Convenient determination of polystyrene microplastics in soils by gel permeation chromatography-ultraviolet detection analysis.

Microplastics (MPs), especially polystyrene microplastics (PS-MPs), have emerged a new worldwide pollutant, prompting significant public concern regarding their detection in environmental media. Analysis of PS-MPs in soil remains as a challenging task for analysts due to the highly intricate matrices. This work presents a practical approach for detecting PS-MPs in soil, which involves dilute HCl-assisted extraction and gel permeation chromatography- ultraviolet detection (GPC-UV) analysis. The presence of MPs in soil was confirmed through the use of a scanning electron microscope in conjunction with energy dispersive spectroscopy investigation. PS-MPs was isolated from soil, by agitating it with a diluted HCl solution, filtering the resulting liquid, and dissolving the residue on the filter with THF. The extractant was subsequently determined by GPC-UV. The introduction of a small amount of HCl into the extraction system was found to greatly expedite the settling of soil in water and enhance the efficacy of extracting PS-MPs in about 30 min. The linear range of PS-MPs was from 1.0 to 100 µg/mL with R2 > 0.999. Good reproducibility was obtained with the intra-day relative standard deviation (RSD, n = 3) of 1.36 % and the inter-day RSD (n = 3) of 4.78 %. The concentration of PS-MPs in soil samples were N.D. - 2.33 µg/g, and the good recoveries were 76.7-100.3 %. The corresponding AFGEEprer score was calculated to be 0.59, indicating the concept of green analytical chemistry for the pretreatment method. These results indicated that this method has a powerful potential for the accurate and rapid determination of PS-MPs in soil.

Interference of the gas chromatography- mass spectrometry instrumental background on the determination of trace cyclic volatile methylsiloxanes and exclusion of it by delayed injection.

Cyclic volatile methylsiloxanes (cVMS) have been widely found in various types of environmental media and attracted increasing attention as new pollutants. However, there is still a great challenge in the accurate quantification of trace cVMS, due to their volatility, and the high background originating from GC/MS accessories and surroundings. In this work, the main sources of the high background were investigated in detail for octamethylcyclotetrasiloxane (D4), decmethylcyclopentasiloxane (D5) and dodecmethylcyclohexosiloxane (D6). Several effective measures were employed to minimize these backgrounds, including the delayed injection method to minimize the interference from the injection septum. Then, a GC-MS method was developed for the accurate determination of D4, D5 and D6, with a linear range of 2 - 200 µg/L. The coefficient of determination was 0.9982-0.9986, the limit of detection (LOD) was 0.40-0.52 µg/L, and the quantitative range was 1.88-190 µg/L. Good reproducibility and recovery were obtained, indicating the reliability of the established analytical method.

Determination of trace chelating carboxylic acids in rice by green extraction combined with liquid chromatography-mass spectrometry analysis and its application in the evaluation of old and new rice.

RATIONALE: Accurate identification of old rice samples from new ones benefits their market circulation and consumers. However, the current detection methods are still not satisfactory because of their insufficient accuracy or (and) time-consuming process. METHODS: Chelating carboxylic acids (CCAs) were selectively extracted from rice, by stirring with chelating resin and a dilute Na2CO3 solution. The green analytical chemistry guidelines for sample preparation were investigated by using the green chemistry calculator AGREE prep. The extractant was determined by liquid chromatography-mass spectrometry (LC/MS), and statistical analysis of the analytical data was carried out to evaluate the significance of the difference by ChiPlot. RESULTS: The limit of quantitation for the CCAs is in the range of 1 to 50 ng/mL, with a reasonable reproducibility. The CCAs in 23 rice samples were determined within a wide concentration range from 0.03 to 1174 µg/g. Intriguingly, the content of citric acid, malonic acid, α-ketoglutaric acid and cis-aconite acid in new rice was each found to be distinctively higher than that in old rice by several times. Even mixtures of old and new rice were found to show much difference in the concentration of citric acid and malic acid. CONCLUSION: A green analytical method has been developed for the simultaneous determination of CCAs by LC/MS analysis, and the identification of old rice samples from new ones was easily carried out according to their CCA content for the first time. The results indicated that the described method has powerful potential for the accurate identification of old rice samples from new ones.

Benzyl Deuteriodifluoromethyl Sulfoxide: An Easily Accessible and Stable Reagent for Direct Deuterodifluoromethylthiolation.

