NanoLC technique

Separation and detection techniques for antibacterials in food mainly focus on the use of LC coupled to MS or tandem MS. Nevertheless, recent studies have suggested capillary electrophoresis coupled to laser-induced fluorescence (LIE) as a way of improving sensitivity [49], HRLC coupled to microTOF-ESI-MS as a highly selective, sensitive, and quick screening method for 100 veterinary drugs in fish, meat, and egg samples [195], and nanoscale LC coupled to UV or ion trap MS, with LODs in the range 0.01-0.51 pg/L (nanoLC-MS) and the possibility that even lower limits could be achieved by using triple quadrupole MS [59]. 

Reverse-phase columns with a gradient elution in combination with UV-Vis spectrophotometers using photodiode-array (PDA) (Fig. 1.6) and spectrofiuorimeters are common devices employed in this technique. In a lesser extent, MS, tandem mass spectrometry (MS-MS), and nano liquid chromatography-electrospray ionization-quadrupole time-of-flight tandem mass spectrometry (nanoLC-nanoESI-Q-qTOF-MS-MS) has been used as detection system. This instrumentation has been mainly used in the analysis of dyes and proteinaceous media, and in some extent, in the analysis of drying oils and terpenoid varnishes [47,48],... 

The nano-electrospray (nanoES) source is essentially a miniaturized version of the ES source. This technique allows very small amounts of sample to be ionized efficiently at nanoliters per minute flow rates and it involves loading sample volumes of 1-2 pi into a gold-coated capillary needle, which is introduced to the ion source. Alternatively for on-line nanoLC-MS experiments the end of the nanoLC column serves as the nanospray needle. The nanoES source disperses the liquid analyte entirely by electrostatic means [27] and does not require assistance such as solvent pumps or nebulizing gas. This improves sample desolvation and ionization and sample loading can be made to last 30 minutes or more. Also, the creation of nanodroplets means a high surface area to volume ratio allowing the efficient use of the sample without losses. Additionally, the introduction of the Z-spray ion source on some instruments has enabled an increase in sensitivity. In a Z-spray ion source, the analyte ions follow a Z-shaped trajectory between the inlet tube to the final skimmer which differs from the linear trajectory of a conventional inlet. This allows ions to be diverted from neutral molecules such as solvents and buffers, resulting in enhanced sensitivity. 

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. 

In order to meaningfully compare MALDI detection limits to the other techniques, specifically defined analytical conditions must be established. The case of peptide mapping is a good starting point because this class of chemical species ionizes well using both MALDI and ESI. Moreover, a relatively large body of work using both NanoLC/ESI and NanoLC/MALDI has been reported from which some initial conclusions may be drawn. As... 

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