Atmospheric pressure solids analysis

DGE a AC AMS APCI API AP-MALDI APPI ASAP BIRD c CAD CE CF CF-FAB Cl CID cw CZE Da DAPCI DART DC DE DESI DIOS DTIMS EC ECD El ELDI EM ESI ETD eV f FAB FAIMS FD FI FT FTICR two-dimensional gel electrophoresis atto, 10 18 alternating current accelerator mass spectrometry atmospheric pressure chemical ionization atmospheric pressure ionization atmospheric pressure matrix-assisted laser desorption/ionization atmospheric pressure photoionization atmospheric-pressure solids analysis probe blackbody infrared radiative dissociation centi, 10-2 collision-activated dissociation capillary electrophoresis continuous flow continuous flow fast atom bombardment chemical ionization collision-induced dissociation continuous wave capillary zone electrophoresis dalton desorption atmospheric pressure chemical ionization direct analysis in real time direct current delayed extraction desorption electrospray ionization desorption/ionization on silicon drift tube ion mobility spectrometry electrochromatography electron capture dissociation electron ionization electrospray-assisted laser desorption/ionization electron multiplier electrospray ionization electron transfer dissociation electron volt femto, 1CT15 fast atom bombardment field asymmetric waveform ion mobility spectrometry field desorption field ionization Fourier transform Fourier transform ion cyclotron resonance... 

There are some variants that have emerged in the wake of DESI. By replacing the electrospray emitter by a metal needle and allowing solvent vapor into the coaxial gas flow desorption APCI (DAPCI) can be performed [106], Other versions are atmospheric-pressure solids analysis probe (ASAP) where a heated gas jet desorbs the analyte, which is subsequently ionized by a corona discharge [107], and electrospray-assisted laser desorption/ionization (ELDI) where a laser ablates the analyte and charged droplets from an electrospray postionizes the desorbed neutrals [108],... 

McEwen et al. have utilized another ambient technique called atmospheric pressure solids analysis probe (ASAP) [84,85] and interfaced it with TWIM-MS [86], This source is now available commercially on the Synapt instrument. They have used m/z vi drift time plots to define compound classes in CTude oil analysis and to resolve isobaric compounds. Excellent agreement was demonstrated for drift times obtained from standards run individually and doped into the crude oil mixture. This work demonstrates the utility of mobility experiments to provide a degree of separation and classification in the study of very complex mixtures where chromatographic separation is either not possible or too time consuming. 

Smith, M.J.P., Cameron, N.R., and Mosely, J.A. (2012) Evaluating Atmospheric pressure Solids Analysis Probe (ASAP) mass spectrometry for the analysis of low molecular weight synthetic polymers. Analyst, 137,... 

Lloyd, J. A. Harron, A. R McEwen, C., Combination Atmospheric Pressure Solids Analysis Probe and Desorption Electrospray Ionization Mass Spectrometry Ion Source. Anal. Chem. 2009, 81, 9158-9162. 

ASAP Atmospheric pressure solids analysis probe Evaporation of solids in hot gas stream and ionization by corona discharge [55]... 

A number of analytical techniques such as FTIR spectroscopy,65-66 13C NMR,67,68 solid-state 13 C NMR,69 GPC or size exclusion chromatography (SEC),67-72 HPLC,73 mass spectrometric analysis,74 differential scanning calorimetry (DSC),67 75 76 and dynamic mechanical analysis (DMA)77 78 have been utilized to characterize resole syntheses and crosslinking reactions. Packed-column supercritical fluid chromatography with a negative-ion atmospheric pressure chemical ionization mass spectrometric detector has also been used to separate and characterize resoles resins.79 This section provides some examples of how these techniques are used in practical applications. 

LC-MS-MS was also the method of choice for the analysis of UV filters in solid matrices. Both LC and UPLC have been applied in three out of the four methods available for the determination of UV filters in sludge. Separation was performed on C8 and C18 LC-chromatographic columns (Zorbax, Eclipse, Vydac, and Purosphere) using binary gradient elution of mobile phases consisting of water/ methanol or water/acetonitrile. MS-MS detection was performed in SRM with ESI and atmospheric pressure photoionization (APPI) in both positive and negative modes. For each compound, two characteristics transitions were monitored. In addition to MS and MS-MS, diode array detection (DAD) was occasionally applied to the determination of OT. Spectra were recorded between 240 and 360 nm and discrete channels at 310 nm. 

