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In mammalian cells, the cohesin protein complex is believed to translocate along chromatin during interphase to form dynamic loops through a process called active loop extrusion. Chromosome conformation capture and imaging experiments have suggested that chromatin adopts a compact structure with limited interpenetration between chromosomes and between chromosomal sections. We developed a theory demonstrating that active loop extrusion causes the apparent fractal dimension of chromatin to cross-over between two and four at contour lengths on the order of 30 kilo-base pairs. The anomalously high fractal dimension D = 4 is due to the inability of extruded loops to fully relax during active extrusion. Compaction on longer contour length scales extends within topologically associated domains (TADs), facilitating gene regulation by distal elements. Extrusion-induced compaction segregates TADs such that overlaps between TADs are reduced to less than 35% and increases the entanglement strand of chromatin by up to a factor of 50 to several Mega-base pairs. Furthermore, active loop extrusion couples cohesin motion to chromatin conformations formed by previously extruding cohesins and causes the mean square displacement of chromatin loci during lag times (Δ t) longer than tens of minutes to be proportional to Δ t 1/3. We validate our results with hybrid molecular dynamics--Monte Carlo simulations and show that our theory is consistent with experimental data. This work provides a theoretical basis for the compact organization of interphase chromatin, explaining the physical reason for TAD segregation and suppression of chromatin entanglements which contribute to efficient gene regulation. [ABSTRACT FROM AUTHOR]

The active loop extrusion hypothesis proposes that chromatin threads through the cohesin protein complex into progressively larger loops until reaching specific boundary elements. We build upon this hypothesis and develop an analytical theory for active loop extrusion which predicts that loop formation probability is a nonmonotonic function of loop length and describes chromatin contact probabilities. We validate our model with Monte Carlo and hybrid Molecular Dynamics-Monte Carlo simulations and demonstrate that our theory recapitulates experimental chromatin conformation capture data. Our results support active loop extrusion as a mechanism for chromatin organization and provide an analytical description of chromatin organization that may be used to specifically modify chromatin contact probabilities. [ABSTRACT FROM AUTHOR]

Determines the interaction between identically charged surfaces immersed in a polyampholyte solution in the framework of the linear response approximation. Similarity of interaction between charged surfaces to that in electrolyte solutions; Effect of the charge redistribution on the length scales of the polymer coils; Result of the charge density fluctuations.

The effects of polydispersity on the linear viscoelastic properties of concentrated polymer solutions and melts are analyzed. Existing theories for the dynamics of linear polymers, based on the idea of each polymer confined in a fixed tube, are shown to be incapable of describing observed rheological response of polydisperse polymers. A model is proposed which, in a self-consistent manner, solves the many chain problem given the solution to the single chain problem. Two types of polymer relaxation are incorporated in the model. The first type is escape of a polymer from its tube by motion of the polymer itself. It includes all dynamic modes available to the single chain in a tube—those due to its reptation—as well as other modes, such as fluctuations in tube length. The second type is relaxation of a polymer chain by the motions of the surrounding polymers forming its tube (constraint release). The relaxation modulus is then the product of two functions μ(t) and R(t). μ(t) is the fraction of tube occupied at time t=0 that has not been evacuated at time t, thereby representing escape of the polymer from its tube (solution to the single chain problem). R(t) represents relaxation by the constraint release process, which is modeled by a Rouse chain with random bead mobilities. The probability distribution of these mobilities is determined, in a self-consistent way, from the disentanglement rates due to the tube evacuation processes of the surrounding chains. Thus R(t) is calculated from the spectrum of relaxation rates of the μ(t) processes for the surrounding chains. The predictions of the model with some single chain solutions μ(t) from the literature are compared with oscillatory shear data for binary blends of nearly monodisperse polybutadiene, in which both components are well entangled. [ABSTRACT FROM AUTHOR]

Central concepts of the reptation model of polymer relaxation by disentanglement are the confining tube, the primitive path, and the entanglement net. These are given more precise definitions and are expounded upon here. The entanglement net is regarded as the set of primitive paths of the molecules. The scaling relation connecting distance between entanglements and concentration is derived by a self-consistency argument. Explicit results on probability distributions characterizing unentangled loops and primitive path lengths are derived. The polymers are modeled as random walks in a regular entanglement net. Results are presented as a function of the spacing between entanglements. [ABSTRACT FROM AUTHOR]

We present a principled framework for inferring pixel labels in weakly-annotated image datasets. Most previous, example-based approaches to computer vision rely on a large corpus of densely labeled images. However, for large, modern image datasets, such labels are expensive to obtain and are often unavailable. We establish a large-scale graphical model spanning all labeled and unlabeled images, then solve it to infer pixel labels jointly for all images in the dataset while enforcing consistent annotations over similar visual patterns. This model requires significantly less labeled data and assists in resolving ambiguities by propagating inferred annotations from images with stronger local visual evidences to images with weaker local evidences. We apply our proposed framework to two computer vision problems, namely image annotation with semantic segmentation, and object discovery and co-segmentation (segmenting multiple images containing a common object). Extensive numerical evaluations and comparisons show that our method consistently outperforms the state-of-the-art in automatic annotation and semantic labeling, while requiring significantly less labeled data. In contrast to previous co-segmentation techniques, our method manages to discover and segment objects well even in the presence of substantial amounts of noise images (images not containing the common object), as typical for datasets collected from Internet search. [ABSTRACT FROM AUTHOR]

