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Transesterification of oil and the kinetics of deep-fat frying
No full textDeep-fat frying is widely used in food processing. Due to the believe that fried foods have desirable flavor, color, and crispy taste, which makes them very popular to consumers, many researchers have postulated a reduction in the final fat content of fried foods. It is therefore useful to understand the mechanism of water loss and oil uptake during deep-fat frying process. Food safety has always received much public attention, and the public is particularly concerned about oils and fats. Besides deep-fat frying, oil is used for shortening, softening, greasing, coating and other purposes. Later, it was found that trans-fatty acid can be generated in hydrogenation reaction, and also has lots of adverse effects on health.
This dissertation has two studies. The objectives of first study were to investigate the most suit GC columns to analyze cis- and trans-fatty acids methyl ester. The qualitative performance was discussed, and the optimal analysis conditions for cis- and trans- FAMEs were also investigated. This study also designs different transesterification conditions to explore the effects of different parameters on the transesterification process. Numerous quantitative calculation methods are established and the FAME and glycerol samples are analyzed in GC-FID and HPLC-RI.
The results showed that HP-88 can analyze our prepared Mixed FAMEs standard solution which has 11cis and 12 trans FAMEs within 30 min. It can also separate Supelco? 37-Component FAME Mix which contain 35 cis and 2 trans within 45 min.
Using CH3ONa as the catalyst provided the best results from transesterification. Adding excessive methanol improved the results of transesterification reaching 104.08±4.15％. In the quantitative determination of fatty acid in oil, besides using GC-FID to analyze the FAME content, HPLC-RI can also be used to analyze the content of byproduct glycerol, and then estimate oil recovery.
The objective of second study was also to fulfill isothermal heating condition. A simultaneous first-order kinetic model correlated with the two irreversible serial rate processes were hypothesized and evaluated during deep-fat frying at 160, 190 and 220℃. The microstructure properties were assessed by Field Emission Scanning Electron Microscope (FESEM).
The proposed empirical two first-order kinetic rate processes showed to fit well with the experimental data of water loss during frying at 160, 190 and 220℃. The effect of temperature on the rate constants, k1 and k2, for both two processes was adequately modeled by the Arrhenius relationship. The average activation energy of the rate constants, k1 and k2, was 3.91 and 7.74 KJ/mol, respectively over the frying temperature from 160 to 220℃.
A simple rational model with two parameters in which r2 reaches 0.983 shows that oil uptake can be expressed by water content. This simple relationship has never been found in previous frying researches. Observations of structural changes at the surface and inner section of potato particulates through the pictures of FESEM are critical. These physical evidences support our previous assumption that the mechanisms of water loss (two-stage rate processes) before and after transition time are different.油炸是常見的加工方式，由於油炸讓食物具有令消費者喜愛的特殊香氣、金黃色澤和酥脆口感。除了油炸，油脂也常用於油酥、軟化、潤滑和包覆等用途，然而當油脂經過氫化反應後，雖然可以降低油脂的沸點，增加油脂的運用，但是氫化過程會形成反式脂肪酸，對於健康上有許多不利的影響。近年來，社會大眾對於食品安全問題日益重視，特別著重於油脂方面的食品安全，以及對於健康上的考量，有許多降低油炸食品吸油量的文章。也因而更加瞭解油炸加工過程，水分流失和油脂吸收的熱傳與質傳。
在此論文中，將分成兩部份，第一部份研究的目的是選擇適合分析順、反式脂肪酸甲酯的氣相層析管柱，並討論其定性表現，找出最適合分析順、反式脂肪酸甲酯的分析條件。在實驗中將設計不同的轉酯化步驟，探索不同參數對於轉酯化反應的影響。建立定量的計算方法，利用GC-FID和HPLC-RI分析脂肪酸甲酯和甘油，作為定量分析方法。
以氣相層析管柱HP-88作為FAME的分析管柱，可適用於各種順、反式脂肪酸甲酯的樣品中，於30分鐘內分析含有11個順式、12個反式脂肪酸甲酯的混合脂肪酸甲酯標準品(Mixed FAMEs standard solution)。而於47分內可分析含有35個順式、2個反式脂肪酸甲酯的Supelco? 37-Component FAME Mix標準品。可作為後續脂肪酸甲酯定性與定量的管柱，並且建立以氣相層析分析脂肪酸甲酯的最適條件。
將油脂樣品進行轉酯化時，以CH3ONa催化效果較佳，且在添加過量甲醇時，會使轉酯化效果提高，可達104.08±4.15％。油脂中脂肪酸的定量方法，除了使用GC-FID分析FAME含量之外，可利用HPLC-RI分析副產物的含量，回推油脂的回收率。
第二部份為恆溫160、190和220℃的油炸加熱下，在一次動力學下，用兩個不可逆的反應程序，去假設及評估油炸時水分減少和油脂吸收的情形，並且以場發射電子掃描顯微鏡(FESEM)觀察油炸馬鈴薯粒的微細結構變化。
在一次動力學反應下，以兩段式水分減少的預測曲線可與實驗數據吻合。其反應速率常數k1和k2的溫度效應符合the Arrhenius relationship，這兩段的平均活化能，在160至220℃範圍下，分別為3.91和7.74 KJ/mol。將水分含量與油脂吸收量作圖，可以用一簡單的方程式來描述水分含量與油脂吸收量的關係，其r2可高達0.983。表示油炸馬鈴薯粒的油脂吸收量與水分含量是有很好的相關性的，這在之前所有油炸的研究中，並未發覺此一簡單的關係存在。以FESEM觀察油炸馬鈴薯粒的結構，在預測曲線開始分段的轉折點前後，馬鈴薯粒表面和內部結構明顯改變，表示由於結構上的變化，導致水分流失速率在機制上的重大變化，支持了快速(fast process)和慢速(slow process)兩階段的假說。Contents
Chapter 1 Introduction 1
Chapter 2 Detection and identification of cis- and trans- fatty acid methyl esters mix in three capillary GC columns 4
Abstract 4
2.1. Introduction 5
2.2. Materials and Methods 7
2.2.1. Fatty Acid Methyl Ester Standards Description 7
2.2.2. Linolenic Acid Methyl Ester Isomer Mix 8
2.2.3. Mixed trans- FAMEs Standard 8
2.2.4. AOCS Low Erucic Rapeseed Oil 9
2.2.5. Mixed FAMEs standard solution 10
2.2.6. Supelco? 37-Component FAME Mix 10
2.2.7. GC capillary columns 11
2.3. Results and Discussion 12
2.3.1. Linolenic Acid Methyl Ester Isomer Mix 12
2.3.2. Mixed trans- FAMEs Standard 14
2.3.3. AOCS Low Erucic Rapeseed Oil 15
2.3.4. Mixed FAMEs Standard Solution 16
2.3.5. Supelco? 37-Component FAME Mix 17
2.4. Conclusions 19
References 31
Chapter 3 Evaluation of the quantitative of oil transesterification 33
Abstract 33
3.1. Introduction 34
3.2. Materials and Methods 36
3.2.1. Materials 36
3.2.2. Different catalyst and different transesterification process 37
3.2.3. Consecutive transesterification processes 38
3.2.4. Quantitative determination of FAME 38
3.2.4.1. Gas Chromatography with flame ionization detector (GC-FID) 38
3.2.4.2. High Performance Liquid Chromatography with Refractive Index Detector (HPLC-RI) 39
3.2.4.3. Dry weight measurement 40
3.2.4.4. Calculations 40
3.3. Results and Discussion 43
3.3.1. The factors of transesterification with different condition 43
3.3.2. Quantitative method for oil recovery 46
3.3.3 Consecutive transesterification processes 47
3.4. Conclusion 50
References 59
Chapter 4 Modeling the kinetics of water loss during deep-fat frying of potato particulates 62
Abstract 63
4.1. Introduction 67
4.2. Materials And Methods 67
4.2.1. Materials 67
4.2.2. Frying conditions 67
4.2.3. Analytical methods 68
4.2.4. Kinetic data analysis 69
4.2.5. Microstructure properties 70
4.2.6. Statistic analysis. 70
4.3. Results and Discussion 71
4.3.1. Isothermal condition. 71
4.3.2. Modeling of two first-order kinetic rate processes 71
4.3.3. Microstructure. 76
4.4. Conclusion 79
References 90
Chapter 5 Relationship between oil uptake and water content during deep-fat frying of potato particulates under isothermal temperature 94
Abstract 94
5.1. Introduction 95
5.2. Materials and Methods 98
