Synthesis and Self-polymerization of Bismacrocyclic acylureas

在合成巨環形碳二亞胺（macrocyclic carbodiimide，MC-CDI）的程序研究過程中，1,3-dimethyl-3-phospholene oxide (DMPO)、3-methyl-1-phenyl-2-phospholene 1-oxide (MPPO)及triphenylarsine oxide (TPAO) 這三種異氰酸鹽預聚物之環閉合劑催化劑，被用來鑑別合成碳二亞胺（MC-CDI）之合成效率。預聚物由甲苯二異氰酸鹽（2,4-Toluene diisocyanate，2,4-TDI）與分子量700之聚異丙二醇中反應製得。在合成MC-CDI環化反應中，以擬高稀（pseudo high dilution）合成法在濃度約8 g/ L甲苯時，TPAO催化劑可達到高選擇率（95%）自我環化的優勢。 單環MC-CDI可進一步藉由管柱層析，從副產物及高分子量混合物中純化出來，並再進一步與芳香族二元酸，如聚醚二元酸［poly(oxypropylene) bis(trimellitic imide acid)，POTDA］，可順利地反應獲得高產率的雙巨環形醯基尿素（bis-macrocyclic acylurea，MC2-ACU）。MC2-ACU亦可直接由Crude MC-CDI與POTDA或間苯二甲酸（isophthalic acid，IPA）反應獲得。 由於MC2-ACU在120℃時，具有熱裂解開環再生異氰酸鹽之特性，因此可視為一種封閉型異氰酸鹽（blocked isocyanate），並依此獨特的性質，可藉由加熱MC2-ACU開環，以濕氣硬化的方式進行自我聚合，獲得光滑的薄膜。這過程可一步獲得高分子量的polyamide- imide-urethane-urea 和polyamide-urethane薄膜。 經過我們連續地改善合成2,4-TDI預聚物與MC-CDI的製程，在未來，MC2-ACU可作為封閉型異氰酸鹽前驅物，量產應用於溫和的溫度下進行硬化反應。On the process refinement study for making macrocyclic carbodiimide (MC-CDI), several carbodiimide catalysts, such as 1,3-dimethyl-3- phospholene 1-oxide (DMPO), 3-methyl-1-phenyl-2-phospholene 1-oxide (MPPO), and triphenylarsine oxide (TPAO) were screened to differentiate their effectiveness as ring-closure agents from the isocyanate prepolymer made from 2,4-toluene diisocyanate (2,4-TDI) and propoxylated polyether diol of 700 molecular weight. It was found that TPAO has the advantage in forming MC-CDI under pseudo high dilution of 8 g/ L in toluene solution with a high selectivity (95%) in ring-formation. Pure MC-CDI could be further purified by column chromatogram to separate it from by-products and higher molecular weight components. Upon treatment of aromatic dicarboxylic acid such as poly(oxypropylene) bis(trimellitic imide acid) (POTDA), MC-CDI was smoothly converted into bis-macrocyclic acylurea (MC2-ACU) in high yield. Alternatively, MC2-ACU could also be prepared directly from crude MC-CDI and two aryl diacids, POTDA or isophthalic acid (IPA) . MC2-ACU can be regarded as a blocked di-isocyanate precursor because it was demonstrated to undergo a ring-opening reaction in generation of di-isocyanate upon thermolysis at 120℃. Because of this unique property, a self ring-opening polymerization was carried out by moisture-curing of the heated MC2-ACU in neat thin-film. This process resulted in formation of a thin-film of polyamide-imide-urethane-urea and polyamide-urethane of high molecular weight in one-step. With our continuous process improvements in synthesis of 2,4-TDI prepolymers and MC-CDI, MC2-ACU can be available as a blocked isocyanate precursor in quantity for future applications in many moderate- temperature curing reactions.