Sensitivity in mass spectrometry

Sensitivity in mass spectrometry is defined as the ratio of the ionic current change to the sample change in the source. The recommended unit is Cpg-1. It is important that the relevant experimental conditions corresponding to sensitivity measurement should always be stated. 

Also HPLC with tandem mass spectrometric detection (HPLC-MS/MS) provides a suitable method of analysis. We have found that a single column is sufficient [3,5], however, we must emphasise that unknown substances similar in mass to 8-oxodG needs to be separated from 8-oxodG. For high sensitivity in mass spectrometry the peak height in HPLC is very important. The amount detected is proportional both to the peak height and to the area under the curve. 

Sensitivity in mass spectrometry is determined by the signal-to-noise ratio, which, in turn, has components of instrumental and chemical noise, the latter arising from the sample. Instrumental noise is generally a fixed parameter, but chemical noise can often be reduced by the user, not only by more efficient sample cleanup but by the way in which the instrument is operated. One such method is the technique of selected reaction monitoring, implemented on... 

Cl is an efficient, and relatively mild, method of ionization which takes place at a relatively high pressure, when compared to other methods of ionization used in mass spectrometry. The kinetics of the ion-molecule reactions involved would suggest that ultimate sensitivity should be obtained when ionization takes place at atmospheric pressure. It is not possible, however, to use the conventional source of electrons, a heated metallic filament, to effect the initial ionization of a reagent gas at such pressures, and an alternative, such as Ni, a emitter, or a corona discharge, must be employed. The corona discharge is used in commercially available APCI systems as it gives greater sensitivity and is less hazardous than the alternative. 

The mass spectrometer is a mass-flow sensitive device, which means that the signal is proportional to the mass flow dm/dl of the analyte, i.e. the concentration times the flow-rate. It is only now possible to realise the high (theoretically unlimited) mass range and the high-sensitivity multichannel recording capabilities that were anticipated many years ago. Of considerable interest to the problem of polymer/additive deformulation are some of the latest developments in mass spectrometry, namely atmospheric pressure ionisation (API), and the revival of time-of-flight spectrometers (allowing GC-ToFMS, MALDI-ToFMS, etc.). 

Enhanced molecular ion implies reduced matrix interference. An SMB-El mass spectrum usually provides information comparable to field ionisation, but fragmentation can be promoted through increase of the electron energy. For many compounds the sensitivity of HSI can be up to 100 times that of El. Aromatics are ionised with a much greater efficiency than saturated compounds. Supersonic molecular beams are used in mass spectrometry in conjunction with GC-MS [44], LC-MS [45] and laser-induced multiphoton ionisation followed by time-of-flight analysis [46]. 

Bayliss M. Little D. Mallett D. Plumb R. Parallel ultra-high flow rate liquid chromatography with mass spectrometric detection using a multiplex electrospray source for direct, sensitive determination of pharmaceuticals in plasma at extremely high-throughput. Rapid Communications in Mass Spectrometry, 2000, 14, 2039-2045. 

Capillary columns may provide the best method for the separation of phenols prior to their quantification (Eichelberger et al. 1983 Shafer et al. 1981 Sithole et al. 1986). Of the various methods available for detection, the two commonly used methods that are most sensitive are mass spectrometry and flame ionization detection. Although electron capture detectors provide good sensitivities for higher chlorine-substituted phenols, they are poor for phenol itself (Sithole et al. 1986). The best method for the quantification of phenol may be mass spectrometric detection in the selected ion mode, but the loss of qualitative information may be significant (Eichelberger et al. 1983). 

Deflnition The sensitivity is the slope of a plot of analyte amount versus signal strength. In mass spectrometry, sensitivity is reported as ionic charge of a specified m/z reaching the detector per mass of analyte used. The sensitivity is given in units of C pg" for solids. [27] For gaseous analytes, it can be specified as the ratio of ion current to analyte partial pressure in units of A Pa . [28,29]... 

P33 Analyses wereper/ormed on a gas chromatograph equipped with an electron capture detector (ECD) and a gas chromatograph coupled to a mass-selective detector working in mass spectrometry-mass spectrometry (MS-MS) mode, to achieve better limits of detection and selectivity. The proposed method yields high sensitivity, good linearity, precision, and accuracy. (From Dellinger et ah, 2001)... 

Electrospray (ESI) is an atmospheric pressure ionization source in which the sample is ionized at an ambient pressure and then transferred into the MS. It was first developed by John Fenn in the late 1980s [1] and rapidly became one of the most widely used ionization techniques in mass spectrometry due to its high sensitivity and versatility. It is a soft ionization technique for analytes present in solution therefore, it can easily be coupled with separation methods such as LC and capillary electrophoresis (CE). The development of ESI has a wide field of applications, from small polar molecules to high molecular weight compounds such as protein and nucleotides. In 2002, the Nobel Prize was awarded to John Fenn following his studies on electrospray, for the development of soft desorption ionization methods for mass spectrometric analyses of biological macromolecules. ... 

MALDI-TOFF MS is a very fast and sensitive technique, implemented on small, relatively inexpensive instruments that do not require extensive expertise in mass spectrometry. Such instruments are ideally suited for biological scientists who need molecular mass information more quickly and more accurately than can be obtained by gel electrophoresis. 

It is important to clarify a confusing issue that is commonly encountered in mass spectrometry and clinical chemistry. Mass spectrometrists define selectivity and sensitivity in quite different terms than do clinical chemists. Analytical selectivity and sensitivity are terms that should help clarify the situation. The measure of sensitiv-... 

Trends in mass spectrometry focus on the improvement of instrumentation, of several techniques in order to minimize sample volume, to improve sensitivity and to reduce detection limits. This is combined with increasing the speed of several analyses, with automation of analytical procedures and subsequently reducing the price of analysis. A minimizing of sample volumes means a reduction of waste volume with the aim of developing green chemistry . Furthermore, new analytical techniques involve a development of quantification procedures to improve the accuracy and precision of analytical data. Special attention in future will be given to the development of hyphenated mass spectrometric techniques for speciation analysis and of surface analytical techniques with improved lateral resolution in the nm scale range. 

The most famous cosmogenic radionuclide is 14C (t1/2 = 5730 a), which is produced by the interaction of cosmic ray neutrons via an (n,p) reaction with nitrogen [14N(n, p)14C], whereas the radioactive decay of 14C takes place by (3 decay to form the stable 14N isotope. 14C is the most important cosmogenic radionuclide for dating (see Section 9.7.5) in archaeology and can be analyzed using isotope sensitive accelerator mass spectrometry. Extremely small isotope ratios 14C/12C = 12 in nature can be measured by means of AMS.28... 

Because the characterization of support-bound intermediates is difficult (see below), solid-phase reactions are most conveniently monitored by cleaving the intermediates from the support and analyzing them in solution. Depending on the loading, 5-20 mg of support will usually deliver sufficient material for analysis by HPLC, LC-MS, and NMR, and enable assessment of the outcome of a reaction. Analytical tools that are particularly well suited for the rapid analysis of small samples resulting from solid-phase synthesis include MALDI-TOF MS [3-5], ion-spray MS [6-8], and tandem MS [9]. MALDI-TOF MS can even be used to analyze the product cleaved from a single bead [5], and is therefore well suited to the identification of products synthesized by the mix-and-split method (Section 1.2). The analysis and quantification of small amounts of product can be further facilitated by using supports with two linkers, which enable either release of the desired product or release of the product covalently bound to a dye [10-13], to an isotopic label [11], or to a sensitizer for mass spectrometry [6,14,15] (e.g., product-linker-dye- analytical linker -Pol). 

---