Temperature-programmed packed capillary liquid

Temperature-programmed packed capillary liquid chromatography (TP-CLC), coupled off-line to solvent elimination FTIR (LC Transform ) has recently been used for gradient separations of Irganox 1010/1076/3114 dissolved in DMF with LOD of about 40 ng [511]. Low... 

Column pressure usually has little effect on enantioselectivity in SFC. However, pressure affects the density of the mobile phase and thus retention factor [44]. Therefore, similar to a modifier gradient, pressure or density programming can be used in fast separation of complex samples [106]. Later et al. [51] used density/temperature programming in capillary SFC. Berger and Deye [107] demonstrated that, in packed column SFC, the effect of modifier on retention was more significant than that of pressure. They also showed that the enhanced solvent strength of polar solvent-modified fluid was nof due fo an increase in densify, caused by fhe addition of fhe liquid phase modifier, buf mainly due fo fhe change in composition. 

Nordstrom, O., Molander, P., Greibrokk, T., Blotnhoff, R., and Lundanes, E., Evaluation of temperature programming for gradient elution in packed capillary liquid chromatography coupled to... 

Trones, R., Andersen, T, Greibrokk, T, and Hegna, D.R. (2000) Hindered amine stabilizers investigated by the use of packed capillary temperature-programmed liquid chromatography. Journal of Chromatography A, 874, 65. 

Many liquid phases for packed-column purposes were unacceptable for capillary GC. Although they offered selectivity, overriding factors responsible for their disfavor were overall lack of thermal stability and the instability of the stationary phase as a thin film at elevated temperatures and during temperature programming. In the latter processes, it is crucial that the phase remain a thin uniform film otherwise, loss of both inermess and column efficiency result. Today, these problems have been solved and the refinements are reflected in the high performance of commercial columns. The impetus has been driven by the improvements in the sensitivity of mass spectrometers such that the MS detector is now the second most popular detector in GC (the FID is the most widely used detector). This rise in the use of GCMS has also necessitated more thermally stabile columns offering much less column bleed. 

Sample introduction is a major hardware problem for SFC. The sample solvent composition and the injection pressure and temperature can all affect sample introduction. The high solute diffusion and lower viscosity which favor supercritical fluids over liquid mobile phases can cause problems in injection. Back-diffusion can occur, causing broad solvent peaks and poor solute peak shape. There can also be a complex phase behavior as well as a solubility phenomenon taking place due to the fact that one may have combinations of supercritical fluid (neat or mixed with sample solvent), a subcritical liquified gas, sample solvents, and solute present simultaneously in the injector and column head [2]. All of these can contribute individually to reproducibility problems in SFC. Both dynamic and timed split modes are used for sample introduction in capillary SFC. Dynamic split injectors have a microvalve and splitter assembly. The amount of injection is based on the size of a fused silica restrictor. In the timed split mode, the SFC column is directly connected to the injection valve. Highspeed pneumatics and electronics are used along with a standard injection valve and actuator. Rapid actuation of the valve from the load to the inject position and back occurs in milliseconds. In this mode, one can program the time of injection on a computer and thus control the amount of injection. In packed-column SFC, an injector similar to HPLC is used and whole loop is injected on the column. The valve is switched either manually or automatically through a remote injector port. The injection is done under pressure. 

There are a variety of column packing materials and liquid phases. Sometimes a very long capillary column is used without a solid packing and only coated with a liquid on the wall. The oven can be operated isothermally at a given temperature or according to a program where temperature is varied as a function of time. 

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