Pressure Chemical Ionization Mass Spectrometry Research Articles

Rapid Analysis of Theaflavins by High Performance Liquid Chromatography / Atmospheric Pressure Chemical Ionization-Mass Spectrometry

A 10 cm x 4.6 mm i.d. SilicaROD RP-18 HPLC column coupled with isocratic elution with a solvent system of acetonitrile-2% acetic acid or acetonitrile-1% citric acid were used to analyze purchased theaflavin mixtures and theaflavin extracts from black tea. Individual theaflavins were well separated and the analysis of theaflavins was achieved in 10 min using this method. HPLC coupled with Atmospheric Pressure Chemical Ionization-Mass Spectrometry (APCI-MS) in the positive ion mode was used to identify individual theaflavins. Quasi-molecular ions and many structural characteristic fragment ions were observed in the mass spectra. Possible fragmentation pathways from the protonated theaflavins were also proposed.

Regioisomeric and enantiomeric analysis of primary triglycerides in human milk by silver ion and chiral HPLC atmospheric pressure chemical ionization-MS

Triglycerides (TG) not only provide energy for infants but have important physiological functions. Understanding the composition and structure of TG in human milk is conducive to the development of infant formulas. In this study, TG species in human milk from 3 provincial capitals (Zhengzhou, Wuhan, and Harbin) in different regions of China were determined through C18 HPLC electrospray ionization tandem mass spectrometry (MS). The results showed that in human milk from these 3 regions, oleoyl-palmitoyl-linoleoylglycerol (OPL; 16.55, 19.20, and 18.67%, respectively) was more abundant than oleoyl-palmitoyl-oleoylglycerol (OPO; 10.08, 10.22, and 12.03%, respectively). Subsequently, regioisomeric and enantiomeric analysis of main TG in the human milk were performed on silver ion and chiral HPLC atmospheric pressure chemical ionization mass spectrometry (APCI)-MS, respectively. The results showed that rac-OPL (above 85%), rac-OPO (above 85%), rac-palmitoyl-oleoyl-oleoylglycerol (PPO; above 90%), and rac-OLaO (above 70%) were the main regioisomers of OPL, OPO, PPO, and lauroyl-oleoyl-oleoylglycerol (LaOO), respectively. The relative ratios of enantiomer pairs of rac-OPL (rac-OPL1 and rac-OPL2) were about 37 and 63%, respectively.

Fragmentation of Saturated Hydrocarbons upon Atmospheric Pressure Chemical Ionization Is Caused by Proton-Transfer Reactions.

Chemical characterization of complex mixtures of large saturated hydrocarbons is critically important for numerous fields, including petroleomics and renewable transportation fuels, but difficult to achieve. Atmospheric pressure chemical ionization (APCI) mass spectrometry has shown some promise in the analysis of saturated hydrocarbons. However, APCI causes extensive fragmentation to these compounds, which impedes its effectiveness. To prevent this fragmentation, its causes were examined via gas-phase ion-molecule reactions in vacuum in a linear quadrupole ion trap mass spectrometer. The results demonstrate that the mechanism proposed previously for ionization of saturated hydrocarbons upon APCI, hydride abstraction by carbocation reagent ions, is not correct. Instead, the fragmentation is caused by ionization of saturated hydrocarbons via exothermic proton-transfer reactions involving highly acidic, protonated atmospheric molecules, such as nitrogen and water. Accordingly, the extent of fragmentation was found to correlate with the proton affinities of the atmospheric molecules studied. Remarkably, controlled experiments involving isolated atmospheric ions and neat saturated hydrocarbons in vacuum yielded almost identical mass spectra as APCI involving atmospheric pressure conditions, the presence of many different chemicals, and an electrical discharge. In order to prevent or reduce the extent of fragmentation of saturated hydrocarbons upon APCI, and therefore enable accurate mass spectrometric characterization of complex mixtures of saturated hydrocarbons, the ion source should be purged of air to remove nitrogen and water and fill it with an inert gas with a substantially lower proton affinity.

Temperature-programmed capillary high-performance liquid chromatography with atmospheric pressure chemical ionization mass spectrometry for analysis of fatty acid methyl esters.

