Positive ion mode

Esi-ms measurements were performed on a Agilent LC M,SD system with the following operational parameters capillary voltage 4.0 kV, cone voltage, 50 V and solvent flow (methanol - water, 50% v/v) 0.3 inL/min. All esi mass specttal data in the positive ion mode were acquired and processed using HP Chem.Station software. The concenttation of aluminum was 0.5 mmol dm while that of mfx were varied in the interval 0.5-1.0 mmol dm. The pH values were pH 4.0, 6.0, 7.2 and 8.5. The specttum obtained at A1 to mfx concenttation ratio 1 2 and pH 4.0 is shown in Fig. 1. 

In the positive ion mode, calibration is most frequently performed using perfluorokerosine, but different instrument manufacturers recommend different reference materials. Consult your instrument manual for the recorn-... 

We have previously considered the mechanism of electrospray ionization in terms of the charging of droplets containing analyte and the formation of ions as the charge density on the surface of the droplet increases as desolvation progresses. The electrospray system can also be considered as an electrochemical cell in which, in positive-ion mode, an oxidation reaction occurs at the capillary tip and a reduction reaction at the counter electrode (the opposite occurs during the production of negative ions). This allows us to obtain electrospray spectra from some analytes which are not ionized in solution and would otherwise not be amenable to study. In general terms, the compounds that may be studied are therefore as follows ... 

Electrospray is the softest mass spectrometry ionization technique and electrospray spectra therefore usually consist solely of molecular ions. Electrospray is unique, however, in that if the analyte contains more than one site at which protonation (in the positive-ion mode) or deprotonation (in the negative-ion mode) may occur, a number of molecular ions with a range of charge states is usually observed. For low-molecular-weight materials (< 1000 Da), the number of sites... 

The reagent species in the positive-ion mode may be considered to be proto-nated solvent ions, and in the negative ion mode 02, its hydrates and clusters. 

Fig. 9.—Schematic Representation of Molecular-ion Signals That May Be Formed in the Positive-ion Mode, Showing Commonly Observed Mass Differences.

Description glycosidic cleavage to form an oxonium ion charge retained on nonreducing end positive-ion mode only often referred to as A -type cleavage, because of similarity to one of the cleavages seen in electron impact-mass spectrometry. 

Description ring cleavage charge retained on nonreducing end infrequent pathway in the positive-ion mode, but a major pathway in the negative mode, because a stable, enolate anion results from loss of the enolic hydrogen atom ions are 42 mass units higher than those formed in Pathway C. 

Fig. 15.—Sequence of One of the Oligosaccharides Obtained from the Trehalose-containing Glycolipids of Mycobacteria kansasii. [Cleavage positions in the positive-ion mode (Pathway C, Section IV,2) are shown above the sequence. Cleavage positions in the negative-ion mode (Pathway B, Section IV,2) are shown below the sequence.

Crescenzi et al. developed a multi-residue method for pesticides including propanil in drinking water, river water and groundwater based on SPE and LC/MS detection. The recoveries of the pesticides by this method were >80%. Santos etal. developed an on-line SPE method followed by LC/PAD and LC/MS detection in a simultaneous method for anilides and two degradation products (4-chloro-2-methylphenol and 2,4-dichlorophenol) of acidic herbicides in estuarine water samples. To determine the major degradation product of propanil, 3,4-dichloroaniline, the positive ion mode is needed for atmospheric pressure chemical ionization mass spectrometry (APCI/MS) detection. The LOD of 3,4-dichloroaniline by APCI/MS was 0.1-0.02 ng mL for 50-mL water samples. 

A triple-quadrupole mass spectrometer with an electrospray interface is recommended for achieving the best sensitivity and selectivity in the quantitative determination of sulfonylurea herbicides. Ion trap mass spectrometers may also be used, but reduced sensitivity may be observed, in addition to more severe matrix suppression due to the increased need for sample concentration or to the space charge effect. Also, we have observed that two parent to daughter transitions cannot be obtained for some of the sulfonylurea compounds when ion traps are used in the MS/MS mode. Most electrospray LC/MS and LC/MS/MS analyses of sulfonylureas have been done in the positive ion mode with acidic HPLC mobile phases. The formation of (M - - H)+ ions in solution and in the gas phase under these conditions is favorable, and fragmentation or formation of undesirable adducts can easily be minimized. Owing to the acid-base nature of these molecules, negative ionization can also be used, with the formation of (M - H) ions at mobile phase pH values of approximately 5-7, but the sensitivity is often reduced as compared with the positive ion mode. 

