Preferential hydration fully controls the renaturation dynamics of collagen in water-glycerol solvents.

Glycerol is one of the additives which stabilize collagen, as well as globular proteins, against thermally induced denaturation --an effect explained by preferential hydration, i.e. by the formation, in water/glycerol solvents, of a hydration layer whose entropic cost favors the more compact triple-helix native structure against the denatured one, gelatin. Quenching gelatin solutions promotes renaturation which, however, remains incomplete, as the formation of a gel network gives rise to growing topological constraints. So, gelatin gels exhibit glass-like dynamical features such as slow aging of their shear modulus and stretched exponential stress relaxation, the study of which gives us access to the re(de)naturation dynamics of collagen. We show that this dynamics is independent of the bulk solvent viscosity and controlled by a single parameter, the undercooling [Formula: see text] below the glycerol-concentration-dependent denaturation temperature. This provides direct proof of i) the presence of a nanometer thick, glycerol-free hydration layer, ii) the high locality of the kinetically limiting process governing renaturation.

Glass-like dynamics of the strain-induced coil/helix transition on a permanent polymer network.

We study the stress response to a step strain of covalently bonded gelatin gels in the temperature range where triple helix reversible crosslink formation is prohibited. We observe slow stress relaxation towards a T-dependent finite asymptotic level. We show that this is assignable to the strain-induced coil → helix transition, previously evidenced by Courty et al. [Proc. Natl. Acad. Sci. U. S. A. 102, 13457 (2005)], of a fraction of the polymer strands. Relaxation proceeds, in a first stage, according to a stretched exponential dynamics, then crosses over to a terminal simple exponential decay. The respective characteristic times τK and τf exhibit an Arrhenius-like T-dependence with an associated energy E incompatibly larger than the activation barrier height for the isomerisation process which sets the clock for an elementary coil → helix transformation event. We tentatively assign this glass-like slowing down of the dynamics to the long-range couplings due to the mechanical noise generated by the local elementary events in this random elastic medium.

Two-step build-up of a thermoreversible polymer network: From early local to late collective dynamics.

We probe the mechanisms at work in the build-up of thermoreversible gel networks, with the help of hybrid gelatin gels containing a controlled density of irreversible, covalent crosslinks (CLs), which we quench below the physical gelation temperature. The detailed analysis of the dependence on covalent crosslink density of both the shear modulus and optical activity evolutions with time after quench enables us to identify two stages of the physical gelation process, separated by a temperature-dependent crossover modulus: (i) an early nucleation regime during which rearrangements of the triple-helix CLs play a negligible role, and (ii) a late, logarithmic aging one, which is preserved, though slowed down, in the presence of irreversible CLs. We show that aging is fully controlled by rearrangements and discuss the implication of our results in terms of the switch from an early, local dynamics to a late, cooperative long-range one.

Microstructuration stages during gelation of gelatin under shear.

We study gelation under shear of aqueous gelatin by measuring the evolution of the apparent viscosity, thus extending the previous study by de Carvalho and Djabourov (W. de Carvalho, M. Djabourov, Rheol. Acta 36, 591 (1997)). From a set of experiments under constant stress, we deduce that the microstructure evolves through the following succession of regimes: i) nucleation and growth until crowding of a microgel suspension; ii) coalescence into strata parallel to the flow; iii) gradual thickening of these strata via transverse cross-linking until the flow finally localizes into two interfacial sliding bands which close sequentially. The transition between these regimes occurs at characteristic viscosity values. This scenario is fully confirmed by experiments performed at constant shear rates. We expect it to be relevant for all materials forming thermoreversible gels.

Interplay between shear loading and structural aging in a physical gelatin gel.

We show that the aging of the mechanical relaxation of a gelatin gel exhibits the same scaling phenomenology as polymer and colloidal glasses. In addition, gelatin is known to exhibit logarithmic structural aging (stiffening). We find that stress accelerates this process. However, this effect is definitely irreducible to a mere age shift with respect to natural aging. We suggest that it is interpretable in terms of elastically aided elementary (coil --> helix) local events whose dynamics gradually slows down as aging increases geometric frustration.

Magic angles and cross-hatching instability in hydrogel fracture.

The full 2D analysis of roughness profiles of fracture surfaces resulting from quasistatic crack propagation in gelatin gels reveals an original behavior characterized by (i) strong anisotropy with maximum roughness at V-independent symmetry-preserving angles and (ii) a subcritical instability leading, below a critical velocity, to a cross-hatched regime due to straight macrosteps drifting at the same magic angles and nucleated on crack-pinning network inhomogeneities. Step height values are determined by the width of the strain-hardened zone, governed by the elastic crack blunting characteristic of soft solids with breaking stresses much larger than low strain moduli.

Fracture of a biopolymer gel as a viscoplastic disentanglement process.

