Aggregation kinetics of a concentrated colloidal suspension under oscillatory flow.

The aggregation behavior of an attractive colloidal silica suspension under oscillatory flow is studied using rheological measurement. We show that the competition between the aggregation of the particles and the aggregate breakup under external stress leads to a non-monotonous evolution of the elastic modulus with time. Remarkably, under certain conditions, the elasticity is not an increasing function of time but exhibits a maximum. The value of the maximum of the elastic modulus depends on the applied shear amplitude and the ionic strength of the suspension. Scaling laws that describes the evolutions of the elastic modulus as a function of the salinity and of the deformation amplitude are proposed and discussed.

Stress overshoot, hysteresis, and the Bauschinger effect in sheared dense colloidal suspensions.

The mechanical nonlinear response of dense Brownian suspensions of polymer gel particles is studied experimentally and by means of numerical simulations. It is shown that the response to the application of a constant shear rate depends on the previous history of the suspension. When the flow starts from a suspension at rest, it exhibits an elastic response followed by a stress overshoot and then a plastic flow regime. Conversely, after flow reversal, the stress overshoot does not occur, and the apparent elastic modulus is reduced while numerical simulations reveal that the anisotropy of the local microstructure is delayed relative to the macroscopic stress.

Magnetic Control over the Fractal Dimension of Supramolecular Rod Networks.

Controlling supramolecular polymerization is of fundamental importance to create advanced materials and devices. Here we show that the thermodynamic equilibrium of Gd3+-bearing supramolecular rod networks is shifted reversibly at room temperature in a static magnetic field of up to 2 T. Our approach opens opportunities to control the structure formation of other supramolecular or coordination polymers that contain paramagnetic ions.

Jet instability of a shear-thickening concentrated suspension.

We investigate the flow of a concentrated suspension of colloidal particles at deformation rates higher than the discontinuous shear-thickening transition shear rate. We show that, under its own weight, a jet of a concentrated enough colloidal suspension, simultaneously flows while it sustains tensile stress and transmits transverse waves. This results in a new flow instability of jets of shear-thickening suspensions: the jet is submitted to rapid transverse oscillations, that we characterize.

Flexibility and thermal dynamic stability increase of dsDNA induced by Ru(bpy)2dppz2+ based on AFM and HRM technique.

Ru(bpy)2dppz2+ has been widely used as a probe for exploring the structure of double-stranded DNA (dsDNA). The flexibility change of DNA helix is important in many of its biological functions but not well understood. Here, flexibility change of dsDNA helix caused by intercalation with Ru(bpy)2dppz2+ was investigated using the atomic force microscopy. At first, the interactions between ruthenium complex and dsDNA helix were characterized and the binding site size (p = 2.87 bp) and binding constant (Ka = 5.9 * 107 M-1) were determined by the relative extension of DNA helix using the equation of McGhee and von Hippel. By measuring intercalator-induced DNA elongation and the mean square of end-to-end distance at different molar ratios of Ru(bpy)2dppz2+ to dsDNA, the changes of persistence length under different ruthenium concentrations were determined by the worm-like chain model. We found that the persistence length of dsDNA decreased with increasing Ru(bpy)2dppz2+ concentration, demonstrating that the flexibility of dsDNA obviously enhanced due to the intercalation. Especially, the persistence length changed greatly from 54 to 34 nm on changing the molar ratio of ruthenium to dsDNA from 0 to 0.2. We speculated that the intercalation of dsDNA with Ru(bpy)2dppz2+ resulted in local deformation or bending of the DNA duplex. In addition, the thermal dynamic stability of DNA helix was measured with high resolution melting method which revealed the increase in thermal dynamic stability of DNA helix due to the ruthenium intercalation.

Polymer-free electrospinning of tannic acid and cross-linking in water for hybrid supramolecular nanofibres.

Electrospinning is the process of choice allowing the preparation of nanofibrous materials from a solution usually based on a high molar mass polymer. The solution must bring enough chain entanglements to avoid any breaking or Rayleigh instability of the electrospun jet resulting thus in the deposition of a continuous and regular solid nanofibre. It has been however shown that some few non-polymeric molecules can be electrospun without using a carrier polymer. We demonstrate here the case of tannic acid. Indeed, it was possible to electrospin this molecule solubilised in a mixture of water and ethanol as well as in pure water. Rheology, dynamic light scattering and cryo-TEM highlight the formation of tannic acid aggregates in solution. Above a critical concentration, these aggregates form a supramolecular interconnected network strong enough to allow the electrospinning of a continuous and regular nanofibre. The resulting nanoweb is mechanically stable and can be handled and wrapped. Furthermore, as opposed to the other small molecules for which polymer-free electrospinning was also demonstrated, tannic acid nanowebs can be efficiently cross-linked in water either by oxidative reaction with sodium periodate or, most interestingly, with FeIII by a combination of oxidative reaction and the formation of coordination complexes. The proposed electrospinning and cross-linking strategy is easy, of low cost, and scalable and uses non-toxic solvents as well as biocompatible and biofunctional molecules. Furthermore, thanks to the chelation capacity of tannic acid having the ability to coordinate with a wide variety of metals, hybrid smart nanowebs can be envisaged for diverse applications such as biomedical, catalysis as well as environment.

