含環胺-亞胺雙牙配基及其鎳錯合物的合成、結構鑑定，及烯烴催化聚合反應
本研究合成含環形胺—亞胺雙牙配基鎳金屬催化劑，用以催化烯烴聚合反應。將2-甲基丙醛經由溴化、胺化及亞胺化的步驟合成含胺—亞胺的雙牙配基，Et2NCMe2CH=N(2,6-iPr2C6H3) (3a)、(c-C4H8)N- CMe2CH=NPh (3b)、RNCMe2CH=N(2,6-Me2C6H3) (R = c-C4H8 3c，c-C5H10 3d)。再將配基和Ni(DME)Br2 (DME = 1,2- 二甲烷氧基乙烷) 反應， 形成鎳金屬錯合物Ni [Et2NCMe2CH=N(2,6-iPr2C6H3)]Br2 (4a)、Ni[RNCMe2CH=N (2,6-Me2C6H3)]Br2 (R = c-C4H8 4c，c-C5H10 4d)，並作結構鑑定。其中3b、3c、3d、4c、4d 均為合成的新化合物，4d 獲得X 光單晶繞射結構。
以合成之鎳錯合物作為催化劑，催化乙烯或降冰片烯(C7H10)的聚合反應，探討反應活性和高分子產物的性質。與含相同碳數的錯合物比較，在胺基具環形取代基的錯合物對乙烯的催化活性較佳，聚乙烯產物分子量較高，分子量分布範圍狹窄；其對降冰片烯的催化活性略遜於非環形者。同為環形取代基時，六環較五環者對乙烯的催化活性較差，但對降冰片烯的催化活性較佳。顯示乙烯聚合與降冰片烯聚合有不同的反應決定步驟。催化劑及配基的設計的確可以操控聚合反應及其高分子產物的性質。
The synthesis of α-amino aldeimines Et2NCMe2CH=N(2,6-iPr2C6H3) (3a), (c-C4H8)NC Me2CH=NPh (3b), RNCMe2CH=N(2,6-Me2C6H3) (R = c-C4H8 3c，c-C5H10 3d), as well as the nickel complexes Ni [Et2NCMe2C- H=N(2,6-iPr2C6H3)]Br2 (4a), Ni[RNCMe2CH=N (2,6-Me2C6H3)]Br2 (R = c-C4H8 4c，c-C5H10 4d) has been succeeded. Their structures were mainly determi ned by spectroscopy or elemental analysis. The complex 4d was characterized by X-ray crysta llographic analysis. It shows that the nickel complex has distorted tetrahedral configuration.
The catalytic reactions of ethylene or norbornene polymerization using the newly synthesized nickel complexes are studied. All catalyts show high activity toward studied olefin polymerization. Comparing the data of the catalytic ethylene polymerization for complex 4c with those of its isomer complex 4a, the former is found to results in higher activity as well as the larger molecular weight of the PE products with the narrower dispersity. On the contrary, 4c shows lower activity in the reactions of norbornene polymerization than 4a. For the cyclic amine derivatives, 4c of five-membered amino group shows better catalytic activity toward ethylene polymerization than 4d of six-membered amino group. But 4d gives better perfomance for norbornene polymerization than 4c. Such results indicate that the processes of ethylene and norbornene polymerization might have different rate-determining steps. These study confirms that the design of ligand and catalyst are crucial with respect to the control of the catalytic olefin polymerization and the properties of the polymeric products.
線鋁之情-以陽極氧化鋁模板製作氧化亞銅奈米線
我們使用陽極氧化鋁(AAO)模板來製備銅及其氧化物的奈米線。以硫酸銅和乳酸配製電鍍液，利用氫氧化鈉水溶液(NaOH)將其pH 值調整到12，供以不同電壓，可電鍍出銅及氧化亞銅奈米線。在較高電壓下可製備出銅奈米線，而在較低電壓下可製成氧化亞銅奈米線，若使用中間電壓則能製得銅及氧化亞銅的混合態。利用x 光繞射分析儀(XRD)來分析其結晶構造、使用場發射掃描式電子顯微鏡(SEM)以得知其表面形貌。電鍍出的奈米線直徑約60 nm。奈米線的長度可藉由調整電鍍時間或電壓來控制。在製作IC 內部導線方面，銅奈米線深具開發潛能；在提升太陽能電池的轉換效率、製作可見光光觸媒方面，氧化亞銅奈米線極具前瞻性。We electrodeposited copper and cuprous oxide (Cu2O) nanowires with anodic aluminum oxide (AAO) templates. Both Cu and Cu2O nanowires could be prepared with an alkaline cupric lactate solution, which was adjusted to pH 12 using a 6 M NaOH, when supplied with different electrolytic voltages. Cu nanowires could be prepared when a higher voltage was supplied, and Cu2O nanowires could be prepared with a lower voltage. A mixture of Cu and Cu2O nanowires could be prepared with a supply of a voltage in between. X-ray diffraction (XRD) is used to determine the phase composition, and scanning electron microscopy (SEM) is employed to characterize the morphology of the nanowires. The length of nanowires can be controlled by adjusting the time spent on electrodeposition and the voltage supplied. The resultant diameter of the nanowires was about 60 nm. Cu nanowires are promising materials for making the conductive wires in IC, and Cu2O nanowires hold great promise for improving the conversion efficiency of solar cells and manufacturing visible-light photocatalyst.
