Improvements in Neoplasm Classification in the International Classification of Diseases, Eleventh Revision: Systematic Comparative Study With the Chinese Clinical Modification of the International Classification of Diseases, Tenth Revision.

BACKGROUND: The International Classification of Diseases, Eleventh Revision (ICD-11) improved neoplasm classification. OBJECTIVE: We aimed to study the alterations in the ICD-11 compared to the Chinese Clinical Modification of the International Classification of Diseases, Tenth Revision (ICD-10-CCM) for neoplasm classification and to provide evidence supporting the transition to the ICD-11. METHODS: We downloaded public data files from the World Health Organization and the National Health Commission of the People's Republic of China. The ICD-10-CCM neoplasm codes were manually recoded with the ICD-11 coding tool, and an ICD-10-CCM/ICD-11 mapping table was generated. The existing files and the ICD-10-CCM/ICD-11 mapping table were used to compare the coding, classification, and expression features of neoplasms between the ICD-10-CCM and ICD-11. RESULTS: The ICD-11 coding structure for neoplasms has dramatically changed. It provides advantages in coding granularity, coding capacity, and expression flexibility. In total, 27.4% (207/755) of ICD-10 codes and 38% (1359/3576) of ICD-10-CCM codes underwent grouping changes, which was a significantly different change (χ21=30.3; P<.001). Notably, 67.8% (2424/3576) of ICD-10-CCM codes could be fully represented by ICD-11 codes. Another 7% (252/3576) could be fully described by uniform resource identifiers. The ICD-11 had a significant difference in expression ability among the 4 ICD-10-CCM groups (χ23=93.7; P<.001), as well as a considerable difference between the changed and unchanged groups (χ21=74.7; P<.001). Expression ability negatively correlated with grouping changes (r=-.144; P<.001). In the ICD-10-CCM/ICD-11 mapping table, 60.5% (2164/3576) of codes were postcoordinated. The top 3 postcoordinated results were specific anatomy (1907/3576, 53.3%), histopathology (201/3576, 5.6%), and alternative severity 2 (70/3576, 2%). The expression ability of postcoordination was not fully reflected. CONCLUSIONS: The ICD-11 includes many improvements in neoplasm classification, especially the new coding system, improved expression ability, and good semantic interoperability. The transition to the ICD-11 will inevitably bring challenges for clinicians, coders, policy makers and IT technicians, and many preparations will be necessary.

Surface multi-walled carbon nanotube modified quaternary amine-functionalized polymers for purification and determination of glyphosate and its four metabolites in plasma samples.

The present study focused on the pretreatment and detection of GLY and its four metabolites AMPA, N-acetyl AMPA, N-methyl GLY and N-acetyl GLY in plasma samples. Multi-walled carbon nanotube-modified quaternary amine-functionalized polymers (QA-PDNV@MWCNTs) were synthesized in a controlled manner by self-assembly, and its morphology and composition were extensively characterized. The QA-PDNV@MWCNTs microspheres were then used as an SPE adsorbent for the preparation and rapid determination of GLY and its four metabolites in plasma samples combined with ultra-performance liquid chromatography-high resolution mass spectrometry (UPLCHRMS). The SPE conditions based on QA-PDNV@MWCNTs were optimized for GLY and its metabolites to obtain the best purification efficiency. The experimental results show that when the adsorbent contains 8% MWCNTs, it can balance the adsorption of target analytes and the purification performance of the adsorbent for impurities. In addition, this study compared the QA-PDNV@MWCNTs based SPE method with the commercial Waters Oasis MAX SPE cartridge and the results showed that the developed method in this study has better resistance to matrix interference. Under optimal conditions, the recoveries of GLY and its metabolites spiked in plasma were 82.6-99.4 % with relative standard deviations (RSDs) of 1.0-7.8 %. The limits of detection (LODs, S/N ≥ 3) and limits of quantification (LOQs, S/N ≥ 9) of the method were 0.05-0.33 µg/L and 0.15-1.00 µg/L, respectively. Finally, the developed QA-PDNV@MWCNTs based SPE-UPLCHRMS method was used to confirm GLY poisoning not only on the basis of the detection of the GLY prototype, but also on the basis of its four metabolites.

Synthesis and application of quaternary amine-functionalized core-shell-shell magnetic polymers for determination of metabolites of benzene, toluene and xylene in human urine samples and study of exposure assessment.

