Exchange of stability as a function of system size in a nonequilibrium system

In equilibrium systems with short-ranged interactions, the relative stability of different thermodynamic states generally does not depend on system size (as long as this size is larger than the interaction range). Here, we use a large deviations approach to show that, in contrast, different states can exchange stability as system size is varied in a driven, bistable reaction-diffusion system. This striking effect is related to a shift from a spatially uniform to a nonuniform transition state and should generically be possible in a wide range of nonequilibrium physical and biological systems.Comment: 7 pages, 4 figures. Supporting Material included in same file with main tex

The isotropic-nematic interface in suspensions of hard rods: Mean-field properties and capillary waves

We present a study of the isotropic-nematic interface in a system of hard spherocylinders. First we compare results from Monte Carlo simulations and Onsager density functional theory for the interfacial profiles of the orientational order parameter and the density. Those interfacial properties that are not affected by capillary waves are in good agreement, despite the fact that Onsager theory overestimates the coexistence densities. Then we show results of a Monte Carlo study of the capillary waves of the interface. In agreement with recent theoretical investigations (Eur.Phys.J. E {\bf 18} 407 (2005)) we find a strongly anistropic capillary wave spectrum. For the wave-numbers accessed in our simulations, the spectrum is quadratic, i.e.elasticity does not play a role. We conjecture that this effect is due to the strong bending rigidity of the director field in suspensions of spherocylinders.Comment: 8 pages, 10 figure

Spatio-temporal correlations can drastically change the response of a MAPK pathway

Multisite covalent modification of proteins is omnipresent in eukaryotic cells. A well-known example is the mitogen-activated protein kinase (MAPK) cascade, where in each layer of the cascade a protein is phosphorylated at two sites. It has long been known that the response of a MAPK pathway strongly depends on whether the enzymes that modify the protein act processively or distributively: distributive mechanism, in which the enzyme molecules have to release the substrate molecules in between the modification of the two sites, can generate an ultrasensitive response and lead to hysteresis and bistability. We study by Green's Function Reaction Dynamics, a stochastic scheme that makes it possible to simulate biochemical networks at the particle level and in time and space, a dual phosphorylation cycle in which the enzymes act according to a distributive mechanism. We find that the response of this network can differ dramatically from that predicted by a mean-field analysis based on the chemical rate equations. In particular, rapid rebindings of the enzyme molecules to the substrate molecules after modification of the first site can markedly speed up the response, and lead to loss of ultrasensitivity and bistability. In essence, rapid enzyme-substrate rebindings can turn a distributive mechanism into a processive mechanism. We argue that slow ADP release by the enzymes can protect the system against these rapid rebindings, thus enabling ultrasensitivity and bistability

Sustainable metal-free carbogels as oxygen reduction electrocatalysts

crosscheck: This document is CrossCheck deposited related_data: Supplementary Information copyright_licence: The Royal Society of Chemistry has an exclusive publication licence for this journal history: Received 5 March 2017; Accepted 2 May 2017; Accepted Manuscript published 2 May 2017Kathrin Preuss would like to thank the Materials Research Institute of Queen Mary, University of London for a PhD studentship. Liviu C. Tănase and Cristian M. Teodorescu acknowledge funding from the UEFISCDI Agency through the Project PN-II-RU-TE-2014-4-0456 and by the NIMP Core Project PN16-48012, both projects being granted by the Romanian Ministry of Research and Innovation

Syntheses, structures, and mesomorphism of a series of Cu(II) salen complexes with 4-substituted long alkoxy chains

This is a preprint of an article whose final and definitive form has been published in the MOLECULAR CRYSTALS AND LIQUID CRYSTALS © 2007 copyright Taylor & Francis; MOLECULAR CRYSTALS AND LIQUID CRYSTALS is available online at : http://www.informaworld.com/openurl?genre=article&issn=1542-1406&volume=466&issue=1&spage=129ArticleMOLECULAR CRYSTALS AND LIQUID CRYSTALS. 466(1): 129-147 (2007)journal articl

Molybdenum-99 (99Mo) Adsorption Profile of Zirconia-Based Materials for 99Mo/99mTc Generator Application

Technetium-99m (99mTc) plays a major role in diagnostic nuclear medicine and has not yet been replaced with any other radionuclides. It is available through the 99Mo/99mTc generator. The use of low-specific-activity 99Mo for 99Mo/99mTc generator application requires high adsorptive capacity sorbents. This study focused on the determination of 99Mo adsorption capacity of several zirconia materials, namely monoclinic nanozirconia, orthorhombic nanozirconia, sulfated zirconia,   and phosphated zirconia. These materials were synthesized by using the sol-gel method and characterized using FT-IR spectroscopy, X-ray diffraction (XRD), and scanning electron microscopy/energy-dispersive X-ray spectroscopy (SEM-EDS). The determination of 99Mo adsorption capacity of these materials was carried out by soaking the materials in a Na299MoO4 solution with pH of 3 and 7, at temperatures ranging from room temperature to 90 °C, for 1 and 3 hours. The results indicated that monoclinic nanozirconia has a 99Mo adsorption capacity of 76.9 mg Mo/g, whereas orthorhombic nanozirconia, sulfated zirconia, and phosphated zirconia have 99Mo adsorption capacities of 150.1 mg Mo/g, 15.58 mg Mo/g, and 12.74 mg Mo/g, respectively. It appears that orthorhombic nanozirconia has the highest 99Mo adsorption capacity among the synthesized materials and can be applied as a candidate material for the 99Mo/99mTc generator

