Residual mass exchange

Tandem mass spectrometry for the residue-level exchange information-. Details of individual amino acid residue-level structures can be explored by acquiring the CID-MS/MS spectrum of the peptide segments formed by pepsin digestion of the exchanged protein. As mentioned earlier in this chapter, the b- and y-ion series are the primary sequence-specific ions under CID conditions. The amide hydrogen of a particular residue that is involved in HX can be identified by an increase in the mass of the sequence ion containing that residue. 

The detection and determination of traces of cobalt is of concern in such diverse areas as soflds, plants, fertilizers (qv), stainless and other steels for nuclear energy equipment (see Steel), high purity fissile materials (U, Th), refractory metals (Ta, Nb, Mo, and W), and semiconductors (qv). Useful techniques are spectrophotometry, polarography, emission spectrography, flame photometry, x-ray fluorescence, activation analysis, tracers, and mass spectrography, chromatography, and ion exchange (19) (see Analytical TffiTHODS Spectroscopy, optical Trace and residue analysis). 

Dichlorodibenzo- -dioxin. 2-Bromo-4-chlorophenol (31 grams, 0.15 mole) and solid potassium hydroxide (8.4 grams, 0.13 mole) were dissolved in methanol and evaporated to dryness under reduced pressure. The residue was mixed with 50 ml of bEEE, 0.5 ml of ethylene diacetate, and 200 mg of copper catalyst. The turbid mixture was stirred and heated at 200°C for 15 hours. Cooling produced a thick slurry which was transferred into the 500-ml reservoir of a liquid chromatographic column (1.5 X 25 cm) packed with acetate ion exchange resin (Bio-Rad, AG1-X2, 200-400 mesh). The product was eluted from the column with 3 liters of chloroform. After evaporation, the residue was heated at 170°C/2 mm for 14 hours in a 300-cc Nestor-Faust sublimer. The identity of the sublimed product (14 grams, 74% yield) was confirmed by mass spectrometry and x-ray diffraction. Product purity was estimated at 99- -% by GLC (electron capture detector). 

Phenylphosphate synthase consists of three subunits with molecular masses of 70, 40, and 24kDa. Subunit 1 resembles the central part of classical phospho-enolpyruvate synthase which contains a conserved histidine residue. It catalyzes the exchange of free [ C] phenol and the phenol moiety of phenylphosphate but not the phosphorylation of phenol. Phosphorylation of phenol requires subunit 1, MgATP, and another protein, subunit 2 (40kDa), which resembles the N-terminal part of phosphoenolpyruvate synthase. Subunit 1 and 2 catalyze the following reaction ... 

Homish, R. E. and Wiest, J. R., Quantitation of spectinomycin residues in bovine tissues by ion-exchange high-performance liquid chromatography with post-column derivatization and confirmation by reversed-phase high performance chromatography-atmospheric pressure chemical ionization tandem mass spectrometry, /. Chromatogr. A, 812, 123, 1998. 

A flow cell-procedure was then applied. The experiment consisted of (a) adsorption of methanol (in a solution containing deuterated methanol and light hydrogen base electrolyte), (b) solution exchange with base electrolyte and (c) application of two potential steps, one of short duration to oxidize the adsorbed residue and then a second one in the negative direction to reduce the ions H+ and/or D+ formed. During this time the mass intensity signals for HD, (m/e = 3) and for COz (m/e = 44) were... 

Figure 8. Results of Mo adsoqjtion experiments of Barling and Anbar (2004). Mo-bearing solutions were exposed to synthetic Mn oxides (5-Mn02) for 2-96 hours at pH 6.5-8.5. Residual Mo in solution ( ) was measured for all experiments. Mo adsorbed to oxide particle surfaces ( ) was either measured or inferred from mass balance. Dissolved Mo was systematically heavier than adsorbed Mo with a fractionation factor of 1.0018 0.0005. The data are consistent with closed system equilibrium, in which isotopes exchange continuously between surface and solution, but incompatible with an irreversible, Rayleigh-type process. Figure modified after Barling and Anbar (2004).

Table 2.1. Mass balance during fractional melting. Note that, in contrast with batch melting, there are no exchanges between the extracted melt and the residual solid (no two-way arrows in the table).

---