全國中小學科展

化學

發光基團與巴克球作為二氧化碳還原光觸媒之研究

本研究使用巴克球C60或巴克球衍生物PC61BM作為主催化劑,發光基團DTBT作為副催化劑,製成混摻催化劑並調控各種變因,進行光催化二氧化碳還原反應,期許能設計催化效果最佳之有機光觸媒,達到開發再生能源與減緩溫室效應之目標,甚至應用於殺菌與分解汙染物等其他方面。 利用氣相層析儀進行二氧化碳還原產物之定性及定量分析,目前產物以一氧化碳為主、甲烷為輔,主、副催化劑混摻之產率優於單一催化劑,主催化劑選用PC61BM優於選用C60,DTBT與PC61BM混摻莫耳比為1:1時一氧化碳的產率最佳,而莫耳比為2:1時甲烷產率較佳。若在反應瓶中添加氫氣或增加水量,皆有助於提高甲烷的產率。在製程中添加奈米銀製成三元混摻元件,可大幅提升產率,是未來研究方向。

Sustainable G-Polymer From Industrial Waste

This study focuses on the pre-treatment of paper sludge ash (PSA) as a by-product of paper milling industry that contains high amount of calcium, yet low in silica. The presence of high calcium content in geopolymer system will accelerate the setting time of fresh geopolymer and may disrupt the development of its mechanical strength. Therefore, in this study, the refinement of PSA properties was conducted by treating raw PSA in hydrochloric acid solution with different molarities of 0.5 M, 1.0 M and 2.0 M. The pre-treatment process was mainly purposed to decrease the amount of calcium and other impurities through leaching mechanism. Based on the experimental results, 2.0 M hydrochloric acid solution (HCl) was determined as the optimum concentration due to its ability in removing higher amount of calcium from the ash, yet still able to increase the amount of silica. Compression test on the hardened properties of geopolymer specimen also showed the deceleration of fresh fly ash based geopolymer and produced a more workable fresh geopolymer.

『冰清欲結』-探討不同條件溶液結冰時溶質匯聚現象的差異

我們發現有些水溶液結冰後會推擠溶質到中央匯聚成顏色較深的區域,但有些溶液卻不會,到底是什麼原因造成此現象的差異?於是我們操縱各種變因來觀察它們對溶液結冰時溶質匯聚表現的影響。 實驗發現並非所有的濃度都會匯聚;不同溶質的匯聚情形也不同;水質所含雜質越多匯聚效果越差,且結冰後氣泡分布也各有特色;上下等寬的容器呈角錐狀匯聚,下窄上寬的容器則為柱狀匯聚;先結冰的地方會推擠溶質到後結冰的地方且結冰速率越慢匯聚程度越好;最後我們利用保麗龍包覆+重力方向來控制結冰順序使冰晶推擠力達到加倍的效果,再透過自製離子濃度檢測器發現冰塊中溶質匯聚區的濃度並非均勻一致,而是依結冰的順序而有低、中、高的「濃度梯度」現象。

單分散原子電催化二氧化碳還原

近年來碳排放的淨零是全人類所想達成的共同目標,因此本研究以電催化劑幫助二氧化碳還原反應進行,降低反應所需電壓,同時提升產一氧化碳的法拉第效率。本研究一共嘗試兩種易於合成的材料作為催化劑前驅物,分別是沸石咪唑骨架和類石墨相氮化碳,搭配三種非貴金屬鐵、鈷、鎳配位合成催化劑。用X光繞射儀、掃描式電子顯微鏡以及能量色散X射線光譜儀鑑定結構後,使用氣相擴散電極搭配三電極系統,進行電解還原二氧化碳的反應,並使用氣象層析儀分析產物及計算其法拉第效率。根據實驗結果,發現以類石墨相氮化碳為前驅物的鎳催化劑有最佳的一氧化碳法拉第效率,在電壓約-0.5V時接近99%,超越以往文獻所即的效率,且具有高專一性及能源轉換率,成本低,可商業化量產。若配合使用非化石的綠色能源來電催化還原二氧化碳,必能達成碳零排放的目標。

