (ANR –CE50-2021-MARCEL project).Q.L. thanks the French Ministry of Research for financial support. The authors are grateful to L.Rault for the assistance in TEM experiments performed on THEMIS platform (CPER-FEDER 2007–2014) and to F. Gouttefangeas for SEM experiments performed on CMEBA platform (THEMIS/CMEBA, ScanMAT, UMS 2R011 University of Rennes 1-CNRS, Rennes, France). B. Lefeuvre (ISCR-OMC, UMR 6226, University of Rennes 1) is thanked for his help with ICP-MS measurements. L. T.-G. is a Chercheur Qualifiéof the Fonds de la Recherche Scientifique –FNRS., and ANR-21-CE50-0034,MARCEL,Booster la sélectivité et l'efficacité des processus ORR et CO2RR en couplant nanomatériaux métalliques et chimie de surface hôte-invité(2021)

Subjects
General Energy, Methanol oxidation reaction, General Chemical Engineering, [CHIM]Chemical Sciences, Environmental Chemistry, General Materials Science, Electrocatalysis, diazonium grafting, Oxygen reduction reaction, surface functionalization
Abstract

International audience; A conceptual challenge toward more versatile direct methanol fuel cell (DMFC) is the design of a single material electrocatalyst with high activity and durability for both oxygen reduction reaction (ORR) and methanol oxidation reaction (MOR). This requires to conciliate methanol tolerance not to hinder ORR at the cathode with a good MOR activity at the anode. This is especially incompatible with Pt materials. We tackled this challenge by deriving a supramolecular concept where surface-grafted molecular ligands regulate the Pt-catalyst reactivity. ORR and MOR activities of newly reported Pt-calix[4]arenes nanocatalysts (PtCF3NPs/C) are compared to commercial benchmark PtNPs/C. PtCF3NPs/C exhibit a remarkable methanol tolerance without losing the MOR reactivity along with outstanding durability and chemical stability. Beyond designing single-catalyst material, operable in DMFC cathodic and anodic compartments, the results highlight a promising strategy for tuning interfacial properties.

Published
2023

5. Highly stable silver nanohybrid electrocatalysts for the oxygen reduction reaction

Author

Quentin Lenne, Maurice Retout, Bryan Gosselin, Gilles Bruylants, Ivan Jabin, Jonathan Hamon, Corinne Lagrost, Yann R. Leroux, Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université libre de Bruxelles (ULB), Institut des Matériaux Jean Rouxel (IMN), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Nantes université - UFR des Sciences et des Techniques (Nantes univ - UFR ST), Nantes Université - pôle Sciences et technologie, Nantes Université (Nantes Univ)-Nantes Université (Nantes Univ)-Nantes Université - pôle Sciences et technologie, Nantes Université (Nantes Univ)-Nantes Université (Nantes Univ)-Nantes Université - Ecole Polytechnique de l'Université de Nantes (Nantes Univ - EPUN), and Nantes Université (Nantes Univ)-Nantes Université (Nantes Univ)

Subjects
Materials Chemistry, Metals and Alloys, Ceramics and Composites, [CHIM]Chemical Sciences, General Chemistry, Catalysis, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials
Abstract

International audience; Silver nanoparticles (AgNPs) were deliberately functionalized via aryl diazonium chemistry with a monolayer of calix[4]arenes. The resulting nanohybrids show high efficiency and high selectivity toward the ORR in alkaline media along with an exceptional durability and a high methanol tolerance.

Published
2022

6. Discovery of a Peptide Nucleic Acid (PNA) aptamer for cardiac troponin I: Substituting DNA with neutral PNA maintains picomolar affinity and improves performances for electronic sensing with graphene field-effect transistors (gFET)

Author

Teresa Rodrigues, Federica Curti, Yann R. Leroux, Alexandre Barras, Quentin Pagneux, Henri Happy, Christoph Kleber, Rabah Boukherroub, Roger Hasler, Stefano Volpi, Maria Careri, Roberto Corradini, Sabine Szunerits, Wolfgang Knoll, Institut d’Électronique, de Microélectronique et de Nanotechnologie - UMR 8520 (IEMN), Centrale Lille-Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Université Polytechnique Hauts-de-France (UPHF)-JUNIA (JUNIA), Université catholique de Lille (UCL)-Université catholique de Lille (UCL), Austrian Institute of Technology [Vienna] (AIT), Università degli studi di Parma = University of Parma (UNIPR), Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), NanoBioInterfaces - IEMN (NBI - IEMN), Université catholique de Lille (UCL)-Université catholique de Lille (UCL)-Centrale Lille-Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Université Polytechnique Hauts-de-France (UPHF)-JUNIA (JUNIA), Carbon - IEMN (CARBON - IEMN), Dipartimento di Scienze Chimiche,della Vita e della Sostenibilità Ambientale, Danube Private University [Krems, Autriche] (DPU), and Financial supports from the Centre National de la Recherche Scientifique (CNRS), the University of Lille are acknowledged. This work has benefited from the equipment and framework of the COMP-HUB Initiative, funded by the ‘Departments of Excellence’ program of the Italian Ministry for University and Research (MUR, 2018–2022) for the Department of Chemistry, Life Sciences and Environmental Sustainability of the University of Parma. The TeachInParma Program is also acknowledged for sponsoring supervision and collaborative work of WK at the University of Parma premises

Subjects
Graphene-based field effect transistor, [SDV.BIO]Life Sciences [q-bio]/Biotechnology, Aptamer, Peptide nucleic acid, Cardiac troponin I, Biomedical Engineering, Pharmaceutical Science, General Materials Science, Bioengineering, [SPI.NANO]Engineering Sciences [physics]/Micro and nanotechnologies/Microelectronics, Biosensor, Biotechnology
Abstract

International audience; DNA-based aptamers are widely employed as bioreceptors, owing to their tuneable affinity and specificity towards their targets. The use of peptide nucleic acids (PNAs) has instead proven challenging for this purpose, due to the absence of selection methods for the independent discovery of suitable receptors and due to the difficult mimicry of established DNA-based ones. Despite that PNAs exceed homologous DNA or RNA in terms of complementary base pairing, they can fail to reproduce alternative modes of binding because of their different structural features. The remarkable stability and charge distribution of PNAs could be beneficial to produce sensing bioreceptors, especially in the development of electronic devices such as field-effect transistor-based (FET) biosensors. We hereby report for the first time a high-affinity PNA aptamer for cardiac Troponin I (cTnI), a biomarker of acute myocardial infarction, able to interact with this specific protein in the picomolar range. The PNA aptamer was immobilized onto a graphene-based FET (gFET) transducer, and its ability in the direct detection of cTnI was compared with that of a DNA-based one of the same sequence. Similar dissociation constants were recorded for both receptors in 0.01 × PBS, as well as comparable detection limits of 6.0 ± 1.0 pg mL-1 (PNA aptamer) and 3.3 ± 0.7 pg mL-1 (DNA aptamer). Apart from the non-trivial demonstration that a PNA can behave as an aptamer, the tested receptor proved to be more consistent upon working in more complex biological matrices.

Published
2023

7. Electrochemical and electronic detection of biomarkers in serum: a systematic comparison using aptamer-functionalized surfaces

Author

Henri Happy, Wolfgang Knoll, Patrik Aspermair, Vladyslav Mishyn, Yann R. Leroux, Teresa Rodrigues, Rabah Boukherroub, Laura Butruille, Sabine Szunerits, David Montaigne, Eloise Woitrain, Institut d’Électronique, de Microélectronique et de Nanotechnologie - UMR 8520 (IEMN), Centrale Lille-Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Université Polytechnique Hauts-de-France (UPHF)-JUNIA (JUNIA), Université catholique de Lille (UCL)-Université catholique de Lille (UCL), Austrian Institute of Technology [Vienna] (AIT), Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Récepteurs Nucléaires, Maladies Métaboliques et Cardiovasculaires (RNMCD - U1011), Institut Pasteur de Lille, Réseau International des Instituts Pasteur (RIIP)-Réseau International des Instituts Pasteur (RIIP)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Université de Lille-Centre Hospitalier Régional Universitaire [Lille] (CHRU Lille), Carbon - IEMN (CARBON - IEMN), Université catholique de Lille (UCL)-Université catholique de Lille (UCL)-Centrale Lille-Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Université Polytechnique Hauts-de-France (UPHF)-JUNIA (JUNIA), Danube Private University [Krems, Autriche] (DPU), NanoBioInterfaces - IEMN (NBI - IEMN), Financial support from the Centre National de la Recherche Scientifique (CNRS), the University of Lille, the Hauts-de-France region and the CPER 'Photonics for Society' is gratefully acknowledged. Financial support came further from the FFG, Austria, within the Comet program., IEMN, Collection, Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), and Récepteurs Nucléaires, Maladies Métaboliques et Cardiovasculaires - U1011 (RNMCD)

Subjects
Analyte, Aptamer, [SPI] Engineering Sciences [physics], 02 engineering and technology, Biosensing Techniques, 010402 general chemistry, 01 natural sciences, Biochemistry, Graphene-based field-effect transistor, Analytical Chemistry, [SPI]Engineering Sciences [physics], Limit of Detection, Troponin I, Humans, Detection limit, Chromatography, Chemistry, Differential pulse voltammetry, Electrochemical Techniques, Aptamers, Nucleotide, 021001 nanoscience & nanotechnology, 0104 chemical sciences, Electrochemical gas sensor, Dissociation constant, Ionic strength, cTnI, 0210 nano-technology, Biomarkers
Abstract

International audience; Sensitive and selective detection of biomarkers in serum in a short time has a significant impact on health. The enormous clinical importance of developing reliable methods and devices for testing serum levels of cardiac troponin I (cTnI), which are directly correlated to acute myocardial infarction (AMI), has spurred an unmatched race among researchers for the development of highly sensitive and cost-effective sensing formats to be able to differentiate patients with early onset of cardiac injury from healthy individuals with a mean cTnI level of 26 pg mL-1. Electronic- and electrochemical-based detection schemes allow for fast and quantitative detection not otherwise possible at the point of care. Such approaches rely largely on voltammetric and field-effect-based readouts. Here, we systematically investigate electric and electrochemical point-of-care sensors for the detection of cTnI in serum samples by using the same surface receptors, cTnI aptamer-functionalized CVD graphene-coated interdigated gold electrodes. The analytical performances of both sensors are comparable with a limit of detection (LoD) of 5.7 ± 0.6 pg mL-1(electrochemical) and 3.3 ± 1.2 pg mL-1 (electric). However, both sensors exhibit different equilibrium dissociation constant (KD) values between the aptamer-linked surface receptor and the cTnI analyte, being 160 pg mL-1 for the electrochemical and about three times lower for the electrical approach with KD = 51.4 pg mL-1. This difference is believed to be related to the use of a redox mediator in the electrochemical sensor for readout. The ability of the redox mediator to diffuse from the solution to the surface via the cTnI/aptamer interface is hindered, correlating to higher KD values. In contrast, the electric readout has the advantage of being label-free with a sensing limitation due to ionic strength effects, which can be limited using poly(ethylene) glycol surface ligands.

