171 research outputs found
Polymer dynamics under tension: Mean first passage time for looping
Full text linkThis study deals with polymer looping, an important process in many chemical and biological systems. We investigate basic questions on the looping dynamics of a polymer under tension using the freely jointed chain (FJC) model. Previous theoretical approaches to polymer looping under tension have relied on barrier escape methods, which assume local equilibrium, an assumption that may not always hold. As a starting point, we use an analytical expression for the equilibrium looping probability as a function of the number of monomers and applied force, predicting an inverse relationship between looping time and looping probability. Using molecular dynamics simulations, the predictions of this theoretical approach are validated within the numerical precision achieved. We compare our predictions to those of the barrier escape approach by way of a calculation of the mean first passage time (MFPT) for the ends of a polymer to cross. For this purpose, we derive the exact free energy landscape, but the resulting temporal predictions do not agree with the observed inverse scaling. We conclude that the traditional barrier escape approach does not provide satisfactory predictions for polymer looping dynamics and that the inverse scaling with looping probability offers a more reliable alternative
Dynamics of vitrimers: defects as a highway to stress relaxation: Defects as a Highway to Stress Relaxation
Full text linkWe propose a coarse-grained model to investigate stress relaxation in star-polymer networks induced by dynamic bond-exchange processes. We show how the swapping mechanism, once activated, allows the network to reconfigure, exploring distinct topological configurations, all of them characterized by complete extent of reaction. Our results reveal the important role played by topological defects in mediating the exchange reaction and speeding up stress relaxation. The model provides a representation of the dynamics in vitrimers, a new class of polymers characterized by bond-swap mechanisms which preserve the total number of bonds, as well as in other bond-exchange materials
Swap-driven self-adhesion and healing of vitrimers
Full text linkVitrimers are covalent network materials, comparable in structure to classical thermosets. Unlike normal thermosets, they possess a chemical bond swap mechanism that makes their structure dynamic and suitable for activated welding and even autonomous self-healing. The central question in designing such materials is the trade-off between autonomy and material stability: the swap mechanism facilitates the healing, but it also facilitates creep, which makes the perfectly stable self-healing solid a hard goal to reach. Here, we address this question for the case of self-healing vitrimers made from star polymers. Using coarse-grained molecular dynamics simulations, we studied the adhesion of two vitrimer samples and found that they bond together on timescales that are much shorter than the stress relaxation time. We showed that the swap mechanism allows the star polymers to diffuse through the material through coordinated swap events, but the healing process is much faster and does not depend on this mobility
Stress relaxation in tunable gels
Full text linkHydrogels are a staple of biomaterials development. Optimizing their use in e.g. drug delivery or tissue engineering requires a solid understanding of how to adjust their mechanical properties. Here, we present a numerical study of a class of hydrogels made of 4-arm star polymers with a combination of covalent and reversible crosslinks. This design principle combines the flexibility and responsivity associated with reversible linkers with stability provided by chemical crosslinks. In molecular dynamics simulations of such hybrid gel networks, we observe that the strength of the reversible bonds can tune the material from solid to fluid. We identify at what fraction of reversible bonds this tunability is most pronounced, and find that the stress relaxation time of the gels in this tunable regime is set directly by the average lifetime of the reversible bonds. As our design is easy to realize in the already widely-used tetraPEG gel setting, our work will provide guidelines to improve the mechanical performance of biomedical gels
Does Indonesia have a"low-pay"civil service?
