ESI FT-ICR Research Articles

Evaluating the selectivity of colorimetric test (Fast Blue BB salt) for the cannabinoids identification in marijuana street samples by UV–Vis, TLC, ESI(+)FT-ICR MS and ESI(+)MS/MS

Marijuana is one of the most marketed illicit drugs in the world. Originated from Cannabis sativa L, Δ9-tetrahydrocannabinol (or Δ9-THC) is proscribed in Brazil by the law number 11.343 from August 23rd of 2006 as well as its isomers, salts, ethers and esters. However, Δ9-THC is the main responsible for the hallucinogenic effects of the plant. The principal screening test used by the Brazilian Forensic Police is a colorimetric test called Fast Blue B or BB salt, in which the development of a reddish color in a basic medium indicates the presence of cannabinoids such as Δ9-THC, cannabinol (CBN) and/or cannabidiol (CBD). However, a better understanding of this chemical reaction is required. In this work, the products of the colorimetric test were identified by positive-ion mode electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI(+)FT-ICR MS), collision-induced dissociation (CID) experiments or ESI(+)MS/MS, ultraviolet–visible (UV–Vis) spectroscopy and thin layer chromatography (TLC). A chemical structure was proposed for the product of the reaction (m/z 626) formed by Fast Blue BB salt (4-amino-2,5-diethoxybenzanilide diazotated zinc double salt) and Δ9-THC molecule. Besides, the selectivity of the colorimetric test was evaluated in presence of interferences from other plants such as Jacaranda decurrens Cham and Paullinia cupana Kunth.

Catalytic aquathermolysis of Shengli heavy crude oil with an amphiphilic cobalt catalyst

An interfacially active cobalt complex, cobalt dodecylbenzenesulfonate, was synthesized. Elemental analysis, atomic absorption spectroscopy, Fourier transform infrared spectroscopy (FT-IR), thermogravimetric analysis, and surface/interfacial tension determination were performed to investigate the properties of the catalyst. Results showed that the synthesized catalyst showed active interfacial behavior, decreasing the surface tension and interfacial tension between heavy oil and liquid phase to below 30 and 1.5 mN/m, respectively. The catalyst was not thermally degraded at a temperature of 400 °C, indicating its high thermal stability. Catalytic performance of the catalyst was evaluated by carrying out aquathermolysis. The viscosity determination showed that the viscosity of the heavy oil decreased by 38 %. The average molecular weight, group compositions, and average molecular structure of various samples were analyzed using elemental analysis, FT-IR, electrospray ionization Fourier transform ion cyclotron resonance (ESI FT-ICR MS), and 1H nuclear magnetic resonance. Results indicated that the catalyst could attack the sulfur- and O2-type heteroatomic compounds in asphaltene and resin, especially the compounds with aromatic structure, leading to a decrease in the molecular weight and then the reduction in the viscosity of heavy oil. Therefore, the synthesized catalyst might find an application in catalytic aquathermolysis of heavy oil, especially for the high-aromaticity heavy oil with high oxygen content.

Structural characterization of the lipid A from the LPS of the haloalkaliphilic bacterium Halomonas pantelleriensis.

Halomonas pantelleriensis DSM9661(Τ) is a Gram-negative haloalkaliphilic bacterium isolated from the sand of the volcanic Venus mirror lake, closed to seashore in the Pantelleria Island in the south of Italy. It is able to optimally grow in media containing 3-15% (w/v) total salt and at pH between 9 and 10. To survive in these harsh conditions, the bacterium has developed several strategies that probably concern the bacteria outer membrane, a barrier regulating the exchange with the environment. In such a context, the lipopolysaccharides (LPSs), which are among the major constituent of the Gram-negative outer membrane, are thought to contribute to the restrictive membrane permeability properties. The structure of the lipid A family derived from the LPS of Halomonas pantelleriensis DSM 9661(T) is reported herein. The lipid A was obtained from the purified LPS by mild acid hydrolysis. The lipid A, which contains different numbers of fatty acids residues, and its partially deacylated derivatives were completely characterized by means of ESI FT-ICR mass spectrometry and chemical analysis. Preliminary immunological assays were performed, and a comparison with the lipid A structure of the phylogenetic proximal Halomonas magadiensis is also reported.

