Potential Shifts in Canadian High Arctic Sedimentary Organic Matter Composition With Permafrost Active Layer Detachments

Increased temperature and precipitation in Arctic regions have led to deeper thawing and structural instability in permafrost soil. The resulting localized disturbances, referred to as active layer detachments (ALDs), may transport organic matter (OM) to more biogeochemically active zones. To examine this further, solid state cross polarization magic angle spinning 13C nuclear magnetic resonance (CPMAS NMR) and biomarker analysis were used to evaluate potential shifts in riverine sediment OM composition due to nearby ALDs within the Cape Bounty Arctic Watershed Observatory, Nunavut, Canada. In sedimentary OM near ALDs, NMR analysis revealed signals indicative of unaltered plant-derived material, likely derived from permafrost. Long chain acyclic aliphatic lipids, steroids, cutin, suberin and lignin occurred in the sediments, consistent with a dominance of plant-derived compounds, some of which may have originated from permafrost-derived OM released by ALDs. OM degradation proxies for sediments near ALDs revealed less alteration in acyclic aliphatic lipids, while constituents such as steroids, cutin, suberin and lignin were found at a relatively advanced stage of degradation. Phospholipid fatty acid analysis indicated that microbial activity was higher near ALDs than downstream but microbial substrate limitation was prevalent within disturbed regions. Our study suggests that, as these systems recover from disturbance, ALDs likely provide permafrost-derived OM to sedimentary environments. This source of OM, which is enriched in labile OM, may alter biogeochemical patterns and enhance microbial respiration within these ecosystems.

Surface active substances in the water column during POLARSTERN cruise ANT-XXI/3 (EIFEX)

Surface active substances (SAS) in the water column were measured by voltammetry using the electrochemical probe o-nitrophenol (ONP) during EIFEX, a mesoscale open ocean iron enrichment experiment in the Southern Ocean. SAS levels were low throughout the experiment (<0.005 - 0.03 mg/L Triton X-100 equivalents). Initially SAS was extremely low in the photic zone, but as the phytoplankton bloom developed concentrations markedly increased throughout the upper 100 m (~0.02 mg/L Triton X-100 equivalents). Highest concentrations of SAS (>0.02 mg/L Triton X-100 equivalents) were found at the end of the bloom particularly at density discontinuities where organic material may accumulate. Exudates from diatoms appeared to be the major source of SAS during EIFEX, either from direct extracellular release or in the action of being grazed upon by zooplankton.

Improving the Manufacturability of Active Microfluidic Devices using Stereolithography (SL)

Thesis (Master's)--University of Washington, 2016-06

Potential to increase yield in lucerne (Medicago sativa subsp sativa) through introgression of Medicago sativa subsp falcata into Australian adapted material

The effect of interspecific heterosis in crosses between Medicago sativa subsp. sativa and M. sativa subsp. falcata was assessed. Three sativa and 3 falcata plants were crossed in a diallel design. Progeny dry matter yield and natural plant height were assessed in a replicated field experiment at Gatton, Queensland. Yield data were analysed using the method of residual maximum likelihood (REML) and Griffing's model 1. There were significant differences between the reciprocal, general combining ability (GCA), and specific combining ability (SCA) effects. As expected, S-1 populations were lower yielding than their respective intraspecific cross and falcata x falcata crosses were significantly lower yielding than sativa x sativa crosses. Some of the interspecific crosses indicated substantial SCA effects, yielding at least as well as the best sativa x sativa crosses. We have demonstrated the potential usefulness of unselected M. sativa subsp. falcata as a heterotic group in the improvement of yield in northern Australian adapted lucerne material, and discuss how it could be incorporated into future breeding to overcome the yield stagnation currently being experienced in Australian programs.

