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    Integrated analyses of ChIP-Seq and gene expression profiles reveal PAICS as the important downstream target of MYCN in neuroblastoma

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    神經母細胞瘤 (Neuroblastoma : 簡稱NBL或NB) 是一種兒童癌症,其源發於胚胎神經脊當中的交感神經系統,臨床期數越高則越難被治癒。在臨床特徵中MYCN致癌基因異常放大是評估神經母細胞瘤不良預後的重要指標,且MYCN在腫瘤學中也被強調其會透過大量轉錄調控使細胞不正常增生。為了探究MYCN所調控的基因在神經母細胞瘤的進程中扮演的重要性,我們首先在大量表現MYCN的SK-N-BE (2) –C細胞株中,利用染色質免疫沉澱定序 (ChIP-Seq) 分析MYCN結合的啟動子區域,再從基因表達綜合數據庫 (Gene Expression Omnibus, GEO)中整合神經母細胞瘤患者的基因數據,並找到那些會和MYCN大量表現有高度相關的基因。結合ChIP-Seq和GEO分析結果,我們選擇了PAICS為候選基因來做更進一步的實驗。我們使用了tet-21n會受四環黴素調控MYCN (tet-off)表現的細胞株,並利用即時聚合酶鏈式反應 (Real-time PCR)偵測,發現PAICS(磷酸氨基咪唑羧化酶、磷酸氨基咪唑琥珀酰甲酰胺合成酶)與嘌呤生合成相關的代謝酶,其在MYCN被抑制時會顯著下降,以及在不同MYCN表現量的組織和細胞也觀察到MYCN與PAICS有正向表現相關,這表示MYCN可能會直接活化PAICS此下游基因,進一步使用啟動子冷光分析也發現PAICS具有受MYCN調節的啟動子存在。降低PAICS基因的表現量亦顯示抑制細胞生長的效果。我們的結果表明,在惡化的神經母細胞瘤中PAICS可能為腫瘤發生和癌症生物學研究裡一個具有潛力的治療靶標。Neuroblastoma is a common neural crest-derived childhood cancer of sympathetic nervous system, which would be difficult to cure if progressed to higher stages. Among several clinical features, v-myc avian myelocytomatosis viral oncogene neuroblastoma derived homolog (MYCN) amplification is a prognostic marker for advanced neuroblastoma, which through massive transcriptional regulation, underlies dysregulated cell proliferation as part of the tumor biology. To investigate MYCN-regulated genes crucial for neuroblastoma progression, we first analyzed the MYCN-bound promoter regions in SK-N-BE(2)-C cells (MYCN-amplified, MNA) using chromatin immunoprecipitation−sequencing (ChIP−seq). Additionally, we integrated several expression datasets from Gene Expression Omnibus (GEO) regarding patients with neuroblastoma and demonstrated some genes which were highly correlated with MYCN expression in MYCN-amplified neuroblastoma. Combining the results from ChIP-Seq and the integrated datasets, we selected PAICS as the candidate gene in the following experiment. Using the tetracycline-repressible (tet-off) system to inhibit MYCN transcription in Tet21n cells, we found that PAICS (phosphoribosyl-aminoimidazole carboxylase, phosphoribosyl-aminoimidazole succino-carboxamide synthetase), a metabolic enzyme in purine biosynthesis and therefore supports DNA and RNA synthesis, was significantly downregulated under MYCN knockdown detected by real-time PCR, suggesting that MYCN may directly activate this downstream gene. The positive correlation between MYCN and PAICS was also observed in cell lines and tissues with different MYCN expression levels. Furthermore, promoter luciferase assay revealed PAICS existing promoter region regulated by MYCN. Knockdown of PAICS also inhibited cell proliferation. Taken together, our results suggest that PAICS is a potential therapeutic target that links tumorigenesis and cancer biology in advanced neuroblastoma

    A Study on the Factors associated with Workplace Violence in Emergency Room: Different Perspectives from Multiple Stakeholders

