Gravimetric analysis was used to determine the release rates and longevities of several designs of pheromone dispensers for mating disruption of leafrollers and codling moth, Cydia pomonella (Linneaus). Release rates were described by linear equations for at least four months, but by the end of the season release rates tended to become erratic. Biocontrol’s red-brown codling moth dispenser lasted for up to four months, and one application of the dispenser in early May should control codling moth for the entire season in Virginia apple orchards. Ecogen and Hercon leafroller dispensers lasted for a shorter time than the codling moth dispensers and would require two applications per season to provide the best control of their target pests. In a commercial northern Virginia apple orchard, the effects of pheromone trap height and pheromone dispenser height on captures of the tufted apple bud moth, Platynota idaeusalis (Walker), were studied. Low traps (2.0 m) were more sensitive than high traps (4.5 m) for monitoring tufted apple bud moth. The number of moths caught in 1994 and 1995 in a two-hectare mating disruption plot with pheromone dispensers placed in the upper third of the tree was not significantly different from the number caught in a plot with pheromone dispensers placed at head height. Fruit damage was very high in both pheromone plots in 1994, but by 1995 it appeared that mating disruption was able to reduce fruit damage due to leafroller larvae. / Master of Science

When severe copper pitting problems impacted customers at a large utility, studies were begun to attempt to diagnose the problem and identify potential solutions. A series of tests were conducted to characterize the nature of pitting. Desktop comparisons of pinhole leak frequency and treatment practices at nearly utilities were also documented to identify treatment factors that might be influencing the initiation and propagation of leaks. Factors identified included the presence of relatively high levels of free chlorine and aluminum in the distribution system. Experiments were conducted to examine the effect of these constituents on copper pitting under stagnant and flow conditions. That led to discovery of a synergistic redox reaction between chlorine, aluminum solids, and copper metal as evidenced by increased chlorine decay rates, non-uniform corrosion, and rising corrosion potentials. Temperature changes had been suspected to increase copper pitting frequency and copper release to drinking water. Experiments examined the effect of temperature gradients on copper pipe corrosion during stagnant conditions. The pipe orientation in relation to the temperature gradient determined whether convective mixing would occur, which influenced temperature gradients within the pipe. This work is the first to demonstrate that temperature gradients lead to thermogalvanic currents, influences copper leaching and scale type. Iron release from corroding water mains is another concern of many water utilities, but little is known about chemistry factors that influence the problem. In laboratory experiments, higher levels of silica caused more iron release to the water and decreased the size of suspended iron particles. Silica levels also changed during the experiment: it decreased through incorporation into a dense scale, and increased by release from cast iron during corrosion. Silica slightly decreased iron corrosion rates near the end of this 6-month test. / Master of Science

Nitrogen deficiency is characteristic of many mid-rotation loblolly pine (Pinus taeda L.) plantations in the Piedmont region of the southeastern USA. Fertilization with urea is the most common method used to correct this deficiency. Previous studies show that urea fertilization produces a rapid pulse of available nitrogen (N) with only a portion being utilized by plantation trees. Controlled release fertilizers release available N more slowly over a longer period of time and therefore may result in greater uptake efficiency. The objective of this study was to compare Nitroform®, a urea-formaldehyde controlled release N fertilizer versus urea and a control by measuring the effects of the two fertilizer treatments on N availability and loss as: total KCl extractable-N, total ion exchange membrane-N (IEM-N), N mineralization, and N volatilization, in a mid-rotation loblolly pine plantation in the Piedmont of Virginia. In addition, mid-summer and mid-winter fertilizations were compared to assess fertilizer uptake as a function of season. After the summer fertilization, Nitroform® significantly increased total KCl-extractable N, IEM-N, and N mineralization for two to three months over urea and the control. Three hundred times more N volatilized from urea than from controlled release Nitroform®. Interestingly, seven months after the summer application, the controlled release Nitroform® showed marked immobilization for three months while urea demonstrated greater N mineralization. After the winter application, fertilization with urea demonstrated greater soil inorganic N concentrations for two to three months over Nitroform®, very little N was immobilized, and volatilization was only 10 times that of Nitroform®. After summer and winter fertilizations, both fertilizer treatments significantly increased soil inorganic N concentrations and N volatilization over controls, however did not significantly increase N mineralization over controls when average response was tested over the entire sampling period. In addition to the fertilizer effects measured, a thinning only treatment was also incorporated into this study with soil N-availability indices compared to a control with no thinning or fertilization. The results from the thinning only treatment demonstrated no significant increases over the control in total KCl extractable-N, IEM-N, N-mineralization, or N volatilization when average responses were tested over the entire sampling period. / Master of Science