We present an extensive experimental study of mode-I, steady, slow crack dynamics in gelatin gels. Taking advantage of the sensitivity of the elastic stiffness to gel composition and history we confirm and extend the model for fracture of physical hydrogels which we proposed in a previous paper (Nature Mater. 5, 552 (2006)), which attributes decohesion to the viscoplastic pull-out of the network-constituting chains. So, we propose that, in contrast with chemically cross-linked ones, reversible gels fracture without chain scission.

Non-Amontons behavior of friction in single contacts.

We report on the frictional properties of a single contact between a glassy polymer lens and a flat silica substrate covered either by a disordered or by a self-assembled alkylsilane monolayer. We find that, in contrast to a widely spread belief, the Amontons proportionality between frictional and normal stresses does not hold. Besides, we observe that the velocity dependence of the sliding stress is strongly sensitive to the structure of the silane layer. Analysis of the frictional rheology observed on both disordered and self-assembled monolayers suggests that dissipation is controlled by the plasticity of a glass-like interfacial layer in the former case, and by pinning of polymer chains on the substrate in the latter one.

Anomalous acoustic reflection on a sliding interface or a shear band.

We study the reflection of an acoustic plane wave from a steadily sliding planar interface with velocity-strengthening friction or a shear band in a confined granular medium. The corresponding acoustic impedance is utterly different from that of the static interface. In particular, the system being open, the energy of an in-plane polarized wave is no longer conserved, the work of the external pulling force being partitioned between frictional dissipation and gain (of either sign) of coherent acoustic energy. Large values of the friction coefficient favor energy gain, while velocity strengthening tends to suppress it. An interface with infinite elastic contrast (one rigid medium) and v-independent (Coulomb) friction exhibits spontaneous acoustic emission, as already shown by Nosonovsky and Adams [Int. J. Eng. Sci. 39, 1257 (2001)]. But this pathology is cured by a moderately large V strengthening of friction, or, for systems with not too large friction coefficients, by any finite elastic contrast. We show that (i) positive gain should be observable for rough-on-flat multicontact interfaces and (ii) a sliding shear band in a granular medium should give rise to sizable reflection, which opens a promising possibility for the detection of shear localization.

Self-healing slip pulses and the friction of gelatin gels.

We present an extensive experimental study and scaling analysis of friction of gelatin gels on glass. At low driving velocities, sliding occurs via propagation of periodic self-healing slip pulses whose velocity is limited by collective diffusion of the gel network. Healing can be attributed to a frictional instability occurring at the slip velocity V=Vc. For V>Vc, sliding is homogeneous and friction is ruled by the shear-thinning rheology of an interfacial layer of thickness of order the (nanometric) mesh size, containing a solution of polymer chain ends hanging from the network. In spite of its high degree of confinement, the rheology of this system does not differ qualitatively from known bulk ones. The observed ageing of the static friction threshold reveals the slow increase of adhesive bonding between chain ends and glass. Such structural ageing is compatible with the existence of a velocity-weakening regime at velocities smaller than Vc, hence with the existence of the healing instability.

Pressure dependence of the sound velocity in a two-dimensional lattice of Hertz-Mindlin balls: mean-field description.

We study the dependence on the external pressure P of the velocities v(L,T) of long wavelength sound waves in a confined two-dimensional hexagonal close-packed lattice of 3D elastic frictional balls interacting via one-sided Hertz-Mindlin contact forces, whose diameters exhibit mild dispersion. The presence of an underlying long range order enables us to build an effective medium description, which incorporates the radial fluctuations of the contact forces acting on a single site. Due to the nonlinearity of Hertz elasticity, self-consistency results in a highly nonlinear differential equation for the "equation of state" linking the effective stiffness of the array with the applied pressure, from which sound velocities are then obtained. The results are in excellent agreement with existing experimental results and simulations in the high- and intermediate-pressure regimes. It emerges from the analysis that the departure of v(L)(P) from the ideal P(1/6) Hertz behavior must be attributed primarily to the fluctuations of the stress field, rather than to the pressure dependence of the number of contacts.

Rheological aging and rejuvenation in solid friction contacts.

We study the low-velocity (0.1-100 microm s(-1)) frictional properties of interfaces between a rough glassy polymer and smooth silanized glass, a configuration which gives direct access to the rheology of the adhesive joints in which shear localizes. We show that these joints exhibit the full phenomenology expected for confined quasi-2D soft glasses: they strengthen logarithmically when aging at rest, and weaken (rejuvenate) when sliding. Rejuvenation is found to saturate at large velocities. Moreover, aging at rest is shown to be strongly accelerated when waiting under finite stress below the static threshold.

Jamming creep of a frictional interface.