We present a versatile synthetic route leading toward generating surface-attached polyacrylamide gels, in which the cross-link density varies continuously and gradually across the substrate in two orthogonal directions. We employ free radical polymerization to synthesize random copolymers comprising -5% of photoactive methacrylyloxybenzophenone (MABP), -5% of thermally active styrene sulfonyl azide (SSAz), and -90% of N-isopropylacrylamide (NIPAAm) units. The presence of MABP and SSAz in the copolymer facilitates control over the cross-link density of the gel in an orthogonal manner using photoactivated and thermally activated cross-linking chemistries, respectively. Spectroscopic ellipsometry is employed to determine the degree of swelling of the gel in water and methanol as a function of position on the substrate. Network swelling varies continuously and gradually across the substrate and is high in regions of low gel fractions and low in regions of high gel fractions. [ABSTRACT FROM AUTHOR]

We develop a scaling model relating the friction forces between two polyelectrolyte brushes sliding over each other to the separation between grafted surfaces, number of monomers and charges per chain, grafting density of chains, and solvent quality. We demonstrate that the lateral force between brushes increases upon compression, but to a lesser extent than the normal force. The shear stress at larger separations is due to solvent slip layer friction. The thickness of this slip layer sharply decreases at distances on the order of undeformed brush thickness. The corresponding effective viscosity of the layer sharply increases from the solvent viscosity to a much higher value, but this increase is smaller than the jump of the normal force resulting in the drop of the friction coefficient. At stronger compression we predict the second sharp increase of the shear stress corresponding to interpenetration of the chains from the opposite brushes. In this regime the velocity-dependent friction coefficient between two partially interpenetrating polyelectrolyte brushes does not depend on the distance between substrates because both normal and shear forces are reciprocally proportional to the plate separation. Although lateral forces between polyelectrolyte brushes are larger than between bare surfaces, the enhancement of normal forces between opposing polyelectrolyte brushes with respect to normal forces between bare charged surfaces is much stronger resulting in lower friction coefficient. The model quantitatively demonstrates how polyelectrolyte brushes provide more effective lubrication than bare charged surfaces or neutral brushes. [ABSTRACT FROM AUTHOR]

We describe a method to accelerate the numerical computation of the coefficients of the polynomials Pk(x) that appear in the conjectured asymptotics of the 2k-th moment of the Riemann zeta function. We carried out our method to compute the moment polynomials for k ≤ 13, and used these to experimentally test conjectures for the moments up to height 108. [ABSTRACT FROM AUTHOR]

Abstract: Conrey, Farmer, Keating, Rubinstein, and Snaith, recently conjectured formulas for the full asymptotics of the moments of L-functions. In the case of the Riemann zeta function, their conjecture states that the 2k-th absolute moment of zeta on the critical line is asymptotically given by a certain 2k-fold residue integral. This residue integral can be expressed as a polynomial of degree , whose coefficients are given in exact form by elaborate and complicated formulas. In this article, uniform asymptotics for roughly the first k coefficients of the moment polynomial are derived. Numerical data to support our asymptotic formula are presented. An application to bounding the maximal size of the zeta function is considered. [Copyright &y& Elsevier]

The winter holidays are fast approaching. You anticipate gathering with family and friends. As you shop for groceries in preparation for the congenial holiday atmosphere, you notice an interesting red machine located near the supermarket's exit. At first, it appears to be a soda machine. Upon further investigation, you discover that the machine is a movie rental kiosk operated by Redbox Automated Retail. The idea of renting some of the blockbuster hits you might have missed this past summer appeals to you. You browse through the selection of movies and recall that you missed "Public Enemies," so you select that title. The screen blinks "Title Unavailable." You experience the same result when you select "Harry Potter: The Half-blood Prince" and "Ice Age: Dawn of the Dinosaurs." These three titles are distributed, respectively, by Universal Studios, Warner Brothers Studios, and Twentieth-Century Fox studios [ABSTRACT FROM AUTHOR]

This article discusses the creation of comics from 3D interactive computer graphics. The system is responsible in extracting a sequence of important events into a graphical representation. The automatic end-to-end transforms interactions in 3D graphics into a succinct representation depicted by comics. Comics can invoke strong emotional reactions, create identification and effectively convey a story in an appealing manner. As a matter of fact, symbolism and abstraction in comics can promote identification.

