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Mass Spectrometric Methods (mass + spectrometric_methods)
Selected AbstractsLigand Effects on the Mechanisms of Thermal Bond Activation in the Gas-Phase Reactions NiX+/CH4,Ni(CH3)+/HX (X=H, CH3, OH, F).HELVETICA CHIMICA ACTA, Issue 12 2008Short Communication Abstract The thermal ion-molecule reactions NiX++CH4,Ni(CH3)++HX (X=H, CH3, OH, F) have been studied by mass spectrometric methods, and the experimental data are complemented by density functional theory (DFT)-based computations. With regard to mechanistic aspects, a rather coherent picture emerges such that, for none of the systems studied, oxidative addition/reductive elimination pathways are involved. Rather, the energetically most favored variant corresponds to a , -complex-assisted metathesis (, -CAM). For X=H and CH3, the ligand exchange follows a ,two-state reactivity (TSR)' scenario such that, in the course of the thermal reaction, a twofold spin inversion, i.e., triplet,singlet,triplet, is involved. This TSR feature bypasses the energetically high-lying transition state of the adiabatic ground-state triplet surface. In contrast, for X=F, the exothermic ligand exchange proceeds adiabatically on the triplet ground state, and some arguments are proposed to account for the different behavior of NiX+/Ni(CH3)+ (X=H, CH3) vs. NiF+. While the couple Ni(OH)+/CH4 does not undergo a thermal ligand switch, the DFT computations suggest a potential-energy surface that is mechanistically comparable to the NiF+/CH4 system. Obviously, the ligands X act as a mechanistic distributor to switch between single vs. two-state reactivity patterns. [source] The synthesis of [3,4,1,- 13C3]genisteinJOURNAL OF LABELLED COMPOUNDS AND RADIOPHARMACEUTICALS, Issue 14 2007Mark F. Oldfield Abstract A facile synthesis is described for [3,4,1,- 13C3]genistein for use as an internal standard in isoflavone analysis by mass spectrometric methods. Ethyl 4-hydroxy[1- 13C]benzoate was first prepared from the reaction of diethyl [2- 13C]malonate and 4H -pyran-4-one. Two further 13C atoms were incorporated using potassium [13C]cyanide as the source to give 4,-benzyloxy-[1,2,1,- 13C3]phenylacetonitrile. [3,4,1,- 13C3]Genistein was then constructed through coupling of the isotopically labelled phenylacetonitrile with phloroglucinol under Hoesch conditions, followed by formylation and cyclization. Copyright © 2007 John Wiley & Sons, Ltd. [source] In-gel deglycosylation of sodiumdodecyl sulfate polyacrylamide gel electrophoresis-separated glycoproteins for carbohydrate estimation by matrix-assisted laser desorption/ionization time-of-flight mass spectrometryJOURNAL OF MASS SPECTROMETRY (INCORP BIOLOGICAL MASS SPECTROMETRY), Issue 3 2002S. Kilz Abstract Mass determination by mass spectrometric methods (electrospray ionization mass spectrometry (ESI-MS), matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOFMS)) of sodiumdodecyl sulfate polyacrylamide gel electrophoresis (SDS-PAGE)-separated proteins is a well known procedure and reliable protocols are available. In our efforts to use the established methods to determine the molecular mass of the disulfide brigded, heterodimeric glycoprotein GP3 and to determine the carbohydrate content of each protein subunit we developed an in-gel chemical deglycosylation method. For this purpose we established experimental conditions that allow maximum extraction of the high molecular mass protein subunits and developed a routine method to apply the HF,pyridine deglycosylation protocol to proteins isolated from polyacrylamide gel pieces. The novel protocol and extraction procedure described can be used to analyze O -glycosylated proteins up to 150 kDa after SDS-PAGE separation. Copyright © 2002 John Wiley & Sons, Ltd. [source] Mass spectrometry analysis of the influenza virus,MASS SPECTROMETRY REVIEWS, Issue 1 2009Kevin M. Downard Abstract The role of mass spectrometry to probe characteristics of the influenza virus, and vaccine and antiviral drugs that target the virus, are reviewed. Genetic and proteomic approaches have been applied which incorporate high resolution mass spectrometry and mass mapping to genotype the virus and establish its evolution in terms of the primary structure of the surface protein antigens. A mass spectrometric immunoassay has been developed and applied to assess the structure and antigenicity of the virus in terms of the hemagglutinin antigen. The quantitation of the hemagglutinin antigen in vaccine preparations has also been conducted that is of importance to their efficacy. Finally, the characterization and quantitation of antiviral drugs against the virus, and their metabolites, have been monitored in blood, serum, and urine. The combined approaches demonstrate the strengths of modern mass spectrometric methods for the characterization of this killer virus. © 2008 Wiley Periodicals, Inc., Mass Spec Rev 28:35,49, 2009 [This article was published online 10 September 2008. An error was subsequently identified. This notice is included in the online and print versions to indicate that both have been corrected 7 November 2008.] [source] Activation of large lons in FT-ICR mass spectrometryMASS SPECTROMETRY REVIEWS, Issue 2 2005Julia Laskin Abstract The advent of soft ionization techniques, notably electrospray and laser desorption ionization methods, has enabled the extension of mass spectrometric methods to large molecules and molecular complexes. This both greatly extends the applications of mass spectrometry and makes the activation and dissociation of complex ions an integral part