ATP synthesis and pyrophosphate-driven proton transport in tonoplast-enriched vesicles isolated from Catharanthus roseus

AbstractIn the presence of PPi as an energy source, the tonoplast-bound inorganic pyrophosphatase from Catharanthus roseus cells is able to create a proton-gradient which can drive the synthesis of ATP from ADP and Pi. ATP synthesis is linked to the pH-gradient dissipation as monitored by the recovery of the fluorescence intensity of quinacrine and by the amount of synthesized ATP measured by the bioluminescent luciferin/luciferase assay. Proton gradient and ATP synthesis were suppressed by the protonic ionophore gramicidin D

Strain Hardening in Polymer Glasses: Limitations of Network Models

Simulations are used to examine the microscopic origins of strain hardening in polymer glasses. While traditional entropic network models can be fit to the total stress, their underlying assumptions are inconsistent with simulation results. There is a substantial energetic contribution to the stress that rises rapidly as segments between entanglements are pulled taut. The thermal component of stress is less sensitive to entanglements, mostly irreversible, and directly related to the rate of local plastic arrangements. Entangled and unentangled chains show the same strain hardening when plotted against the microscopic chain orientation rather than the macroscopic strain.Comment: 4 pages, 3 figure

Viscoplasticity and large-scale chain relaxation in glassy-polymeric strain hardening

A simple theory for glassy polymeric mechanical response which accounts for large scale chain relaxation is presented. It captures the crossover from perfect-plastic response to strong strain hardening as the degree of polymerization $N$ increases, without invoking entanglements. By relating hardening to interactions on the scale of monomers and chain segments, we correctly predict its magnitude. Strain activated relaxation arising from the need to maintain constant chain contour length reduces the $N$ dependence of the characteristic relaxation time by a factor $\sim \dot\epsilon N$ during active deformation at strain rate $\dot\epsilon$. This prediction is consistent with results from recent experiments and simulations, and we suggest how it may be further tested experimentally.Comment: The theoretical treatment of the mechanical response has been significantly revised, and the arguments for coherent relaxation during active deformation made more transparen

A Kalman rank condition for the localized distributed controllability of a class of linear parabolic systems

We present a generalization of the Kalman rank condition to the case of $n\times n$ linear parabolic systems with constant coefficients and diagonalizable diffusion matrix. To reach the result, we are led to prove a global Carleman estimate for the solutions of a scalar $2n-$order parabolic equation and deduce from it an observability inequality for our adjoint system

A generalization of the Kalman rank condition for time-dependent coupled linear parabolic systems

In this paper we present a generalization of the Kalman rank condition for linear ordinary differential systems to the case of systems of n coupled parabolic equations (posed in the time interval (0,T) with T > 0) where the coupling matrices A and B depend on the time variable t . To be precise, we will prove that the Kalman rank condition rank [A|B](t0) = n, with t0 ∈ [0,T], is a sufficient condition (but not necessary) for obtaining the exact controllability to the trajectories of the considered parabolic system. In the case of analytic matrices A and B (and, in particular, constant matrices), we will see that the Kalman rank condition characterizes the controllability properties of the system. When the matrices A and B are constant and condition rank [A|B] = n holds, we will be able to state a Carleman inequality for the corresponding adjoint problem.Agence Nationale de la rechercheDirección General de Enseñanza Superio

Scaling of the Strain Hardening Modulus of Glassy Polymers with the Flow Stress

In a recent letter, Govaert et al. examined the relationship between strain hardening modulus $G_r$ and flow stress $\sigma_{flow}$ for five different glassy polymers. In each case, results for $G_r$ at different strain rates or different temperatures were linearly related to the flow stress. They suggested that this linear relation was inconsistent with simulations. Data from previous publications and new results are presented to show that simulations also yield a linear relation between modulus and flow stress. Possible explanations for the change in the ratio of modulus to flow stress with temperature and strain rate are discussed.Comment: 8 pages, 2 figures: clarified arguments on linear proportionality. Accepted for publication in J. Poly. Sci Part B - Polym. Phy

Strain Hardening of Polymer Glasses: Entanglements, Energetics, and Plasticity

Simulations are used to examine the microscopic origins of strain hardening in polymer glasses. While stress-strain curves for a wide range of temperature can be fit to the functional form predicted by entropic network models, many other results are fundamentally inconsistent with the physical picture underlying these models. Stresses are too large to be entropic and have the wrong trend with temperature. The most dramatic hardening at large strains reflects increases in energy as chains are pulled taut between entanglements rather than a change in entropy. A weak entropic stress is only observed in shape recovery of deformed samples when heated above the glass transition. While short chains do not form an entangled network, they exhibit partial shape recovery, orientation, and strain hardening. Stresses for all chain lengths collapse when plotted against a microscopic measure of chain stretching rather than the macroscopic stretch. The thermal contribution to the stress is directly proportional to the rate of plasticity as measured by breaking and reforming of interchain bonds. These observations suggest that the correct microscopic theory of strain hardening should be based on glassy state physics rather than rubber elasticity.Comment: 15 pages, 12 figures: significant revision

Temperature and rate dependent finite strain behavior of poly(ethylene terephthalate) and poly(ethylene terephthalate)-glycol above the glass transition temperature

Thesis (Ph. D.)--Massachusetts Institute of Technology, Dept. of Mechanical Engineering, 2003.Includes bibliographical references (p. 333-348).Poly(ethylene terephthalate) is widely used for consumer products such as drawn fibers, stretched films, and soda bottles. Much of its commercial success lies in the fact that it crystallizes at large strains during warm deformation processing. The imparted crystallinity increases its stiffness and strength, improves its dimensional stability, and increases its density. The crystallization process and the stress-strain behavior above the glass transition depend strongly on temperature, strain rate, strain magnitude, and strain state. A robust constitutive model to accurately account for this stress-strain behavior in the processing regime is highly desirable in order to predict and computationally design warm deformation processes to achieve desired end product geometries and properties. This thesis aims to better understand the material behavior above the glass transition temperature in the processing regime. It examines the strain rate, strain state, and temperature dependent mechanical behavior of two polymers: PET and PETG, an amorphous non-crystallizing copolymer of PET, in order to isolate the effects of crystallization on the stress-strain behavior. Experiments over a wide range of temperatures and strain rates were performed in uniaxial and plane strain compression. A constitutive model of the observed rate and temperature dependent stress-strain behavior was then developed. The model represents the material's resistance to deformation with two parallel elements: an intermolecular resistance to flow and a resistance due to molecular network interactions.(cont.) The model predicts the temperature and rate dependence of many stress-strain features of PET and PETG very well, including the initial modulus, flow stress, initial hardening modulus, and dramatic strain hardening. The modeling results indicate that the large strain hardening behavior of both materials can only be captured by including a critical orientation parameter to halt the molecular relaxation process once the network achieves a specific level of molecular orientation. This suggests that much of the strain hardening in PET is due to molecular orientation and not to strain-induced crystallization. An example blow molding process is simulated to demonstrate the industrial applicability of the proposed model.by Rebecca B. Dupaix.Ph.D