<p>This thesis presents the application of some of the NMR methods in studying host-guest complexes, mainly in solution. The general focus of the work is on investigating the reorientational dynamics of some small molecules that are bound inside cavities of larger moieties. In the current work, these moieties belong to two groups: cryptophanes and cyclodextrins. Depending on the structure of the cavities, properties of the guest molecules and the formed complexes vary. Chloroform and dichloromethane are in slow exchange between the cage-like cavity of the cryptophanes and the solvent, on the chemical shift time scale, whereas adamantanecarboxylic acid, quinuclidine and 1,7-heptanediol in complex with cyclodextrins are examples of fast exchange. Kinetics and thermodynamics of complexation are studied by measuring exchange rates and translational self-diffusion coefficients by means of 1-dimenssional exchange spectroscopy and pulsed-field gradient (PFG) NMR methods, respectively. The association constants, calculated using the above information give estimates of the thermodynamic stability of the complexes. Carbon-13 spin relaxation data were obtained using conventional relaxation experiments, such as inversion recovery and dynamic NOE, and in some cases HSQC-type (Hetereonuclear Single Quantum Correlation Spectroscopy) experiments. Motional parameters for the free and bound guest, and the host molecules were extracted using different motional models, such as Lipari-Szabo, axially symmetric rigid body, and Clore models. Comparing the overall correlation times and the order parameters of the free and bound guest with the overall correlation time of the host molecule one can estimate the degree of the motional restriction, brought by the complexation, and the coupling between the motion of the bound guest and the reorientation of the host molecule. In one case, the guest motions were also investigated inside the cavities of a solid host material.</p>

Two approaches for creating a new all-cellulose composite material have been studied: the biosynthesis of compartmentalised bacterial cellulose fibril aggregates and the compression moulding of commercial chemical wood pulps processed with only water. The objective was to study the structural changes during processing and the complexity of relating the mechanical properties of the final biocomposites to the nanoscale structure was highlighted. Solid-state CP/MAS 13C NMR spectroscopy was utilised to determine both the fibril aggregate width and the content of the different crystalline cellulose forms, cellulose I and cellulose II. Using this method, the quantities of hemicellulose present inside the fibre wall and localised at the fibre surfaces could be determined. The formation of cellulose fibrils was affected by the addition of hydroxyethylcellulose (HEC) to a culture medium of Acetobacter aceti, and the fibrils were coated with a thin layer of HEC, which resulted in loose bundles of fibril aggregates. The HEC coating, improved the fibril dispersion in the films and prevented fractures, resulting in a biocomposite with remarkable mechanical properties including improved strength (289 MPa), modulus (12.5 GPa) and toughness (6%). The effect of press temperature was studied during compression moulding of sulphite dissolving-grade pulps at 45 MPa. A higher press temperature yielded increases in the fibril aggregation, water resistance (measured as the water retention value) and Young’s modulus (12 GPa) in the final biocomposite. The high pressure was important for fibril aggregation, possibly including cellulose-cellulose fusion bonds, i.e., fibril aggregation in the fibre-fibre bond region. The optimal press temperature was found to be 170°C because cellulose undergoes thermal degradation at higher temperatures. The effect of hemicellulose was studied by comparing a softwood kraft paper-grade pulp with a softwood sulphite paper and a softwood sulphite dissolving-grade pulp. A significant fibril aggregation of the sulphite pulps suggested that the content and distribution of hemicellulose affected the fibril aggregation. In addition, the hemicellulose structure could influence the ability of the hemicellulose to co-aggregate with cellulose fibrils. Both sulphite pulp biocomposites exhibited Young’s moduli of approximately 12 GPa, whereas that of the kraft pulp was approximately half that value at 6 GPa. This result can be explained by a higher sensitivity to beating in the sulphite pulps. The effect of mercerisation, which introduces disordered cellulose, on the softwood sulphite dissolving-grade pulp was also studied under compression moulding at 170°C and 45 MPa. The mechanisms causing an incomplete transformation of cellulose I to II in a 12 wt% NaOH solution were discussed. The lower modulus of cellulose II and/or the higher quantity of disordered cellulose likely account for the decrease in