1,721,041 research outputs found
A Novel Crossover Operator in the Genetic Algorithm for Design of Diffractive Optical Element
Suppression on the mutagenicity of 4-nitroquinoline-N-oxide by the methanol extracts of soybean koji prepared with various filamentous fungi
In this study, solid fermentation of soybean with various GRAS filamentous fungi including Aspergillus sojae BCRC 30103, Aspergillus
oryzae BCRC 30222, Aspergillus awamori, Actinomucor taiwanesis and Rhizopus sp. was performed to prepare various soybean kojis. Toxicity,
mutagenicity and suppression on the mutagenesis induced by a direct mutagen, 4-nitroquinoline-N-oxide (4-NQO) on Salmonella typhimurium TA
100, by the various methanol extracts of the prepared soybean koji and unfermented soybean were determined and compared.
Results revealed that methanol extracts of unfermented soybean and kojis show no toxicity and mutagenic activity within the dose levels
examined on test organism. On the other hand, antimutagenic activity against 4-NQO was observed with the extract of unfermented soybean.
Furthermore, fermentation, regardless of the starter organism employed, resulted in an enhanced antimutagenic effect on the mutagenesis of 4-
NQO by the extracts of the soybean koji. Across the dose range (0.625–5.0 mg/plate) tested, a dose-dependent antimutagenic activity was
observed. Antimutagenic activities of the koji extracts varied with starter organism, with A. awamori-prepared koji extract exhibiting the highest
rate of suppression on the mutagenicity of 4-NQO. Further study with A. awamori also revealed that fermentation temperature affected the
antimutagenic activity of the prepared koji extract. In general, the extract of the A. awamori-soybean koji prepared at 30 °C showed a higher
antimutagenic activity than those prepared at 25 or 35 °C
Antioxidative and antimutagenic activities of the soybean koji extract prepared with different starters
本研究比較5株常用菌酛:Aspergillus sojae BCRC 30103、Aspergillus oryzae BCRC 30222、Aspergillus awamori、Actinomucor taiwanensis及Rhizopus sp.所製備黃豆豆麴甲醇萃出物之抗氧化 (DPPH自由基清除、亞鐵離子螯合及還原力)與對4-Nitroquinoline N-oxide (4NQO)之抗致突變活性。並進一步探討不同溫度下製備Asp. awamori-豆麴之甲醇萃取物對抗氧化活性與抗致突變性之影響。
結果顯示,黃豆對於所有試驗菌株均為一良好生長基質,且黃豆發酵後其所測得之抗氧化活性與總酚類化合物含量均提高。其中以Asp. awamori-豆麴之甲醇萃取物呈現較強之DPPH自由基清除力、亞鐵離子螯合力、還原力及抗致突變活性。此外此豆麴萃出物具有最高之總酚類化合物含量。進一步利用Asp. awamori在不同溫度 (25℃、30℃及35℃)與發酵時間 (1~5天)下製備豆麴,發現以30℃發酵3天之Asp. awamori-豆麴之甲醇萃出物所呈現之抗氧化活性最高,亦具有最高之總酚類化合物含量,顯示總酚含量與抗氧化能力有關連性。而在35℃下製備之Asp. awamori-豆麴之甲醇萃出物所呈現之抗致突變性明顯 (p < 0.05)高於在其他溫度下所製備者。In the present study, methanolic extracts of soybean koji prepared with various starters:Aspergillus sojae BCRC 30103、Aspergillus oryzae BCRC 30222、Aspergillus awamori、Actinomucor taiwanensis or Rhizopus sp. were investigated for their antioxidative activities (DPPH radicals scavenging effects, Fe+2-chelating ability and reducing power) and antimutagic avtivities against 4-Nitroquinoline N-oxide (4NQO). Effects of fermentation temperature and time on the antioxidative and antimutagenic activity of extracts of Asp. awamori-koji were also measured.
The results showed soybean was good substrate for the grown of all the starters tested. The antioxidative activity, antimutagenic activity and total phenolic content of the extract of soybean were increased after fermentation. The soybean koji prepared with Asp. awamori exhibited the highest DPPH free radical scavenging activity, Fe+2-chelating ability, reducing power and contained the highest total phenolic content among the 5 kinds of koji tested. Studies on the soybean koji prepared with Asp. awamori at different temperatures (25℃、30℃ and 35℃) and fermented periods (1~5 days) further revealed that the methanolic extract of Asp. awamori-koji fermented at 30℃ for 3 days showed the highest antioxidative activity and containted the highest amount of total phenolic compounds. It suggested that the total phenolic content might be related to the antioxidative activity observed. In addition, the extract of Asp. awamori-koji fermented at 35℃ showed a higher antimutagenic activity than those prepared at the other temperatures.中文摘要------------------------------------------------------------------------------------ Ⅰ
英文摘要------------------------------------------------------------------------------------ Ⅱ
目錄------------------------------------------------------------------------------------------ Ⅲ
圖次------------------------------------------------------------------------------------------ Ⅵ
表次------------------------------------------------------------------------------------------ Ⅶ
壹、前言------------------------------------------------------------------------------------ 1
貳、文獻回顧------------------------------------------------------------------------------- 3
一、黃豆--------------------------------------------------------------------------------- 3
1. 黃豆簡介-------------------------------------------------------------------------- 3
2. 黃豆之機能性-------------------------------------------------------------------- 3
2.1 異黃酮---------------------------------------------------------------------------- 4