Yes / The molecular stress function model with convective constraint release (MSF with CCR) constitutive model [J. Rheol. 45 (2001), 1387] is capable of fitting all viscometric data for IUPAC LDPE, with only two adjustable parameters (with difference found only on reported ¿steady-state¿ elongational viscosities). The full MSF with CCR model is implemented in a backwards particle-tracking implementation, using an adaptive method for the computation of relative stretch that reduces simulation time many-fold, with insignificant loss of accuracy. The model is shown to give improved results over earlier versions of the MSF (without CCR) when compared to well-known experimental data from White and Kondo [J. non-Newt. Fluid Mech., 3 (1977), 41]; but still to under-predict contraction flow opening angles. The discrepancy is traced to the interaction between the rotational dissipative function and the large stretch levels caused by the contraction flow. A modified combination of dissipative functions in the constraint release mechanism is proposed, which aims to reduce this interaction to allow greater strain hardening in a mixed flow. The modified constraint release mechanism is shown to fit viscometric rheological data equally well, but to give opening angles in the complex contraction flow that are much closer to the experimental data from White and Kondo. It is shown (we believe for the first time) that a constitutive model demonstrates an accurate fit to all planar elongational, uniaxial elongational and shear viscometric data, with a simultaneous agreement with this well-known experimental opening angle data. The sensitivity of results to inaccuracies caused by representing the components of the deformation gradient tensor to finite precision is examined; results are found to be insensitive to even large reductions in the precision used for the representation of components. It is shown that two models that give identical response in elongational flow, and a very similar fit to available shear data, give significantly different results in flows containing a mix of deformation modes. The implication for constitutive models is that evaluation against mixed deformation mode flow data is desirable in addition to evaluation against viscometric measurements.

This study seeks to develop smart hydrogel formulations for injectable controlled drug delivery from Pluronics to enhance patients compliance, decrease side effects, reduce dose and frequency. A biocompatible copolymer, Pluronic F127 was probed as the main ingredient for the injectable systems owing its low gelation concentration and ease of modification the system properties through excipients addition. The matrix properties were studied through a series of thermal, rheological and structural (SAXS/SANS) experiments as a function of concentration and shear rate, covering both static and dynamic environments. It has shown that gelled viscosity (and structure) can be critically controlled by shear rate and the structures recorded do not match those predicted for sheared colloids. Two further Pluronics F68 and F108, were studied showing similar but shifted gelation properties to F127. Effects of additives were studied by introducing different Mw PEGs and a model hydrophobic drug ‘ibuprofen’ to a F127 20% formulation. PEGs addition effects on the system properties and gelation transition were largely dependent on the Mw used in the blend, which became more prominent with increasing chain length. Ibuprofen’s addition has resulted in reduced gelation temperature and smaller hard spheres without having a great effect on the system rheological properties compared to neat gels. Blends containing both additives PEG and ibuprofen exhibited a synergistic effect, where comparisons show that Ibuprofen had the largest effect on the blends lowering gelation boundaries and slightly increasing the size of the hard spheres indicating the necessity of full characterisation of the formulation with any API.

付記する学位プログラム名: 社会を駆動するプラットフォーム学卓越大学院プログラム / 京都大学 / 新制・課程博士 / 博士(農学) / 甲第25317号 / 農博第2583号 / 新制||農||1104(附属図書館) / 学位論文||R6||N5489 / DGAM / 京都大学大学院農学研究科森林科学専攻 / (主査)教授 北島 薫, 教授 小野田 雄介, 教授 井鷺 裕司 / 学位規則第4条第1項該当 / Doctor of Agricultural Science / Kyoto University / DGAM