Abstract: Polyelectrolytes are polymers carrying either positively or negatively charged ionizable groups. The properties of these polymers in solutions and at charged surfaces depend on the fraction of dissociated ionic groups, solvent quality for polymer backbone, solution dielectric constant, salt concentration, and polymer–substrate interactions. In this review, we summarize the current development of theoretical models describing properties of polyelectrolyte solutions and adsorption of charged polymers at surfaces and interfaces. We discuss in detail the conformational properties of polyelectrolyte chains in dilute and semidilute solutions, the phenomenon of counterion condensation, the necklace structure of polyelectrolytes in poor solvent conditions for polymer backbone, the dynamics of polyelectrolyte solutions, the surface overcharging by adsorbed polyelectrolytes and its implication for assembled polyelectrolyte multilayers. [Copyright &y& Elsevier]

The mucus clearance system is the dominant mechanical host defense system of the human lung. Mucus is cleared from the lung by cilia and airflow, including both two-phase gas-liquid pumping and cough-dependent mechanisms, and mucus transport rates are heavily dependent on mucus concentration. Importantly, mucus transport rates are accurately predicted by the gel-on-brush model of the mucociliary apparatus from the relative osmotic moduli of the mucus and periciliary-glycocalyceal (PCL-G) layers. The fluid available to hydrate mucus is generated by transepithelial fluid transport. Feedback interactions between mucus concentrations and cilia beating, via purinergic signaling, coordinate Na+ absorptive vs Cl- secretory rates to maintain mucus hydration in health. In disease, mucus becomes hyperconcentrated (dehydrated). Multiple mechanisms derange the ion transport pathways that normally hydrate mucus in muco-obstructive lung diseases, e.g., cystic fibrosis (CF), chronic obstructive pulmonary disease (COPD), non-CF bronchiectasis (NCFB), and primary ciliary dyskinesia (PCD). A key step in muco-obstructive disease pathogenesis is the osmotic compression of the mucus layer onto the airway surface with the formation of adherent mucus plaques and plugs, particularly in distal airways. Mucus plaques create locally hypoxic conditions and produce airflow obstruction, inflammation, infection, and, ultimately, airway wall damage. Therapies to clear adherent mucus with hydrating and mucolytic agents are rational, and strategies to develop these agents are reviewed. [ABSTRACT FROM AUTHOR]

We give a formula for the number of interior intersection points made by the diagonals of a regular n-gon. The answer is a polynomial on each residue class modulo 2520. We also compute the number of regions formed by the diagonals, by using Euler's formula V - E + F = 2. [ABSTRACT FROM AUTHOR]

Strain-induced crystallization (SIC) prevalently strengthens, toughens, and enables an elastocaloric effect in elastomers. However, the crystallinity induced by mechanical stretching in common elastomers (e.g., natural rubber) is typically below 20%, and the stretchability plateaus due to trapped entanglements. We report a class of elastomers formed by end-linking and then deswelling star polymers with low defects and no trapped entanglements, which achieve strain-induced crystallinity of up to 50%. The deswollen end-linked star elastomer (DELSE) reaches an ultrahigh stretchability of 12.4 to 33.3, scaling beyond the saturated limit of common elastomers. The DELSE also exhibits a high fracture energy of 4.2 to 4.5 kJ m-2 while maintaining low hysteresis. The heightened SIC and stretchability synergistically promote a high elastocaloric effect with an adiabatic temperature change of 9.3°C. [ABSTRACT FROM AUTHOR]

We study piecewise polynomial functions γk(c) that appear in the asymptotics of averages of the divisor sum in short intervals. Specifically, we express these polynomials as the inverse Fourier transform of a Hankel determinant that satisfies a Painlevé V equation. We prove that γk(c) is very smooth at its transition points and also determine the asymptotics of γk(c) in a large neighbourhood of k = c/2. Finally, we consider the coefficients that appear in the asymptotics of elliptic aliquot cycles. [ABSTRACT FROM AUTHOR]

Focuses on the current state of the evolution of polymer science. Possibility of threading some types of polymer chains through hollow ring-shaped molecules; Facilitation of a comprehensive review of the relevant techniques in the field of polymer engineering; Assessment of the thermodynamic stability of novel materials with interpenetrating chemistry.

The mechanical properties of covalent polymer networks often arise from the permanent end-linking or cross-linking of polymer strands, and molecular linkers that break more easily would likely produce materials that require less energy to tear. We report that cyclobutane-based mechanophore cross-linkers that break through force-triggered cycloreversion lead to networks that are up to nine times as tough as conventional analogs. The response is attributed to a combination of long, strong primary polymer strands and cross-linker scission forces that are approximately fivefold smaller than control cross-linkers at the same timescales. The enhanced toughness comes without the hysteresis associated with noncovalent cross-linking, and it is observed in two different acrylate elastomers, in fatigue as well as constant displacement rate tension, and in a gel as well as elastomers. [ABSTRACT FROM AUTHOR]

Let q be an odd prime power, and denote the set of square-free monic polynomials D(x) ∈ Fq [x] of degree d. Katz and Sarnak showed that the moments, over , of the zeta functions associated to the curves y² = D(x), evaluated at the central point, tend, as , to the moments of characteristic polynomials, evaluated at the central point, of matrices in USp(2⌊(d-1)/2⌋). Using techniques that were originally developed for studying moments of L-functions over number fields, Andrade and Keating conjectured an asymptotic formula for the moments for q fixed and . We provide theoretical and numerical evidence in favour of their conjecture. In some cases, we are able to work out exact formulae for the moments and use these to precisely determine the size of the remainder term in the predicted moments. [ABSTRACT FROM AUTHOR]

