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化學

Plexiglas: from synthetic glass to cationic exchanging resin

Plexiglas is a macromolecule (poly-methyl-methacrylate) obtained by polymerization of the Methyl Methacrylate. Cation exchanging resins have acidic groups such as COOH (carboxyl) and SO3H (sulfonic) which fix metallic cations dissolved in water releasing an equivalent of protons through the following reaction: 2 RCOOH + Me2+ (RCOO)2Me + 2 H+ Regeneration is made treating the exhausted resin with diluted hydrochloric acid (HCl) which moves the equilibrium to the left. The aim of our research is to re-use the discarded Plexiglas by transforming it into a cationic exchanging resin. Alkaline hydrolysis transforms the COOCH3 group into COO– group; the obtained group is then transformed into COOH group by means of a treatment with HCl. After the alkaline hydrolysis spectra of the solid show the characteristic band of the asymmetric stretching of the COO– (1610-1550) at 1567 (1st experiment) and at 1555 (2nd experiment). Instead after the acidic treatment the spectra of the solid show that this band has disappeared. On the contrary the characteristic band of the OH stretching of the COOH group (3300-2500) at 3228 (1st experiment) and at 3200 (2nd experiment) appears. The water hardness, due to Ca2+ and Mg2+ ions, is studied to verify the capability of the obtained resin to capture these cations. For this purpose, some mineral water is percolated through the micro-columns. There are three experimental evidences to validate the hypothesis: EDTA molecule (Ethylene Di-amino Tetra-Acetic acid, disodium salt) to estimate hardness is not required The pH of the percolated water through the column decreases from 8 of the mineral water without any treatment, to 6.3 after the treatment as expected The spectrum recorded in the visible range of the percolated mineral water through the column plus EBT (Eriochrome Black T) indicator is the same as the spectrum obtained using de-ionized water plus the same amount of EBT In conclusion, the study has provided evidence that it is possible to convert Plexiglas into cationic exchanging resin.

Stop the Spread of Desertification by Agar

The purpose of this research is to prevent the desertification by using my original “agar sheets”. The dry regions, in other words, the desert has already occupied about forty percent of the surface of the earth (Figure 1). In addition, it is said that land of seven million hectares turn into desert every year. However, we can reproduce the green-bosomed earth by using appropriate means, because this desertification originated in excessive farming, excessive pasturing, and deforestation caused by human beings. I learned “Cape Erimo’s Green Construction Method”, which has succeeded in planting trees in the coast of Japan by using seaweed, and this method led me to use the agar to prevent the desertification, which is a familiar Japanese food made from seaweed. I think that it is possible to prevent the desertification of any conditioned lands by using my original “agar sheets.”

利用電化學探討土壤奈米粒子對重金屬的吸附

由於工商科技的發展帶給環境負面的影響日漸嚴重,其中尤以重金屬對台灣環境的影響較為顯著,故探討能移除排放廢水中的重金屬之有效天然資材有其重要性。以台灣天然存在之大地資源土壤中的奈米粒子來進行對汞、鎘的吸附,試驗結果得知,台灣三種代表性土類土壤中的奈米粒子確實能有效地吸附汞離子和鎘離子,且其中以對汞的吸附要大於對鎘的吸附。屬於砂頁岩沖積土的奈米粒子對汞、鎘的吸附最大,其次是黏板岩沖積土的奈米粒子,而最小的則是屬於台灣紅壤的奈米粒子。以上結果經由電化學方波伏安法的測定、電導度計法的測定與發芽率試驗結果都有相同的趨勢,顯示土壤奈米粒子可用來當作移除汞、鎘等重金屬的天然資材。 ;Effects of heavy metals are significant in Taiwanese environment due to serious impact of environment was made by development of industry and commerce. Therefore, study of removing heavy metals from waste water by natural materials is important. We need nanoparticles of natural soils to study the adsorption of mercury and cadmium ions. The experimental results indicated nanoparticles of three represent soil groups in Taiwan could adsorb effectively mercury and cadmium ions, and the adsorption of mercury ion was more than that of cadmium ion. The nanoparticles of sandstone-shale alluvial soil had largest adsorption for mercury and cadmium ions, and next for that of slate alluvial soil. The nanoparticles of red soil had smallest adsorption. All results were proved by voltammetry of electrochemistry, conductivity method and germinant percentage of vegetable seed. That obviously revealed soil nanoparticles could remove effectively mercury and cadmium ions.

