The use of mass defect in modern mass spectrometry

Mass defect is defined as the difference between a compound's exact mass and its nominal mass. This concept has been increasingly used in mass spectrometry over the years, mainly due to the growing use of high resolution mass spectrometers capable of exact mass measurements in many application areas in analytical and bioanalytical chemistry. This article is meant as an introduction to the different uses of mass defect in applications using modern MS instrumentation. Visualizing complex mass spectra may be simplified with the concept of Kendrick mass by plotting nominal mass as a function of Kendrick mass defect, based on hydrocarbons subunits, as well as slight variations on this theme. Mass defect filtering of complex MS data has been used for selectively detecting compounds of interest, including drugs and their metabolites or endogenous compounds such as peptides and small molecule metabolites. Several strategies have been applied for labeling analytes with reagents containing unique mass defect features, thus shifting molecules into a less noisy area in the mass spectrum, thus increasing their detectability, especially in the area of proteomics. All these concepts will be covered to introduce the interested reader to the plethora of possibilities of mass defect analysis of high resolution mass spectra. Copyright © 2012 John Wiley & Sons, Ltd.     

Mass spectrometry--not just a structural tool: the use of guided ion beam tandem mass spectrometry to determine thermochemistry

Guided ion beam tandem mass spectrometry has proved to be a robust tool for the measurement of thermodynamic information. Over the past twenty years, we have elucidated a number of factors necessary to make such thermochemistry accurate. Careful attention must be paid to the reduction of the raw data, ion intensities versus laboratory ion energies, to a more useful form, reaction cross sections versus relative kinetic energy. Analysis of the kinetic energy dependence of cross sections for endothermic reactions can then reveal thermodynamic data for both bimolecular and collision-induced dissociation (CID) processes. Such analyses need to include consideration of the explicit kinetic and internal energy distributions of the reactants, the effects of multiple collisions, the identity of the collision partner in CID processes, the kinetics of the reaction being studied, and competition between parallel reactions. This work provides examples illustrating the need to consider this multitude of effects along with details of the procedures developed in our group for handling each of them.     

The use of mass spectrometry in obstetric and gynecology

The present review shows the utility of using mass spectrometry (MS) in obstetrics and gynecology. In this review different gas chromatography / mass spectrometry and liquid chromatography / mass spectrometry methods developed before to be used in obstetrics and gynecology are described. These methods are very useful to determine different hormones in pregnancy, fatty acids esters (related to the use of ethanol) in human meconium and toxic compounds in umbilical cord (as ethanol, steroids, morphine, cocaine, methadone and other drugs). It is also shown in this review the progress during last decades in the field of using mass spectrometry in obstetrics and gynecology (for screening in utero exposure of the child to alcohol, drugs and other toxic compounds). In the field of using mass spectrometry in obstetrics and gynecology are still many problems to solve. For example, the detection of fatty acids esters in meconium has several limitations, which affects the results. One limitation is multiple births. Also in fetal distress, meconium may be passed before birth, and in this case, the collection is impossible. Moreover the meconium is formed starting from the fourth month of pregnancy, so the fetal exposure at any toxic compounds during the first three months cannot be detected at all. To solve all of these, the best would be to combine the results obtained from meconium, with other results obtained from pregnancy serum, placenta or umbilical cord. The main reason for using MS in obstetrics and gynecology is that MS is a noninvasive and a complementary method. It offers the results at a very early point in time, even before the act of birth. Sometimes the use of mass spectrometry is the only alternative. This shows that these methods are of great interest for the future and need to be developed further.      

Liquid chromatography-tandem mass spectrometry to determine sedative hypnotic drugs in river water and wastewater

A method for simultaneous determination of four benzodiazepines (bromazepam (BMZ), carbamazepine (CBZ), diazepam (DZP) and nordiazepam (NDZ)) and four barbiturates (barbital (BTL), pentobarbital (PTB), phenobarbital (PNB) and secobarbital (SCB)) in river water and wastewater using solid-phase extraction (SPE) followed by liquid chromatography-(electrospray) tandem mass spectrometry (LC-(ESI)MS/MS) was developed. LC-(ESI)MS/MS analysis was performed in positive and negative modes for benzodiazepines and barbiturates, respectively, and in selected reaction monitoring (SRM). Limits of detection (LODs) were in the range of 0.2–5 ng/L for benzodiazepines and 2.5–50 ng/L for barbiturates. Precision (repeatability and reproducibility between days) expressed as %RSD (n = 5) was lower than 17% for low concentration (depending on the matrix between 50 and 250 ng/L for barbiturates, and between 5 and 25 ng/L for benzodiazepines), and lower than 15% for high concentration (between 200 and 1250 ng/L for barbiturates, and between 20 and 125 ng/L for benzodiazepines). Low matrix effect was observed for all compounds, except for BTL (75%) and PTB (–48%) in wastewater. The method was applied to water samples from two sewage treatment plants (STPs) and the rivers Ebre, Ter and Llobregat, located in Catalonia. CBZ was the target compound found at the highest concentration in river water (2.1–3.3 ng/L). In both influent and effluent wastewater samples, PNB, BMZ, CBZ, DZP and NDZ were determined at concentration levels ranging from 5.0 to 2337.3 ng/L.     

