Chromatography-triple Quadrupole Tandem Mass Spectrometry Research Articles

Prenatal exposure to pesticides and domain-specific neurodevelopment at age 12 and 18 months in Nanjing, China

BackgroundThe extensive usage of pesticides has led to a ubiquitous exposure in the Chinese general population. Previous studies have demonstrated developmental neurotoxicity associated with prenatal exposure to pesticides. ObjectivesWe aimed to delineate the landscape of internal pesticides exposure levels from pregnant women’s blood serum samples, and to identify the specific pesticides associated with the domain-specific neuropsychological development. MethodsParticipants included 710 mother-child pairs in a prospective cohort study initiated and maintained in Nanjing Maternity and Child Health Care Hospital. Maternal spot blood samples were collected at enrollment. Leveraging on an accurate, sensitive and reproducible analysis method for 88 pesticides, a total of 49 pesticides were measured simultaneously using gas chromatography-triple quadrupole tandem mass spectrometry (GC–MS/MS). After implementing a strict quality control (QC) management, 29 pesticides were reported. We assessed neuropsychological development in 12-month-old (n = 172) and 18-month-old (n = 138) children using the Ages and Stages Questionnaire (ASQ), Third Edition. Negative binomial regression models were used to investigate the associations between prenatal exposure to pesticides and ASQ domain-specific scores at age 12 and 18 months. Restricted cubic spline (RCS) analysis and generalized additive models (GAMs) were fitted to evaluate non-linear patterns. Longitudinal models with generalized estimating equations (GEE) were conducted to account for correlations among repeated observations. Weighted quantile sum (WQS) regression and Bayesian kernel machine regression (BKMR) were applied to examining the joint effect of the mixture of pesticides. Several sensitivity analyses were performed to assess the robustness of the results. ResultsWe observed that prenatal exposure to chlorpyrifos was significantly associated with a 4 % decrease in the ASQ communication scores both at age 12 months (RR, 0.96; 95 % CI, 0.94–0.98; P < 0.001) and 18 months (RR, 0.96; 95 % CI, 0.93–0.99; P < 0.01). In the ASQ gross motor domain, higher concentrations of mirex (RR, 0.96; 95 % CI, 0.94–0.99, P < 0.01 for 12-month-old children; RR, 0.98; 95 % CI, 0.97–1.00, P = 0.01 for 18-month-old children), and atrazine (RR, 0.97; 95 % CI, 0.95–0.99, P < 0.01 for 12-month-old children; RR, 0.99; 95 % CI, 0.97–1.00, P = 0.03 for 18-month-old children) were associated with decreased scores. In the ASQ fine motor domain, higher concentrations of mirex (RR, 0.98; 95 % CI, 0.96–1.00, P = 0.04 for 12-month-old children; RR, 0.98; 95 % CI, 0.96–0.99, P < 0.01 for 18-month-old children), atrazine (RR, 0.97; 95 % CI, 0.95–0.99, P < 0.001 for 12-month-old children; RR, 0.98; 95 % CI, 0.97–1.00, P = 0.01 for 18-month-old children), and dimethipin (RR, 0.94; 95 % CI, 0.89–1.00, P = 0.04 for 12-month-old children; RR, 0.93; 95 % CI, 0.88–0.98, P < 0.01 for 18-month-old children) were associated with decreased scores. The associations were not modified by child sex. There was no evidence of statistically significant nonlinear relationships between pesticides exposure and RRs of delayed neurodevelopment (Pnonlinearity > 0.05). Longitudinal analyses implicated the consistent findings. ConclusionThis study gave an integrated picture of pesticides exposure in Chinese pregnant women. We found significant inverse associations between prenatal exposure to chlorpyrifos, mirex, atrazine, dimethipin and the domain-specific neuropsychological development (i.e., communication, gross motor and fine motor) of children at 12 and 18 months of age. These findings identified specific pesticides with high risk of neurotoxicity, and highlighted the need for priority regulation of them.

