Bacteria Colonies Modify Their Shear and Compressive Mechanical Properties in Response to Different Growth Substrates.

Bacteria build multicellular communities termed biofilms, which are often encased in a self-secreted extracellular matrix that gives the community mechanical strength and protection against harsh chemicals. How bacteria assemble distinct multicellular structures in response to different environmental conditions remains incompletely understood. Here, we investigated the connection between bacteria colony mechanics and the colony growth substrate by measuring the oscillatory shear and compressive rheology of bacteria colonies grown on agar substrates. We found that bacteria colonies modify their own mechanical properties in response to shear and uniaxial compression in a manner that depends on the concentration of agar in their growth substrate. These findings highlight that mechanical interactions between bacteria and their microenvironments are an important element in bacteria colony development, which can aid in developing strategies to disrupt or reduce biofilm growth.

Influence of the Graft Length on Nanocomposite Structure and Interfacial Dynamics.

Both the dispersion state of nanoparticles (NPs) within polymer nanocomposites (PNCs) and the dynamical state of the polymer altered by the presence of the NP/polymer interfaces have a strong impact on the macroscopic properties of PNCs. In particular, mechanical properties are strongly affected by percolation of hard phases, which may be NP networks, dynamically modified polymer regions, or combinations of both. In this article, the impact on dispersion and dynamics of surface modification of the NPs by short monomethoxysilanes with eight carbons in the alkyl part (C8) is studied. As a function of grafting density and particle content, polymer dynamics is followed by broadband dielectric spectroscopy and analyzed by an interfacial layer model, whereas the particle dispersion is investigated by small-angle X-ray scattering and analyzed by reverse Monte Carlo simulations. NP dispersions are found to be destabilized only at the highest grafting. The interfacial layer formalism allows the clear identification of the volume fraction of interfacial polymer, with its characteristic time. The strongest dynamical slow-down in the polymer is found for unmodified NPs, while grafting weakens this effect progressively. The combination of all three techniques enables a unique measurement of the true thickness of the interfacial layer, which is ca. 5 nm. Finally, the comparison between longer (C18) and shorter (C8) grafts provides unprecedented insight into the efficacy and tunability of surface modification. It is shown that C8-grafting allows for a more progressive tuning, which goes beyond a pure mass effect.

How Tuning Interfaces Impacts the Dynamics and Structure of Polymer Nanocomposites Simultaneously.

Fundamental understanding of the macroscopic properties of polymer nanocomposites (PNCs) remains difficult due to the complex interplay of microscopic dynamics and structure, namely interfacial layer relaxations and three-dimensional nanoparticle (NP) arrangements. The effect of surface modification by alkyl methoxysilanes at different grafting densities has been studied in PNCs made of poly(2-vinylpyridine) and spherical 20 nm silica NPs. The segmental dynamics has been probed by broadband dielectric spectroscopy and the filler structure by small-angle X-ray scattering and reverse Monte Carlo simulations. By combining the particle configurations with the interfacial layer properties, it is shown how surface modification tunes the attractive polymer-particle interactions: bare NPs slow down the polymer interfacial layer dynamics over a thickness of ca. 5 nm, while grafting screens these interactions. Our analysis of interparticle spacings and segmental dynamics provides unprecedented insights into the effect of surface modification on the main characteristics of PNCs: particle interactions and polymer interfacial layers.

Dynamic remodeling of fiber networks with stiff inclusions under compressive loading.

The ability of tissues to sustain and withstand mechanical stress is critical to tissue development and healthy tissue maintenance. The mechanical properties of tissues are typically considered to be dominated by the fibrous extracellular matrix (ECM) component of tissues. Fiber network mechanics can capture certain mechanical features of tissues, such as shear strain stiffening, but is insufficient in describing the compressive response of certain tissues and blood clots that are rich in extracellular matrix. To understand the mechanical response of tissues, we employ a contemporary mechanical model, a fibrous network of fibrin embedded with inert bead inclusions that preserve the volume-conserving constraints of cells in tissues. Combining bulk mechanical rheology and a custom imaging device, we show that the presence of inclusions alters the local dynamic remodeling of the networks undergoing uniaxial compressive strains and demonstrate non-affine correlated motion within a fiber-bead network, predicted to stretch fibers in the network and lead to the ability of the network to stiffen under compression, a key feature of real tissues. These findings have important implications for understanding how local structural properties of cells and ECM fibers impact the bulk mechanical response of real tissues. STATEMENT OF SIGNIFICANCE: To understand why real tissue stiffens under compression, we study a model tissue system which also stiffens: a fibrin network embedded with stiff beads. We design a device that images compression of both fiber and fiber-bead networks. Distinct from previous imaging studies, this setup can dynamically capture network deformation on scales larger than single fibers. From the videos, we see fluid flow and network remodeling are both critical to compression behavior. The fiber-bead network has faster fluid flow, reduced network recovery, and correlated motion during network relaxation. We hypothesize that the beads hinder network relaxation of stretched fibers, thus retaining the applied stress and exhibiting stiffening. Our findings reveal important details for modeling tissue mechanics towards optimizing healthcare.