We measure the displacement response of a frictional multicontact interface between identical polymer glasses to a biased shear force oscillation. We evidence the existence, for maximum forces close below the nominal static threshold, of a jamming creep regime governed by an aging-rejuvenation competition acting within the micrometer-sized contacting asperities. The time dependence of the creep process deviates from the standard Rice-Ruina [J. R. Rice and A. L. Ruina, J. Appl. Mech. 50, 343 (1983)] phenomenology at early times; this suggests the possibility of an aging-rejuvenation competition at much smaller scales, within the nanometer-thick adhesive junctions.

HLA-A2 restricted, melanocyte-specific CD8(+) T lymphocytes detected in vitiligo patients are related to disease activity and are predominantly directed against MelanA/MART1.

Vitiligo is a skin and hair disorder characterized by circumscribed depigmented lesions due to lack of melanocytes in the respective areas. It has been suggested that vitiligo is caused by an autoimmune-mediated destruction of melanocytes. Recently, the presence of a high frequency of skin-homing melanocyte-specific cytotoxic T lymphocytes in the peripheral blood of patients with vitiligo was reported. Our study examines the frequency of melanocyte-specific cytotoxic T lymphocytes in vitiligo patients and its relationship to disease activity. Thirty-two patients with moderate to active vitiligo and 17 control subjects were included. Melanocyte specific reactive CD8(+) T cells were identified by enzyme-linked immunospot assay after stimulation with five peptides from gp100, four peptides from MelanA/MART1, and two peptides from tyrosinase. In selected patients, intracellular interferon-gamma staining for the detection of specific reactive CD8(+) T cells was additionally performed. In seven of 10 patients (70%) with actively progressive disease CD8(+) T cells directed against melanocyte epitopes were detected, whereas only in four of 22 patients (18%) with moderate disease activity such specific reactivity was found. MelanA/MART1 peptides were immunodominant in nine patients reacting against EAAGIGILTV and three patients reacting against ILTVILGVL. Intracellular interferon-gamma staining confirmed the findings obtained by the enzyme-linked immunospot technique. The present study supports the hypothesis that vitiligo is a cytotoxic T lymphocyte-mediated autoimmune disease. The presence of melanocyte-specific reactive CD8(+) T cells seems to be closely related to disease activity.

Shear response of a frictional interface to a normal load modulation

We study the shear response of a sliding multicontact interface submitted to a harmonically modulated normal load, without loss of contact. We measure, at low velocities (V<100 &mgr;m s(-1)), the average value &Fmacr; of the friction force and the amplitude of its first and second harmonic components. The excitation frequency (f=120 Hz) is chosen much larger than the natural one, associated with the dynamical aging of the interface. We show the following: (i) In agreement with the engineering thumb rule, even a modest modulation induces a substantial decrease of &Fmacr;. (ii) The Rice-Ruina state and rate model, though appropriate to describe the slow frictional dynamics, must be extended when dealing with our "high" frequency regime. That is, the rheology which controls the shear strength must explicitly account not only for the plastic response of the adhesive junctions between load-bearing asperities, but also for the elastic contribution of the asperities bodies. This "elastoplastic" friction model leads to predictions in excellent quantitative agreement with all our experimental data.

Slip pulses at a sheared frictional viscoelastic/nondeformable interface

We study the possibility for a semi-infinite block of linear viscoelastic material, in homogeneous frictional contact with a nondeformable one, to slide under shear via a periodic set of "self-healing pulses," i.e., a set of drifting slip regions separated by stick ones. We show that, contrary to existing experimental indications, such a mode of frictional sliding is impossible for an interface obeying a simple local Coulomb law of solid friction. We then discuss possible physical improvements of the friction model which might open the possibility of such dynamics, among which slip weakening of the friction coefficient, and stress the interest of developing systematic experimental investigations of this question.

[Diastolic left ventricular dysfunction with microvascular angina (Syndrome X)]. / Diastolische linksventrikulare Dysfunktion bei Mikreovaskular-Angina (Syndrom X).

Findings on left ventricular function in microvascular angina (syndrome X) are somewhat controversial. Recently, an increased prevalence of insulin resistance and hyperlipoproteinemia has been demonstrated as well as arterial hypertension potentially impairing the left ventricular diastolic function. In an attempt to analyze the diastolic function at rest, we investigated by Doppler echocardiography the transmitral blood flow in 16 patients (51 +/- 8 years). The diastolic data were compared with those of 12 healthy people (50 +/- 6 years) who were matched for age. The patients with microvascular angina revealed a slightly higher systolic blood pressure (134 +/- 18 mm Hg vs 125 +/- 9 mm Hg, n.s.), but imposed by higher left ventricular mass index (92 +/- 18 g/m2 vs 65 +/- 13 g/m2, p < 0.001). There was a trend to an elevated A-wave-peak during transmitral blood flow (61 +/- 14 cm/s vs 50 +/- 9 cm/s). The findings suggest impairment of the left ventricular relaxation before manifestation of left ventricular hypertrophy and hypertension takes place.