<p>In this study, attempts were made to diversify the application of potato starch based biopolymer as foam-grade materials. To improve foamability, which is largely dependent on melt strength, it is possible to modify hydrolyzed starch based biopolymers by bulk modification with bi- and multi- functional epoxy chain extenders. The modification work was carried out using a twin screw extruder (TSE) and an internal batch mixer (Haake Mixer) with four different chain extenders. The modified blends were characterized by Parallel Plate Rheometry, DSC, Intrinsic Viscosity and SEM techniques. Finally, foamability of the modified blends was examined by using supercritical CO₂ as a physical blowing agent in a high-pressure batch vessel. Variables such as saturation pressure, saturation time and saturation temperature were adjusted to determine their influence on the cell morphology of the foamed parts.</p> <p>The multi-functional epoxy chain extenders effectively increased the bulk melt viscosity and reduced the crystalline content of both hydrolyzed starch based biopolymers. The intrinsic viscosity measurements were quantified the chain extension reaction, which primarily occurred in the PLA/AAC or PLA phase in both biopolymers and the starch phase made no contribution towards increased bulk melt viscosity. The multi-functional Joncryl^® ADR 4370S was the most effective chain extender for improving the stability of foams by yielding smaller cell size and higher cell density in comparison with the original biopolymer during the batch foaming process at 10 MPa saturation pressure and 30 min saturation time. The use of other chain extenders proved to be mostly ineffectual in producing uniform cellular structure in their corresponding modified biopolymer at those same processing conditions.</p> / Master of Applied Science (MASc)

京都大学 / 新制・課程博士 / 博士(農学) / 甲第24672号 / 農博第2555号 / 新制||農||1099(附属図書館) / 学位論文||R5||N5453(農学部図書室) / 京都大学大学院農学研究科応用生命科学専攻 / (主査)教授 小川 順, 教授 井上 善晴, 教授 森 直樹 / 学位規則第4条第1項該当 / Doctor of Agricultural Science / Kyoto University / DFAM

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Yes / By controlling the crystallization behavior of poly(lactic acid) (PLA) in the presence of a hydrazide nucleating agent (HNA), PLA-HNA foams with enhanced microcellular structures were prepared via supercritical CO2 foaming. It was found that HNA can self-assemble into fibrillar networks, inducing the crystallization of PLA on their surface, and "shish-kebab"crystalline structures with high crystallinity formed, which can be maintained during the whole foaming process. Incorporation of HNA promoted the formation of gt conformers, improved the amount of dissolved CO2, hindered the escape of CO2, and increased the viscoelasticity of PLA. Compared with neat PLA foam, for PLA-HNA foam, the average cell diameter decreased obviously, from 64.39 to 6.59 μm, while the cell density increased up to nearly three orders of magnitudes, from 6.82 × 106 to 4.44 × 109 cells/cm3. Moreover, lots of fibrillar structures appeared and entangled with each other on the cell wall of the foam. By forming such dense micropores and enhanced fibrillar structures, PLA foam was highly reinforced with significantly improved compressive strength. / This research was financially supported by National Natural Science Foundation of China (grant no. 51773122) and State Key Laboratory of Polymer Materials Engineering (grant no. sklpme2019-2-21).

京都大学 / 新制・課程博士 / 博士(農学) / 甲第24668号 / 農博第2551号 / 新制||農||1099(附属図書館) / 学位論文||R5||N5449(農学部図書室) / 京都大学大学院農学研究科応用生命科学専攻 / (主査)教授 小川 順, 教授 栗原 達夫, 教授 伊福 健太郎 / 学位規則第4条第1項該当 / Doctor of Agricultural Science / Kyoto University / DFAM

