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We study experimentally and theoretically the dynamics of permanent paramagnetic chains and mixed clusters formed by permanent paramagnetic chains and paramagnetic particles under the influence of a time-varying magnetic field. First, we examine the dynamics of permanent chains at high frequencies (∼50 to 1000 Hz). These permanent chains exhibit continuous rotational motion with a frequency several orders of magnitude lower than that of the magnetic field. We develop a theoretical model that accurately describes the dependence of the rotational dynamics of chains on their length, as well as the amplitude and frequency of the external magnetic field in this high frequency regime. Next, we examine how cluster dynamics are affected by the presence of permanent chains. We show that the rotation of clusters composed of a high proportion of permanent chains is slowed down but remains qualitatively well described by the theoretical model we developed for homogeneous clusters of isotropic particles. We propose that the decrease in angular velocity for mixed clusters is due to the hardening of the cluster's 2D elastic modulus caused by the increase of the steric interaction parameter stemming from the presence of chemical links between particles in the chains. [ABSTRACT FROM AUTHOR]

We study experimentally and theoretically the dynamics of two-dimensional self-assembled binary clusters of paramagnetic colloids of two different sizes and magnetic susceptibilities under a time-varying magnetic field. Due to the continuous energy input by the rotating field, these clusters are at a state of dissipative nonequilibrium. Dissipative viscoelastic shear waves traveling around their interface enable the rotation of isotropic binary clusters. The angular velocity of a binary cluster is much slower than that of the magnetic field; it increases with the concentration of big particles, and it saturates at a concentration threshold. We generalize an earlier theoretical model to successfully account for the observed effect of cluster composition on cluster rotation. We also investigate the evolution of the internal distribution of the two particle types, reminiscent of segregation in a drop of two immiscible liquids, and the effect of this internal structure on rotation dynamics. The binary clusters exhibit short-range order, which rapidly vanishes at a larger scale, consistent with the clusters' viscoelastic liquid behavior. [ABSTRACT FROM AUTHOR]

Metabolic studies and animal knockout models point to the critical role of polyunsaturated docosahexaenoic acid (22:6, DHA)-containing phospholipids (DHA-PLs) in physiology. Here, we investigated the impact of DHA-PLs on the dynamics of transendothelial cell macroapertures (TEMs) triggered by RhoA inhibition-associated cell spreading. Lipidomic analyses showed that human umbilical vein endothelial cells (HUVECs) subjected to a DHA diet undergo a 6-fold enrichment in DHA-PLs at the plasma membrane (PM) at the expense of monounsaturated oleic acid-containing PLs (OA-PLs). Consequently, DHA-PL enrichment at the PM induces a reduction in cell thickness and shifts cellular membranes towards a permissive mode of membrane fusion for transcellular tunnel initiation. We provide evidence that a global homeostatic control of membrane tension and cell cortex rigidity minimizes overall changes of TEM area through a decrease of TEM size and lifetime. Conversely, low DHA-PL levels at the PM lead to the opening of unstable and wider TEMs. Together, this provides evidence that variations of DHA-PL levels in membranes affect cell biomechanical properties. [ABSTRACT FROM AUTHOR]

Two different fullerene-subphthalocyanine-ferrocene conjugates are prepared and electronic absorption and cyclic voltammetry measurements have shown that the [pi]-[pi] distance has a major impact on the ground-state electronic interactions between the subphthalocyanine and the [C.sub.60]. The synthesis and analysis of the ground- and excited-state electronic interactions occurring in the conjugates, as well as their reference [C.sub.60]-subphthalocyanine and subphthalocyanine-ferrocene dyads, is described.

Oligo(p-phenylene-vinylene) oligomers capped with a guanosine or a guanine moiety are prepared via a palladium-catalyzed cross-coupling reaction and their self-assembly is studied in solution, solid state and on surfaces. The studies have shown that these [pi]-conjugated molecules self-associate in a mixture of hydrogen-bonded oligomers, among which the G-quartet structure is predominant if the steric hindrance around the guanine base is important.

