Atmospheric Solids Analysis Probe Research Articles

Atmospheric Solid Analysis Probe Coupled to Ion Mobility Spectrometry-Mass Spectrometry, a Fast and Simple Method for Polyalphaolefin Characterization

Polyalphaolefins (PAOs) are polymers produced from linear alpha olefins through catalytic oligomerization processes. The PAOs are known as synthetic high-performance base stock fluids used to improve the efficiency of many other synthetic products. In this study, we report the direct characterization of PAOs using atmospheric solid analysis probe (ASAP) coupled with ion mobility spectrometry-mass spectrometry (IMS-MS). We studied different PAOs grades exhibiting low- and high-viscosity index. Specific adjustments of the ASAP source parameters permitted the monitoring of ionization processes as three mechanisms could occur for these compounds: hydride abstraction, nitrogen addition, and/or the formation of [M-2H]+• ions. Several series of fragment ions were obtained, which allowed the identification of the alpha olefin used to synthesize the PAO. The use of the ion mobility separation dimension provides information on isomeric species. In addition, the drift time versus m/z plots permitted rapid comparison between PAO samples and to evidence their complexity. These 2D plots appear as fingerprints of PAO samples. To conclude, the resort to ASAP-IMS-MS provides a rapid characterization of the PAO samples in a direct analysis approach, without any sample preparation. Graphical Abstract ᅟ.

Identification of Organic Species Generated at Each Electrode during Potentiostatic Hold of a Two-Compartment Lithium-Ion Cell By Liquid Chromatography-Electrospray Ionization Mass Spectrometry (HPLC/ESI-MS) Analysis

Chemical structure identification of electrolyte decomposition species formed during aging of a lithium-ion battery can help deepen our understanding of the various reaction mechanisms occurring inside the battery, which in the long run can help in a rational design and synthesis of future electrolyte formulations. In this work, a two-compartment cell was made following the design proposed earlier by different groups.1-2 Essentially, a non-porous Li+-ion conductive glass ceramic disc was used as separator instead of the traditional porous polypropylene separator. This will eliminate any cross-talk between the electrodes and identify species formed at anode and cathode individually. NMC532 (LiNi0.5Mn0.3Co0.2O2) was used as the cathode, graphite was used as the anode, and 1.2 M LiPF6 in EC/EMC (3/7 wt./wt.) was used as the electrolyte. For identification of decomposition species, we used HPLC/ESI-MS which has been shown multiple times as a viable technique for identification of decomposition species which are typically present in small concentrations.3-4 Since only molecular weights of the species can be obtained via ESI-MS, structural identification was performed using a combination of isotope-peak analysis and already proposed reaction mechanisms. The results from two-compartment cell were also contrasted with a traditional lithium-ion cell made with porous polypropylene separator and aged under similar conditions. This abstract has been created by UChicago Argonne, LLC, Operator of Argonne National Laboratory (“Argonne”). Argonne, a U.S. Department of Energy Office of Science laboratory, is operated under Contract No. DE-AC02- 06CH11357. The U.S. Government retains for itself, and others acting on its behalf, a paid-up, nonexclusive, irrevocable worldwide license in said article to reproduce, prepare derivative works, distribute copies to the public, and perform publicly and display publicly, by or on behalf of the Government. References Metzger, M.; Strehle, B.; Solchenbach, S.; Gasteiger, H. A., Origin of H2 Evolution in Libs: H2o Reduction Vs. Electrolyte Oxidation. Journal of The Electrochemical Society 2016, 163, A798-A809.Vadivel, N. R.; Ha, S.; He, M.; Dees, D.; Trask, S.; Polzin, B.; Gallagher, K. G., On Leakage Current Measured at High Cell Voltages in Lithium-Ion Batteries. Journal of The Electrochemical Society 2017, 164, A508-A517.Takeda, S.; Morimura, W.; Liu, Y.-H.; Sakai, T.; Saito, Y., Identification and Formation Mechanism of Individual Degradation Products in Lithium-Ion Batteries Studied by Liquid Chromatography/Electrospray Ionization Mass Spectrometry and Atmospheric Solid Analysis Probe Mass Spectrometry. Rapid Communications in Mass Spectrometry 2016, 30, 1754-1762.Laruelle, S.; Pilard, S.; Guenot, P.; Grugeon, S.; Tarascon, J.-M., Identification of Li-Based Electrolyte Degradation Products through Dei and Esi High-Resolution Mass Spectrometry. Journal of The Electrochemical Society 2004, 151, A1202-A1209.

