Pressure Chemical Ionization Mass Spectrometry Research Articles

Temperature dependent stochastic dynamics mass spectrometric analysis of configurationally locked polyenes

This paper derived relation between mass spectrometric variable intensity of analyte peaks and three-dimensional molecular structures of ions toward temperature utilising innovative stochastic dynamics equations, which provide exact analyte quantification and 3D structural analysis and are attractive formulas for modelling of mass spectrometric phenomena. The same equations are opened to develop new relations accounting for temperature; thus, providing argumentation about temperature dependent variables. High-temperature measurement of vapours are important tool, amongst others and use the Arrhenius’s plot. However, there is a variation between experimental and theoretical linear correlation toward temperature; thus, highlighting soft ionisation methods showing significant standard deviations. It could be explained with temperature perturbation of charge values. Descriptive models, so far, provide semi-quantification. This study, first shows validity of new functional model. Straightforwardly, its empirical proof is obtained determining 3D structurally protomers and isotopomers of configurationally locked polyenes via ultra-high resolution electrospray ionization and atmospheric pressure chemical ionization mass spectrometry within the temperature range T=300-450°C. There are used high accuracy quantum chemical static methods, molecular dynamics and chemometrics. There are excellent method performances (|r|=0.99978). The tool could be regarded as an actually honest alternative of available theoretical models.

The role of water in APCI-MS online monitoring of gaseous n-alkanes

In atmospheric pressure chemical ionization mass spectrometry (APCI-MS), [M−3H+H2O]+ ions can deliver analyte-specific signals that enable direct analysis of volatile n-alkane mixtures. The underlying ionization mechanisms have been the subject of open debate, and in particular the role of water is insufficiently clarified to allow for reliable process analytics when the humidity level changes over time. This can be a problem, particularly in online monitoring, where analyte accumulation in the ion source can also occur. Here, we investigated the role of water during APCI-MS of volatile n-alkanes by changing the carrier gas for sample injection from a dry to a wetted state as well as by using 18O-labeled water. This allowed for a distinction between gaseous and surface-adsorbed water molecules. While adsorbed water seems to be responsible for the desired [M−3H+H2O]+ signals through surface reactions with the analyte molecules, gaseous water was found to promote the formation of CnH2n+1O+ of different (and analyte-independent) hydrocarbons, revealing a reaction with hydrocarbon species which accumulated in the ion source during continuous operation. At the same time, gaseous water competed with analyte molecules for ionization and thus suppressed the formation of alkyl (CnH2n+1+) and alkenyl (CnH2n−1+) ions. The results reveal a memory effect due to hydrocarbon adsorption, which may cause severe interpretation difficulties when the ionization chamber undergoes sudden humidity changes. The use of [M−3H+H2O]+ for n-alkane analysis in alkane/water mixtures can be facilitated by constantly maintaining high humidity and hence stabilizing the ionization conditions.Graphical abstract

Nanoelectrode Atmospheric Pressure Chemical Ionization Mass Spectrometry.

A small ionization needle with an ultrasharp, ultrafine tip is introduced. It is lab-fabricated from tungsten wire and serves as a corona discharge emitter in nanoelectrode atmospheric pressure chemical ionization mass spectrometry (nAPCI-MS). Tip radii ranged from 8 to 44 nm, up to 44× smaller than the sharpest previously reported corona needle. Because of this, nAPCI was able to operate at +1.0 kV with no auxiliary counter electrode. Alternatively, at +1.2 kV, nAPCI could be enclosed in a small plastic assembly for headspace analysis with a sampling tube attachment as long as 15 m. No added heat or gas flow was necessary. The efficacy of nAPCI-MS was demonstrated through needle durability studies and direct analysis of vapors from real-world samples. Provisional identifications include ibuprofen from a pharmaceutical tablet, albuterol aerosol sprayed from a medical inhaler, cocaine from paper currency, caffeine from a fingertip, and bisphenol E from a paper receipt.

