Reactions of Bis(oxy)enamines with Transition Metal Halides
Synthesis of halooximes has attracted much attention given their importance as precursors to proline derivatives1, unnatural amino acids2 and a host of alkaloids3. Halooximes have numerous industrial and biological applications 4, for example oxime ethers increases specific channel opening activities, acting as potential targets in drug treatment for various diseases 5, most adrenergic β-receptor blocking compounds also conform to the structure of oxime ethers 6. They also have vitro antifungal activities against certain plants7. A known method for the synthesis of 3 using Me3SiX as a Lewis acid, via intermediate enamines with acyclic/ cyclic bis(oxy)enamines, gives yields between 21-68%. Low yield stems from lack of reaction specificity2. In this work, we investigate coupling nitrogen-oxides with CoBr2 to synthesise halooximes in high yield. Initial cyclic/ acyclic bis(oxy)enamines were prepared by reacting 1 equiv. nitro compound with 2.4 equiv. in excess of dichloromethane under argon atmosphere at a temperature of 0ºC. 2.2 equiv. of TMS-Br was further added and left to stir till thermal equilibrium with room conditions. The cyclic/ acyclic bis(oxy)enamine was isolated upon aqueous work-up, filtration and evaporation. Synthesis of halooximes was carried out by reacting 8mL to 1mmol equiv. of THF and 2 equiv. of CoBr2 under argon atmosphere and left to stir till CoBr2 dissolves. 2mL to 1mmol equiv. of CH2Cl2 was added to 1 equiv. of bis(oxy)enamines. The reaction mixture was left to stir at room temperature for 2 hours, after which aqueous work-up, filtration and evaporation were carried out. Our results are summarized in Table 1. We also obtained relatively high percentage yields for the direct synthesis of bromooximes from cyclic nitronates via a one-pot procedure: Low yield stems from lack of reaction specificity2. In this work, we investigate coupling nitrogen-oxides with CoBr2 to synthesise halooximes in high yield. Initial cyclic/ acyclic bis(oxy)enamines were prepared by reacting 1 equiv. nitro compound with 2.4 equiv. in excess of dichloromethane under argon atmosphere at a temperature of 0ºC. 2.2 equiv. of TMS-Br was further added and left to stir till thermal equilibrium with room conditions. The cyclic/ acyclic bis(oxy)enamine was isolated upon aqueous work-up, filtration and evaporation. Synthesis of halooximes was carried out by reacting 8mL to 1mmol equiv. of THF and 2 equiv. of CoBr2 under argon atmosphere and left to stir till CoBr2 dissolves. 2mL to 1mmol equiv. of CH2Cl2 was added to 1 equiv. of bis(oxy)enamines. The reaction mixture was left to stir at room temperature for 2 hours, after which aqueous work-up, filtration and evaporation were carried out. Our results are summarized in Table 1. We also obtained relatively high percentage yields for the direct synthesis of bromooximes from cyclic nitronates via a one-pot procedure:
低溫二次燃料電池
本實驗係以台灣常見之數種植物(甘蔗、橡膠、破布子、苦苓)乾餾所成之多孔性碳棒鍍上銅和拷上Chitin 為電極兼電容,而以NaOH(aq)為電解液,製成化學電池。希望能研究出一低污染、低成本、能在常溫下經濟運作、並具有教學演示功能之電池。This research is based on the poromeric carbons which are made of several Taiwanese common plants (including: sugarcane, babul, Sabastan Plum Cordia [Cordia dichotoma Forst] , and Chinaberry tree [Melia azedadach L.]) by means of destructive distillation. The copperplating poromeric carbons later covered with Chitin functions as an electrode ac well as capacitance. Along with NaOH(aq) eletrolyte, a accumulator is then produced. The chief objective of this research is to produce a accumulator with low class of pollution and low cost, which is able to function economically under the normal atmospheric temperature. Also,this accumulator can serve as a teaching demonstration.