Asymmetric Total Synthesis of GlaxoSmithKline’s Potent Phosphodiesterase PDE IVb Inhibitor
Phosphodiestarase of subtype PDE IVb inhibitors are considered as perspective drugs for the treatment of the central nervous system disorders (depression, Alzheimer’s disease, Parkinson’s disease). Pyrrolizidinone Glaxo-1, proposed by GlaxoSmithKline, is a highly potent PDE IVb inhibitor (IC50 = 63 nM), then conventional phosphodiesterase inhibitors Ro-20-1724, Rolipram and Cilomilast. However the activity of the Glaxo-1 was studied on a racemic sample, since the asymmetric approach to its synthesis has not been developed. Therefore the purpose of this research was the development of an efficient synthetic scheme enabling enantioselective excess to both (-)- and (+)-Glaxo-1, which can be than subjected to biological studies. \r The key stage in proposed asymmetric synthesis (-)- and (+)-Glaxo-1 is stereoselective [4+2]-cycloaddition of the nitroolefin to an optically activity vinyl ethers, derived from (-)- or (+)-trans-2-phenylcyclohexanols. The resulting chiral cyclic nitronates are transformed into a functionalized cyclic oxime ethers using tandem sylilation-nucleophilic substitution procedure. Reduction and decarboxylation of these products lead to optically pure Glaxo-1 and the regeneration of chiral 2-phenylcyclohexanols (91%). \r Thus both enantiomers (+) and (-)-Glaxo-1 were obtained selectively in average yield 12% from isovaniline and nitroethane. The study of biological profiles of each enantiomer of Glaxo-1 will be conducted in near future.
Vitamin C in Cold and Flu Drinks
This chemistry project was designed to measure the vitamin C levels within liquid cold and flu remedies, and see if they had been accurately stated on the package. A range of Cold and flu drinks was selected, including one made with only cold water (Lemsip Original, Lemsip Max, Effer-C-Cold Water, Relief and Lemting) .The procedure used to carry out the experiment was a redox titration, each trial required two titrations, with the first being a blank titration to determine a sodium thiosulfate concentration in the absence of vitamin C. The following Drinks had more Vitamin C than stated on the packaging – Lemsip Original (19.4%), Lemsip Max (22.1%), Effer-C (17%) and Relief (8.8%). Lemting was the only drink made to directions that had less Vitamin C than stated by 31.8%. Two conclusions can be drawn from these results, the first being that Lemting has the most inaccurately recorded mass of vitamin C and is also the only drink with less vitamin C than stated. The other interesting result is that Effer-C (the only drink made with cold water) had 170mg of extra vitamin C. Of the other drinks that had more vitamin C, Lemsip Max was next with an extra 22.8mg. Early research had showed that Vitamin C was affected by high temperatures (above approximately 70oC) and, as cold and flu drinks are commonly made with hot water the Vitamin C levels might change when they were made up. This poses a further possible research question which is, in making cold and flu remedies with hot water is some of the available Vitamin C being destroyed?
本土藥材金銀花的研究與分析
本實驗以薄膜色層層析（TLC）、高效能液相層析（HPLC）分析等化學方法，進行金銀花品種差異的鑑識；此外，配合生藥學的顯微鏡檢視，如中藥材組織鏡檢、藥材粉末鏡檢等比對，以期找出辨別金銀花品種的方法。研究至目前為止，由金銀花之薄膜色層分析的Rf值（0.225、0.425、0.7、0.85、0.95）可確認出金銀花藥材，並得知金銀花藥材中皆含有綠原酸的成分；以高效能液相層析的圖譜與成分峰的積分面積可用來判別金銀花的品種，並從質譜分析瞭解成分含量；進行生藥學的藥材粉末組織鏡檢，發現無法作為金銀花藥材的分類憑藉。未來將持續延伸實驗，朝向中藥奈米化與一般粉末在藥效、成分上差異的比較，並進行金銀花萃取液的抗菌作用試驗，瞭解不同品種之金銀花藥材在藥理作用的異同，接續著奈米化藥材的應用與實踐。Using thin layer chromatograph (TLC) and high performance liquid chromatography (HPLC), we can study how to differentiate the species variation of honeysuckle; beside, based on the observation of biopharmaceutical microscope, such as comparing the histology of Chinese herbs and its powder, we suggest that we could differentiate the species of honeysuckle. From the present, firstly, we could distinguish the honeysuckle from other herbs by the Rf value of TLC(0.225, 0.425, 0.7, 0.85, 0.95), from which we find that all honeysuckles contain the component of Chlorogenic acid. Secondly, we could tell the species of honeysuckle according to the map of HPLC and the peak area after integration, as well as the integrants of honeysuckle by way of LC-Mass analysis. Thirdly, while studying the histological analysis based on the observation of biopharmaceutical microscope, we found that it shows no difference between all the honeysuckles; thus, it fails to be a scientific method used to distinguish the herb honeysuckle. However, in the biochemical experiments of honeysuckles, we found honeysuckles from different sources and the place of origin shows difference in their antibiotic effect, showing the importance of local medicine. When it comes to my future work, in order to extend my experiments on honeysuckles, I would compare the nano-scale honeysuckle powder with normal-sized one in their clinical effects and components.