Development and Validation of a Rapid and Sensitive LC-APCI-MS/MS Method for the determination of three N-nitrosamine impurities in Varenicline tartrate drug substance and drug products

Nitrosamines impurities may be present in low levels in a variety of products that people are exposed to every day. After thorough investigations, regulatory agencies have outlined that the formation of nitrosamines is possible in the presence of secondary, tertiary, or quaternary amines and nitrite salts under acidic reaction conditions. For safety purpose, all API manufacturers must be developed methods to monitor the low levels of each nitrosamine impurity before the release the individual batches. In this article, we have developed novel, rapid and sensitive liquid chromatography Atmospiric pressure chemical ionization Mass spectroscopy (LC-APCI-MS/MS) method for the determination of N-Nitroso Dimethylamine (NDMA), N-Nitroso Diethylamine (NDEA) and N-Nitroso varenicline impurities in the Varenicline Tartrate drug substance and Drug products. Chromatographic separation is achieved using Inert sustain AQ C18 150 × 4.6mm, 3.0μ column with 0.1% formic acid in water as mobile phase A and 0.1% formic acid in methanol as mobile phase B at the 0.6 mL/min flow rate by using gradient mode of elution upto the 25 minutes total run time. The three impurities are successfully ionized and quantified in positive mode of atmospheric pressure chemical ionization (APCI) using multiple reaction monitoring (MRM). This method was validated according to ICH Q2 (R1) guidelines. The method provided excellent S/N ratios with a high linearity range of 0.66-19.88 ppm with respect to Varenicline Tartrate sample concentrations with a regression coefficient >0.995. The recovery for the method was established with a protocol of three-step sample preparation and was satisfactory within 85-115%. The determined LOQ (0.66 ppm) and LOD (0.22 ppm) values are very low with respect to sample concentration which shows the sensitivity Performance of the method. The method can be routinely applied for the detection of N-nitrosamine impurities (NDMA, NDEA and N-Nitroso varenicline) in Varenicline Tartrate drug substance and Drug products.

Detection of lard adulteration in 3 kinds of vegetable oils by liquid chromatography-mass spectrometry with porous graphite carbon column.

Liquid chromatography‒mass spectrometry employing porous graphite carbon columns and an n-octane-isopropanol mobile phase was utilized for the separation of triacylglycerols (TAGs) in various edible oils, aiming to identify lard adulteration in soybean, corn, and sunflower seed oils. Experiments were conducted using a Hypercarb column (2.1mm × 100mm, 5µm) and an n-octane-isopropanol (70:30, V/V) mobile phase at a flow rate of 0.25mL· min-1 and a column temperature of 60°C. Detection was achieved through atmospheric pressure chemical ionization-mass spectrometry. Analysis of diverse edible oil samples revealed that oils of the same type shared similar TAG compositions, while different types exhibited distinct TAG profiles. Distinct variations in triglyceride composition were observed across different edible oils. Based on liquid chromatography‒mass spectrometry analysis, the characteristic component 1-stearic acid-2-palmitic acid-3-oleic acid glyceride (SPO), which may also include PSO, was identified in lard through principal component analysis and orthogonal partial least squares discriminant analysis. This component served as a marker for detecting as low as 0.1% lard adulteration in soybean, corn, and sunflower seed oils. The technique offers a precise and effective approach for the identification of lard adulteration in these edible oils.

