Ultra-performance Liquid Chromatography-triple Quadrupole Mass Research Articles

Rapid Analysis of Seven Polyamines in Nephotettix cincticeps by Using Ultra-Performance Liquid Chromatography-Triple Quadrupole Mass Spectrometry.

A fast, simple, and sensitive method for the simultaneous determination of seven polyamines in Nephotettix cincticeps was developed based on ultra-performance liquid chromatography-triple quadrupole mass spectrometry (UPLC-3Q-MS) together with liquid phase extraction. Polyamines in insect samples were extracted with HClO4 solution and then were separated and detected by UPLC-3Q-MS, which was equipped with a hydrophilic interaction liquid chromatography column, within 5 min without any derivatization procedure. The method has been successfully used to detect 7 polyamines in healthy and difluormethylornithine-treated adults of Nephotettix cincticeps with a method limit of detection and the method limit of quantitation of 24-139 pg/mg and 82-464 pg/mg, respectively, an intraday and interday relative standard deviation (RSD, n = 5) of 1.97-6.00% and 2.08-5.92% respectively, and a recovery of 86-115%. The success of this study provided a reliable method for the rapid and high-throughput detection of polyamines in the insect sample.

Simultaneous determination of typical toxic aldehydes formed during food frying and digestion using isotope dilution UHPLC-QqQ-MS/MS

An isotope dilution ultra-performance liquid chromatography–triple quadrupole mass spectrometry method was developed to simultaneously detect two typical kinds of α,β-unsaturated aldehydes, namely 4-hydroxy-2-hexenal (4-HHE) and 4-hydroxy-2-nonenal (4-HNE), in foods. The proposed method exhibited a linear range of 10–1000 ng/mL with a limit of detection of 0.1–2.0 ng/g and a limit of quantification of 0.3–5.0 ng/g. The recovery rates of these typical toxic aldehydes (i.e., 4-HHE, 4-HNE) and their d3-labeled analogues were 91.54%–105.12% with a low matrix effect. Furthermore, this proposed method was successfully applied to a real frying system and a simulated digestion system, wherein the contents of 4-HHE and 4-HNE were determined for both. Overall, the obtained results provide strong support for further research into the production of 4-HHE and 4-HNE resulting from foods during oil digestion and frying.

Chemical composition analysis and value evaluation of stems and leaves of Astragalus membranaceus var. mongholicus

This study aimed to provide data support for resource utilization of the stems and leaves of Astragalus membranaceus var. mongholicus(SLAM) by analyzing and evaluating the chemical constituents. The crude protein, crude fiber, and soluble saccharide of SLAM were analyzed by Kjeldahl method, filtration method, and UV-Vis spectrophotometry, respectively. The nucleosides, amino acids, flavonoids, and saponins of SLAM were analyzed by ultraperformance liquid chromatography-triple quadrupole mass spectrometry(UPLC-TQ-MS). Combined with principal component analysis(PCA), the quality difference of resource components of SLAM was comprehensively evaluated. The results showed that the average content of crude protein, crude fiber, total polysaccharide, and redu-cing sugar in SLAM was 5.11%, 30.33%, 11.03 mg·g~(-1), and 31.90 mg·g~(-1), respectively. Six nucleosides, 15 amino acids, 22 flavonoids, and one saponin were detected, with an average content of 1.49 mg·g~(-1), 6.00 mg·g~(-1), 1.86 mg·g~(-1), and 35.67 μg·g~(-1), respectively. The content of various types of chemical components in SLAM differed greatly in different harvesting periods and growing years. The results of PCA showed that the quality of SLAM produced in Ningxia was superior. The results can provide references for the utilization of SLAM.

A comparative UPLC-MS-based metabolomics approach for distinguishing four different cultivars of Qiai (Artemisia argyi Lévl. et Van.)