The details of how a mucus hydrogel forms from its primary structural component, mucin polymers, remain incompletely resolved. To explore this, we use a combination of macrorheology and single-particle tracking to investigate the bulk and microscopic mechanical properties of reconstituted MUC5AC mucin gels. We find that analyses of thermal fluctuations on the length scale of the micrometer-sized particles are not predictive of the linear viscoelastic response of the mucin gels, and that taken together, the results from both techniques help to provide complementary insight into the structure of the network. In particular, we show that macroscopic stiffening of MUC5AC gels can be brought about in different ways by targeting specific associations within the network using environmental triggers such as modifications to the pH, surfactant, and salt concentration. Our work may be important for understanding how environmental factors, including pathogens and therapeutic agents, alter the mechanical properties of fully constituted mucus. [ABSTRACT FROM AUTHOR]

A scaling model of self-similar conformations and dynamics of nonconcatenated entangled ring polymers is developed. Topological constraints force these ring polymers into compact conformations with fractal dimension df = 3 that we call fractal loopy globules (FLGs). This result is based on the conjecture that the overlap parameter of subsections of rings on all length scales is the same and equal to the Kavassalis-Noolandi number OKN 10-20. The dynamics of entangled rings is self-similar and proceeds as loops of increasing sizes are rearranged progressively at their respective diffusion times. The topological constraints associated with smaller rearranged loops affect the dynamics of larger loops through increasing the effective friction coefficient but have no influence on the entanglement tubes confining larger loops. As a result, the tube diameter defined as the average spacing between relevant topological constraints increases with time t, leading to "tube dilation". Analysis of the primitive paths in molecular dynamics simulations suggests a complete tube dilation with the tube diameter on the order of the time-dependent characteristic loop size. A characteristic loop at time t is defined as a ring section that has diffused a distance equal to its size during time t. We derive dynamic scaling exponents in terms of fractal dimensions of an entangled ring and the underlying primitive path and a parameter characterizing the extent of tube dilation. The results reproduce the predictions of different dynamic models of a single nonconcatenated entangled ring. We demonstrate that traditional generalization of single-ring models to multi-ring dynamics is not self-consistent and develop a FLG model with self-consistent multi-ring dynamics and complete tube dilation. This self-consistent FLG model predicts that the longest relaxation time of nonconcatenated entangled ring polymers scales with their degree of polymerization N as trelax ~ N7/3, while the diffusion coefficient of these rings scales as D3d ~ N-5/3. For the entangled solutions and melts of rings, we predict power law stress relaxation function G(t) ~ t-3/7 at t < trelax without a rubbery plateau and the corresponding viscosity scaling with the degree of polymerization N as η ~ N4/3. These theoretical predictions are in good agreement with recent computer simulations and are consistent with experiments of melts of nonconcatenated entangled rings. [ABSTRACT FROM AUTHOR]

The fabrication of multifunctional materials with tunable structure and properties requires programmed binding of their building blocks. For example, particles organized in long-ranged structures by external fields can be bound permanently into stiff chains through electrostatic or van der Waals attraction, or into flexible chains through soft molecular linkers such as surface-grafted DNA or polymers. Here, we show that capillarity-mediated binding between magnetic nanoparticles coated with a liquid lipid shell can be used for the assembly of ultraflexible microfilaments and network structures. These filaments can be magnetically regenerated on mechanical damage, owing to the fluidity of the capillary bridges between nanoparticles and their reversible binding on contact. Nanocapillary forces offer opportunities for assembling dynamically reconfigurable multifunctional materials that could find applications as micromanipulators, microbots with ultrasoft joints, or magnetically self-repairing gels. [ABSTRACT FROM AUTHOR]

Two all-aromatic, high-performance poly(etherimide)s ODPA-P3 ( I ) and BPDA-P3 ( II ) are studied as a function of SWCNT loading. Polyetherimide I is amorphous but SWCNTs nucleate crystallization during imidization to produce a nanocomposite (nc- I ) with SWCNTs embedded in the crystals. This crystalline interphase, with a radial thickness of ∼8 nm, results in a substantial reinforcement efficacy. Melting the interphase and cooling nc- I yields an amorphous nanocomposite with an interphase thickness (3.6 nm) that is smaller and has a lower reinforcement efficacy. Polyetherimide II was used as a reference since SWCNTs reside in the amorphous fraction of its nanocomposite. Consequently, the reinforcement efficiency of the semi-crystalline nc- II and its amorphous analog (prepared by heating above the crystal melting point and cooling) remains unchanged. A crystalline interphase surrounding SWCNT-reinforced poly(etherimide)s appears to be critical in obtaining high reinforcement efficacies. Most high-performance polyimides and poly(etherimide)s are prepared using a thermal imidization step. Our work emphasizes that care has to be taken in selecting the final imidization temperature to avoid melting the crystalline interphase if one is targeting high modulus materials. [ABSTRACT FROM AUTHOR]