A new, stable and scalable reagent based on a sulfoxide skeleton for direct deuteriodifluoromethylthiolation has been developed. The reagent displays excellent reactivities toward Tf2O promoted C-H deuteriodifluoromethylthiolation of electron-rich arenes, indoles, alkenes, and intramolecular lactonization of 2-alkynylbenzoates. Moreover, high deuteration rates and good to excellent yields were achieved under metal-free reaction conditions. As a result, a wide range of deuteriodifluoromethylthilolated compounds were prepared, enabling further applications in drug discovery.

Differentiation of tetracyclines and their 4-epimers by mass spectrometry of the alkali metal adduct ions.

Tetracyclines (TCs) are a family of broad-spectrum antibiotics. During the manufacturing process or storage, epimerization of tetracyclines could occur, leading to 4-epimers which are nearly inactive. From an analytical point of view, isomers are often difficult to distinguish. Previously, four pairs of TCs (oxytetracycline, tetracycline, doxycycline, chlortetracycline and their respective 4-epimers) were differentiated by mass spectrometry (MS) through protonated ions. However, they do not follow common rules and so it is still quite difficult to differentiate between them. In order to solve this, the four pairs were differentiated in the current study by collision induced dissociation (CID) spectra of the alkali adduct ions, including lithium, sodium and potassium. In the spectra of the sodium adducts, all studied tetracyclines showed a tendency to form [M+Na-NH3]+ ions, while the 4-epimers liked to form [M+Na-NH3-H2O]+ ions. Meanwhile, energy resolved mass spectrometry (ERMS) showed that all four 4-epimers' sodium adducts had the tendency to fragment at higher energy points. In the CID spectra of lithium adducts of TCs, a similar trend was observed for three pairs, except for doxycycline. For potassium adducts, the fragmentation was found to be less discriminative. As was derived from the 3D model, the four pairs all interact with the alkali metal through the dimethyl amino group at the C-4 position. The lithium adduct species also bound through the hydroxyl group at the C-5 position. If the TCs did not have a hydroxyl group at the C-5 position, they bound with the hydroxyl group at the C-6 position. For the same TC, with an increase of the diameter of the metal ion, the loss of H2O decreased gradually. As sodium adduct ions are common during the ionization process, TCs and their 4-epimers could be differentiated rapidly by ERMS of the sodium adduct ions.

Determination of adenosine and its modifications in urine and plasma from breast cancer patients by hydrophilic interaction liquid chromatography-tandem mass spectrometry.

RNA modifications have been revealed to be essential in many biological activities, and their disorders are associated with various human diseases, including cancers. 2'-O-methyladenosine (Am), N1-methyladenosine (m1A), N6-methyladenosine (m6A), N6,2'-O-dimethyladenosine (m6Am) and N6,N6-dimethyladenosine (m62A) are important adenosine (A) modifications. The noninvasive collection of urine samples and the diverse contents of metabolites in plasma make them favored biofluids for biomarkers discovery. In this work, we established a hydrophilic interaction liquid chromatography-tandem mass spectrometry (HILIC-MS/MS) method to quantify these six nucleosides in urine and plasma of healthy controls and breast cancer (BC) patients. The limit of detection (LOD) for A, Am, m1A, m6A, m6Am, and m62A were 0.0025, 0.01, 0.05, 0.005, 0.005, and 0.005 nM. The results showed that the concentrations of Am, m6A, and m6Am were increased, whereas m1A was decreased in the urine of BC patients compared with the healthy controls. We also found that the level ratios of m1A/A, m6A/A, and m6Am/A were all reduced in plasma from BC patients, compared with healthy controls. Interestingly, these ratios of methylated adenosine nucleosides to adenosine in plasma could better discriminate BC patients from healthy controls, compared to the levels of these nucleosides. The present study not only suggests these modified adenosines can act as noninvasive biomarkers of BC but also will contribute to investigating the impacts of RNA methylation on the occurrence and development of BC.

Diastereomer recognition of three pairs of tetracyclines by electrospray ionization mass spectrometry.