Carbon fiber brush electrode as a novel substrate for atmospheric solids analysis probe (ASAP) mass spectrometry: Electrochemical oxidation of brominated phenols

A carbon fiber brush electrode (CFBE) was newly designed and used as a substrate for both controlled potential electrolysis and atmospheric solids analysis probe (ASAP) mass spectrometry. Electropolymerized and strongly adsorbed products of electrolysis were directly desorbed and ionized from the electrode surface. Electrochemical properties of the electrode investigated by cyclic voltammetry revealed large electroactive surface area (23 ± 3 cm2) at 1.3 cm long array of carbon fibers with diameter 6–9 μm. Some products of electrochemical oxidation of pentabromophenol and 2,4,6-tribromophenol formed a compact layer on the carbon fibers and were analyzed using ASAP. Eleven new oligomeric products were identified including quinones and biphenoquinones. These compounds were not observed previously in electrolyzed solutions by liquid or gas chromatography/mass spectrometry. The thickness around 58 nm and 45 nm of the oxidation products layers deposited on carbon fibers during electrolysis of pentabromophenol and 2,4,6-tribromophenol, respectively, was estimated from atomic force microscopy analysis and confirmed by scanning electron microscopy with energy-dispersive X-ray spectroscopy measurements.

Application of Atmospheric Solids Analysis Probe Mass Spectrometry (ASAP-MS) in Petroleomics: Analysis of Condensed Aromatics Standards, Crude Oil, and Paraffinic Fraction.

Atmospheric solids analysis probe mass spectrometry (ASAP-MS) is a powerful tool for analysis of solid and liquid samples. It is an excellent alternative for crude oil analysis without any sample preparation step. Here, ASAP-MS in positive ion mode, ASAP(+)-MS, has been optimized for analysis of condensed aromatics (CA) standards, crude oil, and paraffinic fraction samples using a Synapt G2-S HDMS. Initially, two methodologies were used to access the chemical composition of samples: (1) using a temperature gradient varying from 150 to 600 °C at a heating rate of 150 °Cmin-1, and (2) with constant temperature of 300 and 400 °C. ASAP(+)-MS ionized many compounds with a typical petroleum profile, showing a greater signals range of m/z 250-1300 and 200-1400 for crude oil and paraffin samples, respectively. Such performance, mainly related to the detection of high molecular weight compounds (>1000Da), is superior to that of other traditional ionization sources, such as ESI, APCI, DART, and DESI. Additionally, the CA standards were identified in both forms: radicals, [M]+•, and protonated cations, [M + H]+, with minimum fragmentation. Therefore, ASAP was more efficient in accessing the chemical composition of nonpolar and polar compounds. It is promising in its application with ultrahigh resolution MS instruments, such as FT-ICR MS and Orbitrap, since molecular formulas with greater resolution and mass accuracy (<1ppm) would be assigned. Graphical Abstract ᅟ.

Characterization and quantitation of PVP content in a silicone hydrogel contact lens produced by dual-phase polymerization processing.

