Shaping of molecular weight distribution by iterative learning probability density function control strategies

A mathematical model is developed for the molecular weight distribution (MWD) of free-radical styrene polymerization in a simulated semi-batch reactor system. The generation function technique and moment method are employed to establish the MWD model in the form of Schultz-Zimmdistribution. Both static and dynamic models are described in detail. In order to achieve the closed-loop MWD shaping by output probability density function (PDF) control, the dynamic MWD model is further developed by a linear B-spline approximation. Based on the general form of the B-spline MWD model, iterative learning PDF control strategies have been investigated in order to improve the MWD control performance. Discussions on the simulation studies show the advantages and limitations of the methodology

Stress relaxation in F-actin solutions by severing

Networks of filamentous actin (F-actin) are important for the mechanics of most animal cells. These cytoskeletal networks are highly dynamic, with a variety of actin-associated proteins that control cross-linking, polymerization and force generation in the cytoskeleton. Inspired by recent rheological experiments on reconstituted solutions of dynamic actin filaments, we report a theoretical model that describes stress relaxation behavior of these solutions in the presence of severing proteins. We show that depending on the kinetic rates of assembly, disassembly, and severing, one can observe both length-dependent and length-independent relaxation behavior

Polymer-Mode-Coupling Theory of Finite-Size-Fluctuation Effects in Entangled Solutions, Melts and Gels. I. General Formulation and Predictions

The transport coefficients of dense polymeric fluids are approximately calculated from the microscopic intermolecular forces. The following finite molecular weight effects are discussed within the Polymer-Mode-Coupling theory (PMC) and compared to the corresponding reptation/ tube ideas: constraint release mechanism, spatial inhomogeneity of the entanglement constraints, and tracer polymer shape fluctuations. The entanglement corrections to the single polymer Rouse dynamics are shown to depend on molecular weight via the ratio N/N_e, where the entanglement degree of polymerization, N_e, can be measured from the plateau shear modulus. Two microscopically defined non-universal parameters, an entanglement strength 1/alpha and a length scale ratio, delta= xi_rho/b, where xi_rho and b are the density screening and entanglement length respectively, are shown to determine the reduction of the entanglement effects relative to the reptation- -like asymptotes of PMC theory. Large finite size effects are predicted for reduced degrees of polymerization up to N/N_e\le10^3. Effective power law variations for intermediate N/N_e of the viscosity, eta\sim N^x, and the diffusion constant, D\sim N^{-y}, can be explained with exponents significantly exceeding the asymptotic, reptation-like values, x\ge 3 and y\ge2, respectively. Extensions of the theory to treat tracer dielectric relaxation, and polymer transport in gels and other amorphous systems, are also presented.Comment: Latex, figures and styles files included; Macromolecules, in press (1997

Coupling of cytoplasm and adhesion dynamics determines cell polarization and locomotion

Observations of single epidermal cells on flat adhesive substrates have revealed two distinct morphological and functional states, namely a non-migrating symmetric unpolarized state and a migrating asymmetric polarized state. These states are characterized by different spatial distributions and dynamics of important biochemical cell components: F-actin and myosin-II form the contractile part of the cytoskeleton, and integrin receptors in the plasma membrane connect F-actin filaments to the substratum. In this way, focal adhesion complexes are assembled, which determine cytoskeletal force transduction and subsequent cell locomotion. So far, physical models have reduced this phenomenon either to gradients in regulatory control molecules or to different mechanics of the actin filament system in different regions of the cell. Here we offer an alternative and self-organizational model incorporating polymerization, pushing and sliding of filaments, as well as formation of adhesion sites and their force dependent kinetics. All these phenomena can be combined into a non-linearly coupled system of hyperbolic, parabolic and elliptic differential equations. Aim of this article is to show how relatively simple relations for the small-scale mechanics and kinetics of participating molecules may reproduce the emergent behavior of polarization and migration on the large-scale cell level.Comment: v2 (updates from proof): add TOC, clarify Fig. 4, fix several typo

Mitigation of GHGs Emission From Soils by a Catalyzed In-Situ Photo-Oxidative Polymerization of Soil Organic Matter

Agricultural lands under food and bio-energy crops, managed grass and permanent crops including agro-forestry, occupy about 40-50% of the Earth's land surface^1^. In 2005, agriculture accounted for an estimated emission of 5.1 to 6.1 GtCO2-eq/yr (10-12% of total global anthropogenic emissions of greenhouse gases (GHGs))^1^. However, measures to mitigate GHGs emission from agricultural soils are limited to improved cropland practices such as crop rotation, nutrient management, tillage/residue management, agroforestry, and return to natural vegetation^2^. These practices are not only far from substantially reducing GHGs emissions from soils or permanentlystabilizing soil organic matter^1-4^, but are also predicted to hardly match more than amaximum of 25% of the GHGs reductions required by the Kyoto Protocol within 2050^5^.Despite the knowledge that GHGs release from soil largely derives from biochemicaltransformations of plant litter and soil organic matter (SOM)^6-8^, no new and much wished biotechnological measures are adopted so far to augment mitigation^1^. Here we propose an innovative approach to mitigate GHGs emissions from soils based on the insitu photo-polymerization of SOM under biomimetic catalysis. Three Mediterranean soils of different physical and chemical properties were added with a synthetic watersolubleiron-porphyrin, irradiated by solar light, and subjected to 15, and 30 wetting and drying cycles. We found that the in situ catalysed photo-polymerization of SOM increased soil physical aggregation, shifted OC into larger soil aggregates, and reduced CO~2~ released by microbial respiration. Our findings suggest that "green" catalytic technologies can become viable soil management practices to enhance mitigation of GHGs emission from arable soils and contribute to match the expectations of the post-Kyoto Protocol in the agricultural sector

Gas fluidized bed polymerization.

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Predictive PDF control in shaping of molecular weight distribution based-on a new modelling Algorithm

The aims of this work are to develop an efficient modeling method for establishing dynamic output probability density function (PDF) models using measurement data and to investigate predictive control strategies for controlling the full shape of output PDF rather than the key moments. Using the rational square-root (RSR) B-spline approximation, a new modeling algorithm is proposed in which the actual weights are used instead of the pseudo weights in the weights dynamic model. This replacement can reduce computational load effectively in data-based modeling of a high-dimensional output PDF model. The use of the actual weights in modeling and control has been verified by stability analysis. A predictive PDF model is then constructed, based on which predictive control algorithms are established with the purpose to drive the output PDF towards the desired target PDF over the control process. An analytical solution is obtained for the non-constrained predictive PDF control. For the constrained predictive control, the optimal solution is achieved via solving a constrained nonlinear optimization problem. The integrated method of data-based modeling and predictive PDF control is applied to closed-loop control of molecular weight distribution (MWD) in an exemplar styrene polymerization process, through which the modeling efficiency and the merits of predictive control over standard PDF control are demonstrated and discussed