A Torsion-Based Rheometer for Measuring Viscoelastic Material Properties.

Rheology and the study of viscoelastic materials are an integral part of engineering and the study of biophysical systems. Tissue rheology is even used in the study of cancer and other diseases. However, the cost of a rheometer is feasible only for colleges, universities, and research laboratories. Even if a rheometer can be purchased, it is bulky and delicately calibrated, limiting its usefulness to the laboratory itself. The design presented here is less than a tenth of the cost of a professional rheometer. The design is also portable, making it the ideal solution to introduce viscoelasticity to high school students as well as for use in the field for obtaining rheological data.

Direct Structural Evidence for Interfacial Gradients in Asymmetric Polymer Nanocomposite Blends.

Understanding the complex structure of polymer blends filled with nanoparticles (NPs) is key to design their macroscopic properties. Here, the spatial distribution of hydrogenated (H) and deuterated (D) polymer chains asymmetric in mass is studied by small-angle neutron scattering. Depending on the chain mass, a qualitatively new large-scale organization of poly(vinyl acetate) chains beyond the random-phase approximation is evidenced in nanocomposites with attractive polymer-silica interactions. The silica is found to systematically induce bulk segregation. Only with long H-chains, a strong scattering signature is observed in the q range of the NP size: it is the sign of interfacial isotopic enrichment, that is, of contrasted polymer shells close to the NP surface. A quantitative model describing both the bulk segregation and the interfacial gradient (over ca. 10-20 nm depending on the NP size) is developed, showing that both are of comparable strength. In all cases, NP surfaces trap the polymer blend in a non-equilibrium state, with preferential adsorption around NPs only if the chain length and isotopic preference toward the surface combine their entropic and enthalpic driving forces. This structural evidence for interfacial polymer gradients will open the road for quantitative understanding of the dynamics of many-chain nanocomposite systems.

Theranostic Gastrointestinal Endoscopy: Bringing Healing Light to the Lumen.

Current conventional endoscopes have restricted the accuracy of treatment delivery and monitoring. Over the past decade, there have been major developments in nanotechnology and light triggered therapy, potentially allowing a better detection of challenging lesions and targeted treatment of malignancies in the gastrointestinal tract. Theranostics is a developing form of personalized medicine because it combines diagnosis and targeted treatment delivered in one step using advances in nanotechnology. This review describes the light-triggered therapies (including photodynamic, photothermal, and photoimmunotherapies), nanotechnological advances with nanopowder, nanostent, nanogels, and nanoparticles, enhancements brought to endoscopic ultrasound, in addition to experimental endoscopic techniques, combining both enhanced diagnoses and therapies, including a developed prototype of a "smart" multifunctional endoscope for localized colorectal cancer, near-infrared laser endoscope targeting the gastrointestinal stromal tumors, the concept of endocapsule for obscure gastrointestinal bleed, and a proof-of-concept therapeutic capsule using ultrasound-mediated targeted drug delivery. Hence, the following term has been proposed encompassing these technologies: "Theranostic gastrointestinal endoscopy." Future efforts for integration of these technologies into clinical practice would be directed toward translational and clinical trials translating into a more personalized and interdisciplinary diagnosis and treatment, shorter procedural time, higher precision, higher cost-effectiveness, and less need for repetitive procedures.

Understanding the Static Interfacial Polymer Layer by Exploring the Dispersion States of Nanocomposites.

