Traveling Perversion as Constant Torque Actuator.

Mechanical stress and conformation of helical elastic rods clamped at both ends were studied upon unwinding. By axial rotation of one end, the winding number was progressively changed from the natural one (n=n_{0}) to complete chirality inversion (n=-n_{0}) while keeping the total elongation fixed and monitoring the applied torque M and tension T. Along the unwinding process, the system crosses three distinct states: natural helix (+), mixed state (+/-), and inverted helix (-). The mixed state involves two helices with opposite chiralities spatially connected by a perversion (helicity inversion). Upon unwinding, the perversion is "injected" (nucleated) from one side and travels toward the opposite side where it is eventually "absorbed" (annihilated), leaving the system in the (-) state. In the mixed state, the profile of M(n) is almost flat: the system behaves as a constant torque actuator. The three states are quantitatively well described in the framework of a biphasic model which neglects the perversion energy and finite size effects. The latter are taken into account in a numerical simulation based on the Kirchhoff theory of elastic rods. The traveling perversion in helical elastic rods and related topological phenomena are universal, with applications from condensed matter to biological and bioinspired systems, including in particular mechanical engineering and soft robotics.

Metagenomic analysis of pioneer biofilm-forming marine bacteria with emphasis on Vibrio gigantis adhesion dynamics.

Marine biofilms occur frequently and spontaneously in seawater, on almost any submerged solid surface. At the early stages of colonization, it consists of bacteria and evolves into a more complex community. Using 16S rRNA amplicon sequencing and comparative metagenomics, the composition and predicted functional potential of one- to three-day old bacterial communities in surface biofilms were investigated and compared to that of seawater. This confirmed the autochthonous marine bacterium Vibrio gigantis as an early and very abundant biofilm colonizer, also functionally linked to the genes associated with cell motility, surface attachment, and communication via signaling molecules (quorum sensing), all crucial for biofilm formation. The dynamics of adhesion on a solid surface of V. gigantis alone was also monitored in controlled laboratory conditions, using a newly designed and easily implementable protocol. Resulting in a calculated percentage of bacteria-covered surface, a convincing tendency of spontaneous adhering was confirmed. From the multiple results, its quantified and reproducible adhesion dynamics will be used as a basis for future experiments involving surface modifications and coatings, with the goal of preventing adhesion.

Trapping of swimming microalgae in foam.

Massive foam formation in aquatic environments is a seasonal event that has a significant impact on the stability of marine ecosystems. Liquid foams are known to filter passive solid particles, with large particles remaining trapped by confinement in the network of liquid channels and small particles being freely advected by the gravity-driven flow. By contrast, the potential role of a similar retention effect on biologically active particles such as phytoplankton cells is still relatively unknown. To assess if phytoplankton cells are passively advected through a foam, the model unicellular motile alga Chlamydomonas reinhardtii (CR) was incorporated in a bio-compatible foam, and the number of cells escaping the foam at the bottom was measured in time. Comparing the escape dynamics of living and dead CR cells, we found that dead cells are totally advected by the liquid flow towards the bottom of the foam, as expected since the diameter of CR remains smaller than the typical foam channel diameter. By contrast, living motile CR cells escape the foam at a significantly lower rate: after 2 hours, up to 60% of the injected cells may remain blocked in the foam, while 95% of the initial liquid volume in the foam has been drained out of the foam. Microscopic observation of the swimming CR cells in a chamber mimicking the cross-section of foam internal channels revealed that swimming CR cells accumulate near channels corners. A theoretical analysis based on the probability density measurements in the micro chambers has shown that this trapping at the microscopic scale contributes to explain the macroscopic retention of the microswimmers in the foam. At the crossroads of distinct fields including marine ecology of planktonic organisms, fluid dynamics of active particles in a confined environment and the physics of foam, this work represents a significant step in the fundamental understanding of the ecological consequences of aquatic foams in water bodies.

Tannin-controlled micelles and fibrils of κ-casein.