二、發酵食品之抗氧化性與抗致突變性------------------------------------------- 5
1. 微生物之抗氧化性與抗致突變性-------------------------------------------- 5
2. 微生物發酵食品之抗氧化性與抗致突變性-------------------------------- 7
三、氧化作用及抗氧化之機制與原理--------------------------------------------- 9
1. 自由基與活性氧----------------------------------------------------------------- 9
2. 活性氧的種類與來源----------------------------------------------------------- 10
3. 自由基對生物體之作用與傷害----------------------------------------------- 10
4. 氧化性傷害----------------------------------------------------------------------- 12
5. 抗氧化劑作用的原理與機制-------------------------------------------------- 12
(1)自由基終止型 (free radical terminator)----------------------------------- 12
(2)還原劑或氧清除劑 (reducing agent or oxygen scavengers)----------- 12
(3)單重態氧抑制劑 (singlet oxygen inhibitor)------------------------------ 14
(4)金屬螯合劑 (chelating agent)----------------------------------------------- 14
(5)抗氧化酵素 (antioxidative enzyme)--------------------------------------- 14
6.天然抗氧化劑---------------------------------------------------------------------- 15
四、癌症形成原因與抗癌機制------------------------------------------------------ 15
五、安氏實驗法------------------------------------------------------------------------ 19
參、材料與方法--------------------------------------------------------------------------- 23
一、材料--------------------------------------------------------------------------------- 23
1. 菌種-------------------------------------------------------------------------------- 23
2. 黃豆-------------------------------------------------------------------------------- 23
3. 培養基----------------------------------------------------------------------------- 23
4. 試驗藥品-------------------------------------------------------------------------- 23
5. 儀器設備-------------------------------------------------------------------------- 24
二、樣品製備--------------------------------------------------------------------------- 25
1. 菌株之保存與活化-------------------------------------------------------------- 25
2. 冷凍保存-------------------------------------------------------------------------- 25
3. 活化-------------------------------------------------------------------------------- 25
4. 接種源之製備-------------------------------------------------------------------- 25
5. 豆麴之製備----------------------------------------------------------------------- 25
6. 豆麴甲醇萃取物之製備-------------------------------------------------------- 26
三、分析方法---------------------------------------------------------------------------- 26
1. 豆麴萃取物之萃出率----------------------------------------------------------- 26
2. 菌絲含量測定-------------------------------------------------------------------- 26
3. 豆麴萃取液之總酚類化合物含量-------------------------------------------- 27
4. 抗氧化活性之檢測-------------------------------------------------------------- 27
4.1 DPPH自由基清除效力-------------------------------------------------------- 27
4.2 亞鐵離子螯合能力------------------------------------------------------------- 28
4.3 還原力測定---------------------------------------------------------------------- 28
5. 抗致突變性試驗 ---------------------------------------------------------------- 28
5.1 S. typhimurium TA 100 BCRC 12378之保存與活化---------------------- 29
5.2 S. typhimurium TA 100 BCRC 12378之基因型態確認------------------- 29
5.3 毒性試驗------------------------------------------------------------------------- 31
5.4 致突變性試驗------------------------------------------------------------------- 31
5.5 抗致突變性試驗---------------------------------------------------------------- 32
6. 統計分析-------------------------------------------------------------------------- 32
肆、結果與討論--------------------------------------------------------------------------- 33
一、不同菌酛製備豆麴之甲醇萃取物菌絲之增殖------------------------------- 33
二、不同菌酛製備豆麴甲醇萃出物之抗氧化活性------------------------------- 33
1. DPPH自由基清除效力---------------------------------------------------------- 33
2. 亞鐵離子螯合能力-------------------------------------------------------------- 37
3. 還原力----------------------------------------------------------------------------- 39
4. 不同豆麴抗氧化活性之比較-------------------------------------------------- 42
三、豆麴萃取物中總酚類化合物之含量------------------------------------------- 44
四、不同溫度下製備Asp. awamori-豆麴甲醇萃取物及菌絲之增殖---------- 46
五、不同溫度下製備Asp. awamori豆麴之甲醇萃出物之抗氧化活性-------- 46
六、不同溫度下製備Asp. awamori-豆麴中總酚類化合物之含量------------- 52
七、不同發酵時間下製備Asp. awamori-豆麴甲醇萃取物及菌絲之增殖---- 52
八、不同發酵時間下製備Asp. awamori-豆麴之甲醇萃出物之抗氧化活性 55
九、不同發酵時間下製備Asp. awamori-豆麴中總酚類化合物含量測定---- 60
十、不同菌酛製備豆麴萃取物之抗致突變性------------------------------------ 62
1. S. typhimurium TA 100 試驗菌株基因型態之確認------------------------ 62
(1)組酸酸需求性之確認------------------------------------------------------- 62
(2) rfa突變之測試---------------------------------------------------------------- 62
(3) uvrB突變之測試------------------------------------------------------------- 62
(4) R-factor之測試--------------------------------------------------------------- 62
十一、不同菌酛製備豆麴萃取物之毒性與抗致突變性------------------------ 63
十二、不同菌酛製備豆麴萃取物之抗致突變性試驗--------------------------- 63
十三、不同溫度製備豆麴萃取物其抗致突變分析------------------------------ 69