Young’s modulus in the mercerised biocomposites (6.0 versus 3.9 GPa). / Två metoder för att skapa ett nytt kompositmaterial baserat på enbart cellulosa har studerats, biosyntes av fibrillaggregat bestående av bakteriecellulosa och varmpressning av kommersiella träfiberbaserade massor med vatten som den enda processkemikalien. Målet var att studera de strukturella förändringarna som sker under tillverkningsprocessen. Även komplexiteten i att relatera strukturen på nanonivå till de mekaniska egenskaperna hos de slutliga biokompositerna belystes. Med fastfas CP/MAS 13C NMR-spektroskopi var det möjligt att bestämma både fibrillaggregattjockleken och mängden av cellulosakristallformerna; cellulosa I och cellulosa II. Det var också möjligt att bestämma mängden hemicellulosa dels närvarande inuti fiberväggen och dels mängden lokaliserad på fiberytor. Tillsats av hydroxyetylcellulosa (HEC) i odlingsmediet för Acetobacter aceti påverkade bildandet av cellulosafibriller som blev belagda med ett tunt skikt av HEC, vilket också resulterade i löst bundna fibrillaggregat. HEC-beläggningen förbättrade fibrilldispersionen i filmerna och minskade sprickbildningen, vilket gav en biokomposit med mycket goda mekaniska egenskaper med kombinerad hög styrka (289 MPa), styvhet (12.5 GPa) och seghet (6%). Effekten av presstemperatur vid varmpressning (45 MPa tryck) studerades på sulfit dissolvingmassor. Högre presstemperatur gav ökad fibrillaggregering, ökat vattenmotstånd (mätt som vattenretentionsvärde) och högre styvhet (12 GPa) för biokompositen. Det höga trycket var också viktigt för fibrillaggregeringen, som troligen omfattar cellulosa-cellulosa samkristallisation dvs. fibrillaggregering i fiber-fiber-bindningsregionen. Den optimala presstemperaturen föreslogs vara 170° C pga. termisk nedbrytning av cellulosa vid högre temperaturer. Effekten av hemicellulosa studerades genom att jämföra sulfat pappersmassa med sulfit pappersmassa och sulfit dissolvingmassa. Mängden och fördelningen av hemicellulosa föreslogs ligga till grund för skillnaden i fibrillaggregering, som var mera uttalad i sulfitmassorna. Även hemicellulosans struktur kan påverka förmågan hos hemicellulosa att sam-aggregera med cellulosafibriller. Biokompositerna baserade på sulfitmassorna hade en styvhet på ca. 12 GPa, medan sulfatmassan bara hade hälften av den nivån ca. 6 GPa, vilket förklarades av sulfitmassornas högre känslighet för malning. Även effekten av mercerisering av sulfit dissolvingmassa varmpressad vid 170° C och 45 MPa studerades. Mercerisering introducerar oordnad cellulosa och mekanismerna som endast ger en partiell omvandling av cellulosa I till II i en 12 vikt% NaOH-lösning diskuterades. Den sämre styvheten hos den merceriserade biokompositen (6.0 resp. 3.9 GPa) förklaras troligen genom cellulosa II kristallens lägre styvhet och/eller den högre mängden av oordnad cellulosa. / <p>QC 20121106</p> / Wallenberg Wood Science Center / Biomime

This thesis presents the application of some of the NMR methods in studying host-guest complexes, mainly in solution. The general focus of the work is on investigating the reorientational dynamics of some small molecules that are bound inside cavities of larger moieties. In the current work, these moieties belong to two groups: cryptophanes and cyclodextrins. Depending on the structure of the cavities, properties of the guest molecules and the formed complexes vary. Chloroform and dichloromethane are in slow exchange between the cage-like cavity of the cryptophanes and the solvent, on the chemical shift time scale, whereas adamantanecarboxylic acid, quinuclidine and 1,7-heptanediol in complex with cyclodextrins are examples of fast exchange. Kinetics and thermodynamics of complexation are studied by measuring exchange rates and translational self-diffusion coefficients by means of 1-dimenssional exchange spectroscopy and pulsed-field gradient (PFG) NMR methods, respectively. The association constants, calculated using the above information give estimates of the thermodynamic stability of the complexes. Carbon-13 spin relaxation data were obtained using conventional relaxation experiments, such as inversion recovery and dynamic NOE, and in some cases HSQC-type (Hetereonuclear Single Quantum Correlation Spectroscopy) experiments. Motional parameters for the free and bound guest, and the host molecules were extracted using different motional models, such as Lipari-Szabo, axially symmetric rigid body, and Clore models. Comparing the overall correlation times and the order parameters of the free and bound guest with the overall correlation time of the host molecule one can estimate the degree of the motional restriction, brought by the complexation, and the coupling between the motion of the bound guest and the reorientation of the host molecule. In one case, the guest motions were also investigated inside the cavities of a solid host material.

