京都大学 / 0048 / 新制・課程博士 / 博士(農学) / 甲第20423号 / 農博第2208号 / 新制||農||1047(附属図書館) / 学位論文||H29||N5044(農学部図書室) / 京都大学大学院農学研究科食品生物科学専攻 / (主査)教授 安達 修二, 教授 金本 龍平, 教授 谷 史人 / 学位規則第4条第1項該当 / Doctor of Agricultural Science / Kyoto University / DFAM

Due to the very long half-life of Se-79 and its presence in used nuclear fuel, Se is an element of interest in the safety assessment for a deep geological repository (DGR) for used nuclear fuel. Sorption of radionuclides onto the surrounding host rocks and engineered barrier materials is a potential retardation mechanism for radionuclide transport. This thesis investigates the sorption of Se(-II) onto illite, bentonite (engineered barrier material), and shale under high ionic strength conditions relevant to a Canadian DGR. The ionic strength and pH dependence of Se(-II) sorption onto illite, bentonite, and shale were studied. A non-electrostatic surface complexation model was also developed for Se(-II) sorption onto illite and montmorillonite to investigate the sorption mechanisms by which Se(-II) sorbs onto these solids. / Thesis / Master of Applied Science (MASc)

A disposição de resíduos sólidos e a aplicação de pesticidas e fertilizantes podem levar ao aumento da concentração de metais pesados em solos e águas subterrâneas. A legislação sobre metais pesados quase sempre se refere aos seus teores totais, mas a avaliação do potencial de risco e da toxicidade requer a avaliação da proporção de metal que é móvel e, possivelmente, biodisponível. Alguns parâmetros numéricos têm sido utilizados para tomadas de decisões e para direcionar estratégias de prevenção ou de remediação de áreas contaminadas. O coeficiente de distribuição sólido-solução (Kd), definido como a relação entre as concentrações adsorvida e em solução, permite a comparação do comportamento de elementos em diferentes sistemas. Agências de proteção ambiental utilizam valores genéricos de Kd encontrados em referências bibliográficas que, por terem sido gerados a partir de condições distintas das da região tropical, podem levar a incorretas estimativas de risco. É evidente a necessidade da obtenção de valores de Kd que validem estas estimativas de contaminação ou que norteiem estratégias de intervenção em áreas já contaminadas. Os objetivos deste trabalho foram avaliar a retenção de metais pesados em 30 solos representativos do Estado de São Paulo, a partir da quantificação dos valores do coeficiente de distribuição (Kd) e da relação com atributos dos solos, tais como pH, CTC e teores de argila, matéria orgânica e de diversas formas de óxidos de Fe, Al e de Mn. Os coeficientes de distribuição foram obtidos de isotermas lineares de adsorção, construídas após a adição de 0,1; 0,5; 1,0; 2,5 e 5,0 mg L-1 de Cd, Co, Cr, Cu, Ni, Pb e Zn, em experimentos tipo batch. As menores variações nos valores de Kd foram registradas para o Pb (uma ordem de magnitude - 121 a 7.020 L kg-1) e para o Ni (duas ordens de magnitude - 6 a 998 L kg-1), enquanto variações de quatro ordens de magnitude foram observadas para Cd (7-14.339 L kg-1), Co (2-34.473 L kg-1) e para Cr (1-21.267 L kg-1). Coeficientes de distribuição de zinco estiveram entre 5 a 123.849 L kg-1, variando cinco ordens de magnitude. Os valores foram similares àqueles que vêm sendo utilizados pela CETESB, exceto os de Cr e Ni. Obteve-se a seguinte ordem de afinidade: Pb>>>Cu>>Cd>Zn≅Ni≅Cr>Co. Mais de 55% da variação dos coeficientes de distribuição de cátions metálicos dos grupos IIB (Cd e Zn) e VIIIB (Co e Ni) foram