Simultaneous Determination of Fungicides in Wood and Bamboo Food-Contact Materials by High-Performance Liquid Chromatography–Tandem Mass Spectrometry (HPLC–MS/MS)

Bamboo and wood are widely used as food contact materials (FCMs). Fungicides are often applied during the manufacture of these products to prevent mildew; thus, monitoring for fungicide residues is essential because of the possible risks to food safety. However, it is not clear whether residual fungicides in treated bamboo and wood products migrate into food to cause harm to humans, and there is an absence of procedures for these analyses. In this study, the simultaneous determination of fungicides was validated in bamboo and wood FCMs by high-performance liquid chromatography–triple quadrupole tandem mass spectrometry (HPLC–MS/MS). The analytes were extracted with methanol or 1:1 methanol/acetonitrile and purified using 25 mg primary secondary amine adsorbent with 2.5 mg graphitized carbon black or 25 mg PSA with 25 mg octadecylsilane (C18). The recoveries for wood and bamboo FCMs were from 60.0% to 100.7% and 70.0% to 97.5%, respectively. The intra-day precision of wood and bamboo FCMs were from 0.1% to 5.3% and 0.1 to 3.0%, and the inter-day precision from 0.3% to 8.5% and 1.2% to 7.8%, respectively. The limits of detection ranged from 0.11 to 15.38 for wood and 0.25–6.19 μg kg−1 for bamboo. This method provides a reference for the determination of fungicides in bamboo and wood FCMs.

Association between antibiotic exposure and the risk of infertility in women of childbearing age: A case-control study

BackgroundBased on self-report questionnaires, two previous epidemiological studies investigated the association between the exposure of women to antibiotics and their fertility. However, biomonitoring studies on low-dose antibiotic exposure, mainly from food and water, and its relation to the risk of infertility are missing. MethodsBased on a case-control study design, 302 women with infertility (144 primary infertility, 158 secondary infertility) and 302 women with normal fertility, all aged 20–49 years, were recruited from Anhui Province, China, in 2020 and 2021. A total of 41 common antibiotics and two antibiotic metabolites in urine samples were determined by liquid chromatography–triple quadrupole tandem mass spectrometry (LC-QqQ-MS/MS). ResultsTwenty-eight antibiotics with detection rates from 10% to 100% in both cases (median concentration: ∼2.294 ng/mL) and controls (∼1.596 ng/mL) were included in the analysis. Logistic regression analysis revealed that after controlling for confounding factors, high concentrations of eight individual antibiotics (sulfamethoxazole, sulfaclozine, sulfamonomethoxine, penicillin G, chlorotetracycline, ofloxacin, norfloxacin, and cyadox) and four antibiotic classes (sulfonamides, tetracyclines, quinoxalines, and veterinary antibiotics) were related to a high risk of female infertility, with odds ratios (ORs) ranging from 1.30 to 2.86, except for chlorotetracycline (OR = 6.34), while another nine individual antibiotics (sulfamethazine, azithromycin, cefaclor, amoxicillin, oxytetracycline, pefloxacin, sarafloxacin, enrofloxacin, and florfenicol) and classes of chloramphenicol analogs and human antibiotics were related to a reduced risk of infertility, with ORs ranging from 0.70 to 0.20. Based on restricted cubic spline models after controlling for confounding factors, we observed that the relationship between all of the above protective antibiotics and infertility was nonlinear: A certain concentration could reduce the risk of female infertility while exceeding a safe dose could increase the risk of infertility. ConclusionThese results provide preliminary evidence that the effects of antibiotics on female fertility vary based on the active ingredient and usage and imply the importance of exposure dose. Future studies are needed to verify these results by controlling for multiple confounding factors.

Rapid determination, pollution characteristics and risk evaluations of antibiotics in drinking water sources of Hainan, China

A simple method using ultra-performance liquid chromatography-triple quadrupole tandem mass spectrometry (UPLC-MS/MS) was developed for simultaneous determination of 50 antibiotics in drinking water sources of Hainan Province, China. Antibiotics analyzed included 23 sulfonamides, 19 quinolones, 5 tetracyclines, and 3 chloramphenicols. This new method consisted of a simple water sample preparation procedure followed by direct injection into UPLC-MS/MS, rendering the method a time-saver which required much less sample preparation time and also smaller sample volumes than conventional techniques. The method detection limits (MDLs) were 0.8–12.0 ng/L. The average recoveries ranged from 74 to 118%, with a relative standard deviation of 0.21–11.3%. Six antibiotics, i.e., Oxytetracycline (OTC), sulfamonomethoxine (SMM), sulfamethoxazole (SMX), sulfachlorpyridazine (SCP), sulfadiazine (SD), and florfenicol (FF), were detected in drinking water sources of Hainan, with the highest concentrations being 9.5, 79.7, 42.5, 14.1, 41.5, and 62.3 ng/L, respectively. The median concentrations of antibiotics ranged from 5.7 to 20.8 ng/L with 3.3–30% detection frequencies. Based on ecological risk assessment, SMX posed a high risk to the pertinent sensitive aquatic organisms ( Synechococcus leopoliensis ) in two drinking water sources of Hainan. With regard to human health risk, the likelihood of posing a major risk to consumer health due to antibiotic exposure through drinking water intake was extremely low, as the risk quotients were all below 0.005. Nevertheless, the long-term ecological concerns and probable health risks of antibiotics in drinking water sources of Hainan need to be taken into consideration.

