Directeur de recherche
ENS – Département de chimie
24 rue Lhomond, 75005 Paris
Email: olivier.buriez@ens.psl.eu
Phone: 0144323262
Office: E010
Short bio
Olivier Buriez is a Molecular Electrochemist. During his PhD, performed under the supervision of Drs Christian Amatore & Jean-Noël Verpeaux (ENS-Paris), he addressed the reactivity of organometallic complexes activated by electron transfer. Then, he joined the groups of J.B. Kerr and R.H. Fish at the Berkeley Lab. (LBNL, Univ. of California, USA) to investigate the structure-activity relationships and mechanistic aspects of bioorganometallic compounds. In 1999, he obtained a CNRS permanent position in the group of J. Périchon (LECSO lab.) where he used electrochemistry to understand mechanisms involved in metal-catalyzed electro-reductive processes. In 2006, he moved back to ENS to address the reactivity and transport issues related to biological molecules. Since 2015, he’s Officer of the Molecular Electrochemistry Division of the International Society of Electrochemistry (ISE).
Education and professional experience
- Since 2006 CNRS Researcher at ENS, Paris
- 2005 Habilitation
- 1999-2005 CNRS Researcher, LECSO lab., Thiais, France
- 1997-1999 Post doc at the Berkeley lab. (LBNL), USA
- 1996-1997 Assistant Professor, Université Paris XII
- 1993-1996 PhD Thesis, ENS, Paris
Research interests
- Keywords: Electrochemistry; Reactivity; Mechanisms; (bio)-Molecules; Fluorescence; Luminescence
Our ambition is to bring new insights and new entries in major issues such as the metabolism (i.e., the chemical transformations) and the distribution (i.e., the transmembrane passages) of molecules possessing therapeutic properties through lipid membranes. Within this context, we adapt our electrochemical procedures to the experimental constraints of the phenomena investigated rather than adapting the phenomena to our methods. Combining electrochemistry and fluorescence microscopy is a typical example of this guideline.
Significant publications
- “The Fundamental Input of Analytical Electrochemistry in the Determination of Intermediates and Reaction Mechanisms in Electrosynthetic Processes.” ChemElectroChem Minireview 2019 DOI 10.1002/celc.201900045
- “Redox switchable rhodamine-ferrocene dyad: Exploring imaging possibilities in cells.” Electrochemistry Communications, 2018, 97, 46.
- “Selective Electrochemical Bleaching of the Outer Leaflet of Fluorescently Labelled Giant Liposomes.” Chem. Eur.J., 2017, 23, 6781. Front Cover Picture.
- “Monitoring and Quantifying the Passive Transport of Molecules Through Patch–Clamp Suspended Real and Model Cell Membranes.” Angew. Chem. Int Ed. , 2014, 53, 3192. Key Scientific Article of the Global Medical Discovery newsfeed.
- “Electrochemical aerobic oxidation of aminocyclopropanes to endoperoxides”. Angew. Chem. Int Ed. , 2007, 46, 8046.
Publications (full record)
Publications
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. |
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. |
2013 |
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. |
J D J Cázares-Marinero; O Buriez; E Labbé; S Top; C Amatore; G Jaouen Organometallics, 32 (20), p. 5926–5934, 2013. @article{Cazares-Marinero:2013, title = {Synthesis, characterization, and antiproliferative activities of novel ferrocenophanic suberamides against human triple-negative MDA-MB-231 and hormone-dependent MCF-7 breast cancer cells}, author = {J D J C\'{a}zares-Marinero and O Buriez and E Labb\'{e} and S Top and C Amatore and G Jaouen}, url = {https://www.scopus.com/inward/record.uri?eid=2-s2.0-84887042245&doi=10.1021%2fom400490a&partnerID=40&md5=efad7ad74b52eb66a59d23ca2a8a9b3e}, doi = {10.1021/om400490a}, year = {2013}, date = {2013-01-01}, journal = {Organometallics}, volume = {32}, number = {20}, pages = {5926--5934}, abstract = {We report the synthesis and characterization of a new family of organometallic suberamides with strong antiproliferative activities against triple-negative MDA-MB-231 breast cancer cell lines with IC50 values ranging from 0.84 to 0.94 μM. Similar studies on hormone-dependent MCF-7 breast cancer cells were also carried out, revealing the positive effect of the ferrocenophanic moiety on disubstituted ferrocene-1,1′-diyl derivatives versus their monosubstituted ferrocenyl analogues. Cyclic voltammetry analysis showed no substantial differences between ferrocenic and ferrocenophanic suberamides in the absence or presence of a base. However, similar studies performed on related compounds strongly suggest that ferrocenophanic and ferrocenic complexes do not undergo the same redox activation patterns. The electrochemical behavior seems to be in agreement with the antiproliferative activity of this type of organometallic compound. © 2013 American Chemical Society.