5.2.1. Materials 98
5.2.2. Frying conditions 98
5.2.3. Analytical methods 99
5.2.4. Microstructure properties 100
5.2.5. Statistic analysis 100
5.3. Results and Discussion 100
5.3.1. Water loss 101
5.3.2. Oil uptake 102
5.3.3. Microstructure 105
5.4. Conclusions 107
References 114
Chapter 6 Conclusions 116
Chapter 7 Future development 11
大蒜皮中抗氧化成分之萃取及肉製品之應用
No full text脂肪氧化會產生不良氣味、降低產品感官特性並縮短貯藏期限，添加抗氧化 劑可延緩脂肪氧化確保產品之品質；惟人工抗氧化劑食用過量恐有安全顧慮，故天 然抗氧化物質漸受重視。蒜皮為大蒜 (garlic, Allium sativum) 生產過程之廢棄物， 大多廢棄不用，近年來研究指出此類農業副產物中仍富含大量酚類化合物 (phenolic compounds)，具有開發為天然抗氧化物之潛力。研究指出超音波震盪萃取 (ultrasound-assisted extraction) 可 縮 短 萃 取 時 間 並 增 加 萃 取 產 率 ； 反 應 曲 面 法 (response surface methodology, RSM) 可探討不同試驗條件彼此間交互效應得到最 佳萃取條件及試驗結果，故本研究以超音波震盪萃取蒜皮中酚類化合物，配合反應 曲面法尋求最適萃取條件，測定於此條件下所得萃取液中酚類化合物含量、蒜胺酸含量及評估萃取液抗之氧化特性，並進一步將此萃取液應用於法蘭克福香腸中，探 討其於冷藏貯存期間抑制脂質氧化之效果。 結果顯示，蒜皮之酚類化合物含量隨著乙醇濃度升高 (40-60 %) 而下降，但隨著萃取溫度 (30-60 C) 及時間 (10-30 min) 增加而顯著上升；經 RSM 計算出最 適萃取條件為 40 %乙醇，60 C 萃取 30 分鐘，於此條件下萃取所得之總酚含量 (total phenol contents) 及 總 類 黃 酮 含 量 (total flavonoid contents) 分 別 為 170.57 mg GAE/100 g garlic skin 及 48.87 mg quercetin/100 g garlic skin，萃取液之 DPPH 自由 基清除能力、亞鐵離子螯合能力及還原能力皆隨著萃取液中酚類化合物含量增加而顯著上升，經 HPLC 定量分析後發現蒜皮中亦具有含硫化合物蒜胺酸 (30.34 mg/g dry garlic skin)。將最適萃取條件所得之萃取液取代 50, 75 及 100 %冰水添加入法蘭 克福香腸中，製成產品冷藏貯存 4 週後，以萃取液取代 75 及 100 %冰水者可延緩 樣品 a*值 (紅色度) 下降之趨勢，而不影響樣品之 L*值 (亮度) 與 b*值 (黃色度)。 隨著貯存時間延長各組之 TBARS 值 (thiobarbituric acid reactive substances) 及總生 菌數皆顯著上升 (P < 0.05)，且添加萃取液組之數值皆顯著低於對照組 (P < 0.05)， 貯存期間取代 75 及 100 %組之總接受度有高於對照組之趨勢，冷藏貯存 4 週仍可被接受。綜觀上述，使用反應曲面法可以得到蒜皮酚類萃取物含量之最佳萃取條件，此萃取液具有良好之抗氧化能力且具有延緩脂質氧化之效果，法蘭克福香腸製程中添加此超音波蒜皮萃取液取代 75 %或以上之冰水時，可延緩香腸中脂質氧化、抑制微生物生長並可提高產品接受性及貯存品質。Lipid oxidation induces off-flavor, deteriorates sensory qualities of foods, and shortens shelf-life of products. Even though synthetic antioxidants have been applied to retard the development of lipid oxidation for years, concerns regarding its safety therefore trigger the research and development of some natural antioxidants. Garlic skin, which is an inedible waste produced during processing,contains high contents of phenolics, and has great potentials to be utilized for its antioxidant activity. Ultrasonic-assisted extraction has been attracted more attention due to its higher extraction efficiency and shorter extraction time as compared to the traditional maceration extraction. Response surface methodology (RSM) enables to evaluate the effects of process parameters and their interactions on response variables, and it is often applied to obtain the optimal experimental results.The objectives of this study were (1) to obtain the optimal conditions for the extraction of phenolic compounds from the garlic skin through the RSM and (2) to evaluate the efficacy of applying the garlic-extract during the manufacturing of frankfurter sausage. In the experiment 1, the RSM was used to optimize ultrasound-assisted extraction of total phenolic compounds from garlic skin. The result showed that extracted phenolic amounts were decreased with the increased ethanol concentrations, yet it was increased with the increased extraction temperature and time. The highest extraction yield of total phenolics contents and total flavonoid contents (170.57 mg GAE/100 g dried garlic skin and 48.87 mg quercetin/100 g dried garlic skin) were obtained when using ethanol (40 %) and ultrasound-assisted extracted at 60 C for 30 min. DPPH radical scavenging, ferrous chelating and reducing power of extract solution were increased with increased concentration. In the experiment 2, the alliin content was determinated to be 30.34 mg/g dry garlic skin. The garlic-skin extract was applied to replace ice water (0, 50, 75 or 100 %) in the formula during manufacturing of frankfurter sausages. It was found that the 100% replacement samples retarded the decrease of a* values (redness) in frankfurters during the 4-week refrigerated storage. The TBARS values and total plate counts were increased significantly in all treatments throughout the storage (P < 0.05), and both the TBARS and microbial numbers of the treated groups were lower than that of the controls (P < 0.05). The frankfurters with 75 or 100 % replacement of ice water with garlic-skin extract had higher overall sensory acceptability and they were still acceptable until the end of the 4-week storage a 4 C. In conclusion, through the RSM, we could obtain the optimal extract condition of garlic skin extraction. Replacement 75% and above of ice water with the ultrasonic-extracted garlic skin extract in the formula not only retards the lipid oxidation, but also increases the acceptance and extends the shelf-life of frankfurter sausages.壹、前言..........1
貳、文獻檢討..........2
一、大蒜與蒜皮之介紹..........2
(一) 大蒜之簡介..........2
(二) 大蒜之生物活性、醫療用途及抗氧化特性..........2
(三) 蒜皮介紹及其抗氧化特性..........3
二、超音波震盪於植物萃取等之應用..........9
(一) 超音波之簡介..........9
(二) 超音波對於萃取之影響..........9
(三) 影響超音波萃取效率之因素..........14
三、反應曲面法..........16
(一) 反應曲面法之定義..........16
(二) 反應曲面法之優點..........16
(三) 最適化之步驟..........17
四、脂質氧化之機制抗氧化劑之作用機制..........17
(一) 自氧化作用 (autoxidation) ..........17
(二) 其他氧化作用..........19
五、抗氧化劑之作用機制.......... 19
(一) 自由基抑制劑 (free radical inhibitor) ..........20
(二) 金屬螯合劑 (metal chelator) .......... 20
(三) 還原劑 (reducing agent) ..........20
(四) 單態氧之清除劑 (singlet oxygen quencher) ......21
六、抗氧化劑之種類..........23
(一) 人工合成抗氧化劑..........23
(二) 天然抗氧化劑..........24
(三) 多酚類 (polyphenols) ..........25
參、試驗一：利用反應曲面法探討蒜皮酚類化合物最適化超音波震盪萃取條件及其萃取液氧化特性之研究..........30
一、摘要..........30
二、緒言..........30
三、材料與方法..........31
(一) 原料..........31
(二) 反應曲面法試驗設計..........31
(三) 分析項目..........34
四、結果與討論.......... 36
(一) 酚類化合物最適萃取條件..........36
(二) 蒜皮萃取液之抗氧化特性..........51
五、結論..........58
六、參考文獻..........59
七、英文摘要..........62
肆、試驗二：蒜皮超音波震盪萃取液中蒜胺酸含量及法蘭克福香腸中添加蒜皮
萃取液取代部分冰水對於冷藏貯存品質之變化..........63
一、摘要..........63
二、緒言..........63
三、材料與方法.......... 64
(一) 原料..........64
(二) 萃取液中蒜胺酸 (alliin) 含量分析..........64
(三) 法蘭克福香腸之製備..........64
(四) 試驗設計..........65
(五) 分析項目..........67
(六) 統計分析..........68
四、結果與討論.......... 69
(一) 蒜皮超音波震盪萃取液中成分分析..........69
(二) 添加蒜皮乙醇萃取液對法蘭克福香腸冷藏貯存期間品質之影響.72
五、結論..........85
六、參考文獻..........86
七、英文摘要..........90
伍、總結..........91
陸、參考文獻..........92
柒、附錄..........9
Framework Establishment of Prescription Information System for Plant Protection
No full textThe purpose of the study was to reduce pesticide hazards by proper use of a pesticide prescribed by a certified personnel and to achieve effective control of plant diseases. To control plant diseases, farmers have to apply pesticides. However, farmers often lack professional training and tend to over-apply pesticides or apply them inappropriately, both resulting in high residues on crops. To solve these problems, safe and effective use of pesticides recommended by well-trained professionals is critical for integrated pest management.