A new capillary high-performance liquid chromatography method with atmospheric pressure chemical ionization mass spectrometry was developed for the analysis of fatty acid methyl esters and long-chain alcohols. The chromatographic separation was achieved using a Zorbax SB-C18 HPLC column (0.3 × 150mm, 3.5μm) with a mobile phase composed of acetonitrile and formic acid and delivered isocratically at a flow rate of 10μL/min. The column temperature was programmed simply, using a common column oven. Good reproducibility of the temperature profile and retention times were achieved. The temperature programming during the isocratic high-performance liquid chromatography run had a similar effect as a solvent gradient; it reduced retention times of later eluting analytes and improved their detection limits. Two atmospheric pressure chemical ionization sources of the mass spectrometry detector were compared: an enclosed conventional ion source and an in-house made ion source with a glass microchip nebulizer. The enclosed source provided better detectability of saturated fatty acid methyl esters and made it possible to determine the double bond positions using acetonitrile-related adducts, while the open chip-based source provided better analytical figures of merit for unsaturated fatty acid methyl esters. Temperature-programmed capillary high-performance liquid chromatography is a promising method for analyzing neutral lipids in lipidomics and other applications.

Determination of citalopram in fish brain tissue: benefits of coupling laser diode thermal desorption with low- and high-resolution mass spectrometry.

Recent state-of-the-art methods developed for the analysis of polar xenobiotics from different types of biological matrices usually employ liquid chromatography with mass spectrometry. However, there are limitations when a small amount of sample mass is available. For example, individual benthic invertebrates or fish tissue samples often weigh less than 100mg (e.g., brain, liver) but are necessary to understand environmental fate and bioaccumulation dynamics. We developed ultra-fast methods based on a direct sample introduction technique. This included coupling laser diode thermal desorption with atmospheric pressure chemical ionization mass spectrometry (LDTD-APCI-MS). We then quantitated a common selective serotonin reuptake inhibitor (citalopram) in brain tissues of individual juvenile fish after in vivo exposure to environmentally relevant concentration. Two mass spectrometric methods based on low (LDTD-APCI-triple quadrupole (QqQ)-MS/MS) and high (LDTD-APCI-high-resolution product scan (HRPS)) resolutions were developed and evaluated. Individual instrument conditions were optimized to achieve an accurate and robust analytical method with minimum sample preparation requirements. We achieved very good recovery (97-108%) across the range of 1-100ngg-1 for LDTD-APCI-HRPS. LDTD-APCI-QqQ-MS/MS showed poorer performance due to interferences from the matrix at the lowest concentration level. LDTD-APCI ionization was successfully validated for analysis of non-filtered sample extracts. Evaluation of final methods was performed for a set of real fish brain samples, including comparison of LDTD-APCI-HRPS with a previously validated LC-heated electrospray ionization-HRPS method. This new LDTD-APCI-HRPS method avoids the chromatographic step and provides important benefits such as analysis of limited sample masses, lower total sample volume (typically μL), and reduction in analysis time per sample run to a few seconds. Graphical abstract.

Pressurized liquid extraction followed by liquid chromatography coupled to a fluorescence detector and atmospheric pressure chemical ionization mass spectrometry for the determination of benzo(a)pyrene metabolites in liver tissue of an animal model of colon cancer

Since metabolism is implicated in the carcinogenesis of toxicants, an efficient extraction method together with an analytical method is warranted to quantify tissue burdens of a carcinogen and/or its metabolites. Therefore, the aim of this study was to validate a pressurized liquid extraction (PLE) method for measuring metabolites of benzo(a)pyrene [B(a)P; a food-borne carcinogen] from tissue samples. The sample extraction was performed separately by PLE and liquid–liquid extraction (LLE). PLE followed by high-performance liquid chromatography coupled to online fluorescence detector (HPLC-FLD) was used to quantify separated analytes; and by ultra-high-performance liquid chromatography (UHPLC) coupled to atmospheric pressure chemical ionization tandem mass spectrometry (UHPLC-APCI-MS/MS) were used for confirmation purposes. The UHPLC-MS/MS was set-up in the atmospheric pressure chemical ionization (APCI) positive interface with selective reaction monitoring (SRM). The analytical performance characteristics of the PLE technique was assessed at different temperatures, pressure, number of cycles and solvent types. A methanol + chloroform + water mixture (30:15:10, v/v/v) yielded greater recoveries at an extraction temperature range of 60–80°C, pressure of 10 MPa and an extraction time of 10 min. The PLE method was validated by the analysis of spiked tissue samples and measuring recoveries and limits of quantitation for the analytes of interest using HPLC-FLD equipment. The optimized PLE-HPLC-FLD method was used to quantify the concentrations of B(a)P metabolites in liver samples obtained from a colon cancer animal model. Overall, PLE performed better in terms of extraction efficiency, recovery of B(a)P metabolites and shortened sample preparation time when compared with the classic LLE method.

