Valérie Marchi

The V.Marchi’s group has contributed to the development of different strategies directed self-assembly from aqueous suspensions of inorganic nanoparticles. These methods are based on the surface chemistry and shape of the nanoparticles as well as on the use of organic molds (peptides, proteins and / or lipid membranes) for directing the assembly during drying of the colloidal suspension. Thus 3D self-assemblies of metal and semiconductor nanorods were obtained in a smectic phase over distances of one millimeter with controlled geometry. In the case of gold nanorods, the material obtained is considered as a substrate for enhanced Raman spectroscopy surface (SERS) and for the development of chirosensitives sensors.

1. Nanoparticles Self-Assembly Driven by High Affinity Repeat Protein Pairing, K. L. Gurunatha, A. C. Fournier, A. Urvoas, M. Valerio-Lepiniec, V. Marchi, P. Minard, and E. Dujardin, ACS Nano, 2016, 10 (3), pp 3176–3185
2. 2. Self-organization of quantum rods induced by lipid membrane corrugations, Bizien, T.; Ameline, J.-C.; Yager, K.; Marchi, V.; Artzner, F. , Langmuir 2015, 31 (44), pp 12148–12154
3. 3. Peptidic Ligands to Control the Three-Dimensional Self-Assembly of Quantum Rods in Aqueous Media. Bizien, T.; Even-Hernandez, P.; Postic, M.; Mazari, E.; Chevance, S.; Bondon, A.; Hamon, C.; Troadec, D.; Largeau, L.; Dupuis, C.; Gosse, C.; Artzner, F.; Marchi, V. , Small 2014, 10 (18), 370.
4. 4. Three-Dimensional Self-Assembling of Gold Nanorods with Controlled Macroscopic Shape and Local Smectic B Order, Hamon, C. ; Postic, M. ; Mazari, E. ; et al., ACS Nano 2012, 6 (5), 4137-4146.
5. 5. Crystallization of Fluorescent Quantum Dots within a Three-Dimensional Bio-Organic Template of Actin Filaments and Lipid Membranes, Henry, E.; Dif, A. ; Schmutz, M. ; et al., Nano Lett. 2011, 11 (12), 5443-5448.
6. 6. Interaction between water-soluble peptidic CdSe/ZnS nanocrystals and membranes: Formation of hybrid vesicles and condensed lamellar phases, Dif, A.; Henry, E.; Artzner, F.; et al. J. Am. Chem. Soc. 2008, 130 (26), 8289-8296.
7. 7. Hierarchical architectures by synergy between dynamical template self-assembly and biomineralization, Pouget, Emilie; Dujardin, Erik; Cavalier, Annie; et al. Nature Mat. 2007, 6 (6), 434-439.
8. 8. Water-soluble pegylated quantum dots: From a composite hexagonal phase to isolated micelles, Boulmedais, F.; Bauchat, P.; Brienne, M. J.; et al. Langmuir 2006, 22 (23), 9797-9803.

The semiconductor nanorods were exploited for photo-induced redox reactions catalyzed by protein enzymes hydrogenase type. This work contributes to the development of photocathodes adapted for example to the photo-dissociation of water into dihydrogen and oxygen (conversion of light energy into chemical energy) when combined hydrogenase (Chem. Commun., 2014). The V.Marchi’s group has developed a method of photo-redox grafting in aqueous medium on semiconductor nanorods to spatially control their chemical functionalization. This approach provides a route to prepare heterostructures obtained by reduction of gold salts in situ and under irradiation. They are composed of a semiconductor nanorod conductor and a spherical gold nanoparticle located on the tip of the nanorod (Chem. Commun. 2015).

1. 1. Photo-electrochemical properties of quantum rods studied by scanning electrochemical microscopy. S. Lhenry, B. Boichard, Y. R. Leroux, P. Even-Hernandez, V. Marchi, P. Hapiot Physical Chemistry Chemical Physics: PCCP, 2017, 19, 4627-4635.

• 2. An aqueous one-pot route to gold/quantum rod heterostructured nanoparticles functionalized with Q2 DNA. C. Hamon, C. Martini, P. Even-Hernandez, B. Boichard, H. Voisin, L. Largeau, C. Gosse, T. Coradin, C. Aimé and V. Marchi. Chem. Commun. 2015, 51 (89), 16119-16122.