Holographic Traction Force Microscopy.

Traction Force Microscopy (TFM) computes the forces exerted at the surface of an elastic material by measuring induced deformations in volume. It is used to determine the pattern of the adhesion forces exerted by cells or by cellular assemblies grown onto a soft deformable substrate. Typically, colloidal particles are dispersed in the substrate and their displacement is monitored by fluorescent microscopy. As with any other fluorescent techniques, the accuracy in measuring a particule's position is ultimately limited by the number of evaluated fluorescent photons. Here, we present a TFM technique based on the detection of probe particle displacements by holographic tracking microscopy. We show that nanometer scale resolutions of the particle displacements can be obtained and determine the maximum volume fraction of markers in the substrate. We demonstrate the feasibility of the technique experimentally and measure the three-dimensional force fields exerted by colorectal cancer cells cultivated onto a polyacrylamide gel substrate.

Investigation on the pitting of potato starch granules during high frequency ultrasound treatment.

In this paper, the pitting of potato starch granules in aqueous suspensions (1%) by high-frequency high-power ultrasound (850kHz at a power of 0.2W, 2W or 3.7W; and also 500kHz and 1MHz at a power of 2W) is reported. The number of pits per starch granules was found to be independent of the amylose content of starches, and the surface properties of starch granules as modified through SDS and ethanol washing. At 850kHz, the maximum number of pits per starch granule, for both normal and waxy starches, did not exceed 11. However, a close inspection of fractionated starch granules based on their sizes showed that there is an optimum granule size for which a maximum pit number is obtained. For example, starch granules with diameter size range of ∼15 to ∼30µm had a maximum pit number (between 10 and 20 pits per granule) when sonicated (2W, 850kHz and 30min); while sonication of small (<10µm) and very large (>45µm) granules resulted in a smaller number of pits per granule (∼5). Further, the maximum number of pits per granules is also found to be proportional to the ultrasound frequency, with values of approximately 7, 10 and 11 at 0.50, 0.85, and 1MHz, respectively. FTIR measurements did not show any breakup of starch molecules.

Geometrical instability in the imbibition of a sphere.

We study the imbibition of a spherical porous aggregate. When the difference in pressure between the inside and the outside of the aggregate is large enough, the imbibition front becomes unstable. This instability leads to the acceleration of the imbibition process. In more complex geometries with non-constant curvatures, the imbibition becomes locally unstable in the regions with the highest curvatures, leading to spatially heterogeneous front velocities.

Flexibility of short ds-DNA intercalated by a dipyridophenazine ligand.

We use Förster Resonant Energy Transfer (FRET) in order to measure the increase of flexibility of short ds-DNA induced by the intercalation of dipyridophenazine (dppz) ligand in between DNA base pairs. By using a DNA double strand fluorescently labeled at its extremities, it is shown that the end-to-end length increase of DNA due to the intercalation of one dppz ligand is smaller than the DNA base pair interdistance. This may be explained either by a local bending of the DNA or by an increase of its flexibility. The persistence length of the formed DNA/ligand is evaluated. The described structure may have implications in the photophysical damages induced by the complexation of DNA by organometallic molecules.

Complexation of DNA with ruthenium organometallic compounds: the high complexation ratio limit.

Interactions between DNA and ruthenium organometallic compounds are studied by using visible light absorption and circular dichroism measurements. A titration technique allowing for the absolute determination of the advancement degree of the complexation, without any assumption about the number of complexation modes is developed. When DNA is in excess, complexation involves intercalation of one of the organometallic compound ligands between DNA base pairs. But, in the high complexation ratio limit, where organometallic compounds are in excess relative to the DNA base pairs, a new mode of interaction is observed, in which the organometallic compound interacts weakly with DNA. The weak interaction mode, moreover, develops when all the DNA intercalation sites are occupied. A regime is reached in which one DNA base pair is linked to more than one organometallic compound.

UV-vis absorption spectrum of a novel Ru(II) complex intercalated in DNA: [Ru(2,2'-bipy)(dppz)(2,2'-ArPy)]⁺.