Effect of seasonal variation on the chemical composition and antioxidant and antifungal activities of Convolvulus althaeoides L. leaf extracts

The composition of polyphenols, chlorophylls and carotenoids of eight extracts of Convolvulus althaeoides L. leaves, harvested in two different seasons, winter and spring, and extracted by hot extraction method using four solvents (dichloromethane, chloroform, ethyl acetate and ethanol) with increasing polarity, were evaluated along with their antioxidant and antifungal activities. Qualitative and quantitative variations were observed in the composition based on two different high performance liquid chromatography systems, liquid chromatography-photodiode array detection coupled to either atmospheric pressure chemical ionization mass spectrometry or to electrospray ionization mass spectrometry, permitting the identification of 22 polyphenols, 11 chlorophyll derivatives and 10 carotenoid compounds. Polyphenolic compounds were predominant in extracts from leaves collected in winter, whereas pigments were predominant in the spring collections. Antioxidant activities of the extracts were determined by DPPH radical scavenging method, revealing a half inhibition concentration (IC50) ranging from 0.1369 ± 0.0272 mg g−1 to 0.432 ± 0.0018 mg g−1, with no correlation to seasonal fluctuation. Concerning antifungal assays, ethyl acetate and ethanol extracts have been shown to be the most active against dermatophytes (T. rubrum, T. menthagrophytes, M. canis), with inhibiting percentages reaching 100% with 50 mg mL−1. Moreover, ethyl acetate and ethanol extracts showed a maximum inhibition potential with minimum inhibitory/fungicidal concentrations ranging from 0.78 to 6.25 mg mL−1 on Candida spp. cultures. The winter collect of these extracts showed an inhibitory effect of 90% on Candida albicans germ tubes formation, at a concentration of 3.1 mg mL−1. In conclusion, seasonality seems to influence the quality and the quantity of natural substances from leaves of C. althaeoides L., which have major importance on the antioxidant and the antifungal effectiveness.

Rapid differentiation of graft Citrus sinensis with and without Xylella fastidiosa infection by mass spectrometry

Xylella fastidiosa causes citrus variegated chlorosis (CVC) in sweet orange trees. A diagnostic method for detecting CVC before the symptoms appear, which would inform citrus producers in advance about when the plant should be removed from the orchard, is essential for reducing pesticide application costs. Chemometrics was applied to high-performance liquid chromatography diode array detector (HPLC-DAD) data to evaluate the similarities and differences between the chromatographic profiles. A liquid chromatography/atmospheric pressure chemical ionization mass spectrometry selected reaction monitoring (LC/APCI-MS-SRM) method was developed to identify the major compounds and to determine their amounts in all samples. We evaluated the effect of this bacterium on the variation in the chemical profile in citrus plants. The organs of C. sinensis grafted on C. limonia were analyzed. Chemometrics was applied to the obtained data, and two major groups were differentiated. Flavonoids were observed in one group (leaves) and coumarins in the second (roots), both at higher concentrations in the plants with CVC symptoms than in those without the symptoms and those in the negative control. The rootstocks also interfered in the metabolism of the scion. The developed LC/APCI-MS-SRM method for detecting CVC before the symptoms appear is simple and accurate. It is inexpensive, and many samples can be screened per hour using 1 mg of leaves. Knowledge of the influence of the rootstock on the chemical profile of the graft is limited. This study demonstrates the effect of the rootstock in synthesizing flavonoids and increasing its content in all parts of the graft.