[3+3]-annelation of cyclic nitronates with enol diazoacetates

The purpose of this research is to prevent the desertification by using my original “agar sheets”. The dry regions, in other words, the desert has already occupied about forty percent of the surface of the earth (Figure 1). In addition, it is said that land of seven million hectares turn into desert every year. However, we can reproduce the green-bosomed earth by using appropriate means, because this desertification originated in excessive farming, excessive pasturing, and deforestation caused by human beings. I learned “Cape Erimo’s Green Construction Method”, which has succeeded in planting trees in the coast of Japan by using seaweed, and this method led me to use the agar to prevent the desertification, which is a familiar Japanese food made from seaweed. I think that it is possible to prevent the desertification of any conditioned lands by using my original “agar sheets.”

三氮二氧五牙配位基二價鈷擬態化合物與一氧化氮之反應性探討

本研究將三氮二氧五牙配位基H2BDPP去質子化後形成BDPP2-,與二氯化鈷(CoCl2)反應後,製成二價鈷錯合物Co(BDPP) (1)。將1與FcBF4反應,製成三價鈷錯合物[Co(BDPP)(H2O)]BF4 (2),1和2的分子結構可由單晶繞射解析法、可見光-紫外光光譜儀鑑定,並利用循環伏安法量測1的還原半電位。1與一氧化氮反應會有顯著顏色變化,根據UV/vis光譜排除氧化的可能性,表示新生成一錯合物[Co(BDPP)(X)] (3)。利用傅立葉紅外線光譜儀確認此反應有新的振動頻率1615 cm-1產生,意味著在3上觀察到N=O的振動吸收峰(X = NO),推測錯合物3中一氧化氮和鈷中心金屬產生了鍵結。藉由此錯合物可鍵結或釋放一氧化氮之特性,未來可能運用在治療高血壓藥物的開發研究。

Studies of Hydrogen Evolution Reactions from Aluminum Foil using Waste Materials and Their Reaction Mechanism

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.

Reactivity of styrylmalonates as synthetic equivalents of Donor–acceptor cyclopropanes with aldehydes in the presence of BF3•Et2O

Donor–acceptor cyclopropanes (DACs), which can act as sources of 1,2- and 1,3-zwitterions in the presence of Lewis acids, are widely used in organic synthesis for the preparation of various carbo- and heterocyclic compounds, including natural compounds and their analogues. To date, many types of DACs reactivity have been identified. However, the chemistry of styrylmalonates (isomers of DACs, which can be easily generated from DACs) is almost undescribed and has a powerful synthetic potential. The use of styrylmalonates as synthetic equivalents of DACs allows us cardinally change the known reaction pathways of DACs. In this work, a new strategy for cascade assembly of substituted pyrenes based on the reactions of styrylmalonates with aldehydes in the presence of BF3•Et2O has been developed. Generation of formal 1,2-zwitterionic intermediates owing to complexation of dicarboxylate groups with BF3•Et2O is the driving force of the reaction discovered. This method makes it possible to assemble pyrenes or 5,6-dihydro-2H-pyran-2-ones in one synthetic stage from readily available starting compounds with high regio- and diastereoselectivity, and use these pyrenes in futher reactions. We’ve optimized conditions of the reaction and synthesized a number of various substituted pyrenes. Moreover, the reaction shows good results with various aromatic and heteroaromatic substituents. Pyrenes can be easily purified by crystallization. Every product was obtained selectively and determined by full set of physical-chemical methods, including X-ray analysis. 5,6-dihydro-2H-pyran-2-one skeleton is found in various natural compounds demonstrating a broad spectrum of biological activity, such as antiviral and antineoplastic.

