Structural maturation of myofilaments in engineered 3D cardiac microtissues characterized using small angle x-ray scattering.

Understanding the structural and functional development of human-induced pluripotent stem-cell-derived cardiomyocytes (hiPSC-CMs) is essential to engineering cardiac tissue that enables pharmaceutical testing, modeling diseases, and designing therapies. Here we use a method not commonly applied to biological materials, small angle x-ray scattering, to characterize the structural development of hiPSC-CMs within three-dimensional engineered tissues during their preliminary stages of maturation. An x-ray scattering experimental method enables the reliable characterization of the cardiomyocyte myofilament spacing with maturation time. The myofilament lattice spacing monotonically decreases as the tissue matures from its initial post-seeding state over the span of 10 days. Visualization of the spacing at a grid of positions in the tissue provides an approach to characterizing the maturation and organization of cardiomyocyte myofilaments and has the potential to help elucidate mechanisms of pathophysiology, and disease progression, thereby stimulating new biological hypotheses in stem cell engineering.

High-density stable glasses formed on soft substrates.

Enabled by surface-mediated equilibration, physical vapour deposition can create high-density stable glasses comparable with liquid-quenched glasses aged for millions of years. Deposition is often performed at various rates and temperatures on rigid substrates to control the glass properties. Here we demonstrate that on soft, rubbery substrates, surface-mediated equilibration is enhanced up to 170 nm away from the interface, forming stable glasses with densities up to 2.5% higher than liquid-quenched glasses within 2.5 h of deposition. Gaining similar properties on rigid substrates would require 10 million times slower deposition, taking ~3,000 years. Controlling the modulus of the rubbery substrate provides control over the glass structure and density at constant deposition conditions. These results underscore the significance of substrate elasticity in manipulating the properties of the mobile surface layer and thus the glass structure and properties, allowing access to deeper states of the energy landscape without prohibitively slow deposition rates.

Effects of Erucamide on Fiber "Softness": Linking Single-Fiber Crystal Structure and Mechanical Properties.

Erucamide is known to play a critical role in modifying polymer fiber surface chemistry and morphology. However, its effects on fiber crystallinity and mechanical properties remain to be understood. Here, synchrotron nanofocused X-ray Diffraction (nXRD) revealed a bimodal orientation of the constituent polymer chains aligned along the fiber axis and cross-section, respectively. Erucamide promoted crystallinity in the fiber, leading to larger and more numerous lamellae crystallites. The nXRD nanostructual characterization is complemented by single-fiber uniaxial tensile tests, which showed that erucamide significantly affected fiber mechanical properties, decreasing fiber tensile strength and stiffness but enhancing fiber toughness, fracture strain, and ductility. To correlate these single-fiber nXRD and mechanical test results, we propose that erucamide mediated slip at the interfaces between crystallites and amorphous domains during stress-induced single-fiber crystallization, also decreasing the stress arising from the shear displacement of microfibrils and deformation of the macromolecular network. Linking the single-fiber crystal structure with the single-fiber mechanical properties, these findings provide the direct evidence on a single-fiber level for the role of erucamide in enhancing fiber "softness".

Multiscale characterisation of single synthetic fibres: Surface morphology and nanomechanical properties.

HYPOTHESIS: Thermal through-air bonding process and slip additive treatment affect fibre surface structure and nanomechanical properties, which is extremely difficult to characterise on a single-fibre level. EXPERIMENTS: Optical microscopy (OM) was applied to study the effect of air-through bonding, spunbonding, and crimping on fibre geometry and general appearance. A "spray-on" method developed here using a custom-designed fibre holder allowed a direct measurement of static contact angles of water droplets on single fibres. Scanning electron microscopy (SEM) showed different morphological features on the fibre due to the nonwoven fabric-making process and additive treatment. Synchrotron X-ray diffraction (XRD) was applied to study the effect of erucamide presence on polypropylene (PP) fibre crystal structure. Atomic force microscopy (AFM) imaging provided complementary characterization of fibre topographic features such as average surface roughness, along with adhesion force mapping by quantitative nanomechanical (QNM) AFM imaging. FINDINGS: Our results show the effect of nonwoven making process and surfactant additive treatment on the fibre surface structure and nanomechanical properties. Wettability experiment on the single fibre revealed the hydrophobic nature of all the synthetic fibres. For polyethylene/polyethylene terephthalate (PE/PET) bicomponent single fibres, the polyethylene sheath was found to possess fibrillar microstructure - typical for drawn fibres, whereas the fibres entangled in nonwoven fabrics exhibited a uniform, porous surface morphology attributed to the through-air process. Adhesion force mapping allowed us to correlate fibre nanomechanical properties with its topography, with surface pore interiors showing higher adhesion than the flat polyethylene region. Furthermore, on the polypropylene (PP) fibre surface treated with erucamide (13-cis-docosenamide; a common slip additive used in polyolefin film processing), we observed overlapping multilayers consisting of 4 nm erucamide bilayers, attributed to the slip additive migration onto the fibre surface. XRD measurements of the fibres did not detect the presence of erucamide; however, AFM imaging provided evidence for its migration to the fibre surface, imparting influence on the surface structure and adhesive properties of the fibre. Single-fibre AFM imaging also allowed a detailed analysis of different surface roughness parameters, revealing that both through-air bonding in the nonwoven making process and the slip additive (erucamide) treatment affected the fibre surface roughness. The wettability, surface morphology, and adhesion properties from this study, obtained with unprecedented resolution and details on single fibres, are valuable to informing rational design of fibre processing for fibre optimal properties, critically important in many industrial applications.

