从α-蒎烯氧化制备桃金娘烯醛

本文对用二氧化硒氧化α-蒎烯制备桃金娘烯醛进行了研究,探讨了氧化剂、溶剂、反应时间和反应温度的影响。发现活化处理后的二氧化硒,可以明显提高反应的选择性,当产品的收率从45%提高到61%,产品的纯度提高到96%,硒的回收率达到70%。     

桃金娘烯醛合成及其生物活性测试

以α-蒎烯为原料、SeO2为氧化剂,选择性氧化双键α-氢合成了桃金娘烯醛．通过IR、GC—MS对其结构进行了表征。优化了合成反应条件．并对其生物活性进行了测试。结果表明,在反应温度为（60±5）℃、反应时间为6～7h、SeO2与α-蒎烯摩尔比为1：（2～3）、氧气流量约为1000mL·Min。的条件下．所制得的桃金娘烯醛产率较高,α-蒎烯的选择转化率相对稳定。桃金娘烯醛对云南纵坑切梢小蠹有一定诱集作用,其诱集率梢转干期（71．6％）明显高于梢转梢期（46．2％）。     

合成桃金娘烯醛的反应器的模拟设计

以α-蒎烯为原料合成一种重要的化工中间体桃金娘烯醛，对其合成反应器进行了模拟设计。得出了数学模型方程。并对方程的解编写了计算程序，为放大提供了理论基础。     

桃金娘烯醛基噻二唑-酰胺化合物的合成及性能

以α-蒎烯(Ⅰ)为原料,经选择性烯丙位甲基氧化反应制备了桃金娘烯醛(Ⅱ),Ⅱ再经缩合反应得到了桃金娘烯醛缩氨基硫脲(Ⅲ),进一步氧化环化得到了桃金娘烯醛基噻二唑(Ⅳ),然后与系列酰氯化合物进行N-酰化反应,以66%~81%的收率合成得到了11个桃金娘烯醛基噻二唑-酰胺化合物Ⅴa~k。采用FTIR、1HNMR、13CNMR和ESI-MS对目标化合物进行了结构表征,并测试了目标化合物的抑菌和除草活性。结果表明:在化合物Ⅴa~k的质量浓度为50 mg/L时,Ⅴa~k对测试的苹果轮纹病菌、黄瓜枯萎病菌、花生褐斑病菌、小麦赤霉病菌和番茄早疫病菌均显示不同程度的抑菌活性,其中桃金娘烯醛基噻二唑-乙酰胺(Ⅴa)、桃金娘烯醛基噻二唑-氯乙酰胺(Ⅴb)和桃金娘烯醛基噻二唑-正丙酰胺(Ⅴc)对苹果轮纹病菌的相对抑制率分别为93.0%、93.0%和98.2%,化合物Ⅴb对黄瓜枯萎病菌的相对抑制率为84.3%,表现出与阳性对照嘧菌酯(对苹果轮纹病菌和黄瓜枯萎病菌的相对抑制率分别为96.0%和87.5%)相当的抑菌活性。构效分析表明:脂肪族取代基衍生物表现出更好的抑菌活性。此外,在质量浓度为100 mg/L时,化合物Ⅴc对油菜胚根生长的相对抑制率为79.6%,显示出比阳性对照丙炔氟草胺(抑制率为63.0%)更好的除草活性。     

固体超强酸催化异构桃金娘烯醛合成紫苏醛

以桃金娘烯醛为原料,以低温浸渍法制备的SZT-15固体超强酸为新型催化剂,在裂解反应装置中进行催化异构桃金娘烯醛合成紫苏醛反应。考察了异构反应条件对反应转化率和选择性的影响规律,并对催化剂的酸度和晶体结构表征。结果表明：在浸渍浓度1.0 mol/L,焙烧温度550 ℃,进样速度1.0 mL/min,反应温度400 ℃条件下,转化率达87.51%,选择性可达40.56%。催化剂的酸度H0可达?16.0,出现了较强的锐钛矿晶相衍射峰。     

合成桃金娘烯醛的反应器的模拟设计

以α-蒎烯为原料合成一种重要的化工中间体桃金娘烯醛 ,对其合成反应器进行了模拟设计 ,得出了数学模型方程 ,并对方程的解编写了计算程序。为放大提供了理论基础     

Fe_2O_3-V_2O_5/Al_2O_3催化氧化α-蒎烯制备桃金娘烯醛的研究

用不同的方法制备了Fe2O3-V2O5/Al2O3催化剂,用BET、TPD表征了催化剂的表面积和O2吸附性能,并考察了催化剂的制备方法对α-蒎烯合成桃金娘烯醛活性和选择性影响,结果表明,均匀沉淀法制备的催化剂具有较大的比表面积,较多表面氧活性中心和较高的催化活性和选择性,同时用均匀沉淀法制备的催化剂考察了α-蒎烯合成桃金娘烯醛的工艺条件,其最佳条件为:催化剂用量5%、反应温度80℃、反应时间240min,在此条件下,α-蒎烯转化率84.9%,桃金娘烯醛选择性78.4%。     

