scholarly journals Electrospray and tandem mass spectrometry in biochemistry

2001 ◽  
Vol 355 (3) ◽  
pp. 545-561 ◽  
Author(s):  
William J. GRIFFITHS ◽  
Andreas P. JONSSON ◽  
Suya LIU ◽  
Dilip K. RAI ◽  
Yuqin WANG

Over the last 20 years, biological MS has changed out of all recognition. This is primarily due to the development in the 1980s of ‘soft ionization’ methods that permit the ionization and vaporization of large, polar, and thermally labile biomolecules. These developments in ionization mode have driven the design and manufacture of smaller and cheaper mass analysers, making the mass spectrometer a routine instrument in the biochemistry laboratory today. In the present review the revolutionary ‘soft ionization’ methods will be discussed with particular reference to electrospray. The mass analysis of ions will be described, and the concept of tandem MS introduced. Where appropriate, examples of the application of MS in biochemistry will be provided. Although the present review will concentrate on the MS of peptides/proteins and lipids, all classes of biomolecules can be analysed, and much excellent work has been done in the fields of carbohydrate and nucleic acid biochemistry.

2007 ◽  
Vol 53 (8) ◽  
pp. 1462-1469 ◽  
Author(s):  
Diego Rodríguez-Cabaleiro ◽  
Katleen Van Uytfanghe ◽  
Veronique Stove ◽  
Tom Fiers ◽  
Linda M Thienpont

Abstract Background: An international working group convened by the American Diabetes Association (ADA) called for a reference measurement procedure for use in a trueness-based standardization project of insulin immunoassays. In view of this demand, we conducted a pilot study to investigate the feasibility of such a standardization project with our isotope dilution-liquid chromatography/tandem mass spectrometry (ID-LC/tandem MS) procedure. Methods: We evaluated the precision, accuracy, and limit of quantification (LoQ) of the ID-LC/tandem MS procedure by use of insulin-free serum supplemented with insulin to give 3 pools with concentrations of 0.0796, 0.769, and 5.56 μg/L. We conducted a pilot method comparison study with 4 immunoassays and 80 samples from fasting and glucose-stimulated patients. Results: The within-run and total imprecision (CV) ranged from 3.2% to 6.3% and from 4.9% to 12.1% (listing sequence from the high to the low pool). The recovery from supplemented insulin-free sera ranged from 101.8% to 104.1%, and the LoQ was 0.07 μg/L (12 pmol/L). Weighted Deming regression and correlation analysis of the method-comparison data showed considerable between-assay variation for the immunoassays but, with the exception of one assay, excellent correlation with ID-LC/tandem MS. Recalibration of the immunoassay results considerably reduced the between-assay variation. Moreover, after recalibration, 3 of the 4 assays fulfilled the total error specification of 32% proposed by the ADA Workgroup. Conclusions: Recalibration of insulin assays by regression equations established from method comparison with ID-LC/tandem MS can result in successful standardization and fulfillment of the total error criterion proposed by the ADA Workgroup.


2000 ◽  
Vol 6 (2) ◽  
pp. 169-174 ◽  
Author(s):  
Andrea Mele ◽  
Walter Panzeri ◽  
Antonio Selva ◽  
Pierluigi Mauri

The 1:1 inclusion complex of β-cyclodextrin (βCD) with 5-methoxytryptamine (5MTA) hydrochloride was studied by mass spectrometry (MS) and tandem-MS with fast atom bombardment (FAB), electrospray (ES) and ionspray (IS) ionisation and triple quadrupole or ion trap analysers. A protonated 1:1 βCD/MTA gaseous association was always observed; the protonated species of deaminated 5MTA and of some typical βCD fragments were obtained, in addition to the expected protonated 5MTA, as tandem-MS dissociation products. A reaction pattern starting from the deamination of protonated 5MTA, as a recently described high pressure chemical ionisation or ES process of primary amines, was suggested, which accounts for the formation of excited protonated βCD and its fragmentation by tandem-MS, even under unimolecular conditions.


1995 ◽  
Vol 68 (5) ◽  
pp. 783-793 ◽  
Author(s):  
Robert P. Lattimer

Abstract In recent years very effective mass spectrometric methods have been developed for direct polymer compound analysis. The high sensitivity, high specificity, and superb mixture analysis capabilities of modern mass spectrometry make it an invaluable tool in the polymer industry, particularly for qualitative analysis (chemical identification) of organic additives as well as polymeric components. “Survey” mass spectra obtained with soft ionization methods — field ionization (FI-MS) and chemical ionization (CI-MS) — provide diagnostic overviews of chemical composition. The supplemental tandem (MS/MS) and atomic composition (AC-MS) techniques are used to make specific identifications of various organic ingredients. This report describes the direct mass spectrometric analysis of three different elastomer compounds. Organic additives, including curatives, were identified via thermal desorption methods in a commercial EPDM bearing as well as a diene rubber V-belt. The composition of a commercial thermoplastic polyurethane was determined via pyrolysis (Py-CI-MS). These problem-solving examples illustrate the very effective role that mass spectrometry can play in the industrial polymer analysis laboratory.


1990 ◽  
Vol 73 (4) ◽  
pp. 529-533 ◽  
Author(s):  
Jean E Matusik ◽  
Richard S Sternal ◽  
Charlie J Barnes ◽  
James A Sphon

Abstract Four sulfonamide veterinary drug residues were quantltated by electron-capture detection (ECD) after separation by gas chromatography (GC). The Identities of sulfathiazole (ST), sulfamethazine (SM), sulfachloropyridazine (SCP), and sulfadimethoxine (SDM) were confirmed In bovine or swine liver residues by tandem mass spectrometry (MS/MS). Bovine or swine liver tissues were extracted by using either the Tlshler or the Manuel-Steller cleanup. The methylated residues containing ST, SM, SCP, and SDM were separated by GC prior to MS/MS daughter ion analysis. Control tissue, control tissue fortified at 0.1 ppm, and Incurred tissue residues at approximately 0.1 ppm were analyzed for these 4 sulfonamides. A Flnnigan Model TSQ-46 operating in the chemical ionization mode was used to perform the MS/MS daughter Ion experiments. The Identities of all 4 sulfonamides were confirmed In a single GC/MS/MS analysis.


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