第一章 緒論 1 第二章 文獻回顧及研究動機 5 2.1 環形高分子之合成 5 2.1.1 環形高分子合成之方法 6 2.1.1.1高度稀釋法（High dilution） 6 2.1.1.2 擬高稀法（Pseudo high dilution） 7 2.1.2 碳二亞胺（carbodiimide，CDI）之合成 8 2.2 N-醯基尿素之合成 10 2.3 封閉型異氰酸鹽之合成 11 2.4 濕氣硬化之應用 17 2.5 研究動機 18 第三章 實驗 19 3.1 實驗藥品 19 3.1.1 二異氰酸鹽 （Diisocyanate） 19 3.1.2 聚醇（Polyol） 20 3.1.3 聚丙烯醚二元胺（Polyoxypropylene diamine） 21 3.1.4 CDI生成觸媒 21 3.1.5 有機羰酸 （Carboxylic Acid） 22 3.1.6 有機溶劑 （Organic Solvents） 23 3.1.7 終止反應試劑 （Blocking Agent） 26 3.2 合成 27 3.2.1 MC-CDI之合成反應的改進 28 3.2.1.1 以高度稀釋法（high dilution）進行環化反應 28 3.2.1.2 以擬高稀法進行環化反應 29 3.2.2 巨環形碳二亞胺純化方法 30 3.2.3巨環形尿素之合成 31 3.2.3.1以鹽酸催化CDI合成MC-Urea 31 3.2.4雙巨環形醯基尿素之合成 31 3.2.4.1以己二酸（adipic acid）合成MC2-ACU 31 3.2.4.2 聚醚二元酸之製備【Poly(oxypropylene) bis- (trimellitic imide acid)，POTDA】 32 3.2.4.3以MC-CDI與POTDA合成MC2-ACU (POTDA) 33 3.2.4.4以Crude MC-CDI與POTDA合成Crude MC2- ACU (POTDA) 34 3.2.4.5以Crude MC-CDI與IPA合成Crude MC2-ACU (IPA) 34 3.2.5雙巨環形醯基尿素的開環聚合反應 35 3.2.5.1 MC2-ACU (POTDA)開環濕氣硬化反應 35 3.2.5.2 Crude MC2-ACU (POTDA) 開環濕氣硬化反應 36 3.2.5.3 Crude MC2-ACU (IPA) 開環濕氣硬化反應 36 3.2.5.4 Crude MC2-ACU（IPA）與三元醇（triol）的開環加成聚合 37 3.3 實驗儀器 38 1. 傅立葉紅外線光譜儀（Fourier Transform Infeared Spec- trum，FTIR）鑑定： 38 2. 核磁共振光譜儀（Nuclear Magnetic Resonance Spec- trometer，1H-NMR）鑑定： 38 3. 凝膠滲透層析儀（Gel Permeation Chromatography，GPC）測定：（DMF系統） 39 4. 熱重量分析儀 (Thermal Gravimetric Analysis，TGA）: 39 5. 微差掃描熱卡儀 （Differential Scanning Calorimeter，DSC）: 40 6. 萬能材料試驗機 （Universal Testing machines）: 40 7. 動態機械性質分析儀 （Dynamic Mechanical Analysis，DMA） 40 第四章 結果與討論 41 4.1 經由TDI-PPG 700聚醚胺酯預聚物 (T2P700) 之分子內環化反應合成碳二亞胺 (MC-CDI) 41 4.1.1 以高度稀釋法進行環化反應---催化劑與預聚物濃度的影響 41 4.1.2 以擬高稀法進行環化反應 45 4.2 巨環形碳二亞胺純化結果及結構鑑定 48 4.2.1 巨環形碳二亞胺分離及純化 48 4.2.2 巨環形碳二亞胺之結構鑑定 48 4.2.2.1巨環形碳二亞胺之GPC鑑定結果 48 4.2.2.2巨環形碳二亞胺之FTIR鑑定結果 50 4.2.2.3巨環形碳二亞胺之200MHz 1H-NMR鑑定結果 51 4.3 巨環形尿素合成及結構鑑定 52 4.3.1巨環形尿素（MC-Urea）之合成 52 4.3.2 MC-Urea之200MHz 1H-NMR鑑定結果 53 4.3.3 MC-Urea之GPC鑑定結果 54 4.4 經由巨環形碳二亞胺與二元酸合成雙巨環形醯基尿素及其結構鑑定 55 4.4.1 聚醚二元酸POTDA之合成與結構鑑定 55 4.4.2 雙巨環形醯基尿素（MC2-ACU）之合成與鑑定 56 4.4.3 雙巨環形醯基尿素之熱活化與有效NCO之分析 62 4.5 開環濕氣硬化 65 4.5.1 開環濕氣硬化之GPC鑑定結果 66 4.5.2 POTDA系列之MC2-ACU的開環濕氣硬化薄膜 67 4.5.3 IPA系列之MC2-ACU的開環濕氣硬化與開環加成聚合 68 4.5.4 開環濕氣硬化薄膜之熱性質 70 4.5.5 開環濕氣硬化之機械性質 72 第五章 結論 75 第六章 參考文獻 7