Most reported triazine LC applications are reversed-phase utilizing C-8 and C-18 analytical columns, but there are also a few normal-phase (NH2,CN) and ion-exchange (SCX) applications. The columns used range from 5 to 25-cm length and from 2 to 4.6-mm i.d., depending on the specific application. In general, the mobile phases employed for reversed-phase applications consist of various methanol and/or acetonitrile combinations in water. The ionization efficiency of methanol and acetonitrile for atmospheric pressure chemical ionization (APcI) applications were compared, and based on methanol s lower proton affinity, the authors speculated that more compounds could be ionized in the positive ion mode when using methanol than acetonitrile in the mobile phase. 

Subsequently 36 strains of aerobic endospore-forming bacteria, consisting of six Bacillus species and one Brevibacillus species could be discriminated using cluster analysis of ESMS spectra acquired in the positive ion mode (m/z 200-2000).57 The analysis was carried out on harvested, washed bacterial cells suspended in aqueous acidic acetonitrile. The cell suspensions were infused directly into the ionization chamber of the mass spectrometer (LCT, Micromass) using a syringe pump. Replicates of the experiment were performed over a period of six months to randomize variations in the measurements due to possible confounding factors such as instrumental drift. Principal components analysis (PCA) was used to reduce the dimensionality of the data, fol-... 

The typical solution present in the capillary consists of a polar solvent in which electrolytes are soluble. As an example, we can use methanol as solvent and a simple salt like NaCl or BHC1, where B is an organic base, as the solute. Low electrolyte concentrations, 10-5-10 3 mol/L (M), are typically used in electrospray mass spectrometry (ESMS). For simplicity we will consider only the positive ion mode in the subsequent discussion. 

Adduct ions are quite frequent in the mass spectra. In positive ion mode, sodium or potassium cluster ions are commonly found. Mineral compounds often lead to multiple cluster ions. For example, spectra of FeCl3 in negative ion mode lead to several peaks from m/z 35 (Cl ) to m/z 487 ([(FeCl3)2FeCl3] ) [Van Ham et al. 2004],... 

A similar study has been performed on silk [Howell et al. 2007]. The ToF-SIMS fingerprint of silk exhibits the presence of different amino acid fragments (positive ion mode). In contrast to wool, the effect of artificial ageing is not obvious and no modification appears in the ToF-SIMS spectra. Nevertheless, the study of the cleaning procedures leads to the same conclusion as that in the case of wool. The amount of remaining surfactant increases with artificial ageing. 

Spectra of the greasy wool are more complicated than in the previous study. In negative ion mode, different fatty acids, fatty alcohols and alkanes are detected, whereas the positive ion mode shows mainly the presence of cholesterol and the cholesterol oxidation product (Figure 15.6). These ions are attributed to the presence of wool wax on the surface of raw wool. 

ToF-SIMS spectra were acquired in positive ion mode and four different extractives were identified. The two main peaks were assigned to hinokinin (m/z 353) and hinokir-esinol (m/z 252). Lower peaks at m/z 299 and m/z 302 were assigned to hinokione and hinokiol, respectively. These identifications were confirmed by the study of the pure molecules. 

In positive ion mode, the characteristic peaks representative of the binding media were fatty acids from lead soaps (of palmitic acid at m/z 461 463 and of stearic acid at m/z 489 491). Other peaks corresponding to mono- and diacylglycerol cations, protonated stearic acid or its acylium ions could be found in the spectra of the reference products but not in the paint sample. The spectrum of lead white egg tempera paint exhibits peaks of phosphocholine (m/z 184) and protonated ketocholesterol (m/z 401). These peaks were not found in the spectrum from the cross-section. In negative ion mode, the spectrum of the oil... 

After this first step, where some samples are eliminated because they are not suited to the protocol, the positive ion mode is used to investigate haem, an iron porphyrin which is a blood marker. Spectra taken of the haem reference show that it can be detected due to [M]+ and [M+H]+ ions (respectively, at m/z 616.2 and 617.2), and also due to a large distribution of fragment peaks between m/z 350 and m/z 550 (Figure 15.12a). The same spectrum has also been obtained for haemoglobin leading to the conclusion that the presence of protein does not disturb the detection of haem. 

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