Synthesis and characterization of host-guest complexes : metal-organic nanocapsules using aryl-substituted pyrogallol[4]arenes

Title from PDF of title page (University of Missouri--Columbia, viewed on May 21, 2012).The entire thesis text is included in the research.pdf file; the official abstract appears in the short.pdf file; a non-technical public abstract appears in the public.pdf file.Dissertation advisor: Dr. Jerry L. AtwoodVita."July 2011"The desire to synthesize and control self-assembly of molecular nanocapsules has long been a focus within the supramolecular community due to the nanocapsules' potential applications as tools for encapsulation and delivery of host molecules, catalytic media sites, and gas sorption agents. Resorcin[4]arenes (RsC) and pyrogallol[4]arenes (PgC) have received considerable attention due to their preference to form the all-cis cone-shaped (rccc) structure, thus allowing dimeric and hexameric nanocapsule formation through complementary and structurally distinct intermolecular hydrogen bonding interactions or metal coordination. By changing the lower rim R group, one drastically alters the chemical environment. C-arylresorcin[4]arenes, for example, adopt a more kinetically stable 1,2-chair rctt stereostructure but show interconversion to the thermodynamic product, the all-cis rccc cone. In contrast, our studies of the C-arylpyrogallol[4]arenes unexpectedly suggest that the 1,2-chair rctt stereostructure is the thermodynamic product. Herein, we show that complexation of zinc and C-phenylpyrogallol[4]arene, as well as other benzyl derivatives, induces a conformational flip in these macrocycles from chair to cone. This formation of the zinc-seamed metal-organic nanocapsules has been tracked via NMR, X-ray Diffraction and Mass Spectroscopy studies. The results yield several important trends that can be applied towards both the study of supramolecular self-assembly and the utilization of these host-guest capsular entities for other purposes.Includes bibliographical reference

The acclimative biogeochemical model of the southern North Sea

Ecosystem models often rely on heuristic descriptions of autotrophic growth that fail to reproduce various stationary and dynamic states of phytoplankton cellular composition observed in laboratory experiments. Here, we present the integration of an advanced phytoplankton growth model within a coupled three-dimensional physical-biogeochemical model and the application of the model system to the southern North Sea (SNS) defined on a relatively high resolution (∼1.5-4.5 km) curvilinear grid. The autotrophic growth model, recently introduced by Wirtz and Kerimoglu (2016), is based on a set of novel concepts for the allocation of internal resources and operation of cellular metabolism. The coupled model system consists of the General Estuarine Transport Model (GETM) as the hydrodynamical driver, a lower-trophic-level model and a simple sediment diagenesis model. We force the model system with realistic atmospheric and riverine fluxes, background turbidity caused by suspended particulate matter (SPM) and open ocean boundary conditions. For a simulation for the period 2000-2010, we show that the model system satisfactorily reproduces the physical and biogeochemical states of the system within the German Bight characterized by steep salinity; nutrient and chlorophyll (Chl) gradients, as inferred from comparisons against observation data from long-term monitoring stations; sparse in situ measurements; continuous transects; and satellites. The model also displays skill in capturing the formation of thin chlorophyll layers at the pycnocline, which is frequently observed within the stratified regions during summer. A sensitivity analysis reveals that the vertical distributions of phytoplankton concentrations estimated by the model can be qualitatively sensitive to the description of the light climate and dependence of sinking rates on the internal nutrient reserves. A non-acclimative (fixed-physiology) version of the model predicted entirely different vertical profiles, suggesting that accounting for physiological flexibility might be relevant for a consistent representation of the vertical distribution of phytoplankton biomass. Our results point to significant variability in the cellular chlorophyll-to-carbon ratio (Chl : C) across seasons and the coastal to offshore transition. Up to 3-fold-higher Chl : C at the coastal areas in comparison to those at the offshore areas contribute to the steepness of the chlorophyll gradient. The model also predicts much higher phytoplankton concentrations at the coastal areas in comparison to its non-acclimative equivalent. Hence, findings of this study provide evidence for the relevance of physiological flexibility, here reflected by spatial and seasonal variations in Chl : C, for a realistic description of biogeochemical fluxes, particularly in the environments displaying strong resource gradients. © 2017 Author(s)