As production processes have evolved, airborne concentrations of benzene, toluene and xylene in many workplaces are already well below the occupational exposure limits. However, studies have shown that low levels of exposure to benzene, toluene and xylene can still cause health effects in people exposed occupationally. However, there is no literature on health risk assessment of internal exposure. In view of this, an analytical method based on quaternary amine-functionalized core-shell-shell magnetic polymers (QA-CSS-MPs) was developed for the determination of seven metabolites in urine by MSPE-UPLC-DAD-HRMS. Furthermore, an improved QuEChERS method for the extraction of seven metabolites from human urine samples was introduced for the first time and satisfactory extraction rates were achieved. In addition, QA-CSS-MPs microspheres with core-shell-shell structure were designed and synthesized, and the morphology, composition and magnetic properties of the materials were fully characterized to verify the rationality of the synthetic route. Subsequently, QA-CSS-MPs microspheres were used as magnetic solid-phase extraction (MSPE) adsorbents for the purification of urine extracts, and UPLC-DAD-HRMS was used for the detection of seven metabolites. As a result, this method allows the accurate determination of seven metabolites in urine samples over an ultra-wide concentration range (0.001-100 mg/L). Under optimal experimental conditions, i.e., 2% hydrochloric acid in urine for the hydrolysis and 20 mg of QA-CSS-MPs for 5 min purification, the spiked recoveries of the seven target metabolites ranged from 81.5% to 117.7% with RSDs of 1.0%-9.4%. The limits of detection (LODs, S/N≥3) for the established method were in the range of 0.2-0.3 µg/L. The developed method was applied to 254 human urine samples for the determination of seven metabolites. The results showed that the concentration distributions of three xylene metabolites in urine, 2-MHA, 3-MHA, 4-MHA and total MHA, showed statistically significant differences for occupational exposure (p<0.001). In addition, the results of the internal exposure assessment showed that there is a high potential health risk associated with occupational exposure processes.

[Determination of paraquat and diquat residues in urine samples based on solid-phase extraction and ultra performance liquid chromatography-high resolution mass spectrometry].

Determining the presence of paraquat (PQ) and diquat (DQ) in urine samples through physical and chemical testing is challenging. As PQ and DQ have characteristics such as high molecular polarity and good water solubility, they are difficult to be retained by conventional reversed-phase columns. Most of the methods in the literature use hydrophilic interaction chromatography (HILIC) for the retention of PQ and DQ, but they often require high concentrations of buffer salts as the mobile phase, which increase the contamination of the mass spectrometer. In view of the above problems, a rapid and accurate analysis method was developed for the determination of PQ and DQ residuals in urine samples based on weak cation exchange (WCX) solid-phase extraction (SPE) and ultra performance liquid chromatography-high resolution mass spectrometry (UPLC-HRMS) in this study. Urine samples were first diluted with phosphate buffer (pH=6.86) and pretreated using the WCX SPE method. Chromatographic separation was performed on a Syncronis HILIC column (100 mm×2.1 mm, 1.7 µm). An electrospray ion source in the positive (ESI+) mode and full mass-data dependent MS2 (full mass-ddMS2) mode was used for quantification by matrix-matched external standard method. In this study, the concentration of ammonium formate in the mobile phase in the HILIC mode was effectively reduced to 10 mmol/L by the continuous optimization of the chromatographic conditions. MS optimization results indicated that the molecular ion (M+·) of PQ and DQ had the strongest response. In addition, sample pretreatment conditions were also optimized. The obtained results indicated that the hydrophobic polytetrafluoroethylene (PTFE) filter membrane, acetonitrile-water (1∶1, v/v) as a fixing solution, and polypropylene vials were suitable for PQ and DQ analysis. Under the optimal conditions, the linearity of PQ and DQ was good with correlation coefficients (r2) greater than 0.998. The limits of detection (LODs, S/N≥3) and limits of quantification (LOQs, S/N≥10) were 0.2 µg/L and 0.6 µg/L, respectively. Mean spiked recoveries of PQ and DQ at the four spiked levels (1.0, 20.0, 100.0, and 200.0 µg/L) were in the range of 85.8%-101% and 80.3%-86.9%, with the RSDs of 0.8%-5.1% and 0.9%-4.2%. The established method was employed for the analysis and confirmation of PQ and DQ for clinical poisoning cases. In one case, a 23-year-old male who had taken approximately 20 mL of pesticide orally was confirmed as DQ poisoning by the developed method. DQ concentration monitoring of the urine samples was conducted for this case during the clinical treatment process. The patient was successfully discharged from the hospital after five times of blood perfusion and other treatments until the DQ concentration was low in the urine samples. In conclusion, the method developed in this study based on WCX SPE-UPLC-HRMS can be used for the confirmation of poisoning cases and concentration monitoring during clinical treatment, providing strong technical support for clinical precision treatment. The method is rapid, simple, sensitive, and accurate, and it is suitable for the detection of PQ and DQ in urine samples.

[Simultaneous determination of nine estrogens in bullfrogs using filtered solid phase extraction and ultra-performance liquid chromatography-tandem mass spectrometry].

