Spatially orthogonal chemical functionalization of a hierarchical pore network for catalytic cascade reactions

The chemical functionality within porous architectures dictates their performance as heterogeneous catalysts; however, synthetic routes to control the spatial distribution of individual functions within porous solids are limited. Here we report the fabrication of spatially orthogonal bifunctional porous catalysts, through the stepwise template removal and chemical functionalization of an interconnected silica framework. Selective removal of polystyrene nanosphere templates from a lyotropic liquid crystal-templated silica sol–gel matrix, followed by extraction of the liquid crystal template, affords a hierarchical macroporous–mesoporous architecture. Decoupling of the individual template extractions allows independent functionalization of macropore and mesopore networks on the basis of chemical and/or size specificity. Spatial compartmentalization of, and directed molecular transport between, chemical functionalities affords control over the reaction sequence in catalytic cascades; herein illustrated by the Pd/Pt-catalysed oxidation of cinnamyl alcohol to cinnamic acid. We anticipate that our methodology will prompt further design of multifunctional materials comprising spatially compartmentalized functions.

Recent and Miocene carbonate sediments from Indonesia. Available in 2 volumes.

Mapping and sediment sampling in reefs of the Pulau Seribu group (southwest Java Sea) shows the existence of ten physiographic zones and subzones represented by seven lithofacies. Reefs in the northern part of the archipelago are smaller, more closely spaced and morphologically sim pler than those in the south. This pattern is attributed to differences in subsidence rate. A th reedimensional model is proposed for the evo lution of these reefs but borehole data are requi red to test this model. Miocene limestones are described in detail from hydrocarbon reservoirs in the Batu Raja Formation of the same area. Brief comparisons a re made with surface outcrops of approximately coeval carbonate developments. The lithofacies developed within these limestones reflect variations in hydrodynam ic regime and basement topography . Ele\le.n diagenetic processes affected the Batu Raja limestones and the dist ribution of these is primarily related to sealevel fluctuations. Early diagenesis was marine and characterised by micritisation and preCipitation of fibrous and bladed cements. Dolomitisat ion occurred in the mixed- water zone and its variable intensity is attributed to the configuration of the carbonate body relative to this zone. Subsequently the limestones were subjected to freshwater phreatic zone diagenesis resulting in dissolution and cementation, and a t a late stage underwent burial compaction. Secondary porosity, which \ar9e1.y determines the suitability of these limestones as hydrocarbon reserVOirs, is a function of the variable intensity of dissolution and cementation, burial compaction, dolomitisation and possibly micrite neomorphism. The sedimentary processes that generated the Batu Raja buildups are inferred f rom comparisons with the Pulau Seribu and other Recent analogues. The contrasting pinnacle form of the Pulau Seribu patch reefs compared with the low relief of the Batu Raja buUdups results from differences in the initial substrate topography and subsequent subsidence rate

Evaluation of wind-induced internal pressure in low-rise buildings: A multi scale experimental and numerical approach

Hurricane is one of the most destructive and costly natural hazard to the built environment and its impact on low-rise buildings, particularity, is beyond acceptable. The major objective of this research was to perform a parametric evaluation of internal pressure (IP) for wind-resistant design of low-rise buildings and wind-driven natural ventilation applications. For this purpose, a multi-scale experimental, i.e. full-scale at Wall of Wind (WoW) and small-scale at Boundary Layer Wind Tunnel (BLWT), and a Computational Fluid Dynamics (CFD) approach was adopted. This provided new capability to assess wind pressures realistically on internal volumes ranging from small spaces formed between roof tiles and its deck to attic to room partitions. Effects of sudden breaching, existing dominant openings on building envelopes as well as compartmentalization of building interior on the IP were systematically investigated. Results of this research indicated: (i) for sudden breaching of dominant openings, the transient overshooting response was lower than the subsequent steady state peak IP and internal volume correction for low-wind-speed testing facilities was necessary. For example a building without volume correction experienced a response four times faster and exhibited 30–40% lower mean and peak IP; (ii) for existing openings, vent openings uniformly distributed along the roof alleviated, whereas one sided openings aggravated the IP; (iii) larger dominant openings exhibited a higher IP on the building envelope, and an off-center opening on the wall exhibited (30–40%) higher IP than center located openings; (iv) compartmentalization amplified the intensity of IP and; (v) significant underneath pressure was measured for field tiles, warranting its consideration during net pressure evaluations. The study aimed at wind driven natural ventilation indicated: (i) the IP due to cross ventilation was 1.5 to 2.5 times higher for Ainlet/Aoutlet>1 compared to cases where Ainlet/Aoutlet<1, this in effect reduced the mixing of air inside the building and hence the ventilation effectiveness; (ii) the presence of multi-room partitioning increased the pressure differential and consequently the air exchange rate. Overall good agreement was found between the observed large-scale, small-scale and CFD based IP responses. Comparisons with ASCE 7-10 consistently demonstrated that the code underestimated peak positive and suction IP.

