Wrinkling, creasing, and folding in fiber-reinforced soft tissues

Many biological tissues develop elaborate folds during growth and development. The onset of this folding is often understood in relation to the creasing and wrinkling of a thin elastic layer that grows whilst attached to a large elastic foundation. In reality, many biological tissues are reinforced by fibres and so are intrinsically anisotropic. However, the correlation between the fiber directions and the pattern formed during growth is not well understood. Here, we consider the stability of a two-layer tissue composed of a thin hyperelastic strip adhered to an elastic half-space in which are embedded elastic fibers. The combined object is subject to a uniform compression and, at a critical value of this compression, buckles out of the plane — it wrinkles. We characterize the wrinkle wavelength at onset as a function of the fiber orientation both computationally and analytically and show that the onset of surface instability can be either promoted or inhibited as the fiber stiffness increases, depending on the fibre angle. However, we find that the structure of the resulting folds is approximately independent of the fiber orientation. We also explore numerically the formation of large creases in fiber-reinforced tissue in the post-buckling regime

Passivation and dissolution mechanisms in ordered anodic tantalum oxide nanostructures

Tantalum oxide (Ta2O5) nanostructures exhibit outstanding electrical and optical properties, as well as, high chemical resistance and stability. These materials have great potential for biomedical, catalysis, semiconductors and energy applications due to their large surface area and high specific charge, when arranged in nanoporous or nanotubular morphologies. In order to obtain these structures, an anodization process, which is inexpensive, reproducible and easy to scale up, is used. Yet, depending on the anodization conditions, the formation of a nanoporous or nanotubular layer is difficult to stabilize during the anodization process. In this regard, anodized tantalum oxide nanostructures were produced to understand the effect of the anodization conditions, including electrolyte concentration, potential and time. The nanopores or nanotubes morphologies, their chemical composition and structure were investigated by FIB-SEM, double-corrected TEM-STEM and EDS. We found that it is necessary to have high acid concentrations (mixture of H2SO4 with HF) to be able to form nanoporous or nanotubular structures. Despite the capacity of HF to dissolve and create anodic oxide nanostructures, the amount of H2SO4 concentration in the mixture is very important, leading to a dimple morphology. Furthermore, the increase of the anodization potential/electrical field clearly leads to an increase in the dimples diameter.This research is sponsored by FEDER funds through the program COMPETE -Programa Operacional Factores de Competitividade and by the Portuguese Foundation for Science and Technology (FCT) in the framework of the Strategic Funding UIDB/04650/2020, and UID/EMS/00285/2020 and with a PhD fellowship SFRH/BD/98199/2013.The authors thank the financial support in the framework of HEALTHYDENT -POCI-01-0145-FEDER-030708 and PTDC/CTM-NAN/4242/2014 projects.This work was supported by FCT, through IDMEC, under LAETA, project UIDB/50022/2020.The authors would like to acknowledge that this project has received funding from the EU Framework Programme for Research and Innovation H2020, scheme COFUND -Co-funding of Regional, National and International Programmes, under Grant Agreement 713640

Electron dynamics in gold and gold–silver alloy nanoparticles: The influence of a nonequilibrium electron distribution and the size dependence of the electron–phonon relaxation

©1999 American Institute of Physics. The electronic version of this article is the complete one and can be found online at: http://link.aip.org/link/?JCPSA6/111/1255/1DOI: 10.1063/1.479310Electron dynamics in gold nanoparticles with an average diameter between 9 and 48 nm have been studied by femtosecond transient absorption spectroscopy. Following the plasmon bleach recovery after low power excitation indicates that a non-Fermi electron distribution thermalizes by electron–electron relaxation on a time scale of 500 fs to a Fermi distribution. This effect is only observed at low excitation power and when the electron distribution is perturbed by mixing with the intraband transitions within the conduction band (i.e., when the excitation wavelength is 630 or 800 nm). However, exciting the interband transitions at 400 nm does not allow following the early electron thermalization process. Electron thermalization with the lattice of the nanoparticle by electron–phonon interactions occurs within 1.7 ps under these conditions, independent of the excitation wavelength. In agreement with the experiments, simulations of the optical response arising from thermalized and nonthermalized electron distributions show that a non-Fermi electron distribution leads to a less intense bleach of the plasmon absorption. Furthermore, the difference between the response from the two electron distributions is greater for small temperature changes of the electron gas (low excitation powers). No size dependence of the electron thermalization dynamics is observed for gold nanoparticles with diameters between 9 and 48 nm. High-resolution transmission electron microscopy (HRTEM) reveals that these gold nanoparticles possess defect structures. The effect of this on the electron–phonon relaxation processes is discussed. 18 nm gold–silver alloy nanoparticles with a gold mole fraction of 0.8 are compared to 15 nm gold nanoparticles. While mixing silver leads to a blue-shift of the plasmon absorption in the ground-state absorption spectrum, no difference is observed in the femtosecond dynamics of the system

Understanding Charge Transfer in Donor-Acceptor/Metal Systems: A Combined Theoretical and Experimental Study

We develop an effective potential approach for assessing the flow of charge within a two-dimensional donor-acceptor/metal network based on core-level shifts. To do so, we perform both density functional theory (DFT) calculations and x-ray photoemission spectroscopy (XPS) measurements of the core-level shifts for three different monolayers adsorbed on a Ag substrate. Specifically, we consider perfluorinated pentacene (PFP), copper phthalocyanine (CuPc) and their 1:1 mixture (PFP+CuPc) adsorbed on Ag(111).Comment: 12 pages, 10 figure

The Effects of Isoprene and NOx on Secondary Organic Aerosols Formed Through Reversible and Irreversible Uptake to Aerosol Water