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    研究背景與目的   醫院是發生職場暴力的高風險環境,急診室尤其如此。醫護人員若遭受急診暴力,除了身心受傷外,亦可能影響其醫療照護品質、或導致離職。衛福部將急診暴力列為目前台灣急診室的困境之一,社會大眾近年也對醫院職場暴力事件更加關注,為了瞭解事件、解決問題,本研究擬探討急診職場暴力事件的成因,以期防範並且制止。 研究方法   本研究搜尋新聞中的醫院職場暴力事件進行分析,並訪談暴力事件中的各個利害關係人,據此瞭解暴力發生的因子;另外觀察台灣醫院職場暴力之頻率及數量以瞭解嚴重程度;再從不同身份的受訪者中歸納其態度及行為,嘗試針對不同的類別角色提出適當的改善措施。 結果與結論   新聞中提到急診暴力的次數,自2007年開始巨幅上升,可能與當年所發生的暴力事件有關。此後一般民眾對急診暴力的認識大為提升,急診暴力這個詞彙也被新聞媒體廣為使用。   分析新聞及受訪者所描述的暴力事件共計74件,從中歸納高風險因子,發現男性、酒後或有酒癮、病人等均是施暴者方相當明顯的高風險因子,而大夜班及診療、急救、留觀等位置亦是環境方面的高風險因子;此外酒後或有酒癮的施暴者,在74件暴力事件中就佔了32件(43%),是造成台灣急診暴力事件的最重要成因。   利害關係人中,即使是相同的職業角色,面對急診暴力時可能有完全相反的態度與行為,瞭解人員的類型並依其不同角色類型給予協助,應能有助於人員面對暴力,不致讓暴力事件進一步影響人員的服務品質與留任。Background and Purpose   Hospital is a high-risk workplace where the workplace violence occurs, especially in emergency room. Violence makes the staff physical and mental injuries, affects the quality of their medical care, and causes them to leave. Ministry of Health and Welfare pointed Emergency violence as one of Taiwan''s current plight to the emergency room. In recent years, the public concerned the hospital workplace violence more. In order to solve the problem, this study is to investigate the factors of workplace violence in emergency room. Study Methods   In order to understand the factors of workplace violence in emergency room, this study searched the hospital workplace violence news and interviewed multiple stakeholders in violence events. In order to understand the severity in Taiwan, the study observed the frequency and quantity of Taiwan hospital workplace violence. In order to make appropriate recommendations for improvements, this study summarized the attitude and behavior of respondents from different categories of staff. Results and Conclusions   Since 2007, the number in news mentioned emergency violence rose obviously, and might be related to the violence that occurred in the relevant year. Public awareness on emergency violence rises greatly, and emergency violence, this vocabulary is also widely used by the news.   The violence events from news and the respondents totaled 74. The high risk factors includes: men, drink or alcohol addiction, and the emergency room patient. The high risk factors about the environment includes: at 0-8 A.M. and in the process of diagnosis, first aid, and stay in hospital for observation. In this study, drink or alcohol addiction perpetrators caused 32 violence events (43%). The factor, drink or alcohol addiction, is the most important cause of emergency violence in Taiwan.   The same professional roles, stakeholders may have completely opposite attitude and behavior when they faced emergency violence. Understanding the type of staff and giving different assistance according to the types could help people face the violence and not affected about their quality of service and retention

    Factors Associated with the Knowledge, Attitudes and Experiences of Pregnant Women in Down Syndrome Screening and Genetic Diagnostic Process