On-site monitoring of nandrolone in cattle farming samples by portable atmospheric pressure chemical ionization mass spectrometry with ambient sampling

Nandrolone (NT) is a type of androgen anabolic steroid that is often illegally used in cattle farming, leading to unpredictable harm to human health via the food chain. In this study, a rapid detection method for NT in the samples of cattle farming was established using a portable mass spectrometer. The instrument parameters were optimized, including a thermal desorption temperature of 220 °C, a pump speed of 30 %, an APCI ionization voltage of 3900 v, and an injection volume of 6 μL. The samples of bovine urine, feed, sewage, and tissue were selected, and extracted using a solution of methanol:acetonitrile (1:1, v/v), followed by spiking a NT standard solution (1000 ng·mL−1) and ionization through the APCI ion source for detection. The results showed that NT could not be detected in beef and feed due to the complexity of the matrix, while clear signals of NT ions were observed in bovine urine and sewage samples, with LODs of 1000 and 100 ng·mL−1, respectively. Furthermore, quantitative analysis was attempted, and a good linear relationship (R2 = 0.9952) was observed for NT in sewage within the range of 100 to 1000 ng·mL−1. At spiked levels of 100, 500, 1000 and 2000 ng mL−1, the recovery rates ranged from 74.3 % to 92.8 %, with a relative standard deviation (n = 6) of less than 15 %. In conclusion, this detection method offers the advantages of simplicity, rapidity, strong timeliness, and specificity, making it suitable for on-site detection. It can be used for qualitative screening of nandrolone in bovine urine and quantitative analysis of nandrolone in sewage.

Rapid online analysis of n-alkanes in gaseous streams via APCI mass spectrometry.

Online monitoring of dynamic chemical processes involving a wide volatility range of hydrocarbon species is challenging due to long chromatographic measurement times. Mass spectrometry (MS) overcomes chromatographic delays. However, the analysis of n-alkane mixtures by MS is difficult because many fragment ions are formed, which leads to overlapping signals of the homologous series. Atmospheric pressure chemical ionization (APCI) is suitable for the analysis of saturated hydrocarbons and is the subject of current research. Still, although APCI is a "soft ionization" technique, fragmentation is typically inevitable. Moreover, it is usually applied for liquid samples, while an application for online gas-phase monitoring is widely unexplored. Here, we present an automated APCI-MS method for an online gas-phase analysis of volatile and semi-volatile n-alkanes. Mass spectra for n-heptane and n-decane reveal [M-H]+, [M-3H]+ and [M-3H+H2O]+ as abundant ions. While [M-H]+ and [M-3H]+ show an excessive fragmentation pattern to smaller CnH2n+1+ and CnH2n-1+ cations, [M-3H+H2O]+ is the only relevant signal within the CnH2n+1O+ ion group, i.e., no chain cleavage is observed. This makes [M-3H+H2O]+ an analyte-specific ion that is suitable for the quantification of n-alkane mixtures. A calibration confirms the linearity of C7 and C10 signals up to concentrations of ~1000-1500 ppm. Moreover, validated concentration profiles are measured for a binary C7/C10 mixture and a five-alkane C7/C10/C12/C14/C20 mixture. Compared to the 40-min sampling interval of the reference gas chromatograph, MS sampling is performed within 5 min and allows dynamic changesto be monitored.

Ionization behaviors of nitrotoluenes and dinitrotoluenes by reactions with acetone-related reactant ion.

Dinitrotoluenes (DNTs) and nitrotoluenes (NTs) are found in the environment as metabolites of trinitrotoluene (TNT). When acetone is used as the solvent/eluent in atmospheric pressure chemical ionization-mass spectrometry (APCI-MS), the reactant ion is [2Acetone + O2 ]•- for the negative ion mode. The reactant ion reacts with an analyte to produce M•- and/or [M - H]- under atmospheric pressure. In this study, ionization behaviors of NT (2-, 3-, and 4-NTs) and DNT isomers (2,3-, 2,4-, and 2,6-DNTs) by reactions with [2Acetone + O2 ]•- were investigated. The energy-minimized structures of the product ions and their energies were calculated to explain the differences in the ionization behaviors. Typical NT- and DNT-related ions were produced by reactions with [2Acetone + O2 ]•- ; NT•- , [NT - H]- , DNT•- , [DNT - H]- , and [DNT - NO]- ions. The ionization efficiencies of NT- and DNT-related ions increased by increasing the source fragmentor voltage, and those of DNT-related ions were higher than those of the NT-related ions owing to the presence of an additional nitro group. The ionization efficiency of 3-NT•- was higher than that of [NT - H]- , while that of [DNT - H]- was higher than those of DNT•- and [DNT - NO]- . The ionization efficiency order of NT•- was 3-NT > 4-NT > 2-NT, while that of [DNT - H]- was 2,4-DNT > 2,6-DNT > 2,3-DNT. The [NT - H]- and [DNT - H]- ions were stabilized by resonance structures containing nitro groups. The [DNT - NO]- ions were formed through the transition state.