explicados pelo pH. Na análise conjunta, CTC e pH explicaram cerca de 80% da variação dos valores de Kd de Cd, Co e de Ni e evidenciaram que mecanismos de adsorção não-específica estão envolvidos na retenção destes elementos. No caso dos coeficientes de distribuição de Cu e de Pb, o pH e os teores de argila responderam por cerca de 63% da sua variação. Os valores de Kd de Cr apresentaram correlação inversa com o pH, principalmente na análise conjunta com os teores de argila, e 61% da sua variação foi explicada por estas variáveis. / Disposal of solid residues and application of pesticides and fertilizers can lead to an increase in the concentration of heavy metals in soils and groundwater. The legislation on heavy metals nearly always refers to the total contents of these elements; however, an evaluation of their hazard potential and toxicity requires an assessment of the metal fraction that is mobile and possibly bioavailable. A few numerical parameters have been used as a foundation to make decisions and to focus on prevention or remediation strategies in contaminated areas. The solid-solution distribution coefficient (Kd), defined as the relation between metal concentrations that are adsorbed and those present in the solution, allows a comparison between the behavior of elements in different systems. Environmental protection agencies use generic Kd values found in bibliographic references; these values are often obtained under distinct conditions from those found in the tropical region, and may lead to an erroneous hazard estimates. Thus, it becomes clearly necessary to obtain Kd values that will validate these contamination estimates or provide guidance for intervention strategies in already contaminated areas. The objectives of this work were to evaluate heavy metal retention in 30 representative soils of the State of São Paulo, based on a quantification of distribution coefficient values (Kd) and their relation with soil attributes, such as pH, CEC and clay contents, organic matter, and various forms of Fe, Al, and Mn oxides. The distribution coefficients were obtained from linear adsorption isotherms, constructed after the addition of 0.1; 0.5; 1.0; 2.5; and 5.0 mg L-1 Cd, Co, Cr, Cu, Ni, Pb, and Zn, in batch-type experiments. The smallest variations in Kd value were recorded for Pb (one order of magnitude - 121 to 7,020 L kg-1) and Ni (two orders of magnitude - 6 to 998 L kg-1), while variations indicating four orders of magnitude were observed for Cd (7-14,339 L kg-1), Co (2 - 34,473 L kg-1), and Cr (1 - 21,267 L kg-1). Zinc distribution coefficients were between 5 and 123,849 L kg-1, with a variation of five orders of magnitude. The values herein obtained were similar to those that have been used by CETESB, except for Cr and Ni. The following order of affinity was obtained: Pb>>>Cu>>Cd>Zn≅Ni≅Cr>Co. More than 55% of the variation in distribution coefficients for metallic cations of the groups IIB (Cd and Zn) and VIIIB (Co and Ni) were explained by pH. In the joint analysis, CEC and pH explained about 80% of the variation in Kd values for Cd, Co, and Ni, and showed that nonspecific adsorption mechanisms are involved in the retention of these elements. Regarding the distribution coefficients for Cu and Pb, pH and clay content accounted for about 63% of the variation. Kd values for Cr showed an inverse correlation with pH, especially in the joint analysis with clay contents, and 61% of the variation were explained by these variables.