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    在台灣地區,引起智能障礙最常見的染色體異常疾病就是唐氏症,隨著產前唐氏症檢查技術日新月異,檢查的項目有多種不同的選擇,孕婦應該對於產前遺傳診斷的基本認知有所了解。故在進行產前遺傳檢測時,應對孕婦提供正確且完整資訊之相關知識,使其了解產前遺傳檢查及檢查結果的意義,再行最佳判斷並能夠做出適宜之決定,以減少孕婦的壓力和焦慮,使其更能充分瞭解到相關資訊。 本研究目的在探討懷孕婦女對產前唐氏症篩檢和診斷過程中知識、態度與經驗的相關性研究,研究工具採用在澳洲使用過的公開結構式問卷「產前篩檢和產前診斷的調查」翻譯而成,為提高問卷之可信度,先進行信效度的檢定。自2014年11月1日至2015年4月30日期間,於台北市某區域教學醫院婦產科門診收案。對象為懷孕週數滿20週以上到生產前的孕婦,本研究總計實際回收有效問卷共計207份,回收率96.28%。 研究結果:孕婦的年齡平均34.3歲,為高齡孕婦,在接受產前唐氏症篩檢和診斷的知識量表經標準化之後平均得分為62.77分(滿分為100分),知識程度不是很高,得分欠理想,需有加強之必要。孕婦產前唐氏症篩檢和診斷知識之主要相關因素為:年齡、懷孕次數、生產次數其結果皆達統計上顯著意義。態度量表顯示平均得分為68.92分(滿分為100分),顯示孕婦之態度趨向於正向、積極。經驗量表在第一孕期和第二孕期唐氏症篩檢在大部分的孕婦都有聽說過、醫護人員也都有建議、自己也有瞭解檢驗項目目的,差別在第一孕期自己有做佔多數,第二孕期母血唐氏症篩檢自己並沒有做佔多數;絨毛膜取樣術大部分的孕婦都認為有聽說過但是醫護人員沒有建議、也不瞭解檢驗項目目的、自己也並沒有做;羊膜穿刺術方面在大部分的孕婦都表示有聽說過、醫護人員也都有建議、自己也有瞭解檢驗項目目的但是自己並沒有做。孕婦在產前唐氏症篩檢和診斷達顯著相關的因素為知識與態度,而知識與態度、年齡、懷孕次數及生產次數之間的關係達統計上顯著相關,態度與懷孕次數亦達統計上顯著相關。 本研究結果可為臨床實務、醫護教育、政府政策、孕婦健康手冊產檢相關資訊等方面及臨床醫護人員、遺傳諮詢師等相關人員參考,並能夠給予孕婦最適時的協助,以提高孕婦產前唐氏症篩檢和診斷的相關知識,減少國人對遺傳疾病之恐慌及醫療成本的浪費。In Taiwan, the most common cause of chromosomal disorder causing mental retardation is Down syndrome. Along with rapid advanced technology of prenatal Down syndrome screening and diagnosis, there are a number of different options of examination. Pregnant women should possess basic knowledge for understanding their prenatal genetic diagnosis. Therefore, during prenatal genetic examinations, women should be provided accurate and complete relevant information to understand the meaning of prenatal genetic examination results, so that while reducing stress and anxiety, the appropriate decisions could be made. This study aimed to explore the relation between pregnant women’s prenatal Down syndrome screening and diagnosis process knowledge, attitude and experience. A structured questionnaire used in Australia ""prenatal screening and prenatal diagnosis"" was translated into Chinese. The reliability and validity were established. Data were collected from November 1st 2014 to April 30th 2015, at maternity clinics in a regional teaching hospital in Taipei. A total of 207 pregnant women over 20 weeks gestation were recruited, the response rate was 96.28%. The study results showed the average age of pregnant women was 34.3 years old, average prenatal screening and diagnosis of Down syndrome knowledge scale standardized score of 62.77 points, which is not satisfied and should be strengthened. The main factors related to prenatal screening and diagnosis of Down syndrome knowledge including age, number of pregnancies, and the parity. Attitude scale showed an average standardized score of 68.92 points, revealing the attitude of pregnant women tend to be positive and active. As to experience scale, majority of pregnant women have heard the first trimester and the second trimester screening for Down syndrome, also have recommended by health care workers, and have an understanding of the purpose, most of them have done in the first trimester. Most of the pregnant women did not do second trimester maternal serum screening for Down syndrome. Most pregnant women have heard of chorionic villus sampling technique but health care workers did not recommend, do not understand the purpose, and did not do it. Most pregnant women have heard amniocentesis, recommended by health care workers, understanding of the purpose but did not do it. Significant factors of pregnant women’s Down syndrome prenatal screening and diagnostic knowledge and attitude were examined. Age, number of pregnancies, parity were significantly correlated to knowledge. The attitude and the number of pregnancies also significantly statistical correlated. The results of this study may be useful to clinical practice, nursing education, governmental policy, genetic counselors etc. We suggest that timely information of prenatal Down syndrome screening and diagnosis should be given to most pregnant women, thereby reducing panic effectively to the genetic diseases and related medical costs

