Crystal Growth by Electrodeposition with Supercritical Carbon Dioxide Emulsion

葉黃素為護眼保健食品的重要成分，屬於脂溶性營養素，因此限制了保健食品之應用。本研究目的為開發水溶性較高的葉黃素酯，以提升在保健食品之實用性。首先將廠商提供的原料進行超音波攪拌萃取葉黃素酯，溶劑為正己烷、丙酮及四氫呋喃，溶固比為 80，萃取時間為 60 分鐘，結果顯示四氫呋喃萃出物含有 25.3 % 葉黃素。將四氫呋喃萃出物進行甲醇-正己烷(1:1, v/v)的液液萃取，可將葉黃素提純至 44.7 %，但水中溶離率幾近於零。再將提純之材料加入 β - 環狀糊精(β-cyclodextrin, β-CD)進行超臨界二氧化碳抗溶結晶(supercritical carbon dioxide antisolvent, SAS)，產製易溶水的葉黃素酯包覆物。在固定溫度 55 ºC、抗溶時間 10 min、進料流速 0.5 ml/min 下、探討乳化劑種類 (Tween 20、Tween 80)、乳化劑含量(15 %、25 %)、攪拌時間(0.5、2、4、6 hr) 、壓力(120、140 bar)、提純材料和 β- 環狀糊精之進料量比(Wext/Wβ-CD) (0.5、1、2)對包覆物之總產率、葉黃素濃度、包覆率、回收率以及溶離率的影響。結果顯示乳化劑以 25% tween 80、攪拌時間 4 hr、壓力 140 bar、 Wext/Wβ-CD 0.5 可得較佳之包覆效率 77.9 % 、回收率 43.6 % 及溶離率 30.6 %，沉澱物總產率 69.0% 、葉黃素濃度 94.1 mg/g。因此固定上述條件，以應答曲面實驗設計(response surface methodology, RSM)之中心混成方法(central composite design, CCD)尋找 SAS操作溫度(45、55、65 ºC)及乳化劑含量(15、25、35 %)之最適條件。RSM 預測溫度 57.3 ºC及乳化劑含量 33.6 %時，可得包覆效率 68.8 %、回收率 43.3 % 及溶離率 31.4 %，沉澱物總產率 71.7 %、葉黃素濃度 89.2 mg/g。以 SAS 技術進行 β- CD及乳化劑包覆富含葉黃素酯之萃出物可提升其水中溶離度約 31%。包覆後之產物水溶性明顯增加，可提升葉黃素酯在保健食品之應用性。Lutein is an important component of health food for protecting the eyes. However, its applications in actual health supplements are rather limited as the substance is a fat soluble nutrient and has very low water solubility. This study aimed to develop a form of lutein ester with improved water solubility to enhance its applications in health supplements. Raw materials provided by the supplier first underwent ultrasonic stirring to extract lutein ester using hexane, acetone, and tetrahydrofuran (THF) at a solvent-to-solid ratio (SSR) of 80 with an extraction time of 60 minutes. Results found that the THF extract provided 25.3% of lutein. The THF extract was then subject to liquid-liquid extraction using a methanol / hexane (1:1, v/v) solvent to further raise lutein purity to 44.7%. However, the solubility of hexane-extract in water was still very close to zero. β-cyclodextrin (β-CD) was then added to the purified material in the supercritical carbon dioxide antisolvent (SAS) process to generate an encapsulated lutein ester with improved water solubility. The process was carried out under a fixed temperature of 55ºC, time of 10 min, and feed flow rate of 0.5 mL/min. Total yield (TY) of the encapsulated material, lutein ester concentration (Clut), encapsulation efficiency (EE), recovery (R), and dissolution rate (RD) were investigated under different emulsifiers (Tween 20 and Tween 80), emulsifier concentrations (15 % and 25 %), stirring times (0.5, 2, 4, and 6 hr), pressures (120 and 140 bar), and feed