The dynamic and static properties of the interfacial region between polymer and nanoparticles have wide-ranging consequences on performances of nanomaterials. The thickness and density of the static layer are particularly difficult to assess experimentally due to superimposing nanoparticle interactions. Here, we tune the dispersion of silica nanoparticles in nanocomposites by preadsorption of polymer layers in the precursor solutions, and by varying the molecular weight of the matrix chains. Nanocomposite structures ranging from ideal dispersion to repulsive order or various degrees of aggregation are generated and observed by small-angle scattering. Preadsorbed chains are found to promote ideal dispersion, before desorption in the late stages of nanocomposite formation. The microstructure of the interfacial polymer layer is characterized by detailed modeling of X-ray and neutron scattering. Only in ideally well-dispersed systems a static interfacial layer of reduced polymer density over a thickness of ca. 2 nm is evidenced based on the analysis with a form-free density profile optimized using numerical simulations. This interfacial gradient layer is found to be independent of the thickness of the initially adsorbed polymer, but appears to be generated by out-of-equilibrium packing and folding of the preadsorbed layer. The impact of annealing is investigated to study the approach of equilibrium, showing that initially ideally well-dispersed systems adopt a repulsive hard-sphere structure, while the static interfacial layer disappears. This study thus promotes the fundamental understanding of the interplay between effects which are decisive for macroscopic material properties: polymer-mediated interparticle interactions, and particle interfacial effects on the surrounding polymer.

Enhancing the Mechanical Properties of Glassy Nanocomposites by Tuning Polymer Molecular Weight.

The addition of nanoparticles to a polymer matrix is a well-known process to improve the mechanical properties of polymers. Many studies of mechanical reinforcement in polymer nanocomposites (PNCs) focus on rubbery matrices; however, much less effort concentrates on the factors controlling the mechanical performance of the technologically important glassy PNCs. This paper presents a study of the effect of the polymer molecular weight (MW) on the overall mechanical properties of glassy PNCs with attractive interaction by using Brillouin light scattering. We found that the mechanical moduli (bulk and shear) have a nonmonotonic dependence on MW that cannot be predicted by simple rule of mixtures. The moduli increase with increasing MW up to 100 kg/mol followed by a drop at higher MW. We demonstrate that the change in the mechanical properties of PNCs can be associated with the properties of the interfacial polymer layer. The latter depend on the interfacial chain packing and stretching, as well as polymer bridging, which vary differently with the MW of the polymer. These competing contributions lead to the observed nonmonotonic variations of the glassy PNC moduli with MW. Our work provides a simple, cost-effective, and efficient way to control the mechanical properties of glassy PNCs by tuning the polymer chain length. Our finding can be beneficial for the rational design of PNCs with desired mechanical performance.

Focus: Structure and dynamics of the interfacial layer in polymer nanocomposites with attractive interactions.

In recent years it has become clear that the interfacial layer formed around nanoparticles in polymer nanocomposites (PNCs) is critical for controlling their macroscopic properties. The interfacial layer occupies a significant volume fraction of the polymer matrix in PNCs and creates strong intrinsic heterogeneity in their structure and dynamics. Here, we focus on analysis of the structure and dynamics of the interfacial region in model PNCs with well-dispersed, spherical nanoparticles with attractive interactions. First, we discuss several experimental techniques that provide structural and dynamic information on the interfacial region in PNCs. Then, we discuss the role of various microscopic parameters in controlling structure and dynamics of the interfacial layer. The analysis presented emphasizes the importance of the polymer-nanoparticle interactions for the slowing down dynamics in the interfacial region, while the thickness of the interfacial layer appears to be dependent on chain rigidity, and has been shown to increase with cooling upon approaching the glass transition. Aside from chain rigidity and polymer-nanoparticle interactions, the interfacial layer properties are also affected by the molecular weight of the polymer and the size of the nanoparticles. In the final part of this focus article, we emphasize the important challenges in the field of polymer nanocomposites and a potential analogy with the behavior observed in thin films.

Big Effect of Small Nanoparticles: A Shift in Paradigm for Polymer Nanocomposites.

Polymer nanocomposites (PNCs) are important materials that are widely used in many current technologies and potentially have broader applications in the future due to their excellent property tunability, light weight, and low cost. However, expanding the limits in property enhancement remains a fundamental scientific challenge. Here, we demonstrate that well-dispersed, small (diameter ∼1.8 nm) nanoparticles with attractive interactions lead to unexpectedly large and qualitatively different changes in PNC structural dynamics in comparison to conventional nanocomposites based on particles of diameters ∼10-50 nm. At the same time, the zero-shear viscosity at high temperatures remains comparable to that of the neat polymer, thereby retaining good processability and resolving a major challenge in PNC applications. Our results suggest that the nanoparticle mobility and relatively short lifetimes of nanoparticle-polymer associations open qualitatively different horizons in the tunability of macroscopic properties in nanocomposites with a high potential for the development of advanced functional materials.