Published
2022

8. Highly performing graphene-based field effect transistor for the differentiation between mild-moderate-severe myocardial injury

Author

Teresa Rodrigues, Vladyslav Mishyn, Yann R. Leroux, Laura Butruille, Eloise Woitrain, Alexandre Barras, Patrik Aspermair, Henri Happy, Christoph Kleber, Rabah Boukherroub, David Montaigne, Wolfgang Knoll, Sabine Szunerits, Institut d’Électronique, de Microélectronique et de Nanotechnologie - UMR 8520 (IEMN), Centrale Lille-Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Université Polytechnique Hauts-de-France (UPHF)-JUNIA (JUNIA), Université catholique de Lille (UCL)-Université catholique de Lille (UCL), Austrian Institute of Technology [Vienna] (AIT), Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut Européen de Génomique du Diabète - European Genomic Institute for Diabetes - FR 3508 (EGID), Institut Pasteur de Lille, Réseau International des Instituts Pasteur (RIIP)-Réseau International des Instituts Pasteur (RIIP)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Université de Lille-Centre National de la Recherche Scientifique (CNRS), NanoBioInterfaces - IEMN (NBI - IEMN), Université catholique de Lille (UCL)-Université catholique de Lille (UCL)-Centrale Lille-Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Université Polytechnique Hauts-de-France (UPHF)-JUNIA (JUNIA), Carbon - IEMN (CARBON - IEMN), Financial support from the Centre National de la Recherche Scientifique (CNRS), the University of Lille, CPER 'Photonics for Society' and I-Site is acknowledged. DM, LB and EW are supported by grants from Agence Nationale pour la Recherche (ANR-10-LABX-0046, ANR TOMIS-Leukocyte: ANR-CE14–0003-01 and ANR CALMOS: ANR-18-CE17–0003-02), the Leducq Foundation LEAN Network 16CVD01 and the National Center for Precision Diabetic Medicine–PreciDIAB (ANR-18-IBHU-0001, 20001891/NP0025517, 2019_ESR_11)., ANR-10-LABX-0046,EGID,EGID Diabetes Pole(2010), ANR-19-CE14-0003,TOMIS-leukocyte,Impact du moment de la journée sur la réaction inflammatoire péri-opératoire et le remodelage cardiaque inverse après remplacement valvulaire aortique(2019), ANR-18-CE17-0003,CALMOS,Homéostasie calcique mitochondriale dans le contrôle des troubles du rythme associés à la cardiomyopathie métabolique(2018), and ANR-18-IBHU-0001,PreciDIAB,PreciDIAB Institute, the holistic approach of personal diabets care(2018)

Subjects
Graphene-based field effect transistor, cardiac troponin I, Biomedical Engineering, Pharmaceutical Science, aptamer, General Materials Science, Bioengineering, macromolecular substances, [PHYS.PHYS.PHYS-CHEM-PH]Physics [physics]/Physics [physics]/Chemical Physics [physics.chem-ph], musculoskeletal system, biosensor, Biotechnology
Abstract

International audience; Cardiovascular diseases result in millions of deaths around the globe, many of which could have been avoided if identified at an early stage. Preventive cardiovascular disease diagnostics plays a vital role reducing the critical fatality rate by allowing to take timely necessary precautions. Here, we demonstrate the exceptional properties of aptamer modified graphenebased FET (GFET) for cardiac troponin I (cTnI) specific sensing in different bodily fluids. Concentration-dependent measurements made with cardiac troponin I (cTnI) on an aptamer/polyethylene glycol (PEG) modified GFET exhibited real-time detection of cTnI from 1-400 pg mL-1 in 0.01× phosphate-buffered saline (PBS) solution. The sensor performance is within the clinical important window of 10 pg mL-1 to 500 pg mL-1 , allowing the differentiation between healthy, and people with low and high risk for myocardial infraction (AMI). Even more important is the very reproducible shift and neglectable leakage current of the individual IDSVGS-curves upon contact with cTnI solutions. To further evaluate the applicability of the developed point of care device for troponin I sensing in serum, samples of 15 patients with different troponin levels were analysed for their troponin I levels. The 15 patients were grouped

Published
2022

9. Discovery of a Peptide Nucleic Acid (Pna) Aptamer for Cardiac Troponin I: Substituting DNA with Neutral Pna Maintains Picomolar Affinity and Improves Performances in Graphene Field-Effect Transistors (Gfet)

Author

Teresa Rodrigues, Federica Curti, Yann R. Leroux, Alexandre Barras, Quentin Pagneux, Henri Happy, Christoph Kleber, Rabah Boukherroub, Stefan Volpi, Maria Cereri, Roberto Corradini, Sabine Szunerits, and Wolfgang Knoll

Subjects
History, Polymers and Plastics, Business and International Management, Industrial and Manufacturing Engineering
Published
2022

10. Controlled covalent functionalization of a graphene-channel of a field effect transistor as an ideal platform for (bio)sensing applications

Author

Sabine Szunerits, Johannes Bintinger, Rabah Boukherroub, Teresa Rodrigues, Vladyslav Mishyn, Henri Happy, Wolfgang Knoll, Christoph Kleber, Yann R. Leroux, Patrik Aspermair, Institut d’Électronique, de Microélectronique et de Nanotechnologie - UMR 8520 (IEMN), Centrale Lille-Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Université Polytechnique Hauts-de-France (UPHF)-JUNIA (JUNIA), Austrian Institute of Technology [Vienna] (AIT), Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Carbon - IEMN (CARBON-IEMN), Centrale Lille-Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Université Polytechnique Hauts-de-France (UPHF)-JUNIA (JUNIA)-Centrale Lille-Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Université Polytechnique Hauts-de-France (UPHF)-JUNIA (JUNIA), Danube University Krems, NanoBioInterfaces - IEMN (NBI - IEMN), Financial support from the Centre National de la Recherche Scientifique (CNRS) and the University of Lille is acknowledged., Université catholique de Lille (UCL)-Université catholique de Lille (UCL), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Carbon - IEMN (CARBON - IEMN), Université catholique de Lille (UCL)-Université catholique de Lille (UCL)-Centrale Lille-Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Université Polytechnique Hauts-de-France (UPHF)-JUNIA (JUNIA), Renatech Network, and PCMP PCP

Subjects
Materials science, Fabrication, Nanotechnology, 02 engineering and technology, 010402 general chemistry, Electrochemistry, 01 natural sciences, law.invention, chemistry.chemical_compound, [SPI]Engineering Sciences [physics], law, Monolayer, Molecule, [CHIM]Chemical Sciences, General Materials Science, Electrodes, Cycloaddition Reaction, Graphene, Aryl, 021001 nanoscience & nanotechnology, 0104 chemical sciences, chemistry, Electrode, Click Chemistry, Graphite, Field-effect transistor, Gold, 0210 nano-technology
Abstract

International audience; The controlled covalent functionalization of the graphene channel of a field effect transistor, based on interdigitated gold electrodes (source and drain), via electrochemical grafting, using specifically designed aryl diazonium species is demonstrated to allow the simple fabrication of a general platform for (bio)sensing applications. The electrochemical grafting of a protected ethynylphenyl diazonium salt leads to the deposition of only a monolayer on the graphene channel. This controlled covalent functionalization of the graphene channel results in a charge mobility of the GFET of 1739 ± 376 cm2 V−1 s−1 and 1698 ± 536 cm2 V−1 s−1 for the holes and electrons, respectively, allowing their utilization as (bio)sensors. After deprotection, a dense and compact ethynylphenyl monolayer is obtained and allows the immobilization of a wide range of (bio)molecules by a “click” chemistry coupling reaction (Huisgen 1,3-dipolar cycloaddition). This finding opens promising options for graphene-based (bio)sensing applications.

Published
2021

11. On the detection of cTnI - a comparison of surface-plasmon optical-electrochemical-, and electronic sensing concepts

Author

V Mishyn, Wolfgang Knoll, Yann R. Leroux, Henri Happy, Sabine Szunerits, Rabah Boukherroub, Anil Bozdogan, Amal Kasry, Patrik Aspermair, Christoph Kleber, Jakub Dostalek, Johannes Bintinger, T. Rodrigues, Institut d’Électronique, de Microélectronique et de Nanotechnologie - UMR 8520 (IEMN), Centrale Lille-Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Université Polytechnique Hauts-de-France (UPHF)-JUNIA (JUNIA), Université catholique de Lille (UCL)-Université catholique de Lille (UCL), Austrian Institute of Technology [Vienna] (AIT), NanoBioInterfaces - IEMN (NBI - IEMN), Université catholique de Lille (UCL)-Université catholique de Lille (UCL)-Centrale Lille-Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Université Polytechnique Hauts-de-France (UPHF)-JUNIA (JUNIA), and Centrale Lille-Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Université Polytechnique Hauts-de-France (UPHF)-JUNIA (JUNIA)-Centrale Lille-Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Université Polytechnique Hauts-de-France (UPHF)-JUNIA (JUNIA)

Subjects
Materials science, business.industry, Surface plasmon, Graphene field effect transistors, Electrochemistry, [SPI]Engineering Sciences [physics], Cardiac Troponin I, Graphene Field-Effect Transistor, Differential Pulse Voltammetry, Optoelectronics, Differential pulse voltammetry, business, Biosensor, ComputingMilieux_MISCELLANEOUS, Surface-Plasmon Fluorescence Spectroscopy
Abstract

International audience

Published
2021

12. Electrochemical Grafting of Aryl Diazonium Salts in Deep Eutectic Solvents

Author

Ludovic Paquin, Vivien Andrieux, Quentin Lenne, Corinne Lagrost, Pauline Nicolas, Jean-François Bergamini, Yann R. Leroux, Gael Levanen, Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), ANR-18-CE42-0011, Conseil National de la Recherche Scientifique, Université de Rennes 1, Ministère de l'Enseignement Supérieur et de la Recherche, Agence Nationale de la Recherche, ANR-18-CE42-0011,EASCVsens,Voltammétrie par échantillonnage de courant sur réseau d'électrodes pour la détection des éléments-traces métalliques dans les eaux(2018), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
General Chemical Engineering, Inorganic chemistry, 02 engineering and technology, 010402 general chemistry, Electrochemistry, 01 natural sciences, Redox, Metal, chemistry.chemical_compound, Electro-grafting, Eutectic system, Aryl, 021001 nanoscience & nanotechnology, 0104 chemical sciences, Deep eutectic solvent, Deep eutectic solvent (DES), chemistry, visual_art, Surface functionalization, Electrode, visual_art.visual_art_medium, Surface modification, 0210 nano-technology, [CHIM.OTHE]Chemical Sciences/Other, Aryl diazonium
Abstract

International audience; Deep eutectic solvents are seen as a new class of green and cheap solvents in electrochemical processes. Many electrochemical deposition techniques have been reported in the literature mainly focusing on metal electrodeposition and electro-polymerization. Here, we report for the first time the efficient electro-grafting of aryl diazonium salts on carbon surfaces using ethaline as an example of a natural and biodegradable deep eutectic solvent. Three different aryl diazonium salts have been tested, namely the 4-iodophenyldiazonium ion, 4-carboxymethylphenyl diazonium ion and 4-ethynylphenyldiazonium ion. Effect of concentration, deposition time and potential have been studied in relation to electrode blocking behavior toward redox probes in solution and deposited organic films thickness. Post-functionalization with redox active moieties is demonstrated on such electro-grafted organic layer to show their potential usefulness.

Published
2021

13. SECM Investigation of Carbon Composite Thermoplastic Electrodes

Author

Charles S. Henry, Yann R. Leroux, Philippe Hapiot, Kathleen E. Berg, Colorado State University [Fort Collins] (CSU), Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), This material is based upon research supported by the Chateaubriand Fellowship of the Office for Science & Technology of the Embassy of France in the United States. This material is also supported by the National Science Foundation under grant no. CHE-1710222., Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)

Subjects
chemistry.chemical_classification, Thermoplastic, Chemistry, 010401 analytical chemistry, Composite number, chemistry.chemical_element, Polymer, 010402 general chemistry, 01 natural sciences, 0104 chemical sciences, Analytical Chemistry, Scanning electrochemical microscopy, Scanning probe microscopy, Chemical engineering, [CHIM.ANAL]Chemical Sciences/Analytical chemistry, Electrode, [CHIM]Chemical Sciences, Graphite, Carbon
Abstract

International audience; Thermoplastic electrodes (TPEs) are carbon composite electrodes consisting of graphite and thermoplastic polymer binder. TPE production is a solvent-based method, which makes it easy to fabricate and pattern into complex geometries, contrary to classical carbon composite electrodes. Depending on the composition (carbon type, binder, and composition ratio), TPEs can give excellent electrochemical performance and high conductivity. However, these TPEs are relatively new electrode materials, and thorough electrochemical characterization is still missing to understand and predict why large differences between TPEs exist. We used scanning electrochemical microscopy (SECM) as a screening tool to characterize TPEs. SECM data treatment based on scanning probe microscopy imaging allows a fast and easy comparison of the numerous images, as well as the optimization of the preparation. Experiments suggest that TPEs behave as a network of interacting microelectrodes made by electrochemically active islands isolated between less active areas. Higher carbon content in TPEs is not always indicative of more uniform electrodes with better electrochemical performances. Using various SECM redox probes, it is possible to select a specific graphite or polymer type for the analyte of interest. For example, TPEs made with COC:3569 are the best compromise for general detection, whereas PMMA:11 μm is better suited for catechol-like polyphenol analysis.