1. 3. Hydrogen bioelectrooxidation on gold nanoparticle-based electrodes modified by Aquifex aeolicus hydrogenase: Application to hydrogen/ oxygen enzymatic biofuel cells. K. Monsalve, M. Roger, C. Gutierrez-Sanchez, M. Ilbert, S. Nitsche, D. Byrne-Kodjabachian, V. Marchi, E. Lojou. Bioelectrochemistry, 2015, 106 47–55.
2. 4. Synthesis and enzymatic photo-activity of an O2 tolerant hydrogenase–CdSe@CdS quantum rod bioconjugate. C. Hamon, A. Ciaccafava, P. Infossi, R. Puppo, P. Even-Hernandez, E. Lojou and V. Marchi, Chem. Commun., 2014, 50, 4989.
3. 5. Light-induced reactivation of O2-tolerant membrane-bound [Ni–Fe] hydrogenase from the hyperthermophilic bacterium Aquifex aeolicus under turnover conditions, A. Ciaccafava, C. Hamon, P. Infossi, V. Marchi, M.-T. Giudici-Orticoni and E. Lojou, Phys. Chem. Chem. Phys., 2013, 2013, 15, 16463-16467.

The nanoparticles are used for targeting of biomolecules and understanding of their mode of action. Magnetic and fluorescent nanoparticles were used as a modulator of a biological process, the formation of the cytoskeleton in cell extracts, by the action of a magnetic field gradient. In the latter case, the nanoparticle does not only offer a way to mark a biomolecule but also to modulate and act on a biological process controlled by signaling proteins gradients (Nature Nanotech. 2013).

1. 1. Control of microtubule nucleation and assembly using magnetic nanoparticles, C. Hoffmann, E. Mazari, S. Lallet, R. Le Borgne, V. Marchi, C. Gosse and Z. Gueroui, Nature Nanotech. 2013, 8 (3), 199-205.
2. 2. Water Conversion ascendante Soluble nanoparticules par Routes micellaires, N. Sounderya, V. Roullier, M. Amela Cortes, MK Gnanasamandham, A. Dif, F. Grasset, Y. Zhang et V. Marchi, Bionanoscience 2013, 3 (2).
3. 3. Stable functionalized PEGylated quantum dots micelles with a controlled stoichiometry, Amela-Cortes, M.; Roullier, V.; Wolpert, C.; et al. Chem. Comm. 2011, 47 (4), 1246-1248.
4. 4. Small and Stable Peptidic PEGylated Quantum Dots to Target Polyhistidine-Tagged Proteins with Controlled Stoichiometry Dif, A.; Boulmedais, F.; Pinot, M.; et al. J. Am. Chem. Soc. 2009, 131 (41), 14738-14746.
5. 5. High-Affinity Labeling and Tracking of Individual Histidine-Tagged Proteins in Live Cells Using Ni2+ Tris-nitrilotriacetic Acid Quantum Dot Conjugates, Roullier, V.; Clarke, S.; You, C.; et al. Nano Lett. 2009, 9 (3), 1228-1234. Effect of HIV1-1 peptide presentation on the affinity constants of 2 monoclonal-antibodies determined by Biacore™ technology, Mani J.C.; Marchi, V; Cucurou, C, Molecular Immunology 1994 , 31 (6), 439-444.
6. 6. Small Bioactivated Magnetic Quantum Dot Micelles, Roullier, V.; Grasset, F.; Boulmedais, F.; et al. Chem. Mat. 2008, 20 (21), 6657-6665.
7. 7. Synthesis and properties of water-soluble gold colloids covalently derivatized with neutral polymer monolayers, Mangeney, C; Ferrage, F; Aujard, I; et al., J. Am. Chem. Soc. 2002, 124 (20), 5811-5821.

Mimicking Cell adhesion
The lipid bilayers have very versatile physico-chemical properties that allow mimicking cell adhesion. By introducing supramolecular recognition sites on the surface of the membrane, it is thus possible to induce selective adhesion between two adjacent membranes (PNAS 2006). Similarly the introduction of biological recognition sites such as the peptide derivatives Arg-Gly-Asp is effective to induce membrane fusion: i) between endothelial cells and giant vesicles to study the mechanism and kinetics (PRL 2002, BBA 2009), or ii) between lipid supported membrane and giant vesicles (Langmuir, 2003, Chem. Eur. J. 2001). All this research activity was conduced in the laboratory of Jean Marie Lehn in collaboration with the biophysik laboratory of E. Sackmann (TUM, Munich, Germany) and the team of Rumiana Dimova in MPI (Golm, Germany)