Full text linkGovernment officials and polcy analysts maintain that Indonesia's civil servants are poorly paid and have been for decades. This conclusion is supported by anecdotal evidence and casual empiricism. The authors systematically analyze the realtionship between government and private compensation levels using data from two large household surveys carried out by Indonesia's Central Bureau of Statistics: the 1998 Sakernas and 1999 Susenas. The results suggest that government workers with a high school education or less, representing three-quarters of the civil service, earn a pay premium over their private sector counterparts. Civil servants with more than a high school education earn less than they would in the private sector but, on average, the premium is far smaller than commonly is alleged and is in keeping with public/private differentials in other countries. These results prove robust to varying econometric specifications and cast doubt on low pay as an explanation for government corruption.Decentralization,Public Health Promotion,Health Monitoring&Evaluation,National Governance,Knowledge Economy,Health Monitoring&Evaluation,NationalGovernance,Knowledge Economy,Education for the Knowledge Economy,Parliamentary Government
Rigidity percolation on the square lattice
No full textThe square lattice with central forces between nearest neighbors is isostatic with a subextensive number of floppy modes. It can be made rigid by the random addition of next-nearest-neighbor bonds. This constitutes a rigidity percolation transition which we study analytically by mapping it to a connectivity problem of two-colored random graphs. We derive an exact recurrence equation for the probability of having a rigid percolating cluster and solve it in the infinite volume limit. From this solution we obtain the rigidity threshold as a function of system size, and find that, in the thermodynamic limit, there is a mixed first-order–second-order rigidity percolation transition at the isostatic point
Self-consistent field lattice model for polymer networks
Full text linkA lattice model based on polymer self-consistent field theory is developed to predict the equilibrium statistics of arbitrary polymer networks. For a given network topology, our approach uses moment propagators on a lattice to self-consistently construct the ensemble of polymer conformations and cross-link spatial probability distributions. Remarkably, the calculation can be performed "in the dark", without any prior knowledge on preferred chain conformations or cross-link positions. Numerical results from the model for a test network exhibit close agreement with molecular dynamics simulations, including when the network is strongly sheared. Our model captures nonaffine deformation, mean-field monomer interactions, cross-link fluctuations, and finite extensibility of chains, yielding predictions that differ markedly from classical rubber elasticity theory for polymer networks. By examining polymer networks with different degrees of interconnectivity, we gain insight into cross-link entropy, an important quantity in the macroscopic behavior of gels and self-healing materials as they are deformed
Harnessing entropy to enhance toughness in reversibly crosslinked polymer networks
Full text linkReversible crosslinking is a design paradigm for polymeric materials, wherein they are microscopically reinforced with chemical species that form transient crosslinks between the polymer chains. Besides the potential for self-healing, recent experimental work suggests that freely diffusing reversible crosslinks in polymer networks, such as gels, can enhance the toughness of the material without substantial change in elasticity. This presents the opportunity for making highly elastic materials that can be strained to a large extent before rupturing. Here, we employ Gaussian chain theory, molecular simulation, and polymer self-consistent field theory for networks to construct an equilibrium picture for how reversible crosslinks can toughen a polymer network without affecting its elasticity. Maximisation of polymer entropy drives the reversible crosslinks to bind preferentially near the permanent crosslinks in the network, leading to local molecular reinforcement without significant alteration of the network topology. In equilibrium conditions, permanent crosslinks share effectively the load with neighbouring reversible crosslinks, forming multi-functional crosslink points. The network is thereby globally toughened, while the linear elasticity is left largely unaltered. Practical guidelines are proposed to optimise this design in experiment, along with a discussion of key kinetic and timescale considerations
Theoretical models for tension-dependent DNA looping time
No full textThe influence of tension on DNA looping has been studied both experimentally and theoretically in the past. However, different theoretical models have yielded different predictions, leaving uncertainty about their validity. These currently available models rely on approximations, which we here show to be valid only for short molecules. We briefly review the predictions of those models and propose a model that demonstrates exceptional agreement with simulations for long semiflexible chains. Additionally, we elucidate the relationship between our result and that of the previously proposed two-state model, highlighting the distinct interpretative approach that underpins our framework. Our findings offer predictive insights that pave the way for future experimental validation
How accurately do mechanophores report on bond scission in soft polymer materials?
Full text linkMechanophores are molecules that are incorporated into a host material and react to the local mechanical condition—the state of stress or strain—of that host material. Among their many purposes is that of a reporter: Mechanophores whose optical activity changes in response to mechanical cues can reveal bulk material processes that are ordinarily hidden, such as fatigue and fracture. Moreover, they may do so well before a material is fully fractured. To extract quantitative information from the optical signals from embedded mechanophores it is important that the mechanophores, which are generally a minority component of the material, report proportionally and unambiguously on the mechanical condition of the bulk. This is particularly important for early reporting of damage and wear, for which the optical signal from the mechanophore should accurately reflect bulk bond scission. In this article, we develop and analyze a general theory for the quality of optical mechanoreporting by mechanophores in soft materials, based on the Bell-Evans theory of bond breaking. We find, that at the typical low fractions in which mechanophores are incorporated the overall change in strength is limited, but that the proportionality of the reporting can be off by significant amounts, particularly at short times after loading but, for non-scissile bonds, at long times as well
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