Published
2021

14. Functionalizing Gold Nanoparticles with Calix[4]arenes Monolayers for Enhancing Selectivity and Stability in ORR Electrocatalysis

Author

Corinne Lagrost, Ivan Jabin, Yann R. Leroux, Quentin Lenne, Alice Mattiuzzi, Nicolas Le Poul, Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), X4C, Université libre de Bruxelles (ULB), Chimie, Electrochimie Moléculaires et Chimie Analytique (CEMCA), Université de Brest (UBO)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Brestois Santé Agro Matière (IBSAM), Université de Brest (UBO), French Ministry of Research, Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Materials science, 02 engineering and technology, 010402 general chemistry, Electrocatalyst, 01 natural sciences, [CHIM.ANAL]Chemical Sciences/Analytical chemistry, Monolayer, Oxygen reduction reaction, electrocatalysis, [CHIM]Chemical Sciences, [CHIM.COOR]Chemical Sciences/Coordination chemistry, diazonium, surface functionalization, oxygen reduction reaction, Mechanical Engineering, Généralités, 021001 nanoscience & nanotechnology, 0104 chemical sciences, 3. Good health, Chemical engineering, Mechanics of Materials, Colloidal gold, gold nanoparticles, Surface modification, 0210 nano-technology, Selectivity
Abstract

The deliberate surface modification of nanocatalysts with organic ligands has recently emerged as a promising strategy to boost their efficiency, durability, and/or selectivity in key electrocatalytic processes. The interface between the metallic interface and the immobilized ligands promotes high electrocatalytic activity. Herein, the oxygen reduction reaction activity of gold nanoparticles functionalized with a covalently bound monolayer of calix[4]arenes is compared with commercially available gold nanoparticles, classically stabilized through electrostatic adsorption of citrates onto the gold surfaces. Nanocatalysts coated by calix[4]arenes show enhanced selectivity and stability compared to their citrate-stabilized counterparts. These nanohybrids exhibit excellent activity with a dominant 4-electron reduction of O2 with good electrocatalytic performances along with a high robustness under operation as revealed by X-ray photoelectron spectroscopy analyses., SCOPUS: ar.j, info:eu-repo/semantics/published

Published
2020

15. Surface Modification for Promoting Durable, Efficient, and Selective Electrocatalysts

Author

Corinne Lagrost, Quentin Lenne, Yann R. Leroux, Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), French Ministry of ResearchMinistry of Research, France, Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
energy conversion, Chemistry, Nanotechnology, 02 engineering and technology, 010402 general chemistry, 021001 nanoscience & nanotechnology, Electrocatalyst, 01 natural sciences, 7. Clean energy, Catalysis, organic ligands, 0104 chemical sciences, fuel molecules, Electrochemistry, Energy transformation, Surface modification, electrocatalysis, [CHIM]Chemical Sciences, 0210 nano-technology, surface modification
Abstract

International audience; Intensive research into the design of catalysts involved in energy conversion and fuel cell technologies has allowed great progress in the field. However, durable, efficient and selective electrocatalytic systems for the activation of fuel molecules at the lowest cost are still needed. The most developed strategies consist of tailoring the shape, size and composition of metallic nanomaterials. Yet, deliberate surface modification of the catalysts should be considered as a promising alternative approach. The functionalization of metallic catalysts with organic ligands has been recently demonstrated to promote high catalytic activity. This Review focuses on the functionalization of metallic or alloy catalysts with organic ligands, showing the impact of the surface modification for different materials and different reactions. Hybrid systems based on this alternative strategy could contribute to the elaboration of cutting-edge systems for electrocatalysis.

Published
2020

16. Exploiting the versatile alkyne-based chemistry for expanding the applications of a stable triphenylmethyl organic radical on surfaces

Author

Bruno Fabre, Núria Crivillers, Tobias Junghoefer, Erika Giangrisostomi, Ruslan Ovsyannikov, Francesc Bejarano, Maria Benedetta Casu, Concepció Rovira, Marta Mas-Torrent, Diego Gutiérrez, Ewa Malgorzata Nowik-Boltyk, J. Alejandro de Sousa, Yann R. Leroux, Jaume Veciana, Ministerio de Economía y Competitividad (España), Generalitat de Catalunya, Consejo Superior de Investigaciones Científicas (España), Centro de Investigación Biomédica en Red Bioingeniería, Biomateriales y Nanomedicina (España), German Research Foundation, Helmholtz-Zentrum Berlin for Materials and Energy, Universidad de Los Andes [Venezuela] (ULA), Institut de Ciència de Materials de Barcelona (ICMAB), Consejo Superior de Investigaciones Científicas [Madrid] (CSIC), Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Eberhard Karls Universität Tübingen = Eberhard Karls University of Tuebingen, Helmholtz-Zentrum Berlin für Materialien und Energie GmbH (HZB), Spanish Ministry project [FANCYCTQ2016-80030-R], Generalitat de CatalunyaGeneralitat de Catalunya [2017SGR918], Spanish Ministry of Economy and Competitiveness, through the 'Severo Ochoa' Programme for Centers of Excellence in RD [SEV-2015-0496], CSICConsejo Superior de Investigaciones Cientificas (CSIC) [LINKA20128], CIBER-BBN, Spanish Ministry, German Research Foundation (DFG)German Research Foundation (DFG) [CA852/11-1], Helmholtz-Zentrum Berlin, Universidad de Los Andes [Mérida, Venezuela] (ULA), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Thin-film, Chemical substance, Radical, Alkyne, Large scale facilities for research with photons neutrons and ions, Self-assembled monolayers, 02 engineering and technology, Molecular switch, 010402 general chemistry, 01 natural sciences, Terminated monolayers, chemistry.chemical_compound, Oxide-free silicon, chemistry.chemical_classification, [CHIM.ORGA]Chemical Sciences/Organic chemistry, General Chemistry, 021001 nanoscience & nanotechnology, Combinatorial chemistry, 0104 chemical sciences, chemistry, Click chemistry, Surface modification, Azide, 0210 nano-technology, Functional interfaces, Derivative (chemistry)
Abstract

The incorporation of terminal alkynes into the chemical structure of persistent organic perchlorotriphenylmethyl (PTM) radicals provides new chemical tools to expand their potential applications. In this work, this is demonstrated by the chemical functionalization of two types of substrates, hydrogenated SiO2-free silicon (Si–H) and gold, and, by exploiting the click chemistry, scarcely used with organic radicals, to synthesise multifunctional systems. On one hand, the one-step functionalization of Si–H allows a light-triggered capacitance switch to be successfully achieved under electrochemical conditions. On the other hand, the click reaction between the alkyne-terminated PTM radical and a ferrocene azide derivative, used here as a model azide system, leads to a multistate electrochemical switch. The successful post-surface modification makes the self-assembled monolayers reported here an appealing platform to synthesise multifunctional systems grafted on surfaces., S. Ababou-Girard and C. Meriadec (Institut de Physique de Rennes, UMR6251, France) are fully acknowledged for XPS measurements on the Si–H surfaces. Dr Vega Lloveras and Amable Bernab´e are acknowledged for the EPR and MALDI-ToF measurements, respectively. We also would like to thank Thomas Chass´e for allowing us to access the photoelectron laboratory at the University of Tubingen, Hilmar Adler for ¨ technical support, and Helmholtz-Zentrum Berlin (HZB) for providing beamtime at BESSY II. This work was funded by the Spanish Ministry project FANCYCTQ2016-80030-R, the Generalitat de Catalunya (2017SGR918) and the Spanish Ministry of Economy and Competitiveness, through the “Severo Ochoa” Programme for Centers of Excellence in R&D (SEV-2015-0496), the CSIC with the i-Link+ 2018 (Ref. LINKA20128) and CIBERBBN. J. A. de S. is enrolled in the Materials Science PhD program of UAB. J.A. de S. thanks the Spanish Ministry for the FPI fellowship. Financial support from the German Research Foundation (DFG) under the contract CA852/11-1 and from Helmholtz-Zentrum Berlin is gratefully acknowledged.

Published
2020

17. Investigation of Protective Properties of Organic Layers toward Reactive Oxygen Species

Author

Yann R. Leroux, Yara Aceta, Philippe Hapiot, Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), French Ministry of Research, Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)

Subjects
Antioxidant, medicine.medical_treatment, 02 engineering and technology, Electrolyte, 010402 general chemistry, 01 natural sciences, Surface Functionalization, Scanning electrochemical microscopy, Aryl Diazonium, Electrochemistry, medicine, Oxygen reduction reaction, [CHIM]Chemical Sciences, General Materials Science, Spectroscopy, chemistry.chemical_classification, Reactive oxygen species, Surfaces and Interfaces, 021001 nanoscience & nanotechnology, Condensed Matter Physics, 0104 chemical sciences, chemistry, Chemical engineering, Reactive Oxygen Species (ROS), Scanning Electrochemical Microscopy (SECM), Surface modification, 0210 nano-technology
Abstract

International audience; The antioxidant protective properties of polyaromatic organic layers were evaluated toward reactive oxygen species (ROS) using scanning electrochemical microscopy in a foot-printing strategy. The layers were prepared by electrografting of aryldiazonium salts. Where p-(methyl)phenyl films show only weak protective properties toward ROS, p-(ethynyl)phenyl films evidence efficient protection of the covered surfaces. Applied potentials and electrolytes used during oxygen reduction reaction are critical parameters to control, prevent, or reduce the influence of ROS production and hence enhance the device lifetime.

Published
2019

18. Molecular Sieving and Current Rectification Properties of Thin Organic Films

Author

Yara Aceta, Philippe Hapiot, Yann R. Leroux, Corinne Lagrost, Jean-François Bergamini, Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), French Ministry of Research, Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Materials science, chemistry.chemical_element, Infrared spectroscopy, 02 engineering and technology, 010402 general chemistry, 01 natural sciences, Contact angle, X-ray photoelectron spectroscopy, Ellipsometry, Electrochemistry, General Materials Science, Spectroscopy, ComputingMilieux_MISCELLANEOUS, [CHIM.MATE]Chemical Sciences/Material chemistry, Surfaces and Interfaces, 021001 nanoscience & nanotechnology, Condensed Matter Physics, 6. Clean water, 0104 chemical sciences, Characterization (materials science), chemistry, Chemical engineering, Cyclic voltammetry, 0210 nano-technology, Carbon
Abstract

For the purpose of preparing well-organized functional surfaces, carbon and gold substrates were modified using electroreduction of a tetrahedral-shape preorganized tetra-aryldiazonium salt, leading to the deposition of ultrathin organic films. Characterization of the modified surfaces has been performed using cyclic voltammetry, X-ray photoelectron spectroscopy, infrared absorption spectroscopy, ellipsometry, atomic force microscopy, and contact angle measurements. The specific design of the tetra-aryldiazonium salts leads to an intrinsic structuring of the resulting organic films, allowing molecular sieving and current rectification properties toward redox probes in solution.

