化學

In order to recycle disposable diapers, we investigated the conditions where sodium sesquicarbonate (Chemical formula Na2CO3・ NaHCO3・ 2H2O hereinafter called sesqui) precipitates selectively from sodium carbonate and the conditions for high yield. For the selective precipitation of sesqui, we defined the time required for the reaction solution to pass through the sesqui precipitation area in the Na2CO3-NaHCO3-H2O phase diagram (45°C) as Δ t. As a result, we revealed that Δt is involved in the selective precipitation of sesqui, and that we can synthesize sesqui without the expensive addition of L-Arginine as used in a previous research. Also, we proposed the “Stay method”, in which the supply of CO2 is stopped for 30 minutes to the lengthen the Δ t, and found that we could synthesize sesqui selectively even under conditions in which sodium bicarbonate is likely to be precipitated as well. Regarding the high yield of sesqui, the yield was greatly improved by the common ion effect of Na by adding NaOH to the reaction solution, sesqui synthesis by repeated reactions with CO2, and sesqui recovery by adding the anti-solvent ethanol, reaching a sesqui conversion rate of 95%. This means 109 g of sesqui can be synthesized from 100 g of Na2CO3. Moreover, we confirmed that these synthesized samples have almost the same detergency as commercial sesqui. We did a test calculation to reveal the usefulness of this research. First, if diaper recycling technology is put into practical use and all used diaper waste in Saijo City can be recycled, a reduction of 534 t/year of used diaper waste can be expected. This corresponds to a 2.3% reduction in Saijo City's waste output. From the ash that would ultimately remain after being recycled, we expect up to 35.3 t/year of synthesized sesqui using our experimental method. In addition, a CO2 reduction of 8.2 t/year is possible in the process, which is about equivalent to the volume of one gymnasium.

本研究之反應產物Chromeno[4,3-b]pyrrolidine之衍生物含有吡咯烷及二氫苯并哌喃的骨架，而此二者存在於許多藥物及天然物中，例如：尼古丁及蛋白質中的脯胺酸皆為吡咯烷的衍生物，含有二氫苯并哌喃骨架的藥物則通常被應用於消炎藥物中。本研究主要反應是以對甲基苯醌衍生物與亞胺葉立德前驅物在相轉移催化劑及無機鹼的催化下進行(3+2)環加成反應與oxa-1,6-加成反應，合成出Chromeno[4,3-b]pyrrolidine之衍生物。利用改變不同的相轉移催化劑、溶劑和無機鹼的種類及各反應物的當量數，篩選出進行本反應的最佳反應條件。在此優化條件下，進一步使用不同的掌性相轉移催化劑，以探討本反應之光學活性。並利用無機鹼的篩選，以排除背景反應發生的可能性。希望最後能於起始物上替換不同種類的取代基，以探討本反應之反應活性，並增加其未來應用的多樣性。

本研究結合奈米合成技術及生物醫學應用，以牛血清蛋白（BSA）為載體，裝載具化學動力療法的金屬氧化物（CuFe2O4, CFO）及具光治療功能的光敏劑（IR780），製備CFO@BSA-IR780多功能奈米複合材料。 材料鑑定方面由TEM、DLS與UV-Vis等儀器進行組成及光學性質分析。特性方面，CuFe2O4在腫瘤環境由芬頓反應，促使H2O2產生活性極高的氫氧自由基（•OH）。並且IR780在近紅外光照射下同時具光熱與光動力治療特性，可殺死癌細胞。同時CuFe2O4中的Fe3+ 和Cu2+ 進行氧化還原將腫瘤部位的穀胱甘肽（GSH）轉化成氧化型穀胱甘肽，強化化學動力療法及光動力治療效果。 最後，本研究將CFO@BSA-IR780奈米材料實際運用於细胞毒性測試與細胞螢光顯影，確認其效果及低毒性。成功發展出同時具備化學動力療法、光動力治療、光熱治療及細胞螢光顯影之多功能奈米複合材料，期許在醫學治療提供一項新興藥物材料。