Polyvinylpyrrolidone (PVP) has been incorporated over the years into numerous hydrogel contact lenses as both a primary matrix component and an internal wetting agent to increase lens wettability. In this study, complementary analytical techniques were used to characterize the PVP wetting agent component of senofilcon A and samfilcon A contact lenses, both in terms of chemical composition and amount present. Photo-differential scanning calorimetry (photo-DSC), gas chromatography with a flame ionization detector (GC-FID), and high-resolution/accurate mass (HR/AM) liquid chromatography-mass spectrometry (LC-MS) techniques confirmed dual phase reaction and curing of the samfilcon A silicone hydrogel material. Gel permeation chromatography (GPC) demonstrated that high molecular weight (HMW) polymer was present in isopropanol (IPA) extracts of both lenses. High-performance liquid chromatography (HPLC) effectively separated hydrophilic PVP from the hydrophobic silicone polymers present in the extracts. Collectively, atmospheric solids analysis probe mass spectrometry (ASAP MS), Fourier transform infrared (FTIR) spectroscopy, 1 H nuclear magnetic resonance (NMR) spectroscopy, GC-FID, and LC-MS analyses of the lens extracts indicated that the majority of NVP is consumed during the second reaction phase of samfilcon A lens polymerization and exists as HMW PVP, similar to the PVP present in senofilcon A. GC-FID analysis of pyrolyzed samfilcon A and senofilcon A indicates fourfold greater PVP in samfilcon A compared with senofilcon A. © 2017 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater, 106B: 1064-1072, 2018.

Rapid analysis of forensic-related samples using two ambient ionization techniques coupled to high-resolution mass spectrometers.

This paper highlights the versatility of interfacing two ambient ionization techniques, Laser Diode Thermal Desorption (LDTD) and Atmospheric Solids Analysis Probe (ASAP), to high-resolution mass spectrometers and demonstrate the method's capability to rapidly generate high-quality data from multiple sample types with minimal, if any, sample preparation. For ASAP-MS analysis of solid and liquid samples, the material was transferred to a capillary surface before being introduced into the mass spectrometer. For LDTD-MS analysis, samples were solvent extracted, spotted in a 96-well plate, and the solvent was evaporated before being introduced into the mass spectrometer. All analyses were performed using Atmospheric Pressure Chemical Ionization in positive mode. Seven consumer "Spice" packets were combined and analyzed by both ASAP and LDTD, which identified 11 synthetic cannabinoids/cathinones by full MS and MS/MS experiments. To further show the usefulness of these techniques, black tar heroin was analyzed, which resulted in the identification of heroin and its impurities (monoacetylmorphine, papaverine, and noscapine). These experiments were performed on the LTQ-Orbitrap to demonstrate the ability to perform both parallel and serial MS and MSn experiments. Interfacing LDTD and ASAP to high-resolution mass spectrometers allows for expeditious analysis of a wide range of samples, with minimal or no sample preparation. Both allow for rapid full scan, MS/MS, and/or MSn experiments from a single sample introduction. Published in 2017. This article is a U.S. Government work and is in the public domain in the USA.

Infrared atmospheric solids analysis probe (IR-ASAP) mass spectrometry for ambient analysis of volatile compounds without heated gas

The IR-ASAP approach described is a simple yet highly sensitive ambient ionization method for analysis of vaporizable compounds without need of heated pressurized gas, thus making it especially amenable to portable mass spectrometers.

Molecular Weight Distributions and Average Molecular Weights of Pyrolysis Oils from Oil Shales: Literature Data and Measurements by Size Exclusion Chromatography (SEC) and Atmospheric Solids Analysis Probe Mass Spectroscopy (ASAP MS) for Oils from Four Different Deposits