}, keywords = {}, pubstate = {published}, tppubtype = {article} } We report the synthesis and characterization of a new family of organometallic suberamides with strong antiproliferative activities against triple-negative MDA-MB-231 breast cancer cell lines with IC50 values ranging from 0.84 to 0.94 μM. Similar studies on hormone-dependent MCF-7 breast cancer cells were also carried out, revealing the positive effect of the ferrocenophanic moiety on disubstituted ferrocene-1,1′-diyl derivatives versus their monosubstituted ferrocenyl analogues. Cyclic voltammetry analysis showed no substantial differences between ferrocenic and ferrocenophanic suberamides in the absence or presence of a base. However, similar studies performed on related compounds strongly suggest that ferrocenophanic and ferrocenic complexes do not undergo the same redox activation patterns. The electrochemical behavior seems to be in agreement with the antiproliferative activity of this type of organometallic compound. © 2013 American Chemical Society. |
J De Jesús Cázares-Marinero; E Labbé; S Top; O Buriez; C Amatore; G Jaouen Journal of Organometallic Chemistry, 744 , p. 92–100, 2013. @article{DeJesusCazares-Marinero:2013, title = {The effect of protic electron donor aromatic substituents on ferrocenic and [3]ferrocenophanic anilines and anilides: Some aspects of structureeactivity relationship studies on organometallic compounds with strong antiproliferative effects}, author = {J De Jes\'{u}s C\'{a}zares-Marinero and E Labb\'{e} and S Top and O Buriez and C Amatore and G Jaouen}, url = {https://www.scopus.com/inward/record.uri?eid=2-s2.0-84884534415&doi=10.1016%2fj.jorganchem.2013.05.047&partnerID=40&md5=8eb52ab8222684eaee90937ebd7e591c}, doi = {10.1016/j.jorganchem.2013.05.047}, year = {2013}, date = {2013-01-01}, journal = {Journal of Organometallic Chemistry}, volume = {744}, pages = {92--100}, abstract = {A new family of nitrogenous derivatives is synthesized, characterized and evaluated for the investigation of the impact of some structural motifs such as functionalization and conjugation on the antiproliferative activity of ferrocenic complexes against cancer cells. These compounds are 4,40-([3]ferrocenophan-1-ylidenemethylene)dianilides and tetramethylated dianilines derived from Michler's ketone. An alternative McMurry direct heterocoupling method for 4,40-([3]ferrocenophan-1-ylidenemethylene)dianiline synthesis is described and electrochemical studies are also discussed. © 2013 Elsevier B.V. All rights reserved.}, keywords = {}, pubstate = {published}, tppubtype = {article} } A new family of nitrogenous derivatives is synthesized, characterized and evaluated for the investigation of the impact of some structural motifs such as functionalization and conjugation on the antiproliferative activity of ferrocenic complexes against cancer cells. These compounds are 4,40-([3]ferrocenophan-1-ylidenemethylene)dianilides and tetramethylated dianilines derived from Michler's ketone. An alternative McMurry direct heterocoupling method for 4,40-([3]ferrocenophan-1-ylidenemethylene)dianiline synthesis is described and electrochemical studies are also discussed. © 2013 Elsevier B.V. All rights reserved. |
2012 |
Deciphering the activation sequence of ferrociphenol anticancer drug candidates Article de journal P Messina; E Labbé; O Buriez; E A Hillard; A Vessières; D Hamels; S Top; G Jaouen; Y M Frapart; D Mansuy; C Amatore Chemistry - A European Journal, 18 (21), p. 6581–6587, 2012. @article{Messina:2012, title = {Deciphering the activation sequence of ferrociphenol anticancer drug candidates}, author = {P Messina and E Labb\'{e} and O Buriez and E A Hillard and A Vessi\`{e}res and D Hamels and S Top and G Jaouen and Y M Frapart and D Mansuy and C Amatore}, url = {https://www.scopus.com/inward/record.uri?eid=2-s2.0-84861159405&doi=10.1002%2fchem.201103378&partnerID=40&md5=bf764a18b4bd832d2149e1a5cbc90875}, doi = {10.1002/chem.201103378}, year = {2012}, date = {2012-01-01}, journal = {Chemistry - A European Journal}, volume = {18}, number = {21}, pages = {6581--6587}, abstract = {The complete oxidation sequence of a model for ferrociphenols, a new class of anticancer drug candidate, is reported. Cyclic