摘要:A strategy that ultrahigh performance liquid chromatography-quadrupole-exactive orbitrap high resolution mass spectrometry(UHPLC-Q-Exactive orbitrap HRMS) based untargeted metabolomics was developed in combined with chemometric automatic data analysis software(AntDAS-LCHRMS) to investigate the metabolites from four types of E. ulmoides Oliv. leaves processed by different drying treatments(i. e.,freeze drying,heat pump drying,oven drying,sun drying). The data of samples was acquired by UHPLC-Q-Exactive orbitrap HRMS under both positive ionization mode and negative ionization mode,and directly imported into AntDAS-LCHRMS for automatic data analysis. The results indicated that about 71 differential metabolites were identified based on the above-mentioned data analysis workflow,and 40 compounds were further confirmed by standards,including iridoids,organic acids,flavonoids,amino acids,nucleosides,vitamins,sugars,lignans,and coumarins. Among of which 25 metabolites were identified and confirmed by standards under both positive and negative mode,including asperuloside,chlorogenic acid,rutin,isoquercitrin,asperulosidic acid and geniposide,etc. Finally,hierarchical clustering analysis(HCA),principal component analysis(PCA),and heatmap analysis were used for discriminating samples from various drying treatments. The results showed that Eucommiae Folium obtained from different drying treatments could be clearly separated,and compounds of them were significantly different. Heatmap analysis further explicated the compound variations in E. ulmoides Oliv. leaves from different drying groups. Samples of sun drying had higher levels of amino acids such as phenylalanine and tryptophan. Samples of freeze drying and heat pump drying had higher levels in organic acids,iridoids,and sugars. Samples of oven drying had higher levels of nucleotides and flavonoids. The content of flavonoids differed little among freeze drying,heat pump drying,and sun drying. The results could be helpful to offer a scientific guidance for the quality evaluation and application of E. ulmoides Oliv. leaves processed by different drying treatments. In addition,the developed strategy provides a new candidate for the analysis of other complex medicinal plant.
关键词:Eucommiae Folium;metabolomics;chemometrics;AntDAS-LCHRMS software;Ultrahigh performance liquid chromatography-Q-exactive orbitrap high resolution mass spectrometry(UHPLC-Q-Exactive Orbitrap HRMS);drying treatment
摘要:This study used gas chromatography-mass spectrometry and metabolomics-based analytical strategy to investigate the characteristic and differential compositions in four classes of blended flavors and fragrances. The consistency of multiple batches of each class was also evaluated in quality. Results showed that 49,32,48 and 39 compounds were individually identified from the four classes of blended samples,denoted A,B,C and D,respectively. Among them,eight compositions including ethyl acetate,pentanoic acid-4-oxo-ethyl ester,butanoic acid 3-methyl-3-methylbutyl ester,maltol,2-propanol-1,1'-oxybis-,acetic acid,4-oxo-pentanoic acid and 2-furancarboxaldehyde-5-(hydroxymethy)- were the main flavor substances in common. The flavor compositions of both A-class and C-class samples were quite similar,with the most abundant content of ester compounds emitting fruity and floral aromas. The B-class samples were in rich acidic substances with sour aroma characteristics. In contrast,the D-class samples contained a largest number of ketone compounds responsible for aromatic attributes. The deployment of principal component analysis and partial least squares-discriminant analysis was able to discern the characteristic and differential compositions in the blended flavors and fragrances. The variable importance in the projection and statistical analysis screened a total of 40 substances,including diethyl malic acid,nerolidol,ethyl vanillin,and so on. They were used for the quality assessment of samples. Different classes of the blended flavors and fragrances had significant differences in compositions,while the samples of the same class but from different batches had good consistency in quality.
