Self-Assembly of Nanoparticles from Evaporating Sessile Droplets: Fresh Look into the Role of Particle/Substrate Interaction.

We studied the dependence of solid deposit shape obtained by free drying of sessile drops on particle concentration and Derjaguin-Landau-Verwey-Overbeek (DLVO) particle/substrate interaction. In contrast to previous contributions using pH as a control parameter of interactions, we investigated an unprecedentedly wide range of concentrations and particle/substrate DLVO forces by modifying the nature of the substrate and particles as well as their size and surface chemistry, whereas long-distance repulsive interactions between particles were maintained for most of the drying time. Our main result is that the different shapes of deposits obtained by modifying the particle concentration are the same in the different regimes of concentration regardless of particle/substrate interaction in the studied range of DLVO forces and particle concentrations. The second result is that, contrary to expectations, the dominant morphology of dry patterns at low particle concentration always shows a dotlike pattern for all the studied systems.

Long-range ordered nanodomains of grafted electroactive molecules.

We demonstrate the capability to build zero and one-dimensional electroactive molecular nanostructures ordered over a macroscopic scale and stable under ambient conditions. To realize these arrays, we use the selective grafting of functionalized thiols (juglon and terthiophene based) on a self-organized metallic template. The nanoscale patterning of the molecular conductance is demonstrated and analyzed by scanning tunneling spectroscopy. Finally, the influence of the nanostructuring on electro-chemical properties is measured, paving the way to an all-bottom-up fabrication of nanostructured templates for nanosciences.

Directed growth of mixed self-assembled monolayers on a nanostructured template: a step toward the patterning of functional molecular domains.

We report on the elaboration of networks of SAM domains. More precisely, we show the feasibility in making arrays of functionalized alkylthiol nanodomains bordered with an alkylthiol matrix. The several step process relies on the replication of a self-organized cobalt array grown on Au(111). The SAM process takes place in solution. The chemical affinity of thiol for gold leads to the selective grafting of molecules on the surface. After having removed the inorganic array, alkylthiol functionalized with a terthiophene unit is grafted in free gold areas. The efficiency of the replication of the initial template depends on the stability of the first SAM. We also investigate electronic tunnel transport through oligothiophene islands with the STM. The variation of the molecular contrast with bias voltage between the two molecular species indicates a potential resonant tunneling mechanism through the orbitals of the aromatic compound.

STM observation of a single diarylethene flickering.

We report the STM observation of single diarylethene derivatives (DD) embedded into alkylthiol self-assembled monolayers (SAM) on Au(111). Telegraph noise in the data shows that the molecular conductance oscillates between two states. Comparing our results to the ones obtained by other teams observing conductance flickering with systems in the same geometry, we relate the two observed states to the two isomeric configurations of the molecule under study.

In-solution patterning of standing up porphyrin based nanostructures within hydrogen bonded porous networks--a structural effect of a host matrix on guest entities.

Through an all-solution process, we elaborate a host-guest system based on the self-assembly of a porphyrin derivative entrapped in a PTCDI-melamine porous network on Au(111). In contrast to the unpatterned molecular assembly, complementary STM and surface IR spectroscopy show that the host template modifies the packing and the tilt angle of porphyrin nanodomains.

Invariant NKT cells increase drug-induced osteosarcoma cell death.

BACKGROUND AND PURPOSE: In osteosarcoma (OS) patients, only a limited number of drugs are active and the regimens currently in use include a combination of at least two of these drugs: doxorubicin, cisplatin, methotrexate and ifosfamide. Today, 30-40% of patients still die of OS highlighting the urgent need for new treatments. Invariant NKT (iNKT) cells are a lymphocyte lineage with features of both T and NK cells, playing important roles in tumour suppression. Our aim was to test whether the cytoxicity induced by cisplatin, doxorubicin and methotrexate against OS cells can be enhanced by iNKT cell treatment. EXPERIMENTAL APPROACH: iNKT cells were purified from human peripheral blood mononuclear cells by cell sorting (Vα24Vß11(+) cells) and used as effector cells against OS cells (U2-OS, HOS, MG-63). Cell death (calcein-AM method), perforin/granzyme B and Fas/FasL expressions were determined by flow cytometry. CD1d expression was analysed at both the gene and protein level. KEY RESULTS: iNKT cells were cytotoxic against OS cells through a CD1d-dependent mechanism. This activity was specific for tumour cells, because human CD1d(+) mesenchymal stem cells and CD1d(-) osteoblasts were not affected. iNKT cell treatment enhanced drug-induced OS cell death in a concentration-dependent manner and this effect was reduced in CD1d-silenced OS cells. CONCLUSION AND IMPLICATIONS: iNKT cells kill malignant, but not non-malignant, cells. iNKT cell treatment enhances the cytotoxicity of anti-neoplastic drugs against OS cells in a CD1d-dependent manner. The present data encourage further studies on the use of iNKT cells in OS therapy.