The author tries to establish a framework that can help plant health care professionals and farmers by providing proper diagnosis of plant disease, to avoid inappropriate use of pesticides and thus, to achieve agricultural sustainability and food safety.
A prescription issued by a well-trained professional shall include date, creator, farmer, pesticide name, usage, method, gap days and diagnosis. As such, farmers will follow appropriate instructions when applying pesticides and plant diseases can be effectively managed.
Appropriate diagnosis is the key to applying pesticides correctly and effectively. To achieve appropriate diagnosis, the author suggests three steps. First of all, a plant heath care personnel and farmers have to rely on symptomatology; secondly, putative diagnosis will be checked with documented images stored in a assisting diagnosis system; thirdly, correct diagnosis will be discussed with a farmer.
The crop-disease system is provides a platform that integrates the writing prescription system and assisting correct diagnosis system. The assisting diagnosis system can export the diagnosis result to the writing prescription system automatically. The system can display the symptom images in the writing prescription system if the farmers have any doubts on the result of the diagnosis.
Through collaborative efforts between farmers and certified professionals, the described system will help farmers achieve pest management by investing fewer cost and to achieve greater return. Thus, farmers, pesticide sellers, and the society will be all beneficial. Both the writing prescription system and the assisting diagnosis system can help farmers to solve plant diseases effectively. The author intends to create initiative information systems to forecast and track plant diseases, or to schedule application of pesticdes.本論文的研究動機是協助農藥從業人員開立正確處方，讓農民能有效控制病蟲害，進而達到降低農藥公害的目的。在農民至農藥行購買農藥的當下，就已初步決定農藥殘留超標是否會發生。此現象的成因是：農民深怕施用的農藥無效。農藥從業人員能有效解決病蟲害的問題，獲得農民信任，可避免農民浪費時間、物力和人力去加重藥量或密集施藥，是降低農藥殘留最有效的方法。
本研究試圖建立一資訊系統平台，協助農藥從業人員與農民溝通，共同診斷作物遭遇的病蟲害，進而提出解決此病蟲害的處方。
處方開立至少包含幾項內容：日期、開立者、農民、藥名、用量、使用方法、間隔天數以及診斷結果或預防等資訊。其目的在於告訴農民：「只要正確使用這些處方藥物，就足以解決診斷結果的病蟲害問題。」
然而，如何證明讓農民心服口服的診斷結果？本研究提出一診斷輔助措施。此措施包含以下幾個步驟：一、讓農民口述病徵或猜測病因；二、根據農民口述從診斷輔助系統中展示病徵圖片讓農民審視，同時列出其他病徵圖片提供比對；三、與農民討論病徵和病因，證明診斷結果的正確性。
本研究提出以作物病因系統作為系統平台，以整合處方開立系統和診斷輔助系統。基於平台的整合性，診斷輔助系統的診斷結果可直接匯入處方開立系統，協助使用者快速開立處方。相對的，農民對處方開立系統中的診斷結果有疑慮，系統會自動將該作物病因的病徵圖片展示在診斷輔助系統內，供農民審視。
協助農民以最經濟的方式獲利，才能達到農民、農藥從業人員和社會三贏。處方開立系統和診斷輔助系統是以被動方式協助農民解決病蟲害問題。期待將來能發展出以主動方式提醒農民排除病蟲害襲擾的資訊系統，諸如：預測、追蹤或排程等系統，讓病蟲害防患於未然。中文摘要 i
英文摘要 ii
表次目錄 iv
圖次目錄 v
第一章 緒論 1
第一節 研究背景 1
第二節 研究動機 6
第三節 研究目的 8
第二章 文獻回顧 9
第一節 植物保護處方 9
第二節 診斷方法與輔助應用 13
（一）病蟲害診斷方法 13
（二）檢索表的應用 15
（三）專家系統的應用 17
（四）圖形影像的應用 20
（五）影像處理的應用 21
第三章 研究方法 23
第一節 開發工具與使用資料 23
第二節 研究流程 24
第三節 系統整體架構 25
第四節 作物病因系統 26
（一）作業內容 26
（二）系統分析 28
第五節 處方開立系統 31
（一）作業內容 31
（二）系統分析 32
第六節 診斷輔助系統 36
（一）作業內容 36
（二）系統分析 37
第四章 系統實作 40
第一節 作物病因系統 40
（一）系統整體畫面 40
（二）系統操作 41
第二節 處方開立系統 42
（一）新增處方藥劑 42
（二）建立作物病因處方 44
第三節 診斷輔助系統 46
（一）診斷輔助系統畫面 46
（二）病徵放大檢視 47
（三）系統操作步驟 47
第五章 研究結論與未來展望 48
第一節 研究結論 48
（一）作物病因系統 48
（二）處方開立系統 49
（三）診斷輔助系統 49
第二節 展望未來 50
（一）作物病因系統的擴充 50
（二）處方開立系統的延伸 50
（三）診斷輔助系統的加強 50
參考文獻 5
系統計算分析於生物學研究與疫苗設計之應用
No full textRecently, because of the sudden increased prevalence of human and zoonotic infectious diseases, developing the effective vaccines and targeted therapies to prevent and to alleviate the harm as well as the pain caused by disease manifestation become urgent for keeping the individual health. Using computational mathematics to analyze the developmental variations of biological systems, and to apply the derived data to the related medical sciences is an accelerated and the most economical method.
In this study, we used bioinformatics and the associated statistical methods to align biological sequences and to analyze the structural homologies for the hidden features, which are targets of the related medical interests. The resultant methods could therefore be applied to develop a novel analytical platform for predicting the target epitopes, designing antigens to provoke immune responses against these specific epitopes, and applying these strategies to produce effective vaccines in time to prevent spreading of the disease.
First, we design a set of procedures to automatically analyze and calculate the known biological sequences and structures. Through this system, we have designed a faster and more accurate method to obtain the required data. Using these methods, we could solve the artifactual sequences gained in experimental handlings, which could then lead to uncertainty of measurement accuracy in molecular weights. These methods can also be used to fine-tune the gene analysis instruments and to improve machine variation-caused different results.
Moreover, using the same strategy, we r developed a method to utilize evolutionary tree theory to predict the possible mutation sites of influenza viruses, which might affect validity of the available vaccines. In fact, through these stratagems, we are able to estimate the possible next genetic variations in the influenza virus (H1N1) that would affect the potency of the vaccines. The actual proof of immunization effect is carrying out in an ongoing experiment. As expected, the results will be able to confirm our mathematical theory.