Visualizing and Modeling Interior Spaces of Dangerous Structures using Lidar

LIght Detection and Ranging (LIDAR) scanning can be used to safely and remotely provide intelligence on the interior of dangerous structures for use by first responders that need to enter these structures. By scanning into structures through windows and other openings or moving the LIDAR scanning into the structure, in both cases carried by a remote controlled robotic crawler, the presence of dangerous items or personnel can be confi rmed or denied. Entry and egress pathways can be determined in advance, and potential hiding/ambush locations identifi ed. This paper describes an integrated system of a robotic crawler and LIDAR scanner. Both the scanner and the robot are wirelessly remote controlled from a single laptop computer. This includes navigation of the crawler with real-time video, self-leveling of the LIDAR platform, and the ability to raise the scanner up to heights of 2.5 m. Multiple scans can be taken from different angles to fi ll in detail and provide more complete coverage. These scans can quickly be registered to each other using user defi ned \u27pick points\u27, creating a single point cloud from multiple scans. Software has been developed to deconstruct the point clouds, and identify specifi c objects in the interior of the structure from the point cloud. Software has been developed to interactively visualize and walk through the modeled structures. Floor plans are automatically generated and a data export facility has been developed. Tests have been conducted on multiple structures, simulating many of the contingencies that a fi rst responder would face

Seamless integration of the coastal ocean in global marine carbon cycle modeling

We present the first global ocean-biogeochemistry model that uses a telescoping high resolution for an improved representation of coastal carbon dynamics: ICON-Coast. Based on the unstructured triangular grid topology of the model, we globally apply a grid refinement in the land-ocean transition zone to better resolve the complex circulation of shallow shelves and marginal seas as well as ocean-shelf exchange. Moreover, we incorporate tidal currents including bottom drag effects, and extend the parameterizations of the model's biogeochemistry component to account explicitly for key shelf-specific carbon transformation processes. These comprise sediment resuspension, temperature-dependent remineralization in the water column and sediment, riverine matter fluxes from land including terrestrial organic carbon, and variable sinking speed of aggregated particulate matter. The combination of regional grid refinement and enhanced process representation enables for the first time a seamless incorporation of the global coastal ocean in model-based Earth system research. In particular, ICON-Coast encompasses all coastal areas around the globe within a single, consistent ocean-biogeochemistry model, thus naturally accounting for two-way coupling of ocean-shelf feedback mechanisms at the global scale. The high quality of the model results as well as the efficiency in computational cost and storage requirements proves this strategy a pioneering approach for global high-resolution modeling. We conclude that ICON-Coast represents a new tool to deepen our mechanistic understanding of the role of the land-ocean transition zone in the global carbon cycle, and to narrow related uncertainties in global future projections

Small sinking particles control anammox rates in the Peruvian oxygen minimum zone

Anaerobic oxidation of ammonium (anammox) in oxygen minimum zones (OMZs) is a major pathway of oceanic nitrogen loss. Ammonium released from sinking particles has been suggested to fuel this process. During cruises to the Peruvian OMZ in April–June 2017 we found that anammox rates are strongly correlated with the volume of small particles (128–512 µm), even though anammox bacteria were not directly associated with particles. This suggests that the relationship between anammox rates and particles is related to the ammonium released from particles by remineralization. To investigate this, ammonium release from particles was modelled and theoretical encounters of free-living anammox bacteria with ammonium in the particle boundary layer were calculated. These results indicated that small sinking particles could be responsible for ~75% of ammonium release in anoxic waters and that free-living anammox bacteria frequently encounter ammonium in the vicinity of smaller particles. This indicates a so far underestimated role of abundant, slow-sinking small particles in controlling oceanic nutrient budgets, and furthermore implies that observations of the volume of small particles could be used to estimate N-loss across large areas

GWAS meta-analysis followed by Mendelian randomization revealed potential control mechanisms for circulating alpha-Klotho levels

