Aggregating performance measures considerably reduces the complexity of a performance evaluation system. This dissertation analyzes the nature and characteristics of the aggregation of performance measures in institutional settings of multiple tasks and multiple periods. In multi-task settings, the number of tasks restricts the feasibility of a statistically sufficient aggregation and the nature of an economically sufficient aggregation. Statistical sufficiency of aggregation can be achieved only by multi-dimensional aggregate measures, whose minimum dimensionality is given by the number of tasks. If the number of aggregate measures is less than the number of tasks, an economically sufficient aggregation incurs loss of information even if there is no loss of information through the likelihood ratio. The results support the use of multi-dimensional aggregate measures to preserve the information content of performance measures in multi-task agencies. In a multi-period setting, the inter-temporal correlations among performance measures restrict the feasibility of a statistically sufficient aggregation and the nature of an economically sufficient aggregation. When performance measures are inter-temporally correlated, there is no statistically sufficient aggregation and an economically sufficient aggregation of the basic measures depends on the effort level to induce. The optimal aggregation is characterized by the agent's characteristics and the economic situation of the agency as well as the statistical properties of performance measures. In a long-term contract with multiple tasks, the inter-temporal covariance risk has a monotonic impact on the endogenous allocation of effort through the optimal relative incentive rate. The inter-temporal covariance risk, as well as the within-period risk premium, prevents the first best allocation of effort from being endogenously achieved even if the first best allocation is feasible. / Accounting

Aggregative feeding is widespread in Lepidopteran larvae suggesting that this behavior serves on adaptive function. Many studies of the potential benefits of aggregative feeding in Lepidopteran larvae have been conducted. However, no studies have directly examined the benefits of cryptic larvae being both chemically defended and gregarious. Group feeding occurs disproportionately more in chemically defended larvae than in larvae that have no chemical defense. Most of these larvae are cryptic when they are most highly aggregated and most vulnerable to predation. In this study, the benefits of group feeding in terms of decreased predation were explored in first instar larvae of pipevine swallowtail larvae, Battus philenor, a species that exhibits chemical sequestration. Contrary to our expectation, we found that groups of larvae fed a diet with high levels of the toxin aristolochic acid, which they sequester naturally and use as a defense against natural enemies, had significantly lower survivorship due to predation in both the field and in the laboratory experiments compared to groups of larvae fed a diet with low aristolochic acid content. We also found that aristolochic acid does not deter the generalist predator Hippodamia convergens, the ladybird beetle, suggesting that this compound is not a universal predator deterrent as previously assumed. Thus, instead of finding a benefit to group feeding and chemical defense in cryptic larvae, we have found a negative impact of group feeding in this population of B. philenor. Based on this evidence, we speculate that other benefits of group feeding might be outweighing the negative consequences of increased predation during the first instar. Future research on chemical defense, aposematism, and aggregative feeding should take into consideration that chemical defenses might not be universally effective against all natural enemies.