α-蒎烯合成蒎酮酰胺的研究

以松节油的主要成分α-蒎烯为原料,氧化开环得蒎酮酸,蒎酮酸经氯化再氨化合成蒎酮酰胺.在蒎酮酰胺的合成中,着重研究了氯化反应的氯化剂、物料配比、反应温度和反应时间等条件.实验结果表明,以PCl3作氯化剂,反应条件温和,操作方便,蒎酮酰胺产率较高.     

α-蒎烯-马来酸酐加成物的合成

在DLB催化下,α-蒎烯经异构同时和马来酸酐发生Diels-Alder反应制备1-异丙基-4-甲基二环-5-辛烯-2,3-二酸酐(TMA)。运用正交试验法研究了影响合成TMA的主要因素:反应温度、催化剂种类、催化剂用量、反应时间,并确立其最佳合成条件:催化剂用量3%(以α-蒎烯的质量计),反应温度145℃,反应时间1.0 h,(反应物α-蒎烯与马来酸酐摩尔比为1.4:1)。TMA的收率达88%以上,纯度达92%以上,并明显缩短了反应时间。此外,利用红外光谱、薄层色谱、气相色谱和GC-MS等方法对TMA进行了分析和表征。     

α-蒎烯合成香料研究进展

从几方面评述了利用松节油中的α 蒎烯为主要原料合成多种香料、香料中间体的工艺途径, 同时介绍了多种香料化合物和其中一些香料的物理化学特征行为。     

Synthesis and electrochemistry of acetylacetonatolanthanide(III)- phthalocyaninates

The synthesis and electrochemistry of acetylacetonatolanthanide(III)phthalocyaninates are reported. Two new kinds of lanthanide complexes Li[Pc]Ln(acac)₂] and (Pc)Ln(acac) were obtained where Ln is the trivalent ions of Eu, Gd, Dy, Tb, Ho, Er, Tm, Lu, and Pc is the dianion of phthalocyanine and acac is the acetylacetonate anion. These complexes were characterized by infrared and electronic absorption spectroscopy. An overall oxidation reduction mechanism at a platinum electrode in dimethyl sulfoxide is presented.     

电化学法清除金属表面垢层的实验研究

介绍采用电化学法清除附着在金属表面附着物的实验情况，论述了电化学法清洗附着在金属表面附着物的原理和方法。实验发现：更换电极极性并突然增大电流密度能获得比较满意的效果，从而为清除金属表面上的结垢、附生物、海藻、海生物等物质提出一个简便易行的方法。     

电化学方法在常温磷化中的应用研究

对新型磷化方法——电化学磷化进行了探究,采用对工件外加电压的方法对磷化过程进行加速,并获得了优良的磷化效果,证明电化学方法确实有利于磷化过程。通过磷化膜外观评分、磷化膜膜重、硫酸铜点滴时间、3%NaCl浸渍时间4种参数对磷化效果进行评定,初步确定了电化学磷化最佳参数值为:在20℃下,电流密度为7.80~9.00 A/dm2,平均磷化时间为3.8 min,磷化综合评价M值为16.0~17.1。     

Straightforward single-step generation of microswimmers by bipolar electrochemistry

Autonomous microswimmers are of enormous interest not only from an academic point of view, but also for future practical applications ranging from miniaturized motors to nanomedicine. A key step for the generation of such objects is their dissymmetric modification with a catalyst particle that activates the chemical conversion of a fuel molecule, leading ultimately to the propulsion of the object. So far it has been quite difficult to synthesize such dissymmetric objects and most approaches are based on using interfaces to break the symmetry. We demonstrate here that a very simple approach based on bipolar electrochemistry allows the bulk generation of carbon microtubes that are modified selectively at one end with a Pt cluster. The presence of this metal cluster allows the catalytic decomposition of hydrogen peroxide and the resulting oxygen bubbles trigger the propulsion of the object. The type of motion can be switched from linear to circular as a function of the exact position of the Pt cluster.     

