化學

使用濕式製程在製備多層元件時，最大的困難是如何避免前一層的薄膜被後一層的溶液溶解。本研究合成末端具有雙鍵且可熱交聯之材料(FTV)，經熱處理後形成具有溶劑阻抗性之網狀結構，再塗佈發光層做多層元件，使得製程上較簡易，成本也較便宜，較於傳統製備多層元件需以蒸鍍方式來製作，濕式製程是更為方便。 FTV作為電洞傳輸層，元件結構為ITO/PEDOT:PSS/ FTV/PF/LiF(0.5 nm)/Ca(50 nm)/Al(100 nm)，製備為濕式製成的多層元件。並且嘗試不同濃度和轉速尋找電洞傳輸層FTV的最適化條件。本次實驗找出濃度為0.25%，轉速3000 rpm條件最佳，亮度和效率分別為2625cd/m2 and 0.17cd/A，效果遠高於沒有添加電洞傳輸層FTV的元件(795 cd/m2,0.04 cd/A)，為重要發現。 

本研究的方向是以還原氧化石墨烯(RGO)為基礎，利用本材料具有優異的電子傳導以及高比表面積之特性，可成為燃料電池的優良電極觸媒材料。再進一步修飾上金屬奈米粒子以加強其電化學催化活性，並探討其用於甲醇氧化反應的效果。 本研究中藉由調整金屬奈米粒子成長的時間、反應溫度和與RGO的合成比例，探討改變不同變因下製備出的金屬奈米粒子/還原氧化石墨烯材料對催化效能的影響。最後藉由此最佳化的奈米複合材料做為直接甲醇燃料電池的陽極催化劑並探討其催化效果。

Because of the presence of an activated multiple carbon-carbon bond, α,β-unsaturated sulfones are high-reactive compounds which are widely used in organic synthesis. These compounds readily undergo the reactions of nucleophilic addition and pericyclic processes. At the current moment, a wide range of 1,3-dipolar cycloaddition reactions with α,β-unsaturated sulfones as dipolarophilic systems is known. However the interaction of α,β-unsaturated sulfones with azinium ylides is less studied and limited to only a few examples. In the present study, the interaction between a number of stable isoquinolinium and pyridinium ylides with aliphatic and aromatic vinylsulfones has been investigated. We considered the regioselectivity of these reactions. Mostly cycloadditions of isoquinolinium ylides to α,β-unsaturated sulfones led to the mixtures of isomeric sulfonyltetrahydroindolizines in different ratios. Also we found several examples of high-regioselective addition. The stereochemical result of the cycloaddition was examined by methods of 2D correlational 1H-NOESY NMR spectroscopy and X-ray crystallographic analysis. The process of formation of major regioisomer of cycloaddition N-phenacylisoqunolinium ylide to ethylvinylsulfone was highly stereoselective. The series of new sulfonyltetrahydroindolizines with potential bioactivity were obtained. The structure of all products was proved by IR and 1H NMR

生質能源是最佳的能源之一，而固體酸觸媒最能符合綠色化學，因此本研究要開發一種可以水解纖維素得到生質能的固體酸觸媒。將芳香族X與3-氯丙基三甲氧基矽烷反應，產物嫁接至中孔洞SBA-15-p上，再進行磺酸化，得到固體酸TPS-SBA-15-p，將其應用在催化酯化反應及阿斯匹靈的合成，催化效果優於已發表的固體酸觸媒。將TPS-SBA-15-p應用在催化水解纖維素，2 g纖維素與0.5 g觸媒在不鏽鋼高壓反應鍋中加熱至150°C反應7天，轉化率達75.7%，主產物為乙醯丙酸及癸烷，兩者碳數佔全部產物碳數的64%，乙醯丙酸的用途很廣，而癸烷是汽柴油的成分。另外，TPS-SBA-15-p具有兩種催化活性位置，此兩種催化活性官能基具有協同催化作用，因此很容易催化水解二噁烷(dioxane)及苯甲醚，也就具有催化水解纖維素的能力。

Nowadays, the most of waste materials are incinerated and generated the toxic gases in 日本. On the other hand, the Hydrogen gas (H2) has attracted attention as clean energy due to no emissions of toxic gases. In this work, we investigated that the new hydrogen evolution system using waste materials, such as aluminum (Al) foil and lime desiccant, and also investigated their reaction mechanism. The grinded desiccant was added to Erlenmeyer flask containing 300 mL of water. After dissolution the desiccant, the Al foil was added to the solution to begin the reaction. Generated gas was determined by water displacement method. The gas components are identified by gas chromatography. We found that the waste material reaction combined with waste lime desiccant and Al foil could be used for one of the hydrogen evolution system. This reaction is depended on solubility of lime desiccant, thus mean solubility of CaO in water. The Al foil is reacted with the desiccant more than 20 times of reaction stoichiometry. The calcium ion or calcium complex ions are involved with the excess reaction of Al foil.

