2017
|
Molecular electrochemistry: A central method to understand the metabolic activation of therapeutic agents. The example of metallocifen anti-cancer drug candidates Article de journal C Amatore; E Labbé; O Buriez Current Opinion in Electrochemistry, 2 (1), p. 7–12, 2017. @article{Amatore:2017,
title = {Molecular electrochemistry: A central method to understand the metabolic activation of therapeutic agents. The example of metallocifen anti-cancer drug candidates},
author = {C Amatore and E Labb\'{e} and O Buriez},
url = {https://www.scopus.com/inward/record.uri?eid=2-s2.0-85045563679&doi=10.1016%2fj.coelec.2016.12.003&partnerID=40&md5=b531e3c0fb011e978b14c2e30a432353},
doi = {10.1016/j.coelec.2016.12.003},
year = {2017},
date = {2017-01-01},
journal = {Current Opinion in Electrochemistry},
volume = {2},
number = {1},
pages = {7--12},
abstract = {Organometallic chemistry has allowed the design and emergence of a new class of metal-based bioactive molecules and a variety of drugs used or still tested against cancer. In this field, beyond the well-known cisplatin, major contributions have focused on the functionalization of clinically validated purely organic drugs with complexes derivatized by a metallocene group. This approach, which exalts the anti-cancer properties of the organic moiety, has been successfully used to design ferrocifens. These complexes involve a ferrocenyl group covalently grafted onto the tamoxifen skeleton, the current gold standard for endocrine breast cancer therapy. Based on the same strategy, several original ruthenocene (Rc)-tamoxifen derivatives and osmocene (Os)-tamoxifen derivatives have been recently synthesized and successfully tested against breast and other cancer cells. The development of such potent metallodrugs was made possible thanks to the accurate mechanistic understanding of the metallodrugs activation provided by the synergistic combination of electrochemical and biological approaches. © 2017 Elsevier B.V.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
Organometallic chemistry has allowed the design and emergence of a new class of metal-based bioactive molecules and a variety of drugs used or still tested against cancer. In this field, beyond the well-known cisplatin, major contributions have focused on the functionalization of clinically validated purely organic drugs with complexes derivatized by a metallocene group. This approach, which exalts the anti-cancer properties of the organic moiety, has been successfully used to design ferrocifens. These complexes involve a ferrocenyl group covalently grafted onto the tamoxifen skeleton, the current gold standard for endocrine breast cancer therapy. Based on the same strategy, several original ruthenocene (Rc)-tamoxifen derivatives and osmocene (Os)-tamoxifen derivatives have been recently synthesized and successfully tested against breast and other cancer cells. The development of such potent metallodrugs was made possible thanks to the accurate mechanistic understanding of the metallodrugs activation provided by the synergistic combination of electrochemical and biological approaches. © 2017 Elsevier B.V. |
Selective Electrochemical Bleaching of the Outer Leaflet of Fluorescently Labelled Giant Liposomes Article de journal Olivier Buriez; Ana Isabel Perez Jimenez; Lylian Challier; Eric Aït-Yahiatène; Jerome Delacotte; Eric Labbe Chemistry A European Journal, 23 , p. 6781-6787, 2017. @article{RID:0519170943437-64,
title = {Selective Electrochemical Bleaching of the Outer Leaflet of Fluorescently Labelled Giant Liposomes},
author = {Olivier Buriez and Ana Isabel Perez Jimenez and Lylian Challier and Eric A\"{i}t-Yahiat\`{e}ne and Jerome Delacotte and Eric Labbe},
year = {2017},
date = {2017-01-01},
journal = {Chemistry A European Journal},
volume = {23},
pages = {6781-6787},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
|
2016
|
Revisiting the Complex Osmocene Electro-Oxidation Mechanism Article de journal F Chau; C Amatore; E Labbé; O Buriez Electrochimica Acta, 212 , p. 973–978, 2016. @article{Chau:2016,
title = {Revisiting the Complex Osmocene Electro-Oxidation Mechanism},
author = {F Chau and C Amatore and E Labb\'{e} and O Buriez},