醇類凝膠的安定與老化及其結晶情形
在這篇報告中,特別針對了凝膠的機制去做探討,以許多的實驗數據,再輔以凝膠的基本定義,去臆測各種有關於凝膠的老化機制,並藉由其過程中推斷出一些有趣的性質: 1. 當膠體內水分含量不同,與凝結後的醇類膠體有相當的影響。 2. 凝膠老化後形成的結晶形狀,因凝膠溶質、溶液內互溶性的不同,形成了不同凝聚程度的絮聚現象。 3. 同種陰陽離子在不同碳數的醇類凝膠中,因為與水溶液的互溶性也有所不同,間接影響了凝膠的形成速度,這對於安定來說,包含了很大的意義存在。 4. 對於其老化的速度,會因其安定程度而有所影響。 5. 老化後的溶液內的陰陽離子濃度,會直接影響其再次安定與老化的情形。 In this report, we especially do the discussion to the mechanism of the gel. With a lot of experimental data and the basic definition of gel, we conjecture various kinds of aging mechanism about the gel, and infer some interesting problems from its course: 1. Moisture content in the gel effect the gel’s quality after alcohol condensed greatly. 2. Because of dissolving difference between the alcohol and the other substances, crystallization forms after the gel aged have formed different degrees phenomenon of gathered. 3. The same kind of negative and positive ion among the alcohol gel that have different carbon atoms. Because of dissolving difference between the ions and the solution, the ions influence forming speed of gel indirectly. To being stable of the gel, this phenomenon includes very great meaning. 4. Stable degree of the gel can influence its speed of aging. 5. The consistency of negative and positive ion in the aging solution of the gel can influence its stable and aging situation again directly.
A Zero Pollution Process That Convert Non-Biodegradable Plastic Waste Into Hydrocarbon Fuel
Non-biodegradable waste materials like discarded polybags, rubber bottles, broken buckets and sachet water bags constitute a serious environmental problem all over the world. Several steps have been taken to eliminate these waste materials. Burning of these non-biodegradable waste in an incineration only constitute environmental pollution as poisonous gases are release to the environment which are hazardous to lives. The purpose of developing this catalytic conversion of non-biodegradable waste material into fuel is to remove the problem non-biodegradable waste materials poses in its disposal as well as obtaining a precious end product that will supplement fuel supply. Dump side lands that would have been used for dumping waste is also reclaimed. The procedure and chemistry is from the fact that Non-biodegradable waste materials are composes of long chain hydrocarbon. Some are made of polymeric units like polythene. The materials are heated in a closed vessel with coal and a catalyst. Heating is done progressively until condensate from gaseous product is obtained. This condensate is wide range of liquid fuel (Diesel and petrol) including LPG ranges. Further separation processing will give pure product of the different fuel liquids. The Apparatus consist of a cylindrical cooking vessel heated by coal furnace or other heat source like LPG, the vessel is made of steal. The upper side of the vessel provide an outlet vent to connect condensing section/condenser which is required for the conversion of gaseous form of product into liquid state. The fuel produce can find it application in the following areas; Heating of kiln in the cement company, Heating of boilers and Domestic lighting.
Reduction of free radicals and endotoxin by conjugated linoleic acid loaded in-situ synthesized poly
本研究首先利用NaOH 將PAN 薄膜改質形成PAA 水膠膜表面,進一步與異丙胺鍵結形成NIPAAm 結構,以做為藥物傳輸的載體。反應所得之PNIPAAm 薄膜其溫度轉換點為34 °C 其pH 敏感性介於pH 5 至10 之間,實驗進行進一步於34 °C將PNIPAAm 薄膜浸入共軛亞麻油酸(CLA)中,取出後置入4 oC 二次水中,最後測試經改質接枝後PAN 薄膜於膽固醇、三酸甘油酯的吸收效果,並以化學冷光儀分析改質接枝後PAN 薄膜其抗氧化效率。結果顯示改質接枝之PNIPAAm 薄膜於包埋CLA 其對於血液中膽固醇及三酸甘油酯有明顯的吸收效率,此外對血液中的自由基也有明顯較未改質之PAN 薄膜穩定的趨勢。A thin layer of poly(N-isopropyl acrylamide) (pNIPAAm) was synthesized in situ on the surface of hydrolyzed polyacrylonitrile (PAN) membrane. This thin layer exhibited both pH response due to the poly(acrylic acid) moiety and temperature response due to the pNIPAAm moiety. The swelling behavior of the membranes was evaluated under various temperatures and pH. The curve of the swelling ratio for the PAN-NIPAAm showed a lower critical solution temperature (LCST). Then conjugated linoleic acid (CLA) was loaded into the pNIPAAm layer. The effects of CLA on the blood coagulation and oxidative stress were evaluated using human blood. The level of reactive oxygen species (ROS) was measured by chemiluminescence (CL) method to evaluate the oxidative stress. Furthermore, the removal of bacterial endotoxin (lipopolysaccharide, LPS) by CLA-loaded PAN-NIPAAm was measured with ELISA. The results show that the LCST swelling curve was at 37°C. In addition, the swelling ratio increased by 71% when the pH increased from 5 to 10. The concentration of LPS can be reduced by CLA-loaded PAN-NIPAAm 2.1 and 1.2 5 times of that by unmodified PAN and PAN-NIPAAm membranes, respectively. In addition, the level of ROS against CLA-loaded PAN-NIPAAm was reduced significantly than that against unmodified PAN and PAN-NIPAAm. Therefore CLA-loaded PAN-NIPAAm membrane could offer protection for patients against oxidative stress and could also inhibit LPS for clinical applications