不同形態之銀奈米結構及銅銀雙金屬對電催化二氧化碳還原產物的研究

近年來全球暖化與能源危機成為眾人關心的議題,將太陽能轉換成電能並電解還原二氧化碳,生成運用於替代能源的產物,可同時解決兩個議題。本研究以水熱反應製備銅奈米線,以無電電鍍將銀鍍上銅奈米線,並以油浴反應、改變硝酸銀與聚乙烯吡咯烷酮的莫耳數比,合成銀奈米材料。塗布至玻璃碳盤電極後,以穿隧式電子顯微鏡、紫外光-可見光光譜儀、X射線繞射儀鑑定、以氣相質譜層析儀分析其電催化還原二氧化碳之產物與法拉第效率,發現產氫之法拉第效率以奈米銀立方電極 ,在電壓為-0.65 V至 -0.7 V時最高;產一氧化碳之法拉第效率以銀奈米粒,在電壓約為 -1.1 V時最高。銀奈米電極可以產熱值高的氫氣以及可進行多種反應、作為工業原料的一氧化碳,而銅鍍銀之奈米線電解之產物多元,包括碳氫化合物、一氧化碳、甲醇、乙醇等。

Sustainable Graphene Oxide Support for Ruthenium Catalysts to Improve the Efficiency of the Hydrodesulfurization of Thiophenes

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.

