Production of efficiently synthesizable, strongly associating crown ether-based cryptands is desired for pseudorotaxane complexation of bipyridinium guests to produce suprapolymers and supramolecularly-linked block copolymers. Cryptands based on bis(meta-phenylene)-32-crown-10 (BMP32C10) were synthesized. The functionality of phenylenemethanol-BMP32C10 cryptand III-3 (Ka = 2.0 x 104 M-1) did not negatively affect binding strength, although the strength of complexation is marginal to achieve the desired suprapolymers. The cryptand dimethylpyridyl-BMP32C10 IV-2 was synthesized in an attempt to improve over the binding ability of the pyridyl-BMP32C10 cryptand IV-1; instead, interesting host design insights were discovered as binding strengths were reduced over 1000-fold. The crystal structure of IV-2 shows acyl-aryl conjugation which limits the host's ability to accept guests. Synthesis of larger cis-di(carbomethoxybenzo)-3n-crown-n crown ethers was explored using the high concentration, template technique previously reported for cDB24C8 diester. cDB30C10 diester (V-1c) was produced in 93% yield; the desired pyridyl-cDB30C10 cryptand V-12 binds paraquat strongly (Ka = 1-2x105 M-1) and diquat stronger than any other host (Ka = 1.9x106 M-1), both in 1:1 fashions; association constants were measured by ITC. X-ray crystallography of the complexes shows the cryptand's para arm is too far away to interact with paraquat and the host has numerous bifurcated interactions with diquat, explaining the difference in binding strengths. Syntheses of the regioisomers of cDB27C9 diester was also explored; the cyclization yields (cDB27C9S, VI-2: 59% and cDB27C9L, VI-3: 44%) are lower, likely due to poor attack angles due to mismatched arm length in cyclization, than the equivalent length ethyleneoxy-armed cDB24C8 and cDB30C10. Modeling of the cryptand isomers, pyridyl-cDB27C9S and pyridyl-cDB27C9L, showed that the former should improve para arm interaction with paraquat, but should be sterically hindered for diquat and the latter should have a highly flexible, poorly preorganized interaction with either type of guest. ITC, MS, and crystallography data supported the predictions. Derivatization of the pyridyl-cDB30C10 cryptand V-12 was explored using chelidamic acid (VII-1). Schemes yielding alcohol, alkyl halide, alkyne, and TEMPO functionality were followed, but failed. Currently, functionalized cryptand derivatives have not been achieved, future directions are proposed. / Ph. D.

The overall objectives of this dissertation were to (1) determine whether leaf area index (LAI) (Chapter 2), as well as stem density and height to live crown (Chapter 3) can be estimated accurately in intensively managed pine plantations using small-footprint, multiple-return airborne laser scanner (lidar) data, and (2) ascertain whether leaf area index in temperate mixed forests is best estimated using multiple-return airborne laser scanning (lidar) data or dual-band, single-pass interferometric synthetic aperture radar data (from GeoSAR) alone or both in combination (Chapter 4). In situ measurements of LAI, mean height, height to live crown, and stem density were made on 109 (LAI) or 110 plots (all other variables) under a variety of stand conditions. Lidar distributional metrics were calculated for each plot as a whole as well as for crown density slices (newly introduced in this dissertation). These metrics were used as independent variables in best subsets regressions with LAI, number of trees, mean height to live crown, and mean height (measured in situ) as the dependent variables. The best resulting model for LAI in pine plantations had an R2 of 0.83 and a cross-validation (CV) RMSE of 0.5. The CV-RMSE for estimating number of trees on all 110 plots was 11.8 with an R2 of 0.92. Mean height to live crown was also well-predicted (R2 = 0.96, CV-RMSE = 0.8 m) with a one-variable model. In situ measurements of temperate mixed forest LAI were made on 61 plots (21 hardwood, 36 pine, 4 mixed pine hardwood). GeoSAR metrics were calculated from the X-band backscatter coefficients (four looks) as well as both X- and P-band interferometric heights and magnitudes. Both lidar and GeoSAR metrics were used as independent variables in best subsets regressions with LAI (measured in situ) as the dependent variable. Lidar metrics alone explained 69% of the variability in temperate mixed forest LAI, while GeoSAR metrics alone explained 52%. However, combining the LAI and GeoSAR metrics increased the R2 to 0.77 with a CV-RMSE of 0.42. Analysis of data from active sensors shows strong potential for eventual operational estimation of biophysical parameters essential to silviculture. / Ph. D.

