Analysis by SFC

An application of an LC-SFC system has been demonstrated by the separation of non-ionic surfactants consisting of mono- and di-laurates of poly (ethyleneglycol) (23). Without fractionation in the precolumn by normal phase HPLC (Figure 12.18 (a)) and transfer of the whole sample into the SFC system, the different homologues coeluted with each other. (Figure 12.18(b)). In contrast with prior fractionation by HPLC into two fractions and consequent analysis by SFC, the homologues in the two fractions were well resolved (Figures 12.18(c) and 12.18(d)). 

To summarize, SFC using FID extends the molecular weight regime currently accessible by GC. Using K+IDS to identify the constituents of crosslinkers followed by quantitative analysis by SFC provides an accurate measure of the components in commercial... 

Successful derivatization of several compounds has enabled analysis by SFC under more favourable conditions than GC (i.e. lower temperatures), and resulting in superior resolution to that obtained with HPLC. Increase in the MW after derivatization may, in fact, render the product unsuitable for GC. Analysis of the derivatives by SFC can be more rapid than by HPLC. Attainment of very sensitive detection has also been made possible with a range of detectors. 

Lastly, we compared the olefin content in the commercial diesel DECSE from DOE (Department of Energy). It was determined by ASTM D1319 method in the US laboratory to be 2.3 vol%. The saturate and the aromatic contents measured by ASTM D5186 were 71.2 and 28.5 respectively. In comparison, SOAP results for this diesel were 72.1 wt% for saturates, 28. lwt% for aromatics and 1.8wt% for olefins. Analysis by SFC at Syncrude Research Ltd. rendered total saturates 71.2 wt% and total aromatics 28.8 wt%. 

SFC-FID is widely used for the analysis of (nonvolatile) textile finish components. An application of SFC in fuel product analysis is the determination of lubricating oil additives, which consist of complex mixtures of compounds such as zinc dialkylthiophosphates, organic sulfur compounds (e.g. nonylphenyl sulfides), hindered phenols (e.g. 2,6-di-f-butyl-4-methylphenol), hindered amines (e.g. dioctyldiphenylamines) and surfactants (sulfonic acid salts). Classical TLC, SEC and LC analysis are not satisfactory here because of the complexity of such mixtures of compounds, while their lability precludes GC determination. Both cSFC and pSFC enable analysis of most of these chemical classes [305]. Rather few examples have been reported of thermally unstable compounds analysed by SFC an example of thermally labile polymer additives are fire retardants [360]. pSFC has been used for the separation of a mixture of methylvinylsilicones and peroxides (thermally labile analytes) [361]. 

The application range of cSFC-DFI-MS (Table 7.41) appears to be restricted either to the analysis of low-MW substances or to problems related to high-MW samples where low detection limits are not needed [124,444,445], The analysis of surfactants [446] by SFC-MS is frequently performed to demonstrate the feasibility of newly developed interface technology for practical applications. A rugged cSFC-MS method has been developed for the analysis of ethoxylated alcohols (AEs), which are non-ionic surfactants incorporated into a wide variety of industrial and consumer products [447]. cSFC-DFT-DFS was used for the analysis of low-MW, thermally unstable peroxides, and the higher-MW surfactants Triton X-100 and... 

Dobanol Ethoxy late [443], At least 16 Triton units with mass 910 were observed. A study of the reactions of amines and amine derivatives with scC02 using cSFC-MS was also reported [448], Both cSFC-APCI-MS and cSFC-ESI-MS of PEG 600 and PPG 425 were described [416]. Direct insertion probe (DIP) methodology was used for the structure analysis of the antistatic agent V,fV-bis-(2-hydroxyethyl)alkylamine. When analysed by SFC-MS coupling, the same sample could be separated into six components. The alkyl chains consist of saturated Cn, Ci4, C16 and C18 chains and of Cig chains with one double bond where 18 1 and 16 0 chains dominate. 

In supercritical fluid chromatography (SFC) the mobile phase is a supercritical fluid, such as carbon dioxide [15]. A supercritical fluid can be created either by heating a gas above its critical temperature or compressing a liquid above its critical pressure. Generally, an SFC system typically has chromatographic equipment similar to a HPLC, but uses GC columns. Both GC and LC detectors are used, thus allowing analysis of samples that cannot be vaporized for analysis by GC, yet cannot be detected with the usual LC detectors, to be both separated and detected using SFC. SFC is also in other... 

Note that not all enantioseparations in SFC are better than in HPLC [34], Bernal et al. [62] described the enantiomeric separation of several pharmaceutical-related compounds on a polysaccharide-based column using HPLC and SFC. They showed that most of the separations obtained by SFC are better, in terms of resolution and analysis time, than the separations obtained by HPLC. However, one compound could not be resolved using SFC, but LC provided baseline resolution. 