The Artemisia argyi Lévl. et Van. (A. argyi) from Qichun County, Hubei Province, China, also known as Qiai, is the most important crop in the region. The quality of Qiai can be influenced by the cultivar, which is highly associated with its metabolite components. In this study, 63 batches of Qiai samples from four cultivars, Xiangai (XA), Wujian (WJ), Qijian (QJ), and Baiai (BA), were investigated using untargeted ultra-performance liquid chromatography–mass spectrometry (UPLC-MS) and chemometrics. In total, 44 metabolites were tentatively identified by combining ultra-performance liquid chromatography time-of-flight mass spectrometry (UPLC-Q-TOF/MS) data with the UNIFI platform and its embedded Traditional Medicine Library. Combining principal component analysis (PCA), partial least squares discriminant analysis (PLS-DA), and orthogonal partial least squares discriminant analysis (OPLS-DA), twelve chemical markers were found to distinguish the four cultivars, showing a high degree of cultivar variability. Five of these compounds were quantified by ultra-performance liquid chromatography triple-quadrupole mass spectrometry (UPLC-TQ-MS/MS) to obtain more accurate content information. This comprehensive study constitutes a valuable reference for distinguishing the four Qiai cultivars, as well as other cultivars, and has implications for Qiai breeding.

A study on the migration of primary aromatic amines in packaged açaí-based (Euterpe oleracea Mart.) products

An analytical method was developed to determine primary aromatic amines (PAAs) from açaí-based product packaging. First, the migration potential of 19 PAAs was investigated in the packaging using a food simulant (3% acetic acid). Then, the detection of migrants was performed in the açaí-based products. Both analyzes were performed by ultra-performance liquid chromatography-triple quadrupole mass spectrometry (UPLC-QqQ-MS). The proposed methods presented calibration curves with correlation coefficients ≥0.991, limit of detection ranging from 0.05 to 0.67 ug kg−1, appropriate recovery with values between 80% and 112%, and good precision (< 17.3% RSD), under repeatability and within-laboratory reproducibility conditions. The results showed that benzidine, o-toluidine, and 4,4′-methylenedianiline have migrated to food simulants with levels ranging from 0.0015 to 0.0033 mg kg−1. Therefore, these samples do not comply with the Brazilian and European regulations on PAAs, since these PAAs should not be detected in food simulants. In the real matrix, no PAAs were detected.

Associations between Ileal Juice Bile Acids and Colorectal Advanced Adenoma.

There is an urgent need to identify biomarkers for advanced adenoma, an important precursor of colorectal cancer (CRC). We aimed to determine alterations in ileal juice bile acids associated with colorectal advanced adenoma. We quantified a comprehensive panel of primary and secondary bile acids and their conjugates using an ultraperformance liquid chromatography triple-quadrupole mass spectrometric assay in ileal juice collected at colonoscopy from 46 study subjects (i.e., 14 biopsy-confirmed advanced adenomas and 32 controls free of adenoma or cancer). Using analysis of covariance (ANCOVA), we examined the differences in bile acid concentrations by disease status, adjusting for age, sex, body mass index, smoking status and type 2 diabetes. The concentrations of hyodeoxycholic acid (HCA) species in ileal juice of the advanced adenoma patients (geometric mean = 4501.9 nM) were significantly higher than those of controls (geometric mean = 1292.3 nM, p = 0.001). The relative abundance of ursodeoxycholic acid (UDCA) in total bile acids was significantly reduced in cases than controls (0.73% in cases vs. 1.33% in controls; p = 0.046). No significant difference between cases and controls was observed for concentrations of total or specific primary bile acids (i.e., cholic acid (CA), chenodeoxycholic acid (CDCA) and their glycine- and taurine-conjugates) and total and specific major secondary bile acids (i.e., deoxycholic acid and lithocholic acid). Colorectal advanced adenoma was associated with altered bile acids in ileal juice. The HCA species may promote the development of colorectal advanced adenoma, whereas gut microbiota responsible for the conversion of CDCA to UDCA may protect against it. Our findings have important implications for the use of bile acids as biomarkers in early detection of colorectal cancer.