Effects of green tea tannin epigallocatechin-gallate (EGCG) on thermal-stress-induced amyloid fibril formation of reduced carboxymethylated bovine milk protein κ-casein were studied by dynamical light scattering and small angle X-ray scattering (SAXS). Two populations of aggregates, micelles, and fibrils dominated the time evolution of light scattering intensity and of effective hydrodynamic diameter. SAXS experiments allowed us to resolve micelles and fibrils so that the time dependence of the scattering profile revealed the structural evolution of the two populations. The low-Q scattering intensity prior to an expected increase in time due to fibril growth shows an intriguing rapid decrease, which is interpreted as the release of monomers from micelles. This phenomenon, observed both in the absence and in the presence of EGCG, indicates that under thermal stress free conditions, native monomers are converted to amyloid-prone monomers that do not form micelles. The consumption of free native monomers results in a release of native monomers from micelles because only native proteins participate in micelle-monomer (quasi)equilibrium. This release is reversible, indicating also that native-to-amyloid-prone monomer conversion is reversible as well. We show that EGCG does not bind to protein in fibrils, neither does it affect/prevent the proamyloid conversion of monomers. EGCG hinders the addition of monomers to growing fibrils. These facts allowed us to propose the kinetics model for EGCG-controlled amyloid aggregation of micellar proteins. Therein, we introduced the growth-rate inhibition function, which quantitatively accounts for the effect of EGCG on the fibril growth at any degree of thermal stress.

Self-aggregation of oxidized procyanidins contributes to the formation of heat-reversible haze in apple-based liqueur wine.

The ability of tannins to self-associate or form complexes with other macromolecules has important nutritional implications but can also result in defects in beverages. In addition, oxidation may be involved in the aggregation properties of tannins. In order to assess the impact of tannin oxidation on their self-association, oligomeric procyanidins were oxidized in a model solution and their aggregation kinetics were studied using light scattering. Under the conditions tested, only oxidized procyanidins were involved in haze formation. An increase in the level of oxidation and the degree of polymerization of procyanidins enhanced aggregation. Procyanidin oxidation products were depolymerized and the evolution of their markers was monitored throughout the aggregation process using liquid chromatography coupled with mass spectrometry. This revealed the involvement of intramolecular coupling in reversible haze formation. The haze formed in a model solution was partially reversible at high temperature. This property was similar in pommeau, an apple-based beverage. This work highlighted the involvement of oxidized tannins in reversible haze.

Rolling and aging in temperature-ramp soft adhesion.

Immediately before adsorption to a horizontal substrate, sinking polymer-coated colloids can undergo a complex sequence of landing, jumping, crawling, and rolling events. Using video tracking, we studied the soft adhesion to a horizontal flat plate of micron-size colloids coated by a controlled molar fraction f of the poly(lysine)-grafted-poly(N-isopropylacrylamide) (PLL-g-PNIPAM) which is a temperature-sensitive polymer. We ramp the temperature from below to above T_{c}=32±1^{∘}C, at which the PNIPAM polymer undergoes a transition, triggering attractive interaction between microparticles and surface. The adsorption rate, the effective in-plane (x-y) diffusion constant, and the average residence time distribution over z were extracted from the Brownian motion records during last seconds before immobilization. Experimental data are understood within a rate-equations-based model that includes aging effects and includes three populations: the untethered, the rolling, and the arrested colloids. We show that preadsorption dynamics casts a characteristic scaling function α(f) proportional to the number of available PNIPAM patches met by soft contact during Brownian rolling. In particular, the increase of in-plane diffusivity with increasing f is understood: The stickiest particles have the shortest rolling regime prior to arrest, so that their motion is dominated by the untethered phase.

Tailored stimuli-responsive interaction between particles adjusted by straightforward adsorption of mixed layers of Poly(lysine)-g-PEG and Poly(lysine)-g-PNIPAM on anionic beads.