Simultaneous poisoning of 48 birds of prey - bendiocarb determination with the use of UHPLC-ESI-MS/MS method in fatal case from Eastern Europe.

Bendiocarb is used against a wide range of insects but has already been withdrawn from the market in some countries. It poses a high risk to birds as they can accidentally ingest it while searching for food, followed by toxic effects. This paper presents the results of toxicological and histopathological studies of 48 cases of intentional birds of prey poisoning with bendiocarb in Eastern Europe, specifically Poland. A novel ultra-high-performance liquid chromatography-triple quadrupole-tandem mass spectrometry (UHPLC-ESI-MS/MS) method for bendiocarb determination in animal liver samples was developed and fully validated. The sample preparation technique was based on one-step precipitation of proteins with cold acetonitrile. The internal standard used was carbaryl-d7. Full time of analysis was less than 10 minutes. The application of the UHPLC-ESI-MS/MS method allowed us to achieve the lowest LOQ (1 ng/g) of bendiocarb in biological samples to date. Necropsies and histopathological examinations of common ravens (Corvus corax), western marsh harriers (Circus aeruginosus), red kites (Milvus milvus), and a white-tailed eagle (Haliaeetus albicilla) revealed multi-organ toxicity manifested as congestion, oedema, or stagnation of blood. An analytical investigation confirmed the presence of bendiocarb in liver in the 1808-7721 ng/g range. Furthermore, the presence of this compound was qualitatively confirmed in the stomach and beak contents and also in the bait located near the deceased animals. A comprehensive forensic examination is crucial to monitor wildlife fatalities, especially applying a combined analytical and histopathological approach to identify and eliminate highly toxic substances which pose a threat to the ecosystem.

Comparison of Geqingpi and Sihuaqingpi based on ultra-high-performance liquid chromatography-tandem mass spectrometry combined with multivariate statistics, network pharmacology analysis, and molecular docking.

Citri Reticulatae Pericarpium Viride is used in traditional Chinese medicine as Geqingpi and Sihuaqingpi varieties. We used the ultra-high-performance liquid chromatography-quadrupole-Exactive Orbitrap-mass spectrometry method and high-performance liquid chromatography-triple quadrupole-tandem mass spectrometry to analyze the chemical compounds in these varieties. Principal components analysis and orthogonal partial least squares discriminant analysis were used to analyze the quantitative results. Network pharmacology and molecular docking technology were used to forecast Citri Reticulatae Pericarpium Viride treatment mechanisms in irritable bowel syndrome. We identified 44 main compounds in Citri Reticulatae Pericarpium Viride. Compared to Sihuaqingpi, Geqingpi had higher narirutin, didymin, naringenin, and hesperetin, and lower hesperidin, isosinensetin, nobiletin, 3,5,6,7,8,3',4'-hexamethoxyflavone, tangeretin. Tangeretin, nobiletin, narirutin, didymin, and isosinensetin were the main compounds distinguishing Geqingpi from Sihuaqingpi. We found that the MAPK signaling pathway, which is closely related to irritable bowel syndrome, was an important target pathway. TP53, HRAS, MAPK1, AKT1, and EGFR were important targets in this pathway. Eriodictyol-7-O-rutinoside, narirutin, limonin, and hesperidin showed a good binding ability to the five targets. Orientin, unique to Sihuaqingpi, bound well to TP53, MAPK1, AKT1, and EGFR, while rhoifolin bound well to TP53, HRAS, MAPK1, AKT1, and EGFR. Hesperetin, unique to Geqingpi, bound well to TP53, HRAS, and MAPK1, while naringenin bound well to HRAS. Hesperidin and didymin bound well to TP53, MAPK1, AKT1, and EGFR.