of these applications. This review emphasizes the most promising methods for activation and dissociation of complex ions and presents this discussion in the context of general knowledge of reaction kinetics and dynamics largely established for small ions. We then introduce the characteristic differences associated with the higher number of internal degrees of freedom and high density of states associated with molecular complexity. This is reflected primarily in the kinetics of unimolecular dissociation of complex ions, particularly their slow decay and the higher energy content required to induce decomposition,the kinetic shift (KS). The longer trapping time of Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) significantly reduces the KS, which presents several advantages over other methods for the investigation of dissociation of complex molecules. After discussing general principles of reaction dynamics related to collisional activation of ions, we describe conventional ways to achieve single- and multiple-collision activation in FT-ICR MS. Sustained off-resonance irradiation (SORI),the simplest and most robust means of introducing the multiple collision activation process,is discussed in greatest detail. Details of implementation of this technique, required control of experimental parameters, limitations, and examples of very successful application of SORI-CID are described. The advantages of high mass resolving power and the ability to carry out several stages of mass selection and activation intrinsic to FT-ICR MS are demonstrated in several examples. Photodissociation of ions from small molecules can be effected using IR or UV/vis lasers and generally requires tuning lasers to specific wavelengths and/or utilizing high flux, multiphoton excitation to match energy levels in the ion. Photodissociation of complex ions is much easier to accomplish from the basic physics perspective. The quasi-continuum of vibrational states at room temperature makes it very easy to pump relatively large amounts of energy into complex ions and infrared multiphoton dissociation (IRMPD) is a powerful technique for characterizing large ions, particularly biologically relevant molecules. Since both SORI-CID and IRMPD are slow activation methods they have many common characteristics. They are also distinctly different because SORI-CID is intrinsically selective (only ions that have a cyclotron frequency close to the frequency of the excitation field are excited), whereas IRMPD is not (all ions that reside on the optical path of the laser are excited). There are advantages and disadvantages to each technique and in many applications they complement each other. In contrast with these slow activation methods, the less widely appreciated activation method of surface induced dissociation (SID) appears to offer unique advantages because excitation in SID occurs on a sub-picosecond time scale, instantaneously relative to the observation time of any mass spectrometer. Internal energy deposition is quite efficient and readily adjusted by altering the kinetic energy of the impacting ion. The shattering transition,instantaneous decomposition of the ion on the surface,observed at high collision energies enables access to dissociation channels that are not accessible using SORI-CID or IRMPD. Finally, we discuss some approaches for tailoring the surface to achieve particular aims in SID. © 2004 Wiley Periodicals, Inc., Mass Spec Rev 24:135,167, 2005 [source] Mass spectrometric methods for the characterisation and differentiation of isomeric O -diglycosyl flavonoidsPHYTOCHEMICAL ANALYSIS, Issue 3 2001Yu-Liang Ma Abstract Tandem mass spectrometric methods have been evaluated for the characterisation of the type and the differentiation of the interglycosidic linkage of isomeric flavonoid O -diglycosides. Based on the occurrence of internal monosaccharide residue loss and the relative abundances of Y-type ions formed by fragmentation at glycosidic bonds, four pairs of isomeric flavonoid O -diglycosides can be unambiguously differentiated. The different techniques used, i.e. linked scanning at constant B/E without collisional activation and low-energy collision-induced dissociation using methane or helium as collision gas, have been shown to be useful for distinguishing the two most common (1, 2- and 1, 6-) interglycosidic linkages, e.g. flavonoid O -neohesperidosides and O -rutinosides. Copyright © 2001 John Wiley & Sons, Ltd. [source] Urea-based two-dimensional electrophoresis of beta-amyloid peptides in human plasma: Evidence for novel A, speciesPROTEINS: STRUCTURE, FUNCTION AND BIOINFORMATICS, Issue 20 2007Juan Manuel Maler Abstract The detailed analysis of ,-amyloid (A,) peptides in human plasma is still hampered by the limited sensitivity of available mass spectrometric methods and the lack of appropiate ELISAs to measure A, peptides other than A,1,38, A,1,40, and A,1,42. By combining high-yield A, immuno precipitation (IP), IEF, and urea-based A,-SDS-PAGE-immunoblot, at least 30 A,-immunoreactive spots were detected in human plasma samples as small as 1.6,mL. This approach clearly resolved A, peptides A,1,40, A,1-42, A,1-37, A,1-38, A,1-39, the N-truncated A,2,40, A,2,42, and, for the first time, also A,1,41. Relative quantification indicated that A,1,40 and A,1,42 accounted for less than 60% of the total amount of A, peptides in plasma. All other A, peptides appear to be either C-terminally or N-terminally truncated forms or as yet uncharacterized A, species which migrated as trains of spots with distinct pIs. The A, pattern found in