    Synthesis and Characterization of Aromatic Base Polymers with Low Dielectric Constant

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    芳香族聚合物,包含聚芳醚、聚醯亞胺,已被用為電子產品中的介電材料有幾十年之久。近年來,電子裝置的工作頻率已經達到千兆赫的譜帶,且大量資料傳輸的需求會促使電子裝置的中做頻率在未來有增高的趨勢。由於高頻運用的需求,下一代的通信需要具有低介電常數與高熱性能的材料。因此,本論文著重在開發具備新低介電常數以及優越熱性質的芳香族高分子。 本研究第二章,交聯poly[2,6-dimethylphenol (95 mol%)-co- 2,6-diphenylphenol (5 mol%)] [poly(2,6-DMP95-co-2,6-DDP5)]乃是藉由2,6-二甲基苯酚與 2,6-二苯基苯酚共聚,並與交聯劑—MBMP反應後製備。交聯後高分子膜也具備相對優越的熱穩定性與玻璃轉化溫度。在10千兆赫頻率下,其介電常數與消散因子分別為 2.64 與 0.004,這顯示此材料適用於高速與高頻的電子應用。 此外以此材料為絕緣層的雙層覆銅基板已被製作,說明此材料適合高頻應用。 本研究第三章, 氧化耦合反應被用於合成高分子量 poly(2,6-dihydroxy-1,5-naphthalene).此外,一系列不同烷基側鏈的 poly(2,6-dialkoxy-1,5-naphthalene)s被合成製備。由於芳香環結構以及萘環主鏈的高硬度,合成萘環系列高分子具有高熱穩定性,包含熱裂解溫度高於360oC與在30oC 到 300oC區間內觀測不到玻璃轉移溫度。這類高分子具有相對低的介電係數是由於相鄰萘環非常大的二面角造成相當大的自由體積。各高分子薄膜:poly(2,6-dibutoxy-1,5-naphthalene) (PDBN)、poly(2,6-dihexoxy-1,5-naphthalene) (PDHexN)與poly(2,6-dicyclohexyl-methoxy-1,5-naphthalene) (PCHMN) 在10千兆赫頻率下的介電常數分別為2.65、2.82與 2.79。Aromatic polymers, such as poly(aryl ether)s, polyimides, have been used as dielectric materials for microelectronics for decades. In recent years, electronic devices’ working frequency reaches GHz bands, and it is believed that requirement of transmitting lager amount of information will force microelectronics operating in a higher frequency in the future. For such high frequency demand, low dielectric constant with high thermal performances materials are in need for next generation of communication. Therefore, in this thesis we explore new aromatic polymers containing low dielectric constant with intrinsic excellent thermal performances. In chapter 2, The cross-linked poly(2,6-DMP95-co-2,6-DDP5) was prepared by oxidative coupling polymerization of 2,6-DMP with 2,6-DDP, followed by the reaction with 4,4’-methylenebis[2,6-bis(methoxymethyl)]phenol (MBMP) as a cross-linking agent. The cross-linked polymer exhibited a good thermal stability as well as a high glass transition temperature. The dielectric constant and dissipation factor of cross-linked polymer were 2.6 and 0.004 at 10 GHz, respectively. Moreover, a flexible double layer copper clad laminate based on the cross-linked polymer composite was successfully prepared, indicating their potential applications in high-speed and high-frequency electrical applications. In chapter 3, oxidative coupling was used to obtained relative high molecular weight poly(2,6-dihydroxy-1,5-naphthalene). Furthermore, a series of poly(2,6-dialkoxy-1,5-naphthalene)s with different length of alkoxy side chain were synthesized. Out of aromatic geometry and highly rigidity of naphthalene backbone, the synthesized polymers possessed high thermal stability with Td above 360oC, and showed no Tg from 30oC to 300oC. The low e constant of these polymers are caused by a large dihedral angle between the neighboring naphthalene rings, resulting in a large free volume. ε of poly(2,6-dibutoxy-1,5-naphthalene) (PDBN), poly(2,6-dihexoxy-1,5- naphthalene) (PDHexN), and poly(2,6-dicyclohexyl-methoxy- 1,5-naphthalene) (PCHMN) were estimated as 2.65, 2.81, and 2.79 at 10GHz, respectively