Comparison of odor and quality of Galli Gigerii Endothelium Corneum derived from domestic chickens and broilers

Galli Gigerii Endothelium Corneum(GGEC) is commonly used for the clinical treatment of indigestion, vomiting, diarrhea, and infantile malnutrition with accumulation. In recent decades, omnivorous domestic chickens, the original source of GGEC, has been replaced by broilers, which may lead to significant changes in the quality of the yielding GGEC. Through subjective and objective sensory evaluation, biological evaluation, and chemical analysis, this study compared the odor and quality between GGEC derived from domestic chickens and that from broilers. The odor intensity between them was compared by odor profile analysis and it was found that the fishy odor of GGEC derived from domestic chickens was significantly weaker than that of GGEC from broilers. Headspace-solid phase microextraction-gas chromatography-triple quadrupole tandem mass spectrometry(HS-SPME/GC-QQQ-MS/MS) suggested that the overall odor-causing chemicals were consistent with the fishy odor-causing chemicals. According to the odor activity va-lue and the orthogonal partial least squares discriminant analysis(OPLS-DA) result, dimethyl trisulfide, 2-methoxy-3-isobutylpyrazine, and 2-methylisoborneol were responsible for the fishy odor(OAV≥1) and the content of fishy odor-causing chemicals in GGEC derived from broilers was 1.12-2.13 folds that in GGEC from domestic chickens. The average pepsin potency in GGEC derived from broilers was 15.679 U·mg~(-1), and the corresponding figure for the medicinal from domestic chickens was 26.529 U·mg~(-1). The results of pre-column derivatization reverse-phase high-performance liquid chromatography(RP-HPLC) assay showed that the content of total amino acids and digestion-promoting amino acids in domestic chickens-derived GGEC was 1.12 times and 1.15 times that in GGEC from broilers, and the bitter amino acid content was 1.21 times folds that of the latter. In conclusion, GGEC derived from domestic chickens had weaker fishy odor, stronger enzyme activity, higher content of digestion-promoting amino acids, and stronger bitter taste than GGEC from broilers. This study lays a scientific basis for studying the quality variation of GGEC and provides a method for identifying high-quality GGEC. Therefore, it is of great significance for the development and cultivation of GGEC as both food and medicine and breeding of corresponding varieties.

Screening and characterizing the quality markers of Selaginella tamariscina (P. Beauv.) Spring using metabonomics and molecular networking

Quality control of traditional Chinese medicine (TCM) should be linked with the authentication and efficacy of TCM. Selaginella tamariscina is a frequently used traditional Chinese herbal medicine. However, its quality control is still difficult due to its multiple adulterants. We established quality markers (Q-markers) of S. tamariscina by using metabolomics, molecular networking and network pharmacology to improve the authenticity study and quality control of S. tamariscina. In this study, ultra high performance liquid chromatography-mass spectrum (UHPLC-MS) coupled with multivariate statistical analyses was applied to distinguish between S. tamariscina samples and their confusing adulterants. Principal component analysis, hierarchical clustering analysis (PCA), hierarchical clustering analysis (HCA) and partial least squares discriminant analysis (PLS-DA) were employed to screen the distinguishing markers from S. tamariscina samples and their adulterants. The top-2 distinguishing markers were isolated from S. tamariscina and identified by molecular networking together with nuclear magnetic resonance spectroscopy (NMR). Network pharmacology predicted the bioactivity and cytotoxicity of the top-2 distinguishing markers. The top-2 distinguishing markers were adopted as Q-markers of S. tamariscina for content determination. Based on the results of ultra performance liquid chromatography-quardrupole-time of flight mass spectrometry (UHPLC-QTOF-MS) metabolomics, we revealed that selaginellins could only be detected in S. tamariscina samples and contributed greatly to discriminating S. tamariscina samples from their confused species. The top-2 distinguishing markers were isolated and purified from S. tamariscina extract. Then, they were further identified as selaginellin and selaginellin A by molecular networking and NMR. Network pharmacology predicted the antitumor activity of selaginellin and selaginellin A, while the cytotoxicity assay verified their bioactivity. In conclusion, selaginellin and selaginellin A were selected as Q-markers for the determination and quality evaluation of S. tamariscina based on ultra performance liquid chromatography-triple quadrupole tandem mass spectrometry (UHPLC-QQQ-MS). The ranges of the concentrations of selaginellin and selaginellin A were 41.57–44.89 μg/g and 15.09–16.75 μg/g, respectively. This study provides a novel strategy combining Ultra performance liquid chromatography mass spectrometry based (UHPLC-MS-based) metabolomics with molecular networking for rapid species identification of S. tamariscina and discovery of the Q-markers of TCM.