Clinically active Crohn's disease in the presence of a low C-reactive protein

Objective. Clinical interest in C-reactive protein (CRP) - a component of the innate immune system - has focused mainly on its worth as an indicator of disease activity. There has been a resurgence of interest in CRP in the Crohn's disease ( CD) literature because several trials of new treatments for active CD have been characterized by both a large proportion of patients with low CRP ( < 10 mg/l) at entry to the trials and by a negative therapeutic outcome. It is therefore of interest to study the clinical characteristics of patients who are thought to have at the same time both active CD and a low CRP. Material and methods. Patients were prospectively recruited as part of the Brisbane IBD clinical and research programme. Subjects were included in the low CRP group only if there were complete datasets for CRP on all occasions of active CD, and CRP was < 10 mg/l. Active disease was defined as CD activity index (CDAI) > 200. The low CRP group was compared with patients in the raised CRP group for a range of clinical variables as well as the major NOD2 variants. Results. There were data sets for 223 CD patients, with a mean disease duration of 12 years. Of these, 22 patients fulfilled the criteria for low CRP. The low CRP group ( group 1) showed significant differences for disease site (p < 0.01) and for BMI (p = 0.006) compared to the raised CRP group ( group 2). Specifically, group 1 had a predominance of pure ileal disease (95% versus 53%) and lack of pure colonic disease (0% versus 24%) compared to group 2, and their BMI was significantly lower (20.3 kg/m(2) versus 25.0 kg/m(2)). Groups 1 and 2 did not differ with respect to Vienna behaviour at diagnosis, smoking, appendicectomy, extra-intestinal manifestations of CD, or NOD2 SNP variants. There was a trend for low CRP patients with previous ileal resection to evolve to a stricturing phenotype. Fat wrapping was noted in 11/13 (85%) of low CRP patients undergoing ileal resections. Conclusions. Patients with CD and a persistently low CRP in the face of active disease were characterized by an almost exclusive ileal disease distribution and a low BMI, compared to those with a raised CRP. These patients had a similar frequency and distribution of NOD2/CARD15 variants. Stricturing ( v inflammatory or penetrating) behaviour may explain some low CRP. Despite the abnormally low BMI, fat wrapping was noted in the majority of low CRP patients undergoing ileal resection.

Rosemary : a raw material for a new genre of bio-based antioxidants for sustainable applications

The potential replacement, partially or fully, of synthetic additives by bio-based alternatives derived from indigenous renewable non-food crop resources offers a market opportunity for a green supply of raw materials for different industrial and health products, with greater involvement of the farming community in crop production while addressing the ever more stringent environmental and pollution laws that now require the use of less potentially toxic/harmful ingredients, even if they are present in relatively small quantities. The work presented here relates to developing a new genre of environmentally-sustainable bio-based antioxidants (AO) for industrial uses that are obtained from extracts of UK-grown rosemary (Rosmarinus officinalis) plant. The performance of these AOs was tested, and their efficacy compared with some common and benchmark synthetic AOs from the same chemical class, in different products including polymers especially for packaging, as well as lubricants, cosmetics and health products. One of the main active ingredients in rosemary is Rosmarinic acid which is a water-soluble compound. This was chemically transformed into a number of ester derivatives, Rosmarinates, targeted for different applications. The parent and the modified antioxidants (the rosmarinates) were characterised and their antioxidancy were examined and tested in linear low-density polyethylene (LLDPE) and in polypropylene (PP) and compared with compounds of similar structure and with other well known synthetic antioxidants used commercially in polyolefins. The results show that antioxidants sourced from rosemary have the added benefit of being highly efficient and intrinsically more active than many synthetic and bio-based alternatives.

Solar stills:a comprehensive review of designs, performance and material advances

The demand for fresh water production is growing day by day with the increase in world population and with industrial growth. Use of desalination technology is increasing to meet this demand. Among desalination technologies, solar stills require low maintenance and are readily affordable; however their productivity is limited. This paper aims to give a detailed review about the various types of solar stills, covering passive and active designs, single- and multi-effect types, and the various modifications for improved productivity including reflectors, heat storage, fins, collectors, condensers, and mechanisms for enhancing heat and mass transfer. Photovoltaic-thermal and greenhouse type solar stills are also covered. Material advances in the area of phase change materials and nanocomposites are very promising to enhance further performance; future research should be carried out in these and other areas for the greater uptake of solar still technology.