沙烏地阿拉伯 is the largest oil exporter in the world. 64,000,000 tons of sulfur oxides are produced every year through the combustion of organic sulfur compounds in the oil industry. This leads to several environmentally serious problems, including air pollution. This research provides a novel strategy to utilize natural-based Graphene Oxide (GO) as a support for ruthenium (Ru/GO) to functionalize as a green catalyst for hydrodesulfurization. Physical activation of camel bone samples was carried out by carbonizing them at 500oC to produce camel bone charcoal. Modified hammer’s method was employed for GO production, followed by doping of ruthenium in a simple synthesis step. The prepared catalyst has been characterized by XRD, SEM and EDX techniques. Thiophene and 3-methylthiophene were used as model compounds in the hydrodesulfurization process. The catalytic reactions were carried out at atmospheric pressure in a continuous up-flow fixed-bed quartz reactor. The composition of the sulfur containing gaseous products was analyzed by gas chromatography. The product distribution achieved for thiophene was 3-6% butadiene and 76-77% butane. And for 3-methylthiophene, it was 32.3% of pentaned 1-pentene and 2-pentene and the selectivity percentage was 45%. Ru/GO has been found to be an excellent catalyst of thiophene and 3- methylthiophene hydrodesulfurization and is a considerable improvement when compared to the commercially available catalysts. The prepared catalyst shall potentially lead to the reduction of sulfur pollution in the future. The positive effect on the environment could be substantial.

過量的紫外線易引發皮膚病變。因此，我希望找出一種能將紫外光轉為有益皮膚之可見光的方法。我以可發光高分子奈米纖維為素材，嘗試了兩種不同的方法。第一種為利用可發光之PFO、PFBT高分子來製造纖維。發現藉由添加特殊基團(BT)修飾，可改變纖維放光波長。另一種為使用聚乳酸混合聚集誘導發光特性(AIE)小分子。在比較各配方後，以HPS小分子與PLA 120 mg/mL溶於二氯甲烷:二甲基甲醯胺(7:3)製出的纖維最佳。而經由光譜圖的觀察比較可證明:電紡的拉伸特性及奈米尺寸的高比表面積，更能增加纖維的發光效率。期望未來能將其運用於光療面膜、抗紫外線衣物等方面。

Photochromism is determined as reversible transformation between two chemical species, induced by action of light [1]. Herewith, initial form and photoinduced isomer have different properties, first of all, spectral. The phenomenon is attractive for the design of hi-tech materials for different applications, including optical memory elements and molecular switches. Diarylethenes are the most promising class of organic photochromic compounds due to outstanding thermal stability of both isomers and high photostability [2, 3]. Photochromism of diarylethenes explained by reversible electrocyclic reaction of hexatriene system, provoked by UV light, back reaction is induced by visible light. In this work we have proposed a new class of photochromic diarylethenes with cyclohexenone ethene “bridge” 4. The key stage of the synthesis is “one-pot” reaction of ketoesters 1 and chalkones 2 in ethanol in the presence of sodium ethoxide that includes Michael reaction and subsequent intramolecular condensation of the resulting product. The final decarboxylation of semi-product 3 results in target diarylethenes 4. We have prepared a wide range of photochromic diarylethenes with thiophene, oxazole, imidazole and benzene derivatives as aryl moieties. The spectral characteristics of compounds obtained have also been discussed.

Fluorine-containing compounds gained significant attention during the past decade1. About 20% of novel pharmaceuticals and 40% of novel agrochemicals every year contain at least one fluorine atom in the molecule. For a long time the most frequently used was trifluoromethyl group, but nowadays the most promising is the chemistry of partially-fluorinated groups. For example, the difluoromethyl substituent (CHF2) exhibits unique pharmacoforic properties capable of serving as lipophilic hydrogen bond donor thus being bioisosteric to hydroxyl group2. There are several general approaches for the formation of a required fluorinated fragment, one of them is direct nucleophilic fluoroalkylation. This approach is well-developed for trifluoromethylation reactions, such as addition of CF3-anion equivalents to C=O, C=N and electron-deficient C=C bonds or metal-catalyzed substitution in haloarenes3. However the similar difluoromethylation processes are still quite challenging. Herein we present a novel and convenient protocol for the synthesis of β-CF2H functionalized carbonyl compounds and carbinols by nucleophilic difluoromethylation of electron-deficient olefines. The process is based on a 1,4-addition of in situ generated4 phosphorus ylide Ph3P=CF2 2 to the arylidene Meldrum's acid conjugates 1. The resulting phosphobetaines 3 are hydrolized/protodephosphorilated without isolation, giving β-CF2H substituted carboxylic acids 4. The latter may be easily transformed to the corresponding ethers 5 and alcohols 6 without preliminary purification.

1. Introduction In Japan the energy self-efficiency is very low: only 6%. Hydrogen (H2) has been expected as a new and alternative energy source to imported one, such as petroleum resources. Now hydrogen energy comes into the practical use in the field of the fuel cell. Hydrogen must be extracted from other sources, for example, water, fossil fuel, and so on. Hydrogen is obtained from water by using electronic or thermal or photo energy in most cases, whereas it is well-known that hydrogen is given by the oxidation reaction of silicon in alkaline aqueous solution: Si + 2OH- + H2O → SiO32- + 2H2 Free silicon (Si) is not only used in the steel refining, aluminum-casting in the field of fine chemical industries but also is used as a material in semiconductor electronics. However, a lot of used silicon is thrown away as a waste, being not reused and recycled. In this study we try to apply a waste silicon to obtain hydrogen based on the above reaction. The purpose of the study is to develop a safe and convenient manufacturing method to generate hydrogen for an energy source of the fuel cell.