伍、結論------------------------------------------------------------------------------------- 74
陸、參考文獻------------------------------------------------------------------------------- 7
Morphodynamic properties of flowing leukocytes under bright-field microscope
血液檢測為健康檢查中重要參考指標之一,血液中各個角色的數量與比例都可以作為臨床上評估狀況的參考,如紅血球數量可以判斷是否貧血、白血球多寡可以判斷癌症、HIV 等等。傳統血液抹片檢查為相當常見的檢查項目,但相當耗時耗力,而為了達到自動高速計數的目標,科學家們開始發展了血球計數器、血液分析儀,目前最為精確的儀器為流式細胞分選儀,與傳統的血液抹片檢查相比,流式細胞分選儀可以達到相當高速的血球計數且分選特定系細胞目的。 流式細胞分選儀中有四大系統: 液相系統、光學系統、電子系統、分選系統。利用前散射光(Forward Scattering)、側散射光(Side Scattering)、螢光(Fluorescence)作為限制條件以分選出不同種類細胞。然而,流式細胞分選儀常為達到更高的分選精確性,需要添加染劑,但這不僅需要雷射維護費用、染劑費用,亦有可能對於細胞造成傷害,因此本研究室積極尋找其他細胞影像上特徵以提升分選細胞的 可能性。 本研究室先前嘗試以倍頻顯微術觀察中性粒白血球(Neutrophil)、單核球(Monocyte)、淋巴球(Lymphocyte)的三倍頻強度,從影像中可以發現中性粒細胞比淋巴球、單核球三倍頻訊號更強,且細胞內有許多小核體,淋巴球尺寸最小、細胞內常有一圓核並伴隨一圓型亮點,單核球細胞尺寸最大。藉由三倍頻強度、自體紅螢光強度、大小可以作為三維度限制條件分選此三類白血球。 然而,無論是流式細胞儀或倍頻顯微術皆需要依賴雷射光源,為了減少雷射維護與染劑使用上的費用,本研究積極發展一種嶄新方式分選白血球種類,主要利用血球的大小與機械性質的不同在明視野與不須染劑的情況下達到分選中性粒白血球(Neutrophil)、單核球(Monocyte)、淋巴球(Lymphocyte)的目的。首先,本研究對於靜置狀態下的白血球分別以雷射光源的Leica TCS SP5 II 多光子雷射共軛焦顯微鏡與明視野下的螢光顯微鏡Leica DMI 3000B 搭配CCD 做型態上變形分析。再者,將中性粒白血球(Neutrophil)、單核球(Monocyte)、淋巴球(Lymphocyte)分別以微注射幫浦加壓入微流道中,觀察細胞在不同流力場中所受正向應力、剪應力時所產生的形變。研究結果中可以發現在高流速狀態下,淋巴球細胞有較大的變形,而大小也有顯著的差異,意味著明視野顯微影像的確適合應用在高流速環境下的血球觀察,在未來,本研究室希望以雷射層照顯微術以高速成像方式觀察更高流速的細胞影像,以影像上的資訊達到無須染色方式增加流式細胞分選儀的分辨率。從長遠來看,本研究對於血球細胞於流體動力學上的價值除了可以應用離體血液檢查儀器上提高血液分析品質外,在未來亦可以做為非侵入式血液檢查發展中血液流體動力學研究上的參考指標。Blood test is one of the most important indicators of physical examination. The amount and proportion of every role in blood can be direction of medical assessment. For instant, the amount of red blood cell could be the sign of Anemia. Also, the variety of amount of white blood cell could be a guide of HIV, cancer, and other disease. In more detail, traditionally, biopsy is a relatively common inspection, but it wastes many time and artificially efforts. Thus, in order to achieve automatically cell counting goal, in the past decades, scientists have beginning to develop CBC (Complete Blood Count), and Blood analysis technology. In the moment, the most accurate and precise machine is Flow cytometer (FCM). Compare to traditional biopsy inspection, FCM can not only count blood cell with higher speed but also can sort specific cell and particles. FCM was divided into four parts: microfluidic system, optical system, electric system, and sorting system. The intensity of forward scattering, side scattering, and fluorescence serve as the index to distinguish different kinds of cells. Nevertheless, in order to achieve higher accuracy, it frequently is required to add particular biomarker, which probably damage intact cell, moreover, increase the cost for laser maintenance. Therefore, currently our Lab devote to develop cell sorting with higher quality depended on the characteristics of cell image in many ways. Previously, our Lab differentiates Neutrophils, Monocytes, Lymphocytes by the intensity of Third-Harmonic Generation. From the cell image, we can find the intensity of Third-Harmonic Generation of Neutrophils is higher than Monocytes and Lymphocytes. Besides, Neutrophils included many small nucleuses. With the intensity of Third-Harmonic Generation, auto-fluorescence and size and size, we can divide these three kinds of leukocytes into three groups. However, both Flow Cytometry and Harmonic Generation technique need to depend on laser source, so this thesis devote to develop an innovative way to distinguish different kinds of leukocytes without the maintenance of laser source and the waste of biomarker. To achieve our goal, the main approach in this thesis is that by size of leukocytes and morphodynamic properties of leukocytes under bright-field to sort different kinds of leukocytes without biomarker. First, we observe the morphology of stationary leukocytes on cover glass by Leica TCS SP5 II confocal microscope with laser source, resonant scanner and Leica DMI 3000B Fluorescence microscope with CCD under bright-field. Secondly, we pμmp Neutrophils, Monocytes and Lymphocytes into microfluidic channel and observe the deformation of cells suffer from normal stress and shear stress under different flow field. From the result, we can find the lymphocytes deform significantly under higher speed. Moreover, the difference of size of kinds of leukocytes is significantly obvious that means bright-field image is able to be applied to observe blood cells in high speed. In near future, our lab plan to use laser light sheet microscopy to observe cell image with higher speed, which can increase the sorting precision of Flow cytometry without biomarker. In the long run, the value of this thesis not only helps increase the quality and accuracy of blood sorting machine in vitro, but also can be served as haemodynamic reference for in vivo developing non-invasive blood inspection
Studies on the properties of GaAsSbN/GaAs p-i-n devices
氮砷銻化鎵材料在適當的銻/氮莫爾分率比可有晶格匹配砷化鎵以及能隙低於砷化鎵基板的特性。故此材料是一具有潛力應用砷化鎵基板之上的異質接面電晶體(HBT)或是堆疊式太陽電池的子電池。但是摻入氮會造成塊材材料內部或是異質接面處產生缺陷,使得HBT應用上無法得到高增益,太陽電池應用上無法提高開路電壓。
