Base peak, mass spectrometry

The free online resource for the spectroscopy community, contains a section dedicated to mass spectrometry (Base Peak). Much elementary information, many articles on MS subject matter and related can be found here. 

Koch [82] and optimized further by us. The polyphenylene 28, which represents a first-generation dendrimer, forms 28 new bonds yielding the planar polycyclic aromatic hydrocarbon 56 (Scheme 23). Owing to its extreme insolubility in all common solvents, PAH 56 is characterized by laser desorption mass spectrometry based on its M+ peak at miz =1621. 

Mass spectrometry confirming peak identity, quantitation based on retention time mg/kg fresh weight Accept... 

In a study of TATP by IMS and tandem mass spectrometry, the peaks in the mobility spectrum were identified. A peak at mass 223 Da was identified as arising from TATP. In the mobility spectrum, a cluster of three peaks was observed, and a large increase in peak intensity was observed after dissolution of TATP in toluene. The reduced mobility of the main peak was reported as 2.71 cmW s. This high-mobility value must correspond to an ion with low molecular weight, probably a nitrate ion, and not to the molecular ion. A recent study has indeed found a quasi-molecular peak with a mass of 240 Da in the positive ion mobility spectrum of TATP corresponding to an adduct with ammonia, and the intensity of the peak decreased when the ammonia concentration was increased from 4.7 to 8.1 ppmv (Figure 12.5). The reduced mobility of this peak was low, in agreement with the prediction based on the mass of the adduct ion. ... 

Relative mass is an intrinsic molecular property which, when measured with high accuracy, becomes a unique and unusually effective parameter for characterization of synthetic or natural biomolecules. Mass spectrometry based methods can be broadly applied not only to unmodified synthetic biomolecules, but also to modified synthetic and natural biomolecules (e.g. glycosylated proteins). The level of mass accuracy one obtains during the measurement will depend on the capabilities of the mass analyser used. Quad-rupole and TOE instruments yield lower mass accuracies than sector or Fourier transform ion cyclotron resonance (FTICR) instruments. High mass accuracy is not only necessary for qualitative analysis of biomolecules present in a sample, but is necessary to provide unambiguous peak identification in a mass spectrum. 

The mass spectrum of benzene is relatively simple and illustrates some of the mfor matron that mass spectrometry provides The most intense peak m the mass spectrum is called the base peak and is assigned a relative intensity of 100 Ion abundances are pro portional to peak intensities and are reported as intensities relative to the base peak The base peak m the mass spectrum of benzene corresponds to the molecular ion (M" ) at miz = 78... 

The alkaloid Nigellicine proved to be the pyridazino[l,2-u]indazolium-l 1-carboxylate (234) and forms yellow crystals (Scheme 77). It was isolated from the widely distributed herbaceous plant Nigella saliva L., which is used as a spice and for the treatment of various diseases (85TL2759). The structure was determined by an X-ray crystal structure analysis. The carboxylate bond distances are essentially equal (123.3 and 125.6 pm). An intramolecular hydrogen bond was found between the carboxylate oxygen atom and the hydroxy group. In mass spectrometry, the molecular peak was found at mjz —246 (20) and the base peak at mjz —202 which corresponds... 

Mizutani and coworkers57a confirmed the presence of polychloro(methylsulfonyl)biphenyls (159-170) as sulfur-containing metabolites of chlorobiphenyls (Cl-BP) in the feces of mice based on both GLC-mass spectrometry and chemical derivatization. In some cases comparison with authentic samples (161 and 162) was also made. When preparing 161 and 162,2,5-dichloro-3-(methylsulfonyl)aniline, 2,5-dichloro-l-iodo-3-(methylsulfonyl)benzene and 2,2, 5,5 -tetrachloro-3,3 -bis(methyl-sulfonyl)biphenyl were also obtained and their four peak El mass spectra reported572. Similar data were given for the corresponding 4-substituted intermediates, which were involved in the preparation of 162. Also 2,4, 5-trichloro-2 -(methylsulfonyl)-biphenyl was prepared and its four peak mass spectra given. Metabolites 163 and 164 were also identified by comparison with the authentic standards. 

Verification of the molecular weight of thiirene dioxides by mass spectrometry, employing the conventional electron-impact (El) ionization method, has been unsuccessful due to the absence or insignificant intensity of molecular ion peaks in their mass spectra. The base peak is rather characteristic, however, and corresponds to the formation of the disubstituted acetylene ion by loss of sulfur dioxide91 (equation 3). 

Figure 5.2 Electrospray-MS-MS signal response of seven of the pesticides versus eluent flow rate, based on (a) peak area, and (b) peak height , atrazine , simazine , diuron x, isoproturon , chlorfenvinphos , chlorpyrifos O, alachlor. Reprinted from 7. Chromatogr., A, 937, Asperger, A., Efer, J., Koal, T. and Engewald, W., On the signal response of various pesticides in electrospray and atmospheric pressure chemical ionization depending on the flow rate of eluent applied in liquid chromatography-mass spectrometry , 65-72, Copyright (2001), with permission from Elsevier Science.

The mass spectrometry employed electrospray ionization and each metabolite gave an [M + H]+ ion which was then used as a precursor ion for a product-ion MS-MS scan. For subsequent MS" experiments, the base peak of the previous MS-MS experiment was chosen under computer control and this allowed all analytes to be studied in a single chromatographic separation. 

Figure 5.55 MS" spectra from rntz 329, the (M + H)+ ion of an hydroxy metabolite of Praziquantel, and the base peaks in subsequent product-ion spectra. Reprinted from J. Chromatogr., B, 708, Lerch, C. and Blaschke, G., Investigation of the stereoselective metabolism of Praziquantel after incubation with rat liver microsomes by capillary electrophoresis and liquid chromatography-mass spectrometry , 267-275, Copyright (1998), with permission from Elsevier Science.

Flaag et al. found that several species of Haemophilus bacteria can be distinguished by MALDI-TOF mass spectrometry and further showed that different strains of Haemophilus ducreyi tend to exhibit specific unique biomarker peaks between 5000 and 15000 Da.60 Lynn et al. observed a few peaks that could distinguish E. coli strains 0 157 and 7G1, though they specifically note that attempts to identify bacteria based on a limited number of biomarkers can lead to errors.61... 

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