Due to the harmful effects of estrogens and their prevalence in animal foods, accurate analysis of estrogen levels in animal foods is imperative in order to effectively assess food safety risks and ensure consumer safety. Therefore, a rapid and accurate method based on PRiME HLB solid phase extraction (SPE) cartridge purification and ultra-performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) was developed to determine nine estrogen residues in bullfrogs. The nine estrogens included estriol (E3), 17ß-estradiol (ß-E), 17α-estradiol (α-E), 17α-ethinylestradiol (EE2), estrone (EI), diethylstilbestrol (DES), dienestrol (DE), hexestrol (HEX), and dienestrol diacetate (DD). This study optimized the mobile phase system, extraction solvent, and SPE cartridges. Because estrogens present weak alkalinity, adding a small amount of alkaline substance to the mobile phase benefits estrogen ionization into the ionic state, eliminates the peak trailing phenomenon, and enhances the signal response of estrogens to improve sensitivity. Estrogens have one or more hydroxyl groups in their chemical structures. According to the principle of similar solubility, polar solvents are chosen as extraction solvents. Based on the complex matrix composition of meat samples, SPE is required for purification to reduce matrix effects. The liquid chromatographic conditions were optimized, and the 0.5 mmol/L ammonium fluoride aqueous solution-acetonitrile system as mobile phases showed better sensitivity than the ammonium acetate aqueous solution-acetonitrile system and the ammonia-acetonitrile system for the nine estrogens. When acetonitrile was used as the extraction solvent, the extraction rates of all nine estrogens exceeded those of methanol and ethyl acetate and increased by 15%-40%. By focusing on the matrix purification effect of four different SPE cartridges, the results showed that the matrix purification ability of the PRiME HLB cartridge outperformed that of the HLB, C18, and Silica SPE cartridges. After purification by the PRiME HLB cartridge, the recoveries of all compounds were in the range of 70%-125%, and the DD recovery was increased from 47% to 74%, whereas the HEX recovery was reduced from 180% to 123%. Therefore, the PRiME HLB SPE cartridge was selected as the cleanup material for this experiment. Finally, the sample was extracted using acetonitrile, purified by PRiME HLB SPE cartridge, and separated on a Waters Acquity UPLC BEH C18 column (100 mm×2.1 mm, 1.7 µm) with a mobile phase of 0.5 mmol/L ammonium fluoride aqueous acetonitrile solution at a flow rate of 0.3 mL/min. The detection was conducted in positive and negative ion switching mode (ESI+/ESI-) and multiple reaction monitoring (MRM) scanning, and it was quantified using a matrix-matched external standard method. Under the optimal experimental conditions, the linear ranges were 0.5-100.0 µg/L for E3, ß-E, α-E, EI, DE, HEX, and DD, and 1.0-100.0 µg/L for EE2 and DES. The nine estrogens showed good linearity in all linear ranges, with correlation coefficients of 0.9953-0.9994. The limits of detection were 0.17-0.33 µg/kg, and the limits of quantification were 0.5-1.0 µg/kg. The recoveries of the nine estrogens spiked at the three spiked levels of low (2.0 µg/kg), medium (10.0 µg/kg), and high (80.0 µg/kg) were 107.4%-125.3%, 67.0%-123.3%, and 65.1%-128.2%, respectively. The relative standard deviations were 1.9%-17.6%. The method established in this study was applied to detect nine estrogen residues in 50 commercially available bullfrog samples, and the results showed that HEX, EI, and DES were detected in few samples. The method is simple, rapid, sensitive, and reproducible, and can be used for the simultaneous, rapid and accurate determination of large quantities of samples.

Design and synthesis of amphiphilic carboxyl-functionalized magnetic polymer microspheres for fast determination of paraquat and its four metabolites in human urine samples prior to ultra-high performance liquid chromatography-high resolution mass spectrometry.

In cases of low concentration paraquat (PQ) poisoning, as the disease progresses over a long period of time, the prototype PQ may not be detected in the urine, which has a significant negative impact on the precise treatment of the poisoning. But PQ poisoning can also be confirmed by the detection of specific metabolites of PQ in the urine samples. In the present study, core-shell amphiphilic carboxyl-functionalized magnetic polymer microsphere (Amphiphilic-MPs-COOH) was prepared, and the as-prepared Amphiphilic-MPs-COOH was characterized by transmission electron microscope (TEM), scanning electron microscope (SEM), Fourier-transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), and thermogravimetry and differential thermogravimetry analyses (TG-DTG). Then, the Amphiphilic-MPs-COOH was employed as a magnetic solid-phase extraction (MSPE) adsorbent for pretreatment and rapid determination of PQ and its four metabolites from urine samples prior to ultra-high performance liquid chromatography-high resolution mass spectrometry (UPLC-HRMS). The extraction-elution conditions of Amphiphilic-MPs-COOH towards PQ and its metabolites were optimized in spiking urine samples to obtain the best MSPE efficiency. The adsorption mechanism of PQ and its metabolites by Amphiphilic-MPs-COOH involves electrostatic attraction and π-π stacking interactions. Moreover, the effect of different ratios of hydrophilic monomer NVP and functional monomer 4-VBA on the extraction and purification performance of PQ and its metabolites in urine samples. And the results revealed that both hydrophilic monomer and functional monomer were important for the adsorption of PQ and its metabolites, and the addition of the appropriate amount of the hydrophilic monomer NVP can improve the compatibility of the adsorbent with the urine substrate. In addition, this study compared the matrix effect of the Amphiphilic-MPs-COOH based MSPE method and the commercial Waters Oasis WCX SPE method. The results showed that the Amphiphilic-MPs-COOH based MSPE method developed in this paper had better resistance to matrix interference. Under optimal conditions, the recoveries of PQ and its metabolites were ranging from 84.5 to 103%, with relative standard deviations (RSDs) of 1.1-6.3%. While the limits of detection (LODs, S/N ≥ 3) and limits of quantification (LOQs, S/N ≥ 9) of the method were in range of 0.1-1.6 µg/L and 0.3-4.8 µg/L, respectively. Finally, the established MSPE-UPLC-HRMS method in this study was used to confirm PQ poisoning not only based on detecting PQ prototype, but also on its four metabolites, providing strong technical support for clinical precision treatment.

