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Ionization Efficiency (ionization + efficiency)
Selected AbstractsIonization efficiency of ,-helical peptides in laser desorption/ionization mass spectrometryJOURNAL OF MASS SPECTROMETRY (INCORP BIOLOGICAL MASS SPECTROMETRY), Issue 7 2009Yasushi Shigeri [source] Structural analysis of ,-Gal and new non-Gal carbohydrate epitopes from specific pathogen-free miniature pig kidneyPROTEINS: STRUCTURE, FUNCTION AND BIOINFORMATICS, Issue 13 2008Yun-Gon Kim Abstract The major barrier in transplantation of pig organs into humans is the presence of surface carbohydrate antigens (e.g., the Gal,1-3Gal,1-4GlcNAc-R (,-Gal) epitope) expressed on pig endothelial cells. In this study, total N -glycans from membrane glycoproteins derived from specific pathogen-free miniature pig kidney are identified by MALDI-TOF, negative ion ESI MS/MS and normal-phase HPLC (NP-HPLC) combined with exoglycosidase digestion. Over 100 N -glycans, including sialylated and neutral types, were identified. As well as the known ,-Gal antigens, some of these glycans contained novel non-Gal carbohydrate antigens such as (Neu5Gc-Gal-GlcNAc) and Gal,1-3Lewisx (Gal-Gal-(Fuc)GlcNAc) which have not been reported before in N -glycans from pig organs. The ability of MALDI, ESI, and HPLC to measure the relative proportions of the glycans was evaluated. The HPLC resolution was insufficient for accurate work and some minor differences were noted in the ionization efficiencies of different glycan groups when measured by the two mass spectrometric techniques. However, the results indicated that the relative quantity of ,-Gal epitope was in the region of 50% of the complex glycans. High-mannose type glycans were also abundant (35,43%) but appeared to be ionized more efficiently than the complex glycans by ESI than by MALDI. [source] Using multivariate statistical methods to model the electrospray ionization response of GXG tripeptides based on multiple physicochemical parametersRAPID COMMUNICATIONS IN MASS SPECTROMETRY, Issue 14 2009M. A. Raji Response factors were determined for twelve GXG peptides (where G stands for glycine and X is any of alanine [A], arginine [R], asparagine [N], aspartic acid [D], glycine [G], histidine [H], leucine [L], lysine [K], phenylalanine [F], serine [S], tyrosine [Y], valine [V]) by electrospray ionization mass spectrometry (ESI-MS). The response factors were measured using a novel flow injection method. This new method is based on the Gaussian distribution of analyte concentration resulting from band-broadening dispersion experienced by the analyte upon passage through an extended volume of PEEK tubing. This method removes the need for preparing a discrete series of standard solutions to assess concentration-dependent response. Relative response factors were calculated for each peptide with reference to GGG. The observed trends in the relative response factors were correlated with several analyte physicochemical parameters, chosen based on current understanding of ion release from charged droplets during the ESI process. These include analyte properties: nonpolar surface area; polar surface area; gas-phase basicity; proton affinity; and Log D. Multivariate statistical analysis using multiple linear regression, decision tree, and support vector regression models were investigated to assess their potential for predicting ESI response based on the analyte properties. The support vector regression model was more versatile and produced the least predictive error following 12-fold cross-validation. The effect of variation in solution pH on the relative response factors is highlighted, as evidenced by the different predictive models obtained for peptide response at two pH values (pH,=,6.0 and 9.0). The relationship between physicochemical parameters and associated ionization efficiencies for GXG tripeptides is discussed based on the equilibrium partitioning model. Copyright © 2009 John Wiley & Sons, Ltd. [source] Sensitive determination of bromine and iodine in aqueous and biological samples by electrothermal vaporization inductively coupled plasma mass spectrometry using tetramethylammonium hydroxide as a chemical modifierRAPID COMMUNICATIONS IN MASS SPECTROMETRY, Issue 12 2008Hiroko Kataoka A procedure for the simultaneous determination of bromine and iodine by inductively coupled