Insight of “Yin-Jing” medical property ofLigusticum chuanxiong Hort. via pharmacokinetics and tissue distributions by ultra-performance liquid chromatography-triple quadrupole mass spectrometry

Ethnopharmacological relevanceLigusticum chuanxiong Hort. (Chuanxiong, LC), as an important traditional Chinese medicine (TCM), can not only be used as a monarch herb but also be used as a classic “Yin-Jing” (引经) medicine in compound prescriptions, e.g., Buyang Huanwu Decoction (BHD). Although LC has the effect of guiding components into the brain in BHD, there is still a lack of scientific evidence on this “Yin-Jing” effects. Herein, we used pharmacokinetics and tissue distributions to investigate “Yin-Jing” effects of LC. To simplify the study, four major constituents in BHD, i.e., Calycosin (CA), astragaloside IV (AI), paeoniflorin (PA), and amygdalin (AM) were combined to form a simple compound (abbreviated as CAPA here) to replace the original BHD in this paper. The Yin-Jing medical property of LC was confirmed by the compatibility of CAPA with LC or its different fractions (Fr. A ∼ Fr. F). Aim of the studyTo explore the “Yin-Jing” medical property of LC via pharmacokinetics and tissue distributions by ultra-performance liquid chromatography-triple quadrupole mass spectrometry (UPLC-QQQ-MS). Materials and methodsThe contents of CA, AI, PA, and AM were simultaneously determined by the established and validated UPLC-QQQ-MS method in different rat tissues and plasma after administration of CAPA with the combination of LC or Fr. A ∼ Fr. F. The pharmacokinetic parameters, e.g., Tmax, Cmax, AUC0–t and MRT0–t, were calculated to evaluate the efficiency of “Yin-Jing”. ResultsThe Cmax and AUC0–t of CA, AI, PA, and AM were remarkably increased in rat brain tissues compared with those of the control group after compatibility of LC. This demonstrated that LC has the Yin-Jing effects on brain tissues. Additionally, Fr. B or Fr. C might be the material basis by specifically studying the distributions of CA, AI, PA, and AM in brain tissue based on mutual compatibility. The effects of Fr. B and Fr. C on distributions of these constituents in other tissues or plasma was also studied to verify the effects of Yin-Jing of LC. The results showed that the same upward trend is found in heart, liver and plasma, but the intensity is insignificant as that in brain tissue. Furthermore, the Cmax and AUC0–t of some analytes in the rat spleen, lung, and kidney were significantly decreased compared with the control group (P < 0.05 or 0.01). ConclusionsLC has the function of Yin-Jing, especially guiding the components into the brain tissue. Moreover, Fr. B and Fr. C is suggested to be the pharmacodynamic material basis for the effect of Yin-Jing of LC. These finding explained that it was recommended to add LC into some prescriptions for treating cardiovascular and cerebrovascular diseases caused by Qi deficiency and blood stasis. This has laid a certain foundation for the research on the Yin-Jing efficacy of LC to better clarify the theory of TCM and guide the clinical application of Yin-Jing drugs.

Quantitative Analysis and Enantiomeric Separation of Ephedra Alkaloids in Ma Huang Related Products by HPLC-DAD and UPLC-MS/MS

