Localized deformation in soft solids around spherical cavities

Biological tissue, like internal organs, brain, or skin, are soft solids that may be exposed to injury inducing mechanisms at a range of rates, resulting in damage. Sport injuries, car crashes, traumatic brain injury, and ballistic impacts can produce strain rates from 10−10^5 1/s. The parameters governing failure in these soft solids (moduli < 1 MPa) are challenging to quantify, requiring modifications or defying the use of traditional characterization techniques. Driving bubble/droplet growth or contraction provides a way to characterize these materials while avoiding some limitations of traditional techniques. Large deformations in these spherical geometries induce localized deformations at the surface of the cavity. In this thesis, I leverage these localized deformations, cracks during expansion and creases during contractions, to investigate fracture energy and strain stiffening, respectively. A Small-scale Ballistic Cavitation device uses a high-pressure air reservoir to generate spherical deformation at high rates within soft solids. Air accelerates through a needle, reaching the speed of sound at the tip before delivery to the sample. The energy density of the air pulse matches that of bullets, producing small, ballistic-like cavitations. Independent control of pressure, needle diameter, and valve cycle time provides flexibility in experimental control variables not available in other ultrasoft solid cavitation techniques. Using these needle-mediated, high rate spherical expansions, I investigate the parameters governing fracture initiation in soft solids by adapting a theory of fracture traditionally used in dynamic failure in hard materials. I present results from cavity expansions in silicone and gelatin samples. Increasing the rate of expansion increases the number of cracks initiated in the cavity surface, leading to multi-lobed cracks, as opposed to the penny-shaped cracks present in quasi-static cavitations. The elastic wave speed-dependent fracture correlation model I adapt suggests that counting the number of cracks provides a measure of the soft solid’s fracture energy. Additionally, I include the implications of this model for analytical calculations in very tough, nonlinear materials. Finally, I demonstrate the multiple fracture phenomenon in ballistic impacts and present a method for analyzing damage that draws upon the understanding gained in from the bench-scale cavity expansions. In the last chapter, I report on crease morphology and evolution at the surface of contracting cavities embedded within elastomeric solids of varying degrees of crosslinking. Cavity contraction is achieved through evaporation of an embedded water droplet. In validation of theoretical predictions, strain-stiffening is found to govern both crease onset and crease density. Neo-Hookean solids are found to prefer initiating creasing with many short creases that join to form a collapsed state with only a few creases, whereas creasing in Gent solids initiates with a few creases that propagate across the cavity surface

Amino acid racemization dating of marine shells: a mound of possibilities

Shell middens are one of the most important and widespread indicators for human exploitation of marine resources and occupation of coastal environments. Establishing an accurate and reliable chronology for these deposits has fundamental implications for understanding the patterns of human evolution and dispersal. This paper explores the potential application of a new methodology of amino acid racemization(AAR) dating of shell middens and describes a simple protocol to test the suitability of different molluscanspecies. This protocol provides a preliminary test for the presence of an intracrystalline fraction of proteins(by bleaching experiments and subsequent heating at high temperature), checking the closed system behaviour of this fraction during diagenesis. Only species which pass both tests can be considered suitable for further studies to obtain reliable age information. This amino acid geochronological technique is also applied to midden deposits at two latitudinal extremes: Northern Scotland and the Southern Red Sea.Results obtained in this study indicate that the application of this new method of AAR dating of shells has the potential to aid the geochronological investigation of shell mounds in different areas of the world

Amino acid racemization dating of marine shells: a mound of possibilities

Shell middens are one of the most important and widespread indicators for human exploitation of marine resources and occupation of coastal environments. Establishing an accurate and reliable chronology for these deposits has fundamental implications for understanding the patterns of human evolution and dispersal. This paper explores the potential application of a new methodology of amino acid racemization(AAR) dating of shell middens and describes a simple protocol to test the suitability of different molluscanspecies. This protocol provides a preliminary test for the presence of an intracrystalline fraction of proteins(by bleaching experiments and subsequent heating at high temperature), checking the closed system behaviour of this fraction during diagenesis. Only species which pass both tests can be considered suitable for further studies to obtain reliable age information. This amino acid geochronological technique is also applied to midden deposits at two latitudinal extremes: Northern Scotland and the Southern Red Sea.Results obtained in this study indicate that the application of this new method of AAR dating of shells has the potential to aid the geochronological investigation of shell mounds in different areas of the world