关键词:blended flavors and fragrances;differential substances;quality analysis;gas chromatography-mass spectrometry;metabolomics
摘要:Iron-based nanomaterials have attracted plentiful eyes owing to their rich valency states and active sites,and thus possess superior peroxidase-like activity. Herein,Fe7S8 nanoflowers(NFs) were successfully fabricated by a facile hydrothermal approach and applied for the development of a highly sensitive colorimetric detection for hydrogen peroxide(H2O2). The as-constructed approach was based on the chromogenic reaction between 3,3',5,5'-tetramethylbenzidine(TMB) and H2O2.The analysis conditions of the system were optimized, and the steady-state kinetic assay and catalytic mechanism of the Fe7S8 NFs enzyme-like activity were also investigated.In the range of 0.001-9 mmol/L and 9-70 mmol/L,H2O2 concentration showed a good linear relationship with the absorbance value at 652 nm,and the corresponding detection limits were 0.33 μmol/L and 3 mmol/L,respectively. The method had a wide linear range,low detection limits and good anti-interference ability. Integrated with an image-acquiring dark device and colorimetric assay software(Thing Identify),the method based on smartphone was realized and successfully used in actual water samples. Overall,this intelligent and visual colorimetric assay has the advantages of simple operation and low preparation cost,and thus provides a feasible choice for H2O2 assay in real-world samples.
摘要:In this study,a NO recognition molecule,3,4-diaminobenzenethiol(DABT),through a two-step chemical reaction was firstly synthesized. Subsequently,silver-coated gold nanostars(AuNSs@Ag) with strong surface-enhanced Raman scattering(SERS) effect were prepared. Then,AuNSs@Ag was further modified with DABT via Ag—S bonding,resulting in a ratiometric SERS nanoprobe,AuNSs@Ag-DABT. The prepared nanoprobe was characterized using such as transmission electron microscopy (TEM), hydrodynamic particle size analysis (DLS), Zeta potential measurement, and ultraviolet absorption spectroscopy. Subsequently,quantitative detection of NO was carried out. The experimental results showed that the constructed nanoprobe exhibited a star-shaped structure with sharp protrusions on the surface,with a size of approximately 80 nm. In the presence of NO,DABT reacted with NO,leading to the appearance of a new Raman peak near 541 cm-1(attributed to the triazole ring),while the Raman peak at 1 078 cm-1(attributed to C—S out-of-plane bending) remained unchanged. Therefore,NO could be quantitatively detected based on the ratio of I541/I1078. Under the optimal conditions,the ratio of I541/I1078 showed a good linear response to NO concentrations in the range of 10-60 nmol/L,with a detection limit of 3.89 nmol/L. Furthermore,selective experiments demonstrated that the ratiometric SERS nanoprobe exhibited specificity and interference resistance in response to NO.
摘要:A ultra-high performance liquid chromatography-tandem mass spectrometry(UPLC-MS/MS) method was established for the determination of 16 coumarins and vanillins and their derivatives in rice. The rice sample was extracted by acetonitrile with 1% formic acid,purified with a combined dadsorbent with 150 mg C18 and 450 mg anhydrous MgSO4. The chromatography separation for the analytes was achieved on an Agilent SB-C18 column(2.1 mm×50 mm,1.8 µm),and gradient elution was performed using 0.2% formic acid solution(containing 5 mmol/L ammonium formate) and acetonitrile. The analytes were determined by multiple reaction monitoring(MRM) of electrospray ionization in positive and negative ion modes,and quantified by matrix-matched internal standard method. The 16 components measured had good linear relationships within their respective mass concentration ranges(r≥0.998). The limits of detection were 0.001-0.400 mg/kg,and the limits of quantitation were 0.004-0.600 mg/kg. Average recoveries of the 16 components ranged from 71.3% to 120%,the relative standard deviations(RSDs,n=6) ranged from 1.6% to 6.5%,the intra-day RSDs(n=6) ranged from 1.0% to 8.8%,and the inter-day RSDs(n=3) ranged from 0.60% to 14%. The method is simple and easy to operate,with high sensitivity and accuracy,and is suitable for the simultaneous determination of coumarins and vanillins and their derivatives in rice.