本實驗主要將PLA塑膠產品以水解降解、光降解方式形成小分子乳酸單體或其寡聚物，作為燃料電池之燃料，使其再循環產生能量，減少塑膠產品對環境之汙染。PLA降解之方法，可將PLA浸泡於低濃度氫氧化鈉溶液或照射UV光進行前處理再置入乙醇中，或直接放入高濃度氫氧化鈉中並加熱將其迅速降解，後者可於5分鐘內將市售PLA產品完全降解。以上述PLA降解溶液作為燃料電池之燃料，同時以自製氧氣供應裝置提供氧氣，作為電池兩極。電極為鍍鉑鎳鉻絲，電解液為0.7M氫氧化鈉溶液，電壓可達0.85V。PLA雖為生物可分解性塑膠，現今仍主要以燃燒方式處理，此迅速降解PLA之方法可解決目前使用後處理之困境。同時本實驗為首次利用乳酸作為化學燃料電池之燃料，並成功使其產生電力，此研究可提供PLA塑膠分解與利用之新思維。

The development of rapid and efficient synthetic approaches to the bioactive cyclic and polycyclic azaheterocycles is one of the most important challenges in organic synthesis. In this work effective and simple synthetic approaches to polysubstituted pyrrolidin-2-ones 2 and isoindolines 3 from donor-acceptor cyclopropanes 1, bearing the ester group as the one of acceptor substituents, and amines were developed. The γ- pyrrolidone based skeletons and isoindoline ring system is a constituent of many biologically active molecules, both natural and synthetic, and a key component of clinically relevant entities (Fig.1,2) [1,2]. The synthesis of pyrrolidin-2-ones 2 includes Lewis acid-catalyzed opening of the donor-acceptor cyclopropane with primary amines (anilines, benzylamines, etc.) to γ-amino esters, followed by in situ lactamization and dealkoxycarbonylation. The reaction has a broad scope of applicability; a variety of substituted anilines, benzylamines, and other primary amines as well as a wide diversity of donor-acceptor cyclopropanes bearing (hetero)aromatic or alkenyl donor groups and various acceptor substituents, can be involved in this transformation. In this process, donor-acceptor cyclopropanes react as 1,4-C,C-dielectrophiles, and amines as 1,1- dinucleophiles. The resulting di- and trisubstituted pyrrolidin-2-ones can be also used in subsequent chemistry to obtain various nitrogen-containing polycyclic compounds of interest to medicinal chemistry and pharmacology, such as benz[g]indolizidine derivatives. The synthesis of the substituted isoindolines 3 is based on the domino-reaction between donor-acceptor cyclopropanes, bearing in ortho-position of aromatic substituent a bromomethyl group, and different primary amines (e.g., anilines, benzylamines, cycloalkylamines) was developed. The reaction involves the generation of secondary amine followed by nucleophilic ring opening of cyclopropane with amino group. Moreover, this process provided a new practical method for the rapid synthesis of benzo[b]pyrrolizidinone 4 from readily available starting materials.

本研究使用實驗室自製的配基與銠金屬結合為催化劑後，在一次使用銠金屬催化劑下，同時催化烯炔類與苯硼酸進行加成、不對稱環化、chain walking、以及消去反應，在保持鏡像選擇性下獲得具有末端烯的產物。透過改變鹼的加入方式、催化劑的種類等變因，篩選適合的反應條件。 實驗結果顯示，銠金屬催化劑能催化烯炔類與苯硼酸進行不對稱環化反應，最高產率可達88%且e.e.值可達86%。未來希望能將此反應路徑應用於其他不對稱合成，使銠金屬催化劑的應用達到省時、高效的目的，有助於天然物和藥物的研究發展。