    Pseudopolymorphisms of Zeolitic Imidazolate Frameworks and Their Application in Gas Separation

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    本研究第一部份合成及探討了3種以鋅和二甲基咪唑構成的同質異型性沸石咪唑酯骨架材料:ZIF-8、ZIF-L、dia(Zn)。具有六角型片狀dia(Zn)需要添加甲酸鈉、醋酸、氨水做為催化劑,並在攝氏60度下進行反應;而ZIF-8及ZIF-L在室溫且不需添加催化劑即可合成出來。這說明了合成dia(Zn)的活化能高於ZIF-8及ZIF-L。此外三種晶體以攝氏100度進行了水熱處理以檢測其穩定性:ZIF-8具有最高的水熱穩定性,ZIF-L則具有最低的水熱穩定性。在77K的氮氣吸附檢測中,ZIF-8為孔洞材料;ZIF-L及dia(Zn)則不具有孔洞。但在323.15K的二氧化碳熱重分析中,ZIF-8、ZIF-L及dia(Zn)具有相同數量級的二氧化碳吸附。這顯示了ZIF-L及dia(Zn)的結構會隨著溫度的上升而具有彈性。因此,調整有機金屬骨架的彈性程度是一種有效的方法增加分子分離的效率。 在第二部分的研究提出了一種新穎且可靠的薄膜製備方法:使用了擬多晶形的晶種層,以二維平面材料ZIF-L做為晶種層提供ZIF-8生長,形成ZIF-L@ZIF-8混合薄膜。這個方法使得ZIF-L在薄膜中占有約28%的體積占有率。和傳統的純ZIF-8相比,由於片狀的ZIF-L的使用,使得ZIF-8會沿著晶格<100>的方向生長。在氣體分離的檢測中,ZIF-L@ZIF-8混合薄膜具有較高的氫氣滲透性及氫氣/二氧化碳選擇性。本研究另外使用了有限元素分析分析法進行數值計算,模擬了ZIF-L的擴散係數。我們認為具有層間距的ZIF-L是使得ZIF-L@ZIF-8混合薄膜在氣體分離上有更好的表現的主要原因。This work reports on the synthesis and stability of a polymorphic system of a metal-organic framework (MOF) composed of zinc and 2-methylimidazole, as well as its potential applicability in gas storage/separation. Three polymorphs, ZIF-8, ZIF-L, and dia(Zn) are discussed in this work. It was found that the synthesis of dia(Zn) with a crystal morphology of hexagonal nanosheets requires a catalyst (NH4OH, CH3COOH, or HCOONa), and a synthesis temperature of 60 °C. In contrast, the synthesis of ZIF-8 and ZIF-L can be conducted in the absence of a catalyst and at room temperature. This suggests that the activation energy of dia(Zn) exceeds that of ZIF-8 and ZIF-L. The three crystals were subjected to hydrothermal treatment at 100 °C to evaluate their stability. The ZIF-8 presented the highest hydrothermal stability, whereas ZIF-L presented the lowest. Nitrogen physisorption tests performed at 77K suggests that the microporosity of ZIF-8 exceeds that of ZIF-L and dia(Zn), which were nearly nonporous. Interestingly, CO2 thermogravimetric analysis revealed that the CO2 adsorption of ZIF-L and dia(Zn) at 323.15K is on par with that of ZIF-8, which implies that the flexibility of ZIF-L and dia(Zn) framework increased considerably with temperature. Tuning the flexibility of the framework is another effective approach to the design of new MOF materials for molecular separation. A novel methodology involving the use of pseudopolymorphic seeding for the rational synthesis of highly hydrogen-selective hybrid membranes with a zeolitic imidazolate framework (ZIF) was reported. A proof-of-concept was demonstrated using two-dimensional layered ZIF-L as seed crystals for the growth of its pseudopolymorph ZIF-8 in the formation of ZIF-L@ZIF-8 hybrid membranes. This approach enables the incorporation of ZIF-L (with high hydrogen diffusivity) within the ZIF-8 matrix with a volume fraction of ZIF-L of approximately 28%. Compared with conventional secondary growth methods used in the synthesis of pure ZIF-8 membranes, we employed leaf-like ZIF-L with a high aspect ratio as seed crystals for the growth of ZIF-8 membranes with a preferred orientation along the <100> direction. Compared to pure ZIF-8 membranes, the ZIF-L@ZIF-8 hybrid membranes enable a three-fold enhancement in hydrogen permeability and increase the permeative selectivity of hydrogen-over-carbon dioxide from 2.3 to 4.7. Simulation of mass transfer at the microscopic level was used to elucidate the reasons for the enhanced performance of the membrane in gas separation. We determined that the interlayer spacing among ZIF-L crystals, which allows for the rapid diffusion of hydrogen, is probably the key reason for the high separation performance of the ZIF-L@ZIF-8 hybrid membranes