The functional group composition of acid polysaccharides was determined after isolation using cross-flow ultrafiltration, radiolabeling with 234Th(IV) and other isotopes, and separation using isoelectric focusing (IEF) and polyacrylamide gel electrophoresis (PAGE). Phosphate and sulphate concentrations were determined from cultured bacterial and phytoplankton colloid, particulate and colloidal samples collected from the Gulf of M??xico (GOM). Characterization of the 234Th(IV)-binding biomolecule was performed using ion chromatography (IC), and gas chromatography-mass spectrometry (GC-MS). Radiotracer experiments and culture experiments were conducted in determining the binding environment of the 234Th(IV)-binding ligand (i.e., sorption onto suspended particles), as well as the origin of the ligand in seawater systems. In all samples, 234Th(IV) isoelectric focusing profiles indicated that 49% to 65% of the 234Th(IV) labeled EPS from Roseobacter gallaeciensis, Sagittula stellata, Emiliania huxleyi, Synechococcus elongatus and GOM Station 4-72m was found at a pHIEF of 2 in the IEF spectrum. The carboxylic acid group appeared at the same pHIEF as 234Th(IV) for EPS from Roseobacter gallaeciensis, Emiliania huxleyi, Synechococcus elongatus and GOM colloidal organic matter sample. The phosphate group appeared at the same pHIEF as 234Th(IV) for EPS from Roseobacter gallaeciensis, and Synechococcus elongatus sample. The sulphate group was found at the same pHIEF as 234Th(IV) for EPS from S. elongatus and GOM colloidal organic matter sample. The total polysaccharide content was only 14% and 8%, uronic acids were approximately 5.4% and 87.1%, and total protein content was 2.6% and 6.2% of total carbon content of Sagittula stellata and Synechococcus elongatus, respectively. Monosaccharides identified in both Sagittula stellata and Synechococcus elongatus were galactose, glucose, and xylose in common. In addition, Sagittula stellata contained mannose and Synechococcus elongatus had galactoglucuronic acid. Thus, depending on the species, the size, structural composition, and functional groups of the 234Th(IV)-binding, acidic polysaccharides will vary. From these observations, it is concluded that the steric environment and not necessarily the exact functional group might actually be responsible for thorium-234 complexation to macromolecular organic matter. This research helped to improve our understanding of the observed variability in POC/234Th ratios in the ocean and provided insights into factors that regulate organic carbon export fluxes.

The solution of large and sparse eigenvalue problems arising from the discretization of the diffusion equation is considered. The multigroup diffusion equation is discretized by means of the Nodal expansion Method (NEM) [9, 10]. A new formulation of the higher order NEM variants revealing the true nature of the problem, that is, a generalized eigenvalue problem, is proposed. These generalized eigenvalue problems are solved using the Jacobi-Davidson (JD) method [26]. The most expensive part of the method consists of solving a linear system referred to as correction equation. It is solved using Krylov subspace methods in combination with aggregation-based Algebraic Multigrid (AMG) techniques. In that context, a particular aggregation technique used in combination with classical smoothers, referred to as oblique geometric coarsening, has been derived. Its particularity is that it aggregates unknowns that are not coupled, which has never been done to our knowledge. A modular code, combining JD with an AMG preconditioner, has been developed. The code comes with many options, that have been tested. In particular, the instability of the Rayleigh-Ritz [33] acceleration procedure in the non-symmetric case has been underlined. Our code has also been compared to an industrial code extracted from ARTEMIS.

