Molecular physics of a polymer engineering instability: Experiments and computation

Entangled polymer melts exhibit a variety of flow instabilities that limit production rates in industrial applications. We present both experimental and computational findings, using flow of monodisperse linear polystyrenes in a contraction-expansion geometry, which illustrate the formation and development of one such flow instability. This viscoelastic disturbance is observed at the slit outlet and subsequently produces large-scale fluid motions upstream. A numerical linear stability study using the molecular structure based Rolie-Poly model confirms the instability and identifies important parameters within the model, which gives physical insight into the underlying mechanism. Chain stretch was found to play a critical role in the instability mechanism, which partially explains the effectiveness of introducing a low-molecular weight tail into a polymer blend to increase its processability

Color-coordinate system from a 13th-century account of rainbows.

We present a new analysis of Robert Grosseteste’s account of color in his treatise De iride (On the Rainbow), dating from the early 13th century. The work explores color within the 3D framework set out in Grosseteste’s De colore [see J. Opt. Soc. Am. A 29, A346 (2012)], but now links the axes of variation to observable properties of rainbows. We combine a modern understanding of the physics of rainbows and of human color perception to resolve the linguistic ambiguities of the medieval text and to interpret Grosseteste’s key terms

Beyond Barbour : A Theology of Science from Ancient and Modern Thinkers

In this chapter, I will challenge a common background relational assumption behind all of Barbour’s categories as intrinsically unfaithful to the universal nature of both science and religion, arguing instead that it is more fruitful to ask what a ‘theology of science’ might look like. ‘What does science do, and what is it for, within a theological worldview?’ This approach works very well in a teaching context when developed in two ways: (1) historically and (2) using Biblical studies in wisdom, especially in the book of Job. Students of this approach start to think in new ways and ask new questions, suggesting an approach to science or in its more ancient form natural philosophy – the ‘love of wisdom of natural things’ – that can draw on theological and cultural roots. I suggest that deriving a human narrative for science in this way can transform the way political discussions of ‘troubled technologies’ (genetic medicine, genetically modified organisms (GMOs), fracking, etc.) are framed and the way we approach science in education and the media

Modulation of Global Low-Frequency Motions Underlies Allosteric Regulation: Demonstration in CRP/FNR Family Transcription Factors

Allostery is a fundamental process by which ligand binding to a protein alters its activity at a distinct site. There is growing evidence that allosteric cooperativity can be communicated by modulation of protein dynamics without conformational change. The mechanisms, however, for communicating dynamic fluctuations between sites are debated. We provide a foundational theory for how allostery can occur as a function of low-frequency dynamics without a change in structure. We have generated coarse-grained models that describe the protein backbone motions of the CRP/FNR family transcription factors, CAP of Escherichia coli and GlxR of Corynebacterium glutamicum. The latter we demonstrate as a new exemplar for allostery without conformation change. We observe that binding the first molecule of cAMP ligand is correlated with modulation of the global normal modes and negative cooperativity for binding the second cAMP ligand without a change in mean structure. The theory makes key experimental predictions that are tested through an analysis of variant proteins by structural biology and isothermal calorimetry. Quantifying allostery as a free energy landscape revealed a protein ‘‘design space’’ that identified the inter- and intramolecular regulatory parameters that frame CRP/FNR family allostery. Furthermore, through analyzing CAP variants from diverse species, we demonstrate an evolutionary selection pressure to conserve residues crucial for allosteric control. This finding provides a link between the position of CRP/FNR transcription factors within the allosteric free energy landscapes and evolutionary selection pressures. Our study therefore reveals significant features of the mechanistic basis for allostery. Changes in low-frequency dynamics correlate with allosteric effects on ligand binding without the requirement for a defined spatial pathway. In addition to evolving suitable three-dimensional structures, CRP/FNR family transcription factors have been selected to occupy a dynamic space that fine-tunes biological activity and thus establishes the means to engineer allosteric mechanisms driven by low-frequency dynamics

High and low molecular weight crossovers in the longest relaxation time dependence of linear cis-1,4 polyisoprene by dielectric relaxations

The dielectric relaxation of cis-1,4 Polyisoprene [PI] is sensitive not only to the local and segmental dynamics but also to the larger scale chain (end-to-end) fluctuations. We have performed a careful dielectric investigation on linear PI with various molecular weights in the range of 1 to 320 kg/mol. The broadband dielectric spectra of all samples were measured isothermally at the same temperature to avoid utilizing shift factors. For the low and medium molecular weight range, the comparisons were performed at 250 K to access both the segmental relaxation and normal mode peaks inside the available frequency window (1 mHz–10 MHz). In this way, we were able to observe simultaneously the effect of molecular mass on the segmental dynamics—related with the glass transition process—and on the end-to-end relaxation time of PI and thus decouple the direct effect of molecular weight on the normal mode from that due to the effect on the monomeric friction coefficient. The latter effect is significant for low molecular weight (M w < 33 kg/mol), i.e., in the range where the crossover from Rouse dynamics to entanglement limited flow occurs. Despite the conductivity contribution at low frequency, careful experiments allowed us to access to the normal mode signal for molecular weights as high as M w = 320 kg/mol, i.e., into the range of high molecular weights where the pure reptation behavior could be valid, at least for the description of the slowest chain modes. The comparison between the dielectric relaxations of PI samples with medium and high molecular weight was performed at 320 K. We found two crossovers in the molecular weight dependence of the longest relaxation time, the first around a molecular weight of 6.5 ± 0.5 kg/mol corresponding to the end of the Rouse regime and the second around 75 ± 10 kg/mol. Above this latter value, we find a power law compatible with exponent 3 as predicted by the De Gennes theory

A hierarchical algorithm for predicting the linear viscoelastic properties of polymer melts with long-chain branching

The “hierarchical model” proposed earlier [Larson in Macromolecules 34:4556–4571, 2001] is herein modified by inclusion of early time fluctuations and other refinements drawn from the theories of Milner and McLeish for more quantitative prediction. The hierarchical model predictions are then compared with experimental linear viscoelastic data of well-defined long chain branched 1,4-polybutadienes and 1,4-polyisoprenes using a single set of parameter values for each polymer, which are obtained from experimental data for monodisperse linear and star polymers. For a wide range of monodisperse branched polymer melts, the predictions of the hierarchical model for monodisperse melts are very similar to those of the Milner–McLeish theories, and agree well with experimental data for many, but not all, of the branched polymer samples. Since the modified hierarchical model accounts for arbitrary polydispersity in molecular weight and branching distributions, which is not accounted for in the Milner–McLeish theories, the hierarchical algorithm is a promising one for predicting the relaxation of general mixtures of branched polymers.Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/47217/1/397_2004_Article_415.pd

Precise Analysis of Polymer Rotational Dynamics

Through the analysis of individual chain dynamics alongside the corresponding molecular structures under shear via nonequilibrium molecular dynamics simulations of C178H358 linear and short-chain branched polyethylene melts under shear flow, we observed that the conventional method based on the chain end-to-end vector (and/or the gyration tensor of chain) is susceptible to quantitatively inaccurate measurements and often misleading information in describing the rotational dynamics of polymers. Identifying the flaw as attributed to strong irregular Brownian fluctuations inherent to the chain ends associated with their large free volume and strong molecular collisions, we propose a simple, robust way based on the chain center-to-center vector connecting the two centers of mass of the bisected chain, which is shown to adequately describe polymer rotational dynamics without such shortcomings. We present further consideration that the proposed method can be useful in accurately measuring the overall chain structure and dynamics of polymeric materials with various molecular architectures, including branched and ring polymers.open