Composition to Interfacial Activity Relationship Approach of Petroleum Sulfonates by Fourier Transform Ion Cyclotron Resonance Mass Spectrometry

In the present work, petroleum sulfonates were obtained from three atmospheric residues (ARs) and characterized by negative-ion electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry [(−) ESI FT-ICR MS], looking for an approach to establish a relationship between molecular composition and interfacial activity for chemical enhanced oil recovery (CEOR) formulations. From the correlation of the (−) ESI FT-ICR MS data and the interfacial tension measurements, it was possible to infer that the composition and some characteristics, such as aromatic and/or naphthenic condensation, must be taken into account to understand the performance of petroleum sulfonates. Obtained sulfonates contained mainly O3S, NO3S, O3S2, and O4S compounds, but the relative abundance of each class depended directly upon the chemical composition of the raw AR. Both carbon number (CN) and double bound equivalent (DBE) distributions of the main classes provided a way to explain the lipophilicity and interfacial...

Characterization of dissolved organic nitrogen in wet deposition from Lake Erhai basin by using ultrahigh resolution FT-ICR mass spectrometry

Dissolved Organic Nitrogen (DON) of wet deposition in Erhai basin (EWD) was characterized at the molecular level by using electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI FT-ICR MS). The structure and composition of DON were investigated by the combined ESI FT-ICR MS, UV–Vis absorbance and fluorescence techniques. The FT-ICR MS measurements indicate that a large (∼790) number of organic species present in the wet deposition, in which DON account for 18.3%, with most of DON containing a single nitrogen atom. The typical relative molecular mass of the DON species was found to be in the range of 200–400 Da. Approximately 57.2% of DON species are highly unsaturated (DBE (Double Bond Equivalent) > 5) with the nitrogen- and sulfur-containing species, which are probably represented mainly by active nitrooxy organosulfates, accounting for ∼ 19.3% of the total DON. The low average SUVA254 and A253/A203 values (0.02 and 0.06, respectively), indicates that the aromaticity of the EWD samples is particularly weak. The average values of E2/E3 and E4/E6 in the EWD samples were 6.84 and 1.84, respectively. This is a clear indication of the low degree of humification of EWD samples, in agreement with ESI FT-ICR MS measurements. Our study demonstrates that multiple experimental techniques combined with FT-ICR MS, UV–Vis absorbance and fluorescence can be efficiently used for in-depth studying the DON at the molecular level. Thus it allows us to achieve a deep and insightful understanding of the DON structure and composition.

Deposit reduction in a high pour point oil reservoir due to the activity of indigenous bacterial communities

Physical simulation experiments were performed to simulate the reservoir environment and evaluate deposit reduction and oil recovery by indigenous bacteria inhabiting different types of water. The bacterial communities in the samples were identified based on 16S rRNA gene amplicons. Activation resulted in the predominance of Bacillus sp. and Clostridium ultunense in the samples. The oil was investigated before and after stimulation using the GC, GC–MS and ESI FT-ICR MS techniques to evaluate and analyse the deposit reduction on different scales. The n-alkanes (n > 25) in the sample obtained from the physical simulation experiment using production fluid containing nutrients showed a 68.66% reduction, whereas the amount of wax decreased from 46.27% to 38.75%. Additionally, naphthalene and its homologues decreased by approximately 34.0%. The typical polar compounds containing N1, O1 and O2 class compounds also significantly changed, indicating a marked biodegradation of the alkyl side chains of polar compounds and the pathway of wax metabolism by indigenous bacterium indirectly. The indigenous bacteria in the production fluid more effectively degraded the wax and heavy components. Bacteria such as Acinetobacter sp., Pseudomonas sp. and Bacillus sp. played important roles in deposit reduction and were beneficial to the EOR.