A disposição de resíduos sólidos e a aplicação de pesticidas e fertilizantes podem levar ao aumento da concentração de metais pesados em solos e águas subterrâneas. A legislação sobre metais pesados quase sempre se refere aos seus teores totais, mas a avaliação do potencial de risco e da toxicidade requer a avaliação da proporção de metal que é móvel e, possivelmente, biodisponível. Alguns parâmetros numéricos têm sido utilizados para tomadas de decisões e para direcionar estratégias de prevenção ou de remediação de áreas contaminadas. O coeficiente de distribuição sólido-solução (Kd), definido como a relação entre as concentrações adsorvida e em solução, permite a comparação do comportamento de elementos em diferentes sistemas. Agências de proteção ambiental utilizam valores genéricos de Kd encontrados em referências bibliográficas que, por terem sido gerados a partir de condições distintas das da região tropical, podem levar a incorretas estimativas de risco. É evidente a necessidade da obtenção de valores de Kd que validem estas estimativas de contaminação ou que norteiem estratégias de intervenção em áreas já contaminadas. Os objetivos deste trabalho foram avaliar a retenção de metais pesados em 30 solos representativos do Estado de São Paulo, a partir da quantificação dos valores do coeficiente de distribuição (Kd) e da relação com atributos dos solos, tais como pH, CTC e teores de argila, matéria orgânica e de diversas formas de óxidos de Fe, Al e de Mn. Os coeficientes de distribuição foram obtidos de isotermas lineares de adsorção, construídas após a adição de 0,1; 0,5; 1,0; 2,5 e 5,0 mg L-1 de Cd, Co, Cr, Cu, Ni, Pb e Zn, em experimentos tipo batch. As menores variações nos valores de Kd foram registradas para o Pb (uma ordem de magnitude – 121 a 7.020 L kg-1) e para o Ni (duas ordens de magnitude - 6 a 998 L kg-1), enquanto variações de quatro ordens de magnitude foram observadas para Cd (7-14.339 L kg-1), Co (2-34.473 L kg-1) e para Cr (1-21.267 L kg-1). Coeficientes de distribuição de zinco estiveram entre 5 a 123.849 L kg-1, variando cinco ordens de magnitude. Os valores foram similares àqueles que vêm sendo utilizados pela CETESB, exceto os de Cr e Ni. Obteve-se a seguinte ordem de afinidade: Pb>>>Cu>>Cd>Zn≅Ni≅Cr>Co. Mais de 55% da variação dos coeficientes de distribuição de cátions metálicos dos grupos IIB (Cd e Zn) e VIIIB (Co e Ni) foram explicados pelo pH. Na análise conjunta, CTC e pH explicaram cerca de 80% da variação dos valores de Kd de Cd, Co e de Ni e evidenciaram que mecanismos de adsorção não-específica estão envolvidos na retenção destes elementos. No caso dos coeficientes de distribuição de Cu e de Pb, o pH e os teores de argila responderam por cerca de 63% da sua variação. Os valores de Kd de Cr apresentaram correlação inversa com o pH, principalmente na análise conjunta com os teores de argila, e 61% da sua variação foi explicada por estas variáveis. / Disposal of solid residues and application of pesticides and fertilizers can lead to an increase in the concentration of heavy metals in soils and groundwater. The legislation on heavy metals nearly always refers to the total contents of these elements; however, an evaluation of their hazard potential and toxicity requires an assessment of the metal fraction that is mobile and possibly bioavailable. A few numerical parameters have been used as a foundation to make decisions and to focus on prevention or remediation strategies in contaminated areas. The solid-solution distribution coefficient (Kd), defined as the relation between metal concentrations that are adsorbed and those present in the solution, allows a comparison between the behavior of elements in different systems. Environmental protection agencies use generic Kd values found in bibliographic references; these values are often obtained under distinct conditions from those found in the tropical region, and may lead to an erroneous hazard estimates. Thus, it becomes clearly necessary to obtain Kd values that will validate these contamination estimates or provide guidance for intervention strategies in already contaminated areas. The objectives of this work were to evaluate heavy metal retention in 30 representative soils of the State of São Paulo, based on a quantification of distribution coefficient values (Kd) and their relation with soil attributes, such as pH, CEC and clay contents, organic matter, and various forms of Fe, Al, and Mn oxides. The distribution coefficients were obtained from linear adsorption isotherms, constructed after the addition of 0.1; 0.5; 1.0; 2.5; and 5.0 mg L-1 Cd, Co, Cr, Cu, Ni, Pb, and Zn, in batch-type experiments. The smallest variations in Kd value were recorded for Pb (one order of magnitude – 121 to 7,020 L kg-1) and Ni (two orders of magnitude - 6 to 998 L kg-1), while variations indicating four orders of magnitude were observed for Cd (7-14,339 L kg-1), Co (2 - 34,473 L kg-1), and Cr (1 - 21,267 L kg-1). Zinc distribution coefficients were between 5 and 123,849 L kg-1, with a variation of five orders of magnitude. The values herein obtained were similar to those that have been used by CETESB, except for Cr and Ni. The following order of affinity was obtained: Pb>>>Cu>>Cd>Zn≅Ni≅Cr>Co. More than 55% of the variation in distribution coefficients for metallic cations of the groups IIB (Cd and Zn) and VIIIB (Co and Ni) were explained by pH. In the joint analysis, CEC and pH explained about 80% of the variation in Kd values for Cd, Co, and Ni, and showed that nonspecific adsorption mechanisms are involved in the retention of these elements. Regarding the distribution coefficients for Cu and Pb, pH and clay content accounted for about 63% of the variation. Kd values for Cr showed an inverse correlation with pH, especially in the joint analysis with clay contents, and 61% of the variation were explained by these variables.