ratios of the extracted material and β-cyclodextrin (Wext/Wβ-CD) (0.5, 1, and 2). Results showed that the experimental conditions of 25 % of Tween 80 as emulsifier, 4-hr stirring time, 140 bar, and Wext/Wβ-CD of 0.5 gave better results of 77.9% EE, 43.6% R, 30.6% DR, 69.0% TY, and 94.1 mg/g Clut. A response surface methodology (RSM) experiment with central composite design (CCD) was then employed using the aforementioned conditions to identify the optimal SAS temperature (45, 55, and 65ºC) and emulsifier concentration (15, 25, and 35 %). Results of the RSM experiment predicted an optimal condition of 58oC for the temperature and emulsifier concentration of 33.6 %, which would provide the following: 68.8% EE, 43.3% R, 31.0% DR,71.7% TY, and 89.2 mg/g Clut. Using SAS for β-CD with emulsifier encapsulation of extracts rich in lutein ester would help improve dissolution rate in water about 31%. Water solubility was significantly increased for the encapsulated product, improving the applicability of lutein ester in health foods.摘要 i Abstract iii 縮寫表 v 目錄 vi 表目錄 viii 圖目錄 ix 附表目錄. x 第一章 緒論 1 1-1 研究動機 1 1-2 研究目的與規劃 2 第二章 文獻回顧 4 2-1類胡蘿蔔素簡介 4 2-2葉黃素簡介 5 2-2-1 葉黃素及葉黃素酯結構 5 2-2-2葉黃素特性 6 2-3 乳化劑介紹 7 2-4 環糊精介紹 8 2-5 超臨界二氧化碳的技術與應用 11 第三章 實驗材料與方法 15 3-1 原料與材料製備 15 3-2 試劑與藥品 16 3-2-1 氣體 16 3-2-2 藥品 16 3-2-3標準 18 3-3 實驗設備 19 3-3-1 超音波攪拌萃取設備 19 3-3-2 超臨界抗溶結晶設備 20 3-3-3高效能液相層析儀(HPLC)24 3-3-4 場發射掃描式電子顯微鏡 25 3-3-5動態光散射粒徑分析儀 25 3-3-6 其他設備 25 3-4 實驗方法與步驟 26 3-4-1 葉黃素定量 26 3-4-2超音波攪拌萃取葉黃素酯 32 3-4-3 液液萃取葉黃素酯 31 3-4-4 溶解度實驗 32 3-4-5 超臨界抗溶沉澱過程 33 3-4-6 溶離率實驗36 3-5 粒徑分析37 3-6電子顯微鏡(SEM)分析37 第四章 結果與討論 38 4-1超音波萃取 38 4-2液液萃取 41 4-3葉黃素酯液液萃取萃出物與 β-CD 在溶劑的溶解度實驗 45 4-4 SAS包覆液液萃出物的預實驗 45 4-4-1 包覆物及乳化劑的影響 45 4-4-2 攪拌時間以及乳化劑種類的影響 45 4-4-3 乳化劑的影響 46 4-4-4進料量比(Wext/Wβ-cd)的影響 46 4-4-5 壓力(P)的影響 47 4-5 應答曲面設計SAS 實驗 49 4-5-1溶離率(DR)應答分析值 53 4-5-2葉黃素濃度(Clut)應答分析值 53 4-5-3總產率(TY)應答分析值 53 4-5-4包覆率(EE)應答分析值 54 4-5-5回收率(R)應答分析值 55 4-5-6 RSM的預測值與實驗值比較 55 4-6 粒徑分析 58 4-7 電子顯微鏡(SEM)分析 59 第五章 結論 62 參考文獻 68   表目錄 表一、各種化學物質的臨界壓力、溫度和密度 13 表二、HPLC定量葉黃素之檢量線 29 表三、超音波攪拌萃取金盞草萃出物 40 表四、液液萃取 42 表五、溶解度實驗 44 表六、超臨界二氧化碳抗溶沉澱葉黃素酯萃出物預實驗 48 表七、超臨界二氧化碳抗溶沉澱之應答曲面設計實驗數據 50 表八、應答曲面實驗設計的預測值與實驗值比較 57 圖目錄 圖一、實驗流程圖 3 圖二、葉黃素及葉黃素酯結構 5 圖三、三種環狀糊精示意圖 9 圖四、超臨界二氧化碳相圖與臨界點相變圖 12 圖五、二氧化碳的密度-壓力的相圖 12 圖六、原料包裝以及原料 15 圖七、超臨界抗溶沉澱實驗設備圖 23 圖八、HPLC 圖譜 30 圖九、SAS 包覆程序之Tween 80進料量與抗溶溫度應答曲面圖 52 圖十、葉黃素酯萃出物與 β-CD 共沉澱物之粒徑分佈 58 圖十一、金盞草萃出物及液液萃出物 SEM圖 60 圖十二、不同條件下 SAS 沉澱物之 SEM 圖 61 附表目錄 附表一、SAS 溶離率(DR)的變方分析與回歸方程式 63 附表二、SAS 葉黃素濃度(Clut)的變方分析與回歸方程式 64 附表三、SAS 包覆物之總產率(TY)的變方分析與回歸方程式 65 附表四、SAS包覆率(EE)的變方分析與回歸方程式 66 附表五、SAS 回收率(R)的變方分析與回歸方程式 6