Paclitaxel plus Carboplatin Chemotherapy for Primary Peritoneal Carcinoma: A Study of 22 Cases and Comparison with Stage III–IV Ovarian Serous Carcinoma

The aim of this study was to assess the clinical characteristics and outcome of patients with either primary peritoneal carcinoma (PPC) or ovarian serous carcinoma (OSC) treated with paclitaxel plus carboplatin chemotherapy. We retrospectively identified 22 PPC patients and 55 stage III–IV OSC patients treated between 2002 and 2007. After exploratory laparotomy, all patients received paclitaxel and carboplatin every 3 weeks, with the goal of optimal cytoreduction. There were no statistically significant differences between the PPC and OSC groups with regard to tumor stage, residual tumor after debulking surgery (initial or interval), serum cancer antigen (CA) 125 levels at diagnosis, and completion of first-line chemotherapy. The progression-free survival (PFS) durations were 12.7 months (95% CI, 6.3–18.5) in the patients with PPC and 15.9 months (95% CI, 13.3–18.5) in those with OSC (p = 0.016). However, the median survival durations were 26.5 months (95% CI, 14.6–38.3) in the patients with PPC and 38 months (95% CI, 23.8–53.8) in those with OSC (p = 0.188). Survival was longer for all patients whose CA125 levels normalized to 26 U/ml during and after treatment. Overall survival (OS) of the patients with PPC was similar to that of the patients with OSC, suggesting that management for advanced-stage OSC would be similar to that for PPC. The combination of optimal debulking with paclitaxel plus carboplatin chemotherapy may offer patients the most effective treatment. The CA125 nadir after cytoreductive surgery can be considered a prognostic factor for OS and PFS in patients with PPC

Statistical-mechanical formulation of Lyapunov exponents

We show how the Lyapunov exponents of a dynamic system can in general be expressed in terms of the free energy of a (non-Hermitian) quantum many-body problem. This puts their study as a problem of statistical mechanics, whose intuitive concepts and techniques of approximation can hence be borrowed.Comment: 10 pages, 3 figures, RevTex

Dynamics and geometric properties of the k-Trigonometric model

We analyze the dynamics and the geometric properties of the Potential Energy Surfaces (PES) of the k-Trigonometric Model (kTM), defined by a fully-connected k-body interaction. This model has no thermodynamic transition for k=1, a second order one for k=2, and a first order one for k>2. In this paper we i) show that the single particle dynamics can be traced back to an effective dynamical system (with only one degree of freedom); ii) compute the diffusion constant analytically; iii) determine analytically several properties of the self correlation functions apart from the relaxation times which we calculate numerically; iv) relate the collective correlation functions to the ones of the effective degree of freedom using an exact Dyson-like equation; v) using two analytical methods, calculate the saddles of the PES that are visited by the system evolving at fixed temperature. On the one hand we minimize |grad V|^2, as usually done in the numerical study of supercooled liquids and, on the other hand, we compute the saddles with minimum distance (in configuration space) from initial equilibrium configurations. We find the same result from the two calculations and we speculate that the coincidence might go beyond the specific model investigated here.Comment: 36 pages, 13 figure

Interactions between Magnetic Nanowires and Living Cells : Uptake, Toxicity and Degradation

We report on the uptake, toxicity and degradation of magnetic nanowires by NIH/3T3 mouse fibroblasts. Magnetic nanowires of diameters 200 nm and lengths comprised between 1 {\mu}m and 40 {\mu}m are fabricated by controlled assembly of iron oxide ({\gamma}-Fe2O3) nanoparticles. Using optical and electron microscopy, we show that after 24 h incubation the wires are internalized by the cells and located either in membrane-bound compartments or dispersed in the cytosol. Using fluorescence microscopy, the membrane-bound compartments were identified as late endosomal/lysosomal endosomes labeled with lysosomal associated membrane protein (Lamp1). Toxicity assays evaluating the mitochondrial activity, cell proliferation and production of reactive oxygen species show that the wires do not display acute short-term (< 100 h) toxicity towards the cells. Interestingly, the cells are able to degrade the wires and to transform them into smaller aggregates, even in short time periods (days). This degradation is likely to occur as a consequence of the internal structure of the wires, which is that of a non-covalently bound aggregate. We anticipate that this degradation should prevent long-term asbestos-like toxicity effects related to high aspect ratio morphologies and that these wires represent a promising class of nanomaterials for cell manipulation and microrheology.Comment: 21 pages 12 figure