Supercritical Fluid Extraction-supercritical Fluid Chromatography Research Articles

Inline phase transition trapping-selective supercritical fluid extraction-supercritical fluid chromatography: A green and efficient integrated method for determining prohibited substances in cosmetics

BackgroundDeveloping an environmentally friendly and efficient integrated analytical approach is a cutting-edge topic in current analytical science. Due to the unique properties of supercritical carbon dioxide (sc-CO2), online supercritical fluid extraction-supercritical fluid chromatography (SFE-SFC) is developing rapidly and has been widely applied in many fields. However, it still faces several challenges such as peak broadening and matrix interference. In order to solve the problems, we developed an inline phase transition trapping-selective supercritical fluid extraction-supercritical fluid chromatography (PTT-SSFE-SFC)-tandem mass spectrometry (MS/MS) method in this study. ResultsThis method integrated extraction, purification, separation, and detection, which was applied to determine 114 prohibited substances in cosmetics within 33 min, covering ten categories. The PTT strategy trapped the extracts on the head of the column by transforming CO2 from a supercritical state to a gaseous state, preventing peak spreading and improving sensitivity. Several adsorbents were tested when analyzing aqueous samples to reduce matrix interference and absorb water. Compared with conventional online SFE-SFC, this method improved the matrix effects of 93 and 87 target substances in the toner and mask matrix, respectively. Because the integrated method reduced sample loss, it achieved high sensitivity with LODs ranging from 0.00104 μg L−1 to 3.09 μg L−1. Furthermore, compared with other reported green methods, the inline method showed advantages in automation, efficiency, sample amount, and waste volume. Significance and noveltyWith the introduction of the PTT strategy and the adsorbent, the system obtained good peak shapes, high sensitivity, low matrix effect, and good recovery. Based on the results, inline PTT-SSFE-SFC-MS/MS as a green and efficient integrated method has great potential for analyzing low abundance and multiple categories of targets in complex samples.

Facilitated on-line supercritical fluid extraction - supercritical fluid chromatography for nonpolar and polar compounds from milk thistle seeds

Plant seeds, as those from milk thistle (Silybum marianum), are a valuable source of nonpolar and polar compounds with potentially interesting biological activity. The main nonpolar compounds are triglycerides, which are also the main components of all vegetable oils. In addition, specific polar compounds – flavonolignans, called silymarin, have been found in large amounts in milk thistle seeds extract. These flavonoids derivatives have different biological activity, for instance hepatoprotective effects. In order to extract and analyze both nonpolar (triglycerides) and polar compounds (flavonolignans) from milk thistle seeds through a sequential methodology, an on-line supercritical fluid extraction - supercritical fluid chromatography (SFE-SFC) method was developed. Different ways of transferring the extracts from SFE to SFC (i.e. direct on-column transfer and loop transfer) were compared, and particularly for their effect on chromatographic quality. In this respect, nonpolar and polar compounds caused different issues, especially as polar compounds required a significant portion of co-solvent in the extraction step, favoring early elution in the chromatographic column. First, on-line SFE-SFC was used for triglycerides analysis and allowed the comparison of transfer modes. Then, on-line kinetics were performed to measure defatting time before polar molecules extraction. Finally, the eventual benefit of loop transfer was also investigated for the analysis of flavonolignans, polar molecules whose analysis can be difficult by on-line SFE-SFC. The aim of this paper is to discuss the versatility of on-line SFE-SFC and how challenging the coupling can be, especially when both non-polar and polar molecules must be analyzed independently in a single sample.

Rapid Analysis of α-Tocopherol and Its Oxidation Products Using Supercritical Carbon Dioxide and Proton Transfer Reaction Ionization Mass Spectrometry.

We have developed a rapid and sensitive analytical method for α-tocopherol and its oxidative products by combining online hyphenation of supercritical fluid extraction-supercritical fluid chromatography (SFC) with proton transfer reaction (PTR) ionization mass spectrometry (MS). α-Tocopherol is a well-known antioxidant that plays a vital role in the antioxidant defense system in plant cells. However, studies on the cellular mechanisms of α-tocopherol have been limited owing to the lack of a rapid analytical method, which limits the comparison of plant cells incubated in various conditions. Additionally, complex sample preparation and long chromatography separation times are required. Moreover, the majority of the involved molecules are a combination of isomers, which must be separated before applying tandem MS. α-Tocopherol produces the α-tocopheroxyl radical in the first step of its antioxidant function; another ion with the same mass may also be generated from the source. SFC separation effectively distinguished the observed ions from their oxidative products in the sample and those produced during the ionization reaction process. This method enabled the measurement of α-tocopherol and its oxidative products such as α-tocopheroxyl radical and α-tocopheryl quinone in approximately 3 min per sample, including the time required for sample preparation.

Multivariate approach to on-line supercritical fluid extraction – supercritical fluid chromatography - mass spectrometry method development

Coupling supercritical fluid extraction (SFE) on-line with supercritical fluid chromatography (SFC) – tandem mass spectrometry (MS/MS) provides a single platform for efficient extraction, separation, and detection in a chemical analysis. SFE–SFC–MS/MS requires consideration of many extraction and chromatographic variables to not only provide the most efficient extraction, but also to analytically transfer the extracted analytes to the column for separation. There is a fundamental lack of understanding of how the variables in SFE affect those in SFC. Typically, a univariate approach is taken in on-line SFE–SFC–MS/MS method development, but this provides little insight into the relative importance of variables and their potential interactions. Here, a multivariate approach was used to develop a better understanding of the synergistic relationship between the extraction and separation processes by focusing on the optimization of extraction parameters for target analytes with a wide range of physicochemical properties in matrices of variable retentivity. The methodology used a set of optimal on-line SFE–SFC–MS/MS extraction parameters for 18 analytes of variable physicochemical properties in three different silica gel-based sample matrices are presented.

Preparative‐scale supercritical fluid extraction/supercritical fluid chromatography of corn bran

AbstractA preparative‐scale supercritical fluid extraction/supercritical fluid chromatography (SFE/SFC) procedure has been developed for the removal of oil from corn bran to obtain fractions enriched with free sterols and ferulate‐phytosterol esters (FPE). Operational parameters from an analytical‐scale supercritical fluid fractionation technique were translated to and optimized on a home‐built, preparatory‐scale SFE/SFC apparatus. SFE was performed at 34.5 MPa and 40°C using supercritical carbon dioxide. These conditions did not result in exhaustive extraction of the corn bran, but yielded about 96% of the available oil. SFC was conducted in three steps, followed by reconditioning of the sorbent bed. Preparative‐scale SFE/SFC of corn bran produced a fraction enriched greater than fourfold in free sterols and 10‐fold in FPE, suggesting that such a scheme could be used industrially to produce a functional food ingredient.

Development of a novel technique for monitoring of C0 2 gas flow rates as a basis for quantitative analysis of polymer additives using directly coupled SFE/SFC

A novel technique for accurately measuring C0 2 gas flow rates has been used to develop a directly coupled SFE/SFC (supercritical fluid extraction/supercritical fluid chromatography) technique for quantitative analysis of additives in polymers. The apparatus measures the concentration of C0 2 in air at the FID and split restrictor outlets using an electroconductivity principle. Quantitative measurement of triacetin additive in Biopol (a biodegradable polymer) was made. Studies of Irganox 1076 and 1010 additives in polypropylene showed some selectivity of the method over the higher molecular weight additive 1010 which has a molecular weight over 1100.