Bénard-Marangoni Dendrites upon Evaporation of a Reactive ZnO Nanofluid Droplet: Effect of Substrate Chemistry.

Evaporation of a particle laden sessile drop can lead to complex surface patterns with structural hierarchy. Most commonly, the dispersed particles are inert. We have recently reported that when the sessile drop contains reactive ZnO nanoparticles, solidified Bénard-Marangoni (BM) cells with dendritic micromorphology were formed in the residual surface pattern from in situ-generated nanoclusters. Here, we report the effect of substrate chemistry on the residual pattern from the evaporation of nanofluids containing ZnO particles dispersed in a mixture of cyclohexane and isobutylamine, by comparing three different substrates: glass, silicon, and hydrophilized silicon. In particular, we performed a quantitative analysis of the BM cell size, distribution, and the cell morphological characteristics via the fractal dimension analysis. We find that the size dimension λBM of the dendritic Bénard-Marangoni cells varied on the different substrates, attributed to their different hydrophilicity and affinity for water molecules, evident from the different polar components γP in their surface free energy from the Owens-Wendt analysis. The average BM cell size was the smallest for the glass substrate (λBM = 289 µm) and comparable for the unmodified and UV/ozone-treated silicon wafers (with λBM = 466 and 423 µm, respectively). The fractal dimension analysis provided a quantitative description of the BM cells with complex structural hierarchy, highlighting the differences in the geometric features of the surface patterns resulting from different substrate chemistry. We also found that the fractal dimensions depended on the BM cell size, attributing it to two different regimes: the growing fractals and the maturing fractals.

Dendritic surface patterns from Bénard-Marangoni instabilities upon evaporation of a reactive ZnO nanofluid droplet: A fractal dimension analysis.

We present a box counting fractal dimension (FD) analysis of the dendritic patterns obtained under conditions far from equilibrium via rapid evaporation of a sessile drop containing reactive ZnO nanoparticles. These dendrites were manifestations of solidified Bénard-Marangoni (BM) instability convection cells, and we previously noted that their complex hierarchical morphologies were superficially analogous to the foliage of red algae, Spanish dagger, or spider plant. The fractal dimension of the Bénard-Marangoni dendrites was found to vary in the range of 1.77-1.89 and also depend on the size of the Bénard-Marangoni cells. These fractal dimension results were correlated with the morphological details of the Bénard-Marangoni cells and ZnO particle characteristics, providing a quantitative description of such complex surface patterns emerging from the dynamic process of the Bénard-Marangoni instability.

Hierarchical Surface Patterns upon Evaporation of a ZnO Nanofluid Droplet: Effect of Particle Morphology.

Surface structures with tailored morphologies can be readily delivered by the evaporation-induced self-assembly process. It has been recently demonstrated that ZnO nanorods could undergo rapid chemical and morphological transformation into 3D complex structures of Zn(OH)2 nanofibers as a droplet of ZnO nanofluid dries on the substrate via a mechanism very different from that observed in the coffee ring effect. Here, we have investigated how the crystallinity and morphology of ZnO nanoparticles would affect the ultimate pattern formation. Three ZnO particles differing in size and shape were used, and their crystal structures were characterized by powder X-ray diffraction (XRD) and transmission electron microscopy (TEM). Their dispersions were prepared by sonication in a mixture of isobutylamine and cyclohexane. Residual surface patterns were created by drop casting a droplet of the nanofluid on a silicon substrate. The residual surface patterns were analyzed by scanning electron microscopy (SEM) and microfocus grazing incidence X-ray diffraction (µGIXRD). Nanofluid droplets of the in-house synthesized ZnO nanoparticles resulted in residual surface patterns consisting of Zn(OH)2 nanofibers. However, when commercially acquired ZnO powders composed of crystals with various shapes and sizes were used as the starting material, Zn(OH)2 fibers were found covered by ZnO crystal residues that did not fully undergo the dissolution and recrystallization process during evaporation. The difference in the solubility of ZnO nanoparticles was linked to the difference in their crystallinity, as assessed using the Scherrer equation analysis of their XRD Bragg peaks. Our results show that the morphology of the ultimate residual pattern from evaporation of ZnO nanofluids can be controlled by varying the crystallinity of the starting ZnO nanoparticles which affects the nanoparticle dissolution process during evaporation.

Spectroscopic study of ionic liquid adsorption from solution onto gold.

Gold was exposed to ethanol solutions containing 0.1 wt% 1-hexyl-3-methyl-imidazolium bis(trifluoromethanesulfonyl)imide (HMIM NTf2), an ionic liquid (IL). The resulting adsorbed layers were interrogated using X-ray photoelectron spectroscopy (XPS - both conventional and synchrotron-based) and spectroscopic ellipsometry. Ellipsometry indicated that the adsorbed layer thickness was smaller than the size of an IL ion pair, with an average determined layer thickness of 0.15 nm. This value indicates that the adsorbed layer on gold is most likely patchy. Conventional XPS revealed that the IL adsorbs irreversibly to gold, with equal amounts of anion and cation in the adsorbed layer. High signal-to-noise synchrotron XPS spectra permitted detailed deconvolution of the S 2p and N 1s peaks for the IL-treated gold, providing more information on adsorbed layer composition and structure. Spectra acquired as a function of X-ray exposure time indicate that non-interacting physisorbed IL components are preferentially removed at the expense of surface bound components, and that anion and cation are both present in the surface bound layer, and also in the layer above. A model structure for the IL adsorbed on gold is proposed.