plasma (ICP) mass spectrometry was investigated. In order to prevent the decrease in the ionization efficiencies of bromine and iodine atoms caused by the introduction of water mist, electrothermal vaporization was used for sample introduction into the ICP mass spectrometer. To prevent loss of analytes during the drying process, a small amount of tetramethylammonium hydroxide solution was placed as a chemical modifier into the tungsten boat furnace. After evaporation of the solvent, the analytes instantly vaporized and were then introduced into the ICP ion source to detect the 79Br+, 81Br+, and 127I+ ions. By using this system, detection limits of 0.77,pg and 0.086,pg were achieved for bromine and iodine, respectively. These values correspond to 8.1,pg,mL,1 and 0.91,pg,mL,1 of the aqueous bromide and iodide ion concentrations, respectively, for a sampling volume of 95,µL. The relative standard deviations for eight replicate measurements were 2.2% and 2.8% for 20,pg of bromine and 2,pg of iodine, respectively. Approximately 25 batches were vaporizable per hour. The method was successfully applied to the analysis of various certified reference materials and practical situations as biological and aqueous samples. There is further potential for the simultaneous determination of fluorine and chlorine. Copyright © 2008 John Wiley & Sons, Ltd. [source] Effect of eluent on the ionization efficiency of flavonoids by ion spray, atmospheric pressure chemical ionization, and atmospheric pressure photoionization mass spectrometryJOURNAL OF MASS SPECTROMETRY (INCORP BIOLOGICAL MASS SPECTROMETRY), Issue 12 2001Jussi-Pekka Rauha Abstract The effect of nine different eluent compositions on the ionization efficiency of five flavonoids was studied using ion spray (IS), atmospheric pressure chemical ionization (APCI), and the novel atmospheric pressure photoionization (APPI), in positive and negative ion modes. The eluent composition had a great effect on the ionization efficiency, and the optimal ionization conditions were achieved in positive ion IS and APCI using 0.4% formic acid (pH 2.3) as a buffer, and in negative ion IS and APCI using ammonium acetate buffer adjusted to pH 4.0. For APPI work, the eluent of choice appeared to be a mixture of organic solvent and 5 mM aqueous ammonium acetate. The limits of detection (LODs) were determined in scan mode for the analytes by liquid chromatography/mass spectrometry using IS, APCI and APPI interfaces. The results show that negative ion IS with an eluent system consisting of acidic ammonium acetate buffer provides the best conditions for detection of flavonoids in mass spectrometry mode, their LODs being between 0.8 and 13 µM for an injection volume of 20 µl. Copyright © 2001 John Wiley & Sons, Ltd. [source] Copper-coated microsprayer interface for on-line sheathless capillary electrophoresis electrospray mass spectrometry of carbohydratesJOURNAL OF SEPARATION SCIENCE, JSS, Issue 3 2006Alina D. Zamfir Abstract A sturdy home-built sheathless CE/ESI-QTOF-MS system was developed and optimized for carbohydrate analysis. The interface and employed methodology provided a simple analytical solution to laborious CE/MS interfacing methods and to problems in characterization of complex carbohydrate mixtures that require high-resolution separation of the components. The CE/ESI interface, feasible in any MS laboratory, consists of a one-piece CE column having the CE terminus in-laboratory shaped as a microsprayer and coated with copper. The CE microsprayer was inserted into an in-house made stainless steel clenching device and the whole assembly was mounted onto a quadrupole TOF mass spectrometer. The analytical potential of the interface in terms of suitability, microsprayer performance, copper coat durability, ionization efficiency, spray stability, and sensitivity was tested first on a simple mixture of standard saccharides, which were separated, resolved, and detected with high separation efficiency. The approach was next assessed for the screening of a biological sample, a complex mixture of O -glycosylated sialylated amino acids from urine of a patient suffering from Schindler disease. Preliminary data allow this method to be considered as one of general applicability in structural glycobiology and glycomics and easy to be implemented for proteomic surveys as well. [source] Semi-automated