In conclusion, we have developed specific mathematical calculation methods to fast-track analyze viral sequence variations, and to accelerate the development of effective vaccines against the devastating wide spread of potential virus infections.近年來，由於傳染病及人畜、人禽共通疾病大量的衍生，如何開發有效疫苗與急效藥物以預防或減輕疾病對個人健康，實為當務之急。而利用數學計算以進行分析系統生物發育變化，並運用到相關之學科是最簡約的方法。
本研究論文即是以結合生物資訊及統計方法，快速分析大量的生物序列數據資料，探討類似生物間同型序列的排列結構。並藉此尋找其隱藏的生物功能，作為發展相關的生物學研究和醫藥應用，成為預測抗原特異目標胜肽、設計能產生有效抗體之抗原蛋白以及疫苗製造的新分析平臺。
首先，我們針對已知生物序列結構的生物序列設計一套能自動對序的演算方法。透過檢測工具進行分析比較，進而快速、準確地得到計算結果。此演算方法可解決生物實驗操作中經常發生的序列亂碼與分子量變異等測量問題，並可藉此改進基因分析上所發生的差異。
進一步，我們結合生物分子系統發育理論，建構綜合使用演化樹的計算方法，透過全序列比對及統計方法的估計，縮短在流行性感冒病毒疫苗研發的時程。實際上，透過這些理論，我們能預測流行性感冒病毒 H1N1 下一年可能的基因變異點，以及這種變異是否會影響疫苗之效價，真正的免疫實驗已著手進行，期待其結果能證實現在數學推算理論的確實性。
本研究論文之結果顯示，以數學計算方式，我們能具體發展出快速找出病毒序列以供製造具有專一性反應的有效疫苗區段之方法。摘要 ...............................................................................................................................I
Abstract .......................................................................................................................II
目錄 ....................................................................................................................................III
圖目錄 ...............................................................................................................................V
表目錄 ..............................................................................................................................VIII
符號說明 .........................................................................................................................IX
附錄圖目錄 .......................................................................................................................X
附錄表目錄 .......................................................................................................................XI
第一章 前言 ..........................................................................................................1
1-1 文獻探討....................................................................................................1
1-2 研究動機..................................................................................................3
1-3 本文架構與研究目的............................................................................................7
第二章 生物序列的非監督式測序計算探討.....................................................................24
2-1 簡介.......................................................................................................................24
2-2 非監督式演算法設計 ................................................................................29
2-3 實驗步驟 ............................................................................................35
2-4 結果與討論 ........................................................................................................40
第三章 無訓練集的生物序列分類計算探討 ..................................................................45
3-1 簡介......................................................................................................................45
3-2 二維範數距離分類計算方法設計......................................................................47
3-3 實驗步驟..............................................................................................................53
3-4 結果與討論 ........................................................................................................59
第四章 以計算方法設計流感病毒疫苗探討....................................................................62
4-1 簡介.......................................................................................................................62
4-2 計算方法縮短疫苗研發設計...............................................................................65
4-3 實驗步驟...............................................................................................................76
4-4 結果與討論...........................................................................................................81
第五章 台灣地區H1N1序列結構突變趨勢預測及疫苗有效期探討.................................85
5-1 簡介.......................................................................................................................85
5-2 台灣地區H1N1序列結構突變趨勢預測.............................................................88
5-3 實驗步驟.............................................................................................................102
5-4 結果與討論.........................................................................................................107
第六章 討論與結論 .........................................................................................................117
6-1 討論……………................................................................................................117
6-2 結論…………….................................................................................................119
第七章 研究總結與未來展望........................................................................................121
7-1 研究總結………...............................................................................................121
7-2 未來展望……...................................................................................................123
參考文獻 ...........................................................................................................................127
作者簡介 ...........................................................................................................................134
附件一：FCM對非人工的182筆DNA序列樣本分類結果.................................................137
附件二：雜交品系與十四類拖鞋蘭nrDNA之ITS鹼基序列......................................... 144
附件三：十四株流感病毒的PB2鹼基序列(下載自NCBI資料庫) ..................................148
附件四：流感病毒H7N7和H7N9的全序列比對結果..........................................................150
附件五:十四株流感病毒HA的鹼基序列 (下載自NCBI資料庫) .................................. 154
附件六:十四株流感病毒NA的鹼基序列 (下載自NCBI資料庫) .................................. 156
附件七:37隻H1N1病毒的NA鹼基序列 (來自成功大學醫學院之生化分析結果) ...... 158
附件八:42隻H1N1病毒的NA鹼基序列 (來自成功大學醫學院之生化分析結果) ...... 159
圖目錄
圖1：核酸與胺基酸互換的機制及生成示意圖...............................................................9
圖2：研究架構流程圖.....................................................................................................20
圖3:1株雜交種和14株原生種拖鞋蘭的遺傳距離有根樹演化圖.............................60
圖4:兩序列比對結果示意圖.........................................................................................75
圖5：最大概似法求出的流感病毒基因序列的演化樹關係-有根樹...........................77
圖6：最大概似法求出的流感病毒基因序列的演化樹關係-無根樹...........................77
圖7:數學計算疫苗設計流程圖.....................................................................................82
圖8:CLUSTALX2進行十四株病毒_HA(UPGMA)有根樹-未全序列比對前....................90
圖9:CLUSTALX2進行十四株病毒_HA (UPGMA)無根樹-未全序列比對前...................91
圖10:CLUSTALX2進行十四株病毒_HA (UPGMA)有根樹-全序列比對後.....................91
圖11:CLUSTALX2進行十四株病毒_HA (UPGMA)無根樹-全序列比對後.....................92
圖12：PHYLIP進行十四株病毒_HA (ML)有根樹-進行頭尾切割比對.........................92
圖13:PHYLIP進行十四株病毒_HA (ML)無根樹-進行頭尾切割比對.......................93
圖14：十四株病毒_HA先進行多序列的全序列比對(AL)，再進行可能的序列差位點分析-左側(5端)起始：(0-131BP調整值)........................................................93
圖15：十四株病毒_HA先進行多序列的全序列比對(AL)，再進行可能的序列差位點分析-右側(3端)結束：(1719-1849BP調整值)..................................................94
圖16：3株流感_HA先進行多序列的全序列比對，再進行可能的序列差異位點分析H5家族-左側(5端)起始：(0-14 BP 調整值).............................................................94
圖17：3株流感_HA先進行多序列的全序列比對，再進行可能的序列差異位點分析H5家族-右側(3端)結束：(1760-1779 BP調整值)….......................................94
圖18：5株流感_HA先進行多序列的全序列比對，再進行可能的序列差異位點分析H7家族-左側(5端)起始：(0-9 BP調整值).................................................................95
圖19：5株流感_HA先進行多序列的全序列比對，再進行可能的序列差異位點分析H7家族-右側(3端)結束：(1691-1706BP調整值)......................................................95
圖20:CLUSTALX2進行十四株流感_NA(UPGMA)有根樹-未全序列比對.....................97
圖21:CLUSTALX2進行十四株流感_NA(UPGMA)無根樹-未全序列比對.....................97
圖22:CLUSTALX2進行十四株流感_NA(UPGMA)有根樹-全序列比對.....................97
圖23:CLUSTALX2進行十四株流感_NA(UPGMA)無根樹-全序列比對..........................98
圖24:PHYLIP進行十四株流感_NA(ML)有根樹-全序列比對後................................98
圖25:PHYLIP進行十四株流感_NA(ML)無根樹-全序列比對後................................99
圖26：十四株流感_NA先進行多序列的全序列比對，再進行可能的序列差異位點分析-左側(5端)起始：(0-100 BP調整值).................................................................99
圖27：十四株流感_NA先進行多序列的全序列比對，再進行可能的序列差異位點分析-右側(3端)結束：(1351-1504 BP調整值).........................................................100
圖28：2株流感_NA先進行多序列的全序列比對，再進行可能的序列差異位點分析H5N3 & H7N3-左側(5端)起始：(0-0 BP調整值)...........................................100
圖29：2株流感_NA先進行多序列的全序列比對，再進行可能的序列差異位點分析H5N3 & H7N3-右側(3端)結束：(1411-1422 BP 調整值)..............................100
圖30：3株流感_NA先進行多序列的全序列比對，再進行可能的序列差異位點分析H7N7 & H7N9 & H10N7-左側(5端)起始：(0-10 BP調整值)................................101
圖31：3株流感_NA先進行多序列的全序列比對，再進行可能的序列差異位點分析H7N7 & H7N9 & H10N7-右側(3端)結束：(1439-1453 BP調整值)........................101
圖32:民國98-100年台灣H1N1-34株流感的差異位點(橫座標單位BP)................102
圖33:民國101年台灣H1N1-3株流感的突變點(橫座標單位BP)............................103
圖34:民國98-101年台灣H1N1-株-NA流感的差異位點(橫座標單位BP)已扣除左(5端)、右(3端)調整區(間隔25BP)............................................................................104
圖35:民國102年台灣H1N1-5株-NA流感的突變位點(橫座標單位BP) 已扣除左(5端)、右(3端)調整區(間隔25BP).....................................................................104
圖36:民國98-102年台灣H1N1-42株-NA流感的差異位點(橫座標單位BP) 已扣除左(5端)、右(3端)調整區....................................................................................105
圖37：CLUSTALX2進行pH1N1(UPGMA)有根樹-未全序列比對前............................108