RATIONALE: Stereoisomer profiling is always a difficult issue. Based on the difference between diastereomers, usually because of steric hindrance, isomers can be differentiated by mass spectrometry (MS), although it is often not an easy task. In the current study, tetracycline, chlortetracycline and doxycycline could be distinguished from their respective 4-epimers by MS. METHODS: The electrospray ionization tandem mass spectrometry (ESI-MSn ) analyses were carried out on a Bruker 3000plus ion trap mass spectrometer. For MS/MS experiments, the collision energy was set between 0.18 and 0.45 V to perform energy-resolved mass spectrometry (ERMS). Test solutions were prepared in methanol/water (90:10, v/v) at a concentration of 10 µg/mL. RESULTS: Compared with the collision-induced dissociation (CID) spectrum of protonated tetracycline, the most abundant peak changed from m/z 427 to m/z 410 for 4-epitetracycline. For chlortetracycline and its 4-epimer, differences in relative abundance were observed too. In the CID spectrum of a fragment ion of doxycycline, the abundance of m/z 154 was relatively higher than for the 4-epimer, showing the same trend as in the CID spectra of the other two pairs of tetracyclines. CONCLUSIONS: The CID spectra of tetracycline and chlortetracycline were different from those of their 4-epimers. The CID spectra of protonated doxycycline and its 4-epimer showed only a subtle difference, but the m/z 154 fragment ion in the CID spectra of the fragment ion at m/z 428 offers the possibility to differentiate both epimers.

Characterizing Oligomeric Hydroxyl Silicon Oils by MALDI-TOF MS With the Pyridine-Modified Matrix.

Matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF) is a powerful technique for analysis of various polymers, but it is still very difficult to characterize silicone oil due to its poor ionization efficiency. In this work, oligomeric hydroxyl silicone oils were successfully characterized by MALDI-TOF, by using pyridine-modified 2,5-dihydroxylbenzoic acid (DHB) as the matrix. Furthermore, the mixed crystal of DHB and hydroxyl silicone oil was analyzed by scanning electron microscopy (SEM) and energy disperse spectroscopy (EDS), and the analytical results verified that modification with pyridine could remarkably improve the solubility of hydroxyl silicone oil in DHB, leading to the enhancement of its ionization efficiency in MALDI. The analysis of the MS spectra of a series of hydroxyl silicone oils indicated that they tended to be ionized by the attachment with Na+, and the average molecular weight and the degree of polymerization were measured for several oligomeric hydroxyl silicon oils.

Quantification of phytic acid in baby foods by derivatization with (trimethylsilyl)diazomethane and liquid chromatography-mass spectrometry analysis.

RATIONALE: Phytic acid (PA) is both a naturally occurring nutrient and a widely used food additive for conferring antioxidant properties to food. PA can be found in baby foods and it is essential to monitor PA content due to its anti-nutritional properties when present in excess. Current methods for determining PA content are unsatisfactory because interference from inositol phosphates and inorganic phosphates complicates PA quantification. METHODS: Baby foods were extracted using aqueous HCl, and the extractant was subjected to derivatization with (trimethylsilyl)diazomethane after de-metalation using a cation exchange resin. The PA derivative was quantified using liquid chromatography-mass spectrometry (LC/MS/MS) with a multi-response monitoring mode (m/z 829 to 451). RESULTS: The linearity of the developed analytical method ranged from 10 to 1000 ng/mL for PA with R2 > 0.999. Reasonable reproducibility was obtained with an intraday relative standard deviation (RSD; N = 5) of 4.5% and an interday RSD (N = 5) of 5.7% at a concentration of 10 ng/mL. The developed method was successfully applied to determine PA content in various baby foods, with PA recovery between 90.6% and 119.8%. CONCLUSIONS: A robust and sensitive method for the determination of PA in baby foods has been developed by methyl esterification with (trimethylsilyl)diazomethane and using LC/MS/MS analysis. The established method showed good anti-interference and precision, and it has been applied for the determination of PA in various baby foods.

Determination of phytic acid in wheat products by complete methyl esterification and liquid chromatography-mass spectrometry analysis.

Phytic acid, the principal storage form of phosphorus in wheat, plays both beneficial and antinutrient functions for human being, and its analytical method still needs further development. In this work, we have developed a new method for the determination of phytic acid in wheat products based on derivatization with (trimethylsilyl)diazomethane in combination with liquid chromatography-mass spectrometry analysis. Methyl esterification greatly decreased the polarity and the acidity of phytic acid, and thus the corresponding derivative can be easily analyzed by liquid chromatography-mass spectrometry under common conditions. Furthermore, treatment with cation exchange resin removed the polyvalent metal ions in the solutions, and thus derivatization of phytic acid can be achieved efficiently and completely. The standard curve for phytic acid has been well established in the linear range of 0.5-100 ng/mL with squared correlation coefficient more than 0.999 and the quantification limit of 0.25 ng/mL. The phytic acid content varies greatly in different wheat products, ranging from 153.5 to 17299.0 µg/g.