High levels of lactate are positively associated with the prognosis and mortality in patients with heart attack. Endothelial-to-mesenchymal transition (EndoMT) plays an important role in cardiac fibrosis. Here, we report that lactate exerts a previously unknown function that increases cardiac fibrosis and exacerbates cardiac dysfunction by promoting EndoMT following myocardial infarction (MI). Treatment of endothelial cells with lactate disrupts endothelial cell function and induces mesenchymal-like function following hypoxia by activating the TGF-β/Smad2 pathway. Mechanistically, lactate induces an association between CBP/p300 and Snail1, leading to lactylation of Snail1, a TGF-β transcription factor, through lactate transporter monocarboxylate transporter (MCT)-dependent signaling. Inhibiting Snail1 diminishes lactate-induced EndoMT and TGF-β/Smad2 activation after hypoxia/MI. The MCT inhibitor CHC mitigates lactate-induced EndoMT and Snail1 lactylation. Silence of MCT1 compromises lactate-promoted cardiac dysfunction and EndoMT after MI. We conclude that lactate acts as an important molecule that up-regulates cardiac EndoMT after MI via induction of Snail1 lactylation.

Controlling the surface morphology and degree of crystallinity of poly(L-lactic acid) (PLLA) substrates have recently attracted considerable attention because of their applications in cell adhesion, tissue engineering, and drug delivery. Several techniques have been used to fabricate PLLA substrates, some of which may be invalid because PLLA can degrade during fabrication processes. This dissertation provides the Langmuir-Blodgett (LB) technique as a mechanism for fabricating PLLA substrates at temperatures where PLLA degradation is uncommon. In order to fully understand surface morphologies of PLLA LB-films, studies of Langmuir monolayers at the air/water (A/W) interface using surface pressure-area (Pi-A) isotherm and Brewster angle microscopy (BAM) are vital. PLLA exhibits a first-order liquid expanded to condensed (LE/LC) phase transition with molar mass dependent critical phenomena, the first such observation for a homopolymer Langmuir monolayer. Atomic force microscopy (AFM) images of PLLA LB-films prepared in the LC phase exhibit well-ordered lamellar structures. Molar mass scaling of lamellar dimensions, x-ray reflectivity, and reflection absorption infrared spectroscopy (RAIRS) measurements on PLLA LB-films are consistent with PLLA existing as single molecule 10/3-helices at the A/W interface. Morphologies observed after collapse of the LC monolayer are dependent upon the collapse mechanism and subsequent thermal treatment. For temperatures below the LE/LC critical temperature (Tc), two mechanisms are identified for the formation of three dimensional structures: a buckling and stacking of lamellar monolayers on top of existing lamellae during constant compression rate experiments, and a modified nucleation and growth mechanism during isobaric area relaxation experiments. PLLA LB-films prepared in different Langmuir film phases at temperatures below Tc all contain lamellae with different surface roughnesses and similar helical content. Conventional thermal annealing studies on PLLA LB-films reveal that well-ordered lamellar features are destroyed after annealing the LB-films at bulk crystallization temperature through a melting-recrystallization process, which is confirmed by RAIRS and AFM. Our results may prove useful for studying critical behavior and experimentally testing scaling predictions for two dimensions, the development and testing of theories for crystallization in confined geometries, and separating the roles that roughness and crystallinity play in cell adhesion and spreading on biocompatible polymer surfaces. / Ph. D.