Characterization of unknown iodinated disinfection byproducts during chlorination/chloramination using ultrahigh resolution mass spectrometry

Iodinated disinfection byproducts (I-DBPs), formed from the reaction of disinfectant(s) with organic matter in the presence of iodide in raw water, have recently been focused because of their more cytotoxic and genotoxic properties than their chlorinated or brominated analogues. To date, only a few I-DBPs in drinking water have been identified. In this study, C18 solid phase extraction coupled with electrospray ionization ultrahigh resolution Fourier transform ion cyclotron resonance mass spectrometry (ESI FT-ICR MS) was used to characterize unknown I-DBPs in chloraminated/chlorinated water spiked with iodide and humic substances. In total, 178 formulas for one-iodine-containing products, 13 formulas for two-iodine-containing products, and 15 formulas for one-chlorine and one-iodine-containing products were detected in the chloraminated water sample, while only 9 formulas for one-iodine-containing products and 6 formulas for one-chlorine and one-iodine-containing products were found in the chlorinated water sample. Most I-DBPs have corresponding chlorine-containing analogues with identical CHO compositions. As indicated by the modified aromaticity index (AImod), in the C18 extracts, more than 68% of the I-DBPs have aromatic structures or polycyclic aromatic structures. This result demonstrates that the use of chloramination as an alternative disinfection method may lead to the formation of abundant species of I-DBPs in the presence of iodide. Thus, the suitability of adopting chloramination as an alternative disinfection method should be reevaluated, particularly when iodide is present in raw water.

Chemical profile of mango (Mangifera indica L.) using electrospray ionisation mass spectrometry (ESI-MS)

Mangifera indica L., mango fruit, is consumed as a dietary supplement with purported health benefits; it is widely used in the food industry. Herein, the chemical profile of the Ubá mango at four distinct maturation stages was evaluated during the process of growth and maturity using negative-ion mode electrospray ionisation Fourier transform ion cyclotron resonance mass spectrometry (ESI(−)FT-ICR MS) and physicochemical characterisation analysis (total titratable acidity (TA), total soluble solids (TSS), TSS/TA ratio, and total polyphenolic content). Primary (organic acids and sugars) and secondary metabolites (polyphenolic compounds) were mostly identified in the third maturation stage, thus indicating the best stage for harvesting and consuming the fruit. In addition, the potential cancer chemoprevention of the secondary metabolites (phenolic extracts obtained from mango samples) was evaluated using the induction of quinone reductase activity, concluding that fruit polyphenols have the potential for cancer chemoprevention.

Chemical profiles of Robusta and Arabica coffee by ESI(−)FT-ICR MS and ATR-FTIR: a quantitative approach

This paper reports a method to quantify Robusta coffee in Arabica coffee blends using univariate and multivariate models.

Chemical Composition and Potential Environmental Impacts of Water-Soluble Polar Crude Oil Components Inferred from ESI FT-ICR MS.

Polar petroleum components enter marine environments through oil spills and natural seepages each year. Lately, they are receiving increased attention due to their potential toxicity to marine organisms and persistence in the environment. We conducted a laboratory experiment and employed state-of-the-art Fourier-transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) to characterize the polar petroleum components within two operationally-defined seawater fractions: the water-soluble fraction (WSF), which includes only water-soluble molecules, and the water-accommodated fraction (WAF), which includes WSF and microscopic oil droplets. Our results show that compounds with higher heteroatom (N, S, O) to carbon ratios (NSO:C) than the parent oil were selectively partitioned into seawater in both fractions, reflecting the influence of polarity on aqueous solubility. WAF and WSF were compositionally distinct, with unique distributions of compounds across a range of hydrophobicity. These compositional differences will likely result in disparate impacts on environmental health and organismal toxicity, and thus highlight the need to distinguish between these often-interchangeable terminologies in toxicology studies. We use an empirical model to estimate hydrophobicity character for individual molecules within these complex mixtures and provide an estimate of the potential environmental impacts of different crude oil components.