Determination of trace fluoride in water samples by silylation and gas chromatography/mass spectrometry analysis.

RATIONALE: Due to the ubiquity of fluorides and the small gap between a safe dose and a harmful one, it is necessary to develop a robust analytical method for determination of fluoride ions in various water samples with complex matrices. METHODS: Silylation of the fluoride ion was carried out by treatment with hydrochloric acid and phenyldimethylchlorosilane at room temperature. The formed phenyldimethylfluorosilane was detected by gas chromatography/mass spectrometry (GC/MS). RESULTS: Under the optimized conditions, linearity in the analytical method ranged from 0.050 to 5.0 µg/mL for the fluoride ion with R2 >0.9999. Reasonable reproducibility was obtained with the intraday relative standard deviation (RSD) (N = 5) of 2.04% and interday RSD (N = 5) of 3.75% at the concentration of 0.10 µg/mL. The developed method has been successfully applied to determine the fluoride ion in real water samples, including waste water samples, with the recovery between 81.12% and 113.04%. CONCLUSIONS: A robust method for the determination of the fluoride ion has been developed by silylation with phenyldimethylchlorosilane and GC/MS analysis. The established method showed good anti-interference and precision, and it has been applied for determination of the fluoride ion in various water samples.

Formation of the exceptional [M - H]+ cation in atmospheric pressure ionization mass spectrometry analysis of 2-(diphenylsilyl) cyclopropanecarboxylate esters.

RATIONALE: In general, ionization of analytes in atmospheric pressure ionization mass spectrometry (API-MS) in positive ion mode results in the formation of protonated molecules ([M + H]+ ) and/or cationized molecules (e.g., [M + Na]+ ). The formation of specific [M - H]+ cations in the API process is of significant interest for further investigation. METHODS: The ionization processes of 2-(diphenylsilyl)-1-phenyl-cyclopropanecarboxylate esters were investigated using electrospray ionization (ESI)-MS and atmospheric pressure chemical ionization-MS in positive ion mode. Theoretical calculations were carried out with the Gaussian 03 program using the density functional theory (DFT) method at the B3LYP/6-311 + G(2d,p) level. RESULTS: The anomalous [M - H]+ ion and the regular [M + Na]+ ion were both observed using ESI-MS. Interestingly, no [M + H]+ ion was obtained in the ESI-MS analysis, and acidification of the ESI solvent accelerated the formation of [M - H]+ rather than [M + H]+ ion. DFT calculations for the typical methyl 2-(diphenylsilyl)-1-phenyl-cyclopropanecarboxylate (1) indicated that the [1 + H]+ ion can thermodynamically and kinetically undergo facile H2 elimination to generate [1 - H]+ . CONCLUSIONS: The favorable formation of [M - H]+ ions in these compounds is attributed to the unique diphenylhydrosilyl group in their structure. The [M + H]+ ion formed easily underwent H2 elimination to produce the [1 - H]+ ion in the API source, and thus, acidification of the ESI solvent apparently accelerates the formation of the [1 - H]+ ion.

Differentiation of isomeric cresols by silylation in combination with gas chromatography/mass spectrometry analysis.

RATIONALE: m-Cresol is listed as a priority controlled contaminant in many countries, but it is very difficult to accurately determine isomeric cresols due to their incomplete chromatographic separation on commercially available chromatographic columns and their nearly identical mass spectra. METHODS: Silylation of isomeric cresols was carried out by treatment with N-methyl-N-(trimethylsilyl)trifluoroacetamide. The formed trimethyl(tolyloxy)silanes were analyzed by gas chromatography/mass spectrometry (GC/MS). Theoretical calculations were carried out with the Gaussian 03 program using the density functional theory (DFT) method at the B3LYP/6-311 + G(2d,p) level. RESULTS: The derivatives of three isomeric cresols and six isomeric xylenols have been completely separated on an HP-5MS capillary column within a GC run of only 10 minutes. In addition, the derivative o-cresol can be very easily differentiated from its isomers due to its characteristic base peak ion at m/z 91 in electron ionization (EI)-MS. DFT calculation results indicated that the formation of the abundant fragment ion at m/z 91 is attributed to a facile dissociation pathway involving the shift of a neighboring phenylmethyl hydrogen atom in EI-MS of trimethyl(o-tolyloxy)silane. CONCLUSIONS: Silylation provides a promising solution for simultaneous determination of isomeric cresols and isomeric xylenols.

