Equilibrium and Kinetics of Nickel Extraction with 2-Hydroxy-5-nonylbenzophenone Oxime

Abstract

The extraction of nickel with 2-hydroxy-5-nonylbenzophenone oxime (LIX 65N; HL) has been studied into chloroform solution. The extracted species was found to be NiL₂, and its extraction constant of 10^?5.90 was obtained. The rate of extraction of nickel has been found to be first-order in metal and ligand, and inverse first-order in hydrogen ion. The apparent rate constant of extraction (k') was 10^?7.40. These results support the hypothesis that the formation of the 1:1 complex in the aqueous phase is the rate-determining step. The rate constant of the formation of this complex was evaluated as 10^5.90.     

2-(5-溴-2-吡啶偶氮)-5-二甲氨基苯胺分光光度法测定铜的研究

以2-(5-溴-2-吡啶偶氮)-5-二甲氨基苯胺(5-Br-PADMA)为显色剂,建立了分光光度法测定铜的新体系。实验结果表明,在p H=3.75~5.75的HAc-Na Ac缓冲溶液中,室温下铜与试剂形成配位比为1∶2的紫红色配合物,配合物最大吸收波长位于573 nm,表观摩尔吸光系数为5.89×104L·mol-1·cm-1。铜浓度在0~18μg/10 m L范围内符合比耳定律。所拟方法用于矿样中铜的测定,结果满意。     

Kinetics of Photo-isomerization and Photo-degradation of 2-Hydroxy-5-methylbenzophenone (E)- and (Z)-Oximes

The kinetics of photo-isomerization and photo-degradation of 2-hydroxy-5-methylbenzophenone (E)- and (Z)-oximes in ethanol, octane, toluene and a mixture of octane and toluene under exposure to UV light was studied. The products of the photo-isomerization/photo-degradation of both oximes are similar but the conversion rate and amount of photo-degradation products of 2-hydroxy-5-methylbenzophenone (Z)-oxime are much higher. Also the photo-degradation of the (Z)-isomer is quicker than its photo-isomerization to the (E)-isomer. The photo-isomerization and photo-degradation kinetic models were developed for both oximes. The formulated kinetic model contains 12 reaction rate constants which have been estimated from experimental data. Good agreement was found between experimental and predicted data. © 1997 SCI.     

1-(2-羟基-5-甲基苯基)苯乙胺的合成

对甲基苯酚与苯乙酰氯酯化得到苯乙酸 ( 4 -甲基 )苯酯 ;然后在三氯化铝作用下重排得到苄基 ( 2 -羟基 -5 -甲基 )苯基酮 ;此酮经硫酸二甲酯甲基化得到苄基 ( 2 -甲氧基 -5 -甲基 )苯基酮 ,再和甲酸铵反应得到 1-( 2 -甲氧基 -5 -甲基苯基 )苯乙胺 ,最后经氢溴酸水解得到 1-( 2 -羟基 -5 -甲基苯基 )苯乙胺。所有中间体和最终产品的结构均由IR、元素分析、1 HNMR得到证实。     

The catalytic effect of quaternary ammonium salt On the Extraction of Palladium(II) With 2-Hydroxy-5-Nonyi-Benzophenone Oxime(LIX 65N) In Heptane-Chloroform Solvents

Extraction of Pd(II) from acidic chloride media using 2-hydroxy-5-nonyi-benzophenone oxime (LIX 65N,KL) in heptane is 60% more rapid than that using chloroform under comparable conditions, as well as more complete, reflecting an eight-fold increase in the extraction constant. A further substantial increase in the ex traction rate was achieved using the quaternary ammonium sait, Aliquat 336S, without any change in the extraction constant. The extraction probaly occurs through rapid phase transfer of PdCl via ion pair extraction followed by formation of the chelate, PdL₂-, in the organic phase.     