Supercritical fluid chromatography (SFC) has also been used in phospholipid analysis. According to Lafosse et al., phospholipid classes can be separated by SFC using a simple isocratic solvent consisting of 78.4/21.6 (w/w) mixture of carbon dioxide and a mixture of methanol, water, and triethylamine (95/4.95/0.05) in combination with a Zorbax Sil stationary phase detection was performed by evaporative light-scattering (20). 

Another technique is supercritical fluid chromatography (SFC), which is a chromatographic technique that in many ways is a hybrid of GC and HPLC. It is recognized as a valuable technique for the analysis of thermolabile compounds, which would not be amenable to analysis by GC or HPLC. Few applications have been reported for SFC in the field of OCP and OPP determination (16). The advantages reported for SFC are versatility in separation (by the addition of modifier or the choice of stationary phase) and detection (with LC or GC detectors). However, SFC is a little-used technique because it still presents a wide range of instrumental problems (14-16). 

We explain these results based upon the specific arrangement of monomers in the oligomer chain. The exact sequence of monomers will affect their solubility in supercritical COy, therefore, one expects to see more than one envelope for tne MMA oligomers which possess two BA units. In contrast, soft ionization mass spectrometry will not distinguish such isomers. Soft ionization mass spectrometric analysis preceded by SFC separation should yield molecular weight and sequence distribution data on copolymers. 

The first practical example of an on-line SFC-1 NMR separation was recorded by Dorn and co-workers [16] (Figure 7.2.14). Since up to 90% of a fuel is aliphatic, SFC-NMR on-line analysis is the matter of choice for separation and identification. Figure 7.2.14 shows a fuel mixture of isooctane, n-hexane, -nonane, dodecane, and n-hexadecane, separated by SFC and detected by on-line NMR spectroscopy. The SFC separation was accomplished with a flow rate of 2.0ml/min, a C18 250 x 4.6 mm column, operated at an isobaric pressure of 100 bar and a temperature of 323 K, using CO2 with 1% (w/w) CD3CN as solvent. Each NMR spectrum consists of 20 co-added transients at an acquisition time of 1 s per transient. The total separation occurred within 5 min. The first eluting isooctane can be easily identified by the methylene-to-... 

Supercritical fluid extraction (SFE) utilizes the unique properties of supercritical fluids to facilitate the extraction of organics from solid samples. Analytical scale SFE can be configured to operate on- or off-line. In the online configuration, SFE is coupled directly to an analytical instrument, such as a gas chromatograph, SFC, or high-performance liquid chromatograph. This offers the potential for automation, but the extract is limited to analysis by the dedicated instrument. Off-line SFE, as its name implies, is a stand-alone extraction method independent of the analytical technique to be used. Off-line SFE is more flexible and easier to perform than the online methods. It allows the analyst to focus on the extraction per se, and the extract is available for analysis by different methods. This chapter focuses on off-line SFE. 

With the demonstration of supercritical fluid extraction, an obvious extension would be to extract or dissolve the compounds of interest into the supercritical fluid before analysis with SFC.(6) This would be analogous to the case in HPLC, where the mobile phase solvent is commonly used for dissolving the sample. The work described here will employ a system capable of extracting materials with a supercritical fluid and introducing a known volume of this extract onto the column for analysis via SFC. Detection of the separated materials will be by on-line UV spectroscopy and infrared spectrometry. The optimized SFE/SFC system has been used to study selected nonvolatile coal-derived products. The work reported here involved the aliphatic and aromatic hydrocarbon fractions from this residuum material. Residua at several times were taken from the reactor and examined which provided some insight into the effects of catalyst decay on the products produced in a pilot plant operation. 

The application of SCF to the extraction of vitamins has been widely reported. Thus, retinyl palmitate and tocopherol acetate have been extracted from a hydrophobic ointment with supercritical CO2 at 40°C and 196 bar for 4 min, the extract analysis being performed by SFC (137). The calibration graphs were linear from 0.5 to 2.5 pg and the recoveries were quantitative. On the other hand, water-soluble vitamins can be extracted mixing them with low substituted hydroxypropil cellulose. Portions were placed in a column to which a reversed micellar extractant was delivered (138). Extraction of vitamins A and E and their esters from tablet preparations prior to FIPLC was performed in the dynamic mode with CO2 at 40°C and 253 bar for 15 min (139). Calibration graphs were linear from 0.02 to 0.8 and from 0.005 to 0.2 mg/mL of vitamins E and A, respectively. The corresponding RSDs (six... 

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