Published
2018

19. Influence of Fluorene and Spirobifluorene Regioisomerism on the Structure, Organization, and Permeation Properties of Monolayers

Author

Yann R. Leroux, Cyril Poriel, Joanna Jalkh, Sébastien Thiery, Jean-François Bergamini, Philippe Hapiot, Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Region Bretagne [461-ARED], HOME-OLED [11-BS07-020-01], ANR-11-BS07-0020,HOME-OLED,Design de Matériaux hôtes pour des Diodes Organiques Electrophosphorescentes bleues haute performance : une nouvelle approche(2011), Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Materials science, [CHIM.MATE]Chemical Sciences/Material chemistry, 02 engineering and technology, Fluorene, Permeation, 010402 general chemistry, 021001 nanoscience & nanotechnology, Electrochemistry, Photochemistry, 01 natural sciences, Coupling reaction, 0104 chemical sciences, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, chemistry.chemical_compound, Scanning electrochemical microscopy, General Energy, Chemical engineering, chemistry, Monolayer, Click chemistry, Physical and Theoretical Chemistry, Thin film, 0210 nano-technology, ComputingMilieux_MISCELLANEOUS
Abstract

9,9′-Spirobifluorene (SBF) and fluorene derivatives are extensively used as active layer in many organic electronic devices nowadays; thus, careful examination of their structure and organization in thin films and monolayers is of primary importance. In the present work, immobilization of SBF and fluorene isomers was performed via Click Chemistry coupling reaction onto well-ordered ethynylbenzene monolayers on carbon substrates. Characterization of the as-prepared monolayers was performed by classical electrochemical techniques (CV), scanning electrochemical microscopy, and atomic force microscopy, highlighting the effect of SBF and fluorene onto the structure and organization of the obtained monolayers. The significant impact of their positional isomerism on the monolayers structuration was clearly evidenced. Indeed, 2-substituted SBF and fluorene monolayers appear to be more compact and ordered than their 4-substituted analogues and are orientated parallel to the surface. These findings should have an i...

Published
2017

20. Reactivity of Functionalized Ynamides with Tetracyanoethylene: Scope, Limitations and Optoelectronic Properties of the Adducts

Author

Raphaël J. Durand, Elzbieta Trzop, Loïc Toupet, Antoine Sallustrau, Yann Trolez, Claire Gousset, Erwann Le Coz, Yann R. Leroux, Thierry Roisnel, Marie Betou, Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut de Physique de Rennes (IPR), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Centre National de la Recherche Scientifique (CNRS), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), and Université de Rennes (UR)-Centre National de la Recherche Scientifique (CNRS)

Subjects
[PHYS]Physics [physics], optoelectronics, [CHIM.ORGA]Chemical Sciences/Organic chemistry, 010405 organic chemistry, Chemistry, Organic Chemistry, General Chemistry, Tetracyanoethylene, 010402 general chemistry, Electrochemistry, Photochemistry, 01 natural sciences, Biochemistry, Combinatorial chemistry, Cycloaddition, 0104 chemical sciences, Adduct, chemistry.chemical_compound, Yield (chemistry), dienes, ynamides, retro reactions, Reactivity (chemistry), ComputingMilieux_MISCELLANEOUS
Abstract

The reactivity of functionalized ynamides and arylynamines with tetracyanoethylene at room temperature was evaluated. In most cases, the corresponding 1,1,4,4-tetracyanobutadienes (TCBDs) were obtained in good to excellent yields through a [2+2]-cycloaddition/[2+2]-retro-electrocyclization sequence. The influence of diverse functional groups on the yield of the reaction was investigated, in particular concerning multiple ynamides. These TCBDs were characterized by various spectroscopic techniques and electrochemistry and X-ray diffraction in some cases.

Published
2017

21. Tetrathiafulvalene-Tetracyanoquinodimethane Charge-Transfer Complexes Wired to Carbon Surfaces: Tuning of the Degree of Charge Transfer

Author

Yann R. Leroux, Corinne Lagrost, Joanna Jalkh, Philippe Hapiot, Antoine Vacher, Dominique Lorcy, Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Region Bretagne [461-ARED], Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
molecular conductors, salts, ttf-tcnq, Ultramicroelectrode, 02 engineering and technology, Glassy carbon, 010402 general chemistry, Photochemistry, langmuir-blodgett-films, 01 natural sciences, force microscopy, chemistry.chemical_compound, Electron transfer, Monolayer, [CHIM]Chemical Sciences, Organic chemistry, Molecule, Physical and Theoretical Chemistry, ComputingMilieux_MISCELLANEOUS, self-assembled monolayers, Self-assembled monolayer, electron-transfer, 021001 nanoscience & nanotechnology, Tetracyanoquinodimethane, 0104 chemical sciences, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, General Energy, chemistry, rectifiers, interface, glassy-carbon, 0210 nano-technology, Tetrathiafulvalene
Abstract

Charge-transfer complexes involving tetrathiafulvalene (TTF) and tetracyanoquinodimethane (TCNQ) derivatives are engineered in a 2D arrangement onto a carbon surface through the exposure of immobilized TTF units to TCNQ compounds. TTF molecules were immobilized as robust monolayers on carbon surfaces using the electrografting method followed by a click chemistry coupling. When the TTF monolayer is exposed to TCNQ, TCNQF2 (2,5-difluoro-TCNQ), and TCNQF4 (2,3,5,6-tetrafluoro-TCNQ), strong donor–acceptor complexes are formed onto the surface. A considerable decrease of the electrochemical response accompanies the formation of the charge-transfer complex. This observation is rationalized by the analysis of original crystal samples using an ultramicroelectrode cavity, confirming that charge-transfer complexes are electrochemically silent. A fine control of the degree of charge transfer with the judicious choice of different acceptors is evidenced through electrochemical and X-ray photoelectron spectroscopy (XP...

Published
2016

22. Increasing Applications of Graphite Thermoplastic Electrodes with Aryl Diazonium Grafting

Author

Kathleen E. Berg, Yann R. Leroux, Philippe Hapiot, Charles S. Henry, Colorado State University [Fort Collins] (CSU), Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), CHE-1710222, National Science Foundation, Chateaubriand Fellowship of the Office for Science & Technology of the Embassy of France in the United States, Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)

Subjects
thermoplastic electrode, Materials science, Thermoplastic, surface-modified electrode, 02 engineering and technology, Cyclic olefin copolymer, 010402 general chemistry, 01 natural sciences, Catalysis, diazonium reduction, chemistry.chemical_compound, Scanning electrochemical microscopy, Moiety, Methyl methacrylate, chemistry.chemical_classification, Aryl, carbon, [CHIM.MATE]Chemical Sciences/Material chemistry, 021001 nanoscience & nanotechnology, 0104 chemical sciences, chemistry, Chemical engineering, electrochemistry, Click chemistry, 0210 nano-technology, Chemically modified electrode
Abstract

International audience; Carbon composite thermoplastic electrodes (TPEs) consist of graphite and thermoplastic made using an easy, solvent-assisted fabrication. TPEs have the advantages of high conductivity, good electron transfer kinetics, low cost, reusability, and easy patterning, but have only been used with aqueous solvents due to solvent compatibility with the poly(methyl methacrylate) (PMMA) template. The limited solvent compatibility hinders the application range and surface modifications. Here, cyclic olefin copolymer (COC) TPEs in glass templates that are compatible with additional solvents are presented. TPEs are grafted with aryl diazonium salts in acetonitrile, showing covalent surface TPE modification for the first time. Further investigation is carried out with scanning electrochemical microscopy (SECM). The TPEs are post-functionalized with a ferrocene moiety via click chemistry. The diazonium electrografting and click chemistry modifications open up future studies and broader applications of TPEs.

Published
2019

23. 'Click' Chemistry on Gold Electrodes Modified with Reduced Graphene Oxide by Electrophoretic Deposition

Author

Wolfgang Knoll, Vladyslav Mishyn, Henri Happy, Sabine Szunerits, Rabah Boukherroub, Patrik Aspermair, Yann R. Leroux, Institut d’Électronique, de Microélectronique et de Nanotechnologie - UMR 8520 (IEMN), Centrale Lille-Institut supérieur de l'électronique et du numérique (ISEN)-Université de Valenciennes et du Hainaut-Cambrésis (UVHC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Université Polytechnique Hauts-de-France (UPHF), Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Carbon - IEMN (CARBON - IEMN), Centrale Lille-Institut supérieur de l'électronique et du numérique (ISEN)-Université de Valenciennes et du Hainaut-Cambrésis (UVHC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Université Polytechnique Hauts-de-France (UPHF)-Centrale Lille-Institut supérieur de l'électronique et du numérique (ISEN)-Université de Valenciennes et du Hainaut-Cambrésis (UVHC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Université Polytechnique Hauts-de-France (UPHF), Austrian Institute of Technology [Vienna] (AIT), NanoBioInterfaces - IEMN (NBI - IEMN), General financial support from the Centre National de la Recherche Scientifique (CNRS), the University of Lille, the Hauts-de-France region and the EU through FLAG-ERA JTC2015 'Graphtivity' is acknowledged., Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), and Carbon-IEMN (CARBON-IEMN)

Subjects
Materials science, Oxide, surface chemistry, 02 engineering and technology, 010402 general chemistry, 01 natural sciences, Redox, reduced graphene oxide, law.invention, chemistry.chemical_compound, Electrophoretic deposition, law, Potassium ferrocyanide, Graphene, Chemical modification, 021001 nanoscience & nanotechnology, 0104 chemical sciences, 3. Good health, electrophoretic deposition, Chemical engineering, chemistry, Ferrocene, click chemistry, Click chemistry, [PHYS.PHYS.PHYS-CHEM-PH]Physics [physics]/Physics [physics]/Chemical Physics [physics.chem-ph], 0210 nano-technology
Abstract

The coating of electrical interfaces with reduced graphene oxide (rGO) films and their subsequent chemical modification are essential steps in the fabrication of graphene-based sensing platforms. In this work, electrophoretic deposition (EPD) of graphene oxide at 2.5 V for 300 s followed by vapor treatment were employed to coat gold electrodes uniformly with rGO. These interfaces showed excellent electron transfer characteristics for redox mediators such as ferrocene methanol and potassium ferrocyanide. Functional groups were integrated onto the Au/rGO electrodes by the electro-reduction of an aryldiazonium salt, 4-((triisopropylsilyl)ethylenyl)benzenediazonium tetrafluoroborate (TIPS-Eth-ArN) in our case. Chemical deprotection of the triisopropylsilyl function resulted in propargyl-terminated Au/rGO electrodes to which azidomethylferrocene was chemically linked using the Cu(I) catalyzed &ldquo, click&rdquo, chemistry.