Deformation of the Nankai Trough inner accretionary prism: The role of inherited structures

Accretionary prisms commonly grow seaward, with the strata of the inner prism consisting of older, previously accreted outer prism rocks overlain by thick fore-arc basin strata. We focus on the Nankai Trough inner accretionary prism using three-dimensional (3-D) seismic data and logging data from the Integrated Ocean Drilling Program (IODP). We update the 3-D seismic volume using well velocity data to better constrain deeper horizons. Interpretation of these horizons reveals multiple folds with axial surfaces that strike near parallel to modern outer prism thrust faults, and we interpret that these folds formed as a result of thrust faulting. Reactivation of one inner prism thrust fault continued until at least ∼0.44 Ma, after the modern fore-arc basin formed, indicating that the inner prism had continued deformation until that time. Structural restorations of these folded seismic horizons demonstrate that ∼580 m of slip occurred on this steeply dipping reactivated thrust after fore-arc basin formation. Structural interpretation and analysis of logging-while-drilling data, including borehole images, in the deep inner prism revealed intense deformation of a generally homogenous lithology characterized by bedding that dips steeply (60°–90°), intersected by faults and fractures that have a range of dips and densities. Our study of the deep Kumano Basin provides new insights into the structure of the inner prism and reveals that although the inner prism has partially preserved inherited outer prism structures, these older folds and faults are steeply rotated and cut by multiple fracture populations during subsequent deformation.Funding for this research was provided by the National Science Foundation (grant OCE-0451790) and a U.S. Science Support Program Post-Expedition Award.Peer reviewe

Architected syntactic foams: a tale of additive manufacturing and reinforcement parameters

Polymer syntactic foams are lightweight composites made of hollow particles such as Glass Micro-Balloons (GMBs) or cenospheres reinforced in a polymer matrix. We demonstrate for the first time that the size of the GMB controls the interior microscale architecture of syntactic foams with matrix segregation achieved through the selective laser sintering - additive manufacturing process. This manifests as paradoxical macroscale mechanical responses. GMBs with a diameter larger than the gaps between the segregated matrix's cell walls get lodged between and in the cell walls, whereas those with a diameter smaller than the gaps are likely to get lodged inside the cell walls. As a result, larger particles contribute significantly to the stiffness of syntactic foams, whereas smaller particles have a relatively negligible effect. Larger particles with lower crushing strength lowered the densification stress of the foam. In contrast, the foam with smaller particles with higher crushing strength behaved similarly to pure TPU but with substantially less weight. Overall, we show that combining reinforcement parameters with print parameters enables the design and fabrication of hierarchical customized structures and functional features in 3D printed syntactic foams. These findings can be applied to create and design lightweight sandwich structure cores for marine and aerospace applications

Full-field measurements of strain localisation in sandstone by neutron tomography and 3D-volumetric Digital Image Correlation

AbstractRecent studies have demonstrated that the combination of x-ray tomography during triaxial tests (“in-situ” tests) and 3D- volumetric Digital Image Correlation (3D-DIC) can provide important insight into the mechanical behaviour and deformation processes of granular materials such as sand. The application of these tools to investigate the mechanisms of failure in rocks is also of obvious interest. However, the relevant applied confining pressures for triaxial testing on rocks are higher than those on sands and therefore stronger pressure containment vessels, i.e., made of thick metal walls, are required. This makes in-situ x-ray imaging of rock deformation during triaxial tests a challenge. One possible solution to overcome this problem is to use neutrons, which should better penetrate the metal-walls of the pressure vessels. In this perspective, this work assesses the capability of neutron tomography with 3D-DIC to measure deformation fields in rock samples. Results from pre- and post-deformation neutron tomography of a Bentheim sandstone sample deformed ex-situ at 40MPa show that clear images of the internal structure can be achieved and utilised for 3D-DIC analysis to reveal the details of the 3D strain field. From these results the character of the localised deformation in the study sample can thus be described. Furthermore, comparison with analyses based on equivalent x-ray tomography imaging of the same sample confirms the effectiveness of the method in relation to the more established x-ray based approach