Ephedra is a genus of the Ephedraceae family and is found in temperate regions, such as Central Asia and Europe. Among the various ephedra species, Ma Huang (Ephedra herb) is derived from the aerial parts of Ephedra sinica S tapf, Ephedra equisetina Bunge, and Ephedra intermedia Schrenk & C.A. Mey. Ma Huang contains various ephedra alkaloids, including (-)-ephedrine, (+)-pseudoephedrine, (-)-norephedrine, (+)-norpseudoephedrine, (-)-methylephedrine, and (+)-methylpseudoephedrine, which are found naturally as single enantiomers, although they can be prepared as racemates. Although the use of Ma Huang in foods is prohibited in Korea, products containing Ma Huang can be imported, and so it is necessary to develop a suitable analytical technique for the detection of Ma Huang in foods. Herein, we report the development of analytical methods for the detection of ephedra alkaloids in products containing Ma Huang. Following sample purification by solid phase extraction, quantitative analysis was performed using ultra-performance liquid chromatography-triple quadrupole mass spectrometry (UPLC-MS/MS). Additionally, the enantiomers were successfully separated using HPLC-DAD. We successfully analyzed various food samples, where the ephedra alkaloids were qualitatively and quantitatively determined, and the enantiomers were separated. It is expected that these methods may contribute toward preventing the distribution of illegal products containing Ma Huang.

Pharmacokinetics and metabolites of glycosides and lignans of the stem bark of Magnolia officinalis in functional dyspepsia and normal rats using liquid chromatography-tandem mass spectrometry.

The stem bark of Magnolia officinalis is a traditional Chinese medicine for the treatment of abdominal distention and functional dyspepsia. The pharmacokinetics of three glycosides (magnoloside A, magnoloside B, and syringin) and two lignans (honokiol and magnolol) in both normal and functional dyspepsia rats were firstly investigated by ultra-performance liquid chromatography-triple quadrupole mass spectrometry method and the influences of the coexisting compounds on the pharmacokinetic parameters of honokiol and magnolol were also studied. It was found that all of the five target compounds were quickly absorbed and eliminated in both normal and functional dyspepsia rats, while, their residence time was significantly decreased in pathological states except magnoloside A. The coexisting compounds in the stem bark of M. officinalis significantly reduced absorption and increased elimination of honokiol in vivo. It's worth noticing that the volume of distribution of lignan was quite lower than that of a glycoside. Moreover, the metabolic profiling of magnoloside A, honokiol, and magnolol in vivo was analyzed by ultra-performance liquid chromatography-quadrupole time-of-flight mass spectrometry method, from which three prototypes were identified and 35 metabolites were putatively characterized, and 18 unknown metabolites were reasonably characterized for the first time. The results indicated that sulfation and glucuronidation were the main metabolic pathways of honokiol and magnolol.

Profile of Twenty-Three Human Milk Oligosaccharides in Han Chinese Mothers throughout Postpartum 1 year

Human milk oligosaccharides (HMOs) are multifunctional carbohydrates in breast milk, which are composed by a variety of structures. This study aimed to identified HMOs concentration profile, milk microbiota composition, and the associations with major maternal characteristics in Han Chinese mothers in the one-year lactation period. Seventeen healthy mothers aged from 28 to 36 years, who gave birth to healthy term infants, were recruited. Carbohydrates were detected using the MIRIS human milk analyzer (HMA), and twenty-three HMOs were quantified using ultra-performance liquid chromatography-triple quadrupole mass spectrometry (UPLC-MS). Results showed that carbohydrates were relatively stable, while total HMO concentrations ranged from 1.74 to 9.72 g/L and decreased gradually over lactation in breast milk. Based on the structure, seven sialylated HMOs concentration showed the significant decline (p&lt;0.05) after three months in lactation. In addition, the relationships between maternal factors, containing the lactation period, genetic status, delivery mode, parity, and milk microbiota profile, and the HMO composition in healthy women, which still need further investigations, were observed.

Fast screening of tyrosinase inhibitors from traditional Chinese medicinal plants by ligand fishing in combination with in situ fluorescent assay.

