超临界流体色谱流程设计及其应用

本文设计了多功能超临界流体色谱流程,流程中包括毛细管/微填充柱SFC,GC,计算机控制温度、压力、密度及信号采集、处理,配置有超临界流体萃取池,解决了超临界流体色谱分流口易堵问题。利用该流程,将石腊、DC-200气相色谱固定相、黄油、蜂蜡、救心油、红花油等样品进行超临界流体色谱分离。     

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.     

Supercritical CO2 as a superior solvent for the cyclization of diallylmalonate catalyzed by palladium-containing zeolites

Palladium-containing zeolites catalyze the cycloisomerization of diethyl diallylmalonate to dimethylcyclopentenes. When the reaction is carried out in toluene, the performance of the palladium catalyst depends on the pore size of the zeolites. At 60 °C, palladium adsorbed on large pore size Beta zeolite (pore size ∼7.4 Å) is more active than medium pore size ZSM-5 (pore size ∼5.4 Å). This lower activity of ZSM-5 compared to Beta is attributable to the restricted diffusion of reagent and products through the ZSM-5 channels as compared to Beta zeolite. However, due to the gas-like diffusion characteristic of the supercritical state, the activity of ZSM-5 increases and becomes identical to that of Beta zeolite using supercritical CO₂ as medium.     

Lithium heptadecafluorooctanesulfonate catalyzed Mannich-type and aza-Diels-Alder reactions in supercritical carbon dioxide

The Mannich-type reaction of imines with (1-methoxy-2-methylpropenyloxy)trimethylsilane and aza-Diels-Alder reaction of imines with Danishefsky's diene can be carried out in scCO₂ in the presence of lithium heptadecafluorooctanesulfonate which offer a way to synthesize β-amino carbonyl compounds and nitrogen-containing six-membered ring compounds under environmentally benign conditions.     

Towards cooling of high-intensity ion beams

Buffer gas beam coolers may become excellent beam preparation devices for high-resolution mass separation. The small beam emittance provided makes efficient isobar resolution a realistic goal. In order to fulfill the needs of future facilities providing high-intensity beams of rare isotopes, it is desirable to increase the beam intensity limit of such devices from typically several tens of nanoamperes to microamperes. This requires the usage of high-voltage radiofrequencies in a low-pressure gas environment. A buffer gas beam cooler, dedicated to this purpose, is under development at the NSCL. The study of voltage breakdowns under such conditions and the design of an electrode system minimizing them is mandatory.      

Feature of the magnetotransport of a quasi-one-dimensional electrons on the superfluid helium

The magnetotransport in a nondegenerate quasi-one-dimensional (Q1D) electron system over superfluid helium has been investigated experimentally. The measurements are performed in the presence of a perpendicular magnetic field B up to 2.6 T in the temperature range T=0.48–2.05 K in the system of conducting channels of 100–400 nm width. It is shown that the value of longitudinal magnetoresistance ρ_xx increases with B. In the electron-gas scattering region (T>0.9 ), the behaviour of ρ_xx agrees with classical Drude law. In the quantum transport regime, the self-consistent Born approximation (SCBA) theory for a 2D electron system over liquid helium describes the experimental data qualitatively. The deviation due to the difference of the experimentally studied Q1D system of the electrons in a parabolic potential well differs from theoretically analysed one. The experimental data agree with the theoretical calculation for the Q1D electron system at the weak magnetic field and the low temperature.

The negative magnetoresistance of the conducting channels has been observed in both the gas- and the ripplon-scattering region. These effects have been explained by weak carrier localization on the gas atoms at high temperature and by display of the quantum magnetotransport features in a mesoscopic system at low temperature.     

Microsolvation of phthalocyanines in superfluid helium droplets.

Experimental and theoretical investigations of the spectroscopy of molecules in superfluid helium droplets provide evidence for the key role of the first helium layer surrounding the dopant molecule in determining the molecule's spectroscopic features. Recent investigations of emission spectra of phthalocyanine in helium droplets revealed a doubling of all transitions. Herein, we present the emission spectra of Mg-phthalocyanine and of phthalocyanine-argon clusters in helium droplets, which confirm the splitting as a general effect of the helium environment. A scheme of levels is deduced from the emission spectra and attributed to quantized states of the first helium layer surrounding the dopant molecule.     

Investigation on hexamethyldisilazane vapor treatment of plasma-damaged nanoporous organosilicate films

Hexamethyldisilazane (HMDS) vapor treatment of plasma-damaged nanoporous organosilicate thin films has been studied as a function of treatment temperature in this work. Although, the HMDS vapor treatment facilitated incorporation of methyl (CH₃) groups subsequent to the removal of free hydroxyl (OH) groups in the damaged films at treatment temperature as low as 55 °C, the bonded OH groups were not removed. More significantly, detailed analysis of the results reveals that HMDS vapor modified only the surface of the plasma-damaged samples and not the entire film as expected. This is attributed to the formation of a thin solid layer on the surface, which effectively prevents penetration of HMDS vapors into the bulk. The Fourier transform-infrared (FT-IR) absorption and dielectric constant measurements confirm that the vapor treatment assists only partial curing of the plasma-damaged films. Alternative processes of curing the films with HMDS dissolved in supercritical carbon dioxide (SCCO₂) as a medium of reaction in static and pulsed modes were also attempted and the results are presented in this paper.     

Anomalous behavior of conductivity of the confined Q1D electron system over liquid helium

Conductivity of electrons in a quasi-one-dimensional (Q1D) system over liquid helium in narrow channels with the parabolic profile of the potential well has been investigated at temperature T, from 0.4 to 1.8 K, for different driving electric fields and radius of channel curvature. The interval of linear electron densities varied from 2.18×10³ up to 1.7×10⁶ cm⁻¹.

The inverse mobility (1/μ_eff) in the electron-ripplon scattering region at the high linear densities of charges in the channel increases with temperature decreasing. This anomalous behavior of the electron transport in the low-temperature region has been explained by either the electron ordering or the polaronic effects in confined conducting channels. The nonlinear behavior of the electron velocity as a function of a driving electric field is supposed to be due to Breg–Cherenkov radiation of the ripplons. The radiation occurred if the velocity of electrons in the channel approaches to the critical value.