质子化丙酮分子团簇的结构和振动光谱

用密度泛函B3LYP/ 6 3 1G(d)方法 ,对质子化丙酮分子团簇 (CH3COCH3) nH+ (n =1～ 7)弱相互作用体系进行了全自由度能量梯度优化 ,得到了该系列团簇的稳定结构及其对应的体系能量 .通过对构型的分析得出了质子化丙酮分子团簇 (CH3COCH3) nH+ (n =1～ 7)的生长规律 .计算了中性丙酮分子团簇体系的质子亲合能并总结出其变化趋势 .分析讨论了质子化团簇的红外振动光谱 ,发现质子化团簇的振动光谱普遍较中性环型团簇的振动光谱复杂 ,最强的振动峰来源于质子在溶剂壳中两个氧原子之间的振动 ,而且随着团簇尺寸的增加羰基的伸缩振动峰的数目也随之增多     

Comments concerning the HPLC separation of acrolein from other C3 carbonyl compounds as 2,4-dinitrophenylhydrazones: A proposal for improvement

The separation of the toxicologically important aldehyde acrolein from other carbonyl compounds by high performance liquid chromatography after derivatization to 2,4-dinitrophenylhydrazones is critically discussed on the basis of a selection of published methods. A method is proposed whereby the compounds acrolein, acetone, and propanal may be reproducibly separated to baseline by a reversed phase HPLC procedure employing a ternary mixture of methanol, water, and acetonitrile as mobile phase.     

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.     

Headspace SPME–GC Method for Acetone Analysis and its Biomedical Application

A new method for extraction and analysis of acetone in human urine based on headspace solid phase microextraction using a mixture of activated carbon and zeolite as sorbents in a PVC matrix coated on a silver wire and its application to the determination of ketone bodies is described. Unlike commercial fibers, which are coated on fused silica, the coating adheres strongly to the silver wire and is thermally stable up to 250 °C. After optimization of coating composition and microextraction conditions the fiber was used for the analysis of acetone in human urine.     

Synthesis of acetone oxime through acetone ammoximation over TS-1

The ammoximation of acetone to acetone oxime with 30 wt.% hydrogen peroxide over TS-1 has been studied. The conversion of acetone and the selectivity to acetone oxime can reach 99% and 94%, respectively. The by-products are the corresponding hydrazone, imine and small amounts of unidentified compounds. The influence of various parameters such as solvent, temperature, amounts of catalyst and the NH₃ to acetone molar ratio were investigated. This revised version was published online in August 2006 with corrections to the Cover Date.     

Simultaneous Determination of Platinum and Rhodium with Hydroxylamine and Acetone Oxime by Catalytic Adsorptive Stripping Voltammetry (CAdSV)

This paper describes a very sensitive catalytic adsorptive stripping voltammetry (CAdSV) procedure for the simultaneous determination of traces of platinum and rhodium in new supporting electrolyte containing hydroxylamine or acetone oxime and formaldehyde in sulfuric acid medium. Platinum and rhodium were pre‐accumulated simultaneously and after 120 s of accumulation time at 0.0 V, the achieved detection limits were equal 0.1 ng L^?1 and 0.2 ng L^?1 for platinum and rhodium respectively in the presence of acetone oxime and 0.6 ng L^?1 and 0.2 ng L^?1 for platinum and rhodium respectively in the presence of hydroxylamine. Described reagents were successfully applied to the determination of platinum and rhodium in plant material. Inductively coupled plasma mass spectrometry (ICP MS) was used as a reference method to the CAdSV measurements.     

丙酮一步法合成甲基异丁基酮催化剂研究

用浸渍法制备了丙酮一步法合成甲基异丁基酮负载型催化剂，考察了载体的预处理温度、添加镧助剂对催化剂性能的影响；用BET法测定了催化剂的表面积；采用H2-O2滴定法测定Pd的分散度．结果发现，用经过1．023K焙烧过的Al2O3为载体的催化剂具有较好的催化性能，添加镧助剂后催化剂的分散度、活性有较大的提高．     

丙酮在固体碱催化剂上的缩合反应

随着石油化学工业的发展,丙酮产量不断增加,开展丙酮化学的研究及以丙酮为原料开发精细化工产品具有重要意义。丙酮经缩合反应可得到如异丙叉丙酮、异佛尔酮、甲基异丁基酮等一系列重要化工产品。由于异佛尔酮具有共轭不饱和酮结构,故其双键可进一步反     

核磁方法研究离子液体与丙酮的相互作用

运用核磁共振手段, 研究了室温离子液体1-辛基-3-甲基咪唑四氟硼酸盐([C8mim][BF4])在不同比例的离子液体／丙酮混合体系中1H和13C的化学位移及13C的自旋-晶格弛豫时间(T1). 结果表明, 离子液体[C8mim][BF4]的阳离子芳环上的氢原子, 以及与氮原子直接相连的甲基和亚甲基上的氢原子都与丙酮羰基上的氧原子有相互作用, 从而减弱了离子液体阴阳离子间的强相互作用, 使离子液体的运动加快, 黏度降低.     

Heat Capacities of Aqueous Solutions of Acetone; 2,5-Hexanedione; Diethyl Ether; 1,2-Dimethoxyethane; Benzyl Alcohol; and Cyclohexanol at Temperatures to 523 K

The heat capacities of aqueous solutions of acetone, 2,5-hexanedione, diethyl ether, 1,2-dimethoxyethane, benzyl alcohol and cyclohexanol at concentrations of 0.1 to 1.0 mol⋅kg⁻¹ were determined at temperatures of 298.15, 423.15, 473.15 and 523.15 K and pressures up to 28 MPa. The measurements were performed at ambient conditions using the commercial Picker differential flow calorimeter and at high temperatures and pressures with a customized Picker type calorimeter constructed at the Blaise Pascal University, Clermont-Ferrand. Standard molar heat capacities were obtained by weighted extrapolation to the infinite dilution limit. The contributions of –CO–, –O– and –OH groups to the standard molar volume and standard molar heat capacity were determined from the newly determined and literature data. The variation of the three oxygen-containing group contributions with temperature and molecular structure is examined qualitatively.