voltammetry was used to monitor the formation of oxidation intermediates on different timescales, thereby allowing the electrochemical characterization of both the short-lived and stable species obtained from the successive electron-transfer and deprotonation steps. The electrochemical preparation of the ferrocenium intermediate enabled a stepwise voltammetric determination of the stable oxidation compounds obtained upon addition of a base as well as the electron stoichiometry observed for the overall oxidation process. A mechanism has been established from the electrochemical data, which involves a base-promoted intramolecular electron transfer between the phenol and the ferrocenium cation. The resulting species is further oxidized then deprotonated to yield a stable quinone methide. To further characterize the transient species successively formed during the two-electron oxidation of the ferrociphenol to its quinone methide, EPR was used to monitor the fate of the paramagnetic species generated upon addition of imidazole to the electrogenerated ferrocenium. The study revealed the passage from an iron-centered to a carbon-centered radical, which is then oxidized to yield the quinone methide, namely, the species that interacts with proteins and so forth under biological conditions. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.}, keywords = {}, pubstate = {published}, tppubtype = {article} } The complete oxidation sequence of a model for ferrociphenols, a new class of anticancer drug candidate, is reported. Cyclic voltammetry was used to monitor the formation of oxidation intermediates on different timescales, thereby allowing the electrochemical characterization of both the short-lived and stable species obtained from the successive electron-transfer and deprotonation steps. The electrochemical preparation of the ferrocenium intermediate enabled a stepwise voltammetric determination of the stable oxidation compounds obtained upon addition of a base as well as the electron stoichiometry observed for the overall oxidation process. A mechanism has been established from the electrochemical data, which involves a base-promoted intramolecular electron transfer between the phenol and the ferrocenium cation. The resulting species is further oxidized then deprotonated to yield a stable quinone methide. To further characterize the transient species successively formed during the two-electron oxidation of the ferrociphenol to its quinone methide, EPR was used to monitor the fate of the paramagnetic species generated upon addition of imidazole to the electrogenerated ferrocenium. The study revealed the passage from an iron-centered to a carbon-centered radical, which is then oxidized to yield the quinone methide, namely, the species that interacts with proteins and so forth under biological conditions. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim. |
Direct electrochemical reduction of organic halide droplets dispersed in water Article de journal E Deunf; E Labbé; J N Verpeaux; O Buriez; C Amatore RSC Advances, 2 (12), p. 5398–5402, 2012. @article{Deunf:2012, title = {Direct electrochemical reduction of organic halide droplets dispersed in water}, author = {E Deunf and E Labb\'{e} and J N Verpeaux and O Buriez and C Amatore}, url = {https://www.scopus.com/inward/record.uri?eid=2-s2.0-84893242167&doi=10.1039%2fc2ra20215h&partnerID=40&md5=0fb6823ae35567936f7b5119862facae}, doi = {10.1039/c2ra20215h}, year = {2012}, date = {2012-01-01}, journal = {RSC Advances}, volume = {2}, number = {12}, pages = {5398--5402}, abstract = {The direct electroreductive homocoupling of benzyl bromide has been efficiently achieved using water as the solvent. This process does not involve any organic co-solvent, transition metal catalyst, oil, surfactants, but only a cheap and non-toxic supporting electrolyte (KCl). Benzyl bromide droplets dispersed in water were reduced at a low current density, in an undivided cell fitted with a sacrificial aluminum anode. Various cathode materials have been tested (Ni, Pt, C, Ag) to favor organic halide reduction versus hydrogen evolution. Moreover, it was shown that the presence of aluminum cations generated by the oxidation of the anode played a crucial role in the efficiency of the electrochemical reduction step. Surprisingly, this property was exalted in acidic solutions (pH = 1). Under such acidic conditions, both bibenzyl proportion and faradaic yields were considerably improved. The electrochemical activation of energetically stronger C-X bonds such as those encountered in benzyl chloride (Csp3-Cl) or ethyl 4-iodobenzoate (Csp2-I) could be also achieved in water though resulted in lower faradaic yields. From a mechanistic point of view, both the faradaic yields and the product distribution obtained under various conditions suggested the occurrence of a radical coupling pathway occurring within the organic droplets or at their surface. © 2012 The Royal Society of Chemistry.