Development of a program of radiopaque lesions images via radiographic cases for active learning in oral medicine

Through the creation of this project in English, we have made a file of radiographic images that will be used by third year dental students in order to improve the practical teaching part of the subject of Oral Medicine, essentially by incorporating these files to the Virtual Campus. We have selected the most representative radiopaque radiographic images studied in pathology lectures given. We have prepared a file with 59 radiopaque radiographic images. These lesions have been divided according to their relationship and number with the tooth, into the following groups: “Anatomic radiopacities”, “Periapical radiopacities”, “Solitary radiopacities not necessarily contacting teeth”,“Multiple separate radiopacities”, and “Generalized radiopacities”. We created 4 flowcharts synthesizing the mayor explanatory bases of each pathological process in relation to other pathologies within each location. We have focused primarily in those clinical and radiographic features that can help us differentiate one pathology from another. We believe that by giving the student a knowledge base through each flowchart, as well as provide clinical cases, will start their curiosity to seek new cases on the Internet or try to look for images that we have not been able to locate due to low frequency. In addition, as this project has been done in English, it will provide the students with necessary tools to do a literature search, as most of the medical and dental literature is in English; thus far, providing the student with this material necessary to make the appropriate searched using keywords in English.

Mechanochemistry for Active Materials and Devices

The coupling of mechanical stress fields in polymers to covalent chemistry (polymer mechanochemistry) has provided access to previously unattainable chemical reactions and polymer transformations. In the bulk, mechanochemical activation has been used as the basis for new classes of stress-responsive polymers that demonstrate stress/strain sensing, shear-induced intermolecular reactivity for molecular level remodeling and self-strengthening, and the release of acids and other small molecules that are potentially capable of triggering further chemical response. The potential utility of polymer mechanochemistry in functional materials is limited, however, by the fact that to date, all reported covalent activation in the bulk occurs in concert with plastic yield and deformation, so that the structure of the activated object is vastly different from its nascent form. Mechanochemically activated materials have thus been limited to “single use” demonstrations, rather than as multi-functional materials for structural and/or device applications. Here, we report that filled polydimethylsiloxane (PDMS) elastomers provide a robust elastic substrate into which mechanophores can be embedded and activated under conditions from which the sample regains its original shape and properties. Fabrication is straightforward and easily accessible, providing access for the first time to objects and devices that either release or reversibly activate chemical functionality over hundreds of loading cycles.

While the mechanically accelerated ring-opening reaction of spiropyran to merocyanine and associated color change provides a useful method by which to image the molecular scale stress/strain distribution within a polymer, the magnitude of the forces necessary for activation had yet to be quantified. Here, we report single molecule force spectroscopy studies of two spiropyran isomers. Ring opening on the timescale of tens of milliseconds is found to require forces of ~240 pN, well below that of previously characterized covalent mechanophores. The lower threshold force is a combination of a low force-free activation energy and the fact that the change in rate with force (activation length) of each isomer is greater than that inferred in other systems. Importantly, quantifying the magnitude of forces required to activate individual spiropyran-based force-probes enables the probe behave as a “scout” of molecular forces in materials; the observed behavior of which can be extrapolated to predict the reactivity of potential mechanophores within a given material and deformation.

We subsequently translated the design platform to existing dynamic soft technologies to fabricate the first mechanochemically responsive devices; first, by remotely inducing dielectric patterning of an elastic substrate to produce assorted fluorescent patterns in concert with topological changes; and second, by adopting a soft robotic platform to produce a color change from the strains inherent to pneumatically actuated robotic motion. Shown herein, covalent polymer mechanochemistry provides a viable mechanism to convert the same mechanical potential energy used for actuation into value-added, constructive covalent chemical responses. The color change associated with actuation suggests opportunities for not only new color changing or camouflaging strategies, but also the possibility for simultaneous activation of latent chemistry (e.g., release of small molecules, change in mechanical properties, activation of catalysts, etc.) in soft robots. In addition, mechanochromic stress mapping in a functional actuating device might provide a useful design and optimization tool, revealing spatial and temporal force evolution within the actuator in a way that might also be coupled to feedback loops that allow autonomous, self-regulation of activity.

In the future, both the specific material and the general approach should be useful in enriching the responsive functionality of soft elastomeric materials and devices. We anticipate the development of new mechanophores that, like the materials, are reversibly and repeatedly activated, expanding the capabilities of soft, active devices and further permitting dynamic control over chemical reactivity that is otherwise inaccessible, each in response to a single remote signal.