    Synthesis of MIL-101 supported on ceramic membrane for organic solvent nanofiltration

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    The purpose of this study is using an in-situ assisted acetic acid procedure to prepare a MIL-101 as filler in ceramic membrane. The MIL-101 membrane is firstly applied for organic solvent nanofiltration. In this study, the effects of synthetic conditions are investigated to get an invisible defect membrane and nanofiltration performance is also checked to prove the feasible application of MIL-101 membrane. Incorporation of metal organic framework (MIL-101) as filler on ceramic membrane is firstly investigated. In-situ method assisted by acid modular is utilized to synthesize uniform and defect-free MIL-101 membrane. Effect of additives such as NaOH, HF, CH3COOH and concentration of reactants are surveyed to find out the optimal synthetic conditions. Synthesis of MIL-101 membrane by using in-situ acetic acid-assisted method is proved as efficient way to prepare a compact and dense MIL-101 layer compared to other methods as thermal seeding method, layer by layer seeding method. The MIL-101 membranes are characterized by using a variety of different techniques, including X-ray thin film diffraction (XRD), scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy EDX. MIL-101 is chosen as material filler for membrane in nanofiltration application because of its ability to form the largest pore size in the MOFs’ family and a number of its prominent properties for molecular separation applications such as high surface area and well-defined pore size. Besides, MIL-101 and ceramic substrate are inorganic materials, so they are able to be stable in harsh solvent such as N-methyl-2-pyrrolidone (NMP), dimethyl sulfoxide (DMSO), dimethylacetamide (DMAc), those usually dissolve common polymers. The MIL-101 membranes are applied in organic solvent nanofiltration (OSN) by testing separation of Rose Bengal (RB) from NMP, DMSO, DMAc and ethanol. The MIL-101 membranes show a significantly high rejection but lower permeance compared to bare ceramic membrane. The best flux and rejection of MIL-101 membrane with RB ethanol solution are 1.65 lm-2h-1bar-1 and 99.7% respectively where ratio of chromium nitrate, benzendicarboxylic acid and water is 1:1:277, respectively and 0.8 ml of CH3COOH. The MIL-101 membranes also exhibit the stability under harsh solvent with high rejection of RB and constant flux within 3 hours

