On-Fiber Derivatization of SPME Extracts of Phenol, Hydroquinone and Catechol with GC-MS Detection

A gas chromatography-mass spectrometry (GC-MS) method for the simultaneous determination of phenol (PHE), hydroquinone (HQ) and catechol (CAT) in urine was developed and validated. The method was based on the acidic hydrolysis of conjugated phenolic compounds and further extraction of analytes using solid-phase microextraction (SPME). Analytes were extracted by submersing the polar polyacrylate coated fiber (85 μm) into urine (adjusted to pH 3.0 with glacial acetic acid) for 20 min with magnetic stirring. The extracted compounds on the fiber were exposed to hexamethyldisilazane reagent in the vapor phase for 20 min to yield the corresponding trimethysililylated derivates. This on-fiber derivatization procedure allowed the formation of more amenable compounds for GC analysis, without adversely affecting the lifetime of the fiber. The MS was operated in the selected ion monitoring mode (SIM). The limits of detection were 0.3 μg mL⁻¹ for PHE, 0.15 μg mL⁻¹ for HQ and 0.02 μg mL⁻¹ for CAT. Inter and intra-assay precisions were also verified (coefficient of variation < 8%) with the use of deuterated internal standards. This method of GC-MS analysis can be readily utilized to monitor PHE and its metabolites (HQ and CAT) in urine samples.     

Simultaneous determination of eleven amphenicols and antiviral drugs in aquatic products by ultra-high performance liquid chromatography-tandem mass spectrometry coupled with PRIME HLB solid phase extractionEI北大核心CSCD

An efficient ultra-high performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) method was established for the simultaneous determination of 11 amphenicols and antiviral drugs in aquatic products including fish, shrimp, soft-shell turtle and shellfish samples. Each sample was dispersed with 4%(w/w)sodium chloride solution, and extracted with 2%(V/V) ammonia-ethyl acetate solution. After the concentration of the extract, the residue was redissolved in 0.2%(V/V) aqueous solution of formic acid-acetonitrile (20∶80, V∶V), purified with Oasis PRIME HLB cartridge, and detected by UPLC-MS/MS. The samples were analyzed directly on the ZORBAX RRHD Eclipse Plus C18 column using 5 mmol/L ammonium formate and acetonitrile as mobile phase. The quantitative determination of the analytes was carried out under the multiple reaction monitoring mode with positive and negative electrospray ionization using internal standard method. Results showed that there were good linear relationships for all analytes in the corresponding concentration ranges, with the correlation coefficients not less than 0.996. The limits of quantification ranged from 0.2 to 2.0 µg/kg. The average spiked recoveries were between 84.6% and 110% with the relative standard deviations of 1.0% to 14%. The method, which has been used in risk monitoring, is suitable for rapid determination of amphenicols and antiviral drugs in aquatic products. © 2023, Youke Publishing Co.,Ltd. All rights reserved.     

Analysis of Trace-Level Volatile Compounds in Fresh Turf Crop （Lolium perenne L.） by Gas Chromatography Quadrupole Time-of-Flight Mass Spectrometry

In the traditional research of volatile compounds, some trace-level compounds could not be identified by gas chromatography-mass spectrometry. Target and post-targeted methods were applied in the investigation of trace-level volatile compounds in fresh turf crop （Lolium perenne L.） based on gas chromatography in combination with hybrid quadrupole time-of-flight mass spectrometry. According to literatures published, a target analysis was performed by using retention index, accurate masses of characteristic ions and second-stage mass spectra （MS2 spectra）. And a series of experiments showed that low electron impact energy was beneficial to the improvement of the abundances of low abundance molecular ion peak. peak was beneficial to qualitative analysis. Totally, 60 Enhancing the abundances of low abundance molecular ion volatile compounds were identified, the great majority cornpounds of which were benzeneacetaldehyde （14.8%）, 2,5-dimethyl-pyrazine （9.6%）, and hexanal （9.3%）. Identification was complied by mass spectral search, retention index and accurate masses of characteristic ions.     

Determination of macrolides in livestock excreta by syringe purification coupled with liquid chromatography tandem mass spectrometryEI北大核心CSCD

A method of syringe-dispersive solid-phase extraction combined with ultrahigh performance liquid chromatography with tandem mass spectrometry for the simultanous determination of 10 macrolides in manurebased fertilizers was developed. After extraction with methanol and acetonitrile,the extracts were purified by insyringe dispersion solid-phase extraction in syringes pre-filled with 60 mg PSA and 30 mg C18. The resulted extracts were further separated by a BEH C18 column,detected by multiple reaction monitoring in electrospray positive ion mode,and quantified by matrix-matched external standard method. The results showed that the recoveries of the target compounds ranged from 70% to 110% at three spiked levels（10,30,and 50 μµg/kg）with the relative standard deviations ranged from 1.4% to 12%. The limits of detection and quantification were 0.57 1.75 and 2.77-5.40 μµg/kg,respectively. This method was suitable for the simultaneous determination of residual macrolides in organic fertilizers. © 2023, Youke Publishing Co.,Ltd. All rights reserved.     