A simple and rapid method for screening of tyrosinase (TYR) inhibitors present in traditional Chinese medicines (TCMs) was developed by combining ligand fishing and the fluorescent enzymatic assay based on dopamine-functionalized carbon quantum dots (CQDs-Dopa). Ligands of the enzyme present in the TCM extractions were firstly adsorbed on the enzyme-modified magnetic beads, and then the beads were magnetically separated and subjected directly to the CQDs-Dopa-based fluorescent assay. Finally, compounds were desorbed from the "active" beads and identified with ultra-performance liquid chromatography-triple quadrupole mass spectrometry. A known natural TYR inhibitor quercetin was selected to assess the feasibility and quantification performance of this method, and good linearity in the range of 0.01-0.16mM (R2 = 0.992) with a low detection limit of 0.004mM was obtained. This method was then applied to screen TYR inhibitors present in Scutellaria baicalensis and Sophora flavescens. Six TYR inhibitors including baicalin (1), baicalein (2), wogonin (3), oroxylin A (4), kurarinone (5), and sophoraflavanone G (6) were found, among which 1-4 were firstly discovered in this work. This is the first report on the in situ assessment of the target compounds obtained by ligand fishing in the form of a mixture, which exhibited the combined advantages of specific extraction ability of ligand fishing and the high sensitivity of CQDs-based fluorescent assay, showing great potential for fast screening of enzyme inhibitors from TCMs.

Targeted Metabolomics Reveals Birth Screening Biomarkers for Biliary Atresia in Dried Blood Spots

Early diagnosis and timely surgical Kasai portoenterostomy greatly improve the survival of patients with biliary atresia (BA), a neonatal cholestatic disease, which has encouraged investigators to develop newborn screening for BA. In this study, we used ultraperformance liquid chromatography-triple quadrupole mass spectrometry-based targeted metabolomics profiling to identify potential BA biomarkers in dried blood spots (DBS) collected from BA patients (n = 21) and healthy controls (n = 100). A distinctive metabolic profile comprising eight significantly differentially expressed metabolites, taurohyocholic acid (THCA), glutamic acid, 2-hydroxyglutaric acid, ketoleucine, indoleacetic acid, alpha-ketoisovaleric acid, glycocholic acid, and taurocholic acid (TCA), clearly distinguished BA infants from control neonates. Three metabolites, THCA, 2-hydroxyglutaric acid, and indoleacetic acid, were selected using linear regression and receiver operating characteristic (ROC) curve analysis and model construction. The area under the ROC curve for this model to discriminate between BA and comparison infants was 0.938 (95% confidence interval, CI: 0.874-1.000). A cutoff value of -0.336 produced a sensitivity of 90.48% (95% CI: 69.62% - 98.83%) and specificity of 92% (95% CI: 84.84% - 96.48%). In conclusion, the results suggest that metabolic markers in DBS obtained from newborns have a great potential for BA screening.

Effect of glucose oxidase treatment on the aroma qualities and release of cooked off-odor components from heat-treated Hami melon juice

Melon juice produces strong cooked off-odors during heat processing, leading to serious deterioration of aroma quality. In this work, the aroma quality of melon juice, the changes in GOD reaction products, and the interactions of reaction products and cooked off-odor components were analyzed by sensory evaluation, gas chromatography–mass spectrometry/olfactory, ultraperformance liquid chromatography–triple quadrupole mass spectrometry, and isothermal titration calorimetry to study the effect mechanism of glucose oxidase (GOD) on the release of cooked off-odor components from heat-treated melon juice. The results showed that GOD treatment improved the aroma quality mainly by controlling off-odor attributes and maintaining characteristic odor attributes. This was because the reaction products (hydrogen peroxide and gluconic acid) of GOD treatment inhibited the release of cooked off-odor components from heat-treated melon juice through oxidation and hydrophobic effects. Furthermore, these products reduced the loss of characteristic odor compounds by restraining Maillard, degradation, and oxidation reactions during heat processing.