本篇論文的研究主題使用能隙為1.17-eV之砷化鎵/氮砷銻化鎵在砷化鎵基板上成長異質接面p-i-n元件之特性分析。由不同氮砷銻化鎵厚度(250、500、1000和2000 nm)的元件在不同熱退火條件下的電流電壓特性。未經熱退火製程在順向偏壓中,相同電流密度(0.05 mA/cm2)時電壓隨著厚度的減少而上升0.38至0.46伏特,顯示磊晶的缺陷隨著厚度增加而逐漸產生。經熱退火製程後電流密度變化則不明顯,顯示與元件的厚度無關為表面的復合電流所影響。由飽和電流密度對溫度的關係,我們可求得元件飽和電流密度的活化能,我們發現熱退火後可以讓該活化能趨近能隙,表示表面復合電流下降。熱退火後的的元件經鈍化處理後相同電流密度(0.05 mA/cm2)時電壓會上升50~70 mV,在42倍AM1.5G太陽模擬光源照射時太陽電池轉換效率6.6%We study the fabrication and the properties of GaAs/GaAs0.97Sb0.02N0.01 heterjunction diodes deposited on GaAs. The energy gap of the GaAs0.97Sb0.02N0.01 layer is 1.17 eV. We found that all the forward currents are higher than the expected p/n junction diffusion current and increases as the GaAs0.97Sb0.02N0.01 layer thickness increases. In addition, the current is proportional to the perimeter instead of the area of the junction, suggesting that it originates from the recombination on the junction surface. From the Arrhenius plot of the saturation current, we found that the activation energy of the as-grown sample is close to half the energy gap of GaAs0.97Sb0.02N0.01, suggesting that the current is a defect recombination current. After thermal annealing, the activation energy increases, indicating the suppression of the surface recombination current. Coating SiN and SiN/SiO2 passivation layers on the junction surface significantly reduces both the reverse and forward currents. The passivated GaAs/ GaAs0.97Sb0.02N0.01 heterjunction shows an optimum conversion efficiency of 6.6% under 42 times of AM1.5G illumination
DS-CDMA Receiver Design with Joint FDE and Antenna Diversity Techniques
展頻分碼多工(DS-CDMA)技術由於具有提供高速傳輸的特性,因此被廣泛的使用於現今的行動通訊系統當中。然而,隨著科技不斷的進步,使用者對於更高速下載的需求也隨之而起,因此,在如此高速的無線傳輸過程之中,多路徑通道在頻率選擇性衰減所造成的影響之下,傳統上DS-CDMA系統中所使用的耙式接收機,其系統效能將會嚴重的下降。因此,為了克服這個問題,並且同時考慮接收機設計的複雜度因素,我們選擇以頻域等化器設計作為本篇論文探討的主軸。除此之外,由於多工的維度不斷的增加及等化器設計不完美等種種因素,系統效能將會被限制而無法提供準確的資料傳輸,因此,為了克服這些問題,本篇論文提出以一種方塊平行干擾消除的技術以期進一步增進系統效能。同時,為了避免通道嚴重衰減(deep fading)效應對於接收訊號產生影響,接收端的多天線分集技術也將在本篇論文當中使用。最後,為了驗證本篇論文中所提出的接收機設計方法在效能改善上的成效,我們將使用蒙地卡羅(Monte Carlo)模擬法進行分析及驗證。結果顯示,無論使用何種展頻因子或多工維度,我們所提出的接收機設計方法都能夠有效的改善系統效能。若將我們所提出的方法結合接收端的多天線分集技術應用,則系統效能將有更進一步的改善。Rake receiver has been proposed for DS-CDMA system since 1995s. However, the propagation channel suffers from severe frequency-selective fading due to high-speed data transmission so that the performance of Rake receiver severely degrades. Besides, the error floor scenario would appear if the system capacity is high enough. In order to overcome the drawbacks as mentioned above, FDE based receiver structure is introduced in this thesis. Three kinds of implementation methods are taken into account on designing FDE receiver, which are respectively MRC, ZF, and MMSE. From the theoretical and simulation results, MMSE-FDE receiver design method can obtain the best behavior since it can jointly deal with interference and noise effects. However, the system performance with FDE receiver is eliminated if the number of multiplex order increases or the equalization procedure is imperfect. To overcome these restrictions, MMSE-FDE receiver with BPIC technique is proposed to cancel the residual interference and improve the system performance. In addition, receiver antenna diversity technique is also employed in this thesis since it can combat the deep fading effects and provides a diversity gain to improve the system performance. Monte Carlo simulation is performed and the results would show that MMSE-FDE receiver design method can further improve the system performance through applying BPIC technique. Moreover, the performance would approach to the theoretical lower bound more closely if antenna diversity technique is employed.Abstract I
Contents III
List of Figures VII
List of Tables IX
Chapter 1 Introduction……………………………………………………………1
1.1 Multiple Access Principle 1
1.2 Overview of the Mobile Cellular Communication System 2
1.3 Benefits of DS-CDMA System 4
1.4 Motivation 6
1.5 Organization of the Thesis 9
Chapter 2 System Description for DS-CDMA Downlink……....................11
2.1 Transmission Structure for DS-CDMA Downlink 11
2.1.1 The System Details 12
2.1.2 Signal Representation 13
2.1.3 Cyclic-Prefix DS-CDMA (CP-DS-CDMA) 15
2.2 Spreading Codes 16
2.2.1 Channelisation Codes 17
2.2.2 Scrambling codes 18
2.3 Diversity Techniques 19
2.4 Conventional Rake Receiver for DS-CDMA 21
Chapter 3 FDE Receiver for DS-CDMA System………….………………..23
3.1 FDE Receiver Structure for DS-CDMA Downlink 23
3.1.1 FDE Receiver Structure 24
3.1.2 Weights Design Method of FDE Receiver 27
3.2 FDE Receiver with Antenna Diversity Combining Technique 30
3.2.1 FDE-ADC Receiver Structure 31
3.2.2 Weights Design Method of FDE-ADC Receiver 34
3.3 Theoretical BER Performance 37
3.3.1 Expression for Conditional BER 37
3.3.2 Lower Bounded BER 39
Chapter 4 Joint MMSE-FDE and AD Receiver for DS-CDMA System….……………………………………………………………...43
4.1 Interference Cancellation Concepts 43
4.2 The Problem Description 45
4.3 A Novel MMSE-FDE Receiver with BPIC Technique 48
4.3.1 Mathematical Derivation 50
4.3.2 Symbol Decision Methods 56
4.4 A Novel Joint MMSE-FDE and AD Receiver with BPIC Technique 58
