Organic polymer monolith columns

This section provides an overview of properties of polymer monolith columns related to 2D-HPLC. Monolithic organic polymer columns, having longer history than silica monoliths, have been reviewed in detail recently by S vec and by Eeltink including their preparation methods and performance (Eeltink et al., 2004 Svec, 2004a). Polymer monolith columns commercially available include polyfstyrene-co-di vinyl benzene) (PSDVB) columns and poly(alkyl methacrylate) columns. 

Mini-columns for analyte separation/concentration can also behave as reactors, resembling the packed bed reactor. In this context, organic polymer monoliths, largely used in the medical and biological fields [73], should be highlighted. Monolithic mini-columns consist of continuous beds with macropores and mesopores which are characterised by low back-pressure effects. These columns offer several other advantages [74], as emphasised in Chapter 8. In the context of flow analysis, monolithic mini-columns were implemented in a sequential injection analyser in 2003 [75] and the potential and limitations of the approach, called Sequential Injection Chromatography, were recently reviewed [76]. 

Chirica and Remcho first created the outlet frit, packed the column with ODS beads, and then fabricated the inlet frit. The column was filled with aqueous solution of a silicate (Kasil) and the entrapment achieved by heating the column to 160 °C [105,106]. The monolithic column afforded considerably reduced retention times compared to the packed-only counterpart most likely due to a partial blocking of the pores with the silicate solution. This approach was recently extended to the immobilization of silica beads in a porous organic polymer matrix [107]. 

Commercially available monolithic columns are based either on silica or organic polymer and are generally characterized as a polymeric skeleton with macropores, with a diameter of approximately 2 pm, and mesopores, with a diameter of approximately 13 nm. The role of the macropores (through-pores) is to provide channels with high compounds permeability, which permits the use of higher flow rates with respect to columns based on conventional particle size, and an extended surface area, which is comparable to conventional columns packed with 3 pm particles. 

Because of the fact that organic polymers are known to suffer from swelling or shrinkage on changing the solvent [73,74], the inner wall of the column housings (fused silica capillaries or borosilicate columns) has—prior to polymerization—to be derivatized in order to provide chemical attachment of the monolith rod to the wall. 

However, silica monoliths and organic polymers both exhibit very advantageous chromatographic characteristics enhanced mass transfer characteristics, high reproducibility, and versatile surface chemistry, which make monolithic column attractive for a variety of forward-looking applications. 

The molecular imprinting strategy can be applied for the recognition of different kinds of templates from small organic molecules to biomacromolecules as proteins. Some examples of separations investigated with MIP monoliths in CEC and LC are shown in Table 2. The influence of the imprinted monolithic phase preparation procedure and of the separation conditions on the selectivity and chromatographic efficiency have been widely studied [154, 157, 161, 166, 167, 192]. The performance of imprinted monoliths as chromatographic stationary phase has also been compared to that of the traditional bulk polymer packed column [149, 160]. It was shown that the monolithic phases yielded faster analyses and improved chiral separations. 

Monolith Column—Porous silica column prepared in situ to completely fill the column tube with a fully porous silica foam skelton. After the organic polymer support is heated off, the silica surface is silylated in place to product bonded-phase surface. Column is high resolution and can be used at high flow rates with relatively low back-pressure (see Chapter 16). 

In addition to utilization of monoliths as a column material, two reports describing respectively silicate and synthetic organic polymer based monolithic frits were published recently [85,86], The conventional method of frit fabrication for a particle packed column usually involves thermal sintering of a section of the packing material, such as bare or octadecyl silica, using a heating device. This approach has several weaknesses such as the lack of control of the temperature and porous properties of the frit that decreases reproducibly of the fabrication process. 

Monolithic columns are an interesting recent alternative to conventional packed columns. Such columns are created by in situ polymerization from liquid precursors, usually organic polymer- or silica-based. When prepared, monolithic columns have the form of cylindrical rods. They are much more porous than typical packed particle beds, therefore they present significantly lower resistance to mobile phase flow. Consequently, these can be operated at much higher flow rates than conventional columns. The main application of monolithic columns is in high-throughput analysis. 

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