The synthesis of a new Ru(II) complex is reported. Its absorption spectrum when interacting with DNA in water was calculated at the hybrid quantum mechanics molecular mechanics level of theory and compared with experimental data. The vertical transitions were computed using time-dependent density functional theory in the linear response approximation. The complex and its environment were treated at the quantum mechanical and molecular mechanical levels, respectively. The effects of the environment were investigated in detail and conveniently classified into electrostatic and polarization effects. The latter were modeled using the computationally inexpensive "electronic response of the surroundings" method. It was found that the main features of the experimental spectrum are nicely reproduced by the theoretical calculations. Moreover, analysis of the most intense transitions utilizing the natural transition orbital formalism revealed important insights into their nature and their potential role in the irreversible oxidation of DNA, a phenomenon that could be relevant in the field of cancer therapy.

Induction of caspase 8 and reactive oxygen species by ruthenium-derived anticancer compounds with improved water solubility and cytotoxicity.

Organometallic compounds which contain metals, such as ruthenium or gold, have been investigated as a replacement for platinum-derived anticancer drugs. They often show good antitumor effects, but the identification of their precise mode of action or their pharmacological optimization is still challenging. We have previously described a class of ruthenium(II) compounds with interesting anticancer properties. In comparison to cisplatin, these molecules have lower side effects, a reduced ability to interact with DNA, and they induce cell death in absence of p53 through CHOP/DDIT3. We have now optimized these molecules by improving their cytotoxicity and their water solubility. In this article, we demonstrate that by changing the ligands around the ruthenium we modify the ability of the compounds to interact with DNA. We show that these optimized molecules reduce tumor growth in different mouse models and retain their ability to induce CHOP/DDIT3. However, they are more potent inducers of cancer cell death and trigger the production of reactive oxygen species and the activation of caspase 8. More importantly, we show that blocking reactive oxygen species production or caspase 8 activity reduces significantly the activity of the compounds. Altogether our data suggest that water-soluble ruthenium(II)-derived compounds represent an interesting class of molecules that, depending on their structures, can target several pro-apoptotic signaling pathways leading to reactive oxygen species production and caspase 8 activation.

Spectral properties of polypyridyl ruthenium complexes intercalated in DNA: theoretical insights into the surrounding effects of [Ru(dppz)(bpy)2]2+.

The UV/Visible absorption properties of a polypyridyl ruthenium complex upon intercalation on DNA are studied at the mixed quantum mechanics molecular mechanics level of theory. Vertical excitation transitions are computed by time dependent density functional theory. Particular emphasis is put on the different levels at which the macromolecular environment is treated, and in particular on the analysis of the effect of mechanical, electrostatic and polarizable embedding. We show that with the highest level of theory the experimental absorption wavelengths are reproduced with a difference of only 2 or 3 nm for the low energy bands. The systematic analysis of the individual vertical transitions allows us to get much more insights into the role played by the environment, in particular, in metal to ligand and intra ligand charge transfer transitions that can lead to the production of DNA oxidative lesions exploitable in phototherapy.

Quantification of high-power ultrasound induced damage on potato starch granules using light microscopy.

A simple light microscopic technique was developed in order to quantify the damage inflicted by high-power low-frequency ultrasound (0-160 W, 20 kHz) treatment on potato starch granules in aqueous dispersions. The surface properties of the starch granules were modified using ethanol and SDS washing methods, which are known to displace proteins and lipids from the surface of the starch granules. The study showed that in the case of normal and ethanol-washed potato starch dispersions, two linear regions were observed. The number of defects first increased linearly with an increase in ultrasound power up to a threshold level. This was then followed by another linear dependence of the number of defects on the ultrasound power. The power threshold where the change-over occurred was higher for the ethanol-washed potato dispersions compared to non-washed potato dispersions. In the case of SDS-washed potato starch, although the increase in defects was linear with the ultrasound power, the power threshold for a second linear region was not observed. These results are discussed in terms of the different possible mechanisms of cavitation induced-damage (hydrodynamic shear stresses and micro-jetting) and by taking into account the hydrophobicity of the starch granule surface.

DNA binding to an anticancer organo-ruthenium complex.

Because many anticancer drugs interact with DNA, the determination of their association constants to DNA is essential for quantifying their mechanisms of action. The interactions between a new ruthenium-derived compound [ruthenium(phenanthroline)(κ-C,N-(2-phenyl-pyridine)(NCMe)(2)]PF(6), called RDC11] and DNA are studied using different techniques. Fluorescent experiments are used to determine the association and dissociation constants under different salt concentrations. The binding is shown to be reversible and noncovalent. The association constants vary from 1.5 × 10(6) M(-1) to 2.9 × 10(3) M(-1) when increasing the sodium concentration from 0.1 to 200 mM. Single-molecule stretching methods are used to study the interaction of RDC with longer DNA strands (8.6 kbp home-built dimer of pBR322). The affinities of RDC with DNA under different loads are obtained using McGhee and von Hippel analysis. The affinity constant and thermodynamic parameters are in good agreement with the values found in the literature and lead to the conclusion that this molecule intercalates dsDNA.