基于质谱技术识别脂质双键位置的研究进展

脂质在能量贮存和信号传递方面发挥着巨大作用,同时还是生物膜的主要组成成分。不饱和脂质双键位置不同,生理学意义和生物学功能会有很大差异,因此脂质双键位置的识别至关重要。质谱具有灵敏快速、准确度高等优势,已成为脂质结构研究的重要方法。近年来,不同原理的电离技术与选择性衍生反应迅速发展起来,与质谱相结合已广泛应用于多种脂质双键位置的识别。本文主要对这些新型质谱技术进行总结,并展望了其未来发展趋势。     

Novel use of an isotope separator to determine the position of fluorine-18 in labelled 1,1,1,2-tetrafluoroethanes

A novel technique is described for measuring the site selectivity of methods for labelling the major CFC-alternative, 1,1,1,2-tetrafluoroethane (HFA 134a), with fluorine-18 (t_1/2 = 109.7 min). The carbon–carbon bond in radiofluorinated HFA 134a is broken in the ion source of an isotope separator. Radioactivity associated with the ion beam of the [CF₂ ¹⁸F]^+. fragment (m/z = 68) is collected, measured and divided by the integrated mass of the simultaneously collected ion beam for the [CF₃]^+. fragment (m/z = 69) to give the ‘specific radioactivity’ (in nCi nmol^–1) of the radiolabel in the 1-position. Similarly, the ‘specific radioactivity’ of the radiolabel in the 2-position is calculated from the measured radioactivity of the ion beam from the [CH₂ ¹⁸F]^+. fragment (m/z = 32) and the integrated mass of the simultaneously collected ion beam from the [CH₂F]^+. fragment (m/z = 33). The selectivity of the labelling procedure for a particular position is then given by the decay-corrected ratio of specific radioactivity at that position to the sum of specific radioactivities. The labelling of HFA 134a by the reaction of [¹⁸F] fluoride with trifluoroethylene was found to have 97% selectivity for the CF₃ group, whereas labelling by the reaction of [¹⁸F] fluoride with 2,2,2-trifluoroethyl p-toluenesulphonate was found to have 91% selectivity for the CH₂F group. This information is of value for tracer studies of the fate of HFA 134a in man following its inhalation as a drug propellant. The described technique is of potentially wider value for determining the position of fluorine-18 in labelled polyfluorinated molecules.     

The use of mass spectrometry to obtain thermochemical data from series of organometallic compounds

A general procedure is described for deriving, from mass spectrometric measurements, thermochemical data for ions, radicals, and molecules from series of R_nML_x compounds (R = organic group, M = metal, L = ligand).     

The use of laser microprobe mass spectrometry for monitoring the Wittig synthesis

Laser microprobe mass spectrometry provides a means of characterizing intermediates and reaction products of the Wittig reaction. The study of mono- and bisphosphonium halides and oligomers of xylene yields more insight in the mass spectrometric behaviour of these molecules under laser-microprobe ionization conditions.     

Gas chromatography-mass spectrometry/mass spectrometry analysis to determine natural and post-administration levels of oestrogens in bovine serum and urine

A novel analytical approach has been developed and shown to be capable of detecting the isomers of oestradiol in the low ppt (pg mL(-1)) range in bovine serum and urine. Following extractive derivatisation the analytes were detected as their 3-pentafluorobenzoyl 17-trimethylsilyl ether derivatives by gas chromatography-mass spectrometry/mass spectrometry (GC-MS/MS), using electron capture negative ion chemical ionisation. The isomers of oestradiol were quantified in both blank and post-administration urine and serum samples, with a view to setting action/threshold levels for these compounds, to allow discrimination between normal samples and samples from animals treated with growth promoting ear implants. A non-parametric statistical assessment of the data resulted in proposed action levels (with a false positive probability of 1 in 1000) of 1.6 and 2.7 ng mL(-1) for 17alpha-oestradiol, in male and female urine, respectively, and 40 and 44 pg mL(-1) for 17beta-oestradiol, in male and female urine, respectively. An action level of 20 pg mL(-1) was proposed for 17alpha- and 17beta-oestradiol in male serum. In female serum the proposed action levels were 40 and 20 pg mL(-1) for 17alpha- and 17beta-oestradiol, respectively.     

The use of direct probe mass spectrometry for the differentiation of meat species

Two studies were performed in which samples of freeze-dried meat from different species were subjected to replicate analysis by direct probe mass spectromety (DPMS). In the first study samples were obtained from six different muscles from each of three animal species, cattle, chicken and rabbit. In the second study one sample was taken from each of four individual animals from each of six species, cattle, chicken, horse, pig, rabbit and sheep. The spectra were analysed by statistical procedures which determined the ions responsible for the greatest degree of discrimination and the intersample relationships were displayed either as a two-dimensional scatter diagram or non-linear map. The results showed that DPMS was able to differentiate the species of origin of these meats. The reliability of the analysis procedures was tested with further replicates, not included in the original data analysis, which were treated as unknowns and also by using other data analysis techniques which did not require prior knowledge of the groups involved. The test samples fitted extremely well into their respective groups and there was very good agreement between the results from the defined and non-defined data.     

Location of double-bond position in tetradecenols without chemical modification by mass spectrometry

Twelve positional isomers of tetradecenol were analysed by conventional combined gas chromatography/mass Spectrometry without any chemical derivatization for the elucidation of the double-bond position. The spectra were interpreted in terms of similarity of mass spectral patterns based on a fuzzy reasoning method, in which the relative abundances of selected predominant fragment ions were chosen as standard parameters and similarity indices were devised. The method was tested with pure alcohols and enabled the double-bond position to be located with acceptable accuracy.     

Determination of the double-bond position in hexadecenols by mass spectrometry without prior chemical modification

Fourteen isomers of chemically unmodified hexadecenol were analysed by two types of quadrupole mass spectrometer, coupled with a gas chromatograph, for the location of the double-bond position. A series of spectra were interpreted in terms of mass spectral patterns on a fuzzy classification, in which the intensity ratios of six diagnostic pairs of the predominant ions were preferred in devising similarity indices. The accuracy of the method in the location of double-bond position was confirmed by testing with other series of spectra.