In recent decades, there has been increased global concern about observed climate change; however for future climatic impacts and anthropogenic forcings of climate change to be realistically predicted, natural climate variability in the past needs to be better understood. The aim of this research is to develop quantifiable proxy records of past climate change through the calibration of isotope values in modern surface waters and tree ring cellulose with meteorological and atmospheric records. Terrestrial proxy records that utilize oxygen and hydrogen isotope values to reconstruct paleoclimatic and paleohydrologic conditions are limited by a paucity of data on the modification of surface water isotope values prior to sequestration into proxy material. To address this gap in our knowledge and determine the most appropriate study sites, this research focuses on isotopic records preserved in surface water reservoirs, precipitation, and tree-ring cellulose. In the first study, δD, δ18O, and deuterium-excess values were determined for lakes and rivers from Tasmania, southeastern Australia. <p> The second focus of this research was to calibrate the δ18O, δD, and δ13C values of tree-ring cellulose from North America with instrumental records. A new high-resolution sampling procedure that uses a robotic micromilling device to very precisely map and sample along growth rings in trees is discussed. Additionally, a seasonally resolved (early/late wood) 110-year record of δ18O values from tree-ring α-cellulose from spruce species (<i>Picea mariana</i> and <i>P. glauca</i>) from east-central Saskatchewan, Canada is compared to growing season precipitation δ18O values, temperature, and relative humidity. The δ18O time series from α-cellulose display a high correlation with growing season precipitation isotope values (r = 0.86). δ18O α-cellulose time series from a white spruce (<i>Picea glauca</i>) also records seasonal changes in atmospheric circulation associated with the position of the circumpolar vortex and dominate modes of atmospheric variability such as the North Atlantic Oscillation and Pacific Decadal Oscillation.

Dynamic nuclear polarization and dissolution of 13C-labeled metabolite allows dynamic imaging of metabolism in-vivo. However, the spatial and temporal resolutions of magnetic resonance spectroscopic imaging are limited by the duration of free-induction decay acquisitions and the T1-based, non-recoverable polarization decay. This thesis describes the implementation of a spectral-spatial radiofrequency excitation pulse with a `flyback' echo-planar readout trajectory to dynamically image [1-13C]-pyruvate and [1-13C]-lactate in an interleaved manner. This technique excites a single resonance of either [1-13C]-pyruvate or [1-13C]-lactate and generates dynamic images with 5mm in-plane resolution. Metabolite dynamics extracted from the images and the corresponding non-localized spectroscopic data reveal similar kinetic rates upon fitting to a kinetic model. This demonstrates the feasibility of probing metabolism in heterogeneous tissues in-vivo with dynamic interleaved 13C MR imaging.

Dynamic nuclear polarization and dissolution of 13C-labeled metabolite allows dynamic imaging of metabolism in-vivo. However, the spatial and temporal resolutions of magnetic resonance spectroscopic imaging are limited by the duration of free-induction decay acquisitions and the T1-based, non-recoverable polarization decay. This thesis describes the implementation of a spectral-spatial radiofrequency excitation pulse with a `flyback' echo-planar readout trajectory to dynamically image [1-13C]-pyruvate and [1-13C]-lactate in an interleaved manner. This technique excites a single resonance of either [1-13C]-pyruvate or [1-13C]-lactate and generates dynamic images with 5mm in-plane resolution. Metabolite dynamics extracted from the images and the corresponding non-localized spectroscopic data reveal similar kinetic rates upon fitting to a kinetic model. This demonstrates the feasibility of probing metabolism in heterogeneous tissues in-vivo with dynamic interleaved 13C MR imaging.