圖38：CLUSTALX2進行pH1N1(UPGMA)無根樹-未全序列比對前............................109
圖39：CLUSTALX2進行pH1N1(UPGMA)有根樹-全序列比對後..................................109
圖40：CLUSTALX2進行pH1N1(UPGMA)無根樹-全序列比對後..................................110
圖41：PHYLIP進行pH1N1(ML)有根樹-全序列比對後............................................110
圖42：PHYLIP進行pH1N1(ML)無根樹-全序列比對後............................................110
圖43：H1N1先進行多序列的全序列比對，再進行可能的差異點分析-左側(5端)起始(0-54 BP調整值).................................................................................................111
圖44：pH1N1先進行多序列的全序列比對，再進行可能的差異點分析-右側(3端)結束(1371-1422 BP調整值)......................................................................................111
圖45:102M214H1NA核酸轉譯胺基酸輸出圖示..........................................................113
圖46:102年度5株H1N1病毒的NA核酸序列轉譯胺基酸序列整理前的對照圖.....113
圖47:PyMOL離線數據胺基酸三維分子結構圖..........................................................115
圖48:PyMOL離線數據胺基酸三維分子標記結構圖..................................................116
圖49:數學計算疫苗發明專利製程流程圖.................................................................122
表目錄
表1:人工樣本A類的序列22個特徵出現頻率表.........................................................25
表2：信息檢索系統的評價檢測指標表.........................................................................43
表3:計算拖鞋蘭的RNA序列的UPGMA距離矩陣表.....................................................56
表4：數值模擬結果(hybrids):Magi(P.micranthum X P.delenatii) 總表.............58
表5：十四株流感病毒的核酸PB2序列相似性距離矩陣總表......................................81
表6：H5家族序列的HA差異位點相對位置分析結果表...............................................95
表7：H7家族序列的HA差異位點相對位置分析結果表...............................................96
表8：H5N3 & H7N3 序列的NA差異位點相對位置分析結果表....................................101
表9：H7N7 & H7N9 & H10N7序列的NA差異位點相對位置分析結果表.....................101
表10：98年至100年預測101年病毒序列名稱關聯表..............................................103表11：98年至101年預測102年病毒序列名稱關聯表..............................................106
表12：台灣地區98至101年的H1N1的NA差異位點及相對位置分析結果表...........111
表13：102年度五株H1N1病毒的NA核酸序列轉譯胺基酸序列整理前的對照表....113
表14：本論文二至四章的實驗貢獻表.........................................................................121
符號說明
V 表示分成 類的資料群中心的平均數。
表示傳統分類演算方法的目標函數。
U 表示模糊集隸屬度矩陣。
表示模糊分類演算方法的目標函數。
RR Recall Rate：表示性能評價指標召回率。
PR Precision Rate：表示性能評價指標準確率。
FF F-Factor：表示性能評價整合性指標。
HA Hemagglutinin：代表血球凝集素或稱血凝素，數字代表不同類型的抗原。
NA Neuraminidase：代表神經氨酸酶又稱唾液酸酶，數字代表不同類型。
H7N9 代表某一型的流行性感冒病毒。
稱為元素 對模糊集 的隸屬度。
以 稱為模糊集 的隸屬函數。
附錄：圖目錄
附錄圖1：DNA/RNA轉錄轉譯過程示意圖....................................................................160
附錄圖2：遺傳密碼表圖...............................................................................................161
附錄圖3：常用蛋白質22組胺基酸代碼圖..................................................................162
附錄圖4：虛擬擴張序列圖..........................................................................................163
附錄圖5：散彈槍定序示意圖.......................................................................................164
附錄圖6：人工核酸樣本A類的第一筆序列示意圖..................................................165
附錄圖7:原生種P.armeniacum拖鞋蘭鹼基序列圖..................................................166
附錄圖8：新疫苗研發流程圖.......................................................................................167
附錄圖9:最大概似法計算演化樹的樹枝長及其結點-無根樹圖.............................168
附錄圖10:最大概似法求Jukes-Cantor模型的物種演化樹圖................................168
附錄圖11:兩序列比對圖.............................................................................................168
附錄圖12:核酸的轉換(Transition)及顛換(Transversion)機率示意圖.............169
附錄圖13:本研究所改良的反向遺傳(Reversed Genetics)疫苗製程圖................170
附錄圖14:流感病毒細胞內外基因序列分布位置示意圖.........................................171
附錄圖15:可能的免疫位點找尋研究架構圖.............................................................172
附錄圖16:ExPASy網站操作圖示................................................................................173
附錄圖17:DNA序列的轉譯方式圖示..........................................................................174
附錄圖18:Phyre2線上胺基酸三維分子結構分析....................................................175
附錄：表目錄
附錄表1：胺基酸變數設計表.......................................................................................176
附錄表2：A、B序列的二維表..................................................................................17
二維變曲率曲樑穩定分析之解析解
No full textIn this research there are two parts. In part I, the out of plane static analysis and stability analysis of curved beams of variable curvature on 2-D plane are investigated. The general solutions under various loadings are demonstrated. The analytical solutions of circular, cycloid, and spiral curved beams under pure moments are shown. The analytical solutions of circle, cycloid logarithmic spiral and spiral cantilever curved beams under concentrated load are presented as well. The out-of-plane critical load of a circular ring under uniform radial load is derived. Several critical loads are derived for various out-of-plane boundary conditions. The results are compared to the result by ANSYS. The results are consistent.
The second part will study the equilibrium equations of 2-D curved beams of variable curvatures are derived for stability analysis based on principle of virtual work. The buckling effect is included in the equilibrium equations. The critical pressure of a circular ring under uniform pressure is investigated. The solution is compared with the existing solutions. The analytical critical loads of cantilever and simple supported cycloid curved beams under concentrated load are found. The results are consistent with the results by ANSYS. The analytical critical distributed or the weight of cantilever cycloid curved beams are also obtained.1.Introduction1
PART I
2.The Static and Stability Out-of-plane Analysis of 2-D Curved Beam with Variable Curvatures
2.1General Description5
2.2Static out-of-plane analysis7
2.2.1General solutions7
2.2.2Cantilever curved beam under a pure torque10
2.2.3A cantilever curved beam under a concentrated pure bending moment11
2.2.4 A cantilever curved beam under a concentrated load at free end11
2.3 Out of plane stability Analysis13
2.3.1In the case of C→∞14
2.3.2In the limited case EI→∞16
PART II
3In-plane Stability Behavior of 2-D Curved Beams with Variable Curvatures
3.1Fundamental equations.... 18
3.2Critical loads of circular rings 22
3.3Critical loads of cycloid curved beams.. 24
3.3.1Cantilever cycloid curved beams under a concentrated load24
3.3.2Cantilever cycloid curved beams under a distributed load28
3.3.3Simple supported cycloid curved beam under a concentrated load31
4.Conclusion34
References35
Table2-1Dimensionless deflections of various cantilever beams under a concentrated torque37
Table2-2Dimensionless deflections of various curved cantilever beams under a concentrated moment M0 at free end 38
Table 2-3Dimensionless deflections of various curved cantilever beams under a concentrated load P at free end39
Table2-4-1The rotation deformation ξ at α=π/2 of a circular beam with Young's modulus E=2×1011, Poisson's ratio ν=0.3, and R0=1040
Table2-4-2The rotation deformation ϕ at α=π/2 of a circular beam with Young's modulus E=2×1011, Poisson's ratio ν=0.3, and R0=1040
Table2-4-3The displacement w of a circular beam with Young's modulus E=2×1011, Poisson's ratio ν=0.3, and R0=1040
Table3-1Dimensionless critical uniform load qcrr3/EI of existed research40
Table3-2Cantilever cycloid curved beams under a concentrated load. Comparison of dimensionless critical load by ANSYS and present study41
Table3-3Simple supported cycloid curved beam under a concentrated load. Comparison of dimensionless critical load by ANSYS and present study41
Figure 2-1Sign convention of forces and moments of a 2-D curved beam42
Figure 2-2Sign convention of displacement components42
Figure2-3A cantilever curved beam under a concentrated torque M043
Figure2-4A cantilever curved beam under a concentrated moment M0 at free end43
Figure2-5A cantilever curved beam under a concentrated load P44
Figure2-6Acircle ring under a uniform pressure q44
Figure2-7The first buckling mode with out-of-plane circlar ring45
Figure2-8The second buckling mode with out-of-plane circlar ring45
Figure 2-9The buckling mode with out-of-plane circlar ring46
Figure3-1Sign convention of a 2-D curved beam46
Figure3-2Sign convention of forces and moment47
Figure3-3The buckling mode with in-plane circlar ring47
Figure3-4A cantilever cycloid curved beams under a radial concentrated load P48
Figure3-5A curved beam under a pair of vertical loads P48
Figure3-6A cantilever cycloid curved beams under a uniform distributed load q49
Figure3-7Simple support cycloid curved beam under a concentrated radial load P4
以低溫凝膠製備石墨烯甲基壓克力酸酯共聚物運用於綠色樣品前處理技術
No full textIn this study, a novel poly(graphene-methylmethacrylate-ethylene glycol dimethylacrylate) (G-MMA-EGDMA) was synthesis by cryogel method and prepared as the adsorbents for pipette-tip solid phase extraction (PT-SPE) and stir bar sorptive extraction (SBSE), respectively, to increase the extraction efficiency and reduce the flow resistance. In the preparation of modified graphene polymer, the acrylate functional group was first modified on the graphene oxide, then mixed with methyl methacrylate and ethylene glycol dimethacrylate for cryogel polymerization in dimethyl sulfoxide (DMSO) at the temperature of 0.5oC. The modified graphene oxide was identified with infrared spectrum, and the porosity of copolymer was observed by SEM image.