}, keywords = {}, pubstate = {published}, tppubtype = {article} } The direct electroreductive homocoupling of benzyl bromide has been efficiently achieved using water as the solvent. This process does not involve any organic co-solvent, transition metal catalyst, oil, surfactants, but only a cheap and non-toxic supporting electrolyte (KCl). Benzyl bromide droplets dispersed in water were reduced at a low current density, in an undivided cell fitted with a sacrificial aluminum anode. Various cathode materials have been tested (Ni, Pt, C, Ag) to favor organic halide reduction versus hydrogen evolution. Moreover, it was shown that the presence of aluminum cations generated by the oxidation of the anode played a crucial role in the efficiency of the electrochemical reduction step. Surprisingly, this property was exalted in acidic solutions (pH = 1). Under such acidic conditions, both bibenzyl proportion and faradaic yields were considerably improved. The electrochemical activation of energetically stronger C-X bonds such as those encountered in benzyl chloride (Csp3-Cl) or ethyl 4-iodobenzoate (Csp2-I) could be also achieved in water though resulted in lower faradaic yields. From a mechanistic point of view, both the faradaic yields and the product distribution obtained under various conditions suggested the occurrence of a radical coupling pathway occurring within the organic droplets or at their surface. © 2012 The Royal Society of Chemistry. |
Ferrocenyl catechols: Synthesis, oxidation chemistry and anti-proliferative effects on MDA-MB-231 breast cancer cells Article de journal Y L K Tan; P Pigeon; S Top; E Labbé; O Buriez; E A Hillard; A Vessières; C Amatore; W K Leong; G Jaouen Dalton Transactions, 41 (25), p. 7537–7549, 2012. @article{Tan:2012, title = {Ferrocenyl catechols: Synthesis, oxidation chemistry and anti-proliferative effects on MDA-MB-231 breast cancer cells}, author = {Y L K Tan and P Pigeon and S Top and E Labb\'{e} and O Buriez and E A Hillard and A Vessi\`{e}res and C Amatore and W K Leong and G Jaouen}, url = {https://www.scopus.com/inward/record.uri?eid=2-s2.0-84862232784&doi=10.1039%2fc2dt30700f&partnerID=40&md5=45db7f469e25a5ee6075e706de5e52a9}, doi = {10.1039/c2dt30700f}, year = {2012}, date = {2012-01-01}, journal = {Dalton Transactions}, volume = {41}, number = {25}, pages = {7537--7549}, abstract = {The synthesis and anti-tumoral properties of a series of compounds possessing a ferrocenyl group tethered to a catechol via a conjugated system is presented. On MDA-MB-231 breast cancer cell lines, the catechol compounds display a similar or greater anti-proliferative potency (IC 50 values ranging from 0.48-1.21 μM) than their corresponding phenolic analogues (0.57-12.7 μM), with the highest activity found for species incorporating the [3]ferrocenophane motif. On the electrochemical timescale, phenolic compounds appear to oxidize to the quinone methide, while catechol moieties form the o-quinone by a similar mechanism. Chemical oxidation of selected compounds with Ag 2O confirms this interpretation and demonstrates the probable involvement of such oxidative metabolites in the in vitro activity of these species. © 2012 The Royal Society of Chemistry.}, keywords = {}, pubstate = {published}, tppubtype = {article} } The synthesis and anti-tumoral properties of a series of compounds possessing a ferrocenyl group tethered to a catechol via a conjugated system is presented. On MDA-MB-231 breast cancer cell lines, the catechol compounds display a similar or greater anti-proliferative potency (IC 50 values ranging from 0.48-1.21 μM) than their corresponding phenolic analogues (0.57-12.7 μM), with the highest activity found for species incorporating the [3]ferrocenophane motif. On the electrochemical timescale, phenolic compounds appear to oxidize to the quinone methide, while catechol moieties form the o-quinone by a similar mechanism. Chemical oxidation of selected compounds with Ag 2O confirms this interpretation and demonstrates the probable involvement of such oxidative metabolites in the in vitro activity of these species. © 2012 The Royal Society of Chemistry. |