1. 1. Integrin reconstituted in GUVs: A biomimetic system to study initial steps of cell spreading, Streicher, P.; Nassoy, P.; Bärmann, M.; et al. B.B. A. Biomemb. 2009, 1788 (10), 2291-2300.
2. 2. Time scales of membrane fusion revealed by direct imaging of vesicle fusion with high temporal resolution, Haluska, C. K.; Riske, K. A.; Marchi-Artzner, V.; et al. Proc. Nat. Ac. Sci. 2006, 103 (43), 15841-15846.
3. 3. Adhesion of Arg-Gly-Asp (RGD) peptide vesicles onto an integrin surface: Visualization of the segregation of RGD ligands into the adhesion plaques by fluorescence, Marchi-Artzner, V; Lorz, B; Gosse, C; et al., Langmuir 2003, 19 (3), 835-841.
4. 4. Dynamic force Spectroscopy to probe adhesion strength of living cells, Prechtel, K; Bausch, AR; Marchi-Artzner, V; et al., Phys. Rev. Lett. 2002, 89 (2) 89.028101
5. 5. Selective adhesion of endothelial cells to artificial membranes with a synthetic RGD-lipopeptide, Marchi-Artzner, V; Lorz, B; Hellerer, U; et al., Chem. Eur. J. 2001, 7 (5), 1095-1101 11.

Lipid exchange, adhesion and fusion between vesicles

The introduction of supramolecular recognition groups in the lipidic bilayers induces such phenomena as selective fusion (PNAS 2004), selective adhesion between synthetic lipidic membranes (Chem.Phys.Chem. 2001, Langmuir 1998, Chem. Comm. 1997). Controlled permeability can also be observed thanks to a chemical stimulus such as metallic ion complexation (Chem. Eur. J. 2004) or electrostatic interaction (J. Phys. Chem B 1996) or thanks to a physical stimulus such as shearing (J Coll Int Sci 2005). All this research activity was conduced in the laboratory of Jean Marie Lehn.

1. 1. Shear-induced permeation and fusion of lipid vesicles, Bernard, AL; Guedeau-Boudeville, MA; Marchi-Artzner, V; et al. J. Coll. Int. Sci. 2005, 287 (1), 298-306.
2. 2. Fusogenic supramolecular vesicle systems induced by metal ion binding to amphiphilic ligands, Richard, A; Marchi-Artzner, V; Lalloz, M.N.; et al., Proc. Nat. Ac. Sci. 2004, 101 (43), 15279-15284.
3. 3. Selective complexation and transport of europium ions at the interface of vesicles, Marchi-Artzner, V; Brienne, MJ; Gulik-Krzywicki, T; et al. Chem. Eur. J. 2004, 10 (9), 2342-2350.
4. 4. Selective adhesion, lipid exchange and membrane-fusion processes between vesicles of various sizes bearing complementary molecular recognition groups, Marchi-Artzner, V; Gulik-Krzywicki, T; Guedeau-Boudeville, MA; et al., Chem.Phys.Chem. 2001, 2 (6), 367-376.
5. 5. Specific adhesion and lipid exchange between complementary vesicle and supported or Langmuir film, Marchi-Artzner, V; Lehn, JM; Kunitake, T, Langmuir 1998, 14 (22), 6470-6478.
6. 6. Molecular recognition between 2,4,6-triaminopyrimidine lipid monolayers and complementary barbituric molecules at the air/water interface: Effects of hydrophilic spacer, ionic strength, and pH, Marchi-Artzner, V; Artzner, F; Karthaus, O; et al. Langmuir 1998, 14 (18), 5164-5171.
7. 7. Molecular recognition induced aggregation and fusion between vesicles containing lipids bearing complementary hydrogen bonding head-groups, Marchi-Artzner, V; Jullien, L; GulikKrzywicki, T; et al., Chem. Comm. 1997, 1, 117-118.
8. 8. Interaction, lipid exchange, and effect of vesicle size in systems of oppositely charged vesicles, Marchi-Artzner, V; Jullien, L; Belloni, L; et al. J. Phys. Chem. 1996, 100 (32), 13844-13856.
9. 9. Multichromophoric cyclodextrins. 4. Light conversion by antenna effect, Jullien, L; Canceill, J; Valeur, B; et al., J. Am. Chem. Soc. 1996, 118 (23), 5432-5442.