Poly(lactic acid) is biodegradable polymer derived from renewable resources and non-toxic, which has become most interested polymer to substitute petroleum-based polymer. However, it has low glass transition temperature and poor gas barrier properties to restrict the application on hot contents packaging and long-term food packaging. The objectives of this research are: (a) to reduce coagulation of graphene oxide/single-walled carbon nanotube (GOCNT) nanocomposite in poly(lactic acid) matrix and (b) to improve mechanical strength and oxygen barrier property, which extend the application of poly(lactic acid). Graphene oxide has been found to have relatively even dispersion in poly(lactic acid) matrix while its own coagulation has become significant draw back for properties of nanocomposite such as gas barrier, mechanical properties and thermo stability as well as crystallinity. Here, single-walled carbon nanotube was hybrid with graphene oxide to reduce irreversible coagulation by preventing van der Waals of graphene oxide. Mass ratio of graphene oxide and carbon nanotube was determined as 3:1 at presenting greatest performance of preventing coagulation. Four different weight percentage of GOCNT nanocomposite, which are 0.05, 0.2, 0.3 and 0.4 weight percent, were composited with poly(lactic acid) by solution blending method. FESEM morphology determined minor coagulation of GOCNT nanocomopsite for different weight percentage composites. Insignificant crystallinity change was observed in DSC and XRD data. At 0.4 weight percent, it prevented most of UV-B light but was least transparent. GOCNT nanocomposite weight percent was linearly related to ultimate tensile strength of nanocomposite film. The greatest ultimate tensile strength was found at 0.4 weight percent which is 175% stronger than neat poly(lactic acid) film. Oxygen barrier property was improved as GOCNT weight percent increased. 66.57% of oxygen transmission rate was reduced at 0.4 weight percent compared to neat poly(lactic acid). The enhanced oxygen barrier property was ascribed to the outstanding impermeability of hybrid structure GOCNT as well as the strong interfacial adhesion of GOCNT and poly(lactic acid) rather than change of crystallinity. Such a small amount of GOCNT nanocomposite improved mechanical strength and oxygen barrier property while there were no significant change of crystallinity and thermal behavior found. / Master of Science

Thermal processing has been used as a means of modifying the sensory aspects of wine. Cabernet Sauvignon wines were heated prior to dejuicing (3C per day from 25C to 42C) or after bottling (42C for 21 days) to determine the effects on total glycosides and glycosidic fractions. Total and phenol-free glycosidic concentrations in the wine and skins were quantified by analysis of glycosyl-glucose. Pre-dejuicing thermal vinification resulted in higher total glycosides (12%), phenol-free glycosides (18%), total hydroxycinnamates (16%), large polymeric pigments (LPP) (208%) small polymeric pigments (SPP) (41%), and lower monomeric pigments (42%) in wines. Skins had lower total glycosides (-16%), and no significant difference in phenol-free glycosides. Post-bottling heat treatment resulted in lower total (-15%) and phenol-free (-16%) glycosides, increased hue (25%), a 62% increase in LPP and a 29% decrease in monmeric pigments. A second study investigated the potential of enological spoilage microorganisms to affect wine aroma, flavor, and color. The activities of b-glucosidase were determined in model systems for fourteen strains of Brettanomyces bruxellensis yeast and nine strains of lactic acid bacteria (Oenococcus oeni). All Brettanomyces strains and seven Oenococcus strains exhibited enzymatic activity. B. bruxellensis b-glucosidase activity was primarily intracellular; O. oeni showed some extracellular activity. Yeasts and bacteria showing activity greater than 1000 nmole mL-1 g -1 for Brettanomyces, or 100 nmole mL-1 g -1 for Oenococcus, were evaluated for their effect on Viognier grape glycosides. Neither was active on native grape glycosides. / Master of Science

The purpose of the study was to evaluate the generalisability of the heart rate-blood lactate relationship determined in laboratory testing in comparison to running over ground. This plays a crucial role to prescribe exercise intensity from laboratory results. Ten well trained runners performed a maximal oxygen uptake (VO2max) pre-test and an incremental submaximal test performed at a two degrees inclined treadmill and a running track. Statistical analysis included student’s t-test of heart rate at interpolated blood lactate levels and comparison of second order polynomial regression lines. VO2max was 60,4 ± 6 ml/kg/min for men and 56,3 ± 4,3 ml/kg/min for women. There was no significant difference in heart rate at interpolated blood lactate of 3 and 4 mmol/L. There was no significant difference between heart rate values at any running velocity. A significant difference between blood lactate values was observed 14km/h (p=0,04). When considering blood lactate values up to 6mmol/L, heart rate-blood lactate relationships were similar. In conclusion, lactate threshold testing on treadmill through incremental test protocols on a two degrees incline gives similar heart rate- blood lactate relationship as running over ground and may be used to prescribe intensity in training performed over ground.