Sensitivity enhancement with large volume injection

1 Sensitivity enhancement with large volume injection 

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The main aims in environmental analysis are sensitivity (due to the low concentration of microcontaminants to be determined), selectivity (due to the complexity of the sample) and automation of analysis (to increase the throughput in control analysis). These three aims are achieved by multidimensional chromatography sensitivity is enhanced by large-volume injection techniques combined with peak compression, selectivity is obviously enhanced if one uses two separations with different selectivi-ties instead of one, while on-line techniques reduce the number of manual operations in the analytical procedure. 

Various authors have described on-line LC-SFC coupling [947,948]. Coupling of LC to SFC with conventional-size LC columns, where only a small fraction of the peak of interest is transferred to the SFC, allows only for qualitative results, and does not address the need for improved sensitivity in cSFC. Cortes et al. [948] have described relatively large-volume sample introductions (>10 xL) into cSFC, using microcolumn LC in the first dimension. LVI-LC-cSFC provides enhanced sensitivity compared with conventional cSFC injection techniques. LC-cSFC is expected to be of utility in the characterisation of complex samples, and in the determination of components which are thermally labile do not contain significant chromophores or do not have sufficient volatility to be analysed by GC. 

The need for maximum sample throughput and minimal human interaction within analytical procedures has provided considerable impetus to the development of integrated systems. SPE-LC in-tube SPME followed by ultraviolet (UV) or MS detection and membrane introduction mass spectrometry (MIMS) have both been used to this end. Submersible MIMS systems capable of extended underwater deployment down to 200 m and with a mass range of up to 200 amu have recently come onto the market. Elow injection coupled with MIMS allows fast, near-real-time determination of, for example, phenols in water. Derivatization of the phenols with acetic anhydride can be used to enhance both the selectivity and sensitivity of this method. Other online derivatization procedures are under development with a view to increasing the scope for rapid determination of highly polar compounds that have previously proved difficult to analyze. Large volume injection techniques and developments in enzyme-linked immunosorbent assay (ELISA) technologies... 

The low flow rate in the microbore column ensures sample volumes compatible with the secondary conventional column and permits the injection of a small volume onto the secondary column, making the transfer of incompatible solvents possible without peak shape deterioration or resolution losses [63], The possible disadvantage could be the lower sample capacity of microbore LC columns. However, in LCxLC, a sensitivity enhancement can be obtained if the formation of compressed solute bands at the head of the secondary column is achieved during the transfer from the first to the second dimension. Moreover, a larger volume can be injected into the first-dimension microcolumn, used as a highly efficient pre-separation step, and a limited decrease in efficiency due to a large injection volume can be tolerated. 

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