[Contamination status and the health risk evaluation of dietary exposure of quinolone and tetracycline antibiotics in animal derived foods in Ningbo City from 2018 to 2020].

OBJECTIVE: To investigate the dietary exposure of Ningbo residents to quinolones and tetracyclines antibiotics in animal derived foods, so as to estimate the health risk caused by the exposure. METHODS: Animal derived foods in Ningbo markets from 2018 to 2020 were collected and analyzed by ultra-fast liquid chromatography-tandem mass spectrometry. Based on the result of the measurements, median(M), P97.5, average and the maximum values of the data were obtained. Coupling the food intake data of residents in Zhejiang Province, an international point estimate model was applied to evaluate the health risk caused by the dietary exposure. RESULTS: Enrofloxacin, ciprofloxacin, ofloxacin, doxycycline, oxytetracycline were detected in freshwater fishes, cultured pseudosciaena crocea, freshwater shrimps, chicken, eggs and pork. The detection rates of enrofloxacin, ciprofloxacin, ofloxacin, doxycycline, oxytetracycline were 21.2%(77/363), 11.6%(42/363), 2.8%(10/363), 1.4%(5/363), 0.6%(2/363), respectively. The dietary exposure of adults and children from animal derived foods were in the range of 0.8-909.0 and 0.6-518.9 ng/(kg·d), respectively. The hazard quotient(HQ) values were in the range of 0.000030-0.17. CONCLUSION: Quinolone and tetracycline antibiotics such as enrofloxacin and oxytetracycline have no dietary health risk to the population.

Simultaneous determination of 11 quinolone residues in freshwater fish samples by magnetic solid-extraction coupled to liquid chromatography-tandem mass spectrometry.

In this study, well-defined core-shell ethylenediamine-functional magnetic ferroferric oxide polymers were prepared and were fully characterized by transmission electron microscopy, scanning electron microscopy, FTIR spectroscopy, and vibrating sample magnetometry. Then, it was used as a magnetic solid-phase extraction adsorbent for simultaneous determination of 11 trace quinolone residues in freshwater fish samples coupled to liquid chromatography-tandem mass spectrometry. The obtained results revealed that the adsorbent showed good extraction efficiency and the adsorption mechanisms referred to hydrogen bond and π-π stacking interaction. Moreover, the magnetic solid-phase extraction conditions were also carefully optimized. The limits of quantitation of 11 quinolones were in the range of 0.15-0.36 µg/kg, while spiking recoveries were in the range of 80.2-99.5% for the 11 quinolones in freshwater fish samples at four spiked levels including limits of quantitation, 1.0, 40.0, and 80.0 µg/kg with the relative standard deviations ranging from 0.8 to 9.1%. The proposed method was applied to analyze 45 freshwater fish samples, and enrofloxacin was detected in 91.1% samples with concentrations ranging from 0.659 to 333 µg/kg. It could be concluded that the proposed method is fast, simple, sensitive, and accurate for the routine monitor of freshwater fish.

[Simultaneous determination of 29 pesticides residues in bayberry by pass-through solid-phase extraction and ultra-performance liquid chromatography-high resolution mass spectrometry].