关键词:QuEChERS;UPLC-MS/MS;rice;coumarins;vanillins;derivative;isotope internal standard
摘要:A liquid-liquid extraction gas chromatography-tandem mass spectrometry(LLE/GC-MS/MS) method was established for the simultaneous determination of 16 hydroxy polycyclic aromatic hydrocarbons(OH-PAHs) in human urine. β-glucuronidase/sulfatase was added to 1 mL human urine to release target analytes by an enzymatic hydrolysis reaction. Toluene/n-pentane(1∶4) was used for LLE and repeated this process twice. The extraction solution was further cleaned up using silver nitrate solution. The eluate was evaporated under nitrogen to near-dryness and reconstituted with toluene,then derivatized with N-methyl-N-(trimethylsilyl) trifluoroacetamide(MSTFA). After the derivatization,it was separated by TG-5SilMS capillary chromatography column and quantified using the internal standard method in multi reaction monitoring(MRM) mode. In this study,the derivatization reaction conditions,instrument parameters,addition amount of enzyme,and different extraction solvent were compared and optimized. The matrix effect was evaluated while the accuracy and precision of the method was investigated. The results show that 1-hydroxynaphthalene(1-NAP) and 2-hydroxynaphthalene(2-NAP) had good linearities at 0.1-100 μg/L,and other target analytes were 0.02-20 μg/L. The method limits of detection were 0.01-0.19 μg/L,and the limits of quantitation were 0.03-0.62 μg/L. The spiked recoveries were 81.6%-122%,the relative standard deviations of inter-day and intra-day were 0.22%-5.5% and 0.76%-10%,respectively,and the relative deviation between the measured results and the reference value of SRM 3672 was less than 10%. This method was applied to determine 529 urine samples collected from the National Human Biological Monitoring Project. The results showed that a total of 15 OH-PAHs were detected except 3-hydroxychrysene(3-CHR),while 8 compounds had a detection frequency over 90%. The concentrations of 1-NAP and 2-NAP were higher than other components,with median values of 1.09 µg/L and 1.95 µg/L,respectively. This method is suitable for monitoring human urinary OH-PAHs levels based on general population with low cost,good separability,high sensitivity,and less matrix effects.
关键词:liquid-liquid extraction;gas chromatography-tandem mass spectrometry;hydroxy polycyclic aromatic hydrocarbons;human urine
摘要:In this study,an ultra performance liquid chromatography-quadrupole-time-of-flight high-resolution mass spectrometry(UPLC-Q-TOF MS) method was developed for the rapid screening and quantitative analysis of 18 non-steroidal anti-inflammatory drugs(NSAIDs) in cosmetics. The chromatographic and mass spectrometric conditions were optimized in detail. The samples were firstly extracted by ultrasonic extraction with 60% acetonitrile aqueous solution,then separated on an ACQUITY UPLC BEH C18 column(100 mm×2.1 mm,1.7 µm) by gradient elution,with water and acetonitrile both containing 0.1% formic acid as the mobile phases. The 18 NSAIDs were detected by positive ion electrospray ionization(ESI) in the Target MS/MS mode. The retention time,exact mass number of primary parent ions,isotope abundance ratio and secondary sub-ion library matching were collected to construct a screening library with the software. The results of matching were used to rapid identification of 18 NSAIDs in cosmetics. The quantification of primary parent ions was performed by matrix-matched external standard method. The 18 NSAIDs were all well separated,with good linearity. The linear correlation coefficients(r2) were more than 0.99. The limits of detection(LODs) ranged from 0.001-0.050 μg/g and the limits of quantitation(LOQs) ranged from 0.004-0.150 μg/g. The mean spiked recoveries at three spiked levels in cream and lotion matrices ranged from 70.7% to 116%,with intra-day relative standard deviations(RSDs,n=6) of 0.70%-7.5% and inter-day RSDs(n=3) of 3.0%-14%. The 500 batches of cosmetic samples were detected and screened under the same conditions. The TOF MS information,including the retention time,exact mass number of primary parent ions,isotope abundance ratio and secondary sub-ion library,were compared between the cosmetic samples and the standard MS information with PCDL software. Finally,three batches of samples added with acetamidophen were indentified. The amounts of the added drug were very high,indicating high safety risk for cosumers using such cosmetics. With the advantages of simplicity,efficiency and accuracy,the method is suitable for the screening and determination of 18 NSAIDs in cosmetics,providing technical support for cosmetic risk identification.