url = {https://www.scopus.com/inward/record.uri?eid=2-s2.0-84978646014&doi=10.1016%2fj.electacta.2016.07.082&partnerID=40&md5=57bf46e24409b5ec314632cff4c66c9a},
doi = {10.1016/j.electacta.2016.07.082},
year = {2016},
date = {2016-01-01},
journal = {Electrochimica Acta},
volume = {212},
pages = {973--978},
abstract = {The electrochemical oxidation of osmocene was investigated in dichloromethane (DCM) and acetonitrile (MeCN) in the presence of various electrolyte anions ([BF4]−, [PF6]−, and [B(C6F5)4]− (TFAB)). The results showed that the reactivity of the electrogenerated osmocenium cation was dramatically affected by the coordinating properties of the electrolyte anion and the donor strength of the solvent. Cyclic voltammetry allowed the characterization of transient species and led to rationalization of some controversial mechanistic conclusions published before, which were in fact all correct, but referred to different conditions. Notably, the electrochemical signature of the dimer dication [Cp2Os]2 2+ that appears as a crucial species to explain the voltammetric oxidative pattern of osmocene was detected for the first time. © 2016 Elsevier Ltd},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
The electrochemical oxidation of osmocene was investigated in dichloromethane (DCM) and acetonitrile (MeCN) in the presence of various electrolyte anions ([BF4]−, [PF6]−, and [B(C6F5)4]− (TFAB)). The results showed that the reactivity of the electrogenerated osmocenium cation was dramatically affected by the coordinating properties of the electrolyte anion and the donor strength of the solvent. Cyclic voltammetry allowed the characterization of transient species and led to rationalization of some controversial mechanistic conclusions published before, which were in fact all correct, but referred to different conditions. Notably, the electrochemical signature of the dimer dication [Cp2Os]2 2+ that appears as a crucial species to explain the voltammetric oxidative pattern of osmocene was detected for the first time. © 2016 Elsevier Ltd |
2015
|
Access to new endoperoxide derivatives by electrochemical oxidation of substituted 3-azabicyclo[4.1.0]hept-4-enes Article de journal F Nuter; A K D Dimé; C Chen; L Bounaadja; E Mouray; I Florent; Y Six; O Buriez; A Marinetti; A Voituriez Chemistry - A European Journal, 21 (14), p. 5584–5593, 2015. @article{Nuter:2015,
title = {Access to new endoperoxide derivatives by electrochemical oxidation of substituted 3-azabicyclo[4.1.0]hept-4-enes},
author = {F Nuter and A K D Dim\'{e} and C Chen and L Bounaadja and E Mouray and I Florent and Y Six and O Buriez and A Marinetti and A Voituriez},
url = {https://www.scopus.com/inward/record.uri?eid=2-s2.0-84925132703&doi=10.1002%2fchem.201406138&partnerID=40&md5=74df69d010145a217a9973a363748bc7},
doi = {10.1002/chem.201406138},
year = {2015},
date = {2015-01-01},
journal = {Chemistry - A European Journal},
volume = {21},
number = {14},
pages = {5584--5593},
abstract = {A series of substituted 3-azabicyclo[4.1.0]hept-4-ene derivatives were prepared and analysed by cyclic voltammetry. Preparative aerobic electrochemical oxidation reactions were then carried out. Three original endoperoxides were isolated, characterised and subjected to antimalarial and cytotoxicity activity assays. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
A series of substituted 3-azabicyclo[4.1.0]hept-4-ene derivatives were prepared and analysed by cyclic voltammetry. Preparative aerobic electrochemical oxidation reactions were then carried out. Three original endoperoxides were isolated, characterised and subjected to antimalarial and cytotoxicity activity assays. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim. |
Electrochemically driven supramolecular interaction of quinones and ferrocifens: An example of redox activation of bioactive compounds Article de journal Y G De Paiva; F Da Rocha Ferreira; T L Silva; E Labbe; O Buriez; C Amatore; M O F Goulart Current Topics in Medicinal Chemistry, 15 (2), p. 136–162, 2015. @article{DePaiva:2015,
title = {Electrochemically driven supramolecular interaction of quinones and ferrocifens: An example of redox activation of bioactive compounds},