A rapid and accurate analysis method based on PRiME HLB pass-through solid-phase extraction (SPE) and ultra-performance liquid chromatography-high resolution mass spectrometry (UPLC-HRMS) was developed for the determination of 29 pesticide residues in bayberry samples. The bayberry samples were first extracted using acetonitrile by vortexing; then, the extract solution was salted out and purified by PRiME HLB pass-through solid-phase extraction (SPE) cartridges. Chromatographic separation was subsequently carried out on a Waters ACQUITY UPLC HSS T3 column (100 mm×2.1 mm, 1.8 µm) using 5 mmol/L ammonium acetate in water and acetonitrile as the elution solvent. The electrospray ion source in positive (ESI+) mode and full mass-data-dependent MS2 (full mass-ddMS2) mode were used for quantification by the matrix-matched external standard method. The LC conditions were first optimized, and two analytical columns, Waters ACQUITY UPLC HSS T3 and Waters ACQUITY UPLC BEH C18, were investigated for the 29 pesticides. The results indicated that the Waters ACQUITY UPLC HSS T3 column showed better chromatographic retention. Moreover, composites of the mobile phase were also studied. Compared to the acetonitrile-formic acid aqueous solution system and acetonitrile-formic acid-ammonium acetate aqueous solution system, the acetonitrile-ammonium acetate aqueous solution system used as the mobile phase exhibited much better chromatographic behavior for most of the 29 pesticides. In particular, the MS responses of some of the target pesticides were significantly improved when using the ammonium acetate-acetonitrile system as the mobile phase. In addition, the sample pretreatment conditions for the 29 pesticides in bayberry samples were systematically optimized. The matrix effect (ME) for three different types of purification methods were applied to evaluate the purification efficiency for the 29 pesticides in the bayberry samples. The following results were obtained from the post-spiking experiments: (1) For graphitized carbon (GCB) SPE, the post-spiking recoveries of 29 pesticides in the bayberry samples were generally low, less than 60%. (2) For the QuEChERS method, the recoveries of most target pesticides improved. The pesticide ratio with recoveries ranging from 70% to 120% was found to be 41%; however, the pesticide ratio with recoveries of less than 60% was still high (35%). (3) For the PRiME HLB-based pretreatment method, the recoveries of the 29 pesticides obviously improved. The pesticide ratio with recoveries between 70% and 120% was up to 76%, while the pesticide ratios were only 14% and 10% for post-spiking recoveries of 60%-70% and >120%, respectively. Meanwhile, the recoveries of all 29 pesticides were found to be more than 60%. Therefore, the PRiME HLB-based method was better than the GCB SPE and QuEChERS methods for pretreatment of the 29 pesticides in the bayberry samples. In addition, the PRiME HLB-based pretreatment process does not require tedious operation processes such as activation, balance, and elution, and thus, the sample pretreatment time is greatly shortened. Under the optimal conditions, the 29 target pesticides showed good linearity in the range of 1.0-200.0 µg/L, with correlation coefficients (R2) higher than 0.999. The limits of detection (LODs) were 2.0 µg/kg for the 29 target pesticides. The recoveries of the pesticides spiked in the bayberry samples were in the range of 69.2%-135.6% at 6, 200, and 400 µg/kg, respectively, while the relative standard deviations (RSDs) in the range of 0.7%-14.6%. The proposed method based on PRiME HLB-pass through SPE-UPLC-HRMS was adopted to determine these 29 pesticides in 30 bayberry samples purchased from local and online markets. According to the results, pesticides such as methamidamine, difenoconazole, and tebuconazole were frequently detected in the bayberry samples. However, the maximum residue limits (MRLs) of methamidamine, difenoconazole, and tebuconazole in bayberry samples were not provided in GB 2763-2019. In summary, the developed method is fast, simple, sensitive, and accurate, and it can be applied for daily monitoring of pesticides in bayberry samples.

Fabrication of benzenesulfonic acid groups modified magnetic microspheres as an MSPE adsorbent for fast determination of paraquat and diquat in human urine combined with UPLC-HRMS.

In this study, novel benzenesulfonic acid groups modified magnetic microspheres (Fe3O4@SiO2@poly(4-VB)) were synthesized and characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), Fourier-transform infrared spectrometry (FTIR), and vibrating sample magnetometer (VSM). The as-prepared Fe3O4@SiO2@poly(4-VB) was employed as a magnetic-phase extraction (MSPE) adsorbent for rapid determination of paraquat (PQ) and diquat (DQ) in human urine samples coupled with ultra-high performance liquid chromatography-high resolution mass spectrometry (UPLC-HRMS). Moreover, this paper had expounded systematically the mass spectrum cracking mechanisms of PQ and DQ. And a zwitterionic functionalized SIELC Obelisc R column was employed for separation and retention of the above two polar herbicides using 50 mmol/L ammonium formate (pH = 3.7)-acetonitrile as the mobile phase. Besides, the adsorption and desorption conditions of Fe3O4@SiO2@poly(4-VB) toward PQ and DQ were optimized in spiking urine samples to obtain the best adsorption and desorption efficiencies. And the adsorption mechanisms of Fe3O4@SiO2@poly(4-VB) toward PQ and DQ referred to synergetic effect of electrostatic attraction and π-π interaction. Under the optimal conditions, the inter-day and intra-day spiking recoveries of the proposed method were in the range of 86.7-109.9% with RSDs less than 10%. The limits of detection (LODs) were obtained by spiking in blank urine samples at a series of low concentrations and were found to be 0.12 µg/L and 0.14 µg/L for PQ and DQ, respectively, which were lower than the comparing literatures. The developed analytical method was proven to be simple, rapid, sensitive, and accurate for clinical poisoning analysis.

Contamination status of bisphenol A and its analogues (bisphenol S, F and B) in foodstuffs and the implications for dietary exposure on adult residents in Zhejiang Province.