电化学技术降解有机废水研究进展

综述了电催化氧化、光电催化、超声电化学、三维电极电化学技术降解有机废水的研究与应用进展,重点介绍了电化学技术协同降解有机废水的发展现状,对各种电化学方法进行了阐述,探讨了电化学技术降解有机废水的发展趋势,展望了降解有机废水今后的重点研究方向。     

煤的电化学脱硫及其进展

综述了煤炭电化学脱硫的原理 ,借助煤在电解槽阳极发生的电化学氧化反应将煤中的无机硫或有机硫氧化成可溶于水的硫化物 ,介绍了电解脱硫设备及工艺流程、电化学脱硫技术发展方向及趋势 ,认为该方法的显著特点是常温常压下操作 ,工艺简便 ,能量回收率高 ,并可联产大量高纯氢气 ;同时也指出了煤炭电化学脱硫技术中存在的问题     

The characterization and bioelectrocatalytic properties of hemoglobin by direct electrochemistry of DDAB film modified electrodes

Direct electrochemistry of hemoglobin can be performed in acidic and basic aqueous solutions in the pH range 1-13, using stable, electrochemically active films deposited on a didodecyldimethylammonium bromide (DDAB) modified glassy carbon electrode. Films can also be produced on gold, platinum, and transparent semiconductor tin oxide electrodes. Hemoglobin/DDAB films exhibit one, two, and three redox couples when transferred to strong acidic, weak acidic and weak basic, and strong basic aqueous solutions, respectively. These redox couples, and their formal potentials, were found to be pH dependent. An electrochemical quartz crystal microbalance and cyclic voltammetry were used to study the in situ deposition of DDAB on gold disc electrodes and hemoglobin deposition on DDAB film modified electrodes. A hemoglobin/DDAB/GC modified electrode is electrocatalytically reduction active for oxygen and H₂O₂, and electrocatalytically oxidation active for S₂O₄²⁻ through the Fe(III)/Fe(II) redox couple. In the electrocatalytic reduction of S₄O₆²⁻, S₂O₄²⁻, and SO₃²⁻, and the dithio compounds of 2,2′-dithiosalicylic acid and 1,2-dithiolane-3-pentanoic acid, the electrocatalytic current develops from the cathodic peak of the redox couple at a potential of about −0.9 V (from the Fe(II)/Fe(I) redox couple) in neutral and weakly basic aqueous solutions. Hemoglobin/DDAB/GC modified electrodes are electrocatalytically reduction active for trichloroacetic acid in strong acidic buffered aqueous solutions through the Fe(III)/Fe(II) redox couple. However, the electrocatalytic current developed from the cathodic peak of the redox couple at a potential of about −0.9 V (from the Fe(II)/Fe(I) redox couple) in weak acidic and basic aqueous solutions. The electrocatalytic properties were investigated using the rotating ring-disk electrode method.     

Synthesis of copolymer of aniline and pyrrole by inverted emulsion polymerization method for supercapacitor

Copolymer of aniline and pyrrole was synthesized by inverted emulsion polymerization method by oxidizing aniline and pyrrole using benzoyl peroxide in presence of sodium laurylsulphate surfactant and p‐toluenesulphonic acid. Copolymer samples were characterized by infrared, X‐ray diffraction and scanning electron microscopic techniques and compared their properties with the corresponding homopolymers. The optimum reaction conditions for the preparation of copolymer with reasonably good yield (1.72 g) and conductivity (7.3 × 10^?2 S/cm) were established. The synthesis procedure was extended to prepare copolymer samples using various protonic acids. Electrochemical characterization such as cyclic voltammetry, charge‐discharge and impedance were carried out on symmetrical supercapacitor cell consists of poly(aniline‐co‐pyrrole)‐p‐toluenesulfonic acid salt, wherein, the copolymer salt was synthesized using equal amount of aniline and pyrrole monomers. The values of specific capacitance, energy and power densities for poly(aniline‐co‐pyrrole)‐p‐toluenesulfonic acid system (PANI‐PPy) were calculated from charge‐discharge studies and are found to be 21 F/g, 5.7 Wh/Kg and 100 W/Kg respectively. Impedance analysis showed specific capacitance value (57 F/g) at 0.01 Hz at 0.22 V. Among the copolymer salts, copolymer prepared with sulfuric acid showed higher capacitance (66 F/g). © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

离子液体在蛋白质电化学中的应用研究

综述了离子液体作为黏合剂、支持电解质和修饰材料这三种功用在氧化还原蛋白质直接电化学中的研究现状,并提出了目前研究存在的问题及此种生物传感器应用前景的展望。