cerebrospinal fluid (CSF) was substantially less complex. This sensitive method (2-D A,-WIB) might help clarifying the origin of distinct A, species from different tissues, cell types, or intracellular pools as well as their amyloidogenicity. It might further help identifying plasma A, species suitable as biomarkers for the diagnosis of Alzheimer's disease (AD). [source] The determination of N- nitrosamines in foodQUALITY ASSURANCE & SAFETY OF CROPS & FOOD, Issue 1 2010Colin Crews Abstract Introduction N -nitrosamines are formed in food as a result of natural chemical interactions, but mainly through food processing activity. Most are potent carcinogens and their determination is therefore of considerable importance. They exist in various chemical forms and have been measured by colorimetric and spectroscopic methods following gas or liquid chromatography or as a total N -nitroso group by measurement of chemically released nitric oxide. Objectives To provide an overview of the available methods for the analysis of N -nitrosamines in food that includes recently developments. Methods The literature was reviewed from the discovery of the N -nitrosamine problem and the introduction on the N -nitroso-specific detector. Results The evaluation shows that analytical detection methods for volatile N -nitrosamines in food have changed little since the introduction on the N -nitroso-specific detector and that research into the occurrence and formation of both non-volatile N -nitrosamines and the apparent total N -nitroso content (ATNC) have declined. Methods for measuring the apparent total N -nitroso content have not been improved significantly in recent years. Conclusion Modern sample extraction techniques and mass spectrometric methods for the volatile N -nitrosamines have been applied more extensively to water analysis and offer a good opportunity to improve the determination of these carcinogens in food and make the analysis more widely available. Developments in liquid chromatography-mass spectrometry should provide an avenue for renewed interest in non-volatile N -nitrosamines, and could help with the identification of novel compounds whose presence is suggested by the high apparent total N -nitroso content of some foods. [source] Limitations of mass spectrometric methods for the characterization of polydisperse materials,RAPID COMMUNICATIONS IN MASS SPECTROMETRY, Issue 17 2010Alan A. Herod This paper is a review of work on the characterization of coal liquids and petroleum residues and asphaltenes over several decades in which various mass spectrometric methods have been investigated. The limitations of mass spectrometric methods require exploration in order to understand what the different analytical methods can reveal about environmental pollution by these kinds of samples and, perhaps more importantly, what they cannot reveal. The application of mass spectrometry to environmental problems generally requires the detection and determination of the concentration of specific pollutants released into the environment by accident or design. The release of crude petroleum or coal liquids into the environment can be detected and tracked during biodegradation processes through specific chemicals such as alkanes or polyaromatic hydrocarbons (PAHs). However, petroleum asphaltenes are polydisperse materials of unknown mass range and chemical structures and, therefore, there are no individual chemicals to detect. It is necessary to determine methods of detection and the ranges of mass of such materials. This can only be achieved through fractionation to reduce the polydispersity of the initial sample. Comparison of mass spectrometric results with results from an independent analytical method such as size-exclusion chromatography with a suitable eluent is advisable to confirm that all the sample has been detected and mass discrimination effects avoided. Copyright © 2010 John Wiley & Sons, Ltd. [source] Software algorithm for automatic interpretation of mass spectra of glycerolipidsRAPID COMMUNICATIONS IN MASS SPECTROMETRY, Issue 19 2002J.-P. Kurvinen A new software algorithm for automatic interpretation of mass spectra of glycerolipids has been developed. The algorithm utilizes a user-specified list of parameters needed to process the spectra. The compounds in mass spectra are identified according to range of measured m/z values, after which the spectra are automatically corrected by the content of naturally occurring isotopes and ion intensities of identified compounds by response correction factors. Automatic processing of the spectra was shown to be accurate and reliable by testing with numerous spectra of glycerophospholipids obtained by liquid chromatography/electrospray ionization mass spectrometry and by comparing the results with manual interpretation of the spectra. If quantitative analysis using internal standards is performed, all the identified compounds in the sample are quantified automatically. A dilution factor may be defined for each sample and is applied to correct the alterations in sample concentration during sample preparation. Processing of several replicate spectra simultaneously produces mean results with standard deviations. The software may also be used to subtract the results of two analyses and to calculate the mean result of replicate subtractions. The algorithm was shown to save time and labor in repetitive processing of mass spectra of similar type. It may be applied to processing of spectra obtained by various mass spectrometric methods. Copyright © 2002 John Wiley & Sons, Ltd. [source] | ||||||||||