Beta lactoglobulin (βlg) is a major whey protein in the bovine milk. Upon heating above its denaturation temperature (which is pH-dependent), this globular protein undergoes molecular changes leading to the irreversible aggregation. Depending on the pH and ionic strength, either protein aggregates or gels exhibiting various structures and morphologies have been described. Very recently, it was found that in a narrow range of the pH close to iso-electric point, stable suspensions of rather monodisperse spherical particles with a radius of about a hundred nanometers were formed. These spherical particles which were called microgels might be of special interest for the production of liquid dispersions of β-lactoglobulin aggregates exhibiting various functionalities for food applications. The project on which I report here was a collaboration with the Nestlé Reseach Center (Lausanne, Switzerland) and its objective was to study the formation and structural properties of the microgels in different environmental conditions. The first part of the project is to study the influence of the pH on the formation of microgels. Stable suspensions of protein microgels are formed by heating salt free βlg solutions at concentrations up to about C = 50 g.L-1 if the pH is set within a narrow range between 5.75 and 6.1. The internal protein concentration of these spherical particles is about 150 g.L-1 and the average hydrodynamic radius decreases with increasing pH from 200 nm to 75 nm. The formation of the microgels leads to an increase of the pH, which is a necessary condition to obtain stable suspensions. The spontaneous increase of the pH during microgel formation leads to an increase of their surface charge density and inhibits secondary aggregation. This self-stabilization mechanism is not sufficient if the initial pH is below 5.75 in which case secondary aggregation leads to precipitation. Microgels are no longer formed above a critical initial pH, but instead short curved protein strands are obtained with a hydrodynamic radius of about 15-20 nm. The second part of the work is about the formation of microgels driven by the addition of calcium ions. We found that stable suspensions of spherical protein particles (microgels) can be formed by heating βlg solutions in the presence of calcium ions. The conditions for the calcium induced microgel formation were studied at different pH between 5.8 and 7.5 and different protein concentrations between 5 - 100 g.L-1. The results showed that a critical molar ratio of calcium to proteins (R) is needed to form microgels independent of the protein concentration. R decreases with decreasing pH. The microgels have a hydrodynamic radius ranging from 100 to 300 nm and their internal protein concentration ranges from 0.2 to 0.45 g.mL-1. The determination of calcium bound to the microgels suggests that the crucial parameter for microgel formation is the net charge density of the native proteins. The microgel suspensions are stable in a narrow range of R but aggregate at higher Ca2+ concentrations. In the third part, we continued to investigate the formation of microgels at initial step and how it is growing in the presence of calcium ions. We have proposed a mechanism of formation of blg microgels which follows a nucleation and growing process. The nucleus with define size are formed at the initial state and that is growing in size to reach final size of aggregates. At low calcium concentration it stabilizes and then we obtain a stable suspension of microgels. But at high concentrations, the microgels here can jump to form big aggregates and finally a gel. The structure of gel from microgels is heterogenous at the scale of confocal microscopy and similar to those formed in the presence of NaCl 0.3 M. However the process of formation of these gels is not the same...

Ten polyQ (polyglutamine) diseases constitute a group of hereditary, neurodegenerative, lethal disorders, characterized by neuronal loss and motor and cognitive impairments. The only common molecular feature of polyQ disease-associated proteins is the homopolymeric polyglutamine repeat. The pathological expansion of polyQ tract invariably leads to protein misfolding and aggregation, resulting in formation of the fibrillar intraneuronal deposits (aggregates) of the disease protein. The polyQ-related cellular toxicity is currently attributed to early, small, soluble aggregate species (oligomers), whereas end-stage, fibrillar, insoluble aggregates are considered to be benign. In the complex cellular environment aggregation and toxicity of mutant polyQ proteins can be affected by both the sequences of the corresponding disease protein (factors acting in cis) and the cellular environment (factors acting in trans). Additionally, the nucleus has been suggested to be the primary site of toxicity in the polyQ-based neurodegeneration. In this study, the dynamics and structure of nuclear and cytoplasmic inclusions were examined to determine the intrinsic and extrinsic factors influencing the cellular aggregation of atrophin-1, a protein implicated in the pathology of dentatorubral-pallidoluysian atrophy (DRPLA), a polyQ-based disease with complex clinical features. Dynamic