Magnetic nanoparticles used in headspace extraction coupled with DSI-GC-IT/MS for analysis of VOCs in dry Traditional Chinese Medicine

A novel magnetic method using polystyrene modified magnetic nanoparticles to perform thermoheadspace extraction was successfully developed for extraction and preconcentration of volatile organic components in dry Traditional Chinese Medicine(TCM) based on gas chromatography-ion trap/mass spectrometry with a Chromato Probe direct sample introduction device. The dried fruit of Amomum testaceum Ridl. was used as the object TCM. The optimum parameters of headspace magnetic solid-phase extraction were investigated, in which desorption solvent ethyl acetate played a key role in this method,and the headspace extraction temperature of 90℃ and the headspace extraction time of 15 min finally decided. Headspace solid-phase microextraction method was also used to analyze volatile compounds in the TCM to compare with the proposed method. The results show that 60 components were identified totally by two methods; most of the low boiling point chemical compounds are isolated by this new method. In this work, an environmental-friendly and cheap analytical method was established, and a new approach to analyze volatile compounds in dry Traditional Chinese Medicine was also provided.     

Determination of 12 additives in beverages by evaporation-assisted dispersive liquid-liquid microextraction based on the solidification of floating organic droplets combined with liquid chromatographyEI北大核心CSCD

An analytical method for the simultaneous determination of 12 additives in beverages was developed using evaporation-assisted dispersive liquid-liquid microextraction based on the solidification of floating organic droplets EVA-DLLME-SFOcombined with high performance liquid chromatography HPLC. The samples were extracted twice with 70%V/Vmethanol aqueous solution and extracted by EVA-DLLME-SFO method after the combination of the extractsand finally determined by HPLC. Extraction parameterssuch as types and amounts of extractantevaporant and heating agentthe concentration of saltand the extraction time were optimized. Under the optimized conditionsthere were good relationships in the ange of 0.25-50 μµg/mL with the limits of detection of 1.5 to 13.6 mg/kg and limits of quantification of 5.2 to 45.3 mg/kg. The recoveries at three spiked levels1025 and 50 mg/kgwere 76.8% to 101.2% with the relative standard deviations of 0.11% to 4.7%. The method can be used for rapid detection of 12 additives in beverages. © 2022, Youke Publishing Co.,Ltd. All rights reserved.     

Determination of synthetic musk in ground water by liquid-liquid extraction-gas chromatography mass spectrometryEI北大核心CSCD

A gas chromatography-mass spectrometry GC-MS method was established to determine three different synthetic musksSMsfrom ground water. Dichloromethane as the extracting solventthe concentrated extracts were tested by GC-MS using the external standard quantitative method. Each sample was extracted three times with 40 mL dichloromethane respectively. The linearity test was carried out in the range of 20.0 to 2000 μµg/L the relative standard deviationRSDRRFof average relative response factor was less than 8.7%and the limits of detectionLODswere in the range of 0.007 to 0.012 μµg/L. The recoveries of three spiked ground water samples were all between 98.1% and 117.0%and the relative standard deviations were less than 13%. Musk xylene in the ground water sample was 0.013 μµg/Land the spiked real sample had the recoveries higher than 80%. This method was suitable for the detection of trace SMs in ground water. © 2022, Youke Publishing Co.,Ltd. All rights reserved.     

Untargeted screening and quantitation of drug residues in bean sprouts by ul⁃tra performance liquid chromatography-quadrupole/orbitrap high resolution mass spectrometryEI北大核心CSCD

A method for the untargeted screening and quantitative analysis of drug residues in bean sprouts by ultra performance liquid chromatography-quadrupole/ orbitrap high resolution mass spectrometry （UPLC-QOrbitrap HRMS） was developed. In the process of screening, the samples were extracted by acetonitrile and the data were gathered via the full MS-ddMS2 mode. In the absence of standards, qualitative analysis was carried out according to the exact mass number of precursor ions and secondary fragment ions information combined with the database. The optimized dispersive solid-phase extraction （d-SPE） method was used to purify the samples. 9 compounds in bean sprouts were screened and quantified on the basis of the peak areas of the precursor ions. 9 compounds showed good linear relationships （R2＞0.990） in the linear concentration ranges. The limits of detection of this method were between 2.0-5.0 μg/kg. The recoveries of 9 compounds at three spiked levels of 5, 10, 50 μg/kg ranged from 80.1% to 111.1%, and the relative standard deviations were less than 15%. © 2023, Youke Publishing Co.,Ltd. All rights reserved.     