Published
2019

24. Evaluation of Alkyl-Ferrocene Monolayers on Carbons for Charge Storage Applications, a Voltammetry and Impedance Spectroscopy Investigation

Author

Yara Aceta, Yann R. Leroux, Philippe Hapiot, Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Materials science, Nano structuring, 02 engineering and technology, 010402 general chemistry, 01 natural sciences, Catalysis, electrografting, chemistry.chemical_compound, pseudocapacitors, Monolayer, Electrochemistry, [CHIM]Chemical Sciences, diazonium salts, Voltammetry, Alkyl, ComputingMilieux_MISCELLANEOUS, chemistry.chemical_classification, nano-structuring, Charge (physics), 021001 nanoscience & nanotechnology, 0104 chemical sciences, Dielectric spectroscopy, Ferrocene, chemistry, Chemical engineering, carbon surface modification, Pseudocapacitor, 0210 nano-technology
Abstract

International audience

Published
2019

26. Immobilization of Monolayers Incorporating Cu Funnel Complexes onto Gold Electrodes. Application to the Selective Electrochemical Recognition of Primary Alkylamines in Water

Author

Ivan Jabin, Gaël De Leener, Yann R. Leroux, Ana Gabriela Porras-Gutierrez, Corinne Lagrost, Diana Over, Philippe Hapiot, Nicolas Le Poul, Olivia Reinaud, Jeremy Mertens, François Reniers, Ferdinand Evoung-Evoung, Yves Le Mest, Angélique Lascaux, Laboratoire de Chimie Organique, Université Libre de Bruxelles [Bruxelles] ( ULB ), Laboratoire de Chimie et de Biochimie Pharmacologiques et Toxicologiques ( LCBPT - UMR 8601 ), Université Paris Descartes - Paris 5 ( UPD5 ) -Centre National de la Recherche Scientifique ( CNRS ), Chimie, Electrochimie Moléculaires et Chimie Analytique ( CEMCA ), Université de Brest ( UBO ) -IFR148 ScInBioS-Institut de Chimie du CNRS ( INC ) -Centre National de la Recherche Scientifique ( CNRS ), Université libre de bruxelles, Service de chimie analytique et chimie des interfaces (CHANI), Institut des Sciences Chimiques de Rennes ( ISCR ), Université de Rennes 1 ( UR1 ), Université de Rennes ( UNIV-RENNES ) -Université de Rennes ( UNIV-RENNES ) -Ecole Nationale Supérieure de Chimie de Rennes-Institut National des Sciences Appliquées ( INSA ) -Centre National de la Recherche Scientifique ( CNRS ), Fonds de la Recherche Scientifique-FNRS [FRFC 2.4.617.10.F], Agence Nationale de la Recherche [ANR10-BLAN-714], De Brouckere-Solvay fund, Michel Kaisin fund, Université libre de Bruxelles (ULB), Laboratoire de Chimie et de Biochimie Pharmacologiques et Toxicologiques (LCBPT - UMR 8601), Université Paris Descartes - Paris 5 (UPD5)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Chimie, Electrochimie Moléculaires et Chimie Analytique (CEMCA), Institut Brestois Santé Agro Matière (IBSAM), Université de Brest (UBO)-Université de Brest (UBO)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Service de chimie analytique et chimie des interfaces (CHANI), Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Université Libre de Bruxelles [Bruxelles] (ULB), Université Paris Descartes - Paris 5 (UPD5)-Centre National de la Recherche Scientifique (CNRS), Université Paris Diderot - Paris 7 (UPD7), Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Rennes-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES), Université de Brest (UBO)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Brestois Santé Agro Matière (IBSAM), Université de Brest (UBO), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
aqueous-solution, Inorganic chemistry, Alkyne, chemistry.chemical_element, 02 engineering and technology, 010402 general chemistry, Electrochemistry, [ CHIM ] Chemical Sciences, 01 natural sciences, Biochemistry, Redox, Catalysis, beta-cyclodextrin, active-sites, Colloid and Surface Chemistry, aliphatic-amines, Monolayer, neutral molecules, [CHIM]Chemical Sciences, ComputingMilieux_MISCELLANEOUS, copper complex, chemistry.chemical_classification, Aqueous solution, Chemistry, metal-surfaces, self-assembled monolayers, General Chemistry, 021001 nanoscience & nanotechnology, Combinatorial chemistry, Copper, 0104 chemical sciences, alkyl amines, induced electroclick, Electrode, Cyclic voltammetry, 0210 nano-technology
Abstract

International audience; The immobilization of a copper calix[6]azacryptand funnel complex on gold-modified electrodes is reported. Two different methodologies are described. One is based on alkyne-terminated thiol self assembled monolayers. The other relies on the electrografting of a calix[4]arene platform bearing diazonium functionalities at its large rim and carboxylic functions at its small rim, which is post-functionalized with alkyne moieties. In both cases, the CuAAC electroclick methodology proved to be the method of choice for grafting the calix[6]azacryptand onto the monolayers. The surface-immobilized complex was fully characterized by surface spectroscopies and electrochemistry in organic and aqueous solvents. The Cu complex display a well-defined quasi-reversible system in cyclic voltammetry associated with the Cu(II)/Cu(I) redox process. Remarkably, this-redox process triggers a powerful selective detection of primary alkylamines in water at a micromolar level, based on a cavitary recognition process.

Published
2016

27. Molecular nano-structuration of carbon surfaces through reductive diazonium salts grafting

Author

Corinne Lagrost, Yann R. Leroux, Philippe Hapiot, Institut des Sciences Chimiques de Rennes ( ISCR ), Université de Rennes 1 ( UR1 ), Université de Rennes ( UNIV-RENNES ) -Université de Rennes ( UNIV-RENNES ) -Ecole Nationale Supérieure de Chimie de Rennes-Institut National des Sciences Appliquées ( INSA ) -Centre National de la Recherche Scientifique ( CNRS ), Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
chemistry.chemical_element, 02 engineering and technology, 010402 general chemistry, 021001 nanoscience & nanotechnology, Photochemistry, Grafting, 01 natural sciences, [ CHIM ] Chemical Sciences, 0104 chemical sciences, Analytical Chemistry, chemistry, Nano, Monolayer, Electrochemistry, [CHIM]Chemical Sciences, 0210 nano-technology, Carbon
Abstract

International audience; The high versatility of diazonium grafting route opens large possibilities for the structuration of carbon surfaces. This short review describes the formation of modified monolayers through electrografting following two general approaches. In the first one, the nano-structuration is achieved with the grafting process using designed bulky substituents contrarily to the second approach where the nano-structuration comes from pre-built entities that are attached on the surfaces. © 2017 Elsevier B.V.

Published
2018

28. New reactivity of 6,6-bis-donor-substituted pentafulvenes: one-step synthesis of highly substituted [3]cumulene and dihydropentalene

Author

Yann R. Leroux, Nicolas Kerisit, François Diederich, Aaron D. Finke, Nils Trapp, Jean-Claude Guillemin, Yann Trolez, Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Eidgenössische Technische Hochschule - Swiss Federal Institute of Technology [Zürich] (ETH Zürich), This work was supported by the Swiss National Science Foundation and the ERC Advanced Grant No. 246637 (‘OPTELOMAC’). We thank the French Ministry of Higher Education and Research for awarding a Ph.D. fellowship to N.K., Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)

Subjects
Stereochemistry, Pentafulvenes, Electrocyclization, dihydropentalene, Sonogashira coupling, One-Step, Tetracyanoethylene, 010402 general chemistry, 01 natural sciences, Biochemistry, Medicinal chemistry, chemistry.chemical_compound, Drug Discovery, [CHIM]Chemical Sciences, Reactivity (chemistry), Spectroscopy, [2+2] Cycloaddition, [CHIM.ORGA]Chemical Sciences/Organic chemistry, 010405 organic chemistry, Organic Chemistry, Cumulene, [3]Cumulene, 0104 chemical sciences, chemistry, Yield (chemistry), Cyclic voltammetry
Abstract

International audience; We report the preparation of a 6,6-bis[(4-N,N-dimethylanilino)ethynyl]pentafulvene from a 6,6-dibromopentafulvene and 4-ethynyl-N,N-dimethylaniline under Sonogashira cross-coupling conditions. A push–pull [3]cumulene was formed unexpectedly during this reaction in moderate yield. The 6,6-bis[(4-N,N-dimethylanilino)ethynyl]pentafulvene was reacted with tetracyanoethylene, and an unprecedented 1,2-dihydropentalene was obtained in high yield as the exclusive product. The structures of the new compounds are supported by X-ray analysis, and a reasonable mechanism for their formation is proposed. We also report their interesting opto-electronic properties, as studied by UV/vis spectroscopy and cyclic voltammetry (CV).

Published
2015

29. Tunneling Dendrimers. Enhancing Charge Transport through Insulating Layer Using Redox Molecular Objects

Author

Jaime Ruiz, Sebastien Lhenry, Roberto Ciganda, Philippe Hapiot, Joanna Jalkh, Didier Astruc, Yann R. Leroux, Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut des Sciences Moléculaires (ISM), Université Montesquieu - Bordeaux 4-Université Sciences et Technologies - Bordeaux 1 (UB)-École Nationale Supérieure de Chimie et de Physique de Bordeaux (ENSCPB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), and Centre National de la Recherche Scientifique (CNRS)-École Nationale Supérieure de Chimie et de Physique de Bordeaux (ENSCPB)-Université Sciences et Technologies - Bordeaux 1-Université Montesquieu - Bordeaux 4-Institut de Chimie du CNRS (INC)

Subjects
[CHIM.ORGA]Chemical Sciences/Organic chemistry, 010405 organic chemistry, Chemistry, Insulator (electricity), Nanotechnology, General Chemistry, 010402 general chemistry, 01 natural sciences, Biochemistry, Redox, Catalysis, 0104 chemical sciences, Scanning electrochemical microscopy, chemistry.chemical_compound, Colloid and Surface Chemistry, Ferrocene, Chemical physics, Dendrimer, Molecule, Quantum tunnelling
Abstract

International audience; Charge transport through an insulating layer was probed using ferrocenyl-terminated dendrimers and scanning electrochemical microscopy. Experiments show that the passage through the layer is considerably enhanced when the transferred charges are brought globally to the surface by the ferrocenyl dendrimer instead of a single ferrocene molecule. This result shows that charge tunneling through an insulator could be promoted by a purely molecular nano-object. S everal recent studies have highlighted that the charge transfer through an insulating layer from a molecule present in solution to a substrate could be restored by attaching a few nanoparticles 1−4 and even a single nanoparticle on the outside of an insulating layer. 5,6 Theoretical analyses have provided some explanations to understand the origins of this phenomenon. 7,8 A higher density of state in a metallic nanoparticle enhances the electron tunneling across the insulating layer and thus the global kinetics of electron transfer. In other words, tunneling from a nanoparticle to a substrate is much more probable than tunneling from single molecules. Beside the fundamental consequences of this observation, it has already opened a route to the developments of novel analytical methods, whereby a nano-particle deposited on an insulating layer behaves as a functional nanoelectrode. 5,6

Published
2014

30. Reversible on-surface wiring of resistive circuits

Author

Michael S. Inkpen, Luis M. Campos, Yann R. Leroux, Latha Venkataraman, Philippe Hapiot, Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Columbia University [New York], Marie Sklodowska Curie Global Fellowship within the Horizon 2020 Programme [MOLCLICK: 657247], National Science Foundation [DMR-1507440], European Project: 657247,H2020,H2020-MSCA-IF-2014,MOLCLICK(2015), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
In situ, Chemistry, Nanotechnology, 02 engineering and technology, General Chemistry, [CHIM.MATE]Chemical Sciences/Material chemistry, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, Reversible reaction, 0104 chemical sciences, law.invention, law, Monolayer, Molecule, Electronics, Scanning tunneling microscope, 0210 nano-technology, Break junction, ComputingMilieux_MISCELLANEOUS, Electronic circuit
Abstract

Single-molecule circuits are assembled and disassembled using reversible surface-based reactions, and characterized with the scanning tunnelling microscope-based break junction technique., Whilst most studies in single-molecule electronics involve components first synthesized ex situ, there is also great potential in exploiting chemical transformations to prepare devices in situ. Here, as a first step towards this goal, we conduct reversible reactions on monolayers to make and break covalent bonds between alkanes of different lengths, then measure the conductance of these molecules connected between electrodes using the scanning tunneling microscopy-based break junction (STM-BJ) method. In doing so, we develop the critical methodology required for assembling and disassembling surface-bound single-molecule circuits. We identify effective reaction conditions for surface-bound reagents, and importantly demonstrate that the electronic characteristics of wires created in situ agree with those created ex situ. Finally, we show that the STM-BJ technique is unique in its ability to definitively probe surface reaction yields both on a local (∼50 nm2) and pseudo-global (≥10 mm2) level. This investigation thus highlights a route to the construction and integration of more complex, and ultimately functional, surface-based single-molecule circuitry, as well as advancing a methodology that facilitates studies beyond the reach of traditional ex situ synthetic approaches.