Selective Characterization of Olefins by Paternò-Büchi Reaction with Ultrahigh Resolution Mass Spectrometry.

Petroleum olefins play important roles in various secondary processing procedures and are important feedstocks for the modern organic chemical industry. It is quite challenging to analyze petroleum olefins beyond the gas chromatography (GC)-able range using mass spectrometry (MS) due to the difficulty of soft ionization and the matrix complexity. In this work, a Paternò-Büchi (PB) reaction combined with atmospheric pressure chemical ionization and ultrahigh resolution mass spectrometry (APCI-UHRMS) was developed for selective analysis of olefins. Through the PB reaction, C═C bonds were transformed into four-membered rings of oxetane with improved polarity so that soft ionization of olefins could be achieved. The systematic optimization of PB reaction conditions, as well as MS ionization conditions, ensured a high reaction yield and a satisfied MS response. Furthermore, a sound scheme was set up to discriminate the coexisting unsaturated alkanes in complex petroleum, including linear olefins, nonlinear olefins, cycloalkanes, and aromatics, making use of their different behaviors during the PB reaction and chemical ionization. The developed strategy was successfully applied to the analysis of olefins in fluid catalytic cracking oil slurry, a complex heavy oil sample. This method extended the characterization of petroleum olefins from lower to higher with high efficiency and selectivity to provide a comprehensive molecular library for heavy petroleum samples and process optimization.

TLC and HPTLC-APCI-MS for the rapid discrimination of plant resins frequently used for lacquers and varnishes by artists and conservators.

Depending on their terpenoid and phenolic constituents plant resins can be classified as diterpenoid, triterpenoid or phenolic resins; thereby the profile of diterpenes and triterpenes is considered as genus- or even species-specific. We aimed to develop a simple, rapid, inexpensive, sensitive and specific method for the identification of resin-specific triterpenoid and phenolic compounds in plant resins using (HP)TLC [(high-performance) thin-layer chromatography] combined with APCI-MS (atmospheric pressure chemical ionisation mass spectrometry) and post-chromatographic detection reactions. Twenty resin samples from different plant species were analysed. Different extraction procedures, post-chromatographic detection reagents as well as various sorbents and solvents for planar chromatography were tested. To evaluate the potential of the optimised (HP)TLC-APCI-MS methods, parameter such as limit of detection (LOD) was determined for selected marker compounds. Our protocol enabled qualitative analyses of chemotaxonomic molecular markers in natural resins such as dammar, mastic, olibanum and benzoin. For the first time, the application of thionyl chloride-stannic chloride reagent for a specific post-chromatographic detection of triterpenes is reported, sometimes even allowing discrimination between isomers based on their characteristic colour sequences. For triterpene acids, triterpene alcohols and phenolic compounds, detection limits of 2-20ng/TLC zone and a system precision with a relative standard deviation (RSD) in the range of 3.9%-7.0% were achieved by (HP)TLC-APCI-MS. The applicability of the method for the analysis of resin-based varnishes was successfully tested on a mastic-based varnish. Thus, the method we propose is a helpful tool for the discrimination of resins and resin-based varnishes with respect to their botanical origin.