Characterization of bio-oils from the alkanolyses of sweet sorghum stalk by electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry

Bio-oils (BOs) obtained from sweet sorghum stalk (SSS) methanolysis (BOm) and ethanolysis (BOe) at 300°C for 30min were analyzed with an electrospray ionization Fourier transform ion cyclotron resonance mass spectrometer (ESI FT-ICR MS). In negative-ion mode, the predominant compounds in BOm and BOe are On (n=1–10) class species with double bond equivalent (DBE) values of 1–14 and carbon atom numbers (CANs) of 5–35. The most abundant class species in BOm and BOe are O4 and O3, respectively. According to the distribution of On class species and the van Krevelen diagram, lignin-derived compounds are the main acidic species in the BOs. In addition, N1On (n=0–10) class species with DBE values of 1–14 and CANs of 7–35 were also identified. In positive-ion mode, most of detected compounds in BOm and BOe are N2On (n=1–6) class species with DBE values of 1–19 and CANs of 10–40, in which N2O2–N2O4 class species with DBE=8–12 and CAN=19–28 are the most abundant. These results facilitate understanding thermochemical behavior of SSS.

Structural Investigation of the Oligosaccharide Portion Isolated from the Lipooligosaccharide of the Permafrost Psychrophile Psychrobacter arcticus 273-4.

Psychrophilic microorganisms have successfully colonized all permanently cold environments from the deep sea to mountain and polar regions. The ability of an organism to survive and grow in cryoenviroments depends on a number of adaptive strategies aimed at maintaining vital cellular functions at subzero temperatures, which include the structural modifications of the membrane. To understand the role of the membrane in the adaptation, it is necessary to characterize the cell-wall components, such as the lipopolysaccharides, that represent the major constituent of the outer membrane. The aim of this study was to investigate the structure of the carbohydrate backbone of the lipooligosaccharide (LOS) isolated from the cold-adapted Psychrobacter arcticus 273-4. The strain, isolated from a 20,000-to-30,000-year-old continuously frozen permafrost in Siberia, was cultivated at 4 °C. The LOS was isolated from dry cells and analyzed by means of chemical methods. In particular, it was degraded either by mild acid hydrolysis or by hydrazinolysis and investigated in detail by 1H and 13C NMR spectroscopy and by ESI FT-ICR mass spectrometry. The oligosaccharide was characterized by the substitution of the heptose residue, usually linked to Kdo in the inner core, with a glucose, and for the unusual presence of N-acetylmuramic acid.

Temperature-Dependent Lipid Conversion and Nonlipid Composition of Microalgal Hydrothermal Liquefaction Oils Monitored by Fourier Transform Ion Cyclotron Resonance Mass Spectrometry

We illustrate a detailed compositional characterization of hydrothermal liquefaction (HTL) oils derived from two biochemically distinct microalgae, Nannochloropsis gaditana and Chlorella sp. (DOE 1412), for a range of reaction temperature as observed by high-resolution electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI FT-ICR MS). The unique capability to unequivocally derive molecular formulae directly from FT-ICR MS-measured mass-to-charge ratio (for several thousand compounds in each oil) shows that lipids are completely reacted/converted for any reaction temperature above 200 °C and reveals the formation of nonlipid reaction products with increasing temperature. Specifically, lipid-rich oil is obtained at low reaction temperature (<225 °C) for both microalgal strains. For positive ion mode, the major lipid components in Chlorella sp. and N. gaditana HTL oils are betaine lipids and acylglycerols, respectively. Acidic species in the HTL oils (observed by negative ion mode) are dominated by free fatty acids (FFA) regardless of reaction temperature. HTL oils obtained at higher temperatures (≥225 °C) are composed of a variety of basic nitrogen- and oxygen-containing compounds that originate from protein and carbohydrate degradation at elevated temperature. Similar structural features are observed for the abundant nitrogen heterocyclics between the two strains with slightly lower carbon number for Chlorella sp., overall.