以奈米錫奈米銦增益小分子團水製備及促進藥物傳輸效能探討

小分子團水(water cluster)的製備及應用一直是科學界的挑戰。本實驗利用熱蒸鍍法,加熱金屬塊材成原子蒸氣,在氬氣環境配合液態氮溫度下冷凝收集,成功製備了平均粒徑10nm金、20nm銀、54nm銦、71nm錫、14nm鎳奈米顆粒。將定量的奈米顆粒滲入去離子水中,以超聲波分散顆粒團聚,再以波長530奈米的綠光照射,讀取拉曼散射譜圖,判定來自小分子團水的振盪強度,探討5種奈米顆粒對形成小分子團水的功效。我們驚訝的發現奈米銦藉表面電漿共振(surface plasma resonance)及表面電子氧化還原功效,弱化水分子團簇成大分子團的功效為奈米金的16倍,奈米錫為12倍,也均高效於奈米銀及奈米鎳。以奈米銦及奈米錫增益小分子團水後,對將癌細胞藥物、養分帶入細胞的功效明顯提升。

PVA unveiled the actual role of starch in the Briggs-Rauscher reaction

The Briggs Rauscher reaction (BR reaction) is one of the famous oscillating reactions; the aqueous mixture of KIO3, H2SO4, H2O2, C3H4O4, MnSO4, and starch exhibit color change between yellow and blue-purple repeatedly. The blue-purple color formation is due to the iodine test reaction caused by inclusions of polyiodides such as I3- and I5- in the helical structure of starch. Therefore, starch has been regarded as only an indicator in the BR reaction. But our seniors have found that the oscillation did not last without starch. They hypothesized that starch’s linear helical framework is necessary to elongate the lifetime of the oscillating reaction. If this hypothesis is correct, similar BR-type oscillations must be observed when other polymers with helical structures are used instead of starch. We found the literature which reports that polyvinyl alcohol (PVA) forms a helical structure and indicates the iodine test reaction. In our research, we studied the BR reactions using PVA, with different saponification degrees and viscosities. First, we studied the correlation between the structural features of PVA and the iodine color reaction by spectroscopic approach, exhibiting that PVA with low saponification form helical structures and show the iodine color reactions, which gives red color solutions. Second, we found that additions of the helical-structured PVA to the reaction solution instead of starch induces the BR-type oscillating reactions, while PVA without helical structure induces only a few numbers of oscillations. This is the world-first example of the oscillating reaction using PVA. The oscillation that lasted for 6 minutes with 23 oscillations was almost the same as that of the general BR reaction using starch. We concluded that the polymers with helical structures are intrinsic to elongate the lifetime of the BR reaction. Furthermore, we found that the addition of K3[Fe(CN)6], which has a high redox activity, in the reaction solution with PVA drastically elongated the lifetime (50 min) and increased the numbers of the oscillations (nearly 100 times). This result suggests that the oxidation-reduction reactions by the ferricyanide ion promotes the redox process of iodine and iodide ions.

Modification of silica surface with supercritical water as a tool indicating new possibilities of existing separation methods

Silica capillaries have been an integral part of the instrumentation used in many areas of analytical chemistry for decades, especially in analytical separations. In most cases, they are used without treatment, occasionally forceless chemical surface treatments are made to suppress or enhance the activity of silanol groups. The aim of this work was to disrupt the inner surface of the capillary, perfectly smooth from manufactory, so that relatively coarse and various structures would be created, and to study their influence on the separation efficiency. The uniqueness of the used solution is based on the use of special properties of water exposed to high temperatures and pressures (supercritical water), which is able to disrupt this chemically inert material because of its aggressivity. In total, over 2000 experiments were carried out in order to define conditions suitable for the formation of various types of surface structures. Due to the high amount of resulting data, our own database application was created, allowing not only to save the picture of the structure and experimental conditions information, but also to clearly sort them out and create image reports according to the specified parameters. Samples representing individual types of structures were then selected from this database and a number of silica capillaries with a configuration suitable for electromigration analyzes were prepared. The creation of a structured surface in the input part of the separation capillary enabled the separation of some classes of substances and biosamples, which cannot be analyzed on standard capillaries with a smooth surface. An example is the complete separation of two strains of Staphyllococcus aureus bacteria (MRSA and MSSA), or the use of the absorbing capabilities of a structured surface to study the interactions of these bacteria with bacteriophages. This ability was also used in the determination of Aspergillus fungus in a sample taken directly from the patient's lungs, where there was achieved a significant increase in the sensitivity of the analysis. Structured capillaries can also be used in the analysis of food samples, i.e., for the separation of β-lactoglobulins A and B in cow's milk, which belong to its main allergens.