Impact of capsaicin on aroma release: in vitro and in vivo analysis

Capsaicin is the main bioactive compound in chili pepper that leads to the perception of “spiciness”. However, the effect of capsaicin on aroma release in the nose remains unexplained. This is the first study designed to measure capsaicin’s impact on aroma release during consumption. In vitro studies, using static headspace analysis by atmospheric pressure chemical ionization-mass spectrometry (APCI-MS), showed no impact of capsaicin (5 ppm) on the gas-liquid partitioning equilibria of a range of aroma compounds. However, a significant reduction in aroma release was observed in vivo, during oral melting of a model ice cube system (p < 0.05) included 5 ppm capsaicin. The total release of aroma into the nasal cavity was decreased, such that only 49% of 3-methylbutanal, 60% of 1-octen-3-ol and 83% of linalool was released. This is the first evidence of capsaicin’s reduction effect on aroma release during consumption. It was also found that 5 ppm capsaicin increased saliva secretion by 75%, which may have led to the dilution of aroma compounds in the mouth and directly impacted the aroma release into the nasal cavity. The most hydrophilic compound (3-methylbutanal) was affected by capsaicin to a greater extent than the hydrophobic compound (linalool), the solvent effect of the additional saliva may explain this.

Atmospheric pressure chemical ionization mass spectrometry at low flow rates: Importance of ion source housing.

Hyphenation of atmospheric pressure chemical ionization (APCI) mass spectrometry with capillary and micro high-performance liquid chromatography (HPLC) is attractive for many applications, but reliable ion sources dedicated to these conditions are still missing. There are a number of aspects to consider when designing such an ion source, including the susceptibility of the ionization processes to ambient conditions. Here we discuss the importance of ion source housing for APCI at low flow rates. Selected compounds dissolved in various solvents were used to study ionization reactions at 10 μL/min flow rate. APCI spectra were generated using the Ion Max-S source (Thermo Fisher Scientific) operated with or without the ion source housing. The APCI spectra of most compounds measured in the open and enclosed ion sources were markedly different. The differences were explained by water and oxygen molecules that entered the plasma region of the open ion source. Water tended to suppress charge transfer processes while oxygen diminished electron capture reactions and prevented the formation of acetonitrile-related radical cations useful for localizing double bonds in lipids. The effects associated with the ion source housing were significantly less important for compounds that are easy to protonate or deprotonate. The use of ion source housing prevented alternative ionization channels leading to unwanted or unexpected ions. Compared with the conventional flow rate mode (1 mL/min), the effects of ambient air components were significantly higher at 10 μL/min, emphasizing the need for ion source housing in APCI sources dedicated to low flow rates.

Nano-structured lipid particles for controlled transport of hydrophobic volatile and non-volatile molecules

Nano-structured lipid particles can be designed for tailored delivery of small molecules. Liquid lipid nanoparticles (LLN) stabilized by lecithin and solid lipid nanoparticles (SLN) stabilized by sodium caseinate were used to form self-assembled nano-emulsion structures (i.e., colloidosomes) via electrostatic deposition of a solid wall around a liquid reservoir. Particle size and zeta potential were measured at pH 3.5 and 7 to characterize the colloidal dispersions at selected mixing ratios (2:1 to 1:5). The partitioning, kinetic release, and reactivity of non-volatile (4-phenyl-2,2,5,5-tetramethyl-3-imidazoline-1-oxyl nitroxide; PTMIO) and volatile (limonene) molecules were studied using electron paramagnetic resonance (EPR) spectroscopy and atmospheric pressure chemical ionization-mass spectroscopy (APcI-MS), respectively, as a function of pH-change at the 1:3 mixing ratio. Particle size (d32) of LLN (134 nm) and SLN (166 nm) remained unchanged with pH adjustment, and colloidosome particle size (450 nm) was a combination of LLN and SLN particles at pH 3.5. The presence of the solid wall significantly reduced the diffusion rate (ca. 80 %) of PTMIO from the LLN core protecting the compound. APcI-MS measurements showed similar behavior for limonene release to air. These systems can be used for controlled delivery of various active compounds in food and pharmaceutical formulations.

Investigation of chromatographic peak broadening in supercritical fluid chromatography/atmospheric pressure chemical ionization mass spectrometry.