quantification of ivermectin in rat and human plasma using protein precipitation and filtration with liquid chromatography/tandem mass spectrometryRAPID COMMUNICATIONS IN MASS SPECTROMETRY, Issue 12 2004Tony Pereira Ivermectin is a parasiticide commonly used in humans and livestock. It is currently under development for the treatment of pediculosis of humans (head lice) that does not respond to established treatments. A liquid chromatography/turbo ion spray tandem mass spectrometry (LC/TIS-MS/MS) method for the determination of ivermectin in rat and human plasma has been developed that uses emamectin [4,-epi-(methylamino)-4,-deoxyavermectin] as the internal standard. Sample preparation involved protein precipitation and filtration of fortified plasma in the 96-well format. Chromatographic separation was accomplished using fast gradient conditions on a C8 stationary phase. The analytes were detected with the mass spectrometer operated in the positive ion, multiple reaction monitoring mode. The method exhibited good intra- and interday accuracy and precision, and was linear over a dynamic range of 1,2000,ng/mL. In rat plasma, intraday accuracy ranged between 84,93% for the low quality control (QC) sample (1.5 ng/mL), and between 91,109% for the remaining QCs. Intraday precision ranged between 4.9,15% for the low QC, and 0.8,6.3% for the remaining QCs. Interday accuracy ranged between 88,107%, and precision between 4.1,11%. Similar data was obtained using human plasma. An investigation of matrix effects indicated that the ionization efficiency of ivermectin was favored by the presence of an ammonium ion in an aqueous environment. The implications of this observation toward assay sensitivity are discussed. Copyright © 2004 John Wiley & Sons, Ltd. [source] Determination of carbocysteine in human plasma by liquid chromatography/tandem mass spectrometry employing precolumn derivatizationRAPID COMMUNICATIONS IN MASS SPECTROMETRY, Issue 3 2003Xiaoyan Chen A sensitive liquid chromatography/tandem mass spectrometry (LC/MS/MS) method was developed to determine carbocysteine in human plasma using 2-pyridylacetic acid as the internal standard (IS). The method employed derivatization with 10 M hydrochloric acid/methanol, which significantly improved the ionization efficiency of carbocysteine. After methanol-induced protein precipitation of plasma samples, carbocysteine and the IS were derivatized and subjected to LC/MS/MS analysis using atmospheric pressure chemical ionization. The method has a lower limit of quantitation of 20 ng/mL for a 0.2-mL plasma aliquot. The intra- and inter-day precision (RSD), calculated from quality control (QC) samples, was less than 7%. The accuracy, determined using QC samples, was within ±,1%. The method offered increased sensitivity, selectivity and speed of analysis over existing methods. The method was utilized to support clinical pharmacokinetic studies of carbocysteine in volunteers following oral administration. Copyright © 2002 John Wiley & Sons, Ltd. [source] Phosphopeptide analysis by positive and negative ion matrix-assisted laser desorption/ionization mass spectrometryRAPID COMMUNICATIONS IN MASS SPECTROMETRY, Issue 17 2001Katharina Janek This article describes a simple procedure for the detection of phosphorylated peptides by comparable positive and negative ion mode matrix-assisted laser desorption/ionization mass spectrometry measurements. Based on studies with phosphorylated peptides (EAIXAAPFAK, X,=,pS, pT, pY) and their corresponding non-phosphorylated analogs, it was found that phosphopeptides, which are characterized by a low ionization efficiency in the positive ion mode, exhibit drastically increased signal intensities in the negative ion mode compared to their non-phosphorylated analogs. The effect was successfully used to identify phosphorylated sequences of the commonly used phosphoprotein standards, protein kinase A and ,-casein, by peptide mass fingerprint analyses of the corresponding Lys C and trypsin digests using both (positive and negative) ion modes. The comparison of positive and negative ion spectra of a given protein digest (relative intensity[M,,,H],/relative intensity[M,+,H]+) can be used to identify any phosphopeptides present which may then be separated and analyzed further. Copyright © 2001 John Wiley & Sons, Ltd. [source] | ||||||||||