The synthesis and the electrochemical and photophysical properties of a series of three isomeric Pc-AQ-Pc triads, covalently linked by ethenyl spaces are presented. The effect of the aggregation status of the Pc-AQ-Pc triads as a function of molecular topology and solvent environment, on their redox and photoinduced charge-separation properties is demonstrated.

Studies on the photoinduced electron-accepting ability of Subphthalocyanines in a series of dyad having ferrocene donor unit covalently attached through the axial position of the macrocycle are presented. It is shown that charge separation progresses from singlet excited state to a stabilized radical ion pair whose recombination lifetime is among the longest reported for a dyad system.

The second order nonlinear optical properties of a series of trinitrosubphthalocyanine (SubPc) isomers were studied by electric field induced second harmonic (EFISH) generation and hyper Rayleigh scattering (HRS). The results indicate that the dipolar contributions to the beta tensor are dependent on the substitution pattern at the periphery of the subthalocyanine macrocycle, whereas the octupolar contributions remain almost unchanged.

Subphthalocyanines are light harvesting and/or donor units for photosynthetic systems. The study conducted on them, proves that they are synthetically and electronically versatile molecular units used for the construction of multicomponent photoactive systems.

In the tumor environment, interstitial pressure drives interstitial flow drainage from the tumor core to the lymphatic vessels. Recent studies have highlighted the key role of interstitial pressure in tumor development and cell migration. High intratumoral pressures, up to 60 mm Hg , have been reported in cancer patients. In a previous study, we showed that such pressure levels induce fracture in an experimental tumor model consisting of a microfluidic system holding a cellular aggregate. Here, we investigate and quantify the characteristics of tumor model fracture under a range of flow conditions. Our findings suggest a strong dependence of viscoelastic fracture behavior on the loading rate exerted by flow. The aggregate exhibits fragile fracture at high loading rates and ductile fracture at lower rates. The loading rate also modifies the permeability of the cellular aggregate, as well as the persistence time of the load required to induce fracture. The quantification parameters we propose here, evaluated for an in vitro model tumor without the extracellular matrix, could be applied to characterize tumor fracture under more realistic interstitial flow conditions. [ABSTRACT FROM AUTHOR]

Drug-eluting stents (DES), which release anti-proliferative drugs into the arterial wall in a controlled manner, have drastically reduced the rate of in-stent restenosis and revolutionized the treatment of atherosclerosis. However, late stent thrombosis remains a safety concern in DES, mainly due to delayed healing of the endothelial wound inflicted during DES implantation. We present a framework to optimize DES design such that restenosis is inhibited without affecting the endothelial healing process. To this end, we have developed a computational model of fluid flow and drug transport in stented arteries and have used this model to establish a metric for quantifying DES performance. The model takes into account the multi-layered structure of the arterial wall and incorporates a reversible binding model to describe drug interaction with the cells of the arterial wall. The model is coupled to a novel optimization algorithm that allows identification of optimal DES designs. We show that optimizing the period of drug release from DES and the initial drug concentration within the coating has a drastic effect on DES performance. Paclitaxel-eluting stents perform optimally by releasing their drug either very rapidly (within a few hours) or very slowly (over periods of several months up to one year) at concentrations considerably lower than current DES. In contrast, sirolimus-eluting stents perform optimally only when drug release is slow. The results offer explanations for recent trends in the development of DES and demonstrate the potential for large improvements in DES design relative to the current state of commercial devices. [ABSTRACT FROM AUTHOR]

Nanoparticles offer a promising medical tool for targeted drug delivery, for example to treat inflamed endothelial cells during the development of atherosclerosis. To inform the design of such therapeutic strategies, we develop a computational model of nanoparticle internalization into endothelial cells, where internalization is driven by receptor-ligand binding and limited by the deformation of the cell membrane and cytoplasm. We specifically consider the case of nanoparticles targeted against ICAM-1 receptors, of relevance for treating atherosclerosis. The model computes the kinetics of the internalization process, the dynamics of binding, and the distribution of stresses exerted between the nanoparticle and the cell membrane. The model predicts the existence of an optimal nanoparticle size for fastest internalization, consistent with experimental observations, as well as the role of bond characteristics, local cell mechanical properties, and external forces in the nanoparticle internalization process. [ABSTRACT FROM AUTHOR]