关键词:cosmetics;non-steroidal anti-inflammatory drugs;ultra performance liquid chromatography-quadrupole-time-of-flight high-resolution mass spectrometry
摘要:An ultra-high performance liquid chromatography-tandem mass spectrometry method(UPLC-MS/MS) was established to determine niclosamide-olamine residue in 22 kinds of agricultural products. With acetonitrile containing 1% formic acid as the extraction solvent and florisil as purificant,a modified QuEChERS method was chosen to purify the analytes from the different samples. The target niclosamide-olamine was separated by a C18 UPLC column,then detected by negative electro-spray ionization(ESI-) and multiple reaction monitoring(MRM) mode. Quantification was performed by peak area external standard methods using matrix-matched calibration curves,with good linear relationships in the range of 0.005-0.10 μg/mL. The limit of detection(LOD) and limit of quantitation(LOQ) of niclosamide-olamine were 0.003 mg/kg and 0.01 mg/kg in tea sample,and 0.002 mg/kg and 0.005 mg/kg in other samples. At three spiked levels in different food samples,the average recoveries were between 77.3% and 115% with relative standard deviations(RSDs) lower than 10%. The method is simple and rapid with low usage of reagents. It is suitable for the determination of niclosamide-olamine in a variety of matrices for agricultural products.
摘要:A new method for the simultaneous and rapid determination of 8 tidine drugs in 5 different matrix types of cosmetics by ultra high performance liquid chromatography-triple quadrupole mass spectrometry(UHPLC-MS/MS) was established. The different matrix cosmetic samples were dipersed with water-acetonitrile(2∶8,volume ratio) and ultrasonic extraction,and the filtrate was analyzed by UHPLC-MS/MS. A YMC-Triart C18 column(100 mm×2.1 mm,3.0 μm) was used as separation chromatographic column,with 0.2% formic acid aqueous solution and acetonitrile as mobile phases under gradient elution. Eight tidines drugs were analyzed in the positive mode using multiple reaction monitoring mode and electrospray ionization mass spectrometry. The results showed that the correlation coefficients for linear calibration curves were ranged of 0.997 5-0.998 6 in the corresponding concentration range. The limits of detection(LODs) of 8 tidine drugs were in the range of 0.06-0.3 μg/L,and the limits of quantitation(LOQs) were in the range of 0.2-1.0 μg/L. The average recoveries of 8 tidine drugs from water aqua,cream,lotion,gel and powder samples at three different spiked levels ranged of 80.7%-106%,90.1%-102%,82.6%-101%,82.0%-110% and 86.6%-101%,respectively,with relative standard deviations ranged of 0.70%-7.9%. The established method is simple,effective,easy to operate,high sensitive,and accurate,and is suitable for the determination of 8 tidine drugs in 5 different matrixes of cosmetics(including water aqua,cream,lotion,gel and powder samples).
摘要:In this study,a total of 989 pesticide residues were analyzed by gas chromatography and liquid chromatography-time of flight mass spectrometry(GC/LC-Q/TOF MS) in 100 samples of commercially available Angelica sinensis,and the risk levels of detected pesticides were categorized according to the risk ranking method of veterinary drug residue matrix,and the chronic and acute dietary intake risk and cumulative risk values of detected pesticides were calculated by point assessment method and hazard index(HI) method,respectively. The total detection rate in 100 cases of Angelica sinensis was 95%,and 27 pesticides were detected,among which phorate and chlorpyrifos were detected at a higher rate,with pesticide residue levels ranging from 0.001 0 mg/kg to 1.407 7 mg/kg. According to the Chinese Pharmacopoeia 2020 and GB 2763-2021,only phorate,isofenphos-methyl,and terbufos among the detected pesticides had MRL,of which phorate had the highest exceedance rate. The risk ranking results showed that the high-risk pesticides were phorate,terbufos and isofenphos-methyl. The results of dietary intake risk and cumulative risk showed that the average values of chronic dietary intake risk(%ADI) and acute dietary intake risk(%ARfD) of detected pesticides were 0.290 8% and 0.097 8%,both far below 100%;the chronic cumulative risk(HIc) and acute cumulative exposure(HIa) were 0.066 89 and 0.011 73,respectively,both far less than 1. The chronic and acute dietary intake risk and cumulative risk were both at acceptable levels. The dietary intake and cumulative exposure risks of the pesticides detected in Angelica sinensis were low,but the regulation of pesticide use still needs to be strengthened,and it is recommended to set MRLs for medium risk pesticides detected in Angelica sinensis.