An effective method has been developed for the simultaneous determination of four bisphenols (bisphenol A, S, F and B) in various foodstuffs. The contaminants were extracted by QuEChERS-based strategy and subjected to ion-exchange solid-phase extraction for further clean-up. The critical variables were screened by Plackett-Burman design and then optimized by central composite design. Under the optimized conditions, satisfactory accuracy (recoveries 76%-116%) and precision (RSDs < 12%) were achieved. The established method was then used to assess the contamination status of 379 real samples. Bisphenol A was demonstrated to be the predominant bisphenol with highest incidence (79.7%) and average concentration (14.3 µg/kg). The positive rates (mean concentration) of bisphenol S, F and B were 37.7% (1.6 µg/kg), 26.9% (1.4 µg/kg) and 0.0% (not detected), respectively. Finally, the daily dietary intakes of ∑4bisphenolsfor adult residents were estimated (55.9-76.1 ng/kg bw/day) according to the contamination concentrations and the daily recommended intakes.

[Determination of residual glyphosate and aminomethylphosphonic acid in wheat flour and oats samples by non-derivatization method based on ultra-performance liquid chromatography-high resolution mass spectrometry].

A rapid and accurate analysis method based on ultra-performance liquid chromatography-high resolution mass spectrometry (UPLC-HRMS) was developed for the determination of residual glyphosate (GLY) and aminomethylphosphonic acid (AMPA) in wheat flour and oats samples. The wheat flour and oats samples were firstly subjected to vortex and ultrasound extraction; then, the extract solution was purified by MCX solid-phase extraction (SPE) cartridges as well as protein precipitation using acetonitrile. The chromatographic separation was carried out on a Dikma Polyamino HILIC column (150 mm×2.0 mm, 5 µm) by linear gradient elution procedure using 5 mmol/L ammonium acetate in water (pH=10.5) and acetonitrile as the elution solvent. An electrospray ion source in negative mode and parallel reaction monitor (PRM) mode was used for quantification by the internal standard method. The instrument conditions for liquid chromatography (LC) and HRMS, and the sample pretreatment conditions for GLY and its metabolite AMPA were systematically optimized. In addition, the matrix effect and injection system residue were investigated, and a comparison of different analytical methods was carried out. The results indicated that GLY and AMPA showed good linearities in the range of 5.0-100.0 µg/L with coefficients (R2) higher than 0.999. The limits of detection (LODs) were found to be 0.005 and 0.05 mg/kg for GLY and AMPA, respectively. The recoveries of GLY and AMPA in the wheat flour and oats samples were in the range of 93.8%-115% and 89.8%-110% at the spiked levels of 0.1, 0.5, and 2.0 mg/kg, respectively, while the relative standard deviations (RSDs) were all less than 10%. The results of the matrix effect test revealed that the matrix inhibition effect could be reduced by using an isotopic internal standard with the matrix effect parameter |η|<3%. Moreover, the injection system residue was effectively controlled with a residual level of less than 1.0%. A comparison of the developed method with the reported derivatization method indicated little difference, with RSDs of 2.19% and 3.07% to the assigned value, respectively. The established analytical method was used for the Food Analysis Performance Assessment Scheme (FAPAS) proficiency test (No. 09122, GLY in oats), and the results were satisfactory with a z value of 0.2. Moreover, the result obtained using this method was very closed to the assigned value of the FAPAS QC sample, with a recovery of 102.2% (No. T09119QC, GLY in wheat flour). The proposed method is fast, simple, sensitive, and accurate, and it can be applied for the daily monitoring of GLY and its metabolite AMPA in wheat flour and oats samples.

Correction: Surface core-shell magnetic polymer modified graphene oxide-based material for 2,4,6-trichlorophenol removal.

[This corrects the article DOI: 10.1039/C4RA14150D.].

Retracted: Rapid and effective sample cleanup based on graphene oxide-encapsulated core-shell magnetic microspheres for determination of fifteen trace environmental phenols in seafood by liquid chromatography-tandem mass spectrometry.

This article has been retracted at the request of the Editor after the corresponding author pointed the Editor to comments from an anonymous reader. The article reports electron micrographs of different preparations while showing identical images as used in previous publications by the same authors. The particles in Fig. 4C (SEM image of Fe3O4@SiO2) are identical to each other and the corresponding author confirmed that these have been copy-pasted. In addition, these particles have previously been communicated as different substances in Fig. 1B from Pan et al., J. Mater. Chem. A, 2015,3, 23042-23052 (DOI: 10.1039/C5TA05840F) and Fig. 3F from Pan et al., Anal. Methods, 2017,9, 5281-5292 (DOI: 10.1039/C7AY01444A). Furthermore, the curves in Fig. 7, especially the baseline, shows a remarkable similarity to Fig. 8 from Pan et al., J. Mater. Chem. A, 2015,3, 23042-23052 (DOI: 10.1039/C5TA05840F) and Fig. 5F from Pan et al., J. Mater. Chem. A, 2014,2, 15345-15356 (DOI: 10.1039/c4ta02600d). The manipulation of images and data in this way is a serious offense to the integrity of the scientific community and casts doubts on all the data, and accordingly also the conclusions based on that data, in this publication. As such this article represents a severe abuse of the scientific publishing system. The scientific community takes a very strong view on this matter and apologies are offered to readers of the journal that this was not detected during the submission process. This article has been retracted: please see Elsevier Policy on Article Withdrawal (https://www.elsevier.com/about/our-business/policies/article-withdrawal).