Molecular weight (MW) data for shale oils, including molecular weight distributions (MWDs) as well as average MWs, is difficult to find. A thorough literature review of MW data for shale oils from different pyrolysis processes, found scattered across a wide range of topics (or papers on various topics) and analyzed here, was carried out as part of the study. However, because the data are for oils produced under different conditions, and the exact pyrolysis conditions are sometimes not fully described, then the MW values generally are not directly comparable. Therefore, in the experimental part of the current study, average MWs and MWDs were measured for shale oils from four different oil shales (Green River in the western United States, Attarat Umm Ghudran in Jordan, Kukersite in Estonia, and Dictyonema in Estonia) obtained by retorting under identical pyrolysis conditions, using a standardized Fischer assay method. The main goal of the study, to measure the MWDs of the Fischer assay oils, was accomplished using size exclusion chromatography (SEC). The MWD data obtained was also compared to that from atmospheric solids analysis probe mass spectroscopy (ASAP MS). In addition, MWDs of industrial Kukersite shale oil from Kiviter and Galoter processes were evaluated for comparison. The MWDs of Fischer assay shale oils obtained in the current study ranged from 100 g mol–1 to 600 g mol–1. While the oils show comparable average MW values, the parameters describing the width and shape of MWDs were more dependent on the parent oil shale.

Comparison of Atmospheric Pressure Ionization for the Analysis of Heavy Petroleum Fractions with Ion Mobility-Mass Spectrometry

Because of its high molecular complexity, ultra high-resolution Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS) is used to characterize heavy petroleum distillates. However, high peak capacity can also be obtained with ion mobility-mass spectrometry (IM-MS). In this case, the additional separation dimension allows for the compensation of the lower resolving power of the time-of-flight mass analyzer. The processing and elemental composition assignments from such bidimensional IM-MS data cannot be achieved with conventional software packages. PetroOrg, a new software package, was used to compare IM-MS data sets recorded with atmospheric solid analysis probe (ASAP) and three other atmospheric pressure ionization sources. The choice of the ionization source is indeed very critical as it defines the type of compounds that can be detected from mixtures. Electrospray ionization (ESI) is very specific to polar compounds and yields relatively simple data sets that can be readily attributed t...

Identification and formation mechanism of individual degradation products in lithium-ion batteries studied by liquid chromatography/electrospray ionization mass spectrometry and atmospheric solid analysis probe mass spectrometry.

Improvement of lithium ion batteries (LIBs) in terms of performance and robustness requires good understanding of the reaction processes. The analysis of the individual degradation products in LIB electrolytes and on the surface of the electrodes provides vital information in this regard. In this study, mass spectrometric analytical methods were utilized for the identification of the individual degradation products. The degradation products in the electrolytes recovered from cycle-tested cells were separated by liquid chromatography (LC) and their mass spectrometric analysis was conducted by electrospray ionization mass spectrometry (ESI-MS). For identification of degradation products on the surface of electrodes, atmospheric solid analysis probe (ASAP)-MS analysis was conducted by time-of-flight mass spectrometry with an ASAP probe and an atmospheric pressure chemical ionization source. The degradation products in the electrolytes, namely carbonate oligomers and organophosphates, were identified simultaneously by LC/ESI-MS. Their formation mechanisms were estimated, which explain their different compositions at different temperatures. One degradation product was found on the anode surface by ASAP-MS, and its formation mechanism was explained similarly to those in the electrolyte. The results suggest that the electrolyte degradation is correlated with the formation of a solid electrolyte interphase, which is an important factor in the performance of LIBs. We expect that further investigation of the degradation products by LC/ESI-MS and ASAP-MS will be helpful for studying their degradation processes in LIBs. Copyright © 2016 John Wiley & Sons, Ltd.

Atmospheric solids analysis probe mass spectrometry for the rapid identification of pollens and semi-quantification of flavonoid fingerprints.