摘要:To figure out the differences in elemental content of citrus reticulata blanco from different producing areas and establish a rapid method for identifying the origin,42 batches of citrus reticulata blanco sample from 3 origins in Xinhui,Guangxi,Hunan were collected in this study. The contents of 51 mineral elements were determined by inductively coupled plasma-mass spectrometry(ICP-MS). Combined with analysis of variance and partial least squares discriminant analysis(PLS-DA),9 effective indicators were screened out. And the conversion coefficient was studied and the elemental fingerprint was established. The standard fingerprints of Xinhui,Guangxi and Hunan were constructed based on the average values of element content in each production area,serving as the basis for traceability of production areas. SPSS 20. 0 was used to calculate the similarity between the fingerprints and the similarity threshold was determined to be 0.941,which was used to distinguish the producing area. Lastly,24 batches of other sample were used to verify the accuracy of the method,with a accuracy rate of 91.6%. The method is simple and intuitive to operate,and can meet the requirements of experimental analysis. The established standard fingerprint of citrus reticulata blanco can provide a reference method for the traceability of the origin of tangerine peel.
关键词:citrus reticulata blanco;mineral element fingerprint;origin identifying;inductively coupled plasma mass spectrometry(ICP-MS)
摘要:In this paper,a rapid and effective screening method for 34 benzodiazepines(BZDs) in dried blood spots(DBS) using direct analysis in real time-tandem mass spectrometry(DART-MS/MS) was established by optimizing the instrumental conditions and pre-treatment methods. 50 µL of blood was deposited on the blood collection card to form DBS,the upper solution was taken after sufficient solvent extraction and 5 µL was injected using the DART 12Dip-ItTM module and assayed in multiple reaction monitoring(scheduled MRM) mode. The results showed that:400 ℃ was chosen as the carrier gas heater temperature,and the DBS samples were extracted using a solvent mixture of ethyl acetate-water(3∶1,by volume),and the upper layer of the solution was injected,which showed a high response intensity and good selectivity without the influence of delayed effect. The limits of detection were in the range of 5-50 ng/mL for all substances except for adinazolam,oxazepam and α-hydroxytriazolam. BZDs were successfully screened in 90.3% of the positive case samples. The method is fast,simple,effective and suitable for the rapid screening test of DBS samples in cases such as suicide by drug taking.
关键词:direct analysis in real time;dried blood spot;benzodiazepines;rapid screening
摘要:A headspace gas chromatography-mass spectrometry(HS/GC-MS) method for determination of 46 volatile organic compounds(VOCs) in plastic track surface layer material was established. The sample was cut into small pieces,followed by adding glyceryl triacetate and injected by headspace. The target compounds were separated by DB-624UI capillary column,and then identified by selected ion monitoring(SIM) under electron bombardment source(EI),and quantified by external standard method. The chromatographic column,temperature program,headspace parameters and dispersion solvent were optimized respectively. The results showed that under the optimized conditions,46 VOCs exhibited good linearity over their own concentration ranges,the correlation coefficients(r2) were all over than 0.995,the limits of detection(LODs) and limits of quantitation(LOQs)were 0.05-0.60 μg/g and 0.10-1.20 μg/g respectively,the average recoveries at three spiked levels were 82.9% -114%,and the relative standard deviations(RSDs,n=6) were 1.1%-5.6%. This method shows the advantages of simple pretreatment,low detection limit and high accuracy,which can meet the requirement of rapid qualitative and quantitative analysis of VOCs in the plastic track surface layer material.