Wepropose a hopping mechanism for diffusion of large nonstickynanoparticles subjected to topological constraints in both unentangledand entangled polymer solids (networks and gels) and entangled polymerliquids (melts and solutions). Probe particles with size larger thanthe mesh size axof unentangledpolymer networks or tube diameter aeof entangled polymer liquids are trapped by the network orentanglement cells. At long time scales, however, these particlescan diffuse by overcoming free energy barrier between neighboringconfinement cells. The terminal particle diffusion coefficient dominatedby this hopping diffusion is appreciable for particles with size moderatelylarger than the network mesh size axor tube diameter ae. Much larger particles in polymer solids will be permanentlytrapped by local network cells, whereas they can still move in polymerliquids by waiting for entanglement cells to rearrange on the relaxationtime scales of these liquids. Hopping diffusion in entangled polymerliquids and networks has a weaker dependence on particle size thanthat in unentangled networks as entanglements can slide along chainsunder polymer deformation. The proposed novel hopping model enablesunderstanding the motion of large nanoparticles in polymeric nanocompositesand the transport of nano drug carriers in complex biological gelssuch as mucus. [ABSTRACT FROM AUTHOR]

We use molecular dynamics simulationsof the Kremer–Grest(KG) bead–spring model of polymer chains of length between10 and 500, and a closely related analogue that allows for chain crossing,to clearly delineate the effects of entanglements on the length-scale-dependentchain relaxation in polymer melts. We analyze the resulting trajectoriesusing the Rouse modes of the chains and find that entanglements stronglyaffect these modes. The relaxation rates of the chains show two limitingeffective monomeric frictions, with the local modes experiencing muchlower effective friction than the longer modes. The monomeric relaxationrates of longer modes vary approximately inversely with chain lengthdue to kinetic confinement effects. The time-dependent relaxationof Rouse modes has a stretched exponential character with a minimumof stretching exponent in the vicinity of the entanglement chain length.None of these trends are found in models that allow for chain crossing.These facts, in combination, argue for the confined motion of chainsfor time scales between the entanglement time and their ultimate freediffusion. [ABSTRACT FROM AUTHOR]

We report a predefined self-organization of gold nanorods (NRs) end-terminated with multiple polymer arms ("pom-poms") in higher-order structures. The assembly of polymer-tethered NRs was controlled by changing the structure of the polymer pom-poms. We show that the variation in the molecular weight of the polymer molecules and their relative location with respect to the long side of the NRs resulted in two competing association modes of the nanorods, that is, their side-by-side and end-to-end assembly, and produced bundles, chains, rings, and bundled chains of the NRs. The superposition of the two variables controlling the organization of NRs allowed us to create a map showing the variation in the longitudinal plasmonic bands of the NAs achieved by their self-assembly. [ABSTRACT FROM AUTHOR]

The utility and lifetime of materials made from polymer networks, including hydrogels, depend on their capacity to stretch and resist tearing. In gels and elastomers, those mechanical properties are often limited by the covalent chemical structure of the polymer strands between cross-links, which is typically fixed during the material synthesis. We report polymer networks in which the constituent strands lengthen through force-coupled reactions that are triggered as the strands reach their nominal breaking point. In comparison with networks made from analogous control strands, reactive strand extensions of up to 40% lead to hydrogels that stretch 40 to 50% further and exhibit tear energies that are twice as large. The enhancements are synergistic with those provided by double-network architectures and complement other existing toughening strategies. [ABSTRACT FROM AUTHOR]

We present a comprehensive experimental rheological dataset for purified entangled ring polystyrenes and their blends with linear chains in nonlinear shear and elongation. In particular, data for the shear stress growth coefficient, steady-state shear viscosity, and first and second normal stress differences are obtained and discussed as functions of the shear rate, as well as molecular parameters (molar mass, blend composition, and decreasing molar mass of linear component in the blend). Over the extended parameter range investigated, rings do not exhibit clear transient undershoot in shear, in contrast to their linear counterparts and ring-linear blends. For the latter, the size of the undershoot and respective strain appear to increase with the shear rate. The universal scaling of the strain at overshoot and fractional overshoot (the ratio of the maximum to the steady-state shear stress growth coefficient) indicates subtle differences in the shear-rate dependence between rings and linear polymers or their blends. The shear thinning behavior of pure rings yields a slope nearly identical to predictions (−4/7) of a recent shear slit model and molecular dynamics simulations. Data for the second normal stress difference are reported for rings and ring-linear blends. While N2 is negative and its absolute value stays below that of N1, as for linear polymers, the ratio –N2/N1 is unambiguously larger for rings compared to linear polymer solutions with the same number of entanglements (almost by a factor of 2), in agreement with recent nonequilibrium molecular dynamics simulations. Furthermore, –N2 exhibits slightly weaker shear rate dependence compared to N1 at high rates, and the respective power-law exponents can be rationalized in view of the slit model (3/7) and simulations (0.6), although further work is needed to unravel the molecular original of the observed behavior. The comparison of shear and elongational stress growth coefficients for blends reflects the effect of ring-linear threading, which leads to significant viscosity enhancement in elongation. Along the same lines, the elongational stress is much larger than the first normal stress in shear, and their ratio is much larger for rings and ring-linear blends compared to linear polymers. This confirms the interlocking scenario of rings and their important role in mechanically reinforcing linear matrices. [ABSTRACT FROM AUTHOR]