Les liposomes sont des nanovecteurs polyvalents et prometteurs quant à leur utilisation dans plusieurs domaines. Il y a une décennie, un nouveau type de liposome constitué d’amphiphiles monoalkylés et de stérols est né fortuitement dans notre groupe. Ils sont nommés Stérosomes puisqu’ils contiennent une grande proportion de stérols, entre 50 et 70 mol %. Les objectifs de cette thèse sont de développer de nouvelles formulations de Stérosomes ayant des caractéristiques spécifiques et d’acquérir une compréhension plus profonde des règles physicochimiques qui dictent leur comportement de phase. Nous avons spécifiquement examiné le rôle de motifs moléculaires des stérols, de la charge interfaciale et de la capacité à former des liaisons H dans les interactions intermoléculaires menant à l’autoassemblage. Le comportement de phase a été caractérisé par calorimétrie différentielle à balayage (DSC), par spectroscopie infrarouge (IR) et par spectroscopie de résonance magnétique nucléaire du deutérium (²H NMR). Premièrement, nous avons établi certaines corrélations entre la structure des stérols, leur tendance à former des bicouches fluides en présence d'amphiphile monoalkylé et la perméabilité des grandes vésicules unilamellaires (LUV) formées. La nature des stérols module les propriétés de mélange avec de l’acide palmitique (PA). Les stérols portant une chaîne volumineuse en position C17 sont moins aptes à induire des bicouches fluides que ceux qui ont une chaîne plus simple, comme celle du cholestérol. Un grand ordre de la chaîne alkyle de PA est un effet commun à tous les stérols investigués. Il a été démontré que la perméabilité des LUV peut être contrôlée en utilisant des stérols différents. Cependant, ces stérols n’ont aucun impact significatif sur la sensibilité des Stérosomes au pH. Afin de créer des liposomes qui sont sensibles au pH et qui ont une charge positive à la surface, des Stérosomes composés de stéarylamine et de cholestérol (Chol) ont été conçus et caractérisés. Il a été conclu que l’état de protonation de l’amine, dans ce travail, ou du groupe carboxylique, dans un travail précédent, confère une sensibilité au pH et détermine la charge à la surface du liposome. Les premiers Stérosomes complètement neutres ont été fabriqués en utilisant un réseau de fortes liaisons H intermoléculaires. Le groupe sulfoxyde est capable de former de fortes liaisons H avec le cholestérol et les molécules d’eau. Une bicouche fluide métastable a été obtenue, à la température de la pièce, à partir d'un mélange équimolaire d’octadécyl méthyl sulfoxyde (OMSO) et de Chol. Ce comportement distinct a permis d’extruder le mélange pour former des LUV à la température de la pièce. Après 30 h, le temps de vie de la phase métastable, des Stérosomes stables et imperméables existaient toujours sous une forme solide. Un diagramme de température-composition a été proposé afin de résumer le comportement de phase des mélanges d’OMSO/Chol. Finalement, nous avons élaboré des Stérosomes furtifs en incorporant du polyéthylène glycol (PEG) avec une ancre de cholestérol (PEG-Chol) à l’interface de Stérosomes de PA/Chol. Jusqu’à 20 mol % de PEG-Chol peut être introduit sans perturber la structure de la bicouche. La présence du PEG-Chol n’a aucun impact significatif sur la perméabilité de la LUV. L'encapsulation active de la doxorubicine, un médicament contre le cancer, a été réalisée malgré la faible perméabilité de ces LUV et la présence du PEG à l’interface. L’inclusion de PEG a modifié considérablement les propriétés de l’interface et a diminué la libération induite par la variation de pH observée avec des LUV nues de PA/Chol. Cette formulation inédite est potentiellement utile pour l’administration intraveineuse de médicaments. / Liposomes are promising and versatile nanocarriers suitable for potential applications in many fields. A decade ago, a new type of liposomes formed from monoalkylated amphiphiles and sterols was born somehow fortuitously in our group. They are referred to as Sterosomes, because they contain a large proportion of sterols, between 50 and 70 mol %. The objectives of the present thesis are to develop novel Sterosome formulations with specific features, and to gain a deeper understanding of the physicochemical rules that dictate their phase behavior. We have specifically examined the role of the molecular features of sterols, of the interfacial charges and of the H-bond capacity in the intermolecular interactions leading to the self-assembly. The phase behavior was characterized by differential scanning calorimetry (DSC), infrared spectroscopy (IR), and nuclear magnetic resonance spectroscopy of deuterium (2H NMR). First, we have established some correlations between the structure of the sterols, the propensity to form fluid bilayers, and the permeability of the resulting large unilamellar vesicles (LUVs). The nature of the sterol modulates the properties of the mixture with palmitic acid (PA). Sterols bearing a bulky tail chain at C17 are less capable to induce fluid bilayers than those with a non-bulky tail chain, like that of cholesterol. A large ordering of the alkyl chain of PA is an effect exhibited by all of the investigated sterols. It is shown that the permeability of the LUVs can be controlled using different sterols. However, these sterols have no significant impact on the pH-sensitivity of Sterosomes. In order to create liposomes that are pH-sensitive and that have a positive surface charge, Sterosomes composed of stearylamine and cholesterol (Chol) were designed and characterized. It is concluded that the protonation/deprotonation state of the amine (in this work) and carboxylic acid (in previous work) groups confers the pH-sensitivity and determines the surface charge of the liposomes. The first completely neutral Sterosomes were crafted based on the creation of strong intermolecular hydrogen bond networks. The sulfoxide group was capable of forming strong hydrogen bonds with cholesterol and water molecules. In an equimolar octadecyl methyl sulfoxide (OMSO)/Chol mixture, a metastable fluid bilayer was obtained at room temperature. This distinct phase behavior allowed extruding the mixtures to form LUVs at room temperature. After 30 h, the life-time of the metastable phase, stable and impermeable Sterosomes still existed in the solid form. A temperature–composition diagram was proposed to summarize the phase behavior of OMSO/Chol mixtures. Finally, a further step was made to prepare “stealth” Sterosomes by incorporating polyethylene glycol (PEG) with a cholesterol anchor (PEG-Chol) at the interface of PA/Chol Sterosomes. Up to 20 mol % PEG-Chol can be introduced without disturbing the bilayer structure. The presence of PEG-Chol had no significant impact on the permeability of the resulting LUVs. Active-loading of an anti-cancer drug, doxorubicin, can be achieved despite the low permeability of these LUVs and the presence of the PEG at the interface. The inclusion of PEG modified considerably the interface properties and decreased significantly the pH-triggered release observed with naked PA/Chol LUVs. This novel formulation is potentially useful for the application of intravenous administration in the drug delivery field.

