Selectivity changes towards steroids in packed column supercritical fluid chromatography (SFC) induced by temperature and pressure variation

Summary Pressure/temperature variation in SFC was shown to influence selectivity towards steroids. Major changes were observed for polar column packings compared to non-polar packings and variation of the amount of modifier showed that this is valid over the whole investigated range. The effect is underlined by a fall in resolution in the low density range (low pressure/high temperature) for polar stationary phases and appears to be significantly larger than for non-polar phases. Major selectivity shifts induced by variation of the physical properties of the mobile phase are considered to be due to the greater effect of polar modifiers on the nature of polar stationary phases than on non-polar phases.     

Synthesis of Dimethyl Carbonate from CO2 , Methanol, and Epoxides Using Re（CO） 5 Cl/K2 CO3 as Catalyst System

IntroductionOver the past few years, dimethyl carbonate(DMC) has been proven to be an efficientmethylating,methoxylating, and methoxycarbonylating agent inorganic syntheses, in which DMC is used to replace thetoxic methyl halides, dimethyl sulfate or carb     

Fourier transform spectroscopy of CH3OH: rotation-torsion-vibration structure for the CH3-rocking and OH-bending modes

High-resolution Fourier transform spectra of CH₃OH have been investigated in the infrared region from 930 to 1450 cm⁻¹ in order to map the torsion-rotation energy manifolds associated with the ν₇ in-plane CH₃ rock, the ν₁₁ out-of-plane CH₃ rock, and the ν₆ OH bend. Upper-state term values have been determined from the assigned spectral subbands, and have been fitted to power-series expansions to obtain substate origins and effective B-values for the three modes. The substate origins have been grouped into related families according to systematic trends observed in the torsion-vibration energy map, but there are substantial differences from the traditional torsional patterns. There appears to be significant torsion-mediated spectral mixing, and a variety of “forbidden” torsional combination subbands with |Δυ_t|>1 have been observed, where υ_t denotes the torsional quantum number (equivalent to υ₁₂). For example, coupling of the (υ₆,υ_t)=(1,0) OH bend to nearby torsionally excited (υ₇,υ_t)=(1,1) CH₃-rock and (υ₈,υ_t)=(1,1) CO-stretch states introduces (υ₆,υ_t)=(1,0)←(0,1) subbands into the spectrum and makes the ν₇+ν₁₂−ν₁₂ torsional hot band stronger than the ν₇ fundamental. The results suggest a picture of strong coupling among the OH-bending, CH₃-rocking, and CO-stretching modes that significantly modifies the traditional energy structure and raises interesting and provocative questions about the torsion-vibration identity of a number of the observed states.     

激光溅射Ni等离子体与气相CH3OH团簇的反应

用激光溅射 分子束技术研究了气相中Ni的等离子体与甲醇分子团簇的反应 .观察到Ni+ (CH3 OH) n、NiO+ (CH3 OH) n、H+ (CH3 OH) n、H3 O+ (CH3 OH) n 四个种类的团簇正离子和CH3 O-(CH3 OH) n(n≤ 2 5 )一种团簇负离子 .详细考察了激光烧蚀等离子体作用于脉冲分子束的不同位置时 ,对团簇产物种类和团簇尺寸大小的影响 .发现NiO+ (CH3 OH) n 是由Ni+ (CH3 OH) n 团簇内的脱甲烷反应生成的 ,而H+ (CH3 OH) n、H3 O+ (CH3 OH) n主要是激光等离子体中的电子与甲醇团簇碰撞电离产生的     

甲醇在不同形态ZrO2上吸附行为的FTIR研究

用FTIR技术考察了甲醇在不同形态氧化锆上的吸附和活化转化行为.甲醇吸附在无定型和四方氧化锆上生成线式和桥式甲氧基物种,而在单斜氧化锆上还出现锥桥式甲氧基物种.在单斜和无定性氧化锆上的桥式羟基活泼而四方氧化锆上的线式羟基活泼.氧化锆表面吸附的甲氧基物种在晶格氧的作用下进一步转化,在单斜和无定性氧化锆上生成甲酸盐,并且可以进一步氧化为碳酸盐物种;而在四方氧化锆表面,甲氧基物种可以直接氧化为碳酸盐物种,这表明四方氧化锆的晶格氧比其他两种氧化锆上的更为活泼.     

Electrocatalytic activity of ordered intermetallic PtSb for methanol electro-oxidation

Ordered intermetallic PtSb had been synthesized by arc-melted and then sintering treatment. The electro-oxidation of liquid methanol on PtSb was investigated at room temperature by cyclic voltammetry and chronoamperometry. The results are compared to those at a polycrystalline platinum electrode surface. It was found that PtSb intermetallic was catalytically more active than pure platinum according to the onset potential and current density. X-ray diffraction (XRD) and XPS technologies had been used to investigate the crystal structure and electron effect.     

在H－ZSM－5沸石上甲醇转化为汽油的初始产物分布

在Ｈ－ＺＳＭ－５沸石上甲醇转化为汽油的初始产物分布姜玄珍（浙江大学化学系，杭州３１００２７）Ｒ．Ｆ．Ｈｏｗｅ（新南威尔士大学物理化学系，澳大利亚）关键词Ｈ－ＺＳＭ－５沸石，甲醇转化汽油，产物分布以氢型ＺＳＭ－５沸石作催化剂转化甲醇为汽油（ＭＴＧ），在...     

ZrO_2对CuO-ZnO-ZrO_2催化剂低压合成甲醇的促进作用

我们曾报道CO_2/H_2在CuO-ZnO及CuO-ZnO-ZrO_2催化剂上低压合成甲醇的反应,指出CuO-ZnO-ZrO_2对CO_2/H_2制甲醇具有较高的活性和选择性。本文通过TPD-MS测试研究了第3组分ZrO_2的加入对CO_2/H_2在CuO-ZnO-ZrO_2催化剂上低压合成甲醇的促进作用。 1 实验部分 催化剂的评价在恒压流动反应系统内进行。用色谱仪分析产物(Porapak Q柱,4 mm×3m,柱温120℃,CO、CO_2、CH_3OH、H_2O的保留时间分别为0.55、0.84、4.72、6.6 min),热     

一种甲醇直接气相羰基化新催化剂

本世纪７０年代Ｍｏｎｓａｎｔｏ公司成功开发了甲醇液相羰化ＲｈＩ催化体系，使甲醇羰化生产醋酸成为重要的工业过程．然而，由于此工艺产物与催化剂分离复杂、铑资源紧缺以及体系中还必须加大量的碘甲烷（或氢碘酸）作促进剂，设备腐蚀严重．８０年代以来，甲醇气相羰...