Mechanics of Helical and Fabric-Like Mesostructures from Polymer-Nanoparticle Hybrids

Hierarchical structures developed from nanoscale building blocks offer an excellent opportunity to control properties on all length scales, from the molecular level up to the macroscale. Many beautiful examples in Nature have demonstrated the significance of controlling geometry and mechanics on small length scales to control function on an organism-level, shown by the strength of bones, the toughness of a mollusk\u27s shell, or the gecko\u27s ability to climb walls. Inspired by stunning examples in both Nature and common man-made materials and structures, we assemble polymers and inorganic nanoparticles (NPs) with well-defined surface chemistry into long ribbons and fabric-like networks with unprecedented length scales. In particular, we focus on the geometry and mechanics of these structures when released from their underlying substrate, as well as the fabrication methods to create such structures. This thesis describes four concepts in detail: (1) the development of an evaporative assembly method used to prepare polymer and NP mesoscale structures, referred to as flexible blade flow coating, (2) the spontaneous formation of helical ribbons, driven by a 2-phase elastocapillary balance between surface tension and elasticity of an asymmetric geometry, (3) the mechanical stretching properties of NP-based helical ribbons, and (4) the deformation, shape and fluid-structure interactions of small, flexible, polymeric microhelices in viscous flow. We first describe flexible blade flow coating, a technique that enables the fabrication of polymer, NP and hybrid mesostructures spanning several length scales. By controlling the fabrication parameters, a wide range of materials can be used to create a wide range of geometries, such as ribbons and fabrics. This method relies upon controlled evaporation of a dilute solution confined between a thin polymer film and a flat substrate. By taking advantage of crosslinkable ligand chemistry and the use of a water-soluble sacrificial layer, the structures are liberated from their substrates, affording robust structures floating at the air-liquid interface or fully submerged. When fully submerged in a fluid with sufficient interfacial tension, like water, we discovered that ribbons spontaneously formed helices. By starting from a general expression that balances the elastic bending energy and surface tension of an asymmetric cross-sectional geometry, we determined that this helical formation is due to the asymmetric reduction of surface area upon bending (serving to lower the system energy). This leads ribbons to bend into helices with a preferred radius governed by both the modulus and interfacial tension, as well as ribbon thickness (R ~ Et2/γ). This universal, geometry-based mechanism provides a new opportunity to create helices from any class of material, which is demonstrated by implementing metallic, ceramic and magnetic NPs, as well as homopolymers. Upon understanding the mechanics of helical formation, we examined the mechanical properties of NP-based helical ribbons. Through the use of a custom-designed mechanical measurement tool, which is capable of measuring ~nN forces over displacements of 100s of microns or greater, we experimentally measured the force-displacement relationship of these helices. We show that this curve can be predicted through the elastic energy and surface-driven helical shape. Our experiments revealed massive stretchability, where helices are able stretch to their fully straightened contour length, as high as 23 times their original length. At low strains, the helices display stiffness values similar to single polymer chains or biological helices (~10-6 N/m), and when fully stretched, display properties similar to synthetic polymer nanofibers. Motivated by small, flexible helices in fluids found in Nature, like swimming bacterial flagella, we expand our studies to examine single helices in viscous fluid flow. We fixed one end of a helix while leaving the other free, placed it into a microchannel, and applied a controlled fluid flow rate. Using PMMA as our model polymeric material, we found that the axial deformation is well-described by a nonlinear helix of finite extensibility, defined by a balance between the viscous and elastic forces. From our experiments, we describe the pitch distribution of a deformed helix in flow, as well as calculate a frictional coefficient for the helical geometry. At high flow rates, we qualitatively observed a global-to-local helical shape instability. Finally, we extend the study to show preliminary results on the deformation of NP-based helices

When the going gets rough – studying the effect of surface roughness on the adhesive abilities of tree frogs

Tree frogs need to adhere to surfaces of various roughnesses in their natural habitats; these include bark, leaves and rocks. Rough surfaces can alter the effectiveness of their toe pads, due to factors such as a change of real contact area and abrasion of the pad epithelium. Here, we tested the effect of surface roughness on the attachment abilities of the tree frog Litoria caerulea. This was done by testing shear and adhesive forces on artificial surfaces with controlled roughness, both on single toe pads and whole animal scales. It was shown that frogs can stick 2–3 times better on small scale roughnesses (3–6 µm asperities), producing higher adhesive and frictional forces, but relatively poorly on the larger scale roughnesses tested (58.5–562.5 µm asperities). Our experiments suggested that, on such surfaces, the pads secrete insufficient fluid to fill the space under the pad, leaving air pockets that would significantly reduce the Laplace pressure component of capillarity. Therefore, we measured how well the adhesive toe pad would conform to spherical asperities of known sizes using interference reflection microscopy. Based on experiments where the conformation of the pad to individual asperities was examined microscopically, our calculations indicate that the pad epithelium has a low elastic modulus, making it highly deformable

