Selectivity tuning via temperature pulsing using low thermal mass liquid chromatography and monolithic columns.

Low thermal mass LC was applied to the capillary LC separation of a complex insecticide mixture by increasing temperature and decreasing gradients, as well as fast selected temperature pulses to increase resolution of overlapped components. The technology was applied using a new generation of capillary monolithic stationary phases. Considerable peak shifts and selectivity changes were observed for given temperature conditions. The concept of temperature pulsing during an elution profile shows promise for increasing resolution in difficult separations and can provide a relatively simple means to solve coelution problems.

Thermal modulation for multidimensional liquid chromatography separations using low-thermal-mass liquid chromatography (LC).

We report on a proof-of-principle experiment with a novel thermal modulation device with potential use in two-dimensional liquid chromatography (LC × LC) systems. It is based on the thermal desorption concept used in two-dimensional gas chromatography (GC × GC) systems. Preconcentration of neutral analytes eluting from the first dimension column is performed in a capillary "trap" column packed with highly retentive porous graphitic carbon particles, placed in an aluminum low-thermal-mass LC heating sleeve. Remobilization of the trapped analytes is achieved by rapidly heating the trap column, by applying temperature ramps up to +1200 °C/min. Compared to the nonmodulated signal, the presented thermal modulator yielded narrow peaks, and a concentration enhancement factor up to 18 was achieved. With a thermally modulated LC separation of an epoxy resin, it is shown that when the thermal modulation is applied periodically, the trapped and concentrated molecules can be released periodically and that the modulating interface can both serve as a preconcentration device and as an injector for the second dimension column of an LC × LC setup. Because of the thermal modulation, a high-molecular-weight epoxy resin could be adequately separated and the different fractions were identified with a GPC analysis, as well as an offline second dimension LC analysis.

Low thermal mass liquid chromatography.

A novel technique, low thermal mass liquid chromatography (LTMLC), is introduced in this study. The use of an LTM assembly that utilizes the principle of resistive wire heating and a temperature sensor to accurately deliver unprecedented heating (up to 1800 degrees C/min) or cooling (100 to approximately 200 degrees C/min) rates is reported. With the use of packed microcolumns (<0.5 mm i.d.), essentially instantaneous heat transfer from the assembly to the mobile phase was obtained. A systematic investigation was conducted to study the performance of the LTMLC technique. Both isocratic and gradient mobile phase conditions were used. For temperature control, isothermal, temperature-increasing, and temperature-decreasing gradients were applied. Three model mixtures, two of which containing neutral and acidic analytes and the other containing neutral, acidic, and basic analytes, were used to study the effect of temperature on elution time, resolution, column efficiency, and selectivity. It was found that the LTMLC experimental setup delivered reliable temperature control, as evidenced by linear van't Hoff plots for neutral and acidic compounds. The effect of temperature on the elution of basic analytes yielded nonlinear van't Hoff plots, explaining the dramatic selectivity changes observed for bases with changes in column temperature. Column efficiency generally increased with the increase in column temperature in the range of 25 to approximately 75 degrees C and decreased in the range of 75 to approximately 150 degrees C at a fixed column flow rate (3 microL/min), when extra column band broadening was taken into account. The increase in efficiency upon the increase in column temperature in the low temperature range was mainly due to the decreased mass transfer term resulting from increased analyte diffusivity. However, under even higher temperatures, the longitudinal diffusion dominated band broadening, explaining the decrease in column efficiency upon a further increase in column temperature. Resolution and selectivity decreased at elevated temperature for neutral and acidic compounds. For mixtures that contain bases, improved resolution was obtained by simultaneously tuning temperature and solvent programming. In addition to heating ability, LTMLC also demonstrated reliable cooling capability, allowing performance of oscillated or cycled temperature programming for fine-tuning the separation of critical band pairs for the first time. Finally, ultrafast reproducible LTMLC was also demonstrated, showing the potential of utilization of this technology for fast and ultrafast separations.

Determination of short-chain branching content in polyethylene by pyrolysis comprehensive multidimensional gas chromatography using low thermal mass column technology.

A research effort was undertaken to utilize the pyrolysis process to create fragments of polyethylene that could be indicative of branching, and allow quantitiation of said short-chain branches by pyrolysis comprehensive 2-D GC (Py-GC x GC). Several strategies for sample introduction and pyrolysis such as the in-column pyrolysis device and the programmed temperature vaporizer (PTV) were studied. The chromatographic separations were executed using low-thermal mass (LTM) comprehensive 2-D GC (GC x GC). A series of polyethylene-co-hexene samples were analyzed and a linear correlation of 1-hexene content with branching peak ratio was found. Correlation coefficients were determined as 0.97 for the measurements performed.

The determination of tertiary dodecyl mercaptan by low thermal mass gas chromatography-dual plasma sulfur chemiluminescence detection.

Tertiary dodecyl mercaptan (TDM) is commonly used as a chain transfer agent in the manufacturing process of styrene/butadiene latex for use in carpet and paper industries. A gas chromatographic technique has been successfully developed for the measurement of TDM based on its sulfur content for material identification, trend analysis, or for the monitoring of un-reacted residual material in final products. The method employs low thermal mass gas chromatography (LTM-GC) and a dual-plasma sulfur chemiluminescence detector (DP-SCD) to attain a high degree of sensitivity and selectivity. Using the technique described, a detection limit in the range of 0.5 ppm (v/v) TDM and less than 1 min analysis time can be achieved. Response is linear over four orders of magnitude with high degree of repeatability of less than 5% RSD.

Comprehensive two-dimensional gas chromatography using liquid nitrogen modulation: set-up and applications.

An improved modulation system for comprehensive two-dimensional gas chromatography (GC x GC) is presented. It is based on two-jet modulation with liquid nitrogen as cryogen. A valve system was designed to include subsequent re-heating of cooled capillary segments after modulation. It is demonstrated that even volatile components, such as propane or butane, are easily modulated with this system. Thus, the temperature range for GC x GC operation compared to diaphragm valve or liquid CO2 modulation is extended. The system allows highly efficient analysis of volatile and non-volatile components. Applications include separations of alkenes and gasoline samples. Also sulfur-containing hydrocarbon samples were compared via GC x GC and differences among samples of different producers were observed. Finally, headspace GC x GC investigations of volatiles found in polymer latex-coated papers round out the increasing portfolio of valuable applications.

Modelling the thermal behaviour of the low-thermal mass liquid chromatography system.

We report upon the experimental investigation of the heat transfer in low thermal mass LC (LTMLC) systems, used under temperature gradient conditions. The influence of the temperature ramp, the capillary dimensions, the material selection and the chromatographic conditions on the radial temperature gradients formed when applying a temperature ramp were investigated by a numerical model and verified with experimental temperature measurements. It was found that the radial temperature gradients scale linearly with the heating rate, quadratically with the radius of the capillary and inversely to the thermal diffusivity. Because of the thermal radial gradients in the liquid zone inside the capillary lead to radial viscosity and velocity gradients, they form an additional source of dispersion for the solutes. For a temperature ramp of 1 K/s and a strong temperature dependence of the retention of small molecules, the model predicts that narrow-bore columns (i.d. 2.1 mm) can be used. For a temperature ramp of 10 K/s, the maximal inner diameter is of the order of 1 mm before a substantial increase in dispersion occurs.