Spatial and temporal variation in foliar gas exchange on both a diurnal and seasonal scale was examined in 15-year-old fertilized and non-fertilized loblolly pine in the upper and lower thirds of crowns in stands located in the North Carolina sandhills. Photosynthesis rates between control and fertilized stands for both seasonal and diurnal measurement periods were different during only three months. Photosynthesis rates were consistently greater in the upper third of the crown compared to the lower third. Seasonal trends in both conductance and transpiration closely resembled trends found in seasonal photosynthesis. Foliar nitrogen concentrations were greater in fertilized stands for all months sampled. However, nitrogen content generally did not correlate with photosynthesis rates. Mean monthly water use efficiencies were significantly higher in fertilized stands during two months and were usually greater in upper crown foliage. Common empirical gas exchange models reveal that light and vapor pressure deficit (VPD) explain a majority of the variation observed in photosynthesis and transpiration, respectively. Conductance was not modeled since environmental variation did not adequately explain conductance patterns. Predicted light response curves reveal that upper crown foliage has higher maximum photosynthesis rates, respiration rates, light compensation points, and lower initial quantum yield compared to lower crown foliage. Models predict that foliage from fertilized stands is more sensitive to VPD and light during the growing season. Transpiration models predict highly variable responses to VPD depending on the treatment combination and season. Model R-square and predicted gas exchange values suggest that seasonal acclimation occurred. / Master of Science

In recent decades land use and land cover change (LULCC) has occurred throughout the Intermountain West. The Crown of the Continent Ecosystem (CCE) extends along the Rocky Mountains adjacent to the Canada-U.S. International border. In the U.S. portion of the CCE, located in northwestern Montana, development has increased since the 1990s, largely because of urban to rural migration. The CCE has become an amenity-based destination, which in turn is likely to threaten its terrestrial and aquatic ecological diversity (Quinn and Broberg 2007). Specifically, development pressures on private lands surrounding federally protected lands, are intensifying and thus threatening core habitat of native species and connectivity of forested areas. By characterizing the spatial and temporal patterns of LULCC, we can better understand landscape-scale changes influenced by human-environment interactions. Using National Land Cover Database (NLCD) products, I identified areas that have experienced land cover change for three time periods: 1992-2001, 2001-2006, and 2006-2011. Additionally, I used case studies to further investigate LULCC in the study area. The findings suggest that the highest rates of development in proximity to Glacier National Park were dependent on existing urban land cover, meaning existing roadway infrastructure and established urban areas saw the greatest urban development. Additionally, communities adjacent to Glacier National Park were hotspots for urban development. Based on the results, areas in proximity to federally protected lands are likely to experience continued urban intensification over the next few decades. / Master of Science

Nine independent and four dependent variables are used to build a response surface to calculate strip crown using the difference in the industry standard strip height measurements. The single element response surface in use provides the advantages of continuous derivatives and decouples rolling load from the determination of exit height. The data points to build the response surface are the product of a calibrated finite element model. The rolling dynamics in the finite element model creates a transient that requires nonlinear regression to find the system steady-state values. Weighted-least squares is used to build a response surface using isoparametric interpolation with the non-rectangular domain of the mill stands represented as a single element. The regression statistics, the 1-D projections, comparisons against other response surface models and the comparisons against an existing strip crown model are part the validation of the response surface generated. A four-high mill stand is modeled as a quarter-symmetry 3-D finite element model with an elastic-plastic material model. A comparison of the pressure distribution under the arc of contact with existing research supports the pressure distribution found with experiments conducted by Siebel and Lueg [16] and it also suggests the need for one improvement in the initial velocity for the strip in the finite element model. The strip exit heights show more sensitivity to change than strip exit crown in seven out of the nine independent variables, so a response surface built with the strip exit height is statistically superior to using the derived dependent variable strip exit crown. Sensitivity of strip exit crown and the strip exit heights to changes in work-roll crown are about equal. Backup-roll diameter sensitivity is small enough that oversampling for the mean trend has to be considered or ignore backup-roll altogether. Strip entry velocity is a new independent variable, unless the response surface is built from the derived variable, strip exit crown. A problem found is that the sensitivity of strip entry crown and work-roll crown requires a larger than typical incremental change to get a reliable measure of the change strip exit crown. A narrow choice of high and low strip entry crowns limits the usefulness of the final response surface. A recommendation is to consider the use of the strip cross-section as an exit crown predictor. / Master of Science