4.4.1 Mathematical Derivation 58
Chapter 5 Simulation Results and Analysis………………………………....65
5.1 Simulation Environment 65
5.2 Simulation Results 67
5.2.1 Simulation of FDE System 67
5.2.2 Simulation of FDE System with AD Technique 76
Chapter 6 Conclusion………………………………............................................85
References………………………………………………………………………….88
Appendix A…………………………………………………………………………91
Appendix B…………………………………………………………………….......93
Appendix C…………………………………………………………………….......9
Enhanced antioxidative activity of soybean koji prepared with various filamentous fungi
In the present study, soybean koji fermented with various GRAS filamentous fungi, including Aspergillus sojae BCRC 30103,
Aspergillus oryzae BCRC 30222, Aspergillus awamori, Actinomucor taiwanensis and Rhizopus sp. These organisms are commonly used as
starters in the fermentation of many traditional, oriental food products. The growth of starter organisms, total phenolic content, and
antioxidative activities of the methanol extract of these kojis are compared with specific reference to a-diphenyl-2-picryl-hydrozyl
(DPPH) radicals scavenging effects, Fe2+-chelating ability, and reducing power. Depending on starter organism, various extents of
mycelia propagation (35.23–86.29 mg/g koji) were noted after 3 days of fermentation. Total phenolic content increased in soybean after
fermentation. Koji also displayed enhanced antioxidative activates in comparison with the non-fermented soybean. Among the five kinds
of koji tested, those fermented with Asp. awamori exhibited the highest levels of DPPH-free radicals scavenging activity, Fe2+-chelating
ability and reducing power. The DPPH-free radicals scavenging activity and Fe2+-chelating ability of this soybean koji was ca. 8.9 and
6.7 fold that of the control. Analysis of the dose-response effect also revealed that before reaching a threshold point, there is a linear
relationship between increases in antioxidative activity and increases in the concentration of the koji extract. These results show the
potential for developing a healthy food supplement with soybean fermented by the GRAS filamentous fungi
Synthesis, Morphology, and Applications of Block Copolymers with Different Architectures:PS-b-P4VP and F-b-P2VP
在當代巨分子科學領域中,嵌段共聚物是眾多研究工作中的焦點,這歸因於其一系列吸引人的基礎問題,這些問題伴隨著暸解其在溶液及固態的自組裝過程;嵌段共聚物呈現出一個具有廣泛研究重點的主題,這些主題跨越了巨分子化學與物理:包括新合成方法的開發、製備不同構型的共聚物、電腦的理論模擬、自組裝行為與形態的研究及共聚物的應用......等;本研究論文的目標為對於高分子科學中嵌段共聚物的物理與化學性質提供有益的瞭解,本論文研究的重點可以簡述如下,包括對於具有線性及非線性(星狀)之雙親性柔軟-柔軟及共軛性硬桿-柔軟嵌段共聚物的合成、自組裝結構及物理性質探討,及共軛性硬桿-柔軟嵌段共聚物於電紡技術的應用。這些研究主題將於下段開始再進一步描述。第一部份(第二章),新型雜臂星狀雙親性共聚物:polystyrene-b-poly(4- vinylpyridine) (PS-b-P4VP)以陰離子活性聚合法製備出四種不同共聚莫耳比例的樣品;這些共聚物於溶液中在不同構形、選擇性溶劑含量、共同溶劑的極性及不同共聚比例的微胞結構被探討。我們使用動態/靜態光散射儀(DLS/SLS)、穿透式電子顯微鏡(TEM)及原子力顯微鏡(AFM)分析微胞的結構;從實驗結果得知,在DMF/H2O的混合溶劑環境中,星狀共聚物的聚集尺寸及微胞中分子鏈數目均小於其相似比例的線性共聚物,而星狀共聚物的聚集結構也被觀察到當選擇溶劑含量的增加其有了從球狀到柱狀、空心球狀及聚集的空心球狀的轉變。除此之外,當共聚物於DMF/H2O或1,4-dioxane/H2O呈現球狀時,其卻於THF/H2O中呈現大的聚集微胞結構,這是因為PS鏈段在不同溶液環境中有不同的伸展程度。當P4VP鏈段於共聚物中的莫耳比例由0.37降到0.24、0.12及0.07時,其微胞結構呈現了球狀與柱狀混合、空心球狀、巨大空心球狀及大的聚集微胞等不同結構,這些不同結構的原因乃歸因於核心鏈段不同的伸展程度所致。因此,此研究證明了聚合物構形對於聚集行為的影響及星狀共聚物於溶液下可以藉由改變調整溶劑極性及共聚鏈段比例而得到多元的微胞聚集結構。第二部份(第三章),新型硬桿-柔軟雙嵌段式及三嵌段式包含硬桿鏈段為poly(2,7-(9,9-dihexylfluorene))(PF)及柔軟鏈段為poly(2-vinylpyridine) (P2VP)的共聚物以結合耦合反應及陰離子聚合法製備;我們使用原子力顯微鏡(AFM)、穿透式電子顯微鏡(TEM)、動態光散射儀(DLS)及冷凍穿透式電子顯微鏡(cryo-TEM)分析共聚物於不同比例的MeOH/THF混合溶液下之聚集結構,微胞結構對於光電性質的影響將以UV-vis 光吸收及PL光放射光譜圖探討。由實驗結果得知,雙嵌段式共聚物PF-b-P2VP於MeOH比例增加時維持其球狀形狀,然而,三嵌段式共聚物P2VP-b-PF-b-P2VP卻在MeOH增加時聚集成柱狀結構,這是歸因於其對稱性構形;因此,P2VP-b-PF-b-P2VP的共軛部份相較於PF-b-P2VP有較高程度的π-π排列,這導致P2VP-b-PF-b-P2VP有較高的吸收峰位置,而光量子效率會隨著MeOH的增加而逐漸被抑制;除此之外,對於PF-b-P2VP而言,MeOH的增加會導致其在吸收及放射光譜圖有藍位移的現象發生,這被稱為“H-型”的聚集,然而,P2VP-b-PF-b-P2VP卻同樣在增加MeOH的含量時呈現出吸收光譜藍位移及放射光譜紅位移的現象,這反映出其具有不同形式的聚集。本篇研究發現了共軛型硬桿-柔軟嵌段共聚物的不同高分子構形及聚集結構對於及光物理性質的影響。第三部份(第四章),我們發展出一個發法製備新型的星狀硬桿-柔軟共聚物poly(2,7-(9,9-dihexylfluorene))-b-poly(2-vinylpyridine) (star-PF-b-P2VP),這個方法藉由參考前一章陰離子法製備線性雙嵌段式PF-b-P2VP而近一步交相聯接具有活性陰離子末端的PF-b-P2VP。星狀共聚物於旋轉塗佈薄膜的結構將藉由原子力顯微鏡(AFM)分析,熱處理、載台性質、高分子初始濃度及混合溶液的比例等變因被應用於研究可調控的聚集結構,為了更近一步瞭解共聚物的聚集行為,微結構的型態結果將結合PL光放射光譜一同討論,星狀共聚物薄膜在當PF π-π排列程度上升時呈現出放射光譜紅位移的現象;比較線性雙嵌段式及星形共聚物於溶液下的聚集結果,星狀共聚物呈現出不同的聚集行為,這兩者的差異也被歸因於對稱/非對稱構形的影響結果。第四部份(第五章),靜電紡絲纖維藉由使用共軛型硬桿-柔軟雙嵌段式及三嵌段式共聚物PF-b-P2VP 及 P2VP-b-PF-b-P2VP混掺合的混合物被研究其形態及光電性質,良好成形的電紡絲藉由場發射掃描式電子顯微鏡(FE-SEM)及穿透式電子顯微鏡(TEM)確認,所有樣品在螢光顯微鏡(Confocal)呈現出均勻的藍光纖維結構。纖維在由MeOH/H2O製備的管徑約為600-1000奈米, 而由CHCl3 製備的粗細則在幾微米左右, 此製備粗細不同是因為兩個溶劑介電常數不同所致。PF 聚集的區塊隨者共聚物含量的增加而加大。在低分子量PEO(Mn~100,000)的混掺系統中(雙嵌段及三嵌段系統), 纖維在PL放射光譜中相對於薄膜時有紅位移的現象,但在高分子量PEO(Mn~2000,000)的混掺系統中,纖維與薄膜則有差異不大的放射光譜位置。另外,PF的聚集區塊尺度被發現在雙嵌段混掺系統中比三嵌段混掺系統中來的大,此表示了共聚物構形的重要性。