Published
2017

31. Photo-electrochemical properties of quantum rods studied by scanning electrochemical microscopy

Author

Benoit Boichard, Sebastien Lhenry, Valérie Marchi, Pascale Even-Hernandez, Yann R. Leroux, Philippe Hapiot, Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Centre National de la Recherche Scientifique, Agence Nationale de la Recherche, Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Materials science, genetic structures, General Physics and Astronomy, Nanoparticle, Nanotechnology, 02 engineering and technology, Substrate (electronics), Electron, 010402 general chemistry, 021001 nanoscience & nanotechnology, Electrochemistry, 01 natural sciences, Redox, 0104 chemical sciences, Scanning electrochemical microscopy, Quantum rods, Interference (communication), [CHIM]Chemical Sciences, sense organs, Physical and Theoretical Chemistry, 0210 nano-technology, ComputingMilieux_MISCELLANEOUS
Abstract

Scanning electrochemical microscopy (SECM) is used for studying the intrinsic photo-electrochemical properties of CdSe/CdS quantum rods. They are deposited on a transparent and non-conductive glass plate and investigated by SECM in feedback and generator–collector modes using a series of redox mediators. The method allows the interrogation of the quantum rods under illumination without the interference of the substrate, notably that due to the electron photo-ejection from the substrate, a process that is inherent to any polarized electrode material. Beside the methodological demonstration that could easily be extended to the investigations of the photo-redox properties of nanoparticles, studies highlight the strong reductive properties of quantum rods under illumination.

Published
2017

32. Photo-modulation of the permeation in azobenzene derivatives monolayer films electrografted on carbon substrates

Author

Philippe Hapiot, Yann R. Leroux, Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)

Subjects
Materials science, photomodulation permeation azobenzene deriv monolayer film electrografted carbon, chemistry.chemical_element, 02 engineering and technology, 010402 general chemistry, Electrochemistry, Photochemistry, 01 natural sciences, lcsh:Chemistry, chemistry.chemical_compound, Monolayer, Aryl, Permeation, 021001 nanoscience & nanotechnology, 0104 chemical sciences, lcsh:Industrial electrochemistry, lcsh:QD1-999, chemistry, Azobenzene, Covalent bond, Click chemistry, [CHIM.OTHE]Chemical Sciences/Other, 0210 nano-technology, Carbon, lcsh:TP250-261
Abstract

Nanostructured monolayer of azobenzene derivatives was prepared on carbon materials. The method is based on the electrochemical reduction of a specific silyl-protected aryl diazonium salt followed by a deprotection step and a click chemistry coupling reaction. This procedure leads to a robust modification of the surface where molecular entities are placed in a “frozen” structuration thanks to the covalent nature of the modification. The photo-switchable properties of the surface were examined by electrochemistry using different redox probes. UV–visible light irradiation provides an easy way to reversibly modulate the permeability in a monolayer film grafted onto carbon materials. Keywords: Azobenzene, Electrografting of diazonium salt, Carbon surface, Monolayer

Published
2013

33. Localized Electrochemistry for Studying Functional Carbon Surfaces

Author

Yann R. Leroux, Philippe Hapiot, Corinne Lagrost, Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), SECM, Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
secm, redox mediator, electron-transfer kinetics, chemistry.chemical_element, Covalent modification, Nanotechnology, 02 engineering and technology, 010402 general chemistry, Electrochemistry, 01 natural sciences, Analytical Chemistry, tip, [CHIM]Chemical Sciences, ComputingMilieux_MISCELLANEOUS, Chemistry, covalent modification, self-assembled monolayers, Functional interface, Self-assembled monolayer, mode, constant-distance, 021001 nanoscience & nanotechnology, 0104 chemical sciences, microscopy, charge-transfer, 0210 nano-technology, Redox mediator, Carbon
Abstract

The large amount of research about modified surfaces has inspired the concomitant development of analytical methods for investigating the properties of the modified interfaces. Local electrochemical methods offer new possibilities both for studying the properties of the functional interface and for following their preparation after each step. In this review, these different possibilities are illustrated with different examples of SECM analysis of modified surfaces with a special emphasis on carbon materials.

Published
2016

34. Extremely robust and post-functionalizable gold nanoparticles coated with calix[4]arenes via metal-carbon bonds

Author

Ivan Jabin, Yann R. Leroux, Hennie Valkenier, Julie Hubert, Gilles Bruylants, Alice Mattiuzzi, Ludovic Troian-Gautier, Niko Van den Brande, François Reniers, Bruno Van Mele, Corinne Lagrost, Laboratoire de Chimie Organique, Université libre de Bruxelles (ULB), Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Materials and Chemistry, and Physical Chemistry and Polymer Science

Subjects
Materials science, Inorganic chemistry, Thin layer, Physique de l'état solide, Salt (chemistry), chemistry.chemical_element, 02 engineering and technology, 010402 general chemistry, 01 natural sciences, Catalysis, Chimie des solides, Metal, Polymer chemistry, Materials Chemistry, Chimie, [CHIM]Chemical Sciences, ComputingMilieux_MISCELLANEOUS, chemistry.chemical_classification, Metals and Alloys, General Chemistry, Métallurgie, 021001 nanoscience & nanotechnology, Grafting, 3. Good health, 0104 chemical sciences, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, chemistry, Colloidal gold, visual_art, Ceramics and Composites, visual_art.visual_art_medium, 0210 nano-technology, Catalyses hétérogène et homogène, Carbon
Abstract

Gold nanoparticles stabilized with a thin layer of post-functionalizable calix[4]arenes were prepared through the reductive grafting of a calix[4]arene-tetra-diazonium salt. These particles show exceptional stability towards extreme pH, F-, NaCl, and upon drying. Post-functionalization of the calix-layer was demonstrated, opening the way to a wide range of applications., SCOPUS: ar.j, info:eu-repo/semantics/published

Published
2016

35. Robust Assembly of Dendrimers as an Active Redox-Sensing Monolayer: An Example of Oxo-Anion Sensing

Author

Yann R. Leroux, Fei Hui, Didier Astruc, Philippe Hapiot, Jaime Ruiz, Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Institut des Sciences Moléculaires (ISM), Centre National de la Recherche Scientifique (CNRS)-École Nationale Supérieure de Chimie et de Physique de Bordeaux (ENSCPB)-Université Sciences et Technologies - Bordeaux 1-Université Montesquieu - Bordeaux 4-Institut de Chimie du CNRS (INC), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), and Université Montesquieu - Bordeaux 4-Université Sciences et Technologies - Bordeaux 1 (UB)-École Nationale Supérieure de Chimie et de Physique de Bordeaux (ENSCPB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
[CHIM.ORGA]Chemical Sciences/Organic chemistry, 010405 organic chemistry, Chemistry, Organic Chemistry, scanning probe microscopy, Nanotechnology, General Chemistry, sensors, 010402 general chemistry, Electrochemistry, 01 natural sciences, Redox, Catalysis, dendrimers, 0104 chemical sciences, Scanning probe microscopy, Scanning electrochemical microscopy, electrochemistry, redox chemistry, Dendrimer, Monolayer, Electrode, Click chemistry
Abstract

International audience; Redox-active dendrimer electrodes have been prepared based on click chemistry. The presented approach allows the introduction of numerous different functional groups using the same dendrimeric platform (see figure). Special sensing properties are provided to the electrode that could locally be read by using local electrochemical methods such as scanning electrochemical microscopy (SECM).

Published
2012

36. Modular Functionalization of Electrodes by Cross-Coupling Reactions at Their Surfaces

Author

Bernd Gotsmann, Marcel Mayor, Yann R. Leroux, Heike Riel, Marcel Müri, Marius Trouwborst, Emanuel Lörtscher, Department of Chemistry [Basel], University of Basel (Unibas), IBM Research GmbH, IBM Research [Zurich], Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Organic electronics, Bioelectronics, Materials science, [CHIM.ORGA]Chemical Sciences/Organic chemistry, chemical immobilization, Molecular electronics, Nanotechnology, 02 engineering and technology, functionalized electrodes, 010402 general chemistry, 021001 nanoscience & nanotechnology, Condensed Matter Physics, 01 natural sciences, 0104 chemical sciences, Electronic, Optical and Magnetic Materials, organic electronics, Biomaterials, Molecular film, Electrode, Electrochemistry, Surface modification, Cyclic voltammetry, 0210 nano-technology, surface modification, Chemically modified electrode
Abstract

International audience; Due to the increasing importance of modified electrodes for many applications in nanotechnology, including molecular electronics, bioelectronics, and sensors, there is a need to find ways to chemically attach suitable molecular films onto the electrodes. Combining the electroreduction of aryl diazonium salts with the Sonogashira cross-coupling reaction, a new modular technique to modify electrodes is presented. The new technique allows a wide range of functional groups to be introduced onto electrode surfaces with high surface coverage by the functional subunit. Various organic subunits, including redox chromophores, are successfully attached to platinum electrodes. The corresponding films are characterized using cyclic voltammetry, X-ray photoelectron spectroscopy, atomic force microscopy, and contact-angle measurements. The electroreduction of diazonium salts is successfully achieved on a broad variety of conducting and semiconducting surfaces, which shows that the technique is applicable to a broad variety of substrates.

Published
2011

37. SECM Investigations of Immobilized Porphyrins Films

Author

Delphine Schaming, Philippe Hapiot, Laurent Ruhlmann, Yann R. Leroux, Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Laboratoire de Chimie Physique D'Orsay (LCPO), Université Paris-Sud - Paris 11 (UP11)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Kinetics, Substituent, Nanotechnology, [CHIM.MATE]Chemical Sciences/Material chemistry, 02 engineering and technology, Surfaces and Interfaces, 010402 general chemistry, 021001 nanoscience & nanotechnology, Condensed Matter Physics, 01 natural sciences, Redox, Porphyrin, 0104 chemical sciences, chemistry.chemical_compound, chemistry, Chemical engineering, Transition metal, Standard electrode potential, Electrode, Electrochemistry, General Materials Science, 0210 nano-technology, Spectroscopy, Electronic properties
Abstract

International audience; Electronic properties of electrogenerated Zn-porphyrin layers linked by an electroactive linker and immobilized on a semitransparent ITO electrode were investigated by steady-state SECM in unbiased conditions in view of the numerous possible applications of such surface. This SECM strategy took advantage of the variations of the charge transfer kinetics of the organic redox couple (the mediator used in SECM) on ITO surface with the standard potential of the mediator. After preliminary characterization of nonmodified ITO, analysis of the SECM approach curves recorded with a series of redox mediators allows the characterizations of both film permeability and charge transport inside the organic film in conditions close to a "real optoelectronic device". Two types of porphyrin films were considered. In the first one, the film was produced by electropolymerization of a modified zinc-β-octaethylporphyrin in which the bipyridinium pendant substituent is first introduced. The second type of film was prepared directly from an in situ electropolymerization method in which the Zn porphyrin is simply oxidized in the presence of 4,4'-bipyridine. Experiments show the occurrence of efficient charge transport inside both films after initial reduction of the electroactive linker. However, the first preparation method leads to films with stronger blocking character versus organic molecules and higher charge injection rates.