Due in large part to the growth and development of reliable surface characterization techniques, as well as to advances in the physical and chemical techniques used to modify surfaces, the technology of surface modification has seen rapid expansion over the past two decades. A major thrust of this research is the growth of controlled/"living" polymeric brushes from the surface of various substrates, an advance that promises to be a facile and reproducible way of altering surface properties. A unique initiator bearing ATRP (atom transfer radical polymerization), cleavage, and condensation functionalities was prepared and attached to the hydrolyzed surface of silica gel. Preliminary results indicate that control of reversibly terminated grafts of varying degrees of polymerization with polydispersity indices approaching 1.5 can be readily achieved-significant findings in the quest to design desired surface characteristics. Important physical characteristics may also be altered by way of varying molecular topologies. In the second major research thrust, the use of self-assembly to construct such topologies in the form of pseudorotaxanes fashioned from diverse macrocycles with multifarious guest ions is discussed. While the underlying goal was to investigate and understand the mode of complexation based on such environmental factors as substituent affects and neighboring group influences, new insight was gained on the synthetic manipulation of cooperative events-events that freely occur in nature. The complexation behavior of several functionalized bis-(meta-phenylene)-32-crown-10 macrocycles with various paraquat guest moieties was. As expected, studies indicated that electron-donating substituents on the crown ether drive association, a likely result of increased p -p interactions among host and guest species. The association between a bicyclic macrocycle and dimethyl paraquat was also investigated. Not surprisingly, binding of paraquat by the bicyclic was much stronger than the binding found in analogous macrocycles. Lastly, the endgroup functionalization of poly(propyleneimine) dendrimers with two crown ether macrocycles was performed and the complexation with host-specific guests studied. Curiously, two extreme binding regimes were found: the larger 32-membered crown ether assembly displayed anti-cooperative behavior upon complexation with paraquat, while the smaller 24-membered macrocyclic system exhibited cooperative effects with 2o ammonium ions. These cooperative results are among the very first described for non-biological systems and hint at their potential use in developing highly efficient, synthetically designed supramolecular systems. / Master of Science

Stand conditions influence the partitioning of biomass to stem, foliage, branch, and root components. Using data from 4 to 6-year old loblolly pine (Pinus taeda L.) trees grown in a miniature-scale spacing trial, this study determined the effect of initial planting density on the biomass partitioning of loblolly pine. An analysis of covariance concluded that density did not have a significant effect on the relative amount of biomass in aboveground components.Some measures of partitioning tradeoffs (such as root: shoot ratio) showed a significant positive slope when regressed against trees per hectare. Systems of linear equations were developed based on tree measurements and age, and additivity was specified. By taking into account contemporaneous correlations among tree components, seemingly unrelated regression (SUR) methodologies led to efficient parameter estimates. When compared to studies with mature trees at operational scales, results from the miniature-scale trees showed similar trends. Stem and woody roots were 70 and 14% of total mass, respectively. Since these miniature-scale trees were physiologically young at time of harvest, allocation of mass to foliage continued to be a priority, occupying 10% of total mass. / Master of Science

Individual pro-social behaviour has been explored by academics and others in a variety of situations and contexts. Why people act selflessly on behalf of strangers is an intriguing topic and has not been studied in the specific context of the Crown courts before. This study has three phases. The first allows independent witnesses to describe their emotions, decision-making and motivations for taking part in the criminal justice process where there is no overt benefit for themselves to do so. The study identifies three key points in the witnesses’ journey through the process and tests the reactions of the witnesses at these points. This approach allows any changes in their thinking to be recorded and analysed. The second phase of the research asks other participants who have not been witnesses to imagine themselves becoming aware of three different scenarios where a violent crime is occurring. These participants are asked to think about their reactions to each scenario, and if they expect themselves to act as witnesses, asks what their motivations would be. The imagining witnesses’ reflections are compared to those of the real witnesses from Phase 1. Finally, phase three disseminates the results from phases one and two to senior professionals working in the criminal justice sector. Their thoughts and suggestions are also applied to the results to identify and encourage best practise.