    Study of Copper / Ruthenium Chemical Mechanical Polishing in alkaline hydrogen peroxide system with ammonium persulfate and nanoscale silica

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    本研究分三部份進行。首先探討由氫氧化鉀所調整的pH9之鹼性雙氧水系統之下之銅/釕之腐蝕電化學,接著模擬銅與釕同時在化學機械研磨情形搭配不同比例之過硫酸銨以及未添加/添加2wt%之15nm-20nm之奈米級二氧化矽在雙氧水系統之下對於表面性質之交互影響;最後觀察其表面性質;實驗中除了利用直流極化技術了解基本腐蝕電化學性質,也使用五位數的數位電子秤量測銅與釕同時經由化學機械研磨處理前後之重量差了解其研磨移除率(Material Removal Rate, MRR)進而比較銅/釕之移除選擇率,並藉由原子力學顯微鏡(Atomic Force Microscope, AFM)了解其表面粗糙度(Rq)以及使用掃描式電子顯微鏡(Scanning Electron Microscopy, SEM)觀察其表面型態。 實驗結果顯示,藉由氫氧化鉀所調整的pH 9之鹼性雙氧水系統之下,透過電化學測量得知 7wt%的雙氧水比例可以有最大的腐蝕速率;以此為基礎進行不同比例之過硫酸銨測試,發現在7wt%的雙氧水與3wt%過硫酸銨可以有最接近1的移除選擇率,約為0.926,銅移除率約為2.305nm/sec,而釕移除率則約為2.488nm/sec;表面粗糙度的部份,銅由原先約55.8nm下降至9.12nm,釕則由約42.5nm下降到7.78nm。接續探討加入2wt%之15-20nm之奈米級二氧化矽觀察其對於移除率與表面型態之影響,發現7wt%的雙氧水與1wt%過硫酸銨搭配2wt%的15-20nm之奈米級二氧化矽可以擁有較接近1的的移除選擇率,約為0.811,銅移除率為3.457nm/sec,釕移除率為4.265nm/sec,表面粗糙度分別降為則下降至1.01nm與6.97nm;然而,若權衡所有的需求,則7wt%的雙氧水與2wt%過硫酸銨搭配2wt%的15-20nm之奈米級二氧化矽,擁有較好之成果,其選擇比為0.709,銅移除率為4.115 nm/sec,釕移除率為5.805nm/sec,其銅與釕之表面粗糙度分別能下降至6.54nm與2.06nm。The study can be separated to three parts. The first part focus on probing the electrochemical factors when copper and ruthenium film reacting in different concentration of hydrogen peroxide slurries, adjusting to pH9 by sodium hydroxide. For the second part, we mimiced the real situation when copper and ruthenium film are processed during the CMP by using different concentration of ammonium persulfate in hydrogen peroxide slurries, which is adjusting to pH9 by sodium hydroxide, and then we probe the variation of their surface patterns. For the last part, we add fixed amount of 15-20nm nanoscale silica to investigate its surface patterns. In the experiment, not only we use DC polarization technique to find out its electrochemical factors, but we also use Atomic Force Microscope and Scanning Electron Microscopy to probe its root mean square surface roughness and the surface patterns. For the results of the experiments, the first part showed that when the slurries adjusting to pH9 with sodium hydroxide, could have the best corrosion rate with 7wt% hydrogen peroxide for either copper or ruthenium film. Based on the results of the first part, we could find out that slurries with 7wt% hydrogen peroxide and 3wt% ammonium persulfate, adjusting to pH9 with sodium hydroxide, could demonstrate a better removal rate ratio, 0.926 ,of the copper/ruthenium removal rate, with the copper one was about 4.115 nm/sec and the ruthenium one was 5.805nm/sec. For the surface roughness, the copper one was declined from about 55.8nmto 9.12nm while the ruthenium one was declined from 42.5nm to 7.78nm. After adding 2wt% 15-20nm nanoscale silica, we found out that pH9 slurries with 7wt% hydrogen peroxide, 1wt% ammonium persulfate and 2wt% 15-20nm nanoscale silica, with removal rate ratio was 0.811. The copper removal rate was 3.457nm/sec and the ruthenium removal rate was 4.265nm/sec. The surface roughness was declined to 1.01nm and 6.97nm respectively. For requesting a proper result for the use of industries, the pH9 slurries with 7wt% hydrogen peroxide, 1wt% ammonium persulfate and 2wt% 15-20nm nanoscale silica would be the best choice, which removal rate ratio is 0.709, of the copper/ruthenium removal rate, with the copper one was about 4.1153nm/sec and the ruthenium one was 5.80493nm/sec. For the surface roughness, the copper one 6.54nm while the ruthenium one was 2.06nm