Fluid Separation and Network Deformation in Wetting of Soft and Swollen Surfaces

When a water drop is placed onto a soft polymer network, a wetting ridge develops at the drop periphery. The height of this wetting ridge is typically governed by the drop surface tension balanced by elastic restoring forces of the polymer network. However, the situation is more complex when the network is swollen with fluid, because the fluid may separate from the network at the contact line. Here we study the fluid separation and network deformation at the contact line of a soft polydimethylsiloxane (PDMS) network, swollen with silicone oil. By controlling both the degrees of crosslinking and swelling, we find that more fluid separates from the network with increasing swelling. Above a certain swelling, network deformation decreases while fluid separation increases, demonstrating synergy between network deformation and fluid separation. When the PDMS network is swollen with a fluid having a negative spreading parameter, such as hexadecane, no fluid separation is observed. A simple balance of interfacial, elastic, and mixing energies can describe this fluid separation behavior. Our results reveal that a swelling fluid, commonly found in soft networks, plays a critical role in a wetting ridge

Wetting on silicone surfaces

Silicone is frequently used as a model system to investigate and tune wetting on soft materials. Silicone is biocompatible and shows excellent thermal, chemical, and UV stability. Moreover, the mechanical properties of the surface can be easily varied by several orders of magnitude in a controlled manner. Polydimethylsiloxane (PDMS) is a popular choice for coating applications such as lubrication, self-cleaning, and drag reduction, facilitated by low surface energy. Aiming to understand the underlying interactions and forces, motivated numerous and detailed investigations of the static and dynamic wetting behavior of drops on PDMS-based surfaces. Here, we recognize the three most prevalent PDMS surface variants, namely liquid-infused (SLIPS/LIS), elastomeric, and liquid-like (SOCAL) surfaces. To understand, optimize, and tune the wetting properties of these PDMS surfaces, we review and compare their similarities and differences by discussing (i) the chemical and molecular structure, and (ii) the static and dynamic wetting behavior. We also provide (iii) an overview of methods and techniques to characterize PDMS-based surfaces and their wetting behavior. The static and dynamic wetting ridge is given particular attention, as it dominates energy dissipation, adhesion, and friction of sliding drops and influences the durability of the surfaces. We also discuss special features such as cloaking and wetting-induced phase separation. Key challenges and opportunities of these three surface variants are outlined

Pathogenicity of an H5N1 avian influenza virus isolated in Vietnam in 2012 and reliability of conjunctival samples for diagnosis of infection

The continued spread of highly pathogenic avian influenza virus (HPAIV) subtype H5N1 among poultry in Vietnam poses a potential threat to animals and public health. To evaluate the pathogenicity of a 2012 H5N1 HPAIV isolate and to assess the utility of conjunctival swabs for viral detection and isolation in surveillance, an experimental infection with HPAIV subtype H5N1 was carried out in domestic ducks. Ducks were infected with 10[superscript 7.2] TCID[subscript 50] of A/duck/Vietnam/QB1207/2012 (H5N1), which was isolated from a moribund domestic duck. In the infected ducks, clinical signs of disease, including neurological disorder, were observed. Ducks started to die at 3 days-post-infection (dpi), and the study mortality reached 67%. Viruses were recovered from oropharyngeal and conjunctival swabs until 7 dpi and from cloacal swabs until 4 dpi. In the ducks that died or were sacrificed on 3, 5, or 6 dpi, viruses were recovered from lung, brain, heart, pancreas and intestine, among which the highest virus titers were in the lung, brain or heart. Results of virus titration were confirmed by real-time RT-PCR. Genetic and phylogenetic analysis of the HA gene revealed that the isolate belongs to clade 2.3.2.1 similarly to the H5N1 viruses isolated in Vietnam in 2012. The present study demonstrated that this recent HPAI H5N1 virus of clade 2.3.2.1 could replicate efficiently in the systemic organs, including the brain, and cause severe disease with neurological symptoms in domestic ducks. Therefore, this HPAI H5N1 virus seems to retain the neurotrophic feature and has further developed properties of shedding virus from the oropharynx and conjunctiva in addition to the cloaca, potentially posing a higher risk of virus spread through cross-contact and/or environmental transmission. Continued surveillance and diagnostic programs using conjunctival swabs in the field would further verify the apparent reliability of conjunctival samples for the detection of AIV.Japan Society for the Promotion of Science (Grant-in-Aid for Bilateral Joint Projects)Heiwa Nakajima FoundationNational Institute of Allergy and Infectious Diseases (U.S.) (Contract HHSN2662007000010C

