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We performed extensive molecular dynamics simulations using a bead–spring model to investigate the interfacial behavior of blends of linear and cyclic polymer chains confined between two planar, attractive substrates. The model system was studied over a range of chain lengths spanning an order of magnitude in the number of beads for varying blend compositions and for two different levels of substrate affinity. For short chains, we observed the preferential adsorption of linear chains at the substrate interface when they are the majority component (10% cyclic chains) as well as at equimolar composition. In contrast, for longer chains, cyclic chains are preferentially enriched at the interface. These results extend recent findings from neutron reflectivity experiments—where the enrichment of cyclic polystyrene chains at low-energy surfaces was demonstrated—to systems under solid confinement, providing deeper insight into the structural behavior of topologically distinct polymers near interfaces. This work highlights the potential for tuning interfacial composition and properties in polymer blends through topological design, with implications for advanced coatings, membranes, and nanostructured materials.
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Toward a 3D physical model of diffusive polymer chains
Recent studies in polymer physics have created macro-scale analogs to solute microscopic polymer chains like DNA by inducing diffusive motion on a chain of beads. These bead chains have persistence lengths of O(10) links and undergo diffusive motion under random fluctuations like vibration. We present a bead chain model within a new stochastic forcing system: an air fluidizing bed of granular media. A chain of spherical 6 mm resin beads crimped onto silk thread are buffeted randomly by the multiphase flow of grains and low density rising air “bubbles”. We “thermalize” bead chains of various lengths at different fluidizing airflow rates, while X-ray imaging captures a projection of the chains’ dynamics within the media. With modern 3D printing techniques, we can better represent complex polymers by geometrically varying bead connections and their relative strength, e.g., mimicking the variable stiffness between adjacent nucleotide pairs of DNA. We also develop Discrete Element Method (DEM) simulations to study the 3D motion of the bead chain, where the bead chain is represented by simulated spherical particles connected by linear and angular spring-like bonds. In experiment, we find that the velocity distributions of the beads follow exponential distributions rather than the Gaussian distributions expected from polymers in solution. Through use of the DEM simulation, we find that this difference can likely be attributed to the distributions of the forces imparted onto the chain from the fluidized bed environment. We anticipate expanding this study in the future to explore a wide range of chain composition and confinement geometry, which will provide insights into the physics of large biopolymers.
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- Award ID(s):
- 1806833
- PAR ID:
- 10459155
- Date Published:
- Journal Name:
- Frontiers in Physics
- Volume:
- 11
- ISSN:
- 2296-424X
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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Histogram-reweighting grand canonical Monte Carlo simulations are used to obtain the critical properties of lattice chains composed of solvophilic and solvophobic monomers. The model is a modification of one proposed by Larson et al. [J. Chem. Phys. 83, 2411 (1985)], lowering the “contrast” between beads of different types to prevent aggregation into finite-size micelles that would mask true phase separation between bulk high- and low-density phases. Oligomeric chains of lengths between 5 and 24 beads are studied. Mixed-field finite-size scaling methods are used to obtain the critical properties with typical relative accuracies of better than 10−4 for the critical temperature and 10−3 for the critical volume fraction. Diblock chains are found to have lower critical temperatures and volume fractions relative to the corresponding homopolymers. The addition of solvophilic blocks of increasing length to a fixed-length solvophobic segment results in a decrease of both the critical temperature and the critical volume fraction, with an eventual slow asymptotic approach to the long-chain limiting behavior. Moving a single solvophobic or solvophilic bead along a chain leads to a minimum or maximum in the critical temperature, with no change in the critical volume fraction. Chains of identical length and composition have a significant spread in their critical properties, depending on their precise sequence. The present study has implications for understanding biomolecular phase separation and for developing design rules for synthetic polymers with specific phase separation properties. It also provides data potentially useful for the further development of theoretical models for polymer and surfactant phase behavior.more » « less
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null (Ed.)Abstract Electronic biosensors for DNA detection typically utilize immobilized oligonucleotide probes on a signal transducer, which outputs an electronic signal when target molecules bind to probes. However, limitation in probe selectivity and variable levels of non-target material in complex biological samples can lead to nonspecific binding and reduced sensitivity. Here we introduce the integration of 2.8 μm paramagnetic beads with DNA fragments. We apply a custom-made microfluidic chip to detect DNA molecules bound to beads by measuring Impedance Peak Response (IPR) at multiple frequencies. Technical and analytical performance was evaluated using beads containing purified Polymerase Chain Reaction (PCR) products of different lengths (157, 300, 613 bp) with DNA concentration ranging from 0.039 amol to 7.8 fmol. Multi-frequency IPR correlated positively with DNA amounts and was used to calculate a DNA quantification score. The minimum DNA amount of a 300 bp fragment coupled on beads that could be robustly detected was 0.0039 fmol (1.54 fg or 4750 copies/bead). Additionally, our approach allowed distinguishing beads with similar molar concentration DNA fragments of different lengths. Using this impedance sensor, purified PCR products could be analyzed within ten minutes to determine DNA fragment length and quantity based on comparison to a known DNA standard.more » « less
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Short carbon fiber-reinforced polymer composite structures produced using Large Area Additive Manufacturing (LAAM) have garnered significant attention due to the design flexibility, energy savings, and materials selection associated with this process. However, the physical and mechanical properties of the additively manufactured composite parts often fall below expectations due to void formation between printed beads and within the microstructure of individual beads. This study aims to investigate the effect of bed temperature on the microstructure within the beads of two-layer Short Carbon Fiber reinforced Acrylonitrile Butadiene Styrene (SCF/ABS) beads manufactured via the LAAM system. This study employs high-resolution 3D micro-computed tomography (μCT) to evaluate the void shape and distribution within the microstructure of composite parts printed at various bed temperatures. The results of this study demonstrate substantial variation in the void volume fraction among four bead sets deposited at different print bed temperatures. Moreover, within each part, a noticeable discrepancy in void volume fraction is observed between the top and bottom bead of the two-bead test samples. Preliminary results indicate that increasing the bed temperature from 25°C to 75°C reduces void volume fraction within the microstructure of the composite parts. However, an opposite trend emerges when the bed temperature is further increased to 100°C, increasing void volume fraction, which needs further investigation to understand. This study also evaluated the void shapes through the calculation of their sphericity. The preliminary results reveal that as the bed temperature increases from 25°C to 75°C, the voids exhibit higher sphericity within the printed parts as the interconnected voids decrease.more » « less
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Transient DNA loops occur throughout the genome due to thermal fluctuations of DNA and the function of SMC complex proteins such as condensin and cohesin. Transient crosslinking within and between chromosomes and loop extrusion by SMCs have profound effects on high-order chromatin organization and exhibit specificity in cell type, cell cycle stage, and cellular environment. SMC complexes anchor one end to DNA with the other extending some distance and retracting to form a loop. How cells regulate loop sizes and how loops distribute along chromatin are emerging questions. To understand loop size regulation, we employed bead–spring polymer chain models of chromatin and the activity of an SMC complex on chromatin. Our study shows that (1) the stiffness of the chromatin polymer chain, (2) the tensile stiffness of chromatin crosslinking complexes such as condensin, and (3) the strength of the internal or external tethering of chromatin chains cooperatively dictate the loop size distribution and compaction volume of induced chromatin domains. When strong DNA tethers are invoked, loop size distributions are tuned by condensin stiffness. When DNA tethers are released, loop size distributions are tuned by chromatin stiffness. In this three-way interaction, the presence and strength of tethering unexpectedly dictates chromatin conformation within a topological domain.more » « less
- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.3389/fphy.2023.1142004