以分子動力學模擬探討有機分子影響胰島類澱粉蛋白(IAPP)的聚集行為

近年來的研究指出:第二型糖尿病病徵與胰島類澱粉蛋白(islet amyloid polypeptide,簡稱IAPP)之聚集有關。如欲探討IAPP聚集機制以治療病症,需經多樣、多元的實驗條件進行試驗,這無疑是件耗時、耗費資源的大工程!本研究是以電腦軟體進行理論計算分析,採用分子動力學模擬系統,探討不同種類或官能基的有機分子對於IAPP作用之影響,再進一步觀察分子動態、統計系統能量,歸納出分子間的交互作用,釐清可能影響實驗結果的重要變因,期能達到提昇實驗設計、減少耗材浪費的綠色化學願景。本研究結果發現:在純水或稀薄食鹽水中,IAPP構形皆傾向摺疊結構;且具較高極性基團或易產生立障效應的有機分子會拉伸IAPP結構,使其分子間相互靠近聚集,形成β-sheet纖維;具較低極性基團的有機分子,易進入IAPP turn內,破壞引發聚集現象的疏水核心,進而抑制IAPP分子的積聚。

五苯荑衍生物的多重螢光響應行為

本研究探討兩種五苯荑氟鏈取代衍生物(簡稱F5及F9)的刺激響應之特性及應用。F5及F9化合物粉末受到外力研磨以及蒸氣薰致時會產生力致螢光變色(Mechanochromism)及薰致螢光變色(Vapochromism)反應,我們選擇使用F5,利用放光光譜及PXRD對這兩種反應的機制進行探討。 再者,我們利用揮發法把F5及F9粉末製成晶體,以螢光顯微鏡照射340–390nm的紫外光,觀察F5及F9晶體的光致機械螢光變色(Photomechanofluorochromism)及F9晶體的光機械運動(Photomechanical effect),並利用放光光譜對其機制進行研究。 另外,我們將F5粉末長時間照射紫外光製備光二聚體(Photodimer),接著透過加熱使光二聚體熱回復回單體。再利用NMR測得各加熱時間下光二聚體與單體的比例,並由此推算出光二聚體熱回復性的反應速率常數。 此外,我們將F5混摻PEDOT:PSS,用drop-casting製成薄膜,觀察螢光變化,並討論其機制。 最後,我們結合力致螢光變色、薰致螢光變色和光致機械螢光變色,應用於多彩螢光繪圖。

從天然物抓取微量抗癌藥物的工具之研究

本研究嘗試設計並合成出一具有特定結構之分子工具,期望利用化學反應的方式,以化合物結構的性質,與分子工具進行特定的反應,達到精準將目標具特定結構之少量化合物從巨量物質中分離的效果。 以苯環為基本結構,我們在反應中逐步加上我們所要的分子基團,以達成分子工具預期中的功能。在每一步的反應進行分離和純化之後,以NMR來觀察產物的結構與純度。以四步反應成功合成目標的分子工具後,我們以不同的方式測試其在葉片萃取液中大量化合物下的效果,證實分子工具能跟其中的特定成分產生反應,並被氟相溶劑分離出來,具有我們想要的部分功能。 在進行其他更進一步的測試之後,其可能可以成為一種新的方法,用於分離天然物中的一些目標化合物。