Determination of astaxanthin and astaxanthin esters in three samples of shrimp waste (Parapenaeus longirostris) by high performance liquid chromatography coupled photo-diode array and mass spectrometry detection

The present study aimed to identify the content of astaxanthin and its esterified forms using high-performance liquid chromatography coupled with diode array and atmospheric pressure chemical ionisation mass spectrometry detection in three samples of shrimp waste. The analyses revealed twenty-one astaxanthin derivatives, including astaxanthin in free form, across all three extracts with the highest number of derivatives observed in the head extract. The shell extract had a lower content of astaxanthin and its esterified forms, with monoesterified astaxanthins being the major components, with contents ranging from 0.5–1 mg g−1. On the other hand, in both global waste and head extracts, astaxanthin diesters were found to be the dominant bioactive compounds, with contents ranging from 0.7–5.2 mg g−1 and 10.2–18.2 mg g−1, respectively. Notably, the astaxanthin content extracted from head was significantly higher compared to other extracts, indicating its potential as a valuable source of bioactive compounds.

Determination of the Pesticides Ethoprophos and Atrazine in Water by T-Shaped Atmospheric Pressure Chemical Ionization (APCI) Mass Spectrometry (MS)

With the goal of enhancing the low sensitivity of the conventional atmospheric pressure chemical ionization (APCI) source due to the ion divergence, here is reported a T-shaped ion source to improve the sensitivity with a portable mass spectrometer for the rapid determination of the pesticides ethoprophos and atrazine in water. Compared with conventional APCI, the ion source improves the sensitivity for the analytes. The results show that the analysis requires less than 2 s, the limit of detection (LOD) is better than 0.1 and the relative standard deviation (RSD) is 16% at 1, 5, and 25 The recoveries of the analytes are between 80% and 130%, meeting the requirements for rapid pesticide determination in water.

The uropygial gland of the Great Cormorant (Phalacrocorax carbo): II. Biochemical analysis of the uropygial secretion

In contrast to many other water birds, the Great Cormorant, Phalacrocorax carbo (Phalacrocoracidae), shows a typical wing-spreading behavior after diving. This behavior has been linked to the partial wettability of the Cormorant’s feathers based on the unusual structure of the contour feathers. Close to the rachis, these feathers have a closed vane with very densely spaced barbs but have an open vane in more peripheral feather parts. To investigate whether the wettability is connected to the composition of the uropygial gland secretion that is often linked to water repellency of bird feathers, we analyzed the gland secretions of the Great Cormorant and, for comparison, of the Muscovy Duck, Cairina moschata (Anatidae). Using the mass spectrometry techniques, atmospheric solids analysis probe-atmospheric pressure chemical ionization-mass spectrometry (ASAP-APCI-MS) and gas chromatography/mass spectrometry (GC/MS), significant differences in the chemical composition of the secretions were revealed. The Cormorant showed a highly diverse mixture of more than 1000 compounds consisting of methyl-branched aliphatic carboxylic esters with large chain length variability. In contrast, the duck’s secretion is dominated by the two esters octadecyl and eicosyl 2,4,6-trimethyloctanoate. Water contact angle measurements of the secretions showed that the secretion of the Muscovy Duck has higher water repellency than that of the Great Cormorant. Nevertheless, contact angle measurements of feathers before and after removing of feather waxes indicate that these waxes, likely consisting of the uropygial gland secretions, did not influence water repellency of the feathers to a large degree.

Silver Ion High-Performance Liquid Chromatography-Atmospheric Pressure Chemical Ionization Mass Spectrometry: A Tool for Analyzing Cuticular Hydrocarbons.