Abstract 748: Conjugated primary bile acids as a biomarker for hepatocellular carcinoma risk in two prospective cohorts

Abstract Background: Incidence rates of hepatocellular carcinoma (HCC) has been increasing for several decades in the U.S. Non-alcoholic liver disease (NAFLD) increasingly plays a role in the rising rate of HCC. Experimental data have shown that bile acids, which play key roles in the host-gut microbiota co-metabolism, contribute to the development of NAFLD and HCC. We propose to comprehensively examine the associations of bile acids with risk of HCC in two cohorts. Methods: Thirty-five bile acids were quantified using the state-of-the-art ultraperformance liquid chromatography triple-quadrupole mass spectrometry assays in serum samples collected, on average, five years prior to diagnosis of 197 HCC and the same number of individually matched controls from the Singapore Chinese Health Study and the Shanghai Cohort Study. Conditional logistic regression was used to assess the associations for major bile acids and their conjugates, and bile acid ratios with the risk of HCC. Results: Total primary bile acids were significantly elevated whereas the ratio of secondary bile acids over primary bile acids were significantly lower in HCC cases than controls in both cohorts (P's ≤ 0.001). Doubling of tauro- vs. glyco-conjugates of all bile acids, primary bile acids, and specifically chenodeoycholic acid resulted in an increase in HCC risk of 44, 48, and 34% (P = 0.004, &amp;lt;0.001, 0.001) respectively after adjustment for potential confounders. Conclusion: Primary bile acids, especially tauro-conjugated bile acids were strongly associated with increased risk of HCC risk whereas the secondary vs. primary bile acids ratios were associated with decreased risk of HCC. Citation Format: Claire Elizabeth Thomas, Hung Luu, Renwei Wang, Guoxiang Xie, Jennifer Adams-Haduch, Aizhen Jin, Woon-Puay Koh, Wei Jia, Jaideep Behari, Jian-Min Yuan. Conjugated primary bile acids as a biomarker for hepatocellular carcinoma risk in two prospective cohorts [abstract]. In: Proceedings of the American Association for Cancer Research Annual Meeting 2021; 2021 Apr 10-15 and May 17-21. Philadelphia (PA): AACR; Cancer Res 2021;81(13_Suppl):Abstract nr 748.

Association between Pre-Diagnostic Serum Bile Acids and Hepatocellular Carcinoma: The Singapore Chinese Health Study.

Simple SummaryHepatocellular carcinoma (HCC) is a common cancer with poor prognosis. The increasing incidence rate of HCC in developed countries has been linked to increasing prevalence of metabolic dysfunction-associated fatty liver disease, which has characteristics of altered bile acid metabolism that may predate hepatocarcinogenesis. The aim of the present study was to assess the association of circulating bile acid levels in pre-diagnostic serum with the risk of developing HCC in a general population in Singapore. Primary conjugated bile acids were most strongly associated with increased risk of HCC whereas the ratios of secondary over primary bile acids were significantly associated with reduced risk. These results support a contributing role of dysmetabolism of bile acids in the development of HCC. The modulation of bile acid metabolism through alteration of gut microbiota may be an effective strategy for primary prevention against HCC in individuals with metabolic dysfunction-associated fatty liver disease.Hepatocellular carcinoma (HCC) is a commonly diagnosed malignancy with poor prognosis. Rising incidence of HCC may be due to rising prevalence of metabolic dysfunction-associated fatty liver disease, where altered bile acid metabolism may be implicated in HCC development. Thirty-five bile acids were quantified using ultra-performance liquid chromatography triple-quadrupole mass spectrometry assays in pre-diagnostic serum of 100 HCC cases and 100 matched controls from the Singapore Chinese Health Study. Conditional logistic regression was used to assess associations for bile acid levels with risk of HCC. Conjugated primary bile acids were significantly elevated whereas the ratios of secondary bile acids over primary bile acids were significantly lower in HCC cases than controls. The respective odds ratios and 95% confidence intervals of HCC were 6.09 (1.75–21.21) for highest vs. lowest tertile of cholic acid species and 30.11 (5.88–154.31) for chenodeoxycholic acid species. Doubling ratio of taurine-over glycine-conjugated chenodeoxycholic acid was associated significantly with 40% increased risk of HCC whereas doubling ratio of secondary over primary bile acid species was associated with 30–40% reduced risk of HCC. In conclusion, elevated primary bile acids and taurine over glycine-conjugated ratios were strongly associated with HCC risk whereas the ratios of secondary bile acids over primary bile acids were inversely associated with HCC risk.