Block copolymers have attracted extensive research activity in contemporary macromolecular science. This is attributable to a range of fascinating fundamental issues associated with understanding self-assembly processes in both solution and in bulk. One of the main issues on block copolymers requires further exploration is the polymer architecture effect, especially on the conjugated rod-coil systems. The research objectives of this thesis are to explore the synthesis, morphology (solution, film, or fiber), and properties of block copolymers with different polymer architecture, including coil-coil, rod-coil, coil-rod-coil, and star block structures. The following summarize the important discovery of this thesis.n 1st part (Chapter 2), new hetero-arm star amphiphilic block copolymers of polystyrene-block-poly(4-vinylpyridine) (PS4-P4VP4) with four different mole ratios of 4VP moiety (f4VP) were synthesized by sequential living anionic polymerization. Micellar morphologies of the synthesized copolymers in dilute solution were explored through the variation of polymer architecture, selective solvent content, common solvent polarity, and block ratio. Dynamic/static light scattering (DLS and SLS), transmission electron microscopy (TEM) and atomic force microscopy (AFM) were used to characterize the micellar morphologies. The experimental results suggested that the aggregation size and number of PS4-P4VP4 solution micelles were smaller than those of the linear analog. Morphological transformation of hetero-arm PS4-P4VP4 from spheres to cylinders, vesicles, and large compound vesicles was observed as the water content increased. The morphology of PS4-P4VP4 in the solvent mixture of DMF/water or 1,4-dioxane/water was shown sphere but changed into large compound micelles in the THF/water due to the different degree of swelling on the PS block. As the P4VP molar ratio decreased from 0.37 to 0.24, 0.12 and 0.07, the morphology changed from spherical mixed with cylindrical, to vesicles, giant vesicles, and then to large compound micelles due to the core chain stretching.n 2nd part (Chapter 3), new rod-coil diblock and coil-rod-coil triblock copolymers containing conjugated poly[2,7-(9,9-dihexylfluorene)] (PF) and coil-like poly(2-vinylpyridine) (P2VP) were synthesized by combining coupling reaction and living anionic polymerization. The experimental results showed that the diblock PF-b-P2VP maintained spherical micellar aggregates as the methanol content increased. However, the triblock P2VP-b-PF-b-P2VP were found to readily aggregate in elongated cylinders due to its symmetric structure. Consequently, P2VP-b-PF-b-P2VP polymer chains could stack together favorably and have stronger π-πinterchain compared with diblock PF-b-P2VP, leading to the higher absorption maximum. The quantum efficiencies were gradually quenched with increasing the MeOH content for both copolymers. Moreover, for diblock PF-b-P2VP, the increase of the MeOH content induced a blue shift in both absorption and PL spectra, suggesting an “H-type” aggregation. However, triblock P2VP-b-PF-b-P2VP exhibited a blue shift in absorption but a red shift in PL by increasing the MeOH content, which reflected a different type of aggregation. n 3rd part (Chapter 4), we developed the synthetic routine for preparing new rod-coil star-like poly[2,7-(9,9-dihexylfluorene)]-block-Poly(2-vinylpyridine) block copolymer (star-PF-b-P2VP) by cross linking of living anionic PF-b-P2VP chain ends, according to synthetic concepts of preparation of diblock PF-b-P2VP. The morphologies of the copolymers in spin-coated thin films were analyzed via atomic force microscopy (AFM). The annealing treatment, substrate, initial polymer concentration and mixed solvent effects are applied to research to obtain tunable aggregated structures. In order to gain further insight of aggregation behavior, the morphological results are then combined with photoluminescence spectra (PL). By comparing the experimental results with diblock PF-b-P2VP copolymers in solution, star copolymers exhibit different aggregation behavior due to symmetric/asymmetric architectures for two kinds of architectures.n 4th part (Chapter 5), morphology and photophysical properties of electrospun (ES) nanofibers prepared from the blends of conjugated rod-coil diblock PF-b-P2VP and triblock P2VP-b-PF-b-P2VP copolymers with PEO were studied. Well-produced ES fibers are confirmed by field-emission scanning microscopy (FE-SEM) and transmission electron microscopy (TEM), and uniform blue emission is appeared in confocal images for all samples. The prepared ES fiber diameters were around 600-1000 nm using the processing solvent of MeOH/H2O while those from CHCl3 were a few thousands of nm, due to the difference on the dielectric constant. The PF aggregation domain increased with enhancing the block copolymer composition in the ES fibers. In copolymer/low Mw of PEO (Mn~100,000) blending system, it has red-shifting of emission peak from fibers to films, which is different from high Mw of PEO (Mn~2,000,000) blending system, displaying no obvious shifts of emission peaks between films and fibers in both diblock and triblock systems. Furthermore, the PF aggregated domain was larger in the PF-b-P2VP/PEO ES fibers than that of P2VP-b-PF-b-P2VP and led to much reduced aggregation emission, which suggested the importance of polymer architecture.