author = {Y G De Paiva and F Da Rocha Ferreira and T L Silva and E Labbe and O Buriez and C Amatore and M O F Goulart},
url = {https://www.scopus.com/inward/record.uri?eid=2-s2.0-84926286178&doi=10.2174%2f1568026615666141209155300&partnerID=40&md5=d4ea2f1cdfbb9b011dbf22d964fba992},
doi = {10.2174/1568026615666141209155300},
year = {2015},
date = {2015-01-01},
journal = {Current Topics in Medicinal Chemistry},
volume = {15},
number = {2},
pages = {136--162},
abstract = {This review discusses the state of the art, challenges and perspectives in recent applications of electrochemistry in the life sciences. It deals mainly with the elucidation of molecular mechanisms of drug action, drug design and development, involving electron transfer, pharmaco-electrochemistry (the combination of electrochemical and pharmacological assays), and electrochemical studies of membrane models and drug delivery. It aims to shed light on the question: does electrochemistry really contribute to this area? It includes a general introduction for the use of electrochemistry in the life sciences, with a focus on how electrochemistry can uniquely provide both kinetic and thermodynamic information. A number of studies are reported in the literature and from the authors’ laboratories, including the investigation of biooxidative/bioreductive activation of pro-drugs, DNA alkylation, electrochemically-based release of reactive oxygen and nitrogen species, with a particular emphasis on quinones, ferrocifens and compounds with mixed-functionality. Within the context of drug delivery and bioavailability, the electrochemical investigation of supramolecular interactions of the chosen classes of compounds with cyclodextrins and lipid bilayers, in relation to their solubilization and vectorization was also carried out. The updated examples herein illustrate how relevant and challenging the integration of electrochemistry, supramolecular and materials chemistry, biochemistry and medical knowledge for the design and development of redox-selective molecular approaches is. Many questions related to these fields are still unclear and the search for selectivity toward redox therapeutic agents remains of expanding interest. This review hopes to stimulate researchers to become more involved in this fruitful interface between electrochemistry and the life sciences. © 2015 Bentham Science Publishers.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
This review discusses the state of the art, challenges and perspectives in recent applications of electrochemistry in the life sciences. It deals mainly with the elucidation of molecular mechanisms of drug action, drug design and development, involving electron transfer, pharmaco-electrochemistry (the combination of electrochemical and pharmacological assays), and electrochemical studies of membrane models and drug delivery. It aims to shed light on the question: does electrochemistry really contribute to this area? It includes a general introduction for the use of electrochemistry in the life sciences, with a focus on how electrochemistry can uniquely provide both kinetic and thermodynamic information. A number of studies are reported in the literature and from the authors’ laboratories, including the investigation of biooxidative/bioreductive activation of pro-drugs, DNA alkylation, electrochemically-based release of reactive oxygen and nitrogen species, with a particular emphasis on quinones, ferrocifens and compounds with mixed-functionality. Within the context of drug delivery and bioavailability, the electrochemical investigation of supramolecular interactions of the chosen classes of compounds with cyclodextrins and lipid bilayers, in relation to their solubilization and vectorization was also carried out. The updated examples herein illustrate how relevant and challenging the integration of electrochemistry, supramolecular and materials chemistry, biochemistry and medical knowledge for the design and development of redox-selective molecular approaches is. Many questions related to these fields are still unclear and the search for selectivity toward redox therapeutic agents remains of expanding interest. This review hopes to stimulate researchers to become more involved in this fruitful interface between electrochemistry and the life sciences. © 2015 Bentham Science Publishers. |