Asthma-COPD overlap : prevalence and features

Background Asthma-COPD overlap (ACO) is a disease that shares clinical features of both asthma and COPD. The purpose of this study is to investigate the prevalence and clinical features of ACO. Methods We retrospectively reviewed data for 170 patients with persistent airflow limitation and diagnosed them according to “The Japanese Respiratory Society Guidelines for the Management of ACO 2018”. Results Of the 170 patients, 111 were diagnosed as follows : COPD (74 patients, 66.6%), ACO (34 patients, 30.6%), and asthma (3 patients, 2.8%). There was no significant difference in clinical features between ACO and COPD patients. The following pulmonary function tests were significantly lower in ACO than in COPD patients : forced expiratory volume in 1 second/forced vital capacity, peak expiratory flow, maximal mid-expiratory flow, and the maximum expiratory flow at 50% and 75%. The following respiratory impedance parameters were significantly higher in ACO than in COPD patients : respiratory resistance (Rrs) at 5 Hz (R5), Rrsat 20 Hz (R20), R5-R20, and low-frequency reactance area. Conclusions About 30% of patients with persistent airflow limitation were diagnosed with ACO. ACO patients had lower lung function and higher respiratory impedance compared with COPD patients

Mesoscopic Structural Observations of Cores from the Chelungpu Fault System, Taiwan Chelungpu-Fault Drilling Project Hole-A, Taiwan

Structural characteristics of fault rocks distributed within major fault zones provide basic information in understanding the physical aspects of faulting. Mesoscopic structural observations of the drilledcores from Taiwan Chelungpu-fault Drilling Project Hole-A are reported in this article to describe and reveal the distribution of fault rocks within the Chelungpu Fault System

Autoantibodies to IL-1α in sera from rapidly progressive idiopathic pulmonary fibrosis

To clarify the clinical significance of autoantibodies to interleukin-1α (IL-1α autoantibodies) in rapidly progressive idiopathic pulmonary fibrosis ( IPF ), we measured the level of IL-1α autoantibodies in serum of 11 patients on the first hospital day, when patients were admitted due to severe symptoms, and on the 21st hospital day. IL-1α autoantibodies in serum were measured using radioimmunoassay, and the limitation of this assay for IL-1α autoantibodies was 5 ng/ml. These antibodies were detected in 5 of 11 patients on the first hospital day. On the 21st hospital day, these antibodies were detected in all patients, and its level was increased compared with that on the first hospital day. IL-1α autoantibodies that appeared in patients corresponded to that of IgG. The half life of exogeneous autoantibodies was investigated following administration of autoantibody rich plasma obtained from healthy blood donors to 6 control patients (CP) and 6 progressive IPF patients. These autoantibody levels in their serum were less than 5 ng/ml before administration. Serum was obtained at the indicated time after administration of IL-1α autoantibodies and the level of these autoantibodies in serum was measured, then the half life was calculated. Half life of exogeneous IL-1α autoantibodies in progressive IPF patients was significantly shorter than that in CP (71.3±31.8 hr vs 352.0±98.3 hr, p<0.01).These findings suggested that IL-1α autoantibodies were generated in response to the inflammatory process of rapidly progressive IPF and may act as a regulatory factor for IL-1α

Diabetes mellitus itself increases cardio- cerebrovascular risk and renal complications in primary aldosteronism

This is a pre-copyedited, author-produced version of an article accepted for publication in The Journal of Clinical Endocrinology & Metabolism following peer review. The version of record Aya Saiki, Michio Otsuki, Daisuke Tamada, Tetsuhiro Kitamura, Iichiro Shimomura, Isao Kurihara, Takamasa Ichijo, Yoshiyu Takeda, Takuyuki Katabami, Mika Tsuiki, Norio Wada, Toshihiko Yanase, Yoshihiro Ogawa, Junji Kawashima, Masakatsu Sone, Nobuya Inagaki, Takanobu Yoshimoto, Ryuji Okamoto, Katsutoshi Takahashi, Hiroki Kobayashi, Kouichi Tamura, Kohei Kamemura, Koichi Yamamoto, Shoichiro Izawa, Miki Kakutani, Masanobu Yamada, Akiyo Tanabe, Mitsuhide Naruse, Diabetes Mellitus Itself Increases Cardio-Cerebrovascular Risk and Renal Complications in Primary Aldosteronism, The Journal of Clinical Endocrinology & Metabolism, Volume 105, Issue 7, July 2020, Pages e2531–e2537 is available online at: https://doi.org/10.1210/clinem/dgaa177