In recent decades, there has been increased global concern about observed climate change; however for future climatic impacts and anthropogenic forcings of climate change to be realistically predicted, natural climate variability in the past needs to be better understood. The aim of this research is to develop quantifiable proxy records of past climate change through the calibration of isotope values in modern surface waters and tree ring cellulose with meteorological and atmospheric records. Terrestrial proxy records that utilize oxygen and hydrogen isotope values to reconstruct paleoclimatic and paleohydrologic conditions are limited by a paucity of data on the modification of surface water isotope values prior to sequestration into proxy material. To address this gap in our knowledge and determine the most appropriate study sites, this research focuses on isotopic records preserved in surface water reservoirs, precipitation, and tree-ring cellulose. In the first study, δD, δ18O, and deuterium-excess values were determined for lakes and rivers from Tasmania, southeastern Australia. <p> The second focus of this research was to calibrate the δ18O, δD, and δ13C values of tree-ring cellulose from North America with instrumental records. A new high-resolution sampling procedure that uses a robotic micromilling device to very precisely map and sample along growth rings in trees is discussed. Additionally, a seasonally resolved (early/late wood) 110-year record of δ18O values from tree-ring α-cellulose from spruce species (<i>Picea mariana</i> and <i>P. glauca</i>) from east-central Saskatchewan, Canada is compared to growing season precipitation δ18O values, temperature, and relative humidity. The δ18O time series from α-cellulose display a high correlation with growing season precipitation isotope values (r = 0.86). δ18O α-cellulose time series from a white spruce (<i>Picea glauca</i>) also records seasonal changes in atmospheric circulation associated with the position of the circumpolar vortex and dominate modes of atmospheric variability such as the North Atlantic Oscillation and Pacific Decadal Oscillation.

Switchgrass (Panicum virgatum), a perennial C4 grass species, has the capacity to not only improve the quality of the soil in which it grows but also promote soil carbon storage to offset rising atmospheric CO2. This research investigated soil organic carbon (SOC) dynamics beneath switchgrass using natural abundance 13C and soil carbon fractionation following the establishment of this crop in a native and predominantly C3 plant region in southeastern Ontario. I investigated SOC dynamics by sampling adjacent commercial switchgrass fields and appropriate paired control fields at sites where the time since switchgrass establishment varied from 4-11 years. SOC and natural 13C abundance were measured in paired fields to assess management-induced changes in the quantity, source, and turnover time of soil carbon. To better elucidate carbon cycling dynamics over a relatively short time since switchgrass establishment, multiple soil fractionation techniques were applied to better understand carbon dynamics of soil organic matter with various mean residence times. Establishment of switchgrass results in marginal increases in SOC, primarily at sites where intensive soil management (i.e. tillage) practices preceded switchgrass establishment. Changes were observed in some of the more labile SOC pools, as well as in the δ13C values of the bulk soil and soil carbon fractions, indicating that growing switchgrass was causing the incorporation of switchgrass-derived carbon into the soil. Even resistant SOC pools, with turnover times of over 100 years, incorporated significant quantities of switchgrass carbon in 11 years. Annual increases in SOC, however, were less than values reported elsewhere. The potential for soil carbon storage exists, likely due to longer mean residence times of the carbon in soils beneath switchgrass compared with other cultivation systems. Changes in SOC following switchgrass establishment related strongly to the amount of root biomass, time since establishment and prior soil management practices. The decomposition rates derived in this research should be integrated into soil carbon modeling applications intended to support the emergence of switchgrass in southeastern Ontario. The results of my research can advance soil carbon models and be used to make regional assessment of the potential impact of growing switchgrass for bioenergy in southeastern Ontario. / Thesis (Master, Geography) -- Queen's University, 2012-01-30 13:56:06.269

