Molecular assemblies and complex systems

Group leader: Josef HAMACEK

Research theme

Research activities of the group are mainly focused on design, synthesis and characterization of molecular and supramolecular systems of varied complexity. We are interested in a better understanding of structural factors, intra- and intermolecular interactions, thermodynamic and kinetic equilibria within these assemblies or mixtures, and their exploiting for biomedical applications and imaging, nanomaterials and cosmetics. Our approach is interdisciplinary and requires competences in chemistry, biochemistry and biophysics. Few research subjects are presented in more details below, but the list is non-exhaustive. If you would be interested in joining us (at any level: student, researcher, etc.), don’t hesitate to contact us. Actual information can be found at the group website.

If you wish to collaborate with us or join us at the laboratory (trainee level, engineer, researcher, etc.), we will be delighted to welcome you.

On the other hand, if you wish to use the services of the spectroscopic facility of the CBM, do not hesitate to contact us. 

Self-assembled polymetallic complexes

Polynuclear compounds with lanthanides can be advantageously prepared using a supramolecular synthetic approach. The preparation of self-assembled stable systems, where many factors must be taken into account, is not an easy task. In this context, an effort has been made in the design and synthesis of suitable ligands to provide and characterize precursors (polytopic ligands and their complexes) for different applications. Detailed thermodynamic speciation studies of supramolecular complexes with different lanthanide cations are carried out by NMR and different spectroscopic methods (Functionalized Triptycene-Derived Tripodal Ligands : Privileged Formation of Tetranuclear Cage Assemblies with Larger Ln(III). Inorg. Chem. (2017) 56, 2742-2749 - doi : 10.1021/acs.inorgchem.6b02900 - Vuillamy A., Zebret S., Besnard C., Placide V., Petoud S. and Hamacek J.). Between the most important achievements we can highlight the self-assembly of octanuclear helicates Ln8L4 (Designing Artificial 3D helicates: unprecedented self-assembly of Homo-octanuclear Tetrapods with Europium Chem. Eur. J. 2015, 21, 6695-6699 - doi : 10.1002/chem.201500006 - Dr. Soumalia Zebret, Eliane Vögele, Dr. Tomas Klumper, Prof. Josef Hamacek)

Supramolecular Complexes of Lanthanides

The majority of our ligands are so-called “tripods” (tripodal ligands), which can form, in principle, Ln(III) complexes of different structure and nuclearity. (Understanding the Speciation of Ln(III) complexes with octadentale tripodal ligands - New J.chem (2017) 41, 4390-4399 - doi : 10.1039/C7NJ00088j - El Aroussi B. and Hamacek J.)

(Synthetic routes to large tripodal organic receptors and the structurral characterisation of intermediates - Tetrahedron (2016) 72, 928-935 - doi : 10.1016/j.tet.2015.12.048 - Zebret.s, Vogele E., Besnard C. and Hamacek J.)

(Ln(III) complexes with triptycene based tripodal ligands: speciation and equilibria - New J.Chem(2018), 42, 7803-7809 - doi : 10.1039/C8NJ00252E - Josef Hamacek, Alexandra Vuillamy, Lisa Perhans, Laexandre Homberg, Daniele Poggiali, Markus W. Schneider, Michael Mastalerz)

The thermodynamic principles of self-assemblies with lanthanides have been discussed in details in the book “Metallofoldamers : Supramolecular Architectures
from Helicates to Biomimetics.”
(Eds. : Albrecht M. and, Maayan G., Wiley 2013).

Enzymatic Kinetics in Complex Media

This work is carried out in collaboration with Francesco Piazza and his group. We study enzymatic (but not only) reactions in different complex media reminiscent to biological/cellular environments. These may interact with active components and significantly influence reaction rates or pathways. The interactions are investigated with appropriate biophysical methods involving a synchrotron radiation facility (SOLEIL).

Hybrid bio-assemblies

Here, our interest is focused on the preparation of biologically active assemblies using “chemical anchors”. This approach allows a better control of topology and specificity of such systems. Their applications in biological targeting or imaging are multiple and are currently under exploration.