X染色體關聯性視網膜裂損症患者，在青少年時期會逐漸喪失視力，主要是因為RS1基因突變造成視網膜剝離，目前並沒有藥物達到有效的治療效果，即使最新研發的病毒載體基因療法也沒有效果，雖然在動物模型中具有良好的表現，但是在人體試驗中卻沒有獲得任何顯著的改善成果，推測是實驗模型不夠完善，在本實驗中，我們將會採用幹細胞分化成為視網膜類器官，並搭配上超分子奈米粒子運輸基因編輯材料送入，期許達到治療效果。本研究中以超分子奈米粒子(SMNP)將CRISPR/Cas9基因編輯系統及正常RS1基因共同運輸進入細胞來達成基因敲入的效果。我們篩選出兩個具有最佳傳遞性之超分子奈米粒子載體(Cas9/sgRNA-plasmidÌSMNPs及Donor-RS1/GFP-plasmidÌSMNPs)並將其應用於細胞中，於其安全編輯位點(AAVS1 locus)實施基因敲入，接著以PCR及Sanger sequence檢測敲入基因的正確性，並施以免疫螢光法分析RS1蛋白表現。結果顯示在細胞當中，RS1/GFP基因成功敲入AAVS1位點中並能有效進行表現，因此我們進而測試該方法是否能應用於iPSC分化而成的人類視網膜類器官中，其也成功表現RS1/GFP 質體引發的綠色螢光蛋白(GFP)，效果也持續接近40天。總而言之，我們希望目前的研究結果可以作為未來開發遺傳性疾病基因治療法的藍圖，造福受疾病所困擾的病患。

本研究提出一款新型硫化氫偵測之螢光探針，我們選用BTIC作為探針螢光主結構並藉由修飾上疊氮達成偵測硫化氫之目的。帶入設計上，利用PPH3形成與粒線體的電位差使其將探針帶進粒線體，最終進行粒線體內硫化氫之偵測與顯影。 目前本實驗已合成出螢光探針基本結構與側鍊結構，並初步檢測探針對於硫化氫的偵測能力，確認其能夠與之反應並有顯著螢光變化。另外，目前已成功接上側鍊，待純化出目標產物後將進行進一步的性質檢測，包括選擇性、靈敏性、及持久性。 最後，我們預計將探針實際進行生物顯影，做多個結構顯影的比對，確認本研究之成效。此外，我們希望此款螢光探針除硫化氫偵測外，還能夠進行生物機制探討或疾病細胞篩選的應用。

We elucidated the cause of the phenomenon, in which silver deposits on a bamboo charcoal when the bamboo charcoal is soaked in an AgNO3 water solution. From the experimental results, we considered that the hydrogen which is generated while the bamboo wood is carbonized is chemisorbed as C-H bonds on the surface edge of charcoal (the end of the carbon), and that these hydrogen atoms become hydrogen ions,which then reduce the silver ions and deposit silver. In addition, we created a graph of the mass of deposited silver versus the mass of charcoal, and the graph showed that the mass of deposited silver was strongly correlated with the surface area calculated from the mass of the charcoal. Besides, we showed that charcoal can be used in applications for the treatment of inorganic liquid waste, depositing metals from inorganic liquid waste by bamboo charcoals. Also, the charcoal is used for interior decoration because of its deodorizing effect and beauty. In our study, we create a work of art used silverdeposited charcoal with a motif of Karesansui (Traditional Japanese rock garden).

Food safety was an important issue recently. Today sodium percarbonate was used to fake the vitality of shrimps to earn a good sell. However, it may cause harm to health because of the peroxides left over. To handle this problem, we set up two goals to achieve: detecting them and then removing them. In the past, the titration skill was an easy method for determining the concentration of H2O2. It not only spent too much time but also resulted in errors commonly. In this research, titanium sulfate and citric acid were used to prepare the colorimetric reagent. To measure the peroxides in water, several factors were controlled and the SOP for detecting and the calibration line for peroxides finally established. In practical, we turned the colorimetric reagent into the fast test paper which was easily for use. The other part of this research was to clear up the peroxides in water. We use titanium sulfate, hydrogen peroxide and citric acid as starting material via hot-bath method to prepare the nano-photocatalyst of titanium dioxide. Since the powder was inconvenient to deal with large amount of water. The powder-like TiO2 was further made into ball-shaped TiO2 in favor of water treatment and reuse. It was found that the photocatalytic performance of ball-shaped TiO2 was effective to be on duty for removal of the peroxides. In summary, this research provided two techniques to deal with the zombie shrimp. The novel method for synthesis of TiO2 catalyst and the preparation of colorimetric reagent for fast test paper were all in low cost. They had great potential to develop in marketing demand.