关键词:volatile organic compounds(VOCs);headspace(HS);gas chromatography-mass spectrometry(GC-MS);plastic track surface layer material
摘要:Organic aromatic amines in aromatic imine functionalized polyoxometalate derivatives have different substituent positions,to investigate its impact on the derivatives synthesis reaction rate and structural stability,two aromatic imines containing chlorine derivatives of Lindqvist type hexamolybdate were synthesized,they are TBA2[Mo6O18(N-C6H4-Cl-p)](Ⅰ) and TBA2[Mo6O18(N-C6H4-Cl-o)](Ⅱ). The reaction process was monitored in real time by electrospray ionization mass spectrometry(ESI-MS),the variation trend with reaction time of each species in the two reaction systems was analyzed,so as to study the effect of substituent position on the reaction rate. The gas phase cracking reactions of two derivative ions were studied through collision induced dissociation technique(CID),thus obtain on their gas phase cracking pathway and structural stability information. The ESI-MS real-time monitoring results showed,product generation rate is relatively low during 0-3 hours,while the reaction rate was the biggest during 3-6 hours,followed by 6-9 hours,and the reaction rate significantly decreased during 9-12 hours in the synthesis process of Ⅰ and Ⅱ. The pKb of p-chloroaniline is smaller than o-chloroaniline,which is an important reason why the synthesis reaction rate of Ⅰ is higher. The CID results indicate that compared to the Ⅰ ion,the gas-phase structural stability of the Ⅱ ion is weaker. The main reason is that the comprehensive electronic effect of the Cl atom substituent is the electron withdrawing effect,which is closer to the Mo≡N bond that maintains ion stability in ortho substitution than in para substitution. This leads to a greater decrease in the electron cloud density of the Mo≡N bond in the Ⅱ ion,and the stability of the ion is weaker than that of the Ⅰ. In summary,ESI-MS is a reliable technique for studying polyoxometalates organic functionalized derivatives,which can provide basic information for the study of structural stability and subsequent directed design and synthesis of such derivatives.
关键词:electrospray ionization mass spectrometry(ESI-MS);aromatic imine derivatives of hexamolybdate;substituent group;synthesis;gas phase stability
摘要:Aptamers are single-stranded oligonucleotide fragments selected in vitro,mainly through the process known as systematic evolution of ligands by exponential enrichment(SELEX). As aptamers can be artificially synthesized in a large scale and exhibit the intrinsic merits of low price,ease of functional modification,high specificity and affinity,low immunogenicity,minimal interbatch variability,and high thermal stability,they have attracted much attention in diverse fields such as analytical chemistry,disease therapy,and biomedical research. In this review,we describe the representative application of aptamers in electrochemical biosensing. Specifically,the characteristics of aptamers and electrochemical aptasensors are firstly summarized,and then focuses on the introduction of the application of electrochemical aptasensors in the detection of small molecules,proteins,exosomes,circulating tumor cells(CTCs),and pathogenic microbes,along with their detection principle,analytical performances,and the used signal amplification strategies. Also,the further development of electrochemical aptasensors is prospected.
摘要:Fingerprints are one of the most prevalent forms of evidence at the scene of contact-based crimes. By analyzing their morphological characteristics and the substances they contain,fingerprints facilitate individual identification and the resolution of criminal cases. Time-of-flight secondary ion mass spectrometry(TOF-SIMS) is a surface analysis technique that combines high quality resolution and high spatial resolution to simultaneously obtain mass spectra information and imaging distribution of the substance to be measured. Compared with other physicochemical analysis techniques,TOF-SIMS is becoming a frontier topic in fingerprint analysis due to its ability of rapid inspection,no pretreatment,and in situ near-nondestructive. We review the current research status of TOF-SIMS in the field of fingerprint analysis(specifically focusing on imaging enhancement,material analysis,and criminal information mining) and analyze its application prospect in investigating crime,in order to promote the spread of this technology in the domain of fingerprint examination.
关键词:TOF-SIMS;mass spectrometry imaging;fingerprint;application research
摘要:Due to the facile synthesis method,excellent luminescence properties,great water dispersion and biocompatibility of fluorescent polydopamine(FPDA) nanomaterials,it has attracted much attention and potential applications in the fields of chemical sensing,biological detection and cell imaging. However,the intrinsic PDA nanoparticles has no/weak photoluminescence properties by using dopamine(DA) oxidative self-polymerization under the traditional conditions. In this paper,the origin of the non-luminescence/weak fluorescence of the intrinsic PDA was analyzed firstly,and the aggregation induced fluorescence quenching was considered as the main reason that is due to the excessive degree of intra/inter-molecular stacking of PDA. And then,it has summarized the construction methods of FPDA in recent years,including:chemical oxidation,conjugation,chemical degradation,carbonization and etc,which were achievement by inhibiting the polymerization degree of dopamine or reducing the π-π stacking between the aromatic rings in PDA. Meanwhile,the morphology,luminescence mechanism and its applications in metal ions detection of FPDA were discussed in detail.