Multimode ionization source allows for switching between different ionization techniques, for example, electrospray and atmospheric pressure chemical ionization, within a single analysis. Supercritical fluid chromatography can handle a wide polarity range of substances from hydrophilic to lipophilic in a single run and can undoubtedly benefit from versatility of this ion source. Nevertheless, we observed a significant chromatographic peak broadening effect in atmospheric pressure chemical ionization mode during supercritical fluid chromatography-mass spectrometry analysis of volatile flavor compounds with a dual ion source named ESCi (Waters). Surprisingly, this effect was not related to the separation process but was triggered solely by the ion source conditions. Neither of photodiode array detector, electrospray mode nor a dedicated atmospheric pressure chemical ionization source suffered from such a phenomenon. Chromatographic peak profiles of ten test substances obtained with the dual ion source were compared with photodiode array detector data as a reference. The broadening effect was more pronounced for volatile compounds with low polarity. Dependence of peak broadening on the ion source settings was systematically investigated. Tuning of desolvation gas flow and its temperature dramatically reduced peak distortion and increased detection sensitivity.

Rapid Extraction and Analysis of Volatile Solutes with an Effervescent Tablet.

Extraction of volatile compounds from complex liquid matrices is a critical step in volatile compound analysis workflows. Recently, green chemistry principles are increasingly implemented in extraction processes. Some of the available approaches are solvent-free but still require concentration or trapping of analytes. Here, we propose effervescent tablet-induced extraction (ETIE) as a method of transferring volatile/semivolatile compounds from liquid matrices to the gas phase for analysis. This technique relies on the release of carbon dioxide produced in situ during a neutralization reaction, which occurs when a tablet is inserted into an aqueous sample matrix. In this process, many bubbles of carbon dioxide are instantly formed in the sample matrix. The bubbles rapidly extract and liberate volatile compounds from the sample. The gaseous effluent is then immediately transferred to a detector (atmospheric pressure chemical ionization mass spectrometry (MS) or gas chromatography (GC) hyphenated with MS). ETIE-GC-MS can be used for analysis of volatile compounds present in real samples. The method was validated for analysis of selected ethyl esters present in a yogurt drink. The calibration data set was linear over a range from 5 × 10-7 to 1 × 10-5 M. The limits of detection ranged from 1.51 × 10-7 to 6.82 × 10-7 M, while the recoveries ranged from 71 to 118%. Inter- and intraday precision of selected ethyl esters in aqueous solution was satisfactory (relative standard deviation, 3.6-18.3%). Furthermore, it is shown that ETIE improves the performance of headspace solid-phase microextraction while eliminating the need for heating and shaking samples.

Multi-scheme chemical ionization inlet (MION) for fast switching of reagent ion chemistry in atmospheric pressure chemical ionization mass spectrometry (CIMS) applications

Abstract. A novel chemical ionization inlet named the Multi-scheme chemical IONization inlet (MION), Karsa Ltd., Helsinki, Finland) capable of fast switching between multiple reagent ion schemes is presented, and its performance is demonstrated by measuring several known oxidation products from much-studied cyclohexene and α-pinene ozonolysis systems by applying consecutive bromide (Br−) and nitrate (NO3-) chemical ionization. Experiments were performed in flow tube reactors under atmospheric pressure and room temperature (22 ∘C) utilizing an atmospheric pressure interface time-of-flight mass spectrometer (APi-ToF-MS, Tofwerk Ltd., Thun, Switzerland) as the detector. The application of complementary ion modes in probing the same steady-state reaction mixture enabled a far more complete picture of the detailed autoxidation process; the HO2 radical and the least-oxidized reaction products were retrieved with Br− ionization, whereas the highest-oxidized reaction products were detected in the NO3- mode, directly providing information on the first steps and on the ultimate endpoint of oxidation, respectively. While chemical ionization inlets with multiple reagent ion capabilities have been reported previously, an application in which the charging of the sample occurs at atmospheric pressure with practically no sample pretreatment, and with the potential to switch the reagent ion scheme within a second timescale, has not been introduced previously. Also, the ability of bromide ionization to detect highly oxygenated organic molecules (HOM) from atmospheric autoxidation reactions has not been demonstrated prior to this investigation.

Green Extraction Approaches for Carotenoids and Esters: Characterization of Native Composition from Orange Peel.