Physiological and Functional Interactions between Tcf4 and Daxx in Colon Cancer Cells

Daxx, a human cell death-associated protein, was isolated as a Tcf4- interacting protein, using a yeast two-hybrid screen . Co- immunoprecipitation in HEK-293T cells and yeast two- hybrid screen in Y190 cells were performed to identify the interaction between Tcf4 with Daxx and to map the binding regions of Tcf4. In the nucleus, Daxx reduced DNA binding activity of Tcf4 and repressed Tcf4 transcriptional activity . Overexpression of Daxx altered the expression of genes downstream of Tcf4, including cyclin D1 and Hath-1, and induced G1 phase arrest in colon cancer cells. A reduction in Daxx protein expression was also observed in colon adenocarcinoma tissue when compared with normal colon tissue . This evidence suggests a possible physiological function of Daxx, via interaction with Tcf4, to regulate proliferation and differentiation of colon cells

The Process Of A Pre-Adult Daughter’s Role Changing When Experiencing Mother’ Schizophrenia

　　這是一個女兒成長的故事，作者透過敘說與書寫，來回顧自己經歷過母親罹患精神分裂症的歷程。採用一個開放、真實的態度來回憶、書寫自己成長過程中和父母親的關係、探討自己在家庭中角色的轉變。 　　而當母親罹患了精神分裂症之後，對於自己在成長過程帶來的影響，從一個被照顧者的依賴角色，開始感受到自己和家庭的能量，並嘗試在面對母親疾病所帶來的痛苦和影響下，看見自己在成年前期的發展階段，是怎麼掙脫疾病帶來的束縛，並透過學習和成長的方式，來協助自己和家庭因應疾病所帶來的變化。 　　在經歷專業學習，從事社會工作的過程中，看到自己的改變和限制，並透過專業上的發展，進一步回顧自己和父母、和家庭的關係，從而意識到自己是有能力去因應成年前期的階段任務，而且可以擔負起家庭責任。It’s a story about a daughter’ growing. The Author reviews the experience when mother was suffering from the schizophrenia through narrative and writing. By the opening and real attitude, she recalled and wrote down the relationship with parents in her development, and probed into her family role’s changing. When mother suffered from schizophrenia, the disease make change in her growing up. She took the depended and care-receiving role, and tried to feel the power of herself and inside the family, when facing the mother’s disease, the pain ,and impacts. By learning and growing, she could get off the restriction of disease and help herself and family to copy the changes of disease in her pre-adulthood. In the process of profession learning and social work’s practice, she can see the changes and restriction of her growing and recall the relationship between her, parents and family further by developing the social work profession. She can aware that she has abilities to coping the task of pre-adulthood and taking the family’s responsibilities

Realizing the value of mobile services —the verification of “limit-to-value” framework