Rapid and Simultaneous Quantification of Six Aristolochic Acids and Two Lignans in Asari Radix et Rhizoma Using Ultra-Performance Liquid Chromatography-Triple Quadrupole Tandem Mass Spectrometry.

Asari Radix et Rhizoma (AR) is a widely-used Chinese herbal medicine containing multiple active lignans and rare nephrotoxic components-aristolochic acids derivatives (AAs). However, the current quality control method carried out by Chinese Pharmacopoeia has defects in trace AAs detection and insufficient marker ingredients, which is unable to comprehensively evaluate the efficacy and safety of AR. To improve the quality control method of AR, a rapid, sensitive, and reliable chromatographic analytic method based on ultra-high-performance liquid chromatography-triple quadrupole tandem mass spectrometry (UHPLC-QqQ-MS) was established for the simultaneous analysis of multiple AAs and lignans in AR samples. Positive electrospray ionization mode with multiple reaction monitoring (MRM) was applied for the detection of the eight analytes. The method showed available linearity (R2 ≥ 0.991), the limit of quantification (2–5 ng/mL), precision (RSD <8.12%), and accuracy (89.78–112.16%). A total of 6 AAs and 2 lignans were quantified for their content in 15 AR samples. The content of AA-IVa, AA-VIIa, and aristololactam I (AL-I) was much higher than the AA-I controlled by pharmacopoeia. Considering the potential toxicity of AAs, AA-IVa, AA-VIIa, and AL-I should also be controlled in AR. A considerable amount of active sesamin was detected in AR, suggesting that it could be added as a quality marker for the quality control of AR. The newly developed analytical method could be applied for the fast evaluation of toxic AA's content and quality during quality control of AR or preparations containing AR.

Contamination level and population exposure assessment of chloropropanol esters in edible vegetable oil in Shandong Province from 2016 to 2020

To investigate the contamination of 2-chloropropanol esters and 3-chloropropanol esters in commercial edible vegetable oils in Shandong Province, and to assess the dietary 3-chloropropanol esters exposure and the health risk of intaking 3-chloropropanol esters. From 2016 to 2020, 406 individually packaged edible vegetable oils were collected from stores and farmers&apos; markets in 16 prefecture-level cities in Shandong Province. According to the 2016 National Food Contamination and Harmful Factors Risk Monitoring Manual, using gas chromatography-triple quadrupole tandem mass spectrometry detection, isotope internal standard method for quantification, laboratory determination of 2-chloropropanol ester and 3-chloropropanol in vegetable oil ester content. Combined with population weight, oil consumption and monitoring data, the point assessment method was used to evaluate the exposure of residents in Shandong Province to 3-chloropropanol esters. The detection rate of 3-chloropropanol ester was 92.4%(375/406), the concentration range was&lt;limit of detection(LOD)-18.4 mg/kg, the median was 0.470 mg/kg, the average was 0.833 mg/kg, and the maximum value was 18.4 mg/kg in rice oil; the detection rate of 2-chloropropanol ester was 88.7%(360/406), the concentration range was &lt;LOD-8.46 mg/kg, the median value was 0.204 mg/kg, the average value was 0.432 mg/kg, and the maximum value was 8.46 mg/kg in rice oil. The average exposure of each age group was less than the tolerable daily intake, and the high-end exposure of the children(2-6 years old) and adolescents(7-10 years old) group was greater than the tolerable daily intake. The contamination of chloropropanol esters of edible vegetable oil in Shandong Province from 2016 to 2020 is widespread, and the highest detection value appears in rice oil. Children(2-6 years old) and adolescents(7-10 years old) in high-risk situations ingest 3-chloropropanol esters present health risks.

Antidepressants as emerging contaminants: Occurrence in wastewater treatment plants and surface waters in Hangzhou, China.