2-(1-羟基-3-丁炔基)-5-甲基呋喃催化重排合成2-炔丙基-3-甲基-4-羟基-2-环戊烯酮的研究

由 2 (1 羟基 3 丁炔基 ) 5 甲基呋喃催化重排合成 2 炔丙基 3 甲基 4 羟基 2 环戊烯酮 (炔丙菊醇 ) ,将传统的两步反应简化为一步反应 ,简化了工艺流程 ,缩短了反应时间 ,炔丙菊醇的产率较高 ,达到 75 .0 % ,高于文献报道的最大值 6 8.0 %。确定了反应的最佳反应条件为 :水作反应介质 ,m(催化剂 )∶m(反应物 ) =3∶10 0 ,反应时间 2 3h     

Whole Cell Biotransformation of 5-(4-(2-(2-Pyridyl)methylamino)ethoxy)benzylidenethiazolidine-2,4-dione to its Benzyl Derivative Using a Yeast Reductase

Whole yeast cell reductive biotransformation of a benzylidene thiazolidinedione to its corresponding benzyl derivative has been scaled up from laboratory to small pilot plant scale. The fermentation conditions for the yeast Rhodotorula rubra were examined and cell titres increased by optimising the medium. Problems encountered in handling substrates of low water solubility are discussed. Various techniques are described for adapting the procedure for process scale operation using the general principles of process scale-up and integration. Liquid–liquid extraction using a dense solvent was performed on whole broth systems using a continuous flow liquid–liquid separator. Fatty acid impurities were removed using selective solvent extraction. © 1997 SCI.     

2-羟基-4-(3-甲基-2-丁烯基)氧苯乙酮的合成研究

以2,4-二羟基苯乙酮和异戊烯基溴为原料,合成了药物中间体2-羟基-4-(3-甲基-2-丁烯基)氧苯乙酮。通过TLC得到优化反应条件如下:以丙酮为溶剂、反应温度为65℃、n(2,4-二羟基苯乙酮)∶n(K2CO3)=1∶1.8、n(2,4-二羟基苯乙酮)∶n(异戊烯基溴)=1∶1.8,此时反应时间最短,目标产物收率达73%。     

Diffusion Kinetics of Indium in TiO2 (Rutile)

This work determines the self‐diffusion coefficients of indium in TiO₂ single crystal (rutile). Diffusion concentration profiles were imposed by deposition of a thin surface layer of InCl₃ on the TiO₂ single crystal and subsequent annealing in the temperature range 1073–1573 K. The diffusion‐induced concentration profiles of indium as a function of depth were determined using secondary ion mass spectrometry (SIMS). These diffusion profiles were used to calculate the self‐diffusion coefficients of indium in the polycrystalline In₂TiO₅ surface layer and the TiO₂ single crystal. The temperature dependence of the respective diffusion coefficients, in the range 1073–1573 K, can be expressed by the following formulas: and The obtained activation energy for bulk diffusion of indium in rutile (316 kJ/mol) is similar to that of zirconium in rutile (325 kJ/mol). The determined diffusion data can be used in selection of optimal processing conditions for TiO₂–In₂O₃ solid solutions.     

1-羟基-4-(4-甲基苯基)-2-甲肟基咪唑-3-氧化物的合成工艺研究

以2,2-二氯-4'-甲基苯乙酮为原料,在六水合氯化铁促进下,与羟胺盐和乙二醛反应,得到1-羟基-4-(4-甲基苯基)-2-甲肟基咪唑-3-氧化物。研究了反应时间、物料配比、溶剂的种类和三氯化铁的用量等因素对环化反应的影响,优惠条件下的收率达到87.5%。该法原料来源广、成本低、反应条件温和、收率高,具有工业化应用前景。     

苯并呋喃-2,3-二酮3-(O-甲基肟)2-肟的合成工艺

以4-羟基-3-硝基香豆素为起始原料,经过开环、脱羧,得到2-硝基-2'-羟基苯乙酮,再和O-甲基羟胺盐酸盐反应生成中间体1-(2-羟基苯基)-2-硝基-乙酮-O-甲基肟。最后通过碱性条件下关环得到苯并呋喃-2,3-二酮3-(O-甲基-肟)2-肟。目标化合物及中间体结构经1HNMR确证。反应总收率70.4%,产品纯度99.2%。该工艺原料廉价,操作简单,收率较高,具有较好的工业化应用前景。     

生长液滴法Lix54-100萃铜的动力学

采用改进的生长液滴法,研究氨性条件下Lix54-100萃铜的动力学,考察了萃取剂浓度、水相铜离子浓度、pH值等对萃取初速的影响,Lix54-100萃铜的动力学方程为:R0=k[HL]o. 萃取剂进入水相发生构型改变,速度较慢,是整个萃取过程的控制步骤.     

