The effect of charge location in ion mobility mass spectrometry for small molecule analytes

In travelling wave IM-MS an electric field is applied across the IMS cell and analyte collisions with the inert gas give rise to a relationship between the drift time and the molecular shape and overall charge. Recent findings show near baseline IMS separation (R>1) where shape and overall charge appear not to explain the IMS separation. Multiple ion mobility peaks are observed for a single m/z including the fluoroquinolone antibiotics norfloxacin and lomefloxacin, the pesticide indoxacarb and a number of steroids

Can ion mobility mass spectrometry and density functional theory help elucidate protonation sites in 'small' molecules?

Ion mobility spectrometry-mass spectrometry (IMS-MS) offers an opportunity to combine measurements and/or calculations of the collision cross-sections and subsequent mass spectra with computational modelling in order to derive the three-dimensional structure of ions. IMS-MS has previously been reported to separate two components for the compound norfloxacin, explained by protonation on two different sites, enabling the separation of protonated isomers (protomers) using ion mobility with distinguishable tandem mass spectrometric (MS/MS) data. This study reveals further insights into the specific example of norfloxacin and wider implications for ion mobility mass spectrometry

'Soft or 'hard' ionisation? Investigation of metastable gas temperature effect on direct analysis in real time of Voriconazole

The performance of the direct analysis in real-time (DART) technique was evaluated across a range of metastable gas temperatures for a pharmaceutical compound, Voriconazole, in order to investigate the effect of metastable gas temperature on molecular ion intensity and fragmentation. The DART source has been used to analyse a range of analytes and from a range of matrices including drugs in solid tablet form and preparations, active ingredients in ointment, naturally occurring plant alkaloids, flavours and fragrances, from thin layer chromatography (TLC) plates, melting point tubes and biological matrices including hair, urine and blood. The advantages of this technique include rapid analysis time (as little as 5 s), a reduction in sample preparation requirements, elimination of mobile phase requirement and analysis of samples not typically amenable to atmospheric pressure ionisation (API) techniques. This technology has therefore been proposed as an everyday tool for identification of components in crude organic reaction mixture

How useful is molecular modelling in combination with ion mobility mass spectrometry for 'small molecule' ion mobility collision cross-sections?

Ion mobility mass spectrometry is used to measure the drift-time of an ion. The drift-time of an ion can be used to calculate the collision cross-section (CCS) in travelling wave ion mobility (e.g. Waters Synapt and Vion instruments) or directly determine the experimental CCS (e.g. Agilent 6560 instrument and many drift-tube instruments). A comparison of the experimental CCS and theoretical CCS values obtained from trajectory method He(g) parameterised MOBCAL and N2(g) parameterised MOBCAL software, for a range of 20 'small molecules' is presented. This study utilises density functional theory B3LYP methods and the 6-31G+(d,p) basis set to calculate theoretical CCS values. This study seeks to assess the accuracy of a common procedure using CCS calibration with poly-(D/L)-alanine derived from drift-cell measurements and the original release of MOBCAL software and compare it with recent improvements with a drug-like molecule calibration set and a revision of MOBCAL parameterised for N2(g) drift gas. This study represents one of the first quantitative evaluations of the agreement between theoretical CCS and experimental CCS values for a range of small pharmaceutically relevant molecules using travelling wave ion mobility mass spectrometry. Accurate theoretical CCS may allow optimisation of ion mobility separations in silico, provide CCS databases that can confirm structures without the need for alternative analytical tools such as nuclear magnetic resonance spectroscopy (NMR) and assignment of unknowns and positional isomers without requiring reference materials

The effect of charge location in ion mobility mass spectrometry for small molecule analytes

<p>Presented at the British Mass Spectrometry Society meeting in 2014 and awarded the Bordoli Prize</p> <p> </p> <p>In travelling wave IM-MS an electric field is applied across the IMS cell and analyte collisions with the inert gas give rise to a relationship between the drift time and the molecular shape and overall charge.</p> <p>Recent findings show near baseline IMS separation (R>1) where shape and overall charge appear not to explain the IMS separation. Multiple ion mobility peaks are observed for a single m/z including the fluoroquinolone antibiotics norfloxacin and lomefloxacin, the pesticide indoxacarb and a number of steroids.</p> <p> </p> <p>The Bordoli Award was judged by Prof. Graham Cooks (Henry Bohn Hass Distinguished Professor of Chemistry at Purdue University, ISI Highly Cited Chemist with over 950 publications and an H-index of 81) and Prof. Mike Morris (‎Senior Director MS Research at Waters).</p> <p> </p> <p> </p

The application of new approaches to the analysis of deposits from the Jet Fuel Thermal Oxidation Tester (JFTOT)

Studies of diesel system deposits continue to be the subject of interest and publications worldwide. The introduction of high pressure common rail systems resulting in high fuel temperatures in the system with the concomitant use of fuels of varying solubilizing ability (e.g. ULSD and FAME blends) have seen deposits formed at the tip of the injector and on various internal injector components. Though deposit control additives (DCAs) have been successfully deployed to mitigate the deposit formation, work is still required to understand the nature and composition of these deposits.The study of both tip and internal diesel injector deposits (IDID) has seen the development of a number of bench techniques in an attempt to mimic field injector deposits in the laboratory. One of the most used of these is the Jet Fuel Thermal Oxidation Tester or JFTOT (ASTM D3241). The tester was originally designed to assess the oxidation of jet fuel, based on the principle that low stability fuels produce deposits that form on metal surfaces. Recently it has been modified so that under suitable conditions it may be used to determine the deposit forming potential of diesel fuels. The JFTOT technique has been used by a number of groups to try and understand diesel injector deposits. The ineradicable nature of the material on the JFTOT tube has seen the deposits analyzed by laser scanning microscopy, ellipsometry and recently infra-red microscopy. Other methods have been invasive involving either solvent washing or scraping off the deposit. In this paper other techniques for the analysis of deposits will be described yielding both chemical and metrological characteristics of the deposits. Fourier Transform Infrared Microscopy (FTIRM), and Time-of- Flight Secondary Ion Mass Spectrometry (ToFSIMS) will be used to describe the surface characteristics. Measurements from a Profile meter will be used to estimate deposit surface roughness and data from Scanning Electron Microscopy (SEM) will be employed to describe the morphology. The final techniques described will be Direct Analysis In Real Time Mass Spectrometry (DARTMS) using ambient mass spectrometry. and Fourier Transform Ion Cyclotron Resonance Mass spectrometry (FTICRMS) The advantage of the DART method is that mixtures and objects can be subjected to mass spectrometric analysis with the minimum of pre-treatment and sample preparation. Thus the technique is well suited for analyzing deposits on JFTOT tubes as it requires little sample preparation. A number of studies of materials deposited on JFTOT tubes will be described showing the suitability of these techniques for analyzing and providing the potential characterization of JFTOT deposits. The FTICRMS will be used to assign species in the JFTOT test fuels both pre and post test.<br/