Aliphatic hydrocarbons (HCs) are usually analyzed by gas chromatography (GC) or matrix-assisted laser desorption/ionization (MALDI) mass spectrometry. However, analyzing long-chain HCs by GC is difficult because of their low volatility and the risk of decomposition at high temperatures. MALDI cannot distinguish between isomeric HCs. An alternative approach based on silver ion high-performance liquid chromatography (Ag-HPLC) is shown here. The separation of HC standards and cuticular HCs was accomplished using two ChromSpher Lipids columns connected in series. A gradient elution of the analytes was optimized using mobile phases prepared from hexane (or isooctane) and acetonitrile, 2-propanol, or toluene. HCs were detected by atmospheric pressure chemical ionization mass spectrometry (APCI-MS). Good separation of the analytes according to the number of double bonds, cis/trans geometry, and position of double bonds was achieved. The retention times increased with the number of double bonds, and trans isomers eluted ahead of cis isomers. The mobile phase significantly affected the mass spectra of HCs. Depending on the mobile phase composition, deprotonated molecules, molecular ions, protonated molecules, and various solvent-related adducts of HCs were observed. The optimized Ag-HPLC/APCI-MS was applied for characterizing cuticular HCs from a flesh fly, Neobellieria bullata, and cockroach, Periplaneta americana. The method made it possible to detect a significantly higher number of HCs than previously reported for GC or MALDI-MS. Unsaturated HCs were frequently detected as isomers differing by double-bond position(s). Minor HCs with trans double bonds were found beside the prevailing cis isomers. Ag-HPLC/APCI-MS has great potential to become a new tool in chemical ecology for studying cuticular HCs.

Positive Effect of Acetylation on Proteomic Analysis Based on Liquid Chromatography with Atmospheric Pressure Chemical Ionization and Photoionization Mass Spectrometry.

A typical bottom-up proteomic workflow comprises sample digestion with trypsin, separation of the hydrolysate using reversed-phase HPLC, and detection of peptides via electrospray ionization (ESI) tandem mass spectrometry. Despite the advantages and wide usage of protein identification and quantification, the procedure has limitations. Some domains or parts of the proteins may remain inadequately described due to inefficient detection of certain peptides. This study presents an alternative approach based on sample acetylation and mass spectrometry with atmospheric pressure chemical ionization (APCI) and atmospheric pressure photoionization (APPI). These ionizations allowed for improved detection of acetylated peptides obtained via chymotrypsin or glutamyl peptidase I (Glu-C) digestion. APCI and APPI spectra of acetylated peptides often provided sequence information already at the full scan level, while fragmentation spectra of protonated molecules and sodium adducts were easy to interpret. As demonstrated for bovine serum albumin, acetylation improved proteomic analysis. Compared to ESI, gas-phase ionizations APCI and APPI made it possible to detect more peptides and provide better sequence coverages in most cases. Importantly, APCI and APPI detected many peptides which passed unnoticed in the ESI source. Therefore, analytical methods based on chymotrypsin or Glu-C digestion, acetylation, and APPI or APCI provide data complementary to classical bottom-up proteomics.

Constraining the Reaction Rate of Criegee Intermediates with Carboxylic Acids during the Multiphase Ozonolysis of Aerosolized Alkenes

Criegee intermediates (CIs) are central to the ozonolysis of unsaturated organic compounds, controlling the formation of small fragmentation reaction products and higher molecular weight oligomeric compounds through competing unimolecular and bimolecular pathways. In particular, the reaction of thermalized CI with carboxylic acids (RCOOH) to produce oligomeric α-acyloxyalkyl hydroperoxides (AAHPs) is of interest to the chemical transformation of organic compounds in the atmosphere. In the gas phase, the CI + RCOOH reaction proceeds at supercollisional rates, consistent with a barrierless reaction mechanism. However, the rate of this reaction in condensed phases remains uncertain. Here, we report the results of aerosol flow tube studies of the ozonolysis of submicron organic aerosol containing mixtures of an internal n-alkene (Z-9-tricosene, tri) and a saturated acid (2-hexyldecanoic acid, HDA). The decay of the reactants and formation of reaction products are monitored using atmospheric pressure chemical ionization mass spectrometry (APCI–MS). A 6-fold decrease in the reactive uptake of ozone is observed with increasing acid concentration, consistent with a previous study using alcohol additives. The decay of HDA with ozone exposure shows that HDA scavenges CIs at rates comparable to competing unimolecular pathways involving CIs. The decay kinetics of HDA are analyzed using a simple kinetic model in order to constrain the ratio of the CI + RCOOH and unimolecular CI rate constants. Empirical fitting to this model, combined with theoretical estimates of the unimolecular loss rate, yields a CI + RCOOH rate constant of 1.85 ± 0.27 × 10–19 cm3 molec–1 s–1, which is six orders of magnitude slower than the expected diffusion limit in a liquid organic matrix. Stochastic kinetic simulations are conducted with different values of the CI + RCOOH rate constant to validate this result and show that the diffusion-limited rate is indeed much too rapid to reproduce the experimental results.