From allergies to plant reproduction, pollens have important impacts on the health of human and plant populations, yet identification of pollen grains remains difficult and time-consuming. Low-volatility flavonoids generated from pollens cannot be easily characterized and quantified with current analytical techniques. Here we present the novel use of atmospheric solids analysis probe mass spectrometry (ASAP-MS) for the characterization of flavonoids in pollens. Flavonoid patterns were generated for pollens collected from different plant types (trees and bushes) in addition to bee pollens from distinct geographic regions. Standard flavonoids (kaempferol and rhamnazin) and those produced from pollens were compared and assessed with ASAP-MS using low-energy collision MS/MS. Results for a semi-quantitative method for assessing the amount of a flavonoid in pollens are also presented. Flavonoid patterns for pollen samples were distinct with variability in the number and relative abundance of flavonoids in each sample. Pollens contained 2-5 flavonoids, and all but Kochia scoparia contained kaempferol or kaempferol isomers. We establish this method as a reliable and applicable technique for analyzing low-volatility compounds with minimal sample preparation. Standard curves were generated using 0.2-5μg of kaempferol; from these experiments, it was estimated that there is approximately 2mg of kaempferol present in 1g of P. nigra italica pollen. Pollens can be characterized with a simple flavonoid pattern rather than analyzing the whole product pattern or the products-temperature profiles. ASAP-MS is a rapid analytical technique that can be used to distinguish between plant pollens and between bee pollens originating from different regions. Copyright © 2016 John Wiley & Sons, Ltd.

Rapid analysis of the skin irritant p-phenylenediamine (PPD) in henna products using atmospheric solids analysis probe mass spectrometry

Henna (Lawsonia inermis) is applied to stain keratin, present in hair, skin and fingernails, a red-orange or rust colour. Producers of temporary tattoos mix the aromatic amine compound, para-phenylenediamine (PPD) into natural henna to create ‘black henna’ that rapidly stains the skin black. However, PPD may cause severe delayed hypersensitivity reactions following skin contact. This study proposes a rapid direct-analysis method to detect and identify PPD using an atmospheric solids analysis probe (ASAP) coupled to a Q-ToF mass spectrometer (MS). Since laborious, multistep methods of analysis to determine PPD are undesirable, due to the instability of the compound in solution, a screening method involving no sample preparation steps was developed. Experiments were carried out to optimise the corona current, sample cone voltage, source temperature, and desolvation gas temperature to determine ideal ASAP-Q-ToF-MS analysing conditions. Eleven of the 109 henna samples, originating from various countries, tested positive for PPD when henna products were screened using ASAP-MS, without any form of sample preparation other than grinding. Ultra-performance liquid chromatography electrospray ionisation-mass spectrometry (UPLC-Q-ToF-MS) was subsequently used to confirm the results from ASAP and to determine the concentrations of PPD in henna products. The allergen was detected in the same eleven samples, with concentrations ranging from 0.05–4.21% (w/w). It can be concluded that the sensitivity of the ASAP-MS technique is sufficient (limit of detection=0.025% w/w) to allow screening of henna samples for the presence of PPD. This relatively new technique can be applied to commercial products without extraction, sample treatment or chromatographic separation.

Thermal degradation of β-carotene studied by ion mobility atmospheric solid analysis probe mass spectrometry: full product pattern and selective ionization enhancement.

Atmospheric solid analysis probe mass spectrometry has the capability of capturing full product patterns simultaneously including both volatile and semi-volatile compounds produced at elevated temperatures. Real-time low-energy collision-induced fragmentation combined with ion mobility separations enables rapid identification of the chemical structures of products. We present here for the first time the recognition of full product patterns resulting from the thermal degradation of β-carotene at temperatures up to 600 °C. Solvent vapor-induced ionization enhancement is observed, which reveals parallel thermal dissociation processes that lead to even- and odd-numbered mass products. The drift-time distributions of high mass products, along with β-carotene, were monitored with temperature, showing multiple conformations that are associated with the presence of two β-rings. Products of masses 346/347, however, show a single conformation distribution, which indicates the separation of two β-rings resulting from the direct bond scission at the polyene hydrocarbon chain. The thermal degradation pathways are evaluated and discussed.

Direct Analysis of Amphetamine Stimulants in a Whole Urine Sample by Atmospheric Solids Analysis Probe Tandem Mass Spectrometry.

