化學

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。

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.

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。

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.

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

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.

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.

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.