A pilot study of the association between maternal mid-pregnancy cholesterol and oxysterol concentrations and labor duration

BackgroundPrevious animal model studies have highlighted a role for cholesterol and its oxidized derivatives (oxysterols) in uterine contractile activity, however, a lipotoxic state associated with hypercholesterolemia may contribute to labor dystocia. Therefore, we investigated if maternal mid-pregnancy cholesterol and oxysterol concentrations were associated with labor duration in a human pregnancy cohort.MethodsWe conducted a secondary analysis of serum samples and birth outcome data from healthy pregnant women (N = 25) with mid-pregnancy fasting serum samples collected at 22–28 weeks of gestation. Serum was analyzed for total-C, HDL-C, and LDL-C by direct automated enzymatic assay and oxysterol profile including 7α-hydroxycholesterol (7αOHC), 7β-hydroxycholesterol (7βOHC), 24-hydroxycholesterol (24OHC), 25-hydroxycholesterol (25OHC), 27-hydroxycholesterol (27OHC), and 7-ketocholesterol (7KC) by liquid chromatography-selected ion monitoring-stable isotope dilution-atmospheric pressure chemical ionization-mass spectroscopy. Associations between maternal second trimester lipids and labor duration (minutes) were assessed using multivariable linear regression adjusting for maternal nulliparity and age.ResultsAn increase in labor duration was observed for every 1-unit increment in serum 24OHC (0.96 min [0.36,1.56], p < 0.01), 25OHC (7.02 min [1.92,12.24], p = 0.01), 27OHC (0.54 min [0.06, 1.08], p < 0.05), 7KC (8.04 min [2.7,13.5], p < 0.01), and total oxysterols (0.42 min [0.18,0.06], p < 0.01]. No significant associations between labor duration and serum total-C, LDL-C, or HDL-C were observed.ConclusionsIn this cohort, mid-pregnancy concentrations of maternal oxysterols (24OHC, 25OHC, 27OHC, and 7KC) were positively associated with labor duration. Given the small population and use of self-reported labor duration, subsequent studies are required for confirmation.

Effect of sweeteners and carbonation on aroma partitioning and release in beverage systems

The effect of monosaccharides (glucose, fructose and galactose) and disaccharides (sucrose and lactose) at 10, 20 and 30 % w/v on the in-vitro aroma partitioning of C4 – C10 aldehydes and ethyl esters, as well as limonene (concentration of aroma compounds at 1 μg mL−1), was studied using atmospheric pressure chemical ionisation–mass spectrometry. An increase in sugar concentration from 0 to 30 % w/v resulted in a significant increase in partitioning under static headspace conditions for the majority of the compounds (p < 0.05), an effect generally not observed when 10 % w/v sucrose was substituted with low-calorie sweeteners (p > 0.05). The complexity of the system was increased to model a soft drink design – comprising water, sucrose (10, 20 and 30 % w/v), acid (0.15 % w/v), carbonation (∼7.2 g/L CO2) and aroma compounds representative of an apple style flavouring, namely ethyl butanoate and hexanal (10 μg mL−1 each). Although the addition of sucrose had no significant in-vivo effect, carbonation significantly decreased breath-by-breath (in-vivo) aroma delivery (p < 0.05). To understand the physical mechanisms behind aroma release from the beverage matrix, the effect of sucrose on the kinetics of the matrix components was explored. An increase in sucrose concentration from 0 to 30 % w/v resulted in a significant decrease in water activity (p < 0.05), which accounted for the significantly slower rate of self-diffusion of aroma compounds (p < 0.05), measured using diffusion-ordered spectroscopy–nuclear magnetic resonance spectroscopy. No significant effect of sucrose on carbon dioxide volume flux was found (p > 0.05).