Modified oligonucleotides
Examples of oligonucleotides modifications

Novel families of original oligonucleotides have been recently developed to provide tools for basic research, in vitro diagnostics, biological imaging, and potential therapeutic agents. Depending on applications, the oligonucleotides must possess several of the following properties: forming specific and stable complexes with their targets, inducing irreversible modifications of the targets by bridging or cleavage, producing a modified signal in the presence of targets that can be used as evidence interaction. Moreover, in the case of applications in cell culture and in vivo, they must be stable towards nucleases and be capable of reaching their targets inside cells (J. Gene Med. 2014, 16, 157-165). In order to confer specific properties to the oligonucleotides for targeted applications, we chemically modify their structural elements (nucleic bases, sugars, inter-nucleotide linkages (length and nature)). To these oligonucleotides may be attached various ligands: intercalating and/or reactive molecules, peptides, lipophilic molecules, inhibitors, detectable fluorescent markers.



39 documents

Article dans une revue

  • Josef Hamacek, Alexandra Vuillamy, Lisa Peterhans, Alexandre Homberg, Daniele Poggiali, et al.. Ln( iii ) complexes with triptycene based tripodal ligands: speciation and equilibria.. New Journal of Chemistry, Royal Society of Chemistry, 2018, 42 (10), pp.7803-7809. ⟨hal-01966142⟩
  • Josef Hamacek, Alexandra Vuillamy. Front Cover: Controlling the Structures of Lanthanide Complexes in Self-Assemblies with Tripodal Ligands (Eur. J. Inorg. Chem. 10/2018). European Journal of Inorganic Chemistry, Wiley-VCH Verlag, 2018, 2018 (10), pp.1152-1152. ⟨hal-01966132⟩
  • Josef Hamacek, Alexandra Vuillamy. Controlling the Structures of Lanthanide Complexes in Self-Assemblies with Tripodal Ligands. European Journal of Inorganic Chemistry, Wiley-VCH Verlag, 2018, 2018 (10), pp.1155-1166. ⟨hal-01966135⟩
  • Alexandra Vuillamy, Soumaila Zebret, Celine Besnard, Virginie Placide, Stéphane Petoud, et al.. Functionalized Triptycene-Derived Tripodal Ligands: Privileged Formation of Tetranuclear Cage Assemblies with Larger Ln(III). Inorganic Chemistry, American Chemical Society, 2017, 56 (5), pp.2742 - 2749. ⟨10.1021/acs.inorgchem.6b02900⟩. ⟨hal-01672644⟩
  • Badr El Aroussi, Josef Hamacek. Understanding the speciation of Ln( iii ) complexes with octadentate tripodal ligands. New Journal of Chemistry, Royal Society of Chemistry, 2017, 41 (11), pp.4390 - 4399. ⟨10.1039/C7NJ00088J⟩. ⟨hal-01672647⟩
  • Josef Hamacek, Alexandra Vuillamy. Controlling the Structures of Lanthanide Complexes in Self-Assemblies with Tripodal Ligands. European Journal of Inorganic Chemistry, Wiley-VCH Verlag, 2017, ⟨10.1002/ejic.201701075⟩. ⟨hal-01672645⟩
  • Soumaila Zebret, Eliane Vögele, Céline Besnard, Josef Hamacek. Synthetic routes to large tripodal organic receptors and the structural characterisation of intermediates. Tetrahedron, Elsevier, 2016, 72 (7), pp.928 - 935. ⟨10.1016/j.tet.2015.12.048⟩. ⟨hal-01407873⟩