imaging, combined with biochemical and biophysical approaches revealed a large heterogeneity in the dynamics of atrophin-1 within the nuclear inclusions compared with the compact and immobile cytoplasmic aggregates. At least two types of inclusions of polyQ-expanded atrophin-1 with different mobility of the molecular species and ability to exchange with the surrounding monomer pool coexist in the nucleus of the model cell system, neuroblastoma N2a cells. Furthermore, our novel cross-seeding approach which allows for monitoring of the architecture of the aggregate core directly in the cell revealed an evolution of the aggregate core of the polyQ-expanded ATN1 from one composed of the sequences flanking the polyQ domain at early aggregation phases to one dominated by the polyQ stretch in the later aggregation phase. Intriguingly, these changes in the aggregate core architecture of nuclear and cytoplasmic inclusions mirrored the changes in the protein dynamics and physico-chemical properties of the aggregates in the aggregation time course. 2D-gel analyses followed by MALDI-TOF MS (matrix-assisted laser desorption/ionization time of flight mass spectrometry) were used to detect alterations in the interaction partners of the pathological ATN1 variant compared to the non-pathological ATN1. Based on these results, we propose that the observed complexity in the dynamics of the nuclear inclusions provides a molecular explanation for the enhanced cellular toxicity of the nuclear aggregates in polyQ-based neurodegeneration. / Zehn Polyglutamin-basierte (polyQ) Erkrankungen bilden eine Gruppe von erblichen, neurogenerativen, letalen Krankheiten, die durch neuronalen Zellverlust und motorischen und kognitiven Störungen charakterisiert sind. Die mit polyQ Erkrankungen-assoziierten Proteine enthalten eine repetitive Abfolge der Aminosäure Glutamin (den polyQ-Bereich, der die einzige gemeinsame Sequenz aller polyQ Proteine ist). Durch die pathologische Verlängerung des PolyQ-Bereiches bekommen die polyQ Proteine eine Neigung zu aggregieren, und bilden damit unlösliche, fibrilläre Ablagerungen in Neuronen. Es wird vermutet, dass die sich anfangs bildenden kleinen löslichen Ablagerungsvorstufen (Oligomere) toxisch, und die später gebildeten, unlöslichen fibrillären Aggregate jedoch harmlos sind. Im zellulären Milieu werden Aggregations-Prozess und Toxizität durch die polyQ-flankierenden (benachbarten) Sequenzen des jeweiligen Proteins (in cis agierende Faktoren) und unterschiedliche zelluläre Proteine (in trans agierende Faktoren) beeinflusst. Außerdem kann die nukleare Lokalisation der polyQ Spezies mit verlängertem PolyQ-Bereich ihren toxischen Effekt erhöhen. Die Verlängerung des polyQ-Bereiches im Protein Atrophin-1 (ATN1) über 49 Glutamine hinaus, verursacht Dentatorubro-Pallidoluysische Atrophie (DRPLA), eine progressive Erkrankung, die sich durch Muskelzuckungen, Epilepsie, Ataxie und Demenz äußern kann. In dieser Arbeit wurden die dynamischen Eigenschaften und die Struktur der nuklearen und zytoplasmatischen Aggregate systematisch untersucht, um die Faktoren, die das Aggregations-Verhältnis der Atrophin-1 in cis und in trans beeinflussen zu erkennen. Mittels des mit biochemischen und biophysikalischen Analysen kombinierten Dynamic Imaging, konnte gezeigt werden, dass Aggregate der mutierten ATN1 in vivo, im Säugetier-Zellen Model (Neuroblastoma N2a Zellen), sich von den frühen, löslichen zu später gebildeten unlöslichen Spezies entwickeln. Die Resultate der im Rahmen dieser Arbeit entwickelten Cross-Seeding Methode zeigen, dass das Aggregatcore der früheren Aggregate von den polyQ-Bereich flankierenden Sequenzen kontrolliert wurde, während die Transformation zu unlöslichen Aggregaten von dem expandierten polyQ-Bereich dominiert ist. Außerdem, wie die 2D-Gelelectrophorese und die MALDI-TOF MS (matrix-assisted laser desorption/ionization time-of-flight mass spectrometry) Analysen beweisen, beeinflusst die Länge des PolyQ-Bereiches die Interaktionen mit zellulären Proteinen. Wir haben auch festgestellt, dass das in nuklearen Aggregaten abgelagerte polyQ-expandierte ATN1 im Vergleich zu den zytoplasmatischen Ablagerungen eine erhöhte Mobilität aufwies. Mindestens zwei Aggregat-Typen mit unterschiedlichen Mobilitäten von mutierten ATN1 koexistieren im Zellkern der N2a Zellen, während im Gegensatz dazu das Protein in den kompakten zytoplasmatischen Aggregaten ausnahmslos immobil erscheint. Dies stellt eine molekulare Erklärung der erhöhten Toxizität der nuklearen ATN1-Aggregate dar.