2011 |
Electrochemical Analysis of the Interactions and Reactivity of Ferrocene-Based Drugs with a Lipid Environment: A Qualitative Overview Article de journal O Mertins; P Messina; E Labbe; V Vivier; S Arbault; F Lemaitre; O Buriez; C Amatore Inorganica Chimica Acta, 374 (1), p. 59-68, 2011, ISSN: 0020-1693. @article{RN24b, title = {Electrochemical Analysis of the Interactions and Reactivity of Ferrocene-Based Drugs with a Lipid Environment: A Qualitative Overview}, author = {O Mertins and P Messina and E Labbe and V Vivier and S Arbault and F Lemaitre and O Buriez and C Amatore}, doi = {10.1016/j.ica.2011.04.030}, issn = {0020-1693}, year = {2011}, date = {2011-01-01}, journal = {Inorganica Chimica Acta}, volume = {374}, number = {1}, pages = {59-68}, keywords = {}, pubstate = {published}, tppubtype = {article} } |
Kinetic investigations of the electrochemical bromination of peracetylated d-glucal in organic solvents Article de journal D Šegan; R D Vukićević; S Šegan; N Sojic; O Buriez; D Manojlović Electrochimica Acta, 56 (27), p. 9968–9972, 2011. @article{Segan:2011, title = {Kinetic investigations of the electrochemical bromination of peracetylated d-glucal in organic solvents}, author = {D \v{S}egan and R D Vuki\'{c}evi\'{c} and S \v{S}egan and N Sojic and O Buriez and D Manojlovi\'{c}}, url = {https://www.scopus.com/inward/record.uri?eid=2-s2.0-80054931632&doi=10.1016%2fj.electacta.2011.08.085&partnerID=40&md5=c6c44f6eb1b98fe587e4e5ac623bb3d4}, doi = {10.1016/j.electacta.2011.08.085}, year = {2011}, date = {2011-01-01}, journal = {Electrochimica Acta}, volume = {56}, number = {27}, pages = {9968--9972}, abstract = {Cyclic voltammetry and ultramicroelectrodes were used to investigate the kinetic aspects of the electrochemical bromination of 3,4,6-tri-O-acetyl-d- glucal (1) in acetonitrile (AN), dichloromethane (DCM), and dimethylsulfoxide (DMSO). Qualitative and quantitative results, determined notably from the kinetic parameter [glucal]/v representing the competition between glucal concentration and time, clearly showed that glucal bromination depended on the nature of both the solvent and the in situ electrogenerated reactive brominated species (Br2 or Br3 -) obtained from the oxidation of a bromide salt. It was especially shown that Br2 reacted more rapidly than Br3 - towards (1). On the other hand, the reactivity of both brominated species appeared to follow the solvent polarity order since the highest reactivity was obtained in DMSO whereas the lowest one was found in DCM. © 2011 Elsevier Ltd. All Rights Reserved.}, keywords = {}, pubstate = {published}, tppubtype = {article} } Cyclic voltammetry and ultramicroelectrodes were used to investigate the kinetic aspects of the electrochemical bromination of 3,4,6-tri-O-acetyl-d- glucal (1) in acetonitrile (AN), dichloromethane (DCM), and dimethylsulfoxide (DMSO). Qualitative and quantitative results, determined notably from the kinetic parameter [glucal]/v representing the competition between glucal concentration and time, clearly showed that glucal bromination depended on the nature of both the solvent and the in situ electrogenerated reactive brominated species (Br2 or Br3 -) obtained from the oxidation of a bromide salt. It was especially shown that Br2 reacted more rapidly than Br3 - towards (1). On the other hand, the reactivity of both brominated species appeared to follow the solvent polarity order since the highest reactivity was obtained in DMSO whereas the lowest one was found in DCM. © 2011 Elsevier Ltd. All Rights Reserved. |
Tailoring Au-core Pd-shell Pt-cluster nanoparticles for enhanced electrocatalytic activity Article de journal P -P Fang; S Duan; X -D Lin; J R Anema; J -F Li; O Buriez; Y Ding; F -R Fan; D -Y Wu; B Ren; Z L Wang; C Amatore; Z -Q Tian Chemical Science, 2 (3), p. 531–539, 2011. @article{Fang:2011a, title = {Tailoring Au-core Pd-shell Pt-cluster nanoparticles for enhanced electrocatalytic activity}, author = {P -P Fang and S Duan and X -D Lin and J R Anema and J -F Li and O Buriez and Y Ding and F -R Fan and D -Y Wu and B Ren and Z L Wang and C Amatore and Z -Q Tian}, url = {https://www.scopus.com/inward/record.uri?eid=2-s2.0-79952659758&doi=10.1039%2fc0sc00489h&partnerID=40&md5=3667f2602024e8684887359041c3e9d7}, doi = {10.1039/c0sc00489h}, year = {2011}, date = {2011-01-01}, journal = {Chemical Science}, volume = {2}, number = {3}, pages = {531--539}, abstract = {We