  • Soumaila Zebret, Eliane Vögele, Tomas Klumpler, Josef Hamacek. Designing Artificial 3D Helicates: Unprecedented Self-Assembly of Homo-octanuclear Tetrapods with Europium. Chemistry - A European Journal, Wiley-VCH Verlag, 2015, 21 (18), pp.6695-6699. ⟨10.1002/chem.201500006⟩. ⟨hal-02072315⟩
  • Josef Hamacek, Daniele Poggiali, Soumaila Zebret, Badr El Aroussi, Markus Schneider, et al.. Building large supramolecular nanocapsules with europium cations. Chemical Communications, Royal Society of Chemistry, 2012, 48 (9), pp.1281-1283. ⟨10.1039/c2cc17322k⟩. ⟨hal-02122785⟩
  • Soumaila Zebret, Nathalie Dupont, Celine Besnard, Gérald Bernardinelli, Josef Hamacek. Lanthanide-mediated triangular cationic assemblies: structural and physico-chemical properties. Dalton Transactions, Royal Society of Chemistry, 2012, 41 (16), pp.4817. ⟨10.1039/c2dt12227h⟩. ⟨hal-02122895⟩
  • Josef Hamacek, Celine Besnard, Nathalie Mehanna, Jérôme Lacour. Tripodal europium complex with triangulenium dye: a model bifunctional metallo-organic system. Dalton Transactions, Royal Society of Chemistry, 2012, 41 (22), pp.6777-6782. ⟨10.1039/c2dt12332k⟩. ⟨hal-02122869⟩
  • Hauke Schmidt, Luisa Reuter, Josef Hamacek, Oliver Wenger. Multistage Complexation of Fluoride Ions by a Fluorescent Triphenylamine Bearing Three Dimesitylboryl Groups: Controlling Intramolecular Charge Transfer. Journal of Organic Chemistry, American Chemical Society, 2011, 76 (21), pp.9081-9085. ⟨10.1021/jo2019152⟩. ⟨hal-02122777⟩
  • Josef Hamacek, Celine Besnard, Tiphaine Penhouet, Pierre-Yves Morgantini. Thermodynamics, Structure and Properties of Polynuclear Lanthanide Complexes with a Tripodal Ligand: Insight into their Self-Assembly. Chemistry - A European Journal, Wiley-VCH Verlag, 2011, 17 (24), pp.6753-6764. ⟨10.1002/chem.201100173⟩. ⟨hal-02122756⟩
  • Badr El Aroussi, Laure Guénée, Prodipta Pal, Josef Hamacek. Lanthanide-Mediated Supramolecular Cages and Host–Guest Interactions. Inorganic Chemistry, American Chemical Society, 2011, 50 (17), pp.8588-8597. ⟨10.1021/ic201156q⟩. ⟨hal-02122768⟩
  • Soumaila Zebret, Elena Torres, Enzo Terreno, Laure Guénée, Carmine Senatore, et al.. Structure, stability and relaxivity of trinuclear triangular complexes. Dalton Transactions, Royal Society of Chemistry, 2011, 40 (16), pp.4284-4290. ⟨10.1039/c0dt01739f⟩. ⟨hal-02122739⟩
  • Badr El Aroussi, Soumaila Zebret, Céline Besnard, Philippe Perrottet, Josef Hamacek. Rational Design of a Ternary Supramolecular System: Self-Assembly of Pentanuclear Lanthanide Helicates. Journal of the American Chemical Society, American Chemical Society, 2011, 133 (28), pp.10764-10767. ⟨10.1021/ja204474v⟩. ⟨hal-02122228⟩
  • Soumaila Zebret, Celine Besnard, Josef Hamacek. Tris(6-carboxypyridine-2-carboxylato)terbium(III) 2.75-hydrate. Acta Crystallographica Section E: Structure Reports Online, International Union of Crystallography, 2011, 67 (7), pp.m968-m969. ⟨10.1107/S1600536811024135⟩. ⟨hal-02122765⟩
  • Badr El Aroussi, Nathalie Dupont, Gérald Bernardinelli, Josef Hamacek. Unsymmetrical Tripodal Ligand for Lanthanide Complexation: Structural, Thermodynamic, and Photophysical Studies. Inorganic Chemistry, American Chemical Society, 2010, 49 (2), pp.606-615. ⟨10.1021/ic901757u⟩. ⟨hal-02122750⟩