The development of mobile services in the exhibition industry has become a popular issue in a mature internet environment. To successfully implement mobile services in the exhibition industry, exhibitors must be adequately involved in the unprecedented innovation activities. However, for exhibitors to buy into the service, it is essential for them to perceive the value of the service and actually achieve that level of value. With this in mind, this research aims to explore the value of mobile service investment and related value barriers from the perspective of exhibitors. We use the limit-to-value framework to examine the valuation process for mobile services in the context of the exhibition industry and focus on exhibitors in particular. This study can help us to understand the critical value-discounting factors and the valuation process for exhibitors as they consider adopting and using innovative mobile services in the exhibition industry

The relationship between diadochokinetic rate and accuracy, reading, rate, and sentence intelligibility in Cantonese speakers with Parkinsonism

Thesis (B.Sc)--University of Hong Kong, 2001Also available in print."A dissertation submitted in partial fulfilment of the requirements for the Bachelor of Science (Speech and Hearing Sciences), The University of Hong Kong, May 4, 2001."published_or_final_versionSpeech and Hearing SciencesBachelorBachelor of Science in Speech and Hearing Science

Simulation of diffusion behaviors in liquid NMR based on dipolar field theory

通过偶极场理论和密度算符公式相结合推导同核双组分核自旋体系在CRAZED脉冲序列作用下非线性演化的理论表述.采用粒子随机行走模型与偶极场理论相结合的方法,模拟自由扩散的核自旋体系在偶极场作用下非线性演化的特殊性质.模拟与理论预测的结果吻合得很好.In this paper,theoretical expressions of nonlinear evolution were derived for two-component homonuclear spin system under the COSY-revamped by asymmetric Z gradient echo detection(CRAZED) pulse sequence from the combination of the dipolar field theory and product operator formalism.Computer simulations based on the random walk model and dipolar field theory were performed to gain insight into the nonlinear evolution properties of free-diffusion one-and two-component spin systems.The simulation results agree well with theoretical predictions.福建省教育厅科研资助项目(JB06034

一九九九年第十屆國際生物奧林匹亞試題及評析(續)

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SERS Spectrum Recognition for Malachite Green Real-Time Detection in Aquaculture Used Seawater

表面增强拉曼光谱(SErS)是一种重要的高灵敏度分析技术。基于SErS的技术特点,建立了真实体系下孔雀石绿定性检测方法。提出了一种光谱自动识别算法,有机整合了稳健的傅里叶变换基线校正,基于主成分分析的特征提取与人工神经网络分类器。该方法结合基线的低频特征,通过迭代傅里叶变换实现基线校正;通过样本空间中类间与类内的欧氏距离判别自动获取拉曼光谱信号主成分的最优组合,实现光谱数据的降维与特征提取;最后构建三层反向传播神经网络分类器进行样本分类。实验结果表明,基线去除可排除基线变化对检测结果的影响;光谱主成分的优化组合可减小基线校正残余及复杂体系中被测物以外的物质拉曼峰对检测结果的干扰,同时实现了分类器最小化。该方法用于养殖用海水中孔雀石绿的现场检测,最低检出浓度0.1μg·l-1。该方法具有可拓展性,可以直接应用于其他溶胶/凝胶体系中SErS光谱的定性分析。Surface enhanced Raman spectroscopy(SERS)is a useful chemical analysis technique for its high sensitivity,which was used for Malachite Green qualitative analysis in real cases in the present article.Automatic recognition algorithms were put forward,which is a combination of three modules,including a robust Fourier transform for background rejection,aprincipal component analysis based character extraction method and artificial neural networks for classifying.Low-frequency background was rejected by iterative Fourier transform in order to eliminate the effect of variable background.The best principal component combination was obtained according to the Euclidean distances between-class and within-class in the sample space.And a threelayer back-propagating neural network was constructed for classifying.As it was shown,it would both minimize the network and reduce the classifying mistakes from variable baseline and Raman characters of other substances in seawater with best principal component combination.Malachite Green real-time detection in aquaculture used seawater was realized with a lower density limit of 0.1μg·L-1.Moreover,the method proposed in this article could be extended for other sol analysis based on SERS technique.国家重大科学仪器设备开发专项(2011YQ030124); 国家自然科学基金项目(21227004)资