Water driven deformation in soft solids

Plants have utilized water to achieve many different types of motion, using the concepts that they use, we are able to develop a self-actuated soft solid-liquid composite. This self-actuation is driven by the evaporation and resulting tension of water, which can deform soft materials. The effects that water droplets deforming in soft solids have need to be characterized in order to utilize these composites. When water is embedded in elastomeric materials, it can undergo transitions known as breathing, buckling, and creasing. Breathing and creasing have been observed. These droplets are examined in elastomers of two different elastic modulus. When droplets in the stiffer elastomer crease they form just one crease, whereas less stiff elastomers crease in multiple areas, this is the result of the surface tension. Creasing is expected to set in for any embedded droplet when it shrinks to the same relative size ratio. However, there seems to be a dependence on the stiffness, stiffer samples crease at a smaller size. The pressure in the droplets appears to not reach the expected cavitation limit, which could be a result of not taking strain hardening effects into account in calculations. After studying how a single droplet deforms in an elastomer, multiple droplets are used together in order to achieve motion resulting from evaporation

Layer-By-Layer Assembly of Graphene Oxide on Thermosensitive Liposomes for Photo-Chemotherapy

Stimuli responsive polyelectrolyte nanoparticles have been developed for chemo-photothermal destruction of breast cancer cells. This novel system, called layer by layer Lipo-graph (LBL Lipo-graph), is composed of alternate layers of graphene oxide (GO) and graphene oxide conjugated poly (l-lysine) (GO-PLL) deposited on cationic liposomesencapsulating doxorubicin. Various concentrations of GO and GO-PLL were examined and the optimal LBL Lipo-graph was found to have a particle size of 267.9 ± 13 nm, zeta potentialof +43.9 ± 6.9 mV and encapsulation efficiency of 86.4 ± 4.7%. The morphology of LBL Lipo-graph was examined by cryogenic-transmission electron microscopy (Cryo-TEM), atomic force microcopy (AFM) and scanning electron microscopy (SEM). The buildup of LBL Lipo-graph was confirmed via ultraviolet-visible (UV–Vis) spectrophotometry, thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) analysis. Infra-red (IR) response suggests that four layers are sufficient to induce a gel-to-liquid phase transition in response to near infra-red (NIR) laser irradiation. Light-matter interaction of LBL Lipo-graph was studied by calculating the absorption cross section in the frequency domain by utilizing Fourier analysis. Drug release assay indicates that the LBL Lipo-graph releases much faster in an acidic environment than a liposome control. A cytotoxicity assay was conducted to prove the efficacy of LBL Lipo-graph to destroy MD-MB-231 cells in response to NIR laser emission. Also, image stream flow cytometry and two photon microcopy provide supportive data for the potential application of LBL Lipo-graph for photothermal therapy. Study results suggest the novel dual-sensitive nanoparticles allow intracellular doxorubin delivery and respond to either acidic environments or NIR excitation. Statement of Significance Stimuli sensitive hybrid nanoparticles have been synthesized using a layer-by-layer technique and demonstrated for dual chemo-photothermal destruction of breast cancer cells. The hybrid nanoparticles are composed of alternating layers of graphene oxide and graphene oxide conjugated poly-l-lysine coating the surface of a thermosensitive cationic liposome containing doxorubicin as a core. Data suggests that the hybrid nanoparticles may offer many advantages for chemo-photothermal therapy. Advantages include a decrease of the initial burst release which may result in the reduction in systemic toxicity, increase in pH responsivity around the tumor environment and improved NIR light absorption

Evidence for a Double Well in the First Triplet Excited State of 2-Thiouracil

The computationally predicted presence of two structurally distinct minima in the first triplet excited (T₁) state of 2-thiouracil (2TU) is substantiated by sub-picosecond transient vibrational absorption spectroscopy (TVAS) in deuterated acetonitrile solution. Following 300 nm ultraviolet excitation to the second singlet excited state of 2TU, a transient infrared absorption band centered at 1643 cm^–1 is observed within our minimum time resolution of 0.3 ps. It is assigned either to 2TU molecules in the S₁ state or to vibrationally hot T₁-state molecules, with the latter assignment more consistent with recent computational and experimental studies. The 1643 cm^–1 band decays with a time constant of 7.2 ± 0.8 ps, and there is corresponding growth of several further bands centered at 1234, 1410, 1424, 1443, 1511, 1626, and 1660 cm^–1 which show no decline in intensity over the 1 ns time limit of our measurements. These spectral features are assigned to two different conformations of 2TU, corresponding to separate energy minima on the T₁-state potential energy surface, on the basis of their extended lifetimes, computed infrared frequencies, and the observed quenching of the bands by addition of styrene. Corresponding measurements for the 4-thiouracil (4TU) isomer show sub-picosecond population of the T₁ state, which vibrationally cools with a time constant of 5.2 ± 0.6 ps. However, TVAS measurements in the carbonyl stretching region do not distinguish the two computed T₁-state conformers of 4TU because of the similarity of their vibrational frequencies

