Signal suppression

Table 5.15 Relative signal responses from various injection volumes for the LC-MS-MS analysis of a wheat forage matrix sample. Reprinted from J. Chromatogr., A, 907, Choi, B. K., Hercules, D. M. and Gusev, A. L, Effect of liquid chromatography separation of complex matrices on liquid chromatography-tandem mass spectrometry signal suppression , 337-342, Copyright (2001), with permission from Elsevier Science...

Signal response is expressed as a percentage of that obtained from standard samples 100% is indicative of no signal suppression. 

Table 5.16 LC-MS-MS signal responses" obtained from wheat forage matrix samples using various mobile-phase additives (injection volumes of 50 p,l). From Choi, B. K., Hercules, D. M. and Gusev, A. I., LC-MS/MS signal suppression effects in the analysis of pesticides in complex environmental matrices , Fresenius J. Anal. Chem., 369, 370-377, Table 2, 2001. Springer-Verlag GmbH Co. KG. Reproduced with permission...

In isotope dilution inductively coupled plasma-mass spectrometry (ID-ICP-MS) the spike, the unspiked and a spiked sample are measured by ICP-MS in order to determine the isotope ratio. Using this technique, more precise and accurate results can be obtained than by using a calibration graph or by standard addition. This is due to elimination of various systematic errors. Isotopes behave identically in most chemical and physical processes. Signal suppression and enhancement due to the matrix in ICP-MS affects both isotopes equally. The same holds for most long-term instrumental fluctuations and drift. Accuracy and precision obtained with ID-ICP-QMS are better than with other ICP-QMS calibration... 

With the low-frequency H 1-NMR spectrometers of the past, analysis of low-concentration additives such as antioxidants was quite problematic, in view of lack of sensitivity. Moreover, in low-frequency H NMR most polymer solvents may easily interfere with the solute resonances. In higher-field, high-resolution NMR (500 MHz), solute interferences may be overcome by means of selective signal suppression. However, this is no longer a necessary strategy for the present 900-MHz NMR generation, where both sensitivity and resolution are adequate and quantification is facilitated. 

In this chapter we illustrate a direct method of characterisation of polymer/additive dissolutions by means of (500 MHz) NMR, which takes advantage of selective signal suppression allowing elimination of unwanted signals, such as the ca. 105 x more intensive PE signal. The most effective approach to solvent suppression is the destruction of the net solvent magnetisation by pulsed... 

Need for signal suppression techniques (not for >500MHz NMR generation)... 

Apffel, A., Fischer, S., Goldberg, G., Goodley, P.C., Kuhlmann, F.E. (1995). Enhanced sensitivity for peptide mapping with electrospray liquid chromatography—mass spectrometry in the presence of signal suppression due to trifluoroacetic acid-containing mobile phases. J. Chromatogr. A 712, 177-190. 

Matrix effects were evaluated by Gago-Ferrero et al. [23]. Both signal suppression and signal enhancement were observed. The extent of these effects was found to be fairly dependent on the UV filter. Thus, quantification should be performed by standard addition or internal standard calibration. Since standard addition is a high time-consuming procedure, internal standard calibration with appropriate isotopi-cally labeled compounds is the best option. 

It is also important to note that matrix-related effects, either signal enhancement or more commonly signal suppression, can have a pronounced effect on quantitative measurements. Based on these observations, the use of isotope-labeled standards is helpful to achieve accurate analytical measurement data on the diastereoisomers. Several methods found in the open literature include use of both 13C-labeled and d18-labeled surrogates as recovery and/or instrument standards [118],... 

Vandecasteele et al. [745] studied signal suppression in ICP-MS of beryllium, aluminium, zinc, rubidium, indium, and lead in multielement solutions, and in the presence of increasing amounts of sodium chloride (up to 9 g/1). The suppression effects were the same for all of the analyte elements under consideration, and it was therefore possible to use one particular element, 115indium, as an internal standard to correct for the suppressive matrix effect, which significantly improved experimental precision. To study the causes of matrix effect, 0.154 M solutions of ammonium chloride, sodium chloride, and caesium chloride were compared. Ammonium chloride exhibited the least suppressive effect, and caesium chloride the most. The results had implications for trace element determinations in seawater (35 g sodium chloride per litre). 

In PCL systems care must be taken to ensure that the signal received directly from the transmitter does not compete with and swamp that from the target. Typically this will be the case unless measures are taken to suppress the direct signal occurring in the indirect channel. We can formulate a simple expression for the amount of direct signal suppression required by calculating the ratio of the indirect received sig-... 

Matrix-induced signal suppression in LC-MS has been investigated and discussed by several authors [8,9]. In general, an increase in analyte response factor with increasing electrolyte concentrations in the mobile-phase is observed for electrolyte concentrations below... 

T. Kondo, K. Hosoya, S. Hori, M. Tomi, S. Ohtsuki, and T. Terasaki. PKC/MAPK signaling suppression by retinal pericyte conditioned medium prevents retinal endothelial cell proliferation. J. Cell. Physiol. 203 378-386 (2005). 

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