Iodine/water-mediated deprotective oxidation of allylic ethers to access α,ß-unsaturated ketones and aldehydes.

The first iodine/water-mediated deprotective oxidation of allylic ethers to access α,ß-unsaturated ketones and aldehydes was achieved. The reaction tolerates a wide range of functionalities. Furthermore, this protocol was found to be applicable to the oxidative transformation of allylic acetates. The proposed mechanism involves an oxygen transfer from solvent water to the carbonyl products.

Pd-Catalyzed Enantioselective Ring Opening/Cross-Coupling and Cyclopropanation of Cyclobutanones.

A palladium-catalyzed enantioselective sequential ring-opening/cross-coupling of cyclobutanones is disclosed that provides chiral indanones bearing C3-quaternary stereocenters. The reaction process involves palladium-catalyzed nucleophilic addition of cyclobutanones and aryl halides, enantioselective ß-carbon elimination, and intermolecular trapping of a transient σ-alkylpalladium complex with boronic acids. Alternatively, an intramolecular cyclopropanation is realized through C-H bond functionalization in the absence of external coupling reagents, affording chiral cyclopropane-fused-indanones in good yields and enantioselectivity.

Sulfur Transfer Versus Phenyl Ring Transfer in the Gas Phase: Sequential Loss of CH3OH and CH3O-P=O from Protonated Phosphorothioates.

Collisional activation fragmentation of protonated phosphorothioates leads to skeletal rearrangement and formation of aryl sulfenylium cation (R-PhS+) via successive eliminations of CH3OH and CH3O-P=O. To better understand this unusual fragmentation reaction, isotope-labeling experiments and density functional theory (DFT) calculations were carried out to investigate two mechanistic pathways. In route 1, a direct intramolecular transfer of the R-phenyl group occurs from the oxygen atom to the sulfur atom on thiophosphoryl to form methoxyl S-(3-methyl-4-methylsulfanyl-phenyl) phosphonium thiolate (a4), which subsequently dissociates to form the m/z 169 cation. In route 2, the sulfur atom of the thiophosphoryl group undergoes two stepwise transfer (1,4-migration to the ortho-carbon atom of the phenyl ring followed by 1,2-migration to the ipso-carbon atom) to form an intermediate isomer, which undergoes the subsequent dissociation to form the m/z 169 cation. DFT calculations suggested that route 2 was more favorable than route 1 from the point view of kinetics. Graphical Abstract.

A BODIPY derivative for colorimetric fluorescence sensing of Hg2+, Pb2+ and Cu2+ ions and its application in logic gates.

A BODIPY-based colorimetric and fluorescent chemosensor 1 anchored with dipyridylamino (DPA) receptor has been designed, synthesized and characterized. It exhibited a simultaneous sensitive recognition for Cu2+, Hg2+ and Pb2+ ions. With the addition of these three kinds of metal ions into 1 in CH3CN, its initial absorption maximum displayed obvious blue shifts, and the color changes of the solution could be clearly observed by naked eyes. Besides, the fluorescence intensity was significantly enhanced accompanied with the appearance of new emission peaks at 587 nm for Pb2+ and Hg2+ ions and 545 nm for Cu2+ ions. These results were attributed to the π-deconjugation between N-pyridyl and the BODIPY group due to the binding of metal ions with the BODIPY and DPA groups. Based on the sensing behaviors of 1, three logic gates (OR, INHIBT and combinational logic gate) were constructed correspondingly.

Differentiation of isomeric haloanilines by tosylation in combination with electrospray ionization mass spectrometry.

Differentiation of the isomeric haloanilines still remains a challenging and necessary analytic task due to their identical retention time in chromatography and similar mass spectra. In this work, p-tosylation of haloanilines by reaction of haloanilines with p-toluenesulfonyl chloride resulted in the corresponding N-tosyl haloanilines. Fragmentation of protonated N-tosyl haloanilines in electrospray ionization tandem mass spectrometry (ESI-MS/MS) mainly resulted in tosyl cation, haloaniline radical cation, and halohydroxyaniline radical cation. The MS/MS of the three group isomeric derivatives showed significant difference in abundance distribution of these product ions, respectively. Theoretical calculations showed that the stability of the ion-neutral complex (INC) is a key factor influencing the relative intensity of the product ions. The three group isomeric derivatives were also separated by high performance liquid chromatograph (HPLC) at conventional conditions. p-Tosylation combined tandem MS (or HPLC) technique were carried out to realize the differentiation of isomeric haloanilines.