Facile in-situ polymerization of polyaniline-functionalized melamine sponge preparation for mass spectrometric monitoring of perfluorooctanoic acid and perfluorooctane sulfonate from biological samples

In this present work, a novel polyaniline-functionalized melamine sponge (PMs) was successfully prepared using a simple unstirred in-situ polymerization process. The PMs was characterized using a scanning electron microscope and contact angle measurements. Its adsorption performance was initially determined via dye adsorption assays, and the conditions affecting the synthesis including polymerization time, acidity, molar ratio, and number and sizes of raw melamine sponge were optimized. The PMs was then used as an efficient adsorbent for the development of a novel, low-cost method for the detection of two representative perfluorinated chemicals, perfluorooctanoic acid (PFOA) and perfluorooctane sulfonate (PFOS), using ultra-performance liquid chromatography-triple quadrupole mass spectrometry (UPLC-QqQ-MS/MS) with the internal standard method. To achieve the best extraction efficiency with this method, several variables were optimized, including adsorption time, pH value, the number of PMs, and desorption conditions. Calibration graphs showed a good linear degree at concentration ranging from 0.1 to 50 μg L−1 for PFOA and 0.01–10 μg L−1 for PFOS, with a coefficient of detection R2 = 0.998. The intra-day and inter-day relative standard deviations were found to range from 5.9% to 8.2% for PFOA, and 5.5% to 7.7% for PFOS. Under these optimized conditions, the method was successfully used to measure PFOA and PFOS content in real human serum and urine samples, with average spiked recoveries ranging from 79% and 91% for PFOA, and 81% to 87% for PFOS.

Occurrence of 40 pharmaceutically active compounds in hospital and urban wastewaters and their contribution to Mahdia coastal seawater contamination.

In the present study, the occurrence of 40 pharmaceuticals belonging to several therapeutic groups was investigated for the first time in hospital effluent, wastewater treatment plant influent and effluent, and seawater in Mahdia, Tunisia. Forty-six samples were collected within a 6-month sampling period. Pharmaceuticals were analyzed using solid-phase extraction followed by ultra-performance liquid chromatography-triple quadrupole mass spectrometry. Thirty-three out of the forty target compounds were detected over a wide concentration of ranges, from nanograms per liter to micrograms per liter, depending on the type of sample. Maximum values were detected for caffeine at 902 μgL-1 in hospital wastewater. This compound, as well as salicylic acid, sulfadiazine, and sulfamethizole, were detected in all samples. The average concentration of total pharmaceuticals in hospital wastewater (340 μgL-1) was higher than those detected in influent and effluent wastewater and seawater (275.11 and 0.2 μgL-1, respectively). Risk quotients (RQs) were also estimated to provide a preliminary environmental risk assessment and results revealed that sulfadiazine, sulfamethoxazole, and fluoxetine could pose medium/high risk to the tested aquatic organisms for maximum measured concentrations in wastewater (including hospital and WWTP samples). Although the measured environmental concentrations (MECs) detected in seawater samples might not pose a toxic effect to the aquatic organisms (except for salicylic acid, sulfamethoxazole and fluoxetine), further researches are needed due to the continuous release of wastewater in the environment and the limited efficiency of wastewater treatment processes.