Chilling damage in a changing climate in coastal landscapes of the subtropical zone: a case study from south Florida

Extensive portions of the southern Everglades are characterized by series of elongated, raised peat ridges and tree islands oriented parallel to the predominant flow direction, separated by intervening sloughs. Tall herbs or woody species are associated with higher elevations and shorter emergent or floating species are associated with lower elevations. The organic soils in this “Ridge-and-Slough” landscape have been stable over millennia in many locations, but degrade over decades under altered hydrologic conditions. We examined soil, pore water, and leaf phosphorus (P) and nitrogen (N) distributions in six Ridge and Slough communities in Shark Slough, Everglades National Park. We found P enrichment to increase and N to decrease monotonically along a gradient from the most persistently flooded sloughs to rarely flooded ridge environments, with the most dramatic change associated with the transition from marsh to forest. Leaf N:P ratios indicated that the marsh communities were strongly P-limited, while data from several forest types suggested either N-limitation or co-limitation by N and P. Ground water stage in forests exhibited a daytime decrease and partial nighttime recovery during periods of surface exposure. The recovery phase suggested re-supply from adjacent flooded marshes or the underlying aquifer, and a strong hydrologic connection between ridge and slough. We therefore developed a simple steady-state model to explore a mechanism by which a phosphorus conveyor belt driven by both evapotranspiration and the regional flow gradient can contribute to the characteristic Ridge and Slough pattern. The model demonstrated that evapotranspiration sinks at higher elevations can draw in low concentration marsh waters, raising local soil and water P concentrations. Focusing of flow and nutrients at the evapotranspiration zone is not strong enough to overcome the regional gradient entirely, allowing the nutrient to spread downstream and creating an elongated concentration plume in the direction of flow. Our analyses suggest that autogenic processes involving the effects of initially small differences in topography, via their interactions with hydrology and nutrient availability, can produce persistent physiographic patterns in the organic sediments of the Everglades.

Vegetation:environment relationships and water management in Shark Slough, Everglades National Park

The hydrologic regime of Shark Slough, the most extensive long hydroperiod marsh in Everglades National Park, is largely controlled by the location, volume, and timing of water delivered to it through several control structures from Water Conservation Areas north of the Park. Where natural or anthropogenic barriers to water flow are present, water management practices in this highly regulated system may result in an uneven distribution of water in the marsh, which may impact regional vegetation patterns. In this paper, we use data from 569 sampling locations along five cross-Slough transects to examine regional vegetation distribution, and to test and describe the association of marsh vegetation with several hydrologic and edaphic parameters. Analysis of vegetation:environment relationships yielded estimates of both mean and variance in soil depth, as well as annual hydroperiod, mean water depth, and 30-day maximum water depth within each cover type during the 1990’s. We found that rank abundances of the three major marsh cover types (Tall Sawgrass, Sparse Sawgrass, and Spikerush Marsh) were identical in all portions of Shark Slough, but regional trends in the relative abundance of individual communities were present. Analysis also indicated clear and consistent differences in the hydrologic regime of three marsh cover types, with hydroperiod and water depths increasing in the order Tall Sawgrass , Sparse Sawgrass , Spikerush Marsh. In contrast, soil depth decreased in the same order. Locally, these differences were quite subtle; within a management unit of Shark Slough, mean annual values for the two water depth parameters varied less than 15 cm among types, and hydroperiods varied by 65 days or less. More significantly, regional variation in hydrology equaled or exceeded the variation attributable to cover type within a small area. For instance, estimated hydroperiods for Tall Sawgrass in Northern Shark Slough were longer than for Spikerush Marsh in any of the other regions. Although some of this regional variation may reflect a natural gradient within the Slough, a large proportion is the result of compartmentalization due to current water management practices within the marsh.We conclude that hydroperiod or water depth are the most important influences on vegetation within management units, and attribute larger scale differences in vegetation pattern to the interactions among soil development, hydrology and fire regime in this pivotal portion of Everglades.