Contact and stress anisotropies in start-up flow of colloidal suspensions.

Spatiotemporal correlations in start-up flows of attractive colloids are explored by numerical simulations as a function of their volume fraction and shear rate. The suspension is first allowed to flocculate during a time tw, then the stress necessary to induce its flow is computed. We find that, at low volume fractions, the stress is a universal function of the strain. On the contrary, at high volume fractions, this scaling behavior is no longer observed and a supplementary stress becomes necessary to induce flow. To better understand the physical origin of the supplementary stress, we examine the creation, disruption, and orientation of contacts between the particles and the corresponding contribution to stress as a function of strain. Our simulations show that the onset of flow is dominated by the creation of contacts between the particles at low shear rates and by their disruption at high shear rates. However, neither the evolution of the number of contacts with strain nor their orientation can fully account for the nonscaling behavior of the stress at high volume fractions. At small strains, the relative importance of forcing in the compression quadrant increases with volume fraction and with flocculation time. This mechanism of stress transmission through the compression quadrant is not accounted for in the usual description of yield stress, which considers the breaking of bonds oriented in the extension quadrant.

A ruthenium-containing organometallic compound reduces tumor growth through induction of the endoplasmic reticulum stress gene CHOP.

Cisplatin-derived anticancer therapy has been used for three decades despite its side effects. Other types of organometallic complexes, namely, some ruthenium-derived compounds (RDC), which would display cytotoxicity through different modes of action, might represent alternative therapeutic agents. We have studied both in vitro and in vivo the biological properties of RDC11, one of the most active compounds of a new class of RDCs that contain a covalent bond between the ruthenium atom and a carbon. We showed that RDC11 inhibited the growth of various tumors implanted in mice more efficiently than cisplatin. Importantly, in striking contrast with cisplatin, RDC11 did not cause severe side effects on the liver, kidneys, or the neuronal sensory system. We analyzed the mode of action of RDC11 and showed that RDC11 interacted poorly with DNA and induced only limited DNA damages compared with cisplatin, suggesting alternative transduction pathways. Indeed, we found that target genes of the endoplasmic reticulum stress pathway, such as Bip, XBP1, PDI, and CHOP, were activated in RDC11-treated cells. Induction of the transcription factor CHOP, a crucial mediator of endoplasmic reticulum stress apoptosis, was also confirmed in tumors treated with RDC11. Activation of CHOP led to the expression of several of its target genes, including proapoptotic genes. In addition, the silencing of CHOP by RNA interference significantly reduced the cytotoxicity of RDC11. Altogether, our results led us to conclude that RDC11 acts by an atypical pathway involving CHOP and endoplasmic reticulum stress, and thus might provide an interesting alternative for anticancer therapy.

Formation and self-organization kinetics of alpha-CD/PEO-based pseudo-polyrotaxanes in water. A specific behavior at 30 degrees C.

alpha-Cyclodextrins (alpha-CDs) have the ability to form inclusion complexes with poly(ethylene oxide) (PEO) polymer chains. These pseudo-polyrotaxanes (PPRs) can be obtained by quenching an alpha-CD/PEO mixture in water from 70 degrees C down to a lower temperature (typically in the range from 5 to 30 degrees C) thanks to favorable interactions between alpha-CD cavities and PEO chains. Moreover, starting from a liquid alpha-CD/PEO mixture at a total mass fraction of 15% w/w at 70 degrees C, the formation of PPRs with time at a lower temperature induces a white physical gel with time, and phase separation is observed. We established that PPR molecules are exclusively found in the precipitated phase although unthreaded alpha-CD molecules and unthreaded PEO chains are in the liquid phase. At 30 degrees C, the physical gel formation is much slower than at 5 degrees C. At 30 degrees C, we established that, in a first step, alpha-CDs thread onto PEO chains, forming PPR molecules which are not in good solvent conditions in water. At a higher length scale, rapid aggregation of the PPR molecules occurs, and threaded alpha-CD-based nanocylinders form (cylinder length L = 5.7 nm and cylinder radius R = 4.7 nm). At a higher length scale, alpha-CD-based nanocylinders associate in a Gaussian way, engendering the formation of precipitated domains which are responsible for the high turbidity of the studied system. At the end of this first step (i.e., after 20 min), the system still remains liquid and the PPRs are totally formed. Then, in a second step (i.e., after 150 min), the system undergoes its reorganization characterized by a compacity increase of the precipitated domains and forms a physical gel. We found that PPRs are totally formed after 20 min at 30 degrees C and that the system stays in a nongel state up to 150 min. This opens new perspectives regarding the PPR chemical modification: between these two characteristic times, we can easily envisage an efficient chemical modification of the PPR molecules in water, as for instance an end-capping reaction leading to the synthesis of polyrotaxanes.