A modified QuEChERS-gas chromatography-mass spectrometry method for the determination of pesticide residues in Lonicera japonicae FlosEI北大核心CSCD

A modified QuEChERS-gas chromatography-mass spectrometry method using multi-walled carbon nanotubes （MWCNTs）as adsorbent was established for the determination of 72 pesticide residues in Lonicera japonicae Flos. The sample was extracted with Association of Official Agricultural Chemists （AOAC）extracting package，purified with MWCNTs-modified purification tube，analyzed with dynamic multiple reaction monitoring mode，and quantified with external standard method of matrix-matched standard curve. The 72 pesticides showed good linearities in the corresponding concentration ranges with correlation coefficients greater than 0.9936. The limits of detection were 0.001-0.178 μµg/kg，and the limits of quantitation were 0.002-0.593 μµg/kg. The average recoveries for four spiked levels ranged from 60.1% to 118.0%，with the relative standard deviations of 2.2%-17%. © 2023, Youke Publishing Co.,Ltd. All rights reserved.     

High performance liquid chromatography analysis of p-aminophenol synthesized by nitrobenzene transfer hydrogenation using formic acid as hydrogen sourceEI北大核心CSCD

Qualitative analysis of the main by-product of 4-hydroxybenzamide in the synthesis of p-aminophenol bynitrobenzene transfer hydrogenation with formic acid as hydrogen source was carried out by electrospray ionization mass spectrometry. The reaction system was quantitatively analyzed by high performance liquid chromatography. The chromatographic conditions were shown as followsShim pack VP-ODS column250 mm× 4.6 mm5 μµmdetection wavelength of 254 nmVmethanolVbuffer solution=114.8 mmol/L sodium dihydrogen phosphate solution1.9 mmol/L dibasic sodium phosphate solutionas the mobile phase and the flow rate of 0.8 mL/min with a column temperature of 35. Nitrobenzenep-aminophenolaniline and formylaniline in the reaction system were quantitatively analyzed by standard curve method with methyl N-phenylcarbamate as internal standard. The correlation coefficientsR2were 0.99930.99950.9998 and 0.9992 for these analytes respectively. The relative standard deviations RSDs were less than 1.0% 0.3% 0.2% and 0.4% respectively. The recoveries were in the ranges of 95.5%-102.6%101.2%-104.8%95.1%-99.8% and 95.7%-101.1%respectively. This method can be used for the simultaneous determination of main and by-products in the transfer hydrogenation of nitrobenzene with formic acid as hydrogen source. © 2022, Youke Publishing Co.,Ltd. All rights reserved.     

Analysis of nitrobenzene compounds in water and soil samples by graphene composite-based solid-phase microextraction coupled with gas chromatography–mass spectrometry

In this work, solid-phase microextraction coupled with gas chromatography–mass spectrometry was developed to determine trace levels of nitrobenzene compounds in water and soil samples. Graphene was chosen as the extraction material and its composite was coated on a stainless steel wire through sol–gel technique for the solid phase microextraction. The key parameters influencing the extraction efficiency were optimized. Under the optimal conditions, the linearity for the compounds was observed in the range of 0.02–15.0 mg/L for water samples, and 0.2–60.0 mg/kg for soil samples, with the correlation coefficients（r） of 0.9966–0.9987. The limits of detection of the method were 0.0025–0.005 mg/L for water samples, and 0.02–0.04 mg/kg for soil samples. The recoveries for the spiked samples were in the range of 72.0%–113.2%, and the precision, expressed as the relative standard deviations, was less than 12.1%.     

Comparison of Constituents and Insecticidal Activities of Essential Oil from Artemisia lavandulaefolia by Steam Distillation and Supercritical-CO2 Fluid Extraction