Published
2010

38. Catechol-Based Macrocyclic Rods: En Route to Redox-Active Molecular Switches

Author

Markus Neuburger, Marcel Mayor, Thomas Wandlowski, Artem Mishchenko, Nicolas Weibel, Yann R. Leroux, Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Molecular switch, Catechol, 010405 organic chemistry, Stereochemistry, Hydrogen bond, Organic Chemistry, Arylene, 010402 general chemistry, 01 natural sciences, 0104 chemical sciences, Quinone, chemistry.chemical_compound, chemistry, Turnstile, Intramolecular force, [PHYS.PHYS.PHYS-CHEM-PH]Physics [physics]/Physics [physics]/Chemical Physics [physics.chem-ph], Physical and Theoretical Chemistry, Cyclic voltammetry, ComputingMilieux_MISCELLANEOUS
Abstract

The design and synthesis of the macrocyclic turnstile 1 comprising a terminally sulfur-functionalized molecular rod and a redox-active catechol subunit is described. The shape-persistent macrocyclic scaffold consists of alternating arylene and ethynylene units. A freely rotating 2,6-diethynyl-catechol subunit is clamped between both terminal arylene subunits as molecular turnstile. While the electrochemical switching between the catechol and the quinone form of this catechol subunit is displayed by cyclic voltammetry, conformational rearrangements by favoring and disfavoring the formation of intramolecular hydrogen bonds are the subject of current investigations. Terminal acetyl-protected sulfur anchor groups enabled the immobilization of the macrocycle between an Au tip and an Au substrate of a STM set-up. Preliminary single-molecule transport investigations of the turnstile 1 display comparable values as for the parent molecular rod. An electrochemically-controlled single-molecule transport experiment to investigate redox-state-dependent transport properties is currently under way.

Published
2009

39. Amine-terminated monolayers on carbon: preparation, characterization, and coupling reactions

Author

Philippe Hapiot, Alison J. Downard, Lita Lee, Yann R. Leroux, MacDiarmid Institute for Advanced Materials and Nanotechnology, University of Canterbury [Christchurch], DEPARTMENT OF CHEMISTRY AND DEPARTMENT OF PHYSICS (DCDPA), Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), MacDiarmid Institute, Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)

Subjects
Carboxylic acid, 02 engineering and technology, Photoresist, Glassy carbon, 010402 general chemistry, Electrochemistry, 01 natural sciences, Coupling reaction, chemistry.chemical_compound, Amide, Monolayer, Polymer chemistry, Organic chemistry, General Materials Science, Spectroscopy, ComputingMilieux_MISCELLANEOUS, chemistry.chemical_classification, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Surfaces and Interfaces, 021001 nanoscience & nanotechnology, Condensed Matter Physics, 0104 chemical sciences, chemistry, Amine gas treating, 0210 nano-technology
Abstract

Aminophenyl and aminomethylphenyl monolayers have been electrografted to glassy carbon and pyrolyzed photoresist film from the corresponding diazonium ions using a protection–deprotection strategy based on Boc (tert-butyloxycarbonyl) and Fmoc (fluorenylmethyloxycarbonyl) groups. After grafting and then deprotecting films of Boc-NH-Ar, Fmoc-NH-Ar, and Fmoc-NH-CH2-Ar, depth profiling by atomic force microscopy confirmed that the resulting amine-terminated films were monolayers. In contrast, after deprotection, Boc-NH-CH2-Ar gave a multilayer film. Electroactive carboxylic acid derivatives were coupled to the monolayers through amide linkages. Electrochemical measurements revealed that the deprotected Fmoc-NH-CH2-Ar monolayer gave the highest surface concentration of coupled nitrophenyl and ferrocenyl groups and DFT calculations established that this monolayer has the highest theoretical surface concentration of those examined.

Published
2015

41. Synthesis of Functionalized Few-Layer Graphene Through Fast Electrochemical Expansion of Graphite

Author

Philippe Hapiot, Yann R. Leroux, Jean-Christophe Le Breton, Jean-François Bergamini, Soraya Ababou, Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Institut de Physique de Rennes (IPR), Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Centre National de la Recherche Scientifique (CNRS), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), and Université de Rennes (UR)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Aryldiazonium electroreduction, Chemistry, Graphene, General Chemical Engineering, Aryl, Electrochemical exfoliation, Nanotechnology, [CHIM.MATE]Chemical Sciences/Material chemistry, Electrochemistry, Analytical Chemistry, Cathodic protection, law.invention, chemistry.chemical_compound, Few layer graphene, Carbon surface modification, law, HOPG, Surface modification, [CHIM]Chemical Sciences, Graphite, ComputingMilieux_MISCELLANEOUS, Graphene oxide paper
Abstract

Fast and reproducible production of graphene flaks from graphite is an important process considering the possible industrial applications of graphene. We propose an electrochemical method to produce functionalized few-layer graphenes in minutes, without the need of prolonged ultrasonic treatment. It mainly consists in the cathodic electrochemical expansion of graphite in DMF. Functionalization of graphite is achieved by reducing aryl diazonium salts in organic solution. This simple methodology allows easily and quickly preparation of modified few-layer graphenes. Two different graphite sources were considered in this work for electrochemical graphene flaks production.

Published
2015

42. Comparative Electrochemical Investigations in Ionic Liquids and Molecular Solvents of a Carbon Surface Modified by a Redox Monolayer

Author

Yann R. Leroux, Philippe Hapiot, Corinne Lagrost, Joanna Jalkh, Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Chemistry, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Kinetics, Inorganic chemistry, Ionic bonding, Substrate (chemistry), Electrochemistry, Redox, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, chemistry.chemical_compound, General Energy, Chemical engineering, Covalent bond, Monolayer, Ionic liquid, Physical and Theoretical Chemistry
Abstract

International audience; Electrochemical properties of carbon surfaces modified by a covalently attached redox monolayer (alkyl-ferrocenyl) have been investigated in three different classical room temperature ionic liquids (RTILs): BMIPF6, BMINTf2, Me3BuNNTf2, and in two common molecular solvents (ethanol and CH2Cl2) for evidencing special aspects of the electronic transfer in RTILs. If the redox activity and the stability of the layer are globally preserved in the RTILs, a considerable decrease of the amount of active redox groups is observed when the layer is examined in the RTILs. The oxidation potentials are only slightly higher in the RTILs contrarily to the charge transfer kinetics that decrease by a factor of 10–20 as measured for the rates between the attached redox moieties and the substrate. These behaviors that appear as possible limitations for practical applications of such systems in RTILs could be ascribed to specific ionic associations and a large reorganization of the layer during its charging process.

Published
2014

43. One-Pot Electrografting of Mixed Monolayers with Controlled Composition

Author

Sebastien Lhenry, François Reniers, Olivia Reinaud, Yann R. Leroux, Nicolas Vandencasteele, Alice Mattiuzzi, Luis Santos, Philippe Hapiot, Corinne Lagrost, Ivan Jabin, Institut des Sciences Chimiques de Rennes ( ISCR ), Université de Rennes 1 ( UR1 ), Université de Rennes ( UNIV-RENNES ) -Université de Rennes ( UNIV-RENNES ) -Ecole Nationale Supérieure de Chimie de Rennes-Institut National des Sciences Appliquées ( INSA ) -Centre National de la Recherche Scientifique ( CNRS ), Laboratoire de Chimie Organique, Université Libre de Bruxelles [Bruxelles] ( ULB ), Computer Science Department [Bruxelles] ( ULB ), Laboratoire de Chimie et de Biochimie Pharmacologiques et Toxicologiques ( LCBPT - UMR 8601 ), Université Paris Descartes - Paris 5 ( UPD5 ) -Centre National de la Recherche Scientifique ( CNRS ), Institut des Sciences Chimiques de Rennes (ISCR), Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Rennes-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES), Université Libre de Bruxelles [Bruxelles] (ULB), Computer Science Department [Bruxelles] (ULB), Laboratoire de Chimie et de Biochimie Pharmacologiques et Toxicologiques (LCBPT - UMR 8601), Université Paris Descartes - Paris 5 (UPD5)-Centre National de la Recherche Scientifique (CNRS), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université libre de Bruxelles (ULB), Département d'Informatique [Bruxelles] (ULB), Faculté des Sciences [Bruxelles] (ULB), Université libre de Bruxelles (ULB)-Université libre de Bruxelles (ULB), Université Paris Descartes - Paris 5 (UPD5)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Materials science, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Nanotechnology, Mole fraction, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, Scanning electrochemical microscopy, General Energy, X-ray photoelectron spectroscopy, Covalent bond, [ CHIM.ORGA ] Chemical Sciences/Organic chemistry, Monolayer, Calixarene, Surface modification, Wetting, Physical and Theoretical Chemistry
Abstract

International audience; Surface functionalization with ultrathin layers exhibiting a highly robust interface is of paramount importance for designing materials with tailored properties or operating functions, without modifying drastically the material’s bulk structures. A fine-tuning of the surface composition obtained, for instance from binary mixed layers, is also a key issue for developing high value-added applications like efficient sensors. Herein, binary mixtures of calix[4]arene-tetra-diazonium salts generated in situ from their corresponding calix[4]tetra-anilines are electrografted to form covalently bound monolayers onto substrates for yielding versatile functionalizable molecular platforms. Wettability studies, X-ray photoelectron spectroscopy analyses, and scanning electrochemical microscopy show the formation of homogeneous mixed monolayers. The distribution of the two calixarenes on the surface is directed by their relative molar fraction in the deposition solution. The strategy allows the control of the composition of mixed monolayers in a one-step approach. Postfunctionalization of the mixed layers with ferrocene centers is performed to exemplify the benefit of a dilution procedure when functional groups are introduced at the calix[4]arene small rim. This study highlights the potential of diazonium salt electrografting as a competitive alternative to chemisorption strategies such as self-assembled monolayers of alkyl thiols in the field of surface functionalization.

Published
2014

44. Covalently anchored carboxyphenyl monolayer via aryldiazonium ion grafting: a well-defined reactive tether layer for on-surface chemistry

Author

Haifeng Ma, Simon Brown, Yann R. Leroux, Paula A. Brooksby, Philippe Hapiot, Alison J. Downard, Lita Lee, MacDiarmid Institute for Advanced Materials and Nanotechnology, University of Canterbury [Christchurch], DEPARTMENT OF CHEMISTRY AND DEPARTMENT OF PHYSICS (DCDPA), Biomathematics Research Centre, Department of Physics and Astronomy [Christchurch] (DPA), Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Department of Mathematics and Statistics [Christchurch], DEPARTMENT OF CHEMISTRY AND DEPARTMENT AND ASTRONOMY, Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
chemistry.chemical_classification, Chemistry, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Carboxylic acid, Aryl, Inorganic chemistry, Substituent, 02 engineering and technology, Surfaces and Interfaces, Glassy carbon, 010402 general chemistry, 021001 nanoscience & nanotechnology, Condensed Matter Physics, Electrochemistry, 01 natural sciences, 0104 chemical sciences, chemistry.chemical_compound, Covalent bond, Monolayer, Polymer chemistry, General Materials Science, 0210 nano-technology, Layer (electronics), Spectroscopy
Abstract

International audience; Electrografting of aryl films to electrode surfaces from diazonium ion solutions is a widely used method for preparation of modified electrodes. In the absence of deliberate measures to limit film growth, the usual film structure is a loosely packed multilayer. For some applications, monolayer films are advantageous; our interest is in preparing well-defined monolayers of reactive tethers for further onsurface chemistry. Here, we describe the synthesis of an aryl diazonium salt with a protected carboxylic acid substituent. After electrografting to glassy carbon electrodes and subsequent deprotection, the layer is reacted with amine derivatives. Electrochemistry and atomic force microscopy are used to monitor the grafting, deprotection, and subsequent coupling steps. Attempts to follow the same procedures on gold surfaces suggest that the grafted layer is not stable in these reaction conditions.