Nonderivatization method for determination of glyphosate, glufosinate, bialaphos, and their main metabolites in environmental waters based on magnetic metal-organic framework pretreatment.

A novel magnetic metal-organic framework composite was prepared by a self-assembly approach. The material properties were characterized by Fourier-transform infrared spectroscopy, vibrating sample magnetometry, thermogravimetry and differential thermogravimetric analysis, and X-photoelectron spectroscopy. Then, the as-prepared material was used as an adsorbent and indicated great enrichment ability toward glyphosate, glufosinate, bialaphos, and their main metabolites aminomethylphosphonic acid and 3-methylphosphinicopropionic acid. Based on this, an efficient magnetic solid-phase extraction method combined with ultra high performance liquid chromatography with high-resolution mass spectrometry for the pretreatment and determination of five target compounds in environmental waters was established. Parameters that could impact on the adsorption performance had been studied in detail. The proposed method was successfully applied for the simultaneous determination of glyphosate, glufosinate, bialaphos, and their main metabolites aminomethylphosphonic acid and 3-methylphosphinicopropionic acid in environmental water with recoveries in range of 86.2-104.6% with relative standard deviations less than 10%. Desired linearity was achieved varying from 1 to 100 µg/L for five target analytes, respectively. The limits of detection were between 0.01 and 0.03 µg/L.

[Simultaneous determination of insecticide in tea samples using QuEChERS-based clean up and ultra-fast liquid chromatography-tandem mass spectrometry].

OBJECTIVE: To develop a method for determination of imidacloprid, acetamiprid, chlorobenzamide and indoxacarb in tea samples using Qu ECh ERS-based pretreatment method and ultra-fast liquid chromatography-tandem mass spectrometry( UFLC-MS/MS). METHODS: Tea samples were firstly extracted by acetonitrile-water solution( 4∶ 1, V/V) by vortex and ultrasound, and then 1 g Na Cl and 4 g Mg SO4 were added into the mixture, following by vortex and centrifugation at 8500 r/min for 5 min. Finally the supernatant was purified by Mg SO4 and PSA power, and then the chromatographic separation process was performed on a Waters ACQUITY UPLC BEH C18 column( 2. 1 mm × 100 mm, 1. 7 µm) with a linear gradient elution procedure ofacetonitrile and 0. 1%( V/V) formic acid-5 mmol/L ammonium acetate in water as elution solvent. The multiple reaction monitoring( MRM) in positive mode was used for quantification by internal standard method. RESULTS: The four insecticides including imidacloprid, acetamiprid, chlorobenzamide, and indoxacarb showed good linearity in the range of 0. 20-50. 0 µg/L with coefficients( r) higher than 0. 9998. The limits of detection( LODs) varied from 0. 1 µg/kg to 0. 3 µg/kg. The recoveries of spiked tea samples in the range of 88. 4%-98. 8% at the three concentrations of 1. 0 µg/kg, 40. 0µg/kg and 80. 0 µg/kg, while the relative standard deviations( RSD) were all less than10%. CONCLUSION: The proposed method is simple, fast, sensitive and accuracy, and can be used for qualitative and quantitative analysis of imidacloprid, acetamiprid, chlorobenzamide, andindoxacarb in tea samples.

High-affinity graphene oxide-encapsulated magnetic Zr-MOF for pretreatment and rapid determination of the photosensitizers hematoporphyrin and hematoporphyrin monomethyl ether in human urine prior to UPLC-HRMS.

In this paper, a high-affinity graphene oxide-encapsulated magnetic Zr-MOF (GO-Mag@Zr-MOF) was synthesized and characterized by SEM, TEM, and XPS for its morphology, structure, and components. Subsequently, the as-prepared GO-Mag@Zr-MOF was, for the first time, employed as magnetic solid-phase extraction (MSPE) adsorbent for pretreatment and determination of photodynamic therapy (PDT) with the photosensitizers hematoporphyrin (Hp) and hematoporphyrin monomethyl ether (HMME) in human urine samples coupled with ultra-performance liquid chromatography-high resolution mass spectrometry (UPLC-HRMS). The synthesized GO-Mag@Zr-MOF revealed excellent adsorption efficiency for Hp and HMME in urine samples. Under optimal conditions, the spiked recoveries of the developed method were in the range of 89.5-105.6% with RSDs less than 10%. The limits of detection (LODs) were found to be 0.036 and 0.042 µg/L for Hp and HMME, respectively, while limits of quantitation (LOQs) were 0.12 and 0.14 µg/L. The proposed method was found to be rapid, effective, sensitive, and accurate for clinical analysis. Moreover, this paper, for the first time, carefully expounded the mass spectrum cracking mechanisms of Hp and HMME. Graphical abstract ᅟ.

