摘要:In order to effectively solve the problem of“incomplete and slow detection”of risk substances in cream cosmetics,a rapid screening method for 297 risk substances in cosmetics using QuEChERS combined with high-performance liquid chromatography quadrupole time of flight mass spectrometry(HPLC-Q-TOF MS) was established. The sample was dispersed with saturated sodium chloride,extracted with anhydrous ethanol,extracted with C18 dispersion solid phase extraction,and determined by HPLC-Q-TOF MS. The optimization of QuEChERS method is based on ultra high performance liquid chromatography triple quadrupole tandem mass spectrometry(UPLC-MS/MS) technology. 45 risk substances were selected as quality control compounds,with limits of detection(LODs) of 0.01 mg/kg to 0.20 mg/kg,and limits of quantitation(LOQs) of 0.04 mg/kg to 0.40 mg/kg. Average recoveries for the three spiked levels(low,medium and high) were in range of 81.5%-117%,with relative standard deviations(RSDs,n=6) of 2.0% to 14%. The QuEChERS method was extended to the HPLC-Q-TOF MS targeted screening of 297 risk substances,namely,collecting the primary and secondary mass spectrometry informations of compounds,establishing a high-resolution mass spectrometry screening table,and comparing the informations collected by HPLC-Q-TOF MS with the screening table to identify“suspicious targets”,further using UPLC-MS/MS for quantitative confirmation. 29 cream samples were targeted and screened with this method,and mefenamic acid,cyproheptadine hydrochloride,clindamycin and lincomycin were screened,with the detection amount of 0.042-3 180 mg/kg. The method provides a technical basis for rapid screening of risk substances in cosmetics.
摘要:Heavy metal ions in environmental water are extremely harmful to human health and the ecological environment. This paper proposes a miniaturized heavy metal ion detector,which has the advantages of high precision,stability,and portability. The device can accurately output excitation signals in the -2.5-+2.5 V range,and by adjusting 8 different gains,it can detect the current in range of pA-mA to meet the detection requirements of trace heavy metal ions. Four tests are carried out to verify the hardware parameter performance of the heavy metal detector,including:the accuracy of the stimulus signal,the stability of the potentiostatic circuit,the accuracy of microcurrent detection and the overall volt-ampere performance test. The electrochemical performance was verified by cyclic voltammetry experiments at different scanning speeds in potassium ferricyanide solution,and the linear relationship between the peak current height and the square root of scanning speed was obtained,and the linear correlation coefficients(r2) were all greater than 0.99. Square wave anodic stripping voltammetry(SWASV) was used to detect Pb2+ with unmodified screen printed gold electrode as the sensor. The calibration curve in the concentration range of 10-100 μg/L was obtained,and the detection limit was 0.295 μg/L with good repeatability. By comparing with the bench-top electrochemical analytical equipment Gamry Reference 600+,nearly consistent calibration curves were obtained,with r2 being 0.998 9 and 0.999 1,respectively,indicating the reliability of the developed equipment. The proposed heavy metal detector not only provides strong detection performance and reliability,but also achieves low cost and portability,and can be used for on-site detection of heavy metal ions in environmental water.
关键词:potentiostat;electrochemistry;heavy metal ion detection;lead;square wave anodic stripping voltammetry;microcurrent sensing
摘要:A nitrogen-doped carbon nanotubes(N-CNTs) reinforced hollow fiber liquid-phase microextraction(HF-LPME) combined with high performance liquid chromatography(HPLC) was established for the simultaneous determination of tetrabromobisphenol A(TBBPA) and decabromodiphenyl oxide(BDE209) in biological samples. The serum and urine samples were extracted with 15 μL toluene-n-octanol(1∶1,by volume) and toluene-ethyl acetate(1∶1,by volume) at room temperature for 10 min,respectively. During the extraction process,the hollow fiber membrane blocked the interference of macromolecules in the sample,which played a role in purification. The target compounds were separated on a Kjnetex EVO C18(2.1 mm×150 mm,5 μm) column by gradient elution,using water and acetonitrile as mobile phases at a flow rate of 0.3 mL/min and a column temperature of 30 ℃. The effects of different extraction solvent type,extraction time,nitrogen-doped carbon nanotubes amount,sample pH value,stirring rate,NaCl concentration and desorption solvent type on extraction efficiencies of the target compound were investigated. External standard method was used for the quantitative analysis. The results showed that under the optimum conditions,the calibration curves were linear in the range of 2-200 ng/mL for TBBPA,and 10-200 ng/mL for BDE209. The correlation coefficients(r2) were not less than 0.995,the detection limits(LODs) and the quantitation limits(LOQs) of the method were in the ranges of 0.375-2.8 ng/mL and 1.25-9.4 ng/mL,respectively. The average recoveries for the two target analytes at three spiked levels ranged from 84.5% to 114%,with relative standard deviations(RSDs) of 1.4%-7.5%. This method could not only enrich TBBPA and BDE209,but also remove protein from biological samples at the same time. The method was sensitive,reproducible,green and environmentally friendly,and was suitable for the detection of TBBPA and BDE209 in complex matrices.