The Role of the Everglades Mangrove Ecotone Region (EMER) in Regulating Nutrient Cycling and Wetland Productivity in South Florida

The authors summarize the main findings of the Florida Coastal Everglades Long-Term Ecological Research (FCE-LTER) program in the EMER, within the context of the Comprehensive Everglades Restoration Plan (CERP), to understand how regional processes, mediated by water flow, control population and ecosystem dynamics across the EMER landscape. Tree canopies with maximum height <3 m cover 49% of the EMER, particularly in the SE region. These scrub/dwarf mangroves are the result of a combination of low soil phosphorus (P < 59 μg P g dw−1) in the calcareous marl substrate and long hydroperiod. Phosphorus limits the EMER and its freshwater watersheds due to the lack of terrigenous sediment input and the phosphorus-limited nature of the freshwater Everglades. Reduced freshwater delivery over the past 50 years, combined with Everglades compartmentalization and a 10 cm rise in coastal sea level, has led to the landward transgression (1.5 km in 54 years) of the mangrove ecotone. Seasonal variation in freshwater input strongly controls the temporal variation of nitrogen and P exports (99%) from the Everglades to Florida Bay. Rapid changes in nutrient availability and vegetation distribution during the last 50 years show that future ecosystem restoration actions and land use decisions can exert a major influence, similar to sea level rise over the short term, on nutrient cycling and wetland productivity in the EMER.

Characteristics of surface-water flows in the ridge and slough landscape of Everglades National Park: implications for particulate transport

Over the last one hundred years, compartmentalization and water management activities have reduced water flow to the ridge and slough landscape of the Everglades. As a result, the once corrugated landscape has become topographically and vegetationally uniform. The focus of this study was to quantify variation in surface flow in the ridge and slough landscape and to relate flow conditions to particulate transport and deposition. Over the 2002–2003 and 2003–2004 wet seasons, surface velocities and particulate accumulation were measured in upper Shark River Slough in Everglades National Park. Landscape characteristics such as elevation, plant density and biomass also were examined to determine their impact on flow characteristics and material transport. The results of this study demonstrate that the release of water during the wet season not only increases water levels, but also increased flow speeds and particulate transport and availability. Further, flow speeds were positively and significantly correlated with water level thereby enhancing particulate transport in sloughs relative to ridges especially during peak flow periods. Our results also indicate that the distribution of biomass in the water column, including floating plants and periphyton, affects velocity magnitude and shape of vertical profiles, especially in the sloughs where Utricularia spp. and periphyton mats are more abundant. Plot clearing experiments suggest that the presence of surface periphyton and Utricularia exert greater control over flow characteristics than the identity (i.e., sawgrass or spike rush) or density of emergent macrophytes, two parameters frequently incorporated into models describing flow through vegetated canopies. Based on these results, we suggest that future modeling efforts must take the presence of floating biomass, such as Utricularia, and presence of periphyton into consideration when describing particulate transport.