Why People Are Not Willing to Let Their Children Ride in Driverless School Buses: A Gender and Nationality Comparison

As driverless vehicles proliferate, it is possible that this technology will be applied in mass transport vehicles. School buses may be suited for autonomous operations as they follow set routes and schedules. However, a research gap exists in whether or not parents would be willing to have their children ride in autonomously operated school buses. The purpose of this study was to examine parents’ willingness to allow their child to ride in an autonomous school bus. Participant gender and nationality were also two independent variables, along with affect measures as a possible mediating variable. The research used a two-study approach. In study one, it was found that participants were less willing to have their child ride in a driverless school bus than a traditional human-operated vehicle. In study two, findings suggest a significant interaction between the type of driver, participant gender, and nationality. In general, American females were less willing than Indian females and overall, Americans were less willing than Indians in the driverless conditions. Affect was found to be a mediating variable, which suggests that emotions were playing a role in the responses of participants. The paper concludes with theoretical contributions, practical applications, and suggestions for future research

Assessing the relationship between human well-being and ecosystem services: a review of frameworks

Focusing on the most impoverished populations, we critically review and synthesise key themes from dominant frameworks for assessing the relationship between well-being and ecosystem services in developing countries. This requires a differentiated approach to conceptualising well-being that appropriately reflects the perspectives of the poorest-those most directly dependent on ecosystem services, and their vulnerability to external and policy-driven environmental change. The frameworks analysed draw upon environmental sciences, economics, psychology, sociology, and anthropology, and were selected on the basis of their demonstrated or potential ability to illustrate the relationship between environmental change and human well-being, as well as their prevalence in real world applications. Thus, the synthesis offered here is informed by the various theoretical, methodological, and hermeneutical contributions from each field to the notion of well-being. The review highlights several key dimensions that should be considered by those interested in understanding and assessing the impact of environmental change on the well-being of the world's poorest people: the importance of interdisciplinary consideration of well-being, the need for frameworks that integrate subjective and objective aspects of well-being, and the central importance of context and relational aspects of well-being. The review is of particular interest to those engaged in the post-2015 development agenda

Vanguards and avant-gardes : The reason in revolt online project on political and cultural radicalism

The 'Reason in Revolt' project aims to bring together primary source documents of Australian radicalism as a readily accessible digitised resource. By 'radical' we refer to those who aimed to make society more equal and to emancipate the exploited or oppressed. As it grows and develops, the project website will become an expanding record of the movements, institutions, venues and publications through which radicals sought to influence Australian society. Burgmann, Macintyre and Milner intend to utilise the technological benefits of this website in the production of a monograph on the role of intellectuals in the development of radical thought and practice

Cloning the barley nec3 disease lesion mimic mutant using complementation by sequencing

Disease lesion mimic (DLM) or necrotic mutants display necrotic lesions in the absence of pathogen infections. They can show improved resistance to some pathogens and their molecular dissection can contribute to revealing components of plant defense pathways. Although forward-genetics strategies to find genes causal to mutant phenotypes are available in crops, these strategies require the production of experimental cross populations, mutagenesis, or gene editing and are time- and resource-consuming or may have to deal with regulated plant materials. In this study, we described a collection of 34 DLM mutants in barley (Hordeum vulgare L.) and applied a novel method called complementation by sequencing (CBS), which enables the identification of the gene responsible for a mutant phenotype given the availability of two or more chemically mutagenized individuals showing the same phenotype. Complementation by sequencing relies on the feasibility to obtain all induced mutations present in chemical mutants and on the low probability that different individuals share the same mutated genes. By CBS, we identified a cytochrome P450 CYP71P1 gene as responsible for orange blotch DLM mutants, including the historical barley nec3 locus. By comparative phylogenetic analysis we showed that CYP71P1 gene family emerged early in angiosperm evolution but has been recurrently lost in some lineages including Arabidopsis thaliana (L.) Heynh. Complementation by sequencing is a straightforward cost-effective approach to clone genes controlling phenotypes in a chemically mutagenized collection. The TILLMore (TM) collection will be instrumental for understanding the molecular basis of DLM phenotypes and to contribute knowledge about mechanisms of host-pathogen interaction