Essential oil was extracted from Artemisia lavandulaefolia DC.by steam distillation(SD) and supercritical-CO2 fluid extraction(SFE),respectively.The constituents of the essentil oils extracted with those two methods were analyzed by gas chromatography-mass spectrometry(GC-MS) and insecticidal activities of the essential oils were evaluated,then the results were compared to assess their biological activity.Thirty-one compounds were identified in the essential oil extracted by SD,and its main components were eucalyptol,α,α,4-trimethyl-3-cyclohexene-1-methanol and so on.Twenty-two compounds were identified for the essential oil extracted by SFE,and its main components were cyclodecene,n-hexadecanoic acid and so on.Six chemical compositions were all contained in the essential oils extracted by the two methods,i.e.,eucalyptol,α,α,4-trimethyl-3-cyclohexene-1-methanol,caryophyllene,[3aS-(3aα,3bβ,4β,7α,7aS)]-octahydro-7-methyl-3-methylene-4-(1-methylethyl)-1H-cyclopenta[1,3]cyclopropa-[1,2]benzene,nerolidol and(-)-Spathulenol.The fumigation toxicity of the essential oil obtained by means of SD to the adults of Sitophilus zeamais is significantly higher than that of the essential oil by means of SFE.The contact toxicity of the essential oil obtained by means of SFE to the adults of S.zeamais is higher than that of the essential oil obtained by means of SD,but the difference is not significant.     

Investigations on the degradation of aspartame using high-performance liquid chromatography/tandem mass spectrometry

Aspartame is a widely used sweetener,the long-term safety of which has been controversial ever since it was accepted for human consumption.It is unstable and can produce some harmful degradation products under certain storage conditions.A high-performance liquid chromatography/tandem mass spectrometry method was developed for the simultaneous analysis of aspartame and its four degradation products,including aspartic acid,phenylalanine,aspartyl-phenylalanine and 5-benzyl-3,6-dioxo-2-piperazieacetic acid in water and in diet soft drinks.Aspartame and its four degradation products were quantified by a matrix matched external standard calibration curve with excellent correlation coefficients.The limits of detection were 0.16–5.8 mg/L,which exhibited higher sensitivity than common methods.This method was rapid,sensitive,specific and capable of eliminating matrix interferences.It was also applied to the study of the degradation of aspartame at various pH and temperatures.The results indicated that aspartame was partly degraded under strong acidic or basic conditions and the extent of degradation increased with increasing temperature.     

Effects of Protein on the Detection of Chlorobenzenes in Fish and Their Elimination by Modified QuEChERS Method

Molecular fluorescence spectrometry, resonance Rayleigh scattering and gas chromatography-mass spectroscopy（GC-MS） were used to study the effect of pure fish serum albumin（FSA） as the model protein on the extraction of three chlorobenzenes（CBs： 1,3-DCB, 1,2-DCB and 1,2,4-TCB; DCB=dichlorobenzene; TCB=trichlorobenzene） in fish samples. The results show that there was a strong binding effect between CB and FSA. In an aqueous solution of 90%（volume fraction） acetone, a slow but full protein denaturation might take place, which would cause the unfolding of protein and the releasing of CBs. Based on these results, a QuEChERS（quick, easy, cheap, effective, rugged and safe） method was modified by replacing the traditional acetonitrile with acetone aqueous solution in the present work. This modified QuEChERS method was applied in the determination of CBs in fish samples. The spiked recoveries and the limits of detection were 80.4%--118.3% and 2.4--7.3 ng/g, respectively. This paper proposes a new strategy by slowing down the protein denaturation and releasing bound organic compounds to enhance the extraction efficiency of CBs in fish samples.     

Determination of hydroxypropyl bis (N-hydroxyethyl-p-phenylenediamine) hydrochloride in hair dye products by HPLC and its verification by LC-MS/MSEI北大核心CSCD

A method for the determination of hydroxypropyl bis (N-hydroxyethyl-p-phenylenediamine)hydrochloride in hair dye products by high performance liquid chromatography (HPLC) and liquid chromatography-tandem mass spectrometry (LC-MS/MS) was developed. The sample was ultrasonically extracted with 50% (V/V) ethanol. Chromatographic separation was carried out on a Waters Symmetry C18 column (250 mm×4.6 mm, 5 µm) by isocratic elution. The mobile phase was 0.02 mol/L ammonium acetate aqueous solution and acetonitrile (84∶16, V/V). The detection wavelength was 258 nm. Quantification was performed by external standard method. Verification for positive samples was performed by LC-MS/MS. The results showed good linearity from 2 mg/L to 200 mg/L, with the correlation coefficients (r) higher than 0.999. The limit of detection (LOD) was 0.003%(w/w), and the limit of quantification (LOQ) was 0.01%(w/w). The average spiked recoveries at three levels in both cream and liquid substrates were from 97.5% to 103.4%, with the relative standard deviations (RSDs) from 1.7% to 3.9%. The method could be used to detect hydroxypropyl bis (N[1]hydroxyethyl-p-phenylenediamine)hydrochloride in hair dye products, which could fill the gap of the current standard. © 2023, Youke Publishing Co.,Ltd. All rights reserved.     