Smoke on the water: the interplay of fire and water flow on Everglades restoration

Recent research makes clear that much of the Everglade’s flora and fauna have evolved to tolerate or require frequent fires. Nevertheless, restoration of the Everglades has thus far been conceptualized as primarily a water reallocation project. These two forces are directly linked by the influence of water flows on fire fuel moisture content, and are indirectly linked through a series of complex feedback loops. This interaction is made more complex by the alteration and compartmentalization of current water flows and fire regimes, the lack of communication between water and fire management agencies, and the already imperiled state of many local species. It is unlikely, therefore, that restoring water flows will automatically restore the appropriate fire regimes, leaving the prospect of successful restoration in some doubt. The decline of the Cape Sable seaside sparrow, and its potential for recovery, illustrates the complexity of the situation.

Does variation in movement tactics and trophic interactions among American alligators create habitat linkages?

1. Highly mobile top predators are hypothesized to spatially and/or temporally link disparate habitats through the combination of their movement and feeding patterns, but recent studies suggest that individual specialization in habitat use and feeding could keep habitats compartmentalized. 2.  We used passive acoustic telemetry and stable isotope analysis to investigate whether specialization in movement and feeding patterns of American alligators (Alligator mississippiensis) in an oligotrophic subtropical estuary created habitat linkages between marine and estuarine/freshwater food webs. 3.  Individual alligators adopted one of the three relatively distinct movement tactics that were linked to variation in diets. Fifty-six per cent of alligators regularly travelled from the upstream (freshwater/mid-estuary) areas into the downstream (marine-influenced) areas where salinities exceed those typically tolerated by alligators. Thirty-one per cent of the alligators made regular trips from the mid-estuarine habitat into the upstream habitat; 13% remained in the mid-estuary zone year-round. 4.  Stable isotopic analysis indicated that, unlike individuals remaining in the mid-estuary and upstream zones, alligators that used the downstream zone fed at least partially from marine food webs and likely moved to access higher prey abundance at the expense of salt stress. Therefore, ‘commuting’ alligators may link marine food webs with those of the estuary and marshes in the coastal Everglades and create an upstream vector for allochthonous nutrient inputs into the estuary. 5.  This study lends further support to the hypothesis that large-bodied highly mobile predators faced with trade-offs are likely to exhibit individual specialization leading to habitat linkages, rather than compartmentalization. However, the conditions under which this scenario occurs require further investigation.

The Monitoring and Assessment Plan (MAP) Greater Everglades Wetlands Module- Landscape Pattern- Ridge, Slough, and Tree Island Mosaics: Year 1 Annual Report

In the current managed Everglades system, the pre-drainage, patterned mosaic of sawgrass ridges, sloughs and tree islands has been substantially altered or reduced largely as a result of human alterations to historic ecological and hydrological processes that sustained landscape patterns. The pre-compartmentalization ridge and slough landscape was a mosaic of sloughs, elongated sawgrass ridges (50-200m wide), and tree islands. The ridges and sloughs and tree islands were elongated in the direction of the water flow, with roughly equal area of ridge and slough. Over the past decades, the ridge-slough topographic relief and spatial patterning have degraded in many areas of the Everglades. Nutrient enriched areas have become dominated by Typha with little topographic relief; areas of reduced flow have lost the elongated ridge-slough topography; and ponded areas with excessively long hydroperiods have experienced a decline in ridge prevalence and shape, and in the number of tree islands (Sklar et al. 2004, Ogden 2005).

Loaxahatchee Impoundment Landscape Assessment (LILA): Tree Island Experiments and Management; May 1, 2005 to September 4, 2009: Final Report