have rationally synthesized and optimized catalytic nanoparticles consisting of a gold core, covered by a palladium shell, onto which platinum clusters are deposited (Au@Pd@Pt NPs). The amount of Pt and Pd used is extremely small, yet they show unusually high activity for electrooxidation of formic acid. The optimized structure has only 2 atomic layers of Pd and a half-monolayer equivalent of Pt (θPt ≈ 0.5) but a further increase in the loading of Pd or Pt will actually reduce catalytic activity, inferring that a synergistic effect exists between the three different nanostructure components (sphere, shell and islands). A combined electrochemical, surface-enhanced Raman scattering (SERS) and density functional theory (DFT) study of formic acid and CO oxidation reveals that our core-shell-cluster trimetallic nanostructure has some unique electronic and morphological properties, and that it could be the first in a new family of nanocatalysts possessing unusually high chemical reactivity. Our results are immediately applicable to the design of catalysts for direct formic acid fuel cells (DFAFCs). © The Royal Society of Chemistry 2011.}, keywords = {}, pubstate = {published}, tppubtype = {article} } We have rationally synthesized and optimized catalytic nanoparticles consisting of a gold core, covered by a palladium shell, onto which platinum clusters are deposited (Au@Pd@Pt NPs). The amount of Pt and Pd used is extremely small, yet they show unusually high activity for electrooxidation of formic acid. The optimized structure has only 2 atomic layers of Pd and a half-monolayer equivalent of Pt (θPt ≈ 0.5) but a further increase in the loading of Pd or Pt will actually reduce catalytic activity, inferring that a synergistic effect exists between the three different nanostructure components (sphere, shell and islands). A combined electrochemical, surface-enhanced Raman scattering (SERS) and density functional theory (DFT) study of formic acid and CO oxidation reveals that our core-shell-cluster trimetallic nanostructure has some unique electronic and morphological properties, and that it could be the first in a new family of nanocatalysts possessing unusually high chemical reactivity. Our results are immediately applicable to the design of catalysts for direct formic acid fuel cells (DFAFCs). © The Royal Society of Chemistry 2011. |
2010 |
Aminocyclopropanes as precursors of endoperoxides with antimalarial activity Article de journal C Madelaine; O Buriez; B Crousse; I Florent; P Grellier; P Retailleau; Y Six Organic and Biomolecular Chemistry, 8 (24), p. 5591–5601, 2010. @article{Madelaine:2010, title = {Aminocyclopropanes as precursors of endoperoxides with antimalarial activity}, author = {C Madelaine and O Buriez and B Crousse and I Florent and P Grellier and P Retailleau and Y Six}, url = {https://www.scopus.com/inward/record.uri?eid=2-s2.0-78649506056&doi=10.1039%2fc0ob00308e&partnerID=40&md5=f96ad4b84369abf15d7e7587373db1d1}, doi = {10.1039/c0ob00308e}, year = {2010}, date = {2010-01-01}, journal = {Organic and Biomolecular Chemistry}, volume = {8}, number = {24}, pages = {5591--5601}, abstract = {This contribution describes the synthesis of several novel bicyclic α-amino endoperoxides, including CF3-substituted compounds, prepared by the aerobic electrochemical oxidation of a family of bicyclic aminocyclopropanes. These, in turn, are readily synthesised by a titanium-mediated intramolecular cyclopropanation process (Kulinkovich-de Meijere reaction), starting from N-alkenyl amides that contain a vic-disubstituted double bond, with high diastereoselectivity. An evaluation of the biological activities of several of the molecules produced, against the parasite Plasmodium falciparum, is also presented. © 2010 The Royal Society of Chemistry.}, keywords = {}, pubstate = {published}, tppubtype = {article} } This contribution describes the synthesis of several novel bicyclic α-amino endoperoxides, including CF3-substituted compounds, prepared by the aerobic electrochemical oxidation of a family of bicyclic aminocyclopropanes. These, in turn, are readily synthesised by a titanium-mediated intramolecular cyclopropanation process (Kulinkovich-de Meijere reaction), starting from N-alkenyl amides that contain a vic-disubstituted double bond, with high diastereoselectivity. An evaluation of the biological activities of several of the molecules produced, against the parasite Plasmodium falciparum, is also presented. © 2010 The Royal Society of Chemistry. |