  • Soumaila Zebret, Nathalie Dupont, Gérald Bernardinelli, Josef Hamacek. Self-Assembly of a Trinuclear Luminescent Europium Complex. Chemistry - A European Journal, Wiley-VCH Verlag, 2009, 15 (14), pp.3355-3358. ⟨10.1002/chem.200802676⟩. ⟨hal-02122718⟩
  • Josef Hamacek, Soumaila Zebret, Gérald Bernardinelli. Supramolecular structure of the polymeric Eu(III) complex with pyridine-2,6-dicarboxylic acid. Polyhedron, Elsevier, 2009, 28 (11), pp.2179-2182. ⟨10.1016/j.poly.2009.04.011⟩. ⟨hal-02122728⟩
  • Josef Hamacek. Unravelling self-assembly of lanthanide helicates: Switching from deduction to induction. Journal of Alloys and Compounds, Elsevier, 2008, 451 (1-2), pp.347-351. ⟨10.1016/j.jallcom.2007.04.196⟩. ⟨hal-02122692⟩
  • Natalia Dalla-Favera, Josef Hamacek, Michal Borkovec, Damien Jeannerat, Frédéric Gumy, et al.. Linear Polynuclear Helicates as a Link between Discrete Supramolecular Complexes and Programmed Infinite Polymetallic Chains. Chemistry - A European Journal, Wiley-VCH Verlag, 2008, 14 (10), pp.2994-3005. ⟨10.1002/chem.200701465⟩. ⟨hal-02122703⟩
  • Josef Hamacek, Gérald Bernardinelli, Yaroslav Filinchuk. Tetrahedral Assembly with Lanthanides: Toward Discrete Polynuclear Complexes. European Journal of Inorganic Chemistry, Wiley-VCH Verlag, 2008, pp.3419-3422. ⟨10.1002/ejic.200800455⟩. ⟨hal-02122713⟩
  • Gianfranco Ercolani, Claude Piguet, Michal Borkovec, Josef Hamacek. Symmetry Numbers and Statistical Factors in Self-Assembly and Multivalency. Journal of Physical Chemistry B, American Chemical Society, 2007, 111 (42), pp.12195-12203. ⟨10.1021/jp0740705⟩. ⟨hal-02122669⟩
  • Natalia Dalla-Favera, Josef Hamacek, Michal Borkovec, Damien Jeannerat, Gianfranco Ercolani, et al.. Tuneable Intramolecular Intermetallic Interactions as a New Tool for Programming Linear Heterometallic 4f−4f Complexes. Inorganic Chemistry, American Chemical Society, 2007, 46 (22), pp.9312-9322. ⟨10.1021/ic701308h⟩. ⟨hal-02122662⟩
  • Markus Albrecht, Olga Osetska, Roland Fröhlich, Jean-Claude Bunzli, Annina Aebischer, et al.. Highly Efficient Near-IR Emitting Yb/Yb and Yb/Al Helicates. Journal of the American Chemical Society, American Chemical Society, 2007, 129 (46), pp.14178-14179. ⟨10.1021/ja0768688⟩. ⟨hal-02122681⟩
  • Josef Hamacek, Claude Piguet. How to Adapt Scatchard Plot for Graphically Addressing Cooperativity in Multicomponent Self-Assemblies. Journal of Physical Chemistry B, American Chemical Society, 2006, 110 (15), pp.7783-7792. ⟨10.1021/jp056932c⟩. ⟨hal-02122656⟩
  • Josef Hamacek, Michal Borkovec, Claude Piguet. Simple thermodynamics for unravelling sophisticated self-assembly processes. Dalton Transactions, Royal Society of Chemistry, 2006, pp.1473-1490. ⟨10.1039/b518461d⟩. ⟨hal-02122650⟩
  • Kornelia Zeckert, Josef Hamacek, Jean-Michel Senegas, Natalia Dalla-Favera, Sébastien Floquet, et al.. Predictions, Synthetic Strategy, and Isolation of a Linear Tetrametallic Triple-Stranded Lanthanide Helicate. Angewandte Chemie International Edition, Wiley-VCH Verlag, 2005, 44 (48), pp.7954-7958. ⟨10.1002/anie.200503040⟩. ⟨hal-02122645⟩