A genome-engineered bioartificial implant for autoregulated anticytokine drug delivery

[Figure: see text]

Ecosystem Interactions Underlie the Spread of Avian Influenza A Viruses with Pandemic Potential

Despite evidence for avian influenza A virus (AIV) transmission between wild and domestic ecosystems, the roles of bird migration and poultry trade in the spread of viruses remain enigmatic. In this study, we integrate ecosystem interactions into a phylogeographic model to assess the contribution of wild and domestic hosts to AIV distribution and persistence. Analysis of globally sampled AIV datasets shows frequent two-way transmission between wild and domestic ecosystems. In general, viral flow from domestic to wild bird populations was restricted to within a geographic region. In contrast, spillover from wild to domestic populations occurred both within and between regions. Wild birds mediated long-distance dispersal at intercontinental scales whereas viral spread among poultry populations was a major driver of regional spread. Viral spread between poultry flocks frequently originated from persistent lineages circulating in regions of intensive poultry production. Our analysis of long-term surveillance data demonstrates that meaningful insights can be inferred from integrating ecosystem into phylogeographic reconstructions that may be consequential for pandemic preparedness and livestock protection.National Institutes of Health (U.S.) (NIH Centers for Excellence in Influenza Research and Surveillance (CEIRS, contract # HHSN266200700010C))National Institutes of Health (U.S.) (NIH Centers for Excellence in Influenza Research and Surveillance (CEIRS, contract # HHSN272201400008C))National Institutes of Health (U.S.) (NIH Centers for Excellence in Influenza Research and Surveillance (CEIRS, contract # HHSN272201400006C)

Change in physical activity level and clinical outcomes in older adults with knee pain: a secondary analysis from a randomised controlled trial

BACKGROUND: Exercise interventions improve clinical outcomes of pain and function in adults with knee pain due to osteoarthritis and higher levels of physical activity are associated with lower severity of pain and higher levels of physical functioning in older adults with knee osteoarthritis in cross-sectional studies. However, to date no studies have investigated if change in physical activity level during exercise interventions can explain clinical outcomes of pain and function. This study aimed to investigate if change in physical activity during exercise interventions is associated with future pain and physical function in older adults with knee pain. METHODS: Secondary longitudinal data analyses of a three armed exercise intervention randomised controlled trial. Participants were adults with knee pain attributed to osteoarthritis, over the age of 45 years old (n = 514) from Primary Care Services in the Midlands and Northwest regions of England. Crude and adjusted associations between absolute change in physical activity from baseline to 3 months (measured by the self-report Physical Activity Scale for the Elderly (PASE)) and i) pain ii) physical function (Western Ontario and McMaster Universities Osteoarthritis Index) and iii) treatment response (OMERACT-OARSI responder criteria) at 3 and 6 months follow-up were investigated using linear and logistic regression. RESULTS: Change in physical activity level was not associated with future pain, function or treatment response outcomes in crude or adjusted models at 3 or 6 months (P > 0.05). A 10 point increase in PASE was not associated with pain β = - 0.01 (- 0.05, 0.02), physical function β = - 0.09 (- 0.19, 0.02) or likelihood (odds ratio) of treatment response 1.02 (0.99, 1.04) at 3 months adjusting for sociodemographics, clinical covariates and the trial intervention arm. Findings were similar for 6 month outcome models. CONCLUSIONS: Change in physical activity did not explain future clinical outcomes of pain and function in this study. Other factors may be responsible for clinical improvements following exercise interventions. However, the PASE may not be sufficiently responsive to measure change in physical activity level. We also recommend further investigation into the responsiveness of commonly used physical activity measures. TRIAL REGISTRATION: ( ISRCTN93634563 ). Registered 29th September 2011