Desorption Electrospray Ionization (DESI). DESI is a novel gentle ionization method for surface analysis (Figure 2.6).[19,20] Like classical ESI, it operates at atmospheric pressure. No sample preparation is required. A solvent passes through the capillary of the electrospray source charged droplets are produced (primary ions) and they are directed to a solid sample. Their impact with the surface causes sample molecules to be ionized and... 

C. N. McEwen, R. G. McKay, and B. S. Larsen. Analysis of Solids, Liquids, and Biological Tissues Using Solids Probe Introduction at Atmospheric Pressure on Commercial LC/MS Instruments. Anal. Chem., 77(2005) 7826-7831. 

The advantages of this technique are that they are applicable to probes in ultra high vacuum, where any impurities are excluded, and also to samples at atmospheric pressure. The diameter of the evaporated cavity can be varied between 10 jam and 1 mm, and the quantity of the evaporated material may be less than 10" g. Solids in any desired form, crystalline or powered, are accessible to analysis. 

API offers unique opportunities for the implementation of new sources or to develop new applications. Atmospheric pressure matrix assisted laser desorption (AP-MALDI) [21] can be mounted on instruments such as ion traps which were originally designed only for electrospray and LC-MS. New API desorption techniques such as desorption electrospray (DESI) [22] or direct analysis in real time (DART) [23] have been described and offer unique opportunities for the analysis of surfaces or of solid samples. 

Direct analysis of solid samples or analytes present on solid surfaces without any sample preparation has always been a topic of interest. Desorption electrospray ionization (DESI) is an atmospheric pressure desorption ionization method introduced by Cooks et al., producing ions directly from the surface to be analyzed, which are then sampled with the mass spectrometer [22, 37]. DESI is based on charged liquid droplets that are directed by a high velocity gas jet (in the order of 300 m s ) to the surface to be analyzed. Analytes are desorbed from the surface and analyzed by mass spectrometer (Eig. 1.15). 

The introduction of inductively coupled plasma (ICP) in inorganic mass spectrometry means that there is an effective ion source operating at atmospheric pressure. Whereas solid mass spectrometric techniques allow direct analysis of solid samples in ICP-MS, the determination of trace impurities or isotope ratios in solid samples is often carried out after digestion and dissolution of the material. For the determination of trace impurities and isotope ratios in liquids, an additional nebulization... 

Once a bulk sample is selected, a laboratory sample must be prepared for analysis (Figure 28-2). A coarse solid sample should be ground and mixed so that the laboratory sample has the same composition as the bulk sample. Solids are typically dried at 110°C at atmospheric pressure to remove adsorbed water prior to analysis. Temperature-sensitive samples may simply be stored in an environment that brings them to a constant, reproducible moisture level. 

McEwen, C. N., McKay, R. G., and Larsen, B. S. (2005). Analysis of solids, liquids, and biological tissues using solids probe introduction at atmospheric pressure on commercial LC/MS instruments. Anal. Chem. 77 7826-7831. 

Application of LC-MS/MS techniques to the analysis of phthalate ester metabolites in urine have also been developed. For example, Blount et al. (2000b) have developed an assay to quantify the monoester metabolites (including MEHP) of eight phthalate diesters in urine, utilizing HPLC coupled with atmospheric pressure chemical ionization and tandem mass spectrometric (APCI-MS/MS) detection techniques. Urine samples were treated with -glucuronidase to release the free phthalate monoesters followed by a two-step solid phase extraction procedure. After evaporative concentration of the eluant, the analytes in the purified samples are further separated on a phenyl reverse phase HPLC column and quantified by APCI-MS/MS, following careful optizimation of the APCI-MS/MS instrument. The limits of detection for MEHP were determined to be 1.2 ng/ml urine with recovery efficiencies of between 78 and 91%. 

The determination of a one-dimensional ladder molecular array structure of O2 molecules was first performed using in situ synchrotron powder XRD measurements on CPL-1 accommodating O2 molecules.77 78 The intermolecular distance of the adsorbed O2 molecules (3.28(4) A) is close to the nearest distance in the solid a-02 phase, whose close-packed structure appears below 24 K. This result indicates that O2 molecules adsorbed in the nanochannels form van der Waals dimers, (02)2- The X-ray structural analysis shows that 02 molecules are in the solid state rather than the liquid state, even at 130 K and 80kPa, which are much higher than the boiling point of bulk O2 at atmospheric pressure, 54.4 K. This result is ascribed to the strong confinement effect of CPL-1. 

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