Evaluation of photosynthetic electrons derivation by exogenous redox mediators Article de journal Guillaume Longatte; Han-Yi Fu; Olivier Buriez; Eric Labbé; Francis-André Wollman; Christian Amatore; Fabrice Rappaport; Manon Guille-Collignon; Frédéric Lemaître Biophysical Chemistry, 205 , p. 1-8, 2015. @article{RID:0721150706473-48b,
title = {Evaluation of photosynthetic electrons derivation by exogenous redox mediators},
author = {Guillaume Longatte and Han-Yi Fu and Olivier Buriez and Eric Labb\'{e} and Francis-Andr\'{e} Wollman and Christian Amatore and Fabrice Rappaport and Manon Guille-Collignon and Fr\'{e}d\'{e}ric Lema\^{i}tre},
year = {2015},
date = {2015-01-01},
journal = {Biophysical Chemistry},
volume = {205},
pages = {1-8},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
|
Synthesis, Characterization, and Biological Properties of Osmium-Based Tamoxifen Derivatives – Comparison with Their Homologues in the Iron and Ruthenium Series Article de journal Hui Zhi Shirley Lee; Olivier Buriez; François Chau; Eric Labbé; Rakesh Ganguly; Christian Amatore; Gérard Jaouen; Anne Vessières; Weng Kee Leong; Siden Top European Journal of Inorganic Chemistry, p. n/a, 2015. @article{RID:0827151219509-49b,
title = {Synthesis, Characterization, and Biological Properties of Osmium-Based Tamoxifen Derivatives \textendash Comparison with Their Homologues in the Iron and Ruthenium Series},
author = {Hui Zhi Shirley Lee and Olivier Buriez and Fran\c{c}ois Chau and Eric Labb\'{e} and Rakesh Ganguly and Christian Amatore and G\'{e}rard Jaouen and Anne Vessi\`{e}res and Weng Kee Leong and Siden Top},
year = {2015},
date = {2015-01-01},
journal = {European Journal of Inorganic Chemistry},
pages = {n/a},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
|
Three-electrode analytical and preparative electrochemistry in micro-volume hanging droplets Article de journal Ana Isabel Perez Jimenez; Lylian Challier; Margherita Di Pisa; Manon Guille-Collignon; Frédéric Lemaître; Solange Lavielle; Christelle Mansuy; Christian Amatore; Eric Labbé; Olivier Buriez Electrochemistry Communications, 54 (0), p. 41-45, 2015. @article{RID:0721150706473-46b,
title = {Three-electrode analytical and preparative electrochemistry in micro-volume hanging droplets},
author = {Ana Isabel Perez Jimenez and Lylian Challier and Margherita Di Pisa and Manon Guille-Collignon and Fr\'{e}d\'{e}ric Lema\^{i}tre and Solange Lavielle and Christelle Mansuy and Christian Amatore and Eric Labb\'{e} and Olivier Buriez},
year = {2015},
date = {2015-01-01},
journal = {Electrochemistry Communications},
volume = {54},
number = {0},
pages = {41-45},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
|
2014
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Electrochemically Driven Supramolecular Interaction of Quinones and Ferrocifens: An Example of Redox Activation of Bioactive Compounds Article de journal Paiva Yen G de; Rocha Ferreira Fabricia da; Thaissa Lucio Silva; Eric Labbe; Olivier Buriez; Christian Amatore; Goulart Marilia Oliveira Fonseca Curr Top Med Chem, 2014. @article{RID:0721150706473-45b,
title = {Electrochemically Driven Supramolecular Interaction of Quinones and Ferrocifens: An Example of Redox Activation of Bioactive Compounds},
author = {Paiva Yen G de and Rocha Ferreira Fabricia da and Thaissa Lucio Silva and Eric Labbe and Olivier Buriez and Christian Amatore and Goulart Marilia Oliveira Fonseca},
year = {2014},
date = {2014-01-01},
journal = {Curr Top Med Chem},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
|
Monitoring and Quantifying the Passive Transport of Molecules Through Patch–Clamp Suspended Real and Model Cell Membranes Article de journal Pierluca Messina; Frédéric Lemaître; François Huet; Kieu An Ngo; Vincent Vivier; Eric Labbé; Olivier Buriez; Christian Amatore Angewandte Chemie International Edition, p. n/a, 2014. @article{RID:0721150706473-40b,
title = {Monitoring and Quantifying the Passive Transport of Molecules Through Patch\textendashClamp Suspended Real and Model Cell Membranes},