[EN] The influence of the type of armor on wave overtopping on mound breakwaters is usually represented by the roughness factor. However, different values of roughness factor for the same armor unit are given in the literature. Thus, the roughness factor depends not only on the type of armor, number of layers and permeability but also on the formula and database considered. In the present thesis, a new methodology based on bootstrapping techniques is developed and applied to characterize the roughness factors for different armor units. Differences up to 20% appeared when comparing the optimum roughness factors with those given in the literature. Armor porosity greatly affects the roughness factor and the armor stability: higher armor porosities reduce wave overtopping as well as hydraulic stability. Therefore, armor porosity values usually recommended in the literature should be used to avoid damage during lifetime. Formulas with few variables are easy to apply but they allow the roughness factor to absorb the information not explicitly included in the formula. However, the CLASH neural network avoids this problem and gives excellent estimation for wave overtopping on mound breakwaters. In this thesis, a new formula which emulates the behavior of the CLASH neural network is developed. The new formula has 16 parameters, six dimensionless input variables (Rc/Hm0, Ir, Rc/h, Gc/Hm0, Ac/Rc and a toe berm variable based on Rc/h) and two reduction factors (¿f and ¿ß). The new formula is built-up after systematic simulations using the CLASH neural network and provides the lowest prediction error. Wave overtopping on mound breakwaters can be minimized by increasing the crest freeboard, usually with a concrete crown wall. Crown walls must resist wave loads and armor earth pressure to be stable. In the present study, small-scale test results with cube- and Cubipod-armored mound breakwaters are used to develop a new estimator for calculating horizontal and up-lift forces from waves. The new formulas include four dimensionless input variables (¿f Ru0.1%/Rc, (Rc-Ac)/Ch, ¿(L_m/G_c ) and Fc/Ch) and the crown wall geometry. The roughness factor selected for overtopping prediction is used to consider the type of armor. Up-lift forces decreased sharply with increasing foundation levels. The new formulas provide the lowest error when predicting wave forces on crown walls. / [ES] La influencia del tipo de elemento del manto sobre le rebase de diques en talud se caracteriza habitualmente mediante el factor de rugosidad (¿f). Sin embargo, en la literatura existen diferentes valores del factor de rugosidad para el mismo tipo de elemento. El factor de rugosidad no depende solo del tipo de elemento, número de capas y permeabilidad del núcleo sino también de la formulación y de la base de datos empleada. En la presente tesis se desarrolla y aplica una nueva metodología basada en técnicas de bootstrapping para caracterizar estadísticamente el factor de rugosidad de diferentes elementos (entre ellos el Cubípodo) sobre diferentes formulaciones de rebase. Se observan diferencias de hasta el 20% entre los factores de rugosidad óptimos y los que se proporcionan en la literatura. La porosidad del manto afecta notablemente al factor de rugosidad pero también a la estabilidad del manto; mayores porosidades proporcionan menor rebase pero también menor estabilidad hidráulica. Por ello, las porosidades de diseño recomendadas deben emplearse para evitar daños durante la vida útil. Fórmulas con pocas variables de entrada son sencillas de emplear pero absorben a través del factor de rugosidad toda la información que no se incluye explícitamente en las variables de entrada. En cambio, la red neuronal de CLASH evita en gran medida estos inconvenientes y al mismo tiempo proporciona excelentes para estimar el rebase sobre diques en talud convencionales. En la presente tesis se ha desarrollado una fórmula