<p>In this thesis, different types of chemical and physical distribution coefficients are identified, examined and used to describe the fate and transport pathways of substances in aquatic systems. </p><p>Observations from field experiments in streams with non-reactive and reactive tracers constituted the basis for development of an advection-dispersion model. Differences in the concentrations in both the water and sediment data for the tracers were due to the particle affinity of the reactive tracer. This difference in behaviour could be described by including an instantanous and a kinetically controlled sorption, which included distribution coefficients, in the water column (<i>K</i><i>d</i>) and in the streambed sediment (<i>K</i><i>B</i>), respectively.</p><p>The results presented in this thesis also include a model for the lake characteristic concentration of suspended particulate matter (SPM). The SPM-model can be used to describe mass flows of particles in lakes. The traditional distribution (or partition) coefficient <i>K</i><i>d</i> has been found to be unsuitable for interpretations of the particle association of solutes and also for distributing solute mass flows. Instead, the particulate or the dissolved fraction, <i>PF</i> and <i>DF</i>, defined as ratios of the particulate or dissolved concentration to the total concentration respectively, is recommended for mass-balance calculations. A new <i>PF</i>-model for phosphorus has meant that this part is no longer the most sensitive part of predicting concentrations of phosphorus in lakes using a more extensive dynamic model. </p><p>New methods have also been developed to describe the shape of lakes. Together with the mixing depth of lakes, the shape of a lake can be transformed into a distribution coefficient that physically determines the portion of a lake that is exposed, both areally and vertically, to continuously mixing.</p>

In this thesis, different types of chemical and physical distribution coefficients are identified, examined and used to describe the fate and transport pathways of substances in aquatic systems. Observations from field experiments in streams with non-reactive and reactive tracers constituted the basis for development of an advection-dispersion model. Differences in the concentrations in both the water and sediment data for the tracers were due to the particle affinity of the reactive tracer. This difference in behaviour could be described by including an instantanous and a kinetically controlled sorption, which included distribution coefficients, in the water column (Kd) and in the streambed sediment (KB), respectively. The results presented in this thesis also include a model for the lake characteristic concentration of suspended particulate matter (SPM). The SPM-model can be used to describe mass flows of particles in lakes. The traditional distribution (or partition) coefficient Kd has been found to be unsuitable for interpretations of the particle association of solutes and also for distributing solute mass flows. Instead, the particulate or the dissolved fraction, PF and DF, defined as ratios of the particulate or dissolved concentration to the total concentration respectively, is recommended for mass-balance calculations. A new PF-model for phosphorus has meant that this part is no longer the most sensitive part of predicting concentrations of phosphorus in lakes using a more extensive dynamic model. New methods have also been developed to describe the shape of lakes. Together with the mixing depth of lakes, the shape of a lake can be transformed into a distribution coefficient that physically determines the portion of a lake that is exposed, both areally and vertically, to continuously mixing.