The last couple of years the trend within the software industry has been to releasesmaller software updates more frequent, to overcome challenges and increase flexibility, to alignwith the swiftly changing industry environment. As an effect, we now see companies moving over tocapitalizing on subscriptions and incremental releases instead of charging for upgrades. By utilizingneo-institutional theory and Oliver’s (1991) strategic response theory, an enterprise systemsvendor’s response to the emerging DevOps trend can be determined.

To assess acute performance-related effects of foam rolling, this study investigated the immediate effects of a standard foam rolling protocol on explosive strength of the plantarflexors and alpha motor neuron excitability in the soleus. Explosive strength was measured via vertical jump height (JUMP) and the Reactive Strength Index (RSI) obtained from a single leg drop jump. Alpha motor neuron excitability was measured by H reflex amplitude as H wave to M wave ratio (HM) obtained from the soleus muscle. JUMP and RSI measures were analyzed from nineteen subjects (12 male, 7 female) HM data were analyzed from 15 subjects (9 male, 6 female). Subjects attended one day of practice and instruction for the single leg drop jump and one day for data collection. One leg was randomly assigned to be the test leg (FL) and the other as the control (NL). The reported dominant leg and gender were also recorded for each subject. Subjects performed two single leg drop jumps per leg from a box height of 30 cm and then 10 soleus H reflexes were obtained. The intervention, which followed standard professional guidelines, consisted of 2.5 minutes of foam rolling for the FL and rest for the NL, followed by a 5 minute warm up on a cycle ergometer. The best jump and the average HM ratio were chosen for analysis. For each variable a post/pre ratio was calculated for statistical analysis. A 2x2x2 factor ANOVA with repeated measures on both factors was used for each variable. Analysis revealed no statistically significant differences for any of the variables, either as main effects or any of the interaction effects. Subjects trended towards a slightly larger post-intervention decrease in JUMP and RSI for the FL than the NL but this was not significant. It was concluded that a 2.5 minute intervention of foam rolling had no acute effect on explosive strength of the plantarflexors or alpha motor neuron excitability of the soleus. / text

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