Objective: Ethanol ablation, the injection of ethanol to induce necrosis, was originally used to treat hepatocellular carcinoma, with survival rates comparable to surgery. However, efficacy is limited due to leakage into surrounding tissue. To reduce leakage, we previously reported incorporating ethyl cellulose (EC) with ethanol as this mixture forms a gel when injected into tissue. To further develop EC-ethanol injection as an ablative therapy, the present study evaluates the extent to which salient injection parameters govern the injected fluid distribution. Methods: Utilizing ex vivo swine liver, injection parameters (infusion rate, EC%, infusion volume) were examined with fluorescein added to each solution. After injection, tissue samples were frozen, sectioned, and imaged. Results: While leakage was higher for ethanol and 3%EC-ethanol at a rate of 10 mL/hr compared to 1 mL/hr, leakage remained low for 6%EC-ethanol regardless of infusion rate. The impact of infusion volume and pressure were also investigated first in tissue-mimicking surrogates and then in tissue. Results indicated that there is a critical infusion pressure beyond which crack formation occurs leading to fluid leakage. At a rate of 10 mL/hr, a volume of 50 μL remained below the critical pressure. Conclusions: Although increasing the infusion rate increases stress on the tissue and the risk of crack formation, injections of 6%EC-ethanol were localized regardless of infusion rate. To further limit leakage, multiple low-volume infusions may be employed. Significance: These results, and the experimental framework developed to obtain them, can inform optimizing EC-ethanol to treat a range of medical conditions. [ABSTRACT FROM AUTHOR]

Molecular dynamics simulations confirm recent extensional flow experiments showing ring polymer melts exhibit strong extension-rate thickening of the viscosity at Weissenberg numbers Wi≪1. Thickening coincides with the extreme elongation of a minority population of rings that grows with Wi. The large susceptibility of some rings to extend is due to a flow-driven formation of topological links that connect multiple rings into supramolecular chains. Links form spontaneously with a longer delay at lower Wi and are pulled tight and stabilized by the flow. Once linked, these composite objects experience larger drag forces than individual rings, driving their strong elongation. The fraction of linked rings depends nonmonotonically on Wi, increasing to a maximum when Wi∼1 before rapidly decreasing when the strain rate approaches 1/τe. [ABSTRACT FROM AUTHOR]

The second virial coefficient, A[SUB2], is evaluated between pairs of short chain molecules by direct simulations using a parallel tempering Monte Carlo method where the centers of mass of the two molecules are coupled by a harmonic spring. Three off-lattice polymer models are considered, one with rigid bonds and two with flexible bonds, represented by the finitely extensible nonlinear elastic potential with different stiffness. All the models considered account for excluded volume interactions via the Lennard-Jones potential. In order to obtain the second virial coefficient we calculate the effective intermolecular interaction between the two polymer chains. As expected this intermolecular interaction is found to be strongly dependent upon chain length and temperature. For all three models the θ temperature (θ[SUBn]), defined as the temperature at which the second virial coefficient vanishes for chains of finite length, varies as θ[SUBn]-θ[SUB∞]&vprop;n[SUP-1/2], where n is the number of bonds in the polymer chains and θ[SUB∞] is the θ point for an infinitely long chain. Introducing flexibility into the model has two effects upon θ[SUBn]; the θ temperature is reduced with increasing flexibility, and the n dependence of θ[SUBn] is suppressed. For a particular choice of spring constant an n-independent θ temperature is found. We also compare our results with those obtained from experimental studies of polystyrene in decalin and cyclohexane, and for poly(methyl methacrylate) in a water and tert-butyl alcohol mixture, and show that all the data can be collapsed onto a single universal curve without any adjustable parameters. We are thus able to relate both A[SUB2] and the excluded volume parameter v, to the chain interaction parameter z, in a way relating not only the data for different molecular weights and temperatures, but also for different polymers in different solvents. [ABSTRACT FROM AUTHOR]

Chiral packing of ligands on the surface of nanoparticles (NPs) is of fundamental and practical importance, as it determines how NPs interact with each other and with the molecular world. Herein, for gold nanorods (NRs) capped with end‐grafted nonchiral polymer ligands, we show a new mechanism of chiral surface patterning. Under poor solvency conditions, a smooth polymer layer segregates into helicoidally organized surface‐pinned micelles (patches). The helicoidal morphology is dictated by the polymer grafting density and the ratio of the polymer ligand length to nanorod radius. Outside this specific parameter space, a range of polymer surface structures was observed, including random, shish‐kebab, and hybrid patches, as well as a smooth polymer layer. We characterize polymer surface morphology by theoretical and experimental state diagrams. The helicoidally organized polymer patches on the NR surface can be used as a template for the helicoidal organization of other NPs, masked synthesis on the NR surface, as well as the exploration of new NP self‐assembly modes. Gold nanorods, end‐grafted with achiral polymer ligands, show a new mechanism of chiral surface patterning giving a helicoidal morphology. This morphology is dictated by the relationship between the polymer grafting density and the ratio of the polymer length to the nanorod radius. [ABSTRACT FROM AUTHOR]