Original estimates of phosphorus (P) concentrations in the Precambrian oceans before 1.9 Ga gave a budget of ~10-25% of modern day levels. This budget was challenged by accounting for high silica (Si) concentrations that were believed to have outcompeted P for binding sites on precipitating iron oxide-hydroxide particles during the chemical oxidation and burial of iron (Fe). Such iron oxide-hydroxide particles are considered as proxies of ancient iron-rich sedimentary rocks, such as banded iron formations, which are often used to infer the dissolved chemistry of trace elements in the ancient oceans. This study raises the question of wether arsenic (As) had an effect of the binding of P to precipitating iron minerals, during the co-precipitation of Iron oxide- hydroxide in elevated Fe and Si concentrations characteristic of the early oceans. This hypothesis is based on the chemical similarities seen between P and As. Results show a more pH dependent competition between P and AsIII, whereby P outcompetes AsIII at a pH &lt;7. The effect decreases as the pH rises until pH ~8 at which the effect cancels out and AsIII becomes somewhat predominant over P. AsV on the other hand, an analogue to P, is outcompeted by P throughout pH 5-10. Distribution coefficients (Kd) of P on iron oxide-hydroxide particles were not affected by the concentration of Si in solution. Average Kd and standard error between concentrations of Si, across the sample pH of 5-10 revealed an average Kd of 0.072 (±0.01) μM-1. This is strikingly similar to another experimental Kd at 0.075 (±0.003) μM-1, when the effects of Si are excluded. The average Kd in this study is also consistent with the average Kd of 0.06 μM-1 from a range of As-rich hydrothermal systems reported in a previous study, supporting the original idea of Precambrian P levels being low. The average Kd between concentrations of Fe revealed a Kd of 0.12 (±0.03) μM-1 although this was not statistically significant from the average Kd between groups of Si. In addition to low levels of P, the Precambrian oceans likely also contained high levels of As, due to the high hydrothermal activity. This scavenging of P from oceanic waters would have become increasingly important as surface oceans became more oxygenated and the presence of AsV would have been greater. Because the availability of Si does not show any great effect on the uptake of P by precipitating iron oxide-hydroxides, Si concentration is likely not a proxy for oceanic P concentrations. It is proposed that low dissolved P levels are consistent with early oceans that w!ere a lot more hydrothermally influenced than the oceans of today. / Prekambriska fosfor (P) nivåer var ursprungligen estimerade till ca 10-25% utav koncentrationen funnen i dagens havsvatten. Denna budget blev motsagd i och med att kisel (Si) sades kunna ersätta bundet fosfor på järn oxid-hydroxid partiklar som precipiterade genom kemisk oxidation och sedimentering av järn (Fe). Dessa järn oxid-hydroxid partiklar anses användbara som proxy för formationen av uråldriga järn-rika sedimentära bergarter såsom banded iron formation (BIF), vilka används idag för att bestämma mängden spårämnen i de uråldriga haven. Denna studie ställer frågan huruvida arsenik (As) påverkar mängden P som binder till precipiterande järn mineral under procession av co-precipitering av järn oxid-hydroxid i lösning med förhöjda koncentrationer av Fe och Si, karakteristiska för the uråldriga haven. Denna hypotes är baserad på de kemiska likheter som finns mellan P och As. Resultaten påvisar en pH beroende konkurrens mellan P och AsIII där P utkonkurrerar AsIII vid låg pH. Effekten av denna konkurrans minskar med ökande pH tills effekten blir omvänd omkring pH 8 och P blir istället till viss del utkonkurrerad av AsIII. AsV å andra sedan, en verklig kemisk analog till P, är kontinuerligt utkonkurrerad av P genom alla utförda pH, pH 5-10. Distribueringskoefficienter (Kd) för P på järn oxid-hydroxid partiklar visade ingen påverkan av mängden Si tillgängligt. Medelvärdet av Kd och standard error mellan data av alls pH, grupperat av Si, gav ett värde av 0.072 (±0.01) μM-1. Detta är påfallande nära ett experimentellt framtaget Kd värde av 0.075 (±0.03) μM-1 då effekten av Si är borttagen. Medelvärdet i denna studie är också sammanfallande med det Kd medelvärde man