AimsAntidepressants have aroused wide public concern due to their widespread presence in water and their harm to human health and environment. This study was designed to evaluate the contribution of wastewater treatment plants (WWTPs) to the presence of antidepressants in the surface water.MethodsData was evaluated by analyzing water samples collected from the influent, effluent, upstream and downstream of the WWTPs on the rivers of interest in Hangzhou, Zhejiang Province, China. Besides, the study also assessed the impact of the release of antidepressants from WWTPs to the surface water on the drinking water. An automatic solid-phase extraction combined with ultra-high performance liquid chromatography-tandem triple quadrupole mass spectrometry (UPLC-MS/MS) was used to detect antidepressants.ResultsThe most abundant compound was venlafaxine, followed by citalopram, sertraline, and fluvoxamine with concentrations between 0.6 and 87 ng/L. Antidepressants showed maximum concentrations at the effluent outlets of the WWTPs, and greater concentrations were found downstream than upstream of the WWTPs in Qiantang River. The results of source water and finished water showed that the detection concentration was lower than the detection limit of the method.ConclusionsThe less impact of the release of antidepressants from WWTPs to the surface water on the drinking water was identified. Nevertheless, these compounds were hardly removed by wastewater treatment processes. Thus, their risks deserve close attention.

Antibiotic Pollution Characteristics and Ecological Risk Assessment in Jinjiang River Basin, Jiangxi Province

The concentration and distribution characteristics of 27 antibiotics, including 8 sulfonamides, 9 quinolones, 4 tetracyclines, 4 macrolides, and 2 nitroimidazoles, in the surface water, groundwater, and wastewater of the Jinjiang River basin in Jiangxi province were determined using solid-phase extraction combined with ultra-performance liquid chromatography-tandem triple quadrupole mass spectrometry. The results showed that there was antibiotic pollution in the waters of the Jinjiang River basin. A total of 20 antibiotics were detected in the surface water, with a concentration range of 32.3-280 ng·L-1. There were 15 types of antibiotics detected in the groundwater, and the concentration range was 28.4-55.8 ng·L-1. Twenty-one types of antibiotics were detected in the wastewater, with a concentration range of 231-8.71×104 ng·L-1. A comparison with the concentrations of eight common antibiotics in rivers and lakes in China and abroad showed that the pollution level in the Jinjiang River basin was at a medium level. By comparing the concentrations of sulfamethoxazole in groundwater from domestic and international samples, the groundwater pollution in the Jinjiang River basin was clearly in the middle and lower range. A comparison of the concentrations of the three antibiotics in the aquaculture wastewater from domestic and abroad samples indicated that the pollution level of sulfadiazine in the aquaculture wastewater from the Jinjiang River basin was relatively high. The ecological risk assessment results showed that there were nine medium- and high-risk antibiotics, which were clarithromycin, erythromycin, ciprofloxacin, sulfathiazole, roxithromycin, tetracycline, ofloxacin, enrofloxacin, and sulfamethoxazole; the rest were low-risk or no-risk antibiotics.

Phenolic compositions and antioxidant activities of Hippophae tibetana and H. rhamnoides ssp. sinensis berries produced in Qinghai-Tibet Plateau.

Phenolic ingredients of Hippophae tibetana (Tib) and H. rhamnoides ssp. sinensis (Rha) berry from Qinghai-Tibet Plateau were identified by Ultra Performance Liquid Chromatography-triple Quadrupole Tandem Mass Spectrometry. Results demonstrated that both of them possessed high levels of total phenolic and flavonoid, and compared to Tib, Rha berry exhibited higher contents. Moreover, flavonols was the most predominant subclass in Rha berry, flavonols and flavanols were the two most abundant subclasses in Tib berry. Among them, rutin and narcissin were present in the most abundant amounts in Rha berry, while (-)-epigallocatechin was the richest substance in Tib berry. Furthermore, both phenolic extracts of sea buckthorn berry exhibited strong in vitro and cellular antioxidant properties. Rha berry extract exhibited much stronger effects because of its higher levels of phenolic and flavonoid profiles. This finding proved that the Rha berry could serve as a food source for better health with great potential antioxidant activity.