  • Josef Hamacek, Michal Borkovec, Claude Piguet. A Simple Thermodynamic Model for Quantitatively Addressing Cooperativity in Multicomponent Self-Assembly Processes—Part 2: Extension to Multimetallic Helicates Possessing Different Binding Sites. Chemistry - A European Journal, Wiley-VCH Verlag, 2005, 11 (18), pp.5227-5237. ⟨10.1002/chem.200500289⟩. ⟨hal-02122627⟩
  • Josef Hamacek, Michal Borkovec, Claude Piguet. A Simple Thermodynamic Model for Quantitatively Addressing Cooperativity in Multicomponent Self-Assembly Processes—Part 1: Theoretical Concepts and Application to Monometallic Coordination Complexes and Bimetallic Helicates Possessing Identical Binding Sites. Chemistry - A European Journal, Wiley-VCH Verlag, 2005, 11 (18), pp.5217-5226. ⟨10.1002/chem.200500290⟩. ⟨hal-02122633⟩
  • Mourad Elhabiri, Josef Hamacek, Nicolas Humbert, Jean-Claude Bunzli, Anne-Marie Albrecht-Gary. Proton-assisted dissociation of a triple-stranded dinuclear europium helicate. New Journal of Chemistry, Royal Society of Chemistry, 2004, 28 (9), pp.1096-1099. ⟨10.1039/B405934D⟩. ⟨hal-02122591⟩
  • Kornelia Zeckert, Josef Hamacek, Jean-Pierre Rivera, Sébastien Floquet, André Pinto, et al.. A Simple Thermodynamic Model for Rationalizing the Formation of Self-Assembled Multimetallic Edifices: Application to Triple-Stranded Helicates. Journal of the American Chemical Society, American Chemical Society, 2004, 126 (37), pp.11589-11601. ⟨10.1021/ja0483443⟩. ⟨hal-02122608⟩
  • Michal Borkovec, Claude Piguet, Josef Hamacek. Statistical mechanical approach to competitive binding of metal ions to multi-center receptors. Dalton Transactions, Royal Society of Chemistry, 2004, pp.4096-4105. ⟨10.1039/b413603a⟩. ⟨hal-02122620⟩
  • Mourad Elhabiri, Josef Hamacek, Jean-Claude g. Bünzli, Anne-Marie Albrecht-Gary. Lanthanide Homobimetallic Triple-Stranded Helicates: Insight into the Self-Assembly Mechanism. European Journal of Inorganic Chemistry, Wiley-VCH Verlag, 2004, 2004 (1), pp.51-62. ⟨10.1002/ejic.200300549⟩. ⟨hal-02122586⟩
  • J. Hamacek, Sylvie Blanc, M. Elhabiri, E. Leize, A. van Dorsselaer, et al.. Self-assembly mechanism of a bimetallic europium triple-stranded helicate. Journal of the American Chemical Society, American Chemical Society, 2003, 125 (6), pp.1541-1550. ⟨https://doi.org/10.1021/ja028861q⟩. ⟨10.1021/ja028861q⟩. ⟨hal-01458133⟩
  • Josef Hamacek, J. Havel. Determination of platinum (II,IV) and palladium(II) as thiocyanate complexes by capillary zone electrophoresis analysis of carboplatin and similar drugs.. Journal of Chromatography A, Elsevier, 1999, 834 (1-2), pp.321-7. ⟨hal-02122578⟩
  • A. Revilla, J. Hamacek, P. Lubal, J. Havel. Determination of rimantadine in pharmaceutical preparations by capillary zone electrophoresis with indirect detection or after derivatization. Chromatographia, Springer Verlag, 1998, 47 (7-8), pp.433-439. ⟨10.1007/BF02466475⟩. ⟨hal-02122570⟩

Chapitre d'ouvrage

  • Josef Hamacek. Self-Assembly Principles of Helicates. Physicochemical Principles of Self‐Assembly Processes, John Wiley & Sons, Ltd, pp.91-123, 2013. ⟨hal-02122929⟩