finner idag från olika hydrotemala system av 0.063 (±0.01) μM-1. Detta ger support till den originala idén att de prekambriska haven troligen hade låga halter P tillgängligt. Medelvärdet av Kd mellan koncentrationer av Fe gav ett värde av 0.12 (±0.03) μM-1, dock var detta värde ej statistiskt significant från det Kd utifrån koncentrationer av Si. Förutom de låga nivåer av P i de Prekambriska haven så var det troligen även höga halter av As på grund av utbredd hydrotermal aktivitet. Detta uppfångande av P i de tidiga haven var troligen en alltmer viktigare process då ytvatten blev syrerikare och den oxiderade formen av As, det vill säga AsV hade varit mer vanligt förekommande. Framför allt då den konkurrerande effekten av Si kan bortses när P såväl som As inte påverkas av dess närvaro till den grad man hade trott. Detta gör även att mängden Si troligen inte är en tillförlitlig proxy för att estimera P nivåer i de uråldriga haven. Därmed föreslås det att de prekambriska haven var k!arakteriserade av låga P nivåer, jämfört med idag.

Univerzita Karlova v Praze Lucie Ramešová Přírodovědecká fakulta Květen 2014 Ústav pro životní prostředí a VÚV T.G.M. v.v.i. OPTIMIZATION OF CONDITIONS FOR DETERMINATION OF BOTTOM SEDIMENT SORPTION CHARACTERISTICS ABSTRACT An option of this study was to optimize conditions of distribution coefficients determination in the water-sediment system. The study results will be applied in the task A research on influence of Temelín Nuclear Power Plant accident on the Vltava and Labe water environment contamination to the border profile Labe - Hřensko. After finding optimal conditions for sorption experiments, these will be applied on the experiments using real sediment samples and corresponding surface water extracted from different localities of Vltava River, Labe River respectively. A goal of the whole project is to contribute to creation of a crisis scenario of potential accident of Temelin Nuclear Power Plant and its impact on Vltava and Labe water environments. Above all, the aim is to answer the question which processes would take place in dams and basins during the contamination by fission and activation products, whether and which products would be preferably adsorbed and would consequently settle down and which would supposedly be transported to the lower parts of the watershed. The practical part of the...

In this work we study properties of branched polymers in a good solvent. We focus on problematic related to the size exclusion chromatography and predicting elution behavior of randomly branched polymers. We developed a software for generating self-avoiding walks (SAW) of any given non-looping architecture on a cubic lattice using Monte Carlo (MC) simulation and vali- date its reliability by presenting the scaling of different architectures: linear, 3-arm star and 6-arm star and asymmetric star. We calculate distribu- tion coefficients and calibration curves for size exclusion chromatography for various architectures to validate that the hydrodynamic radius is more suitable for predicting elution volume than the radius of gyration. Then we propose a new method for, although approximate, a very fast estimation of radius of gyration and hydrodynamic radius for different architecture using a graph method. It is done by comparing MC results with results obtained from graph theory. Then we introduce a correction to graph-theory results to fit the MC. At the end we present depletion layer calculation from MC and self-consistent field (SCF) method for polymers and their comparison. We show how calculation of depletion layer using SCF can be improved to get significantly better agreement with MC results. v

Liquid chromatography is an essential technique in manufacturing biopharmaceuticals where it is used on all scales from analytical applications in R&amp;D to full-scale production. In chromatography the target molecule, typically a protein, is separated and purified from other components and contaminants. Separation is based on different affinities of different molecules for the chromatographic medium and the physical and chemical properties of the latter determine the outcome. Controlling and designing those properties demand efficient analytical techniques. In this thesis the approach was to develop characterization methods based on nuclear magnetic