The protein alpha-Klotho acts as transmembrane co-receptor for fibroblast growth factor 23 (FGF23) and is a key regulator of phosphate homeostasis. However, alpha-Klotho also exists in a circulating form, with pleiotropic, but incompletely understood functions and regulation. Therefore, we undertook a genome-wide association study (GWAS) meta-analysis followed by Mendelian randomization (MR) of circulating alpha-Klotho levels. Plasma alpha-Klotho levels were measured by enzyme-linked immunosorbent assay (ELISA) in the Ludwigshafen Risk and Cardiovascular Health and Avon Longitudinal Study of Parents and Children (mothers) cohorts, followed by a GWAS meta-analysis in 4376 individuals across the two cohorts. Six signals at five loci were associated with circulating alpha-Klotho levels at genome-wide significance (P 9% of the variation in circulating alpha-Klotho levels. MR analyses revealed no causal relationships between alpha-Klotho and renal function, FGF23-dependent factors such as vitamin D and phosphate levels, or bone mineral density. The screening for genetic correlations with other phenotypes followed by targeted MR suggested causal effects of liability of Crohn's disease risk [Inverse variance weighted (IVW) beta = 0.059 (95% confidence interval 0.026, 0.093)] and low-density lipoprotein cholesterol levels [-0.198 (-0.332, -0.063)] on alpha-Klotho. Our GWAS findings suggest that two enzymes involved in post-translational modification, B4GALNT3 and CHST9, contribute to genetic influences on alpha-Klotho levels, presumably by affecting protein turnover and stability. Subsequent evidence from MR analyses on alpha-Klotho levels suggest regulation by mechanisms besides phosphate-homeostasis and raise the possibility of cross-talk with FGF19- and FGF21-dependent pathways, respectively. Significance statement: alpha-Klotho as a transmembrane protein is well investigated along the endocrine FGF23-alpha-Klotho pathway. However, the role of the circulating form of alpha-Klotho, which is generated by cleavage of transmembrane alpha-Klotho, remains incompletely understood. Genetic analyses might help to elucidate novel regulatory and functional mechanisms. The identification of genetic factors related to circulating alpha-Klotho further enables MR to examine causal relationships with other factors. The findings from the first GWAS meta-analysis of circulating alpha-Klotho levels identified six genome-wide significant signals across five genes. Given the function of two of the genes identified, B4GALNT3 and CHST9, it is tempting to speculate that post-translational modification significantly contributes to genetic influences on alpha-Klotho levels, presumably by affecting protein turnover and stability

E-Government in Russia : Plans, Reality, and Future Outlook

Peer reviewe

Characterization of the Temperature-Sensitive Mutations un-7 and png-1 in Neurospora crassa

The model filamentous fungus Neurospora crassa has been studied for over fifty years and many temperature-sensitive mutants have been generated. While most of these have been mapped genetically, many remain anonymous. The mutation in the N. crassa temperature-sensitive lethal mutant un-7 was identified by a complementation based approach as being in the open reading frame designated NCU00651 on linkage group I. Other mutations in this gene have been identified that lead to a temperature-sensitive morphological phenotype called png-1. The mutations underlying un-7 result in a serine to phenylalanine change at position 273 and an isoleucine to valine change at position 390, while the mutation in png-1 was found to result in a serine to leucine change at position 279 although there were other conservative changes in this allele. The overall morphology of the strain carrying the un-7 mutation is compared to strains carrying the png-1 mutation and these mutations are evaluated in the context of other temperature-sensitive mutants in Neurospora

Patch occupancy of stream fauna across a land cover gradient in the southern Appalachians, USA

We modeled patch occupancy to examine factors that best predicted the prevalence of four functionally important focal stream consumers (Tallaperla spp., Cambarus spp., Pleurocera proxima, and Cottus bairdi) among 37 reaches within the Little Tennessee River basin of the southern Appalachian Mountains, USA. We compared 34 models of patch occupancy to examine the association of catchment and reach scale factors that varied as a result of converting forest to agricultural or urban land use. Occupancy of our taxa was linked to parameters reflecting both catchment and reach extent characteristics. At the catchment level, forest cover or its conversion to agriculture was a major determinant of occupancy for all four taxa. Patch occupancies of Tallaperla, Cambarus, and C. bairdi were positively, and Pleurocera negatively, correlated with forest cover. Secondarily at the reach level, local availability of large woody debris was important for Cambarus, availability of large cobble substrate was important for C. bairdi, and stream calcium concentration was important for P. proxima. Our results show the abundance of stream organisms was determined by the taxon-dependent interplay between catchment- and reach-level factors.Keywords: Patch occupancy, Stream chemistry, Appalachians, Consumers, Land us