Application of Isotope Dilution to the Determination of Anthracene in Environmental Samples by Headspace Solid-Phase Microextraction and Gas Chromatography–Mass Spectrometry

A method using headspace solid-phase microextraction (HS-SPME) followed by gas chromatography–mass spectrometry with selected ion monitoring (GC–MS, SIM) has been developed for the determination of trace amounts of anthracene in sea water, wastewater, honey and saliva samples. Anthracene was extracted on to a fused-silica fibre coated with 85 μm polyacrylate (PA). Quantification of anthracene was carried out by isotope dilution mass spectrometry. The detection limit and the quantification limit found were 0.02 and 0.06 ng mL⁻¹, respectively. The method was validated by analysis of spiked matrix samples and used to investigate the presence of anthracene above the stated detection limit in sea water, wastewater, honey and saliva samples.     

Simultaneous LC-MS/MS Determination of Danshensu and Paeoniflorin for Permeability Studies in Caco-2 Intestinal Absorption Model

A high sensitive method based on liquid chromatography tandem mass spectrometry（LC-MS/MS） was developed and validated for the study of permeability of danshensu（DS） and paeoniflorin（PF） in Caco-2 intestinal absorption model. The DS and PF were extracted from cell culture by vacuum-lyophilizing and then separated on a Zorbax Stable Bond C18 column with 0.1% acetic acid aqueous solution and methanol as mobile phase. Detection was carried out by negative electrospray ionization（ESI ） with selected reaction monitoring（SRM） mode. The apparent permeability coefficients（Papp） of DS and PF in Caco-2 cell medium were calculated and the effects of verapamil on the coefficients Papp of the two test compounds were also illustrated. The permeability of PF was much better than that of DS when the two compounds were administrated individually. Co-administration of DS and PF led to the decrease of the transport from apical side to basolateral side for both the compounds. However, the transport in the contrary direction were accelerated. It was also observed that verapamil could accelerate the transport of the test compounds from apical side to basolateral side. However, the absorption-enhanced effect of verapamil was attenuated when DS and PF were co-administrated. These observations suggest that both passive diffusion and active efflux involved in P-gp would effect the passage of DS and PF across Caco-2 cell monolayer. At the same time, the co-administration of DS and PF to an alteration of transport behavior, which suggests that the interaction must be taken into account when ‘n-in-one＇ samples were used in Caco-2 intestinal model.     

Preparation of Phenolic Resin／Silver Nanocomposites via in—situ Reduciton

Resol type phenolic resin/silver nanocompostie was prepared by in-sinu reduction method,in which the curing of phenolic resin and the formation of silvernano-particles took place simultaneously.The silver ions were reduced completely to silver nanoparticles,which were dispersed homogeneously in the resinmatrix with narrow size distribution.     

Simultaneous kinetic spectrophotometric determination of norfloxacin and rifampicin in pharmaceutical formulation and human urine samples by use of chemometrics approaches

A kinetic spectrophotometric method with aid of chemometrics is proposed for the simultaneous determination of norfloxacin and rifampicin in mixtures. The proposed method was applied for the simultaneous determination of these two compounds in pharmaceutical formulation and human urine samples,and the results obtained are similar to those obtained by high performance liquid chromatography.     

Rapid and Sensitive LC-MS/MS Method for Quantification of Fexofenadine in Human Plasma——Application to a Bioequivalence Study in Chinese Volunteers

A rapid and sensitive liquid chromatography-tandem mass spectrometry method（LC-MS/MS）was developed and validated for the quantification of fexofenadine in human plasma,to conduct comparative bioavailability studies.Human plasma was extracted with a mixture of dichloromethane-diethyl ether（volume ratio 2∶3）in a basic environment and the extract was separated on a C18 column with a mobile phase consisting of acetonitrile-methanol-10 mmol/L ammonium acetate（volume ratio 45∶45∶10）.The analytes were detected via electrospray ionization（ESI）tandem mass spectrometry in the multiple-reaction-monitoring（MRM）mode.The linearity was within a range of 1-1000 ng/mL.The intra-and inter-day precision were〈4.1% and〈4.8%,respectively,and the accuracy was in the range of 95.0%-105%.The method was applied to the quantification of fexofenadine human plasma from 20 healthy male Chinese volunteers,according to a single dose,randomized,two-way crossover design with a two-week washout period.The mean values of major pharmacokinetic parameters of ρmax,AUC0-48,AUC0-∞,tmax,and t1/2 were determined from the plasma concentration.The analysis of variance（ANOVA）did not show any significant difference between the two products of fexofenadine and 90% confidence intervals fell within the acceptable range for bioequivalence.