Published
2014

45. Locally Induced and Self-Induced 'Electroclick' onto a Self-Assembled Monolayer: Writing and Reading with SECM under Unbiased Conditions

Author

Christophe Orain, Philippe Hapiot, Yann R. Leroux, Yves Le Mest, Sebastien Lhenry, Nicolas Le Poul, Nathalie Cosquer, Françoise Conan, Olivia Reinaud, Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Chimie, Electrochimie Moléculaires et Chimie Analytique (CEMCA), Institut Brestois Santé Agro Matière (IBSAM), Université de Brest (UBO)-Université de Brest (UBO)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Laboratoire de Chimie et de Biochimie Pharmacologiques et Toxicologiques (LCBPT - UMR 8601), Université Paris Descartes - Paris 5 (UPD5)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut des Sciences Chimiques de Rennes ( ISCR ), Université de Rennes 1 ( UR1 ), Université de Rennes ( UNIV-RENNES ) -Université de Rennes ( UNIV-RENNES ) -Ecole Nationale Supérieure de Chimie de Rennes-Institut National des Sciences Appliquées ( INSA ) -Centre National de la Recherche Scientifique ( CNRS ), Chimie, Electrochimie Moléculaires et Chimie Analytique ( CEMCA ), Université de Brest ( UBO ) -IFR148 ScInBioS-Institut de Chimie du CNRS ( INC ) -Centre National de la Recherche Scientifique ( CNRS ), Laboratoire de Chimie et de Biochimie Pharmacologiques et Toxicologiques ( LCBPT - UMR 8601 ), Université Paris Descartes - Paris 5 ( UPD5 ) -Centre National de la Recherche Scientifique ( CNRS ), Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Rennes-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES), Université Paris Descartes - Paris 5 (UPD5)-Centre National de la Recherche Scientifique (CNRS), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université de Brest (UBO)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Brestois Santé Agro Matière (IBSAM), and Université de Brest (UBO)

Subjects
chemistry.chemical_classification, Microscopy, Chemistry, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Analytical chemistry, Substrate (chemistry), Alkyne, Self-assembled monolayer, Surfaces and Interfaces, Condensed Matter Physics, Photochemistry, Coupling reaction, Catalysis, Scanning electrochemical microscopy, [ CHIM.ORGA ] Chemical Sciences/Organic chemistry, Monolayer, Electrochemistry, Molecule, General Materials Science, Spectroscopy
Abstract

International audience; Localized “electroclick” was achieved on azido-terminated self-assembled monolayers using Scanning Electrochemical Microscopy (SECM) in feedback mode, in which the substrate is not electrically connected (unbiased conditions). The method allows both the local immobilization of diverse functional moieties and the monitoring of each modification step at a micrometer scale. Conditions of the “click” coupling reaction were optimized especially to avoid the deposit of metallic copper by the choice of a specific ligand to stabilize the Cu(I) species. The catalytic efficiency in localized “electroclick” reaction of Cu(II)TMPA (TMPA: tris(2-pyridylmethyl)amine) as the “click” catalyst was compared with a derivative containing an alkyne group Cu(II)6eTMPA, the same molecule playing the role of the catalyst and the substrate. Evidences for surface self-catalysis propagation are demonstrated through SECM imaging showing a random 2D progression of the catalytic modification.

Published
2014

46. Scanning Tunneling and Atomic Force Microscopy Evidence for Covalent and Noncovalent Interactions between Aryl Films and Highly Ordered Pyrolytic Graphite

Author

Lita Lee, Yann R. Leroux, Philippe Hapiot, Alison J. Downard, Sara J. Fraser, Simon Brown, Paula A. Brooksby, Keith C. Gordon, Haifeng Ma, Biomathematics Research Centre, University of Canterbury [Christchurch], MacDiarmid Institute for Advanced Materials and Nanotechnology, Graphics and Vision Research Laboratory (Graphics Lab), University of Otago [Dunedin, Nouvelle-Zélande], Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Department of Mathematics and Statistics [Christchurch], Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Materials science, Analytical chemistry, 02 engineering and technology, 010402 general chemistry, 01 natural sciences, law.invention, chemistry.chemical_compound, law, Monolayer, Non-covalent interactions, Graphite, Pyrolytic carbon, Physical and Theoretical Chemistry, chemistry.chemical_classification, Graphene, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Aryl, 021001 nanoscience & nanotechnology, 0104 chemical sciences, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, Crystallography, General Energy, chemistry, Covalent bond, Scanning tunneling microscope, 0210 nano-technology
Abstract

International audience; Electroreduction of 4-nitrobenzenediazonium ions at highly ordered pyrolytic graphite (HOPG) gives a nitrophenyl film that is shown by noncontact atomic force microscopy (AFM) to be continuous and of multilayer thickness. Investigation of the same surface by ultrahigh vacuum scanning tunneling microscopy (UHV-STM) reveals molecular species immobilized on the step edges, but only mobile species on the basal planes. After several scans across an area of basal plane, atomic-level resolution images of clean, defect-free graphite surfaces are obtained. The same behavior is observed with a film deposited by reduction of 4-((triisopropylsilyl)ethynyl)benzenediazonium ion. Throughout extensive STM measurements we find no evidence for covalent attachment of aryl groups to the basal plane and conclude that our results can be best explained by the formation of films of physisorbed oligomeric species. After heating above 300 °C, nitrophenyl films are more stable to STM imaging but no longer contain nitro groups. Increased cross-linking within the film from coupling of radicals formed by thermal decomposition of nitrophenyl groups may be responsible for the more robust film structure.

Published
2014

47. High-Yield Formation of Substituted Tetracyanobutadienes from Reaction of Ynamides with Tetracyanoethylene

Author

Yann Trolez, Claudine Katan, Jean-Claude Guillemin, Yann R. Leroux, Nicolas Kerisit, Esme Meledje, Marie Betou, Jean-François Halet, Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), This work was granted access to the HPC resources of CINES and of IDRIS under the allocations 2012-[x2012080649] and 2013-[x2013080649] made by GENCI (Grand Equipement National de Calcul Intensif). N.K. acknowledges a PhD fellowship from the French Ministry of Research. M.B. thanks the Région Bretagne for a post-doctoral grant., Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
[2+2] cycloaddition, tetracyanoethylene, 010405 organic chemistry, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Organic Chemistry, General Chemistry, Tetracyanoethylene, 010402 general chemistry, Photochemistry, 01 natural sciences, Catalysis, 0104 chemical sciences, chemistry.chemical_compound, chemistry, Computational chemistry, Yield (chemistry), ynamides, tetracyanobutadienes
Abstract

The authors gratefully acknowledge Dr. L. Toupet from Institut de Physique de Rennes for solving X-ray structures, T. C. Nguyen for help in performing DFT calculations and Pr. A. Boucekkine for useful discussions.; International audience; A high-yielding sequence of [2+2] cycloaddition-retroelectrocyclization of ynamides with tetracyanoethylene (TCNE) is described. The reaction provided tetracyanobutadiene (TCBD) species, which were characterized by various techniques. DFT and TD-DFT calculations were also performed to complement experimental findings.

Published
2014

48. Efficient Covalent Modification of a Carbon Surface: Use of a Silyl Protecting Group To Form an Active Monolayer

Author

Yann R. Leroux, Clément Roux, Jean-Marc Noël, Philippe Hapiot, Hui Fei, Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Steric effects, Silylation, Aryl, [CHIM.MATE]Chemical Sciences/Material chemistry, 02 engineering and technology, General Chemistry, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, Biochemistry, Combinatorial chemistry, Catalysis, 0104 chemical sciences, chemistry.chemical_compound, Colloid and Surface Chemistry, chemistry, Functional group, Monolayer, Surface modification, Molecule, Organic chemistry, 0210 nano-technology, Protecting group
Abstract

International audience; A global strategy to prepare a versatile and robust reactive platform for immobilizing molecules on carbon substrates with controlled morphology and high selectivity is presented. The procedure is based on the electroreduction of a selected triisopropylsilyl (TIPS)-protected ethynyl aryldiazonium salt. It avoids the formation of multilayers and efficiently protects the functional group during the electrografting step. After TIPS deprotection, a dense reactive ethynyl aryl monolayer is obtained which presents a very low barrier to charge transfer between molecules in solution and the surface. As a test functionalization, azidomethylferrocene was coupled by "click" chemistry with the modified surface. Analysis of the redox activity highlights a surface concentration close to the maximum possible attachment considering the steric hindrance of a ferrocenyl group.

Published
2010

49. Bilayer Molecular Electronics: All-Carbon Electronic Junctions Containing Molecular Bilayers Made with 'Click' Chemistry

Author

Richard L. McCreery, Yann R. Leroux, Philippe Hapiot, Mykola Kondratenko, Sayed Youssef Sayed, Akhtar Bayat, Department of Chemistry, University of Alberta, University of Alberta, Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Natiional Institute for Nanotechnology National Research Co, Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
molecular electronics, alkyne derivative, chemistry.chemical_element, Alkyne, reduction, Nanotechnology, 02 engineering and technology, 010402 general chemistry, Photochemistry, 01 natural sciences, Biochemistry, Catalysis, chemistry.chemical_compound, Colloid and Surface Chemistry, Click reaction, Molecule, Molecular junction, Diazonium reduction, alkane derivative, chemistry.chemical_classification, molecule, [CHIM.ORGA]Chemical Sciences/Organic chemistry, carbon, Bilayer, Redox-active, Molecular electronics, Electronic junctions, Top contact, General Chemistry, Reproducibilities, Molecules, 021001 nanoscience & nanotechnology, 0104 chemical sciences, chemistry, bilayer membrane, click chemistry, chemical structure, Click chemistry, Azide, diazonium compound, 0210 nano-technology, oxidation reduction reaction, Layer (electronics), Carbon, Current voltage
Abstract

Bilayer molecular junctions were fabricated by using the alkyne/azide "click" reaction on a carbon substrate, followed by deposition of a carbon top contact in a crossbar configuration. The click reaction on an alkyne layer formed by diazonium reduction permitted incorporation of a range of molecules into the resulting bilayer, including alkane, aromatic, and redox-active molecules, with high yield (>90%) and good reproducibility. Detailed characterization of the current-voltage behavior of bilayer molecular junctions indicated that charge transport is consistent with tunneling, but that the effective barrier does not strongly vary with molecular structure for the series of molecules studied. © 2013 American Chemical Society.

Published
2013

50. Mixed monolayer organic films via sequential electrografting from aryldiazonium ion and arylhydrazine solutions

Author

Paula A. Brooksby, Alison J. Downard, Lita Lee, Yann R. Leroux, Philippe Hapiot, Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)

Subjects
Alkyne, 02 engineering and technology, Glassy carbon, 010402 general chemistry, Photochemistry, Electrochemistry, 01 natural sciences, chemistry.chemical_compound, Polymer chemistry, Monolayer, General Materials Science, Reactivity (chemistry), Spectroscopy, chemistry.chemical_classification, Surfaces and Interfaces, [CHIM.MATE]Chemical Sciences/Material chemistry, 021001 nanoscience & nanotechnology, Condensed Matter Physics, 6. Clean water, 0104 chemical sciences, chemistry, Ferrocene, Covalent bond, Click chemistry, 0210 nano-technology
Abstract

International audience; Sequential electrografting at glassy carbon from aryldiazonium salt solutions, or an aryldiazonium salt followed by an arylhydrazine, leads to the formation of covalently attached monolayer films incorporating two modifiers. In the first step, a 4-((triisopropylsilyl)ethynyl)phenyl film is electrografted to the surface, followed by removal of the triisopropylsilyl group to give a submonolayer of phenylethynylene groups. Two general strategies can then be applied to "fill in" the sparse monolayer with a second modifier. In the first route, nitrophenyl groups are grafted to the phenylethynylene-modified surface by the oxidation of 4-nitrophenylhydrazine. Ferrocene can be coupled to the terminal alkyne groups on the surface via a click reaction with azidomethylferrocene; an electrochemical measurement of the amount of immobilized ferrocene demonstrates that the phenylethynylene layer retains close to full reactivity after the second grafting step. In the alternative strategy, ferrocene is coupled to the phenylethynylene layer prior to grafting nitrophenyl groups by the reduction of the 4-nitrobenzenediazonium ion or by the oxidation of 4-nitrophenylhydrazine. For all approaches, the optimization of the grafting conditions gives surface concentrations of ferrocene and nitrophenyl groups that are consistent with those of a mixed monolayer. The stepwise generation of mixed monolayers is also monitored by film thickness measurements by depth profiling using the atomic force microscope. Thickness values are consistent with the proposed film structure in each preparation step.

Published
2013

Catalog

Books, media, physical & digital resources
See catalog results