ORGANIC AND NON ORGANIC CEREALS The experimental pattern that marks the difference
1. Purpose of the research The purpose of this research is to make a suitable experimental pattern to distinguish, by scientific method, organic cereals from non organic cereals. The reference ideas consider cereals (rice, barley and maize) as a complex system that possesses its own chemical–physical properties. These cereals are able to maintain traces of the cultivation process. In non organic cereal grains foreign molecules, from synthesis substances used during their cultivation and/or in their final processing, can be found. These kinds of molecules would be absent in organic cereals. The effect of these foreign molecules traces on the principal components (glucides, proteins, lipids) of cereals is investigated by Infrared Spectroscopy (IR). 2. Procedures The spectra of a small quantity of cereal meal are recorded by the ATR (Attenuated Total Reflectance) sampling method. The meal is obtained from selected grains of rice and barley, that are grated near the germ. On the contrary, the maize grains, are cut lengthwise and the two halves are grated on the interior surface. This procedure of preparing samples, withdraws that part of the non organic cereal grains where foreign molecules are more abundant. The meal mass amounts to only a few milligrams; so in this way the dilution effect caused by starchy and proteinic parts onto the lipid part, is reduced. The cereal packaging has to be intact, well preserved and the expiry date has to be far–off. The organic packaging has the European Certification symbol and that of the authorizing agency. The cereals used in this research, have been labelled with symbols. The experimental data are processed by the NMC (Nearest Means Classification: J.Chem. Educ. 2003, 80, 542) method, adapted to cereals. 3. Data The NMC method is based on the individuation of suitable absorption bands of the IR spectrum and, for each of them, the calculation of the following quantities: the average value of the wave number (); the (Σ) value; the |diff.|=|(ῡ–)| value and the Σ|diff.| value. At the end the sum of the Σ|diff.| for all selected bands is computed in order to obtain the Σ(Σ|diff.|). Then a graph is plotted using (Σ) and Σ(Σ|diff.|) variables. The graph has a gap between the organic cereals and the non organic ones; in other words the organic cereals are found in a particular area, whilst the non organic cereals are found in another area. The boundary between the two areas is a particular value of the Σ(Σ|diff.|). This is the pattern that distinguishes organic cereals from non organic ones. 4. Conclusions For some cereals, the gap is bigger than others; but in any case the position of the cereals on one side of the boundary line or on the other, is clear. An experimental scientific pattern that marks the difference between organic cereals and non organic ones, can be useful to organic farms, authorizing agencies and consumers. This research has planned a route to find such a pattern.
鈦鈦相傳-以新穎水熱-化學電池法製備二氧化鈦
In our experiment, the novel hydrothermal-galvanic couple method is used to produce nanostructured TiO2 thin film. Compared with the traditional hydrothermal method, whose process is conducted under high temperature and high pressure, the hydrothermal-galvanic couple method is a thermally and electrochemically driven process. The titanium atom is gradually oxidized on the surface driven by potential difference, and eventually become nanostructured TiO2. The advantages of the hydrothermal-galvanic couple method are numerous: they are simple, environment-friendly and energy-saving. Experimental parameters include time, concentration and types of solution. The hydrothermal method is used for comparison. By the cross-section and surface pictures of Field-emission scanning electron microscopy (FE-SEM), we can clearly observe that there is obvious change on the titanium surface, along with increased thickness and altered surface structure. The film of hydrothermal-galvanic couple method is thicker than that of hydrothermal method. Thickness increases with time and concentration as well. Both the hydrophile and decomposition of methylene blue examination indicate that the product on the surface contains photocatalyst-like feature.我們利用新穎水熱-化學電池法製備奈米級二氧化鈦薄膜。相較於一般傳統水熱法高溫高壓的製程,水熱-化學電池法結合了熱能與化學電能,讓鈦原子在電位差的驅動下於表面逐步氧化,最終形成奈米級二氧化鈦粒子,具備簡易、環保、省能的優點。實驗參數包括時間、濃度、溶液種類,並以水熱法作為對照組。由FE-SEM 橫截面圖及表面圖可清楚看到鈦的表面有明顯變化,膜厚增加、表面結構改變;以水熱-化學電池法所得的薄膜明顯較水熱法厚,而其厚度隨著濃度及時間的增加也有增加的趨勢,由試片親水性測試與亞甲基藍吸光度測試,皆顯示試片的表面產物具有類似光觸媒的性質。