Monitoring DNA adducts in human blood samples using magnetic Fe3O4@graphene oxide as a nano-adsorbent and mass spectrometry

DNA adducts usually occur at a level of 0.1–1 adducts per 108 unmodified DNA bases, which can cause many adverse health effects if not normally repaired. Using microgram amounts of DNA to detect DNA adducts remains challenging due to the extremely low levels. Commercial solid phase extraction is the most widely used method for extracting DNA adducts from biological samples, but it is time consuming and costly, and the hydrophobic interactions between various alkyl-bonded phases and analytes typically lack selectivity when used to extract DNA adducts. Therefore, an effective method for DNA adducts analysis based on Fe3O4@graphene oxide (GO) nano-adsorbent and ultra-performance liquid chromatography-triple quadrupole mass spectrometry detection was developed in this study, in which the selectivity may also be increased by π-π stacking interactions between GO and adduct molecules. Several variables, including the extraction time, extraction pH, nano-sorbent amount and elution solvent were optimized, to achieve the best extraction efficiency using the proposed method. A small amount of Fe3O4@GO (2.5 mg) exhibited a good adsorption performance for the model DNA adducts, and butanol containing 4% NH3·H2O showed good elution effects. Under the optimized conditions, satisfying recoveries (78–107%) from calf thymus DNA samples were achieved, and 2 adducts were detected in only 2 μg of blood DNA. This method can be used as an effective strategy for DNA adduct analysis, and can be extended to other biological samples.

Determination of Flavonoid Glycosides by UPLC-MS to Authenticate Commercial Lemonade.

So far, there is no report on the quality evaluation of lemonade available in the market. In this study, a sample preparation method was developed for the determination of flavonoid glycosides by ultra-performance liquid chromatography–mass spectrometry (UPLC-MS) based on vortex-assisted dispersive liquid-liquid microextraction. First, potential flavonoids in lemonade were scanned and identified by ultra-performance liquid chromatography–time of flight mass spectrometry (UPLC-TOF/MS). Five flavonoid glycosides were identified as eriocitrin, narirutin, hesperidin, rutin, and diosmin according to the molecular formula provided by TOF/MS and subsequent confirmation of the authentic standard. Then, an ultra-performance liquid chromatography–triple quadrupole mass spectrometry (UPLC-QqQ/MS) method was developed to determine these five flavonoid glycosides in lemonade. The results showed that the content of rutin in some lemonade was unreasonably high. We suspected that many illegal manufacturers achieved the goal of low-cost counterfeiting lemonade by adding rutin. This suggested that it was necessary for relevant departments of the state to make stricter regulations on the quality standards of lemonade beverages.

Comparative quality of the forms of decoction pieces evaluated by multidimensional chemical analysis and chemometrics: Poria cocos, a pilot study

Many Chinese medicinal materials (CMMs) are parts of plants or fungi that have been processed into different physical forms, termed decoction pieces, that are typically boiled in water for consumption. One CMM may have several decoction pieces forms, e.g., slices, small cubes (dice), or grains. The specifications that have different morphological parameters (shape, size and thickness) for these various decoction pieces have been developed over, in some cases, centuries of practice. Nevertheless, whether and how the form of decoction pieces affects the extraction (decoction) dynamics, and quality stability during storage has not been studied. Here, we investigated Poria cocos (PC) as a pilot study; we explore how the form of PC decoction pieces affects its chemistry using multidimensional chemical evaluation such as ultra-performance liquid chromatography-photodiode array-quadrupole time-of-flight mass spectrometry (UHPLC-PDA-QTOF-MS/MS), ultra-performance liquid chromatography-triple quadrupole mass spectrometry (UHPLC-QqQ-MS/MS) and high performance gel permeation chromatography coupled with charged aerosol detector (HPGPC-CAD), combined with analysis of variance (ANOVA), principal component analysis (PCA), factor analysis (FA) and hierarchical cluster analysis (HCA). The results indicated that different specifications had significant differences, and these specifications could be divided into four groups. The comprehensive results of the chemical analyses undertaken here indicate that the highest potentially available quality of PC decoction pieces was in the forms of curl, ultra-small grains and small grains, followed by thin slices. This information not only is conducive to promoting the standardization of the specification/form of PC decoction pieces and maximizing the benefits from its utilization, but also provide a promising strategy for assessing other CMM decoction pieces in different forms.