Potential Shifts in Canadian High Arctic Sedimentary Organic Matter Composition With Permafrost Active Layer Detachments

Increased temperature and precipitation in Arctic regions have led to deeper thawing and structural instability in permafrost soil. The resulting localized disturbances, referred to as active layer detachments (ALDs), may transport organic matter (OM) to more biogeochemically active zones. To examine this further, solid state cross polarization magic angle spinning 13C nuclear magnetic resonance (CPMAS NMR) and biomarker analysis were used to evaluate potential shifts in riverine sediment OM composition due to nearby ALDs within the Cape Bounty Arctic Watershed Observatory, Nunavut, Canada. In sedimentary OM near ALDs, NMR analysis revealed signals indicative of unaltered plant-derived material, likely derived from permafrost. Long chain acyclic aliphatic lipids, steroids, cutin, suberin and lignin occurred in the sediments, consistent with a dominance of plant-derived compounds, some of which may have originated from permafrost-derived OM released by ALDs. OM degradation proxies for sediments near ALDs revealed less alteration in acyclic aliphatic lipids, while constituents such as steroids, cutin, suberin and lignin were found at a relatively advanced stage of degradation. Phospholipid fatty acid analysis indicated that microbial activity was higher near ALDs than downstream but microbial substrate limitation was prevalent within disturbed regions. Our study suggests that, as these systems recover from disturbance, ALDs likely provide permafrost-derived OM to sedimentary environments. This source of OM, which is enriched in labile OM, may alter biogeochemical patterns and enhance microbial respiration within these ecosystems.

Synthesis and Characterization of Nanostructured Electro-active Materials

Thesis (Ph.D.)--University of Washington, 2016-08

Material paradidático em educação ambiental para o 6º ano do ensino fundamental

Acompanha: Material paradidático em educação ambiental para o 6º ano do ensino fundamental

Shared active site architecture between archaeal PolD and multi-subunit RNA polymerases revealed by X-ray crystallography

Archaeal replicative DNA polymerase D (PolD) constitute an atypical class of DNA polymerases made of a proofreading exonuclease subunit (DP1) and a larger polymerase catalytic subunit (DP2), both with unknown structures. We have determined the crystal structures of Pyrococcus abyssi DP1 and DP2 at 2.5 and 2.2 angstrom resolution, respectively, revealing a catalytic core strikingly different from all other known DNA polymerases (DNAPs). Rather, the PolD DP2 catalytic core has the same 'double-psi beta-barrel' architecture seen in the RNA polymerase (RNAP) superfamily, which includes multi-subunit transcriptases of all domains of life, homodimeric RNA-silencing pathway RNAPs and atypical viral RNAPs. This finding bridges together, in non-viral world, DNA transcription and DNA replication within the same protein superfamily. This study documents further the complex evolutionary history of the DNA replication apparatus in different domains of life and proposes a classification of all extant DNAPs.

Synthesis of active Belite-Alite-Ye'elimite clinker (BAY)

Ordinary Portland cement (OPC) is an environmentally contentious material, as for every ton of OPC produced, on average, 0.97 tons of CO2 are released. Ye'elimite-rich cements are considered as eco-cements because their manufacturing process releases less CO2 into the atmosphere than OPC; this is due to the low calcite demand. Belite-Alite-Ye’elimite (BAY) cements are promising eco-friendly building materials as OPC substitutes at a large scale. The reaction of alite and ye´elimite with water should develop cements with high mechanical strengths at early ages, while belite will contribute to later curing times. However, they develop lower mechanical strengths at early-medium ages than OPC. It is known that the presence of different polymorphs of ye'elimite and belite affects the hydration due to the different reactivity of those phases. Thus, a solution to this problem may be well the activation of BAY clinkers by preparing them with 'H-belite and pseudo-cubic-ye'elimite, jointly with alite. The aim of this work is the preparation and characterization of active-BAY clinkers which contain high percentages of coexisting 'H-belite and pseudo-cubic-ye'elimite, jointly with alite to develop, in a future step, comparable mechanical strengths to OPC. The parameters evolved in the preparation of the clinker have been optimized, including the selection of raw materials (mineralizers and activators) and clinkering conditions. Finally, the clinker was characterized through laboratory X-ray powder diffraction, in combination with the Rietveld methodology, and scanning electron microscopy.