Chiral packing of ligands on the surface of nanoparticles (NPs) is of fundamental and practical importance, as it determines how NPs interact with each other and with the molecular world. Herein, for gold nanorods (NRs) capped with end‐grafted nonchiral polymer ligands, we show a new mechanism of chiral surface patterning. Under poor solvency conditions, a smooth polymer layer segregates into helicoidally organized surface‐pinned micelles (patches). The helicoidal morphology is dictated by the polymer grafting density and the ratio of the polymer ligand length to nanorod radius. Outside this specific parameter space, a range of polymer surface structures was observed, including random, shish‐kebab, and hybrid patches, as well as a smooth polymer layer. We characterize polymer surface morphology by theoretical and experimental state diagrams. The helicoidally organized polymer patches on the NR surface can be used as a template for the helicoidal organization of other NPs, masked synthesis on the NR surface, as well as the exploration of new NP self‐assembly modes. [ABSTRACT FROM AUTHOR]

Clearance of intrapulmonary mucus by the high-velocity airflow generated by cough is the major rescue clearance mechanism in subjects with mucoobstructive diseases and failed cilial-dependent mucus clearance, e.g., subjects with cystic fibrosis (CF) or chronic obstructive pulmonary disease (COPD). Previous studies have investigated the mechanical forces generated at airway surfaces by cough but have not considered the effects of mucus biophysical properties on cough efficacy. Theoretically, mucus can be cleared by cough from the lung by an adhesive failure, i.e., breaking mucus-cell surface adhesive bonds and/or by cohesive failure, i.e., directly fracturing mucus. Utilizing peel-testing technologies, mucus-epithelial surface adhesive and mucus cohesive strengths were measured. Because both mucus concentration and pH have been reported to alter mucus biophysical properties in disease, the effects of mucus concentration and pH on adhesion and cohesion were compared. Both adhesive and cohesive strengths depended on mucus concentration, but neither on physiologically relevant changes in pH nor bicarbonate concentration. Mucus from bronchial epithelial cultures and patient sputum samples exhibited similar adhesive and cohesive properties. Notably, the magnitudes of both adhesive and cohesive strength exhibited similar velocity and concentration dependencies, suggesting that viscous dissipation of energy within mucus during cough determines the efficiency of cough clearance of diseased, hyperconcentrated, mucus. Calculations of airflow-induced shear forces on airway mucus related to mucus concentration predicted substantially reduced cough clearance in small versus large airways. Studies designed to improve cough clearance in subjects with mucoobstructive diseases identified reductions of mucus concentration and viscous dissipation as key therapeutic strategies. [ABSTRACT FROM AUTHOR]

We use molecular simulations to probe the local viscoelasticity of an entangled polymer melt by tracking the motion of embedded nonsticky nanoparticles (NPs). As in conventional microrheology, the generalized Stokes-Einstein relation is employed to extract an effective stress relaxation function GGSE(t) from the mean square displacement of NPs. GGSE(t) for different NP diameters d are compared with the stress relaxation function G(t) of a pure polymer melt. The deviation of GGSE(t) from G(t) reflects the incomplete coupling between NPs and the dynamic modes of the melt. For linear polymers, a plateau in GGSE(t) emerges as d exceeds the entanglement mesh size a and approaches the entanglement plateau in G(t) for a pure melt with increasing d. For ring polymers, as d increases towards the spanning size R of ring polymers, GGSE(t) approaches G(t) of the ring melt with no entanglement plateau. [ABSTRACT FROM AUTHOR]

Although the human visual system is remarkable at perceiving and interpreting motions, it has limited sensitivity and we cannot see motions that are smaller than some threshold. Although difficult to visualize, tiny motions below this threshold are important and can reveal physical mechanisms, or be precursors to large motions in the case of mechanical failure. Here, we present a "motion microscope," a computational tool that quantifies tiny motions in videos and then visualizes them by producing a new video in which the motions are made large enough to see. Three scientific visualizations are shown, spanning macroscopic to nanoscopic length scales. They are the resonant vibrations of a bridge demonstrating simultaneous spatial and temporal modal analysis, micrometer vibrations of a metamaterial demonstrating wave propagation through an elastic matrix with embedded resonating units, and nanometer motions of an extracellular tissue found in the inner ear demonstrating a mechanism of frequency separation in hearing. In these instances, the motion microscope uncovers hidden dynamics over a variety of length scales, leading to the discovery of previously unknown phenomena. [ABSTRACT FROM AUTHOR]