Amphetamine-type stimulants (ATS) are among illicit stimulant drugs that are most often used worldwide. A major challenge is to develop a fast and efficient methodology involving minimal sample preparation to analyze ATS in biological fluids. In this study, a urine pool solution containing amphetamine, methamphetamine, ephedrine, sibutramine, and fenfluramine at concentrations ranging from 0.5 pg/mL to 100 ng/mL was prepared and analyzed by atmospheric solids analysis probe tandem mass spectrometry (ASAP-MS/MS) and multiple reaction monitoring (MRM). A urine sample and saliva collected from a volunteer contributor (V1) were also analyzed. The limit of detection of the tested compounds ranged between 0.002 and 0.4 ng/mL in urine samples; the signal-to-noise ratio was 5. These results demonstrated that the ASAP-MS/MS methodology is applicable for the fast detection of ATS in urine samples with great sensitivity and specificity, without the need for cleanup, preconcentration, or chromatographic separation. Thus ASAP-MS/MS could potentially be used in clinical and forensic toxicology applications.

Atmospheric Solid Analysis Probe-Ion Mobility Mass Spectrometry: An Original Approach to Characterize Grafting on Cyclic Olefin Copolymer Surfaces.

A cyclic olefin copolymer (COC) was grafted with aryl layers from aryldiazonium salts, and then we combined infrared spectrometry, atomic force microscopy (AFM), and ion mobility mass spectrometry with atmospheric solid analysis probe ionization (ASAP-IM-MS) to characterize the aryl layers. ASAP is a recent atmospheric ionization method dedicated to the direct analysis of solid samples. We demonstrated that ASAP-IM-MS is complementary to other techniques for characterizing bromine and sulfur derivatives of COC on surfaces. ASAP-IM-MS was useful for optimizing experimental grafting conditions and to elucidate hypotheses around aryl layer formation during the grafting process. Thus, ASAP-IM-MS is a good candidate tool to characterize covalent grafting on COC surfaces.

A fast and reliable detection of indigo in historic and prehistoric textile samples

Across all cultures and over all time periods, as early as the third millennium BC, indigo, a very intense blue vat dye, has been used to dye textiles. Even today, indigo is regarded as one of the most popular blue colorants in items such as blue jeans. While synthetic indigo is used to color textiles today, throughout history, a variety of plants have provided indigo. In this special feature article, René Csuk and co-authors propose to use atmospheric solids analysis probe mass spectrometry (ASAP-MS) to very rapidly and reliably identify indigo colorants tiny amounts in ancient historic fabrics without any sample preparation. The ionization in ASAP experiments is effected by Penning ionization or by the transfer of protons originating from protonated clusters of water. Dr. René Csuk is Professor of organic bioorganic chemistry at the Martin-Luther Universität Halle-Wittenberg (Halle, Germany). His main research interests are in organic and medicinal chemistry, chemical biology and phytochemistry. Graphical Abstract: Historical samples can be investigated conveniently using ASAP®-MS experiments. ASAP®-MS allowed for rapid direct sampling without any preparation of the sample prior to its measurements, and reliable results were generated in less than 1 minute. As demonstrated for indigoid-type dyes, the efficacy of ASAP®-MS analysis is independent of the type of fiber, the age of the sample, the workmanship, and the state of preservation.

Direct characterization of polyurethanes and additives by atmospheric solid analysis probe with time-of-flight mass spectrometry (ASAP-TOF-MS).

Because of the wide range of formulations, polyurethanes (PURs) are among the most used copolymers. According to their applications, the nature and concentration of the monomers, as well as the additives, are adjusted. As copolymer, this material is difficult to characterize directly by mass spectrometry without sample pretreatment. In this work, atmospheric solid analysis probe mass spectrometry (ASAP-MS) is used to characterize model and commercial PURs with different formulations. Application of a temperature gradient over the ASAP probe allows a soft vaporization of all sample components: additives are detected at lower gas temperature, whereas the polymer is detected at higher gas temperature. Thus, a temporal separation of the molecules as a function of their volatilization and/or degradation temperature is observed. The vaporized products are identified by ASAP thanks to pyrolysis, but also by low energy source fragmentation observed during the analysis. Thus, complete analysis of PURs with only a single time-of-flight (TOF) mass analyzer is realized. The ability of ASAP-MS for differentiation of different chemical structures of PURs (polyester and polyether based PURs) is demonstrated; the main advantage of this technique being that the analysis is performed in one step, directly on the crude polymer.