Effect of Hydrophobicity and Interfacial Activity of 2-Hydroxy-5-alkylbenzophenone Oximes upon the Rate of Copper Extraction from Acidic Sulfate Solution

Abstract

The rates of copper extraction from acidic sulfate solutions with 2-hydroxy-5-alkylbenzophenone oximes of various hydrophobicities were measured by means of the drop ascending method, and they are discussed from the view of hydroxyoxime partition between both extraction phases and hydroxyoxime interfacial activity. The measured extraction rates are compared with those predicted from partition and interfacial activity data for various versions of the extraction mechanism. The ratios of specific extraction constants for oximes of various hydrophobicities are estimated for the interfacial mechanism with the preadsorption of hydroxyoximes at the hydrocarbon/water interface. The order of the specific rate constants determined for the interfacial reaction is in agreement with the order of the free energy of hydroxyoxime adsorption at the hydrocarbon/water interface.     

1-(2-羟基-3-甲氧苯基)乙酮的合成

1-(2-羟基-3-甲氧苯基)乙酮是一种重要的有机中间体。以邻香兰素为起始原料,经苄基保护、烃化、氧化、脱保护4步反应合成了标题化合物。该方法具有原料廉价易得、操作简便易控、反应条件温和的优点,总收率为66.3%。     

1-(2-Hydroxy-5-methylphenyl)-3-phenyl-1,3-propanedione Induces G1 Cell Cycle Arrest and Autophagy in HeLa Cervical Cancer Cells

The natural agent, 1-(2-hydroxy-5-methylphenyl)-3-phenyl-1,3-propanedione (HMDB), has been reported to have growth inhibitory effects on several human cancer cells. However, the role of HMDB in cervical cancer remains unclear. Herein, we found that HMDB dose- and time-dependently inhibited growth of HeLa cervical cancer cells, accompanied with G1 cell cycle arrest. HMDB decreased protein expression of cyclins D1/D3/E and cyclin-dependent kinases (CDKs) 2/4/6 and reciprocally increased mRNA and protein levels of CDK inhibitors (p15, p16, p21, and p27), thereby leading to the accumulation of hypophosphorylated retinoblastoma (Rb) protein. HMDB also triggered the accumulation of acidic vesicles and formation of microtubule-associated protein-light chain 3 (LC3), followed by increased expression of LC3 and Beclin-1 and decreased expression of p62, suggesting that HMDB triggered autophagy in HeLa cells. Meanwhile, suppression of the expression of survivin and Bcl-2 implied that HMDB-induced autophagy is tightly linked to apoptosis. Exploring the action mechanism, HMDB induced autophagy via the modulation of AMP-activated protein kinase (AMPK) and mTOR signaling pathway rather than the class III phosphatidylinositol 3-kinase pathway. These results suggest that HMDB inhibits HeLa cell growth by eliciting a G1 arrest through modulation of G1 cell cycle regulators and by concomitantly inducing autophagy through the mediation of AMPK-mTOR and Akt-mTOR pathways, and may be a promising antitumor agent against cervical cancer.     

4-羟基-3,5-二硝基吡啶氮氧化物铅及铜盐的合成

从吡啶出发经过多步反应以较高的产率制得了4－羟基－3，5－二硝基吡啶氮氧化物的铅、铜盐，并通过质谱及元素分析等方法对其进行了结构确定，经DSC及TG的分析表明，该类化合物对RDX、AP及NC＋NG等的热分解都具有催化作用，且使其产生出更多的分解热，表现出良好的含能催化剂的特征。     

2—[2—（5—甲基苯并噻唑）偶氮]—5—二乙按基苯甲酸与钴（Ⅱ）显色反？…

研究了2-[2-(5-甲基苯并噻唑)偶氮]-5-二乙氨基苯甲酸(5-Me-BTAEB)与钴(Ⅱ)的显色反应。结果表明,在十二烷基硫酸钠(SDS)存在下,试剂与Co(Ⅱ)在pH4．1～7．3HAc－NaAc的缓冲溶液中形成稳定的蓝紫色配合物,该配合物组成为n(Co(Ⅱ))∶n(5-Me-BTAEB)＝1∶2,最大吸收波长为645nm,表观摩尔吸光系数为1．30×10