Deprotonation of trinitrotoluene by dichloromethane in atmospheric pressure chemical ionization mass spectrometry.

Trinitrotoluene (TNT) and its derivatives are found in the environment. Depending on the analysis conditions, TNT may be detected as a deprotonated molecule or a molecular ion through atmospheric pressure chemical ionization (APCI). Dichloromethane (CH2 Cl2 ) is used as an extraction solvent for TNT from environmental samples and as an ionizing agent to generate chlorinated species. APCI mass spectra of TNT dissolved in CH2 Cl2 revealed the presence of only the [TNT - H]- ion. This phenomenon was investigated by reactions with the CH2 Cl2 -related reactant ions. TNT in CH2 Cl2 was ionized through APCI, and CH2 Cl2 and acetone were used as the eluent. The vaporizing temperature was varied from 200 to 350°C. TNT-related ions and reactant ions were analyzed. Detection limits for TNT were determined under different conditions. Energy-minimized structures of the product ions were used to interpret the analysis results. Significant [TNT - H]- ion was observed, but the [TNT + Cl]- and TNT•- ions were not detected. The [HCl + Cl]- and [3acetone + Cl]- ions were detected as reactant ions when using CH2 Cl2 and acetone as eluent, respectively. Other potential reactant ions such as CH2 Cl2 •- and [CH2 Cl2 + Cl]- were not observed. The detection limit improved as the vaporizing temperature increased. The favorability of [TNT - H]- formation was explained on the basis of the heats of reactions. The [TNT - H]- ion was primarily produced by the deprotonation reaction between CH2 Cl2 •- and neutral TNT. This reaction was determined to be significantly exothermic. CH2 Cl2 can be helpful for the analysis of TNT in environmental samples through APCI mass spectrometry.

Group 6 germylidyne complexes in the gas phase by LIFDI and APCI mass spectrometry.

Although showing fascinating chemical properties and reactivity in solution, heavier tetrelylidyne complexes with M≡E triple bonds have not been studied in the gas phase before due to their high sensitivity towards air and moisture. We selected four group 6 germylidyne complexes, [Cp(PMe3)2M≡GeArMes] (M = Mo (1-Mo), W (1-W), ArMes = 2,6-dimesitylphenyl) and [Tp'(CO)2M≡GeArMes] (M = Mo (2-Mo), W (2-W), Tp' = κ3-N,N',N''-hydridotris(3,5-dimethylpyrazolyl) borate), for a mass-spectrometric study. Liquid Injection Field Desorption Ionization (LIFDI) proved to be a well-suited technique to ionize these sensitive compounds as the spectra show the molecular ions as radical cations and only minor traces of fragmentation or degradation products. In addition, Atmospheric Pressure Chemical Ionization (APCI) connected to a high-resolving tandem mass spectrometer allowed us to study the gas-phase fragmentation behaviour of these compounds. The fragmentation patterns not only comprise the expected losses of phosphane or carbonyl ligands, respectively, but also indicate C-H bond activation by the electron-deficient metal centre. An enhanced reactivity of the tungsten species is visible in a preferred methyl abstraction in the phosphane complex 1-W compared to 1-Mo. Although degradation in solution before ionization obviously can destroy the M≡Ge triple bond, the cleavage of the M≡Ge bond upon gas-phase activation is not observed for the Mo species and only as a minor pathway for the W compounds, highlighting the high bonding energy between metal and tetrel.