口試委員審定書..........................................i謝...................................................iibstract .............................................iii文摘要 ..............................................viontents ..............................................ixable Captions .......................................xivcheme Captions .......................................xvigure Captions ......................................xvihapter 1 Introduction .................................1-1 An overview of amphiphilic block copolymers....1-2 Synthesis of block copolymers by living anionic polymerization.................................7 1-2-1 General characteristics of living anionic polymerization ................................7 1-2-2 Synthesis of block copolymers with star architectures.................................10 1-2-3 Purification of block copolymers..............12-3 Self-assembly micellization of amphiphilic block copolymer ....................................14 1-3-1 General concepts of micellization of block copolymer ....................................14 1-3-2 Theoretical aspects ..........................15 1-3-3 Preparation and characterization of micelles..18 1-3-4 Micellar morphologies from amphiphilic coil-coil block copolymers ............................19 1-3-5 Factors c.ontrolling the micellar morphologies.20-4 Supramolecular structures from rod-coil block copolymers ...................................24 1-4-1 General aspects of rod-coil block copolymers..24 1-4-2 Self-assembly aspects of π-conjugated systems.28 1-4-3 Chemical structures of π-conjugated systems...32 1-4-4 Self-assembly of π-conjugated based rod-coil block copolymers .............................33 1-4-4-1 In solid state ............................34 1-4-4-2 In solution ...............................39-5 Formation of electrospinning nanofibers ..... 45 1-5-1 General aspects of electrospinning nanofiber techniques ...................................45 1-5-2 Electrospun nanofibers from coil-coil block copolymers ...................................47 1-5-3 Electrospun nanofibers from conjugated polymers ..............................................50-6 Research objects .............................52-7 References ...................................56hapter 2 Synthesis and micellar morphologies of amphiphilic coil-coil hetero-arm star block copolymers of polystyrene-block-poly(4-vinylpyridine) (PS-b-P4VP) in dilute solutions ......................................64-1 Introduction .................................64-2 Experimental sections ........................66 2-2-1 Materials ....................................66 2-2-2 Synthesis ....................................66 2-2-3 Preparation of micellar morphologies in dilute solution .....................................68 2-2-4 Characterization .............................69-3 Results and discussion .......................71 2-3-1 Polymer structure characterization ...........71 2-3-2 Morphological transformation induced by adding selective solvent ............................74 2-3-3 Effect of solvent polarity on micellar morphologies .................................82 2-3-4 Multiple morphologies of PS4-P4VP4 with different block ratios .................................83-4 Conclusions ..................................86-5 References ...................................87hapter 3 Synthesis, morphologies, and photophysical properties of conjugated-based rod-coil diblock and coil-rod-coil triblock copolymers of poly[2,7-(9,9 dihexylfluorene)]-block- poly(2-vinylpyridine)(PF-b-P2VP) in dilute solutions ................ ..................90-1 Introduction .................................90-2 Experimental sections ........................92 3-2-1 Materials.....................................92 3-2-2 Synthesis .....................................93 3-2-3 Preparation of block copolymer aggregates in dilute solutions ..............................96 3-2-4 Characterization ..............................97-3 Results and discussions ......................99 3-3-1 Polymer structure characterization ...........99 3-3-2 Micellar morphologies in dilute solution ....103 3-3-3 Photophysical properties ....................113-4 Conclusions .................................116-5 References ..................................118hapter 4 Synthesis, morphologies and photophysical properties of conjugated-based rod-coil block-arm star block copolymers of poly[2,7-(9,9-dihexylfluorene)]-block-poly (2-vinylpyridine) (PF-b-P2VP) ...................120-1 Introduction ................................120-2 Experimental sections .......................122 4-2-1 Materials ...................................122 4-2-2 Synthesis ...................................122 4-2-3 Preparation of block copolymer aggregates ...123 4-2-4 Characterization ............................124-3 Results and discussions .....................124 4-3-1 Polymer structure characterization ..........124 4-3-2 Thin film structure morphology and optical properties ..................................128-4 Conclusions .................................137-5 References ..................................138hapter 5 Electrospun nanofibers from