Insight into the structural features of Zhaotong lignite using multiple techniques

The chemical structures of Zhaotong lignite (ZL) were characterized with multiple direct tools, including solid-state 13C nuclear magnetic resonance (NMR), X-ray photoelectron spectrometer (XPS), Fourier transform infrared (FTIR) spectrometer, and thermogravimetric (TG) analyzer, combined with ZL ethanolysis and subsequent electrospray ionization Fourier transform ion cyclotron resonance mass spectrometer (ESI FT-ICR MS) analysis of the resulting ethanol-soluble portion (ESP). According to 13C NMR analysis, ZL mainly consists of aliphatic (52.3%) and aromatic (42.2%) carbons. Methylene is the most abundant among the aliphatic carbons. Each aromatic cluster contains 2 rings on average and the number of substituents on each aromatic ring is 3 or 4. XPS analysis suggests that oxygen atoms mainly exist in CO moieties, which is consistent with 13C NMR and FTIR analyses, and pyrrolic nitrogen species are the main nitrogen form in ZL. Based on TG analysis, cleavage of CalO and CalCal bonds should be the major reactions during ZL ethanolysis. A series of neutral nitrogen compounds (NNCs, i.e., pyrrolic nitrogen) in the ESP were detected by negative-ion ESI FT-ICR MS analysis. The identified NNCs are N1Ox (x = 0–5) class species with 3–13 double bond equivalent (DBE) values and 10–31 carbon numbers, in which N1O2 class species are predominant NNCs. According to DBE distributions of NNCs, pyrroles, indoles, and carbazoles account for most of the neutral nitrogen occurrences in ZL. Such multiple characterizations proved to be an effective method for fully understanding the chemical structures of coals, especially lignites.

Compositional Characterization of Phase-Separated Pine Wood Slow Pyrolysis Oil by Negative-Ion Electrospray Ionization Fourier Transform Ion Cyclotron Resonance Mass Spectrometry

The chemical composition of slow pyrolysis oil made from unbarked Scots pine (Pinus sylvestris) was characterized by negative-ion electrospray ionization Fourier transform ion cyclotron resonance (ESI FT-ICR) mass spectrometry and various bulk analyses. The wood pieces were heated stepwise in a batch pyrolysis reactor to the target temperature of 320 °C. The resulting pyrolysis oil spontaneously separated into aqueous and oily phases. The water content of the aqueous phase was as high as 60.4 wt %, whereas for the oily phase it was only 8.1 wt %. The bulk O/C ratio (on a dry basis) was more than twice as high for the aqueous phase as compared to the oily phase (0.61 vs 0.29), suggesting different chemistry between the two phases. On the basis of pH and total acid number measurements, the aqueous phase was more acidic than the oily phase. The ESI FT-ICR technique was used to characterize pyrolysis oils’ heavier, nonvolatile, and thermally labile species. The total amounts of the identified chemical formulas were ∼540 and ∼630 for the aqueous and oily phases, respectively. The majority of the detected compounds were oxygen-containing species, representing heteroatom classes O2–O14. The O9–O14 class compounds were present only in the aqueous phase. The O2–O4 compounds were comprised of different acids, including resin acids and several types of fatty acids, such as hydroxy fatty acids and diacids, which were concentrated in the oily phase. However, saturated fatty acids were more dominant in the aqueous phase, possibly due to their increased solubility through micelle formation in a more aqueous environment. Anhydrosugars and other high oxygen-containing compounds were present only in the aqueous phase. Both phases also contained condensed aromatic compounds (pyrolytic lignin), representing heteroatom classes O3–O8.

Characterization of basic heteroatom-containing organic compounds in liquefaction residue from Shenmu–Fugu subbituminous coal by positive-ion electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry

Extracts of liquefaction residue from Shenmu–Fugu subbituminous coal (LRSFSBC) were obtained by sequential extraction with petroleum ether, methanol, and carbon disulfide. They were analyzed using a Fourier transform infrared (FTIR) spectrometer and a positive-ion (PI) electrospray ionization Fourier transform ion cyclotron resonance mass spectrometer (ESI FT-ICR MS). In total, 65.37% of LRSFSBC was extracted. Aromatic C=C, C=O, and CO were identified in the extracts by FTIR analysis. Nitrogen, oxygen, and sulfur forms of LRSFSBC and the inextractable portion were characterized using X-ray photoelectron spectrometry. A series of basic N1, N2, N1O1, N1O2, N2S2, and N2O5S1 class species were identified in the extracts using ESI FT-ICR MS in PI mode. The ring plus double bond equivalents of the extracts ranges from 1–47, but is mainly below 23. In LRSFSBC some compounds are enwrapped into “capsules”, which are formed from different species associated with each other by hydrogen bonds, π–π interaction, and/or π–hydrogen bonds.