We report a simple and versatile method to functionalize anionic colloid particles and control particle solubility. Poly(lysine)-based copolymers (PLL) grafted with polyethylene oxide (PLL-g-PEG) or poly(N-isopropylacrylamide) (PLL-g-PNIPAM) spontaneously adsorb on bare beads dispersed in aqueous solutions of the copolymers. The final composition of the mixed ad-layers formed (i.e. PEG/PNIPAM ratio) was adjusted by the polymer concentrations in solutions. While the (PLL-g-PEG)-coated particles were stable in a wide range of temperature, the presence of PLL-g-PNIPAM in the outer layer provided a reversible temperature-triggered aggregation at 32±1 °C. In the range of PNIPAM fraction going from 100% (beads fully covered by PLL-g-PNIPAM) down to a threshold 20% weight ratio (with 80% PLL-g-PEG), the particles aggregated rapidly to form micrometer size clusters. Below 20% weight fraction of PLL-g-PNIPAM, the kinetic was drastically lowered. Using PLL derivatives provides a straightforward route allowing to control the fraction of a functional chain (here PNIPAM) deposited on PEGylated particles, and in turn to adjust surface interaction and here the rate of particle-particle aggregation as a function of the density of functional chains. This approach can be generalized to many anionic surfaces onto which PLL is known to adhere tightly, such as glass or silica.

Structural properties of colloidal complexes between condensed tannins and polysaccharide hyaluronan.

Interactions of plant tannins with polysaccharide hyaluronan are studied by means of light scattering and small-angle X-ray scattering (SAXS). In this paper, we show that (1) the tannin-polysaccharide complexes remain stable in colloidal suspension; (2) the masses and structures of colloidal tannin-polysaccharide objects depend on the tannin degree of polymerization; and (3) the densities of tannin-polysaccharide aggregates are about 7 times lower than the density of a single solvated polysaccharide molecule. Short tannins and polysaccharides are aggregated in loose oligomeric structures whose sizes are comparable to a single polysaccharide molecule. Tannins longer than 10 nm and polysaccharides are aggregated in larger microgel-like particles whose sizes exceed 200 nm.

Rigidity, conformation, and solvation of native and oxidized tannin macromolecules in water-ethanol solution.

We studied by light scattering and small angle x-rays scattering (SAXS) conformations and solvation of plant tannins (oligomers and polymers) in mixed water-ethanol solutions. Their structures are not simple linear chains but contain about 6% of branching. Ab initio reconstruction reveals that monomers within a branch are closely bound pairwise. The chains are rather rigid, with the Kuhn length b = 13+/-3 nm, corresponding to about 35 linearly bound monomers. Contribution of solvation layer to SAXS intensity varies in a nonmonotonic way with ethanol content phi(A), which is an indication of amphipathic nature of tannin molecules. Best solvent composition phi(A)(B) is a decreasing function of polymerization degree N, in agreement with increasing water solubility of tannins with N. Polymers longer than b present a power-law behavior I approximately Q(-d) in the SAXS profile at high momentum transfer Q. The monotonic decrease in d with increasing phi(A) (from 2.4 in water to 1.9 in ethanol) points that the tannins are more compact in water than in ethanol, presumably due to attractive intramolecular interactions in water. Tannins were then oxidized in controlled conditions similar to real biological or food systems. Oxidation does not produce any intermolecular condensation, but generates additional intramolecular links. Some oxidation products are insoluble in water rich solvent. For that reason, we identify these species as a fraction of natural tannins called "T1" in the notation of Zanchi et al. [Langmuir 23, 9949 (2007)]. Within the fraction left soluble after oxidation, conformations of polymeric tannins, despite their higher rigidity, remain sensitive to solvent composition.

Colloidal dispersions of tannins in water-ethanol solutions.

The molecular interactions of grape-seed tannins dissolved in water-ethanol solutions have been studied through small angle neutron scattering, light scattering, and physical separation techniques. Through selective precipitation in different solvent mixtures, three populations of tannin macromolecules have been identified: T1 (2% of the total tannin), which forms colloidal particles when the ethanol content of the solvent is brought below phiA = 0.6; T2a (33% of the tannin), which phase-separates below phiA = 0.08 in ionic conditions that are typical of wine; and T2b (65% of the tannin), which remains in solution regardless of ethanol content. Each population remains molecularly dissolved (i.e., it does not form any association structures such as stacks or micelles) until the threshold where dense colloidal particles are formed through nucleation and growth. The colloidal dispersions are metastable, due to the adsorption of organic acids on the particle surfaces; increasing ionic strength and reducing ethanol content cause the loss of this metastability and the aggregation of the particles.