Orange peel is a by-product produced in large amounts that acts as a source of natural pigments such as carotenoids. Xanthophylls, the main carotenoid class found in citrus fruit, can be present in its free form or esterified with fatty acids, forming esters. This esterification modifies the compound’s chemical properties, affecting their bioavailability in the human body, and making it important to characterize the native carotenoid composition of food matrices. We aimed to evaluate the non-saponified carotenoid extracts of orange peel (cv. Pera) obtained using alternative green approaches: extraction with ionic liquid (IL), analyzed by high performance liquid chromatography coupled to a diode array detector with atmospheric pressure chemical ionization and mass spectrometry HPLC-DAD-APCI-MS, and supercritical fluid extraction (SFE), followed by supercritical fluid chromatography with atmospheric pressure chemical ionization and triple quadrupole mass spectrometry detection (SFC-APCI/QqQ/MS) in an online system. Both alternative green methods were successfully applied, allowing the total identification of five free carotenoids, one apocarotenoid, seven monoesters, and 11 diesters in the extract obtained with IL and analyzed by HPLC-DAD-APCI-MS, and nine free carotenoids, six carotenoids esters, 19 apocarotenoids, and eight apo-esters with the SFE-SFC-APCI/QqQ/MS approach, including several free apocarotenoids and apocarotenoid esters identified for the first time in oranges, and particularly in the Pera variety, which could be used as a fruit authenticity parameter.

The H3O+(H2O)n Reagent Ion: Calculations of the Structure, Thermodynamic Parameters of Hydration, Equilibrium Composition, and Mobility

The H3O+(H2O)n reagent ion is widely used in ion mobility spectrometry and atmospheric pressure chemical ionization mass spectrometry. In this work, calculated data on the structure and properties of the H3O+(H2O)n (n = 0–4) reagent ion are obtained. They are of interest for the study of the regularities of chemical ionization and the prediction and interpretation of ion mobility spectra and mass spectra. Using quantum chemical methods, we calculated the structures and refined the isomeric composition of the H3O+(H2O)n ions. It was found that ions with n = 2, 3, and 4 have 2, 5, and 15 isomers, respectively. The most stable isomers, which possess branched non-cyclic structures with the H3O+ core, were determined. The thermodynamic parameters of hydration reactions of the most stable isomers of H3O+(H2O)n (n = 0–3) ions and the equilibrium composition of the reagent ion in a wide range of temperatures and concentrations of water vapor are computed. The obtained results agree with the available experimental and calculated data. Using the computed structural data and data on the composition of the reagent ion, its mobility was calculated by the trajectory method. The error of calculations is close to the experimental one.

Floral volatiles identification and molecular differentiation of Osmanthus fragrans by neutral desorption extractive atmospheric pressure chemical ionization mass spectrometry

Floral volatiles are commonly present only at trace amounts and can be degraded or lost during vapor collection, which is often challenging from the analytical standpoint. Osmanthus fragrans Lour. is a widely cultivated plant known for the highly distinct fragrance of its flowers. The identification of specific volatile organic compounds (VOCs) and molecular differentiation of O. fragrans without any chemical pretreatment and VOC collection are important. Twenty-eight VOCs released by the flowers from ten different cultivars of O. fragrans were identified using neutral desorption extractive atmospheric pressure chemical ionization mass spectrometry (ND-EAPCI-MS) without any chemical pretreatment or VOC collection. Chemical identification was performed by high-resolution MSn analysis and whenever possible was confirmed by the analysis of standards. According to our literature search, nine of the identified VOCs, 3-buten-2-one, cyclohexadiene, 2-methylfuran, 3-allylcyclohexene, cuminyl alcohol, hotrienol oxide, epoxy-linalool oxide, N-(2-hydroxyethyl) octanamide, and 3-hydroxy-dihydro-β-ionone, have not been reported in O. fragrans in earlier studies. Confident differentiation between ten different cultivars of O. fragrans was achieved by the principal component analysis of the mass spectrometric results. The results of our ND-EAPCI-MS analysis substantially increase our knowledge about the chemistry of the O. fragrans floral fragrance and demonstrate the power of this technique for direct molecular profiling for plant recognition or in biotechnological applications.

