Michael-Addition Reaction of Malononitrile with a,β-Unsaturated Cycloketones Catalyzed by KF/Al_2O_3

The utility of fluoride salts as potential base in a va-riety of synthetic reactions has been recognized in re-cent years.1 However, low solubility of fluoride salts in ordinary solvents hampers their wide applications in organic synthesis. On the other hand, there has been increasing use of inorganic solid supports as catalysts for many years2 resulting in higher selectivity, milder reaction conditions and easier work-up. Especially po-tassium fluoride-coated alumina (KF-alumina) has been a …     

Spectroscopic study on the complex formation of chromogenic bridged calixarenes with aliphatic amines

The complex formation between chromogenic capped calix 4 arene derivatives comprising indophenol indicator group(s), and aliphatic amines has been studied by UV/Vis spectroscopy. The equilibrium constants have been determined in ethanol, and—for one ligand—also in dimethylsulfoxide. The results have been interpreted in terms of various types of host–guest interactions and of steric effects.     

Difference in micellar properties of sodium dodecyl sulfonate from sodium 4-decyl naphthalene sulfonate in D2O solution studied by 1H NMR relaxation and 2D NOESY

¹H chemical shift changes of sodium 4-decyl naphthalene sulfonate (SDNS) at 313 K show that its critical micellar concentration lies between 0.82 and 0.92 mmol/dm³, which is in the same range as that of the previous study at 298 K. The spin–lattice relaxation time, spin–spin relaxation time and two-dimensional nuclear Overhauser enhancement spectroscopy experiments give information about the structure of the SDNS micelle and the dynamics of the molecules in the micelle. The size of the SDNS micelle remains almost unchanged in the temperature range from 298 to 313 K as deduced by analyzing the self-diffusion coefficient. Special arrangement of the naphthyl rings of SDNS in the micelles affects the packing of these hydrophobic chains. The methylene groups of the alkyl chain nearest the naphthalene groups penetrate into the aromatic region, which results in a more tightly packed hydrophobic micellar core than that of sodium dodecyl sulfonate.     

111In–L–LDL and 153Gd–L–LDL as radiotracers for detection of AR4‐2J rat pancreatic tumors

Pancreatic cancer has an extremely poor prognosis, due, in part, to lack of methods for early diagnosis. The present study was designed to evaluate the potential of labeling low‐density lipoprotein (LDL) with a radionuclide using a lipid chelating agent, bis(stearylamide) of diethylenetriaminepentaacetic acid (L), to detect pancreatic tumors by gamma‐scintigraphy. Previous studies indicated that the difficulty of visualization of pancreatic tumors was due to their poor vascularization. This study compares the ability of two radiotracers, ¹¹¹In–L–LDL and ¹⁵³Gd–L–LDL to target highly vascularized rat pancreatic tumors (AR4‐2J) implanted in nude mice. Biodistribution studies showed that the tumor uptake of ¹¹¹In–L–LDL and ¹⁵³Gd–L–LDL tracers was twofold and fivefold higher respectively than with the controls (¹¹¹In citrate and ¹⁵³Gd citrate respectively). These tracers would thus be suitable for scintigraphic imaging. We show here that LDL could be employed as a delivery system for tracers such as ¹¹¹In or ¹⁵³Gd when these two radionuclides are complexed by a lipid‐chelating anchor, and that ¹¹¹In–L–LDL and ¹⁵³Gd–L–LDL enabled better visualization of the pancreatic tumor tissues, with a better result with ¹⁵³Gd–L–LDL. Copyright © 2004 John Wiley & Sons, Ltd.     

Fenton 试剂处理2,4-D废水研究

利用Fenton试剂(Fe2+/H2O2)处理含有除草剂2,4-二氯苯氧乙酸(2,4-D)的模拟废水.结果显示,Fenton试剂对2,4-D有很好的去除效果.Fe2+和H2O2的摩尔比为1:20,在H2O2为1/2Qth理论投加量的条件下处理30mtn,2,4-D去除率达到80.0%.考察了Fe2+投加量、Fe2+和H2O2投加比、2,4-D初始浓度和pH等因素对2,4-D降解的影响.通过GC-MS和HPLC检测到反应中间产物有2,4-二氯苯酚、邻氯苯酚和对氯苯酚,氯离子在这些中间产物上释放.通过离子色谱检测到进一步氧化的产物还有小分子酸,如乙醇酸、乙醛酸、顺丁烯二酸,提出了Fenton降解2,4 -D的可能途径.     

Crystallographic report: Crystal structure of tetra(4‐methyl‐5‐imidazole‐carboxyaldehyde)zinc(II) diperchlorate

The central zinc(II) atom in the title complex is tetrahedrally coordinated by four nitrogen atoms derived from 4‐methyl‐5‐imidazolecarboxyaldehyde ligands with Zn? N in the range 2.007(3) to 2.026(4) Å. Copyright © 2003 John Wiley & Sons, Ltd.     

Synthesis and characterization of a novel nano-scale magnetic solid base catalyst involving a layered double hydroxide supported on a ferrite core

A nano-scale magnetic solid base catalyst MgAl-OH-LDH/MgFe₂O₄ (where LDH denotes layered double hydroxide) composed of MgAl-OH-LDH Brønsted base catalytic layers coated on MgFe₂O₄ spinel cores has been prepared. A magnetic precursor MgAl-CO₃-LDH/MgFe₂O₄ was prepared by a method involving separate nucleation and aging steps, and subsequently calcined to give a mixed metal oxide composite MgAl(O)/MgFe₂O₄ which was rehydrated to give MgAl-OH-LDH/MgFe₂O₄. The structure and magnetic properties of the nano-scale magnetic solid base MgAl-OH-LDH/MgFe₂O₄, together with those of the magnetic precursor MgAl-CO₃-LDH/MgFe₂O₄ and MgFe₂O₄ were characterized by XRD, XPS, low temperature N₂ adsorption and vibrating sample magnetometry (VSM). The MgAl-OH-LDH/MgFe₂O₄ composite possesses a mesoporous structure with pore size ranging from 2 to 20 nm with particle size mainly in the range 35-130 nm. The catalytic properties of MgAl-OH-LDH/MgFe₂O₄ were evaluated using the self-condensation of acetone at 273 K as a probe reaction. The results showed that the conversion of acetone to diacetone alcohol reached the thermodynamic equilibrium value of 23% at 273 K. The catalyst was easily recovered through application of an external magnetic field, and when the reclaimed catalyst was used in a second run for the same reaction, the reactivity remained unchanged.