Understanding of the conformational ensemble of flexible polyelectrolytes, such as single-stranded nucleic acids (ssNAs), is complicated by the interplay of chain backbone entropy and saltdependent electrostatic repulsions. Molecular elasticity measurements are sensitive probes of the statistical conformation of polymers and have elucidated ssNA conformation at low force, where electrostatic repulsion leads to a strong excluded volume effect, and at high force, where details of the backbone structure become important. Here, we report measurements of ssDNA and ssRNA elasticity in the intermediate-force regime, corresponding to 5- to 100-pN forces and 50-85% extension. These data are explained by a modified wormlike chain model incorporating an internal electrostatic tension. Fits to the elastic data show that the internal tension decreases with salt, from >5 pN under 5 mM ionic strength to near zero at 1 M. This decrease is quantitatively described by an analytical model of electrostatic screening that ascribes to the polymer an effective charge density that is independent of force and salt. Our results thus connect microscopic chain physics to elasticity and structure at intermediate scales and provide a framework for understanding flexible polyelectrolyte elasticity across a broad range of relative extensions. [ABSTRACT FROM AUTHOR]

The estimation of material properties is important for scene understanding, with many applications in vision, robotics, and structural engineering. This paper connects fundamentals of vibration mechanics with computer vision techniques in order to infer material properties from small, often imperceptible motions in video. Objects tend to vibrate in a set of preferred modes. The frequencies of these modes depend on the structure and material properties of an object. We show that by extracting these frequencies from video of a vibrating object, we can often make inferences about that object's material properties. We demonstrate our approach by estimating material properties for a variety of objects by observing their motion in high-speed and regular frame rate video. [ABSTRACT FROM PUBLISHER]

The motion of nanoparticles (NPs) in entangled melts of linear polymers and nonconcatenated ring polymers are compared by large-scale molecular dynamics simulations. The comparison provides a paradigm for the effects of polymer architecture on the dynamical coupling between NPs and polymers in nanocomposites. Strongly suppressed motion of NPs with diameter d larger than the entanglement spacing a is observed in a melt of linear polymers before the onset of Fickian NP diffusion. This strong suppression of NP motion occurs progressively as d exceeds a and is related to the hopping diffusion of NPs in the entanglement network. In contrast to the NP motion in linear polymers, the motion of NPs with d > a in ring polymers is not as strongly suppressed prior to Fickian diffusion. The diffusion coefficient D decreases with increasing d much slower in entangled rings than in entangled linear chains. NP motion in entangled nonconcatenated ring polymers is understood through a scaling analysis of the coupling between NP motion and the self-similar entangled dynamics of ring polymers. [ABSTRACT FROM AUTHOR]

Stable microbubbles can be prepared by evaporation of a liquid core inside an expandable polymeric shell. To control the expansion temperature and the size of resulting microbubbles, we prepared polymeric microcapsules that contain multiple liquids in their core. One-step suspension polymerization allowed for encapsulation of at least two different liquids with near quantitative yield. The liquids may be miscible or immiscible, which directly affects the vapor pressure inside the capsule according to either Raoult's or Dalton's law, respectively. In the case of miscible liquids, e.g., perfluorohexane and perfluoropentane, both the vapor pressure and the expansion temperature vary within a range bounded by the properties of the neat liquids. For immiscible liquids, e.g. perfluoropentane and isopentane, the total vapor pressure is above this range as it equals to a sum of the individual pressures. Due to increased vapor pressure, encapsulation of two immiscible liquids significantly lowers the expansion temperature below the corresponding temperatures observed during expansion of microcapsules with neat perfluoropentane and isopentane cores. The microbubble diameter and shell thickness were controlled within ca. 10–50 μm and 0.1–3 μm, respectively, by varying the fractions and vapor pressure of the core fluids. We also showed that the effect of core composition on the expansion temperature was more significant than the effect of the shell thickness. Furthermore, one of the encapsulated materials may carry additional functions including imaging contrast, catalysis, and density compensation. To that end, these designer microcapsules may find applications in the fields of drug delivery, acoustic imaging, drilling, and self-healing materials. [ABSTRACT FROM AUTHOR]

Molecular dynamics simulations of a coarse-grained bead-spring model have been used to study the effects of molecular crowding on the accumulation of tension in the backbone of bottle-brush polymers tethered to a flat substrate. The number of bottle-brushes per unit surface area, Σ, as well as the lengths of the bottle-brush backbones Nbb (50 ≤ Nbb ≤ 200) and side chains Nsc (50 ≤ Nsc ≤ 200) were varied to determine how the dimensions and degree of crowding of bottle-brushes give rise to bond tension amplification along the backbone, especially near the substrate. From these simulations, we have identified three separate regimes of tension. For low Σ, the tension is due solely to intramolecular interactions and is dominated by the side chain repulsion that governs the lateral brush dimensions. With increasing Σ, the interactions between bottle-brush polymers induce compression of the side chains, transmitting increasing tension to the backbone. For large Σ, intermolecular side chain repulsion increases, forcing side chain extension and reorientation in the direction normal to the surface and transmitting considerable tension to the backbone. [ABSTRACT FROM AUTHOR]