Rapid characterization of heteroatomic molecules in a bio-oil from pyrolysis of rice husk using atmospheric solids analysis probe mass spectrometry

Bio-oil from pyrolysis of rice husk (RHBO) was investigated using a time-of-flight mass spectrometer equipped with an atmospheric solids analysis probe ion source to afford rapid and accurate characterization of molecular information. RHBO was sequentially extracted with n-hexane, tetrachloromethane, benzene, dichloromethane, trichloromethane and ethyl acetate in order of increasing solvent polarity to acquire extracts E1 to E6. Heteroatomic species, especially oxygen-containing compounds, in the extracts were well characterized and statistically compared. Solvents with low polarity inclined to extract species with relative low molecular mass and low polarity from RHBO. There were amounts of lignin monomers identified in the extracts and most of them contained 1∼4 oxygen atoms, which was consistent with the acidity of bio-oil due to the existence of phenolic OH inside. Species with molecular mass over 500Da were detected with around 5% of relative content, which could not be revealed by other analytical methods such as gas chromatography/mass spectrometry.

Molecular characterization of heteroatomic compounds in a high-temperature coal tar using three mass spectrometers

A high-temperature coal tar (HTCT) was extracted by petroleum ether (PE) and the extract (denoted by PE-HTCT) was characterized using three mass spectrometers to obtain and compare molecular compositional information. Gas chromatography/mass spectrometry detected molecules with low molecular weight and polarity such as hydrocarbons. A time-of-flight MS coupled with an atmospheric solids analysis probe ion source realized rapid and in-situ analysis of compounds with mid-polarity in PE-HTCT without sample pretreatment. An electrospray ionization (ESI) Orbitrap MS was used to characterize heteroatom-containing compounds in PE-HTCT. Most heteroatomic species identified by ESI-Orbitrap MS contained oxygen, nitrogen, or both atoms, and the total percentage of both Oo and Nn species was approximate 13%. Ketene and furan derivatives were identified in Oo class, as well as aliphatic amine compounds, azoles, aniline and pyridine derivatives for Nn class. The combination of three mass spectrometers gave a detailed characterization of coal tar and provided a full view of the corresponding constituents.

Rapid analysis of forensic samples using an atmospheric solid analysis probe interfaced to a linear ion trap mass spectrometer.

This paper highlights the simplicity of interfacing an Atmospheric Solid Analysis Probe (ASAP) to a Linear Ion Trap Mass Spectrometer and shows that this technique can be used for the rapid generation of high-quality data from a range of sample types with minimal or no sample preparation. For a solid sample or surface deposit, the process entails rubbing a capillary melting tube a few times on the sample to transfer material to the capillary surface and then introducing it into the source of the mass spectrometer. Similarly, for a liquid sample, a capillary tube is dipped into the sample to just coat the surface or a few microliters may be applied to the tip of a capillary before being analyzed by Atmospheric Pressure Chemical Ionization in both positive and negative mode. A rodenticide containing brodifacoum, black tar heroin and its impurities (morphine, codeine, noscapine, papaverine, and monoacetylmorphine), crack cocaine and 1-methylaminoanthraquinone dyestuff were successfully analyzed directly without any sample preparation. All compounds were detected using full scan mass spectrometry (MS), followed by confirmation by MS/MS. Preliminary results suggest that this technique could be used for quantitation. Interfacing the ASAP to an ion trap mass spectrometer allows the ability to perform full scan, MS(n) experiments, and rapid positive/negative switching from a single sample introduction. Because of these features, this instrument is very useful for rapid, routine analysis and for confirmation with the use of in-house MS/MS libraries.