A new quantitative method for pseudouridine and uridine in human serum and its clinical application in acute myeloid leukemia

Pseudouridine, a C-C glycosidic isomer of uridine, is derived from uridine via isomerization, and pseudouridylation is the most common post-transcriptional modification. Our previous study shows pseudouridine may serve an important role in acute myeloid leukemia (AML). The clinical value of pseudouridine and uridine is hampered by the lack of a quantitative methods with high sensitivity, specificity, and stability. Here, we established a supercritical fluid chromatography-tandem triple quadrupole mass spectrometry (SFC-TQ-MS)-based method to quantitate serum pseudouridine and uridine simultaneously. The procedure involves protein precipitation of sample, extraction with solid phase extraction (SPE) plate, 5-min SFC separation by applying gradient elution on a Acquity UPC2 Torus DIOL column, and analysis by TQ-MS using well-characterized calibration standards. After validation, the method was used to measure pseudouridine and uridine concentrations in 143 serum samples from healthy controls (HCs) and AML patients to evaluate their prognostic potential. The successfully validated assay had a linear range of 5–5000 ng/mL, accuracies between 97 % and 102 %, and intra- and inter-assay imprecision <10 %. Compared to HCs, pseudouridine was raised significantly, while uridine was curtailed severely in patients with AML. With a median concentration of 671.4 ng/mL as the prognostic cut-off value, high level pseudouridine independently predicted poor survival of AML patients. Quantification of serum pseudouridine and uridine by SFC-TQ-MS provides an analytically sensitive and reproducible method for clinical diagnosis, and high concentration of pseudouridine is an independent prognostic factor for patients with AML.

The variation of odor characteristics of wastewater sludge treated by advanced anaerobic digestion (AAD) and the contribution pattern of key odorants

Identification of the odor characteristics of wastewater sludge is important in the evaluation of sludge quality and disposal options considering that sludge odor nuisance may cause major environmental issues. In this study, raw sludge and sludge cake were collected from five WWTPs applied advanced anaerobic digestion (AAD) sludge treatment process to clarify the variation of odor characteristics using sensory analysis and instrumental analysis. The electronic nose, gas chromatography-ion mobility spectrometry (GC-IMS) and gas chromatography-triple quadrupole tandem mass spectrometry (GC–MS/MS) were used to profile and identify the chemical composition of key odorants. A total of 20 odorants were identified and quantified, including 6 groups of chemicals, among which volatile sulfur compounds (VSCs), indole, 3-methylindole and geosmin were identified as key odorants. The odor of the dewatered digested sludge was improved by means of changing the odor character from fecal/sulfide to earthy odor due to the reduction in VSCs concentration. The AAD and subsequent dewatering process resulted in effective removal of VSCs, which are important constituents that impact the sludge odor characteristics through synergistic effect on fecal odorants and masking effect on earthy odorants. Moreover, due to the variation of sludge quality after AAD treatment, the emission capacity of indole, 3-methylindole, and other volatiles increased, which could not be neglected for the formation of unique sludge odor.

Carbon Isotope Composition and Geochemical Features of Sediments From Gongga Mountain, China, and Potential Environmental Implications

Using gas chromatography-triple quadrupole tandem mass spectrometry (GC-MS/MS), the soluble organic matter was analyzed for the first time in twenty-two sediment samples from the eastern slopes of the Gongga Mountain, China, at high altitudes between 4,600 and 6,700 m. The C11-C33n-alkanes and C9-C33n-alkan-2-ones were identified in these samples. Both compounds were dominated by odd carbon numbers in the long-chain molecules and contained a maximum of n-C27 or n-C29, indicating that the sediments were predominantly of higher plant origin. However, the short-chain n-alkan-2-ones, with a maximum content of n-C17 or i-C18 (phytone, 6, 10, 14-trimethylpentadecan-2-one), did not show a predominance of odd and even numbers, suggesting that they were predominantly derived from bacteria and algae. Therefore, we suggest that the organic matter in Gongga Mountain comes from three sources, i.e. bacteria, algae, and higher plants. Stable carbon isotope (δ13C) values ranged from −24.6‰ to −27.3‰, indicating that C3 plants were the dominant organic input to the sediments and suggesting a relatively colder and drier depositional environment. However, C4 plants increase sharply at high altitudes of 6,300–6,600 m, suggesting that the paleoclimate of Gongga Mountain became drier and wetter with the increase of altitude.

Characterization of aroma-active compounds in Dongli by quantitative descriptive analysis, gas chromatography-triple quadrupole tandem mass spectrometry, and gas chromatography-olfactometry.

The online version contains supplementary material available at 10.1007/s13197-022-05463-8.