A Study of the Influence of the HCl Concentration on the Composition and Structure of (Hydroxy)Arylsiloxanes from the Hydrolysis–Condensation Reaction of Aryltrichlorosilanes

The hydrolysis–condensation reactions of m-tolyl, m-chlorophenyl, and α-naphtyl-trichlorsilanes, (1, 2, and 3, respectively) in water-acetone solutions were examined for how they were influenced by the change in the concentration of HCl (CHCl). The composition of the products was monitored by 29Si NMR spectroscopy and atmospheric pressure chemical ionization mass spectrometry (APCI-MS). The acidity of the medium was shown to affect the yields of the products, and so, what products were formed. For 3, e.g., APCI-MS showed peaks of α-naphtyl-T8 and α-naphtyl-T10 as the most abundant in the spectra taken after 48 and 240 h for the reaction conducted at CHCl = 0.037 mol L−1. Unlike this, at CHCl = 0.15 mol L−1, those peaks were of [α-naphtyl(HO)2SiO]2(α-naphtyl)(HO)Si and/or [α-naphtyl(HO)Si]3, [α-naphtyl(HO)Si]4,5, and α-naphtyl-T8 after 192 h. However, at both CHCl values, the main product (and an intermediate) after 24 h was trans-1,1,3,3-tetrahydroxy-1,3-di-α-naphtyldisiloxane. It was isolated and its structure established by 1H-, 29Si-NMR, and X-ray powder diffraction.

Characterization of Chinese Grape Seed Oil by Physicochemical Properties, Fatty Acid Composition, Triacylglycrol Profiles, and Sterols and Squalene Composition

Abstract This work focused on physicochemical property assaying, fatty acid composition, triacylglycerol profiles, and sterols and squalene composition of the Chinese grape seed oil. Three different methods were used to extract oil from Chinese grape seeds, solvent extraction, cold press and hot press methods. Three oils all possess very low acid value and peroxide value, suggesting their good quality as edible oil. Fatty acid composition results indicated that the total content of unsaturated fatty acids was 89.14 %, within which the majority fatty acid was linoleic acid with content of 64.11 %. Characterization of triacylglycerol profiles was achieved by a two-dimensional HPLC coupling of nonaqueous reverse-phase and silver ion HPLC with atmospheric pressure chemical ionization mass spectrometry method. There was a total of 30 TAGs including 23 regioisomers that have been determined. Unsaponifiable matters composition results revealed that the total sterols content and the squalene content were 278.49 mg/100 g and 17.81 mg/100 g, respectively.

Development of a liquid chromatography atmospheric pressure chemical ionization mass spectrometry method for determining off-flavor compounds and its application toward marine recirculating aquaculture system monitoring and evaluation of aeration as a depuration approach

The off-flavor compounds geosmin and 2-methylisoborneol (2-MIB) are well-known to impact the quality of farmed freshwater fish species, but little is known about off-flavors in marine aquaculture. To begin addressing this knowledge gap, a method for determining geosmin and 2-MIB using LC with atmospheric pressure chemical ionization (APCI) MS detection was developed. While 2-MIB was readily detected using LC-APCI/MS, geosmin exhibited on-column degradation that was independent of column chemistry and could not be eliminated. Optimized conditions were identified that balanced the separation and ionization efficiency of 2-MIB and geosmin while minimizing geosmin degradation, but the overall method sensitivity for geosmin was reduced by the on-column losses. The method was used with direct aqueous injections to determine the volatilization rates of geosmin and 2-MIB at ppb levels during aeration under laboratory conditions in both salt water and pure water to simulate marine and fresh water aquaculture, respectively. The volatilization rates of both compounds were 30% faster in salt water than in fresh water with or without aeration, but aeration was found to enhance the rate by a factor of 2.5 in both water types. The LC-APCI/MS method was combined with stir bar sorptive extraction (SBSE) to achieve greater sensitivity for determining off-flavors in recirculating aquaculture system (RAS) water. Using SBSE-LC-APCI/MS, the LODs for geosmin and 2-MIB were 70 ng/kg (part per trillion) and 6 ng/kg, respectively. The on-column losses resulted in a relatively high LOD for geosmin that renders this method unsuitable for determining geosmin at the low ng/kg levels expected in RAS. SBSE using both grab water samples and an in-situ diving unit were used to evaluate 2-MIB levels in the culture water of two separate marine RAS that were supporting the growth of European sea bass but had differing levels of water treatment. 2-MIB was readily detected using both SBSE approaches in the RAS with less sophisticated treatment when the animal stocking density was at its highest (50 kg/m3) but was not detected in the more sophisticated RAS regardless of stocking density. Geosmin was not detected in either system, but the results were inconclusive given its higher LOD. These limited results suggest that the anaerobic water treatment components, present only in the more sophisticated RAS, maintained the level of 2-MIB below the LOD.