author = {Pierluca Messina and Fr\'{e}d\'{e}ric Lema\^{i}tre and Fran\c{c}ois Huet and Kieu An Ngo and Vincent Vivier and Eric Labb\'{e} and Olivier Buriez and Christian Amatore},
year = {2014},
date = {2014-01-01},
journal = {Angewandte Chemie International Edition},
pages = {n/a},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
|
Oxidative Sequence of a Ruthenocene-Based Anticancer Drug Candidate in a Basic Environment Article de journal Hui Zhi Shirley Lee; Olivier Buriez; Eric Labbe; Siden Top; Pascal Pigeon; Gerard Jaouen; Christian Amatore; Weng Kee Leong Organometallics, 33 (18), p. 4940-4946, 2014. @article{RID:0721150706473-44b,
title = {Oxidative Sequence of a Ruthenocene-Based Anticancer Drug Candidate in a Basic Environment},
author = {Hui Zhi Shirley Lee and Olivier Buriez and Eric Labbe and Siden Top and Pascal Pigeon and Gerard Jaouen and Christian Amatore and Weng Kee Leong},
year = {2014},
date = {2014-01-01},
journal = {Organometallics},
volume = {33},
number = {18},
pages = {4940-4946},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
|
Uncovering the Missing Link between Molecular Electrochemistry and Electrocatalysis: Mechanism of the Reduction of Benzyl Chloride at Silver Cathodes Article de journal Oleksiy V Klymenko; Olivier Buriez; Eric Labbé; Dong-Ping Zhan; Sandra Rondinini; Zhong-Qun Tian; Irina Svir; Christian Amatore ChemElectroChem, 1 (1), p. 227-240, 2014. @article{RID:0721150706474-41b,
title = {Uncovering the Missing Link between Molecular Electrochemistry and Electrocatalysis: Mechanism of the Reduction of Benzyl Chloride at Silver Cathodes},
author = {Oleksiy V Klymenko and Olivier Buriez and Eric Labb\'{e} and Dong-Ping Zhan and Sandra Rondinini and Zhong-Qun Tian and Irina Svir and Christian Amatore},
year = {2014},
date = {2014-01-01},
journal = {ChemElectroChem},
volume = {1},
number = {1},
pages = {227-240},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
|
2013
|
Electrochemistry and Supramolecular Interactions of “Ferrocifen” Anticancer Drugs with Cyclodextrins and Lipid Bilayers: An Electrochemical Overview Book Chapter Olivier Buriez; Eric Labbé; Christian Amatore Advances in Organometallic Chemistry and Catalysis, p. 631-651, 2013. @inbook{RID:0721150706474-43,
title = {Electrochemistry and Supramolecular Interactions of “Ferrocifen” Anticancer Drugs with Cyclodextrins and Lipid Bilayers: An Electrochemical Overview},
author = {Olivier Buriez and Eric Labb\'{e} and Christian Amatore},
year = {2013},
date = {2013-01-01},
booktitle = {Advances in Organometallic Chemistry and Catalysis},
pages = {631-651},
keywords = {},
pubstate = {published},
tppubtype = {inbook}
}
|
NHC-capped cyclodextrins (ICyDs): Insulated metal complexes, commutable multicoordination sphere, and cavity-dependent catalysis Article de journal M Guitet; P Zhang; F Marcelo; C Tugny; J Jiménez-Barbero; O Buriez; C Amatore; V Mouriès-Mansuy; J -P Goddard; L Fensterbank; Y Zhang; S Roland; M Ménand; M Sollogoub Angewandte Chemie - International Edition, 52 (28), p. 7213–7218, 2013. @article{Guitet:2013,
title = {NHC-capped cyclodextrins (ICyDs): Insulated metal complexes, commutable multicoordination sphere, and cavity-dependent catalysis},
author = {M Guitet and P Zhang and F Marcelo and C Tugny and J Jim\'{e}nez-Barbero and O Buriez and C Amatore and V Mouri\`{e}s-Mansuy and J -P Goddard and L Fensterbank and Y Zhang and S Roland and M M\'{e}nand and M Sollogoub},
url = {https://www.scopus.com/inward/record.uri?eid=2-s2.0-84880180264&doi=10.1002%2fanie.201301225&partnerID=40&md5=35bafe7534b6206686defb64d4d4e698},
doi = {10.1002/anie.201301225},
year = {2013},
date = {2013-01-01},
journal = {Angewandte Chemie - International Edition},
volume = {52},
number = {28},
pages = {7213--7218},
abstract = {Don't slam the door! Cyclodextrins capped with an N-heterocyclic carbene (ICyDs) entrapped metal ions within their cavity through a novel set of interactions, including X×××π, which enabled the cavity to be closed by ligand exchange (see scheme; Bn=benzyl). Although insulated from an electrode, the deeply buried metal ions retained catalytic activity. The cavity influenced the regio- and stereochemical outcome of the catalyzed reactions. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