Dewetting is the spontaneous withdrawal of a liquid film from a non-wettable surface by nucleation and growth of dry patches. Two recent reports now propose that the principles of dewetting explain the physical phenomena underpinning the opening of transendothelial cell macroaperture (TEM) tunnels, referred to as cellular dewetting. This was discovered by studying a group of bacterial toxins endowed with the property of corrupting actomyosin cytoskeleton contractility. For both liquid and cellular dewetting, the growth of holes is governed by a competition between surface forces and line tension. We also discuss how the dynamics of TEM opening and closure represent remarkable systems to investigate actin cytoskeleton regulation by sensors of plasma membrane curvature and investigate the impact on membrane tension and the role of TEM in vascular dysfunctions. [ABSTRACT FROM AUTHOR]

Pathogenic bacteria can cross from blood vessels to host tissues by opening transendothelial cell macroapertures (TEMs). To induce TEM opening, bacteria intoxicate endothelial cells with proteins that disrupt the contractile cytoskeletal network. Cell membrane tension is no longer resisted by contractile fibers, leading to the opening of TEMs. Here we model the opening of TEMs as a new form of dewetting. While liquid dewetting is irreversible, we show that cellular dewetting is transient. Our model predicts the minimum radius for hole nucleation, the maximum TEM size, and the dynamics of TEM opening, in good agreement with experimental data. The physical model is then coupled with biological experimental data to reveal that the protein missing in metastasis (MIM) controls the line tension at the rim of the TEM and opposes its opening. [ABSTRACT FROM AUTHOR]

Oscillating water tunnels are experimental facilities commonly used in coastal engineering research. They are intended to reproduce near-bed hydrodynamic and sediment transport phenomena at a realistic scale. In an oscillating water tunnel, a piston generates an oscillatory motion that propagates almost instantaneously to the whole tunnel; consequently, flow is uniform along the tunnel, unlike the propagating wave motion in the sea or in a wave flume. This results in subtle differences between the boundary-layer hydrodynamics of an oscillating water tunnel and of a propagating wave, which may have a significant effect in the resulting sediment transport. In this paper, we present a zeroth-order analytical model of the turbulent boundary-layer hydrodynamics in an oscillating water tunnel. By using a time-varying eddy viscosity and by accounting for the constraints arising from the tunnel's geometry, the model predicts the oscillating water tunnel hydrodynamics and yields analytical expressions to compute bed shear stresses for asymmetric and skewed waves, both in the absence or presence of an imposed current. These expressions are applied to successfully quantify bedload sediment transport in oscillating water tunnel experiments. [ABSTRACT FROM AUTHOR]

Abstract: A simple conceptual formulation to compute seabed shear stress due to asymmetric and skewed waves is presented. This formulation generalizes the sinusoidal wave case and uses a variable friction factor to describe the physics of the boundary layer and to parameterize the effects of wave shape. Predictions of bed shear stresses agree with numerical computations using a standard boundary layer model with a k–ε turbulence closure. The bed shear stress formulation is combined with a Meyer-Peter and Müller-type formula to predict sheet flow bedload transport under asymmetric and skewed waves for a horizontal or sloping bed. The predictions agree with oscillatory water tunnel measurements from the literature. [Copyright &y& Elsevier]

Discusses the synthesis and the chemical and physical properties of aromatic compound subphtalocyanines as well as their relatives subazaporphyrins and subnaphthalocyanines. Composition of subphthalocyanines; Preparation of unsubstituted subphthalocyanine 1; Subphthalocyanines obtained by condensation of a phthalonitrile derivative; Peripheral reactivity of subphthalocyanines.

Mitochondria are dynamic cell organelles that constantly undergo fission and fusion events. These dynamical processes, which tightly regulate mitochondrial morphology, are essential for cell physiology. Here we propose an elastocapillary mechanical instability as a mechanism for mitochondrial fission. We experimentally induce mitochondrial fission by rupturing the cell's plasma membrane. We present a stability analysis that successfully explains the observed fission wavelength and the role of mitochondrial morphology in the occurrence of fission events. Our results show that the laws of fluid mechanics can describe mitochondrial morphology and dynamics. [ABSTRACT FROM AUTHOR]