explícita que permite emular el comportamiento de la red neuronal de CLASH. La nueva fórmula posee 16 parámetros, seis variables de entrada (Rc/Hm0, ¿0,-1, Rc/h, Gc/Hm0, Ac/Rc y una variable para representar a la berma de pie basada en Rc/h) y dos factores de reducción (¿f y ¿ß). La nueva fórmula se construye en base a simulaciones controladas empleando la red neuronal de CLASH y proporciona el menor error en la predicción de rebase sobre diques en talud de entre los estimadores estudiados. Una de las maneras más efectivas de disminuir el rebase sobre diques en talud es incrementar la cota de coronación mediante un espaldón de hormigón. Estas estructuras sufren el impacto del oleaje y deben ser diseñadas para resistirlo. En la presente tesis se han empleado ensayos de laboratorio de cubos y Cubípodos para desarrollar una nueva fórmula que permita calcular las fuerzas horizontales y verticales del oleaje sobre el espaldón. Las nuevas fórmulas incluyen la influencia de cuatro variables adimensionales (¿f Ru0.1%/Rc, (Rc-Ac)/Ch, ¿(L_m/G_c ) y Fc/Ch) y de la geometría del espaldón. Incluyen la influencia del tipo de elemento mediante el factor de rugosidad al igual que las fórmulas de rebase. Las fuerzas verticales disminuyen significativamente con el aumento de la cota de cimentación. Las nuevas fórmulas proporcionan el menor error de predicción sobre los registros de laboratorio analizados. / [CA] La influència del tipus d'element del mantell principal en l'ultrapassament dics en talús és caracteritza habitualment mitjançant el factor de rugositat (¿f). En canvi, en la literatura existeixen diferents valors del factor de rugositat per al mateix tipus d'element. Així doncs, el factor de rugositat no depèn només del tipus d'element, nombre de capes i permeabilitat del nucli però també de la formulació i de la base de dades utilitzada. En la present tesi es desenvolupa i aplica una nova metodologia basada en tècniques de bootstrapping per a caracteritzar estadísticament el factor de rugositat de diferent elements (entre ells el Cubípode) utilitzant diferents formulacions d'ultrapassament. S'observen diferències fins al 20% entre els factors de rugositat òptims i els que apareixen en la literatura. La porositat del mantell afecta notablement el factor de rugositat però també a l'estabilitat del mantell; majors porositats proporcionen menor ultrapassament però també menor estabilitat hidràulica. Per això, les porositats de disseny recomanades deuen emprar-se per a evitar danys durant la vida útil. Formules amb poques variables d'entrada són senzilles d'utilitzar però absorbeixen mitjançant el factor del factor de rugositat tota la informació que no s'inclou de manera explícita en les variables d'entrada. D'altra banda, la xarxa neuronal de CLASH evita en gran mesura aquests inconvenients i al mateix temps proporciona excel·lents resultats per a estimar l'ultrapassament sobre els dics en talús convencionals. En la present tesi s'ha desenvolupat una formulació explícita que permet emular el comportament de la xarxa neuronal de CLASH. La nova formulació té 16 paràmetres, sis variables d'entrada (Rc/Hm0, Ir, Rc/h, Gc/Hm0, Ac/Rc i una variable per a representar la berma de peu basada en Rc/h) i dos factors de reducció (¿f y ¿ß). La nova fórmula es construeix mitjançant simulacions controlades amb la xarxa neuronal de CLASH i proporciona el menor error en la predicció de l'ultrapassament sobre dics en talús de entre els estimadors analitzats. Una de les maneres més efectives de disminuir l'ultrapassament sobre dics en talús és incrementar la cota de coronació mitjançant un espatller de formigó. Aquestes estructures sofreixen l'impacte de les ones i deuen ser dissenyades per a resistir. En la present tesi, s'utilitzen assajos de laboratori de cubs i Cubípodes per a desenvolupar una nova formulació per a calcular les forces horitzontals i verticals causades per l'onatge