Liquids in Separation Techniques

Berthod A, Ruiz-Angel M, Carda-Broch S. Ionic liquids in separation techniques. J. Chromatogr. A. 2008. 1184, 6-18. 

Principles and Characteristics The main reasons for hyphenating MS to CE are the almost universal nature of the detector, its sensitivity and the structural information obtainable, including assessment of peak purity and identity. As CE is a liquid-phase separation technique, coupling to the mass spectrometer can be achieved by means of (modified) LC-MS interfaces. Because of the low flow-rates applied in CE, i.e. typically below lOOnLmin-1, a special coupling device is required to couple CE and the LC-MS interface. Three such devices have been developed, namely a... 

Also, specific chapters deal with the use of CL reactions as detection mode in FIA (Chapter 12), in separational techniques, such as liquid chromatography (LC) (Chapter 14) or capillary electrophoresis (CE) (Chapter 15), in immunoassay (Chapter 18), and in the development of sensors (Chapter 20). The recent use of this technique for the analysis of DNA (Chapter 19) and a photosensitized CL mode for medical routine and industrial applications (Chapter 17) are also considered in this book. 

ZANKER, A. In Separation Techniques Vol 2 Gas Liquid Solid Systems (McGraw-Hill, 1980), p. 178. Hydrocyclones dimensions and performance. 

The first approaches to the coupling of liquid-phase separation techniques with mass spectrometry were designed for HPLC needs, starting in the 1970s with since-forgotten techniques such as direct liquid introduction (DLI) and moving belt. In the 1980s, techniques such as thermospray, continuous-flow-fast atom bombardment (CF-FAB), and particle beam arose. 

Compared with conventional particle-packed SPE cartridges, FIT-SPE provides an increased surface area for the extraction medium and a reduced pressure drop during extraction and desorption. Also, the undesirable plugging effect from insoluble materials in real samples can be very much diminished. Utilization of FIT-SPE has been discussed in a few review articles concerning the on-line coupling of miniaturized SPE to microcolumn liquid-phase separation techniques.24,25... 

The use of mass spectrometry (MS) as a detection system is inevitable in the evolution of any separation method, especially CE where the liquid flow rate ( 1 ml/min) is compatible with conventional mass spectrometers. The combination of a high-efficiency liquid-phase separation technique, such as capillary electrophoresis, with MS detection provides a powerful system for the analysis of complex mixtures. Analyte sensitivity and the mass spectrum obtained depend on the electrospray ionization (ESI) voltage, ion-focusing parameters, and buffer composition. In general, the greatest sensitivity is obtained by employing conditions that facilitate desolvation and minimize cluster formation.47 Three ways of interfacing for CE-MS... 

In continuos flow FAB (CFFAB) [7,24,47] the analyte-matrix mixture is delivered continuously to the probe tip through a fused silica capillary which terminates at the probe tip. This configuration provides a means of coupling liquid phase separation techniques with FAB-MS. Addition of the matrix to the analyte solution is accomplished by one of two methods. (1) The matrix is added at concentrations of 5-10% to the mobile phase, and the column effluent is directly fluxed into the CFFAB ion source or (2) column effluent and matrix solution are delivered independently to the probe tip by a coaxial arrangement of two concentric fused silica capillaries. 

Mass analyzers are devices which separate and detect ions according to their mass-to-charge (m/z) ratios. The choice of an appropriate mass analyzer that is used in combination with liquid phase separation techniques depends on a number of interrelated factors, including (1) the range of detectable m/z values (mass range), (2) ability to separate ions of closely similar m/z (resolution), (3) accuracy of m/z measurement... 

It was also shown that the adsorptive capacity of the mesoporous materials is in excess of an order of magnitude superior than that of conventional porous adsorbent materials thus, MCM-41 has the potential as a selective adsorbent in separation techniques, for example, high-performance liquid chromatography and supercritical fluid chromatography [122],... 

In addition [103,104], a new type of composite that combines DNA with silica components via a sol-gel method was described. The DNA-silica hybrid material is advantageous with respect to its mechanical and chemical stability in both aqueous and organic solvents. Similar to the previously described hybrids, the specific functions of the DNA molecules were retained and maintained the DNA-silica hybrid materials adsorb DNA-interactive chemicals from diluted aqueous solution. In another series of reports [105-109], DNA-loaded PSf microspheres were fabricated by means of a liquid-liquid phase separation technique. The release rate of DNA from the microspheres can be controlled by manipulating the microsphere structure. Increasing the polymer concentration causes lower porosity and smaller pores on the outer surface of the microspheres, and leads to a low release rate of DNA from the microspheres. The DNA-loaded PSf microspheres could effectively accumulate harmful DNA-intercalating pollutants and endocrine disruptors, as described in previous reports. 

The majority of enantioseparations are performed by pressure-driven liquid chromatography. However, in the last decade other liquid-phase separation techniques have evolved and demonstrated their usefulness for enantioseparations, including supercritical fluid chromatography (SFC), capillary electrophoresis (CE), micellar electrokinetic chromatography (MEKC), and open-tubular and packed-bed electrochromatography (OT-EC and CEC). 

The gradient elution scheme is a scaled-up procedure originally described by Middleton (10) that has been extended to handle highly refractive materials such as coal liquids. This separation technique uses Alcoa F-20 alumina activated to a 5.5 wt % moisture level as the stationary phase. Details of this separation procedure are given elsewhere (2). This method separates SRC into 13 fractions and these fractions are listed in Table II along with some key chemical and physical descriptions of the cuts. The structural types indicated in Table II for Fractions 1-6 have been assigned based upon model compound studies and low resolution mass spectrometry (MS) (2), whereas the chemical types indicated for Fractions 7-13 are based upon IR observations and additional model compound studies. Recoveries in these separations are normally greater than 90%. 

Although liquid chromatography techniques have become quite popular in the separation of peptides in complex protein digests, they are yet to make an impact for the separation of protein samples for proteome-wide applications. It is envisioned that in the future their application for protein separation will increase. Various combinations of reversed-phase (RP)-HPLC with ion-exchange, size-exclusion, chromato-focusing (CF), IEF, and capillary electrophoresis (CE) have emerged for 2D separation of complex mixtures of proteins and peptides. A recent addition in this field is the use of CF as the first dimension and RP-FIPLC as the second-dimension separation device.14 CF is a column-based liquid-phase separation technique, in which proteins are fractionated on the basis of differences in their p/values in a weak ion-exchange column. 

As ESI works on a continuous flow of liquid, it has quickly been coupled to LC or other liquid-phase separation techniques as an alternative to optical detection.15 Mass spectrometry gives more information on the eluted compound, and the resulting hyphenated technique enables one to decrease the complexity of samples before their analysis by MS. High performance liquid chromatography (HPLC) is coupled to conventional ESI-MS while nanoLC is connected to nanoESI-MS for a better match in the flow-rate values. 

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