conjugated-based rod-coil diblock and coil-rod-coil tri-block copolymers of poly[2,7-(9,9-dihexylfluorene)]-block-poly(2-vinylpyridine) (PF-b-P2VP) ..........................................140-1 Introduction ................................140-2 Experimental sections .......................142 5-2-1 Materials ...................................142 5-2-2 Preparation of electrospun nanofibers .......142 5-2-3 Characterization ............................143-3 Results and discussions .....................143 5-3-1 Morphology of ES fiber from di-PFPVP/PEO blends .............................................143 5-3-2 Morphology of ES Fiber from tri-PFPVP/PEO blends.......................................146 5-3-3 Optical properties...........................148-4 Conclusions .................................156-5 References ..................................158hapter 6 Conclusions .................................160ublication lists ....................................163utobiography ........................................165ppendix A Preparation of nanoporous poly(methyl silsesquioxane) (PMSSQ) thin films from using templates of amphiphilic polystyrene-block-poly(2-vinylpyridine) (PS-b-P2VP) block copolymers with different architectures ..166eferences ...........................................179ppendix B Selected journal papers ............18
RTL Design Debugging and Verification by Formal Semantic Modeling and Inference of Design Knowledge
暫存器轉換層級設計的除錯與驗證一直是個很有挑戰的問題,傳統的除錯方式常使用將多工器插入設計中以找出可能發生錯誤的位置。然而,因為設計的複雜度以及工程師本身對設計知識的了解,大部分工程師選擇藉由觀察波型圖找出可能的錯誤而非使用自動診斷及除錯工具。若能在除錯及驗證上整合人類的使用行為及知識將會是一個值得研究的方向。 我們提出一個新方法以及建構一個系統以對暫存器轉換層級進行除錯,就像平常工程師所習慣的藉由引進設計知識的正規語意模型及推論來除錯。透過程式語言以及設計知識的語意我們可以容易的找出可能發生錯誤的位置,此外我們也可以使用語意模型及設計知識將確認及監視自動地寫入設計中,最後,我們得出這個系統的優缺點,以及未來可行的研究方向來改進此系統。RTL (Register Transaction Level) design debugging and verification is always a challenging problem. Traditionally, the research of debugging used to insert MUX (Multiplexer) into design to find the bugs. However, because of the complexity and designer’s design knowledge of RTL design, most engineers used to use waveform tools (e.g. Verdi) with design knowledge to debug rather than using automatic debugging tool. Combining the human’s behavior and knowledge on debugging and verification is a good perspective to research. We proposes a new approach and builds a system to debug RTL design by introducing formal semantic model and inference with design knowledge just like what designers used to do. With semantic of RTL code, design knowledge, we can easily infer what may cause these bugs. Also, we can use this semantic model and design knowledge to automatically write assertion and monitor into design. Finally, we point out the strengths and weaknesses of this approach, and possibilities on future research to improve our system
Modeling of MOSFET Devices : capacitance behavior analysis and gate tunneling current model
本篇論文研究金氧半場效電晶體元件的電容行為和閘極穿遂電流模型。第一章簡介high-k材料的重要性。第二章考慮垂直及邊緣電通密度效應,模擬高介電係數閘極氧化層全解離絕緣體上矽互補式金氧半奈米元件之電容行為,根據二維模擬的結果,在1.5nm氧化鉿(HfO2)閘極氧化層元件上看到一條獨特的兩個步階(two-step)電容曲線,我們歸因於垂直及邊緣電通密度效應所造成的。第三章考慮電流分佈效應,推導超薄閘極氧化層(1nm)n型金氧半元件閘極穿遂電流模型,此模型把電流分佈分成三個區間探討,經由實驗數據驗證後,對於長通道或短通道元件的閘極電流皆能做出準確的預測。對長通道元件而言,閘極穿遂電流主要由前飽和區域(pre-saturation region)主導。對短通道元件,操作在飽和區時,閘極電流有可能變為負值,這是因為靠近汲極處通道表面垂直電場反向的緣故。第四章為總結。The thesis analyzes the capacitance behavior and gate tunneling current model of MOS devices. Chapter 1 introduces the importance of high-k materials applied to gate dielectrics. Chapter 2 discusses the gate capacitances behavior of nanometer FD SOI CMOS devices with HfO2 high-k gate dielectric considering vertical and fringing displacement effects using 2D simulation. Based on the 2D simulation results, a unique two-step CS(D)G/CGS versus VG curve could be identified for the device with the 1.5nm HfO2 gate dielectric due to the vertical and fringing displacement effects. Chapter 3 derives the partitoned gate tunneling current model for NMOS devices with an ultra-thin(1nm) gate oxide considering the distributed effects. As verified by the experimentally measured data, this partitioned gate tunneling current model based on the three segment approach provides an accurate prediction of the gate current for the device with a long or short channel. Chapter 4 is the conclusion of this research.1 簡介••••••••••••••••••••••••••••••1
2 考慮垂直及邊緣電通密度效應,模擬高介電係數閘極氧化層全解離絕緣體上矽互補式金氧半奈米元件之電容行為
2.1 摘要••••••••••••••••••••••••••••4
2.2 簡介••••••••••••••••••••••••••••5
2.3 電容行為••••••••••••••••••••••••••6
2.4 討論••••••••••••••••••••••••••••10
2.5 結論••••••••••••••••••••••••••••13
2.6 參考資料••••••••••••••••••••••••••13
3 考慮電流分佈效應之超薄閘極氧化層(1nm)n型金氧半元件閘極穿遂電流模型
3.1 摘要••••••••••••••••••••••••••••29
3.2 簡介••••••••••••••••••••••••••••30
3.3 模型推導••••••••••••••••••••••••••30
3.3.1 三極區•••••••••••••••••••••••31
3.3.2 飽和區•••••••••••••••••••••••34
3.4 模型驗證••••••••••••••••••••••••••39
3.5 討論••••••••••••••••••••••••••••41
3.6 總結••••••••••••••••••••••••••••42
3.7 參考資料••••••••••••••••••••••••••43
4 總結••••••••••••••••••••••••••••••5
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