Hydrologic modifications have negatively impacted the Florida Everglades in numerous significant ways. The compartmentalization of the once continuously flowing system into the Water Conservation Areas (WCAs) caused disruption of the slow natural flow of water south from Lake Okeechobee through the Everglades to Florida Bay. The ponding of water in the WCAs, the linking of water flow to controlled water levels, and the management of water levels for anthropogenic vs. ecological well-being has caused a reduction in the spatial heterogeneity of the Everglades leading to greater uniformity in topography and vegetation. These effects are noticeable as the degradation in structure of the Everglades Ridge and Slough environment and associated Tree Islands. In aquatic systems water flow is of fundamental importance in shaping the structure and function of the ecosystem. The organized patterns of parallel orientation of ridges, sloughs, and tear-drop shaped tree islands along historic flow paths attest to the importance of water movement in structuring this system. Our main objective was to operate and manage the LILA facility to provide a broad potential as a research platform for an integrated group of multidisciplinary, multi-agency scientists collaborating on multifunctional studies aimed primarily at determining the effects of CERP water management scenarios on the ecology of tree islands and ridge and slough habitats. We support Everglades water management, CERP, and the Long-Term Plan by defining hydrologic regimes that sustain healthy tree islands and ridge and slough ecosystems. Information gained through this project will help to reduce the uncertainty of predicting the tree island and ridge and slough ecosystem response to changes in hydrologic conditions. Additionally, we have developed the LILA site as a visual example of Everglades restoration programs in action.

Everglades Ridge, Slough, and Tree Island Mosaics: Year 2 Annual Report

Status and history of the Ridge-Slough Mosaic The Florida Everglades is a large subtropical wetland with diverse hydrologic, edaphic, and vegetative characteristics. Historically, a significant portion of this system was a slow moving river originating from the Kissimmee River floodplain, flowing into the vast but shallow Lake Okeechobee, and draining south-southwest over extensive peatlands into Florida Bay (McVoy 2011). Human-induced alterations to the hydrologic regime, including reduction, stabilization, and impoundment of water flow through diversion and compartmentalization of water via canals and levees have degraded pre-drainage vegetation patterns and microtopographic structure (Davis and Ogden 1994, Ogden 2005, McVoy 2011). The Everglades peatland emerged 5,000 years ago with the stabilization of sea level at approximately current elevations (Loveless 1959, Gleason and Stone 1994). This, combined with subtropical rainfalls, allowed a vast mass of water to slowly flow over a limestone bedrock platform 160 km long and 50 km wide at a near uniform descent totaling about 6 m, ultimately reaching Florida Bay (Stephens 1956, Gleason and Stone 1994, McVoy 2011). Vegetation quickly colonized the area, and peat, in the absence of adequate respiration, accumulated on the limestone bedrock to a depth of 3-3.7 m (Gleason and Stone 1994, McVoy et al. 2011). The “River of Grass” referenced by Douglas (1947) alludes to the dually intertwined processes of the historic riverine nature of the Everglades and the vast sawgrass (Cladium jamaicense) communities that have dominated the landscape for about the last 1,000 years (Bernhardt and Willard 2009).

Caracterização citoarquitetônica e por imunoistoquímica para tirosina-hidroxilase da substância negra, área tegmentar ventral e zona retrorubral do Sagui (Callithrix jacchus)

It is known that the catecholamine group is constituted by dopamine, noradrenaline and adrenaline, in which the synthesis is regulated by an enzyme named tyrosine hydroxylase. Thus, 3-hydroxytyramine/dopamine (DA) is a precursor of the noradrenaline and adrenaline synthesis and acts as a neurotransmitter in the central nervous system. The three main nuclei, named the retrorubral field (A8 group), the substantia nigra pars compacta (A9 group) and the ventral tegmental area (A10 group), are arranged in the die-mesencephalic portion and are involved in three complexes circuitries - the mesostriatal, mesolimbic and mesocortical pathways. These pathways are related to behavioral manifestations, motricity, learning, reward and pathologies such as Parkinson’s Disease and Schizophrenia. Thus, the aim of this study was to perform de morphological analysis of the A8, A9 and A10 nuclei of the common marmoset (Callithrix jacchus). The marmoset is a neotropical primate, whose morphological and functional characteristics supports the suitability of use of this animal in biomedical research. Coronal sections of the marmoset brain were submitted to cytoarchitectonic characterization and TH-immunohistochemistry. Based on the morphology of the neurons, it was possible to subdivide the A10 group in seven regions: interfascicular nucleus, raphe rostral linear nucleus and raphe caudal linear nucleus, in the middle line; paranigral and parainterfascicular nucleus, in the middle zone; rostral portion of the ventral tegmental area nucleus and parabrachial pigmented nucleus, located in the dorsolateral portion of the mesencephalic tegmentum. A9 group was divided into four regions: substantia nigra compacta dorsal and ventral tiers; substantia nigra compacta lateral and medial clusters. No subdivisions were founded into A8 group. These results revealed that A8, A9 and A10 are phylogenetically conserved between species, but it’s necessary to expand the studies about this compartmentalization, investigating its occurrence in other primate species or investigating its functional relevance.