H.E.L.P. Heart Empowers Lifelong Pacemaker

EXPERIMENT 1---The effect of NaCl and Glucose Concentration on the efficiency of the cell I. Introduction Experiment on different concentrations of standard glucose solution (ranged from 0.125 M to 1.000 M) and standard sodium chloride solution (ranged from 0.250 M to 4.000 M) were done. We investigated the full concentration effect, which included both concentration of glucose solution and sodium chloride solution on the fuel cell’s output voltage, current and power. II. Procedures 1. Add 25.0 cm3 of Glucose solution of the tested concentration to the beaker representing the anode, and add 25.0 cm3 of distilled water to the beaker representing the cathode. 2. Add 50.0 cm3 of 0.250 M NaCl (aq) to both beakers representatively. 3. Fold a piece of filter paper and soak in fully into NaCl (aq) at cathode. 4. Clean and place the silver wires into the beakers representatively, and connect the air pump to the cathode. 5. Connect the cell to two multi-meters, each acting as a voltmeter and an ammeter respectively 6. Take the readings of multi-meters after 30 seconds. 7. Repeat steps 1 to 6 twice for the second and third reading of the cell. 8. Take average value among three values as the final reading of the cell. 9. Repeat steps 1 to 8 by replacing the NaCl (aq) with concentrations of 0.000 M, 0.500 M, 1.000 M, 2.000 M and 4.000 M, and the standard glucose solution with concentrations of 0.000 M, 0.125 M, 0.250 M, 0.500 M, 0.750 M and 1.000 M. III. Result of Experiment 1 When glucose concentration is increased from 0.000 M to 0.250 M, the output power increases, it is found that power generated is maximized at glucose concentrations between 0.125 M and 0.250 M. However, with further increase in glucose concentration from 0.250 M to 1.000 M, the power generated decreases. This shows that high concentration of glucose inhibits the generation of electricity, while higher concentration of sodium chloride solution can increase the output. EXPERIMENT 2---The effect of temperature on the efficiency of the cell I. Introduction In this experiment, the second effect - temperature on the fuel cell’s output voltage, current and power was investigated. In order to get a significant result, the effect of temperature on these measures with fixed 0.250 M glucose solution and sodium chloride solution concentrations varied from 0.500 M to 4.000 M had been investigated. II. Procedures 1. Add 25.0 cm3 of Glucose solution of the tested concentration (0.25 M) to the beaker representing the anode, and add 25.0 cm3 of distilled water to the beaker representing the cathode. 2. Add 50.0 cm3 of 0.500 M NaCl (aq) to both beakers representatively. 3. Fold a piece of filter paper and soak in fully into NaCl (aq) at cathode. 4. Clean and place the silver wires into the beakers respectively, and connect the air pump to the cathode. 5. Connect the cell to two multi-meters, each acting as a voltmeter and an ammeter respectively 6. Take the readings of multi-meters after 30 seconds. 7. Repeat steps 1 to 6 twice for the second and third reading of the cell. 8. Take average value among three values as the final reading of the cell. 9. Repeat steps 1 to 8 by varying the temperature from 42℃ to 32℃. 10. Repeat steps 1 to 9 by replacing the NaCl solution of 0.000 M, 1.000 M, 2.000 M, and 4.000 M respectively. III. Result of Experiment 2 The results showed a consistent trend and relationship of the effect of temperature on the output current, voltage and power of the fuel cell for 4 different concentrations of sodium chloride solution with fixed 0.25 M glucose solution. Generally, the results showed that the output power increases with temperature. EXPERIMENT 3---The effect of dialysis tubing and Nafion 117 on the efficiency of the cell I. Introduction Semi-permeable membrane separating glucose and oxygen, ensure the glucose oxidation only occurs at the anode, and preventing glucose oxidation occurs at the cathode, responds to maximize power output. Experimental study on two kinds of membranes, dialysis membranes and Nafion 117 films were done, by studying their fuel cell output voltage, current and power effects. Previous experiments showed that the optimal output of the battery is at 0.250 M glucose solution, Therefore, experimental conditions for glucose concentration is fixed on 0.250 M and sodium chloride solution concentration varies from 0.500 to 4.000 M. II. Procedures The Effect of Dialysis Tubing on voltage and current of the fuel cell 1. Pour 50 cm3 1.000 M NaCl (aq) to each compartment of the beaker separated by dialysis tubing. 2. Pour 0.250 M Glucose Solution into the compartment representing anode. 3. Connect the cell to two multimeters, which act as a voltmeter and ammeter respectively 4. Take the reading of the multimeters after 30 seconds 5. Repeat steps 1 to 4 twice for the second and third reading of the cell. 6. Take average value among three values as the final reading of the cell. 7. Repeat steps 1 to 6 with NaCl (aq) with concentration of 0.000 M, 0.250 M, 0.500 M, 2.000 M and 4.000 M to obtain the remaining data. The Effect of Nafion 117 on voltage and current of the fuel cell 1. Add 50 cm3 1.000 M NaCl (aq) and 50 cm3 of 0.250 M of glucose solution to the beaker. 2. Add 1.000 M NaCl (aq) to the Nafion 117 membrane pouch, and silver plate was put inside to become the anode. 3. Connect the cell to two multimeters, which act as a voltmeter and ammeter respectively 4. Take the reading of the multimeters after 30 seconds 5. Repeat steps 1 to 4 twice for the second and third reading of the cell. 6. Take average value among three values as the final reading of the cell. 7. Repeat steps 1 to 6 with NaCl (aq) with concentration of 0.000 M, 0.250 M, 0.500 M, 2.000 M and 4.000 M to obtain the remaining data. III. Result of Experiment 3 The result had shown that when the solution does not contain glucose (i.e. Glucose concentration equals to 0.000 M), Nafion 117 Membrane Cells have similar power outputs compared to the dialysis tubing cells. However, in 0.250 M glucose solution, the output of Nafion 117 membrane cell is about 1 to 5 times more compared to that of dialysis tubing cell. According to the experiment results, it was found out that the power output was maximized when the concentration of glucose solution and NaCl (aq) are 0.250 M and 4.000 M respectively. Under this concentration, the out of Nafion 117 membrane cell was 1336.68 nW which was 5 times higher than that of dialysis tubing cell. Hence, adopting Nafion 117 as the selectively membrane can greatly enhance the output of cell. It is believed that the special structure of Nafion 117 has limited the movement of glucose molecules, and prevented their oxidation at cathode. This has enhanced the oxidation of glucose at anode, and thus increased the power output of the cell.