    Surface Modification and Applications of Metal-Organic Frameworks

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    本研究嘗試以金屬有機骨架為主體,於其外包覆二種或二種以上的微孔洞材料(金屬有機骨架、沸石、非結晶性二氧化矽),以合成高效能、高穩定性的核殼式吸附劑,並對材料進行多種檢測,包含酸性環境中的穩定性、水熱環境中的穩定性、水氣吸附性及離子吸附性,從檢測結果挑選適當的材料組合做為核殼式材料。將吸附性良好的材料做為核,於其外以另一種穩定的材料做為殼將核包覆住,藉由殼的保護增加核的穩定性,達到延長吸附材壽命的效果。 在水氣吸脫附的應用方面,我們選用吸附效果最佳,但水氣吸脫附循環不穩定的FeBTC做為核的材料,於其外分別以ZIF-7、ZIF-8、SiO2包覆,根據合成手法不同,共合成出了6種核殼式材料,雖然做成核殼式材料後,會因外層材料的水氣吸附率不如FeBTC,且增加水氣進入FeBTC孔道中的質傳阻力,使得整體水氣吸附率降低,但整體而言,穩定性皆有上升,而其中又以外層為ZIF-7進行三次生長的效果最好,不僅穩定性十分良好,水氣吸附率降低的情況也在可容許的範圍之內。 離子吸附的應用方面,我們選擇常見於電子面板廠廢液中的貴重金屬離子:銦離子,做為探討的主軸,核材的選擇為ZIF-8,因其吸附效果最好,不過ZIF-8在酸性環境中不穩定,而工業上含有銦離子的廢液為酸液,所以選用酸穩定性良好的SiO2做為殼材。雖然目前尚未能用SiO2完整的包覆住ZIF-8,導致酸穩定性還是不佳,但預計未來發展出能完整包覆ZIF-8的實驗方法後,穩定性定會有所提升。This work is aimed at enhancing the sorption performance of metal-organic frameworks (MOFs) by coating another porous material (a different MOF, zeolite, or amorphous silicon oxide) to create novel core-shell materials. A number of properties, including the acidic resistance, hydrothermal stability, water sorption capacity, and ion sorption capacity, were investigated to determine the appropriate “core” material and “shell” materials. To design high-performance sorbents, materials with high sorption capacity would serve as “core”, and those with high stability would serve as “shell”. For water vapor adsorption, FeBTC with high sorption capacity but poor cyclic stability was chosen as the “core” material. ZIF-7, ZIF-8, and amorphous SiO2 were deposited on FeBTC respectively as the “shell” material. 6 core-shell materials were synthesized under various conditions. In general the core-shell materials have lower water vapor sorption capacity at the first adsorption cycle in comparison to pristine FeBTC. However, the cyclic adsorption stability has been improved through the creation of core-shell materails. For ionic sorption application, we discussed the sorption of indium ion because it is a common waste of electronic panel factory. ZIF-8 was chosen as the core material due to its high indium sorption capacity. ZIF-8 has low acid resistance, but the indium solution is usually acidic. We attempt to deposit materials with high acid resistance on ZIF-8, such as amorphous silica. Although the ZIF-8@silica did not show an improvement of acidic stability, we believed that it was due to the low coverage of the silica on ZIF-8

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