en l'espatller. Les noves fórmules inclouen la influència de quatre variables adimensionals (¿f Ru0.1%/Rc, (Rc-Ac)/Ch, ¿(L_m/G_c ) y Fc/Ch) i de la geometria de l'espatller. Inclouen la influència del tipus d'element mitjançant el factor de rugositat al igual que les fórmules d'ultrapassament. Les forces verticals disminueixen significativament amb l'augment de la cota de cimentació. Les noves fórmules proporcionen el menor error en la predicció sobre els registres de laboratori analitzats. / Molines Llodra, J. (2016). Wave overtopping and crown wall stability of cube and Cubipod-armored mound breakwaters [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/62178

Les chromènes photochromiques sont largement utilisés dans les technologies modernes en raison de leur capacité à changer les propriétés sous irradiation UV. Les chromènes présentés dans ce travail possèdent en outre des fragments pouvant participer à la coordination avec des cations métalliques, acides aminés, ou de l'ADN. Pour ce type de molécule, l'interdépendance éventuelle entre les propriétés photochromiques et complexantes permet d'envisager soit le photo-contrôle de la complexation, soit la modulation du photochromisme par le biais de coordination.Ce travail est divisé en deux parties : la première est consacrée à la préparation des molécules cibles et la seconde à l'étude de la complexation. Les approches synthétiques élaborées ont permis d'obtenir une série de nouveaux chromènes annelés par des éthers couronnes de taille et de composition hétéroatomique différentes. Le processus de complexation de certains dérivés a été étudié en détail par spectroscopie RMN et absorptionUV-Visible. Il a été établi que la nature des cations métalliques détermine la stoechiométrie du complexe formé ainsi que la structure spatiale. Pour tous les composés étudiés, la complexation affecte les paramètres photochromiques notamment la vitesse de décoloration. En ce qui concerne la complexation des chromènes synthétisés avec les acides aminés protonés, il a été établi qu'en fonction de la longueur de chaine de ces acides, la formation de complexe mono- ou ditopique est favorisée.De plus, l'interaction d'un nouveau chromène cationique avec l'ADN a été étudiée. Il a été constaté que contrairement à la forme initiale, la forme colorée de ce composé générée sous irradiation UV permet l'intercalation au sein de l'ADN / Photochromic chromenes are widely used in modern technologies due to their abilityto change their properties upon UV irradiation. The chromenes presented in this work alsopossess fragments able to participate to the coordination with metal cations, amino acids, orDNA. These properties may sustain mutual influence on each other resulting in either photocontrolof complexing ability or photochromism tunable by complex formation.This work is divided in two parts, one devoted to the synthesis of the targetcompounds and the second to study on the complexing ability of the substances,respectively. Thus, the synthetic approaches to photochromic benzo- and naphthopyrans,annelated to the crown ether moieties of different size and heteroatomic composition, weredeveloped. The complex formation of several chromenes with metal cations wasinvestigated by means of UV-Vis absorption and NMR spectroscopies. The metal cationnature was found to determine the stoichiometry of the complexes as well as their spatialstructure. The complex formation was found to affect the photochromic properties of thecompounds, especially the bleaching rate. Investiga.on of complexation of the chromeneswith protonated amino acids revealed that, depending on the length of the carbon chain ofthe acid used, mono- or ditopic complexes may be formed.The interaction of the new chromene, possessing a positively charged group, with DNAwas also studied. In contrast to the initial form, the photo-induced colored form was foundto intercalate with DNA.