Characterization of N,O-heterocycles in green tea during the drying process and unraveling the formation mechanism

N,O-Heterocycles play an important role in the characteristic flavor of green tea owing to their strong odors and low odor thresholds. In this study, a rapid and sensitive method was developed to determine seven N,O-heterocycles in green tea by using headspace solid-phase microextraction Arrow (HS-SPME-Arrow) coupled with gas chromatography-triple quadrupole-tandem mass spectrometry. The HS-SPME-Arrow extraction was performed using a Carbon WR SPME Arrow fiber. Good linear ranges (5–1000 ng/mL) were obtained, with correlation coefficients (R2) higher than 0.99 for all target compounds. LODs and LOQs were in the range of 0.44–5.12 and 1.48–17.04 μg/kg, respectively. The recoveries of seven N,O-heterocycles were found to vary from 83.1% to 117.3%, with RSDs being lower than 10%. The dynamic changes of N,O-heterocycles during the drying process revealed that 25- and 40-min-long drying processes were key transition points. Furfural could be used as a key indicator compound for evaluating the extent of the drying. Moreover, furfural and 2-methylfuran revealed a significant positive correlation with proline (p < 0.05). The possible formation mechanisms of N,O-heterocycles were further elaborated by simulated Maillard reactions. Our results provide a theoretical foundation for the improvement and directional regulation of aroma quality of green tea during manufacturing.

Simultaneous focused ultrasound solid–liquid extraction and dispersive solid-phase extraction clean-up for gas chromatography–tandem mass spectrometry determination of polycyclic aromatic hydrocarbons in crustacean gammarids meeting the requirements of the European Union Water Framework Directive

The study presents the development and validation of a method for the determination of seven priority polycyclic aromatic hydrocarbons (PAHs, including fluoranthene and benzo[a]pyrene, for which the EU has set environmental quality standards, EQS, for biota) in gammarid samples combining focused ultrasound solid–liquid extraction and dispersive solid-phase extraction clean-up in one step followed by gas chromatography–triple quadrupole tandem mass spectrometry (GC–QqQ-MS/MS). The method is designed to analyse small about 100 mg dry weight (dw) samples obtained after lyophilisation of 500 mg wet weight (ww) samples. The sample preparation procedure is simple, environment friendly (method was classified as “an excellent green analysis” according to the analytical Eco-Scale assessment), non-laborious and low-cost and, apart from the sample extract concentration step, is quick. Thorough disintegration of the gammarids is achieved by a combination of sonication and the addition of granular anhydrous Na2SO4 to the gammarid suspension, thus avoiding the need to grind the sample prior to analysis. The QqQ-MS/MS detector, thanks to its excellent selectivity and sensitivity, allows to meet the EQS requirements for PAHs in biota with a good margin (limits of quantification in the range of 0.12 and 0.56 ng g‒1 ww). The method has been successfully validated (in terms of linearity, method limits, precision, trueness, robustness, measurement uncertainty and comparative analysis of real samples), and has been shown to be suitable for monitoring and evaluating the PAHs contamination in surface water biota.

High quality standard of Scutellariae Radix based on plant metabolomics and index components

Scutellariae Radix(SR), derived from the dried root of Scutellaria baicalensis in the family Lamiaceae, commonly serves as Chinese medicinal material. Affected by producing areas, growing years, and harvesting periods, the quality of SR fluctuates in the market. However, baicalin≥9% in SR required in the Chinese Pharmacopoeia(2020 edition) can only determine the qualified SR but cannot identify high-quality SR. To improve the quality control methods of SR, the present study analyzed the accumulation of metabolites in SR of different growth years by plant metabolomics, and identified 28 metabolites increasing with growth years(1-3 years). Subsequently, 14 main metabolites were quantitatively analyzed by ultra-high performance liquid chromatography-tandem triple quadrupole mass spectrometry(UPLC-QQQ-MS). Among them, baicalin, wogonoside, baicalein, and wogonin with high content and good activity were selected as the index components of SR for quality evaluation. A high-performance liquid chromatography(HPLC) method was established to determine the content of four index components in 32 batches of SR from different producing areas, harvesting perio-ds, and growth years. The results showed that the growth years could greatly affect the content of index components. The total content of four index components in 2-year SR was the highest, followed by the 3-/4-year SR and 1-year SR. Based on HPLC data and verification results by enterprises, baicalin ≥12.0%, wogonoside ≥2.3%, baicalein ≥0.1%, and wogonin ≥0.03% were proposed as the evaluation criteria for the high-quality SR. The findings of this study are expected to provide a basis for improving the quality of SR.