The porous graphene copolymer was prepared in a pipette-tip as the adsorbent for PT-SPE of six triazine herbicides in aqueous solution. Parameters affecting the extraction efficiency such as the pH of sample solution, the salt addition, the flow-rate for sample loading, rinsing solution and desorption solution were investigated thoroughly. Results indicate that the optimal conditions for PT-SPE of six triazine herbicides in 5 mL of aqueous solution at pH 7 with 0.2 % NaCl can be obtained with the flow-rate of 3 mL/min for sample loading, then rinsed with 1 mL of pure water, and eluted with 300 μL of acetone for the analysis with high performance liquid chromatography (HPLC) and ultraviolet (UV) detection. Under the optimal conditions, the limit of determination (LOD) and limit of quantitation (LOQ) for six triazine herbicides were below 0.4 ng/mL and 1 ng/mL, respectively. It only took less than 5 min for the PT-SPE of triazine herbicides. The relative standard deviations (RSD) were less than 7.8%. Recovery were between 90.6-103.5% and the RSDs were less than 9.3%. These results indicated that the poly(G-MMA-EGDMA) based PT-SPE is a rapid, sensitive, and eco-friendly sampling method.
The porous graphene copolymer was prepared and coated onto the surface of a stir bar as the adsorbent for SBSE of bisphenol A and four alkylphenols in aqueous solution. Parameters affecting the extraction efficiency such as the pH of sample solution, the salt addition, the stirring-rate, the extraction time, and the desorption solution were investigated thoroughly. Results indicate that the optimal conditions for SBSE of bisphenol A and four alkylphenols in 50 mL of aqueous solution without salt-addition can be achieved with the stirring-rate of 400 rpm for 40 min extraction, then desorbed with 100 μL of ethanol for the analysis with HPLC-UV. Under the optimal conditions, the LOD and LOQ for bisphenol A and four alkylphenols were below 0.04 ng/mL and 0.1 ng/mL, respectively. The RSDs were less than 7.2%. Recovery were between 90.5-106.4% and the RSDs were less than 7.2%. These results indicated that the poly(G-MMA-EGDMA) based SBSE is a convenience, sensitive, and eco-friendly sampling method.
In this study, poly(G-MMA-EGDMA) was successfully synthesized by cryogel and prepared as the adsorbents for PT-SPE and SBSE. From the performance of both proposed methods, it indicated that the porous poly(G-MMA-EGDMA) material is a high potential adsorbent for convenience, sensitive, and eco-friendly sample pretreatment methods.本研究以低溫凝膠方式合成多孔性石墨烯-甲基丙烯酸甲酯共聚物，製備為多孔性吸附材料運用於綠色樣品前處理技術。研究中在氧化石墨烯表面修飾上丙烯酸酯官能基作為高分子單體，再加入甲基丙烯酸甲酯和乙二醇二甲基丙烯酸酯後，以低溫凝膠的方式進行聚合反應，產生具連續性孔洞的石墨烯-甲基丙烯酸甲酯共聚物，在樣品前處理技術上除了增加萃取表面積外，亦可減少液流背壓。為了證明此材料在綠色樣品前處理技術之應用潛力，對將所製備的多孔性石墨烯-甲基丙烯酸甲酯共聚物分別運用於移液管尖固相萃取技術與攪拌棒吸附萃取技術。
在多孔性石墨烯-甲基丙烯酸甲酯共聚物運用於移液管尖固相萃取技術的研究中，將石墨烯-甲基丙烯酸甲酯共聚物合成於移液管尖尖端處製備為固相萃取管，並運用於六種triazine除草劑的萃取。為了獲得最佳萃取效果，研究中對可能影響的參數，如樣品溶液pH值、沖提溶劑種類、沖提溶劑體積、鹽類添加與進樣速率等進行探討。實驗結果發現，對5 mL之pH 7水樣品，添加0.2 %氯化鈉後，以移液管尖吸取後再推出，接著吸取1 mL超純水潤洗後推出，最後以300 μL丙酮沖提具有最佳萃取效果。以最佳化條件下對於六種triazine除草劑水樣品進行萃取後，以液相層析儀-紫外光偵測器分析，其偵測極限低於0.4 ng/mL，定量極限低於1 ng/mL，相對標準偏差小於7.8 %，偵測真實水樣品回收率範圍為90.6-103.5 %，相對標準偏差小於9.2 %，且整體萃取過程時間花費小於5分鐘。由實驗結果可以證明以多孔性石墨烯-甲基丙烯酸甲酯共聚物作為吸附材料之移液管尖固相萃取技術是一種簡單、快速、低有機溶劑使用量且高靈敏度的綠色萃取技術。
運用多孔性石墨烯-甲基丙烯酸甲酯共聚物於攪拌棒吸附萃取的研究中，將石墨烯-甲基丙烯酸甲酯共聚物合成於攪拌磁棒外層，製備為攪拌棒萃取吸附材料，運用於雙酚A與四種烷基酚類化合物萃取。為獲得最佳萃取效果，研究中將對可能影響之參數，如攪拌速率、萃取時間、脫附溶劑種類、脫附溶劑體積與鹽析效應影響等進行探討。由實驗結果發現取50 mL不添加鹽類之水樣品，以400 rpm萃取40 分鐘，並使用100 μL之乙醇脫附具有最佳萃取效果。利用最佳化之條件對於水樣品中雙酚A與四種烷基苯酚化合物進行萃取，以液相層析儀-紫外光偵測器分析，其偵測極限低於0.04 ng/mL，定量極限低於0.1 ng/mL，相對標準偏差小於7.2 %，運用於真實水樣品偵測回收率範圍為90.5-106.4 %，相對標準偏差小於7.2 %。由實驗結果可以證明以多孔性石墨烯-甲基丙烯酸甲酯共聚物作為吸附材料之攪拌棒吸附萃取技術，是一種簡單、低有機溶劑使用量且高靈敏度的綠色萃取技術。
以多孔性石墨烯-甲基丙烯酸甲酯共聚物作為吸附材料的結果，已證明使用低溫凝膠合成的多孔性石墨烯-甲基丙烯酸甲酯共聚物是一種極具潛力的萃取材料。摘要 I
ABSTRACT III
目錄 V
圖目錄 VIII
表目錄 X
第1章 製備多孔性氧化石墨烯-甲基丙烯酸甲酯共聚物 1
1.1. 緒論 1
1.1.1. 石墨烯歷史 1
1.1.2. 石墨烯特性 1
1.1.3. 石墨烯在樣品前處理運用 4
1.1.4. 石墨烯多孔性整體柱材料 8
1.1.5. 低溫凝膠 10
1.1.6. 研究目的 13
1.2. 實驗 15
1.2.1. 化學藥品 15
1.2.2. 實驗器材 16
1.2.3. 氧化石墨烯製備 16
1.2.4. 氧化石墨烯修飾 17
1.2.5. 低溫凝膠製備甲基丙烯酸甲酯-石墨烯共聚多孔性材料 17
1.3. 結果與討論 18
1.3.1. 氧化石墨烯製備 18
1.3.2. 氧化石墨烯修飾 22
1.3.3. 低溫凝膠製備石墨烯-甲基丙烯酸甲酯多孔性材料 24
1.4. 小結 27
第2章 應用多孔性石墨烯-甲基丙烯酸甲酯共聚物於移液管尖固相萃取 28
2.1. 緒論 28
2.1.1. Triazine 除草劑介紹 28
2.1.2. Triazine除草劑分析方法 30
2.1.3. 移液管尖固相萃取技術 37
2.1.4. 研究目的 38
2.2. 實驗 40
2.2.1. 化學藥品 40
2.2.2. 實驗器材 40
2.2.3. 玻璃器皿去活化 41
2.2.4. Triazine 標準品配置 42
2.2.5. 緩衝溶液配置 44
2.2.6. 實驗方法 45
2.2.7. 條件探討步驟 49
2.2.8. 方法可行性之評估 50
2.3. 結果與討論 52
2.3.1. 樣品pH值影響 52
2.3.2. 沖提溶劑選擇 57
2.3.3. 沖提溶劑體積 59
2.3.4. 鹽析影響 61
2.3.5. 進樣速率影響 63
2.3.6. 方法可行性之評估 65
2.3.7. 方法比較 66
2.4. 小結 75
第3章 應用多孔性石墨烯-甲基丙烯酸甲酯共聚物於攪拌棒吸附萃取技術對水樣品中雙酚Ａ與烷基苯酚類化合物進行分析 76
3.1. 前言 76
3.1.1. 雙酚A與烷基苯酚類化合物介紹 76
3.1.2. 雙酚A與烷基苯酚類化合物分析方法 77
3.1.3. 攪拌棒吸附萃取 81
3.1.4. 研究目的 85
3.2. 實驗 89
3.2.1. 化學藥品 89
3.2.2. 實驗器材 89
3.2.3. 玻璃器皿去活化 90
3.2.4. 標準溶液配置 90
3.2.5. 實驗方法 92
3.2.6. 條件探討步驟 96
3.2.7. 方法可行性之評估 97
3.3. 結果與討論 99
3.3.1. 攪拌速度探討 99
3.3.2. 萃取時間影響 102
3.3.3. 脫附溶劑選擇 104
3.3.4. 脫附溶劑體積探討 106
3.3.5. 鹽析影響 108
3.3.6. 方法可行性之評估 110
3.3.7. 方法比較 111
3.4. 小結 119
第4章 結論 120
第5章 參考文獻 12
Content Similarity Assessment for Group Photo Retrieval