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Made available in DSpace on 2014-06-11T19:32:25Z (GMT). No. of bitstreams: 0 Previous issue date: 2011-01-31Bitstream added on 2014-06-13T20:23:43Z : No. of bitstreams: 1 silva_ac_dr_botfca.pdf: 2162493 bytes, checksum: cfb1fbe284f06f4a0cbe2296e71c7ffb (MD5) / Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) / No presente trabalho determinou-se no primeiro capítulo o crescimento através dos parâmetros: diâmetro do ramo, comprimento do ramo, número de folhas, número de entrenós e número de frutos a cada 21 dias, em plantas da figueira ‘Roxo de Valinhos’ utilizando cobertura morta, composta por bagaço de cana-de-açúcar triturado, e irrigação, na área experimental do Departamento de Produção Vegetal da Faculdade de Ciências Agronômicas da UNESP, Campus de Botucatu-SP. E no segundo capítulo objetivou-se avaliar o tempo de translocação, a relação fonte-dreno nos diferentes órgãos bem como, saber em que órgão se encontraria o carbono-13 após determinados intervalos de tempo, em plantas em estádio reprodutivo e em formação da espécie Ficus carica L. Para tanto, uma folha da figueira considerada adulta através da caracterização fotossintética com um medidor portátil de fotossíntese IRGA-6400, foi colocada dentro de uma câmara de acrílico construída para este fim, e submetida a um ambiente com enriquecimento de 13CO2 por 30 minutos. No experimento tempo de alocação, as plantas de Ficus carica L. foram arrancadas ao longo das horas: 6, 24, 48, 72, 120, 168, 360. Após o tempo especificado as partes (meristema apical, folhas, ramos, caule e sistema radicular) das plantas em estudo foram coletados e imediatamente imersos em nitrogênio líquido (-196 ºC), para evitar que os tecidos permanecessem vivos e conseqüentemente pudessem consumir os fotoassimilados no processo da respiração. As amostras, previamente identificadas foram secas em estufa de circulação forçada a 65º C por 72 horas, em seguida moídas em moinho criogênico, para que houvesse uma perfeita homogeneização, sendo posteriormente analisadas no espectrômetro de massas de razão isotópica, para a determinação do enriquecimento relativo de 13C. Naturalmente a planta apresenta valores... / In this study determined the growth in the first experiment using the parameters: diameter branch, length branch, leaf number, number of internodes and number of fruit every 21 days, plant the fig tree 'Roxo de Valinhos' mulch using, composed of lither sugar cane, and irrigation in the experimental area in the Department of Plant Production, Faculty of Agronomic Sciences, State University of São Paulo. In the second experiment it planned be quizzed, the time of the translocation and allocation of fotoassimilados, as well as, evaluate the relation spring-drain in the different organs like well as, know in that organ would be found the carbon-13 after determined breaks of time, in plants in reproductive stadium of the sort Ficus carica L. A fig tree leaf considered adult through the photosynthetic with a portable meter of photosynthesis IRGA-6400 characterization. Was put inside a acrylic chamber, and submitted to an environment with 13CO2 enrichment for 30 minutes. In experiment time allocation, where the plants of Ficus carica L. were lurches to the long one of the hours: 6, 24, 48, 72, 120, 168, 360. After the time specified the studied plant parts (meristem, sheets, branches, stem and system roots) were collected and immediately immersed in liquid nitrogen (-196 ºC), for avoid that the fabrics remained alive and consequently could consume the fhotosynthates in the breath trial. The samples, previously identified were droughts in of circulation forced to 65º C for 72 hours, right away ground in cryogenic mill, for that had a perfect homogenization, being subsequently analyzed in the mass spectrometry of isotopic reason, for the relative enrichment 13C determination. . Naturally the plant presents values of 13C relative enrichment of -27.92 ‰, allocating more than 90% of the dry mass and the total carbon in the woody part. The results obtained indicated that fig tree ‘Roxo de ...