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 a theoretical study on optical properties of molecular materials. Special emphasis has been put on the influence of solvent environment, nuclear vibrations, and aggregation effects on molecular properties like linear and nonlinear polarizabilities, one- and two-photon absorption probabilities. All calculations have been performed by means of time independent and dependent quantum chemical methods at the Hartree-Fock and density functional theory levels. Solvation models that include both long range and short range interactions have been employed for calculations of optical properties of molecules in solutions. Pure vibrational and zero-point vibrationally averaged contributions have been taken into account for linear and nonlinear polarizabilities. The linear coupling model is applied to simulate vibronic profiles of optical absorption spectra. The computational strategies described in this thesis are very useful for the design of efficient molecular photonic materials. More specifically, the nonmonotonic behavior of the solvatochromic shifts and the first hyperpolarizability of para-nitroaniline (pNA) with respect to the polarity of the solvents have been theoretically confirmed for the first time. The significant contributions of the hydrogen bonding on the electronic structures of pNA are revealed. Vibrational contributions to the linear and nonlinear polarizabilities of methanol, ethanol and propanol have been calculated both at the static limit and in dynamic optical processes. The importance of vibrational contributions to certain nonlinear optical processes have been demonstrated. A series of end-capped triply branched dendritic chromophores have been studied with the result that their second order nonlinear optical properties are found strongly dependent on the mutual orientations of the three chromophores, numbers of caps and the conjugation length of the chromophores. Several possible mechanisms for the origin of the Q-band splitting of aluminum phthalocyanine chloride have been examined. Calculated vibronic one-photon absorption profiles of two molecular systems are found to be in very good agreement with the corresponding experiments, allowing to provide proper assignments for different spectral features. Furthermore, effects of vibronic coupling in the nonradiative decay processes have been considered which helps to understand the aggregation enhanced luminescence of silole molecules. The study of molecular aggregation effects on two-photon absorption cross sections of octupolar molecules has highlighted the need to use a hybrid method that combines density functional response theory and molecular dynamics simulations for the design of molecular materials. / QC 20100820

Inter-molecular interactions have significant influences on linear and nonlinear optical properties of molecules including one- and two-photon absorptions, emissions, and various high order nonlinear polarizations. The related investigation has become an active and challenging research area. The theoretical structure-to-property relationship obtained from quantum chemical calculations of single organic conjugated molecules often can not be directly applied to real materials in condensed phases. One has to consider the effect of environment, that is, inter-molecular interactions, where the model systems experience in real experiments or applications. The change of molecular conformations under all kinds of interactions and its effects on linear and nonlinear optical properties are the central issue of this thesis. Special attentions have been paid to symmetrical diamino substituted distyrylbenzene chromophores with different torsional angles, two dipolar merocyanine dyes of various orientations, two isomers of a V-shaped 2-hydroxypyrimidine derivative and their various dimers, and the structural fluctuations of interacting polar chromophores in solutions. Quantum chemical methods in combination with molecular dynamics simulations have been employed to study molecular conformations and optical properties in solutions, in particular the solvent and aggregation effects on one- and two-photon absorption. More specifically, time-dependent density functional theory has been used for all electronic calculations, while the polarizable continuum model and supermolecule approach have also been employed to take into account solvent effects. Moreover, the propagation of an ultrashort laser pulse through a one-dimensional asymmetric organic molecular medium which possesses large permanent dipole moments has been simulated by solving full Maxwell-Bloch equations using predictor-corrector finite-difference time-domain method. We have focused on the supercontinuum generation of spectra and the formation of attosecond pulses. / QC20100630

Denna undersökning gjordes för att studera solitära steklars boplatsval speciellt med avseende på spatiala mönster. Aggregat av lämpliga bohål (bibatterier) tillverkades och gjordes tillgängliga förfrilevande steklar. Resultatet visade att steklar tenderar att anlägga bon i närheten av andra stekelbon. Ingen tendens fanns att anlägga bon i centralt belägna positioner. Steklarna verkar också föredra att anlägga bon till vänster om en tänkt mittllinje på bibatterierna. Aggregation kan vara ett sätt att undgå parasitering och predation vid boplatsen. Om detta orsakade aggregationstendensen var det dock något oväntat att inte också en central tendens kunde påvisas. Att steklarna föredrog bohål i bibatteriernas vänstra del är svårt att förklara.