No full textIn this paper, we aim to achieve the group photo retrieval by assessing the content similarity of subjects in the group photos. We consider the spatial arrangements and gender information of people to assess the visual similarity between two group photos. For each group photo, we represent detected faces by using the spatial face context. Then, a graph matching with face orientation and gender information is performed to assess the similarity between two group photos. As shown in the experimental results, our method can retrieve group photos with similar orientations and genders of subjects compared to state-of-the-art methods.本論文探討如何由團體照片中人物的空間排列與性別組成來評估團體照片之間的相似性，並且根據此相似性來進行團體照片的檢索。為達此目的，我們先偵測每一張照片裡人臉的位置，並以空間臉部分布圖來建立人物在照片中的空間關係。最後利用出現在團體照片的人物的性別，以比較兩張團體照片的相似性。在實驗結果裡，我們列舉出與檢索照片的團體照性質最像的前三張照片。經問卷調查後，相較於過去的方法，我們的方法在人物空間排列和團體性別組成這兩項條件下，可以找到與檢索照片最相似的照片，從而解決團體照片檢索問題。摘要..................................................i
Abstract.............................................ii
Index...............................................iii
Figure and Table Index...............................iv
1. Introduction..................................1
2. Related Work..................................5
3. Method........................................9
3.1. Spatial Face Context..........................9
3.2. Gender Recognition Using Image Sets..........10
3.3. Training and Testing of SVM Classifier.......15
3.4. Similarity Assessment Using SFC with Face Information..........................................17
4. Experimental Results.........................22
4.1. Results of Gender Recognition................22
4.2. Results of Group Photo Retrieval.............22
5. Conclusion...................................29
6. Appendix: More experimental results..........30
7. References...................................3
Dictionary Based Trajectory Classification
No full textTrajectory classification is one of the most important topics in surveillance video analysis. To classify trajectories of the same events, assessing the similarity between trajectories with different lengths is required and remains a challenge problem. In this paper, we propose a new trajectory entropy descriptor (TED) to represent a trajectory without the interference of lengths. Then, we apply sparse representation to model the trajectories of the same event and design a new decision approach based on the sparsity and reconstruction errors to identify the class labels of the query trajectories by using the pre-trained dictionaries. Experimental results show the robustness of TEDs and also demonstrate the performance of the proposed classification method compared to the state-of-the-art methods.軌跡分類是現今監視影片分析中最重要的議題之一。因此要如何對於影片中所出現之長度不同的軌跡，比較軌跡之相似性並將同類型的軌跡進行分類是極具挑戰性的問題。在此篇論文中，我們提出了一個新的描述元來表示每一條軌跡在影片中的運動方式，並且不受軌跡長短不同所影響。接著我們套用了稀疏表示法來對於軌跡做學習並建立字典，接著利用稀疏性和重構錯誤值的資訊來對軌跡做事件分類。實驗結果顯示，利用本文提出之描述元來表示軌跡配合稀疏表示法，相較於過去其他方法更為精確。1. Introduction...3
2. Related Work...5
2.1 Unsupervised Methods...5
2.2 Supervised Methods...6
3. Method...7
3.1 Trajectory Entropy Descriptor...7
3.1.1 Velocity...7
3.1.2 Acceleration...8
3.1.3 Direction...8
3.1.4 Entropy Description...8
3.2 Sparse Representation Based TED Learning and Testing ...11
3.3 Sparsity as the Cue for Trajectory Classification ...12
4. Experiments...20
4.1 Dataset...20
4.1.1 Simulation dataset...20
4.1.2 Real dataset...20
4.2 Comparative Baselines...21
4.3 Parameter Setting...21
4.4 Results...21
4.4.1 Simulation...21
4.4.2 Real datasets...22
5. Conclusion...27
References...2
Effects of different process parameters on the properties of carbon films prepared by thermal chemical vapor deposition using propane/ammonia mixtures
No full textThis study investigates the effects of C3H8/(C3H8+NH3) ratio on the properties of carbon films prepared by thermal chemical vapor deposition. We also investigate the effects of mass flow rate, deposition temperature and working pressure on the deposition rates of carbon films. The thickness, microstructure, surface property, electrical property of carbon films and residual gas of process were investigated by field emission scanning electron microscopy, X-ray diffraction spectrometer, Raman scattering spectrometer, X-ray photoelectron spectrometer, atomic force microscopy, contact angle meter, four-points probe, and residual gas analyzer. Experimental results indicate that the deposition rate raises with increasing the C3H8/(C3H8+NH3) ratio, residence time, deposition temperature, and working pressure. About sixteen NH3 molecules will suppress one C3H8 molecule to form the carbon film. Moreover, the pyrolysis of C3H8/NH3 mixtures is dominated by about a first order process, which is arisen from the adsorption of main product gases methane (CH4), acetylene (C2H2), and ethylene (C2H4) on the silica glass plate substrate. The activation energy of this process is 439 kJ/mol. The surface roughness and electrical resistivity of carbon films increase with increasing the C3H8/(C3H8+NH3) ratio, but the crystallinity, degree of ordering, size of mean crystallite (La and Lc), content of sp2 C=C bonding and water contact angle of carbon films decrease. Finally, the results of thermal CVD carbon deposition using C3H8/NH3 mixtures are compared with those using CH4/NH3, C2H2/NH3, C2H4/NH3, and C3H8/N2 mixtures.本篇論文以熱化學氣相沉積法製備碳薄膜，探討不同C3H8/(C3H8+NH3)比例對碳薄膜性質之影響。並探討不同氣體總流量、沉積溫度和工作壓力對沉積速率的影響。利用場發射掃描式電子顯微鏡、X光繞射儀、拉曼散射光譜儀、X光光電子能譜儀、原子力顯微鏡、接觸角量測儀、四點探針儀和殘留氣體分析儀量測碳薄膜的沉積厚度、微觀結構、表面特性、電學性質和製程上之殘留氣體。實驗結果發現，碳薄膜的沉積速率會隨著C3H8/(C3H8+NH3)比例、停留時間、沉積溫度以及工作壓力的增加而上升。在沉積過程中，16個氨氣會抑制1個丙烷形成碳薄膜。碳薄膜主要是由氣體中的CH4、C2H2和C2H4裂解沉積於石英玻璃平板上，其為1次方反應過程。此實驗之活化能約為439 kJ/mol。碳薄膜的表面粗糙度與電阻率會隨著C3H8/(C3H8+NH3)比例增加而上升；而碳薄膜的結晶度、結構有序程度、平均晶粒大小 (La和Lc)、sp2 C=C鍵結的相對含量與水接觸角會隨著C3H8/(C3H8+NH3)比例增加而下降。最後，將本實驗丙烷/氨氣與甲烷/氨氣、乙炔/氨氣、乙烯/氨氣和丙烷/氮氣之碳薄膜性質互相比較。摘要 iv