Sulfur-containing species in the extraction residue from Xianfeng lignite characterized by X-ray photoelectron spectrometry and electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry

Detailed composition of sulfur-containing species in the extraction residue from Xianfeng lignite was characterized by XPS and ESI FT-ICR MS.

2-(4-IODINE-2,5-DIMETHOXYPHENYL)-N-[(2-METHOXYPHENYL)METHYL]ETAMINE OR 25I-NBOMe: CHEMICAL CHRACTERIZATION OF A DESIGNER DRUG

Drug trafficking and the introduction of new drugs onto the illicit market are one of the main challenges of the forensic community. In this study, the chemical profile of a new designer drug, 2-(4-iodine-2,5-dimethoxyphenyl)-n-[(2-methoxyphenyl)methyl]etamine or 25I-NBOMe was explored using thin layer chromatography (TLC), ultraviolet-visible spectrophotometry (UV-Vis), attenuated total reflection with Fourier transform infrared spectroscopy(ATR-FTIR), gas chromatography mass spectrometry (GC-MS) and electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI-FT-ICR MS). First, the TLC technique was effective for identifying spots related to 25C-, 25B- and 25I-NBOMe compounds, all with the same retention factor, Rf ≈ 0.50. No spot was detected for 2,5-dimethoxy-4-bromoamphetamine, 2,5-Dimethoxy-4-chloroamphetamine or lysergic acid diethylamide compounds. ATR-FTIR preserved the physical-chemical properties of the material, whereas GC-MS and ESI-MS showed better analytical selectivity. ESI(+)FT-ICR MS was used to identify the exact mass (m/z428.1706 for the [M + H]+ ion), molecular formula (M = C18H22INO3), degree of unsaturation (DBE = 8) and the chemical structure (from collision induced dissociation, CID, experiments) of the 25I-NBOMe compound. Furthermore, the ATR-FTIR and CID results suggested the presence of isomers, where a second structure is proposed as an isomer of the 25I-NBOMe molecule.

Top-down analysis of highly post-translationally modified peptides by Fourier transform ion cyclotron resonance mass spectrometry.

Bovine κ-caseinoglycomacropeptide (GMP) is a highly modified peptide from κ-casein produced during the cheese making process. The chemical nature of GMP makes analysis by traditional proteomic approaches difficult, as the peptide bears a strong net negative charge and a variety of post-translational modifications. In this work, we describe the use of electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI FT-ICR MS) for the top-down analysis of GMP. The method allows the simultaneous detection of different GMP forms that result from the combination of amino acid genetic variations and post-translational modifications, specifically phosphorylation and O-glycosylation. The different GMP forms were identified by high resolution mass spectrometry in both negative and positive mode and confirmation was achieved by tandem MS. The results showed the predominance of two genetic variants of GMP that occur as either mono- or bi-phosphorylated species. Additionally, these four forms can be modified with up to two O-glycans generally sialylated. The results demonstrate the presence of glycosylated, bi-phosphorylated forms of GMP never described before.

Waxy Crude Oil Emulsion Gel: Chemical Characterization of Emulsified Phase Extract Components

Emulsions of several waxy crude oils exhibiting similar properties were prepared and characterized to better understand the nature of their polar components. Both crude oils and their corresponding emulsions were analyzed by negative-ion electrospray Fourier transform ion cyclotron resonance mass spectrometry [ESI (−) FT-ICR MS]. The most abundant classes found in these crude oils were neutral N, acidic O, and O2 heteroatomic compounds. The N class was present in higher relative abundance in all samples, followed by the O class (phenolic-like compounds). The O2 class was minor in all crude oils, corroborating their low total acid number (TAN) values. The O/O2 class ratios were directly correlated with their rheological properties. Higher O/O2 class ratios were associated with crude oils that formed gel emulsions, indicating that O class compounds play an important role in gel emulsion stabilization. The identified phenolic compounds possess a structure that allows for (i) intermolecular hydrogen-bonding i...