Probing Tissue Microstructure Using Susceptibility Contrast Magnetic Resonance Imaging

Magnetic resonance imaging is a research and clinical tool that has been applied in a wide variety of sciences. One area of magnetic resonance imaging that has exhibited terrific promise and growth in the past decade is magnetic susceptibility imaging. Imaging tissue susceptibility provides insight into the microstructural organization and chemical properties of biological tissues, but this image contrast is not well understood. The purpose of this work is to develop effective approaches to image, assess, and model the mechanisms that generate both isotropic and anisotropic magnetic susceptibility contrast in biological tissues, including myocardium and central nervous system white matter.

This document contains the first report of MRI-measured susceptibility anisotropy in myocardium. Intact mouse heart specimens were scanned using MRI at 9.4 T to ascertain both the magnetic susceptibility and myofiber orientation of the tissue. The susceptibility anisotropy of myocardium was observed and measured by relating the apparent tissue susceptibility as a function of the myofiber angle with respect to the applied magnetic field. A multi-filament model of myocardial tissue revealed that the diamagnetically anisotropy α-helix peptide bonds in myofilament proteins are capable of producing bulk susceptibility anisotropy on a scale measurable by MRI, and are potentially the chief sources of the experimentally observed anisotropy.

The growing use of paramagnetic contrast agents in magnetic susceptibility imaging motivated a series of investigations regarding the effect of these exogenous agents on susceptibility imaging in the brain, heart, and kidney. In each of these organs, gadolinium increases susceptibility contrast and anisotropy, though the enhancements depend on the tissue type, compartmentalization of contrast agent, and complex multi-pool relaxation. In the brain, the introduction of paramagnetic contrast agents actually makes white matter tissue regions appear more diamagnetic relative to the reference susceptibility. Gadolinium-enhanced MRI yields tensor-valued susceptibility images with eigenvectors that more accurately reflect the underlying tissue orientation.

Despite the boost gadolinium provides, tensor-valued susceptibility image reconstruction is prone to image artifacts. A novel algorithm was developed to mitigate these artifacts by incorporating orientation-dependent tissue relaxation information into susceptibility tensor estimation. The technique was verified using a numerical phantom simulation, and improves susceptibility-based tractography in the brain, kidney, and heart. This work represents the first successful application of susceptibility-based tractography to a whole, intact heart.

The knowledge and tools developed throughout the course of this research were then applied to studying mouse models of Alzheimer’s disease in vivo, and studying hypertrophic human myocardium specimens ex vivo. Though a preliminary study using contrast-enhanced quantitative susceptibility mapping has revealed diamagnetic amyloid plaques associated with Alzheimer’s disease in the mouse brain ex vivo, non-contrast susceptibility imaging was unable to precisely identify these plaques in vivo. Susceptibility tensor imaging of human myocardium specimens at 9.4 T shows that susceptibility anisotropy is larger and mean susceptibility is more diamagnetic in hypertrophic tissue than in normal tissue. These findings support the hypothesis that myofilament proteins are a source of susceptibility contrast and anisotropy in myocardium. This collection of preclinical studies provides new tools and context for analyzing tissue structure, chemistry, and health in a variety of organs throughout the body.

Quantifying and Modeling the Influence of Forest on the Magnitude and Duration of Mountain Snow Storage in the Pacific Northwest, USA

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