resonance (NMR) spectroscopy for the assessment of various important physico-chemical properties. The rationale behind this strategy was that the versatility of NMR – with its chemical and isotopic specificity, high dynamic range, and direct proportionality between the integral intensity of the NMR signal and the concentration of spin-bearing atomic nuclei (e.g., 1H, 13C, 31P and 15N) – often renders it a very good choice for both qualitative and quantitative evaluations. These characteristics of NMR enabled us to develop two quantification methods for chromatography-media ligands, the functional groups that provide the specific interactions for the molecules being separated. Furthermore, a new method for measuring the distribution of macromolecules between the porous chromatographic beads and the surrounding liquid was established. The method, which we have named size-exclusion quantification (SEQ) NMR, utilizes the fact that it is possible to assess molecular size distribution from corresponding distribution of the molecular self-diffusion coefficient where the latter is accessible by NMR. SEQ-NMR results can also be interpreted in terms of pore-size distribution within suitable models. Finally, we studied self-diffusion of small molecules inside the pores of chromatographic beads. The results provided new insights into what affects the mass transport in such systems. The methods presented in this thesis are accurate, precise, and in many aspects better than conventional ones in terms of speed, sample consumption, and potential for automation. They are thus important tools that can assist a better understanding of the structure and function of chromatography media. In the long run, the results in this project may lead, via better chromatographic products, to better drugs and improved health. / Vätskekromatografi är en viktig teknik för tillverkning av biologiska läkemedel och används för alltifrån småskaliga analytiska applikationer till fullskalig produktion. I kromatografi separeras och renas målmolekylen (oftast ett protein), från andra komponenter och föroreningar genom att utnyttja molekylernas olika affinitet för det kromatografiska mediumet, vars fysikaliska och kemiska egenskaper har stor betydelse för hur separationen fungerar. För att kunna kontrollera och designa dessa egenskaper krävs effektiva analysmetoder. Strategin i den här avhandlingen var att utveckla metoder baserade på kärnmagnetisk resonans (NMR) spektroskopi för att karaktärisera flera viktiga fysikalisk-kemiska egenskaper. Anledningen till denna strategi är att mångsidigheten hos NMR – med dess kemiska och isotopiska specificitet, stora dynamiska omfång och direkta proportionalitet mellan NMR-signalens integralintensitet och koncentrationen av spinnbärande atomkärnor (t.ex. 1H, 13C, 31P och 15N) - ofta gör den till det bästa valet för både kvalitativa och kvantitativa tillämpningar. Dessa egenskaper hos NMR gjorde att vi kunde utveckla två kvantifieringsmetoder för kromatografimedia-ligander, dvs de funktionella grupperna som ger de specifika interaktioner som gör att molekylerna kan separeras. Dessutom har en ny metod för att mäta fördelningen av makromolekyler mellan de porösa kromatografiska pärlorna och den omgivande vätskan tagits fram. Metoden, som vi har valt att kalla size-exclusion quantification (SEQ) NMR, utnyttjar det faktum att det är möjligt att mäta molekylstorleksfördelningen genom att mäta motsvarande fördelning av självdiffusionskoefficienter, där den sistnämnda kan bestämmas med NMR. Resultaten från SEQ-NMR kan tolkas i termer av porstorleksfördelningar genom att använda lämpliga modeller. Slutligen studerade vi självdiffusion av små molekyler inuti porerna i kromatografiska pärlor. Resultaten gav nya insikter om vad som påverkar masstransporten i sådana system. De metoder som presenteras i denna avhandling är noggranna, precisa och på många sätt bättre än konventionella metoder när det gäller hastighet, låg provförbrukning och automatiseringspotential. De nya metoderna är därför viktiga verktyg som kan hjälpa till att ge en bättre förståelse av struktur och funktion hos kromatografimedia. I det långa loppet kan resultat från det här projektet kunna bidra till effektivare kromatografiska produkter, vilket i slutändan kan leda till bättre läkemedel och hälsa. / <p>QC 20170403</p>