Don't slam the door! Cyclodextrins capped with an N-heterocyclic carbene (ICyDs) entrapped metal ions within their cavity through a novel set of interactions, including X×××π, which enabled the cavity to be closed by ligand exchange (see scheme; Bn=benzyl). Although insulated from an electrode, the deeply buried metal ions retained catalytic activity. The cavity influenced the regio- and stereochemical outcome of the catalyzed reactions. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim. |
Surface grafting of a π-conjugated amino-ferrocifen drug Article de journal O Buriez; F I Podvorica; A Galtayries; E Labbé; S Top; A Vessières; G Jaouen; C Combellas; C Amatore Journal of Electroanalytical Chemistry, 699 , p. 21–27, 2013. @article{Buriez:2013,
title = {Surface grafting of a π-conjugated amino-ferrocifen drug},
author = {O Buriez and F I Podvorica and A Galtayries and E Labb\'{e} and S Top and A Vessi\`{e}res and G Jaouen and C Combellas and C Amatore},
url = {https://www.scopus.com/inward/record.uri?eid=2-s2.0-84877353375&doi=10.1016%2fj.jelechem.2013.04.004&partnerID=40&md5=cc8f92b1f9773aaf470dc72898d53827},
doi = {10.1016/j.jelechem.2013.04.004},
year = {2013},
date = {2013-01-01},
journal = {Journal of Electroanalytical Chemistry},
volume = {699},
pages = {21--27},
abstract = {The electrochemical grafting of a π-conjugated amino-ferrocifen complex (1) at gold surfaces may be achieved through the direct electrochemical oxidation of the amino group (+0.9 V/SCE) but is prone to proceed also indirectly through the oxidation of the ferrocene moiety (+0.45 V). The modification and characterization of the gold electrode surfaces are demonstrated by cyclic voltammetry, ellipsometry, Infra-Red Reflection- Absorption Spectroscopy (IRRAS), Time-of-Flight Secondary Ion Mass Spectrometry (ToF-SIMS), and X-ray Photoelectron Spectroscopy (XPS). Combination of these techniques clearly demonstrates that (1) is covalently attached to the gold surfaces via an AuNH bond. The crucial role played by the electrogenerated aminyl radical in the grafting process is highlighted. This transient species, which is responsible for the covalent grafting of (1) onto the gold surface was also found able to react with the amino-ferrocifen parent complex to form multilayers. This detailed characterization of the grafted electrode surface finally brings insight into the overall mechanistic frame related to the grafting of conjugated amino compounds and, consequently, allowing establishing definitively the occurrence of the intramolecular redox catalysis process which is key to their cytotoxic properties against cancer cells. © 2013 Elsevier Inc. All rights reserved.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
The electrochemical grafting of a π-conjugated amino-ferrocifen complex (1) at gold surfaces may be achieved through the direct electrochemical oxidation of the amino group (+0.9 V/SCE) but is prone to proceed also indirectly through the oxidation of the ferrocene moiety (+0.45 V). The modification and characterization of the gold electrode surfaces are demonstrated by cyclic voltammetry, ellipsometry, Infra-Red Reflection- Absorption Spectroscopy (IRRAS), Time-of-Flight Secondary Ion Mass Spectrometry (ToF-SIMS), and X-ray Photoelectron Spectroscopy (XPS). Combination of these techniques clearly demonstrates that (1) is covalently attached to the gold surfaces via an AuNH bond. The crucial role played by the electrogenerated aminyl radical in the grafting process is highlighted. This transient species, which is responsible for the covalent grafting of (1) onto the gold surface was also found able to react with the amino-ferrocifen parent complex to form multilayers. This detailed characterization of the grafted electrode surface finally brings insight into the overall mechanistic frame related to the grafting of conjugated amino compounds and, consequently, allowing establishing definitively the occurrence of the intramolecular redox catalysis process which is key to their cytotoxic properties against cancer cells. © 2013 Elsevier Inc. All rights reserved. |