Isoprene oxidation produces water-soluble organic gases capable of partitioning to aerosol liquid water. The formation of secondary organic aerosols through such aqueous pathways (aqSOA) can take place either reversibly or irreversibly; however, the split between these fractions in the atmosphere is highly uncertain. The aim of this study was to characterize the reversibility of aqSOA formed from isoprene at a location in the eastern United States under substantial influence from both anthropogenic and biogenic emissions. The reversible and irreversible uptake of water-soluble organic gases to aerosol water was characterized in Baltimore, Maryland, USA, using measurements of particulate water-soluble organic carbon (WSOCp) in alternating dry and ambient configurations. WSOCp evaporation with drying was observed systematically throughout the late spring and summer, indicating reversible aqSOA formation during these times. We show through time lag analyses that WSOCp concentrations, including the WSOCp that evaporates with drying, peak 6 to 11 h after isoprene concentrations, with maxima at a time lag of 9 h. The absolute reversible aqSOA concentrations, as well as the relative amount of reversible aqSOA, increased with decreasing NOx / isoprene ratios, suggesting that isoprene epoxydiol (IEPOX) or other low-NOx oxidation products may be responsible for these effects. The observed relationships with NOx and isoprene suggest that this process occurs widely in the atmosphere, and is likely more important in other locations characterized by higher isoprene and/or lower NOx levels. This work underscores the importance of accounting for both reversible and irreversible uptake of isoprene oxidation products to aqueous particles

Nature of intrinsic and extrinsic electron trapping in SiO 2

Using classical and ab initio calculations we demonstrate that extra electrons can be trapped in pure crystalline and amorphous SiO2 (a-SiO2) in deep band gap states. The structure of trapped electron sites in pure a-SiO2 is similar to that of Ge electron centers and so-called [SiO4/Li]0 centers in α quartz. Classical potentials were used to generate amorphous silica models and density functional theory to characterize the geometrical and electronic structures of trapped electrons in crystalline and amorphous silica. The calculations demonstrate that an extra electron can be trapped at a Ge impurity in α quartz in six different configurations. An electron in the [SiO4/Li]0 center is trapped on a regular Si ion with the Li ion residing nearby. Extra electrons can trap spontaneously on pre-existing structural precursors in amorphous SiO2, while the electron self-trapping in α quartz requires overcoming a barrier of about 0.6 eV. The precursors for electron trapping in amorphous SiO2 comprise wide (≥132∘) O–Si–O angles and elongated Si–O bonds at the tails of corresponding distributions. Using this criterion, we estimate the concentration of these electron trapping sites at ≈4×1019 cm−3

Identification of intrinsic electron trapping sites in bulk amorphous silica from ab initio calculations

Using ab initio calculations we demonstrate that extra electrons in pure amorphous SiO2 can be trapped in deep band gap states. Classical potentials were used to generate amorphous silica models and density functional theory to characterise the geometrical and electronic structures of trapped electrons. Extra electrons can trap spontaneously on pre-existing structural precursors in amorphous SiO2 and produce ≈≈3.2 eV deep states in the band gap. These precursors comprise wide (⩾⩾130°°) O–Si–O angles and elongated Si–O bonds at the tails of corresponding distributions. The electron trapping in amorphous silica structure results in an opening of the O–Si–O angle (up to almost 180°°). We estimate the concentration of these electron trapping sites to be View the MathML source≈5×1019cm-3

Minimal conditions on Clifford semigroup congruences

A known result in groups concerning the inheritance of minimal conditions on normal subgroups by subgroups with finite indexes is extended to semilattices of groups [E(S),Se,ϕe,f] with identities in which all ϕe,f are epimorphisms (called q partial groups). Formulation of this result in terms of q congruences is also obtained

Live Imaging of Type I Collagen Assembly Dynamics in Osteoblasts Stably Expressing GFP and mCherry-Tagged Collagen Constructs

Type I collagen is the most abundant extracellular matrix protein in bone and other connective tissues and plays key roles in normal and pathological bone formation as well as in connective tissue disorders and fibrosis. Although much is known about the collagen biosynthetic pathway and its regulatory steps, the mechanisms by which it is assembled extracellularly are less clear. We have generated GFPtpz and mCherry-tagged collagen fusion constructs for live imaging of type I collagen assembly by replacing the α2(I)-procollagen N-terminal propeptide with GFPtpz or mCherry. These novel imaging probes were stably transfected into MLO-A5 osteoblast-like cells and fibronectin-null mouse embryonic fibroblasts (FN-null-MEFs) and used for imaging type I collagen assembly dynamics and its dependence on fibronectin. Both fusion proteins co-precipitated with α1(I)-collagen and remained intracellular without ascorbate but were assembled into α1(I) collagen-containing extracellular fibrils in the presence of ascorbate. Immunogold-EM confirmed their ultrastuctural localization in banded collagen fibrils. Live cell imaging in stably transfected MLO-A5 cells revealed the highly dynamic nature of collagen assembly and showed that during assembly the fibril networks are continually stretched and contracted due to the underlying cell motion. We also observed that cell-generated forces can physically reshape the collagen fibrils. Using co-cultures of mCherry- and GFPtpz-collagen expressing cells, we show that multiple cells contribute collagen to form collagen fiber bundles. Immuno-EM further showed that individual collagen fibrils can receive contributions of collagen from more than one cell. Live cell imaging in FN-null-MEFs expressing GFPtpz-collagen showed that collagen assembly was both dependent upon and dynamically integrated with fibronectin assembly. These GFP-collagen fusion constructs provide a powerful tool for imaging collagen in living cells and have revealed novel and fundamental insights into the dynamic mechanisms for the extracellular assembly of collagen