[Determination of glyphosate, glufosinate, and main metabolite aminomethylphosphonic acid residues in dry tea using ultra-high performance liquid chromatography-tandem mass spectrometry].

A method has been developed for the determination of glyphosate (GLY), glufosinate (GLUF), and the main metabolite aminomethylphosphonic acid (AMPA) residues in dry tea based on ultra-high performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) coupled with pre-column derivatization. A systematic study of the effects of pretreatment methods including extraction and purification procedures was designed and carried out for the determination of GLY, GLUF, and AMPA. The results indicated that the optimal pretreatment method was as follows:the tea sample was first extracted by water in vortex, and then purified by a cation exchange solid-phase extraction column with the elution of 0.5% (v/v) formic acid aqueous solution. Finally, the eluant was derivatized by 9-fluorenylmethyl chloroformate, and the target compounds were separated on a C18 chromatographic column and analysed by UPLC-MS/MS (ESI+). GLY, GLUF, and AMPA showed good linearity in the range of 1-100 µ g/L, with correlation coefficients above 0.991. The limits of detection and limits of quantification were found to be 0.0160-0.0300 mg/kg and 0.0530-0.100 mg/kg, respectively. The average spiked recoveries of GLY, GLUF, and AMPA varied from 78.3% to 108% at three spiked levels (0.0500, 0.400, and 1.20 mg/kg), while the relative standard deviations ranged from 5.46% to 9.63%. The proposed method was utilized to detect 837 batches of tea samples. The detection ratios of GLY, GLUF, and AMPA were 3.46%, 0.24%, and 4.42%, respectively, while 0.24% of the investigated tea samples had values above maximum residue limits. The developed method is simple, rapid, sensitive, and accurate for the determination of GLY, GLUF, and AMPA in dry tea and may be used for routine analysis.

[Determination of pentachlorophenol in food by solid phase extraction-ultrafast liquid chromatography-tandem mass spectrometry].

OBJECTIVE: A method was developed for the determination of pentachlorophenol( PCP) in food by ultrafast liquid chromatography-tandem mass spectrometry after solid phase extraction. METHODS: The sample was extracted in 8%triethylamine/acetonitrile( 70/30, V/V) and purified on a MAX-SPE cartridge. The UFLC separation was performed on a Shim-pack XR-ODS Ⅲ column( 150 mm × 2. 0 mm, 2. 2µm) with a linear gradient elution program of acetonitrile and 5 mmol/L ammonium acetate( 0. 1% formic acid) as the mobile phase. Electrospray ionization was applied and operated in the negative ion mode. RESULTS: The limit of quantitation( LOQ) and limit of detection( LOD) for PCP were 0. 4-0. 5 µg/kg and 0. 12-0. 15 µg/kg. The calibration curve showed good linearity between 0. 5-50. 0 µg/L, and the correlative coefficients( r) were more than 0. 999. The recovery was between 82. 0%-108. 0%, and the RSD was between 1. 89%-5. 09%( n = 6). CONCLUSION: The method is sensitive, reproducible, and adapts to determination of PCP in variety of foods.

[Rapid determination of four phenolic environmental estrogen residues in cooking oil by ultra-performance liquid chromatography-high resolution mass spectrometry coupled with solid-phase extraction].

A fast, sensitive and accurate method for the determination of trace bisphenol S (BPS), bisphenol F (BPF), bisphenol A (BPA) and 4-nonylphenol (4-NP) in cooking oil samples was developed by ultra-performance liquid chromatography-high resolution mass spectrometry (UPLC-HRMS) coupled with solid-phase extraction (SPE). Cooking oil samples were extracted by acetonitrile, then the supernatant was purified by SLC SPE cartridges. The chromatographic separation was carried out on a Waters ACQUITY UPLC HSS T3 column (100 mm×2.1 mm, 1.8 µm) with a linear gradient elution procedure using 0.05% (v/v) triethanolamine aqueous solution and methanol as mobile phases. The quantification analysis was operated in a negative electrospray ion (ESI-) source mode under the selected ion monitoring (SIM) mode with internal standard method. The four target analytes showed good linearity with correlation coefficients (r) greater than 0.999. The limits of detection (LODs, S/N=3) and limits of quantification (LOQs, S/N=10) were in the ranges of 0.03-0.11 µg/kg and 0.10-0.36 µg/kg, respectively. The recoveries of the four target analytes spiked in oil samples were in the range of 86.3%-96.1% at spiked levels of 1.0, 10.0 and 80.0 µg/kg, respectively, while the relative standard deviations (RSDs) were in range of 2.2%-8.8% (n=6). No significant matrix interference was found in this method. The proposed method is simple and fast. It can be applied for the rapid determination of trace BPS, BPF, BPA, and 4-NP in cooking oil samples.