ABSTRACT v
總目錄 vi
圖目錄 ix
表目錄 xii
第 1 章 緒論 1
1.1 碳材料介紹 1
1.2 熱化學氣相沉積法 6
1.2.1 熱化學氣相沉積法簡介與特色 6
1.2.2 熱化學氣相沉積法機制 7
1.2.3 薄膜成長機制 10
1.3 研究動機與目的 12
1.4 論文概述 13
第 2 章 實驗步驟 14
2.1 試片準備與前處理 16
2.2 碳薄膜的製備 17
2.2.1 熱化學氣相沉積系統之簡介 17
2.2.2 沉積參數和實驗流程 20
2.3 碳薄膜的量測 23
2.3.1 薄膜厚度量測 23
2.3.2 微觀結構分析 24
2.3.3 表面特性量測 34
2.3.4 電學性質量測 39
2.3.5 殘留氣體分析 42
第 3 章 結果與討論 44
3.1 不同丙烷/氨氣比例對碳薄膜性質之影響 44
3.1.1 沉積厚度變化 44
3.1.2 微結構分析 47
3.1.3 表面粗糙度及抗水性質 59
3.1.4 電學性質分析 64
3.1.5 殘留氣體分析 66
3.2 改變不同製程參數對碳薄膜之影響 68
3.2.1 不同氣體總流量對碳薄膜之影響 68
3.2.2 不同沉積溫度對碳薄膜之影響 71
3.2.3 不同工作壓力對碳薄膜之影響 73
3.2.4 不同丙烷/氨氣比例、氣體總流量、沉積溫度及工作壓力之討論與比較 75
第 4 章 結論 79
參考文獻 80
作者簡介 8
Preparation and Crystallization of Syndiotactic Polystyrene/MMT nanocomposites
No full textSyndiotactic polystyrene (sPS), a crystalline polymer with a high melting point, exhibits four different polymorphic crystalline behavior, namely α, β, γ and δ. The α- and β-form, both containing planar zigzag chains with the all-trans conformation, can be obtained from the melt or glass state of sPS under different thermal crystallization conditions. For the γ and δ forms, the molecular chains have the helical conformation, which is strongly depended on the solution treatment.
The sPS/montmorillonite (MMT) nanocomposites prepared by modified MMT were well dispered in sPS. X-ray diffraction data show the montmorillonite are intercalated into the sPS molecular chain with the interlayered spacing of 3.74 nm. TEM micrographs shows the montmorillonite was well distributed in sPS/MMT nanocomposites.
XRD analysis operated from room temperature to 250℃, was perfomed to investigate the structural changes in sPS. The δ form can be obtained by supplying 1,2,4-Trichlorobenzene (TCB) in sPS. By heating the δ form above 110℃, it can be transformed to the γ form. This γ form was further transferred into the α form by heat treatment over 190℃. The in-situ FTIR results were also observed a similar transition temperature of crystallization. The results indicate that the addition of more than 2wt% montmorillonite induces α-form at room temperature. With the continuous increase of montmorillonite content, the transformation temperature was reduced from 190℃ to 130℃. TGA results revealed the thermal properties of sPS/MMT composites were improved by increasing content of MMT.
DSC scans were used to investigate the nonisothermal crystallization behavior and crystallization kinetics mechanism. The addition of MMT into sPS matrices induces faster crystallization rate. These results of sPS/MMT nanocomposites shows that the addition of MMT caused heterogeneous nucleation. 1 wt% MMT-containing sPS/MMT nanocomposites shows the highest crystallization peak temperature, but the addition of more MMT into sPS matrix causes lower crystallization peak temperature. These results indicate that MMT also cause steric hindrance and reduces the transportation ability of polymer chains during crystallization processes. For nonisothermal crystallization processes, the crystallization parameters k, n and activation energy can be analyzed by using Ozawa equation to understand the influence of the addition of modified MMT into sPS.對位聚苯乙烯 (Syndiotactic polystyrene, sPS) 為一種結晶性高分子，具有高熔點，並且隨結晶環境的不同，會有α、β、γ、δ四種結晶形態產生；α、β晶相一般為熱熔結晶時形成，屬於TTTT平面鋸曲狀結構，而γ、δ晶型則屬於立體螺旋結構，需在溶劑誘導下才會產生。
本研究利用改質蒙脫土 (Montmorillonite, MMT) 均勻分散在對位聚苯乙烯中，製備對位聚苯乙烯/蒙脫土奈米複合材料。藉X光繞射結果得知，蒙脫土經改質後層間距離被撐開至3.74 nm；以穿透式電子顯微鏡觀察，蒙脫土在對位聚苯乙烯基材中呈現均勻分散而無明顯團聚現象發生。
我們利用X光繞射分析儀 (X-Ray diffraction, XRD) 搭載溫控加熱器，分析由室溫升溫至250℃，觀察sPS及sPS/MMT複材的結晶結構變化，首先藉由溶劑1,2,4-三氯苯 (1,2,4-Trichlorobenzene, TCB) 誘導sPS形成δ晶型，在升溫至110℃可得到γ晶型，再將溫度升高至190℃之後轉變為α晶型，變溫FTIR之結果也可觀察到類似變溫XRD的晶相轉變趨勢。本研究發現，sPS/MMT複材中添加2%以上的蒙脫土會在室溫下形成部分α晶型，且隨著蒙脫土含量的增加，會降低α-form的轉換區間溫度由190℃降至130℃。利用熱重損失儀 (Thermogravimetric Analysis, TGA) 的結果中發現隨著MMT含量的增加，複材熱穩定性質得到明顯的提升。
我們也以微差掃描式熱分析儀 (Different Scanning Calorimeter, DSC) 研究sPS及sPS/MMT奈米複材的非等溫結晶行為及動力學機制。從結果中發現添加蒙脫土可使sPS結晶行為提早發生，顯示MMT在sPS基材中扮演異質成核的角色，但是sPS添加1wt% MMT時的結晶峰溫度達到最高，隨著MMT添加量的上升，高分子的結晶溫度並無進一步的提升，代表MMT也在結晶成長過程中扮演著干擾sPS分子鏈段排列結晶的立體空間障礙而影響整體結晶。在非等溫結晶動力學部分，本研究以Ozawa equation 來進行探討sPS及sPS/MMT複材的結晶指數 (n)、結晶速率常數 (k) 及活化能的變化，加以瞭解添加改質MMT對sPS基材所產生的影響。中文摘要 I
英文摘要 II
目錄 III
圖目錄 V
表目錄 VIII
一、緒論 1
1.1. 前言 1
1.2. 研究動機與目的 1
1.3. 研究方向 2
二、文獻回顧 3
2.1. 對位-聚苯乙烯 3
2.2. 對位-聚苯乙烯的結晶結構 4
2.3. 對位-聚苯乙烯的結晶控制條件 5
2.4. 對位-聚苯乙烯的結晶鑑定 8
2.5. 蒙脫土簡介與表面改質 9
2.6. 對位-聚苯乙烯複合材料 11
2.7. 高分子結晶動力學 12
三、實驗方法及步驟 15
3.1. 實驗材料 15
3.2. 實驗步驟 16
3.3. 實驗流程圖 17
3.4. 實驗儀器 18
四、結果與討論 20
4.1. 蒙脫土表面改質 20
4.2. 對位-聚苯乙烯/蒙脫土奈米複合材料 23
4.3. 對位聚苯乙烯/蒙脫土奈米複合材料溶劑誘導結晶的探討 30
4.4. 對位-聚苯乙烯/蒙脫土奈米複合材料非等溫結晶行為分析 47
4.5. 對位-聚苯乙烯/蒙脫土奈米複合材料非等溫結晶動力學 52
五、結論 66
六、參考文獻 6