Sensitivity ESI-MS

E. S. Grumbach, D. M. Wagrowski-Diehl, J. R. Mazzeo, B. Alden, and P. C. Iraneta. Hydrophilic Interaction Chromatography Using Silica Columns for the Retention of Polar Analytes and Enhanced ESI-MS Sensitivity, LCGC 2004,... 

ESI-MS Sensitivity, Resolution Control of device parameters at r plar intervals by analysis of peptide standards to guarantee optimal detection conditions. 

ESI-MS has emerged as a powerful technique for the characterization of biomolecules, and is the most versatile ionization technique in existence today. This highly sensitive and soft ionization technique allows mass spectrometric analysis of thermolabile, non-volatile, and polar compounds and produces intact ions from large and complex species in solution. In addition, it has the ability to introduce liquid samples to a mass detector with minimum manipulation. Volatile acids (such as formic acid and acetic acid) are often added to the mobile phase as well to protonate anthocyanins. A chromatogram with only the base peak for every mass spectrum provides more readily interpretable data because of fewer interference peaks. Cleaner mass spectra are achieved if anthocyanins are isolated from other phenolics by the use of C18 solid phase purification. - ... 

In another example, a multiresidue method using HPLC/ESI-MS was developed to determine six imidazolinone herbicides in five different soil types. Good recoveries (80-120%) and adequate sensitivity at the 2.0 ngg level were obtained for the compounds investigated. In the method, a 50-g soil sample was extracted for 1 h in 0.5N NaOH solution. A portion of the extract was acidified, to precipitate the humic acids, and the supernatant was then loaded on to a preconditioned trifunctional Cig SPE cartridge and eluted with ethyl acetate. Further cleanup was achieved using a tandem strong anion-exchange (SAX)-SCX SPE combination. Analytes were eluted... 

The corresponding liquid-phase chemistry can be used to promote ion formation by appropriate choice of solvent and pH, salt addition to form M.Na+ or M.NH4+, and postcolumn addition of reagents. The primary applications of ESI-MS are in the biopolymer field. The phenomenon of routine multiple charging is exclusive to electrospray, which makes it a very valuable technique in the fine chemical and biochemical field, because mass spectrometers can analyse high-molecular-mass samples without any need to extend their mass range, and without any loss of sensitivity. However, with ESI, molecules are not always produced with a distribution of charge states [137], Nevertheless, this phenomenon somehow complicates the determination of the true mass of the unknown. With conventional low-resolution mass spectrometers, the true mass of the macromolecule is determined by an indirect and iterative computational method. 

ESI and APCI are soft ionisation techniques which usually result in quasi-molecular ions such as [M + H]+ with little or no fragmentation molecular weight information can easily be obtained. However, experimental conditions can also be chosen in such a way that a sufficiently characteristic pattern is obtained, allowing verification [540]. ESI is amenable to thermally labile and nonvolatile molecules. Both ESI and APCI are much more sensitive than PB and very well suited for quantitative analysis, but less so for unknown samples. The choice among the two is usually determined by the application. Recently, nanoscale LC-ESI-MS has been developed [541]. The nano-electrospray ion source offers the highest sensitivity available for LC-MS (atto-to femtomole range) and can also be used as an off-line ion source. 

Electrospray has been successful for numerous azo dyes that are not ionic salts. Several anthraquinone dyes have been analysed by LC-ESI-MS [552]. Electrospray achieves the best sensitivity for compounds that are precharged in solution (e.g. ionic species or compounds that can be (de)protonated by pH adjustment). Consequently, LC-ESI-MS has focused on ionic dyes such as sulfonated azo dyes which have eluded analysis by particle-beam or thermospray LC-MS [594,617,618]. Techniques like LC-PB-MS and GC-MS, based on gas-phase ionisation, are not suitable for nonvolatile components such as sulfonated azo dyes. LC-TSP-MS on... 

Mass spectrometry can be specific in certain cases, and would even allow on-line QA in the isotope dilution mode. MS of molecular ions is seldom used in speciation analysis. API-MS allows compound-specific information to be obtained. APCI-MS offers the unique possibility of having an element- and compound-specific detector. A drawback is the limited sensitivity of APCI-MS in the element-specific detection mode. This can be overcome by use of on-line sample enrichment, e.g. SPE-HPLC-MS. The capabilities of ESI-MS for metal speciation have been critically assessed [546], Use of ESI-MS in metal speciation is growing. Houk [547] has emphasised that neither ICP-MS (elemental information) nor ESI-MS (molecular information) alone are adequate for identification of unknown elemental species at trace levels in complex mixtures. Consequently, a plea was made for simultaneous use of these two types of ion source on the same liquid chromatographic effluent. 

Statistical evaluation of HPLC UV MS[19] and CE UV MS[20] methods proves that MS detection of anthraquinone dyes is more sensitive than UV, especially in the case of chromatographic analysis of laccaic acids (almost 20 times) and purpurin (almost 40 times). However, detection limits of HPLC ESI MS determination of alizarin and purpurin (0.03 gg ml ) are about 20 times lower than those of CE ESI MS (0.52 0.58 gg ml x). 

In the field of analysis, important progress has been made in terms of sensitivity and selectivity. LC-ESI-MS/MS appears to be the technique of choice for their determination as it provides reliable results at subnanogram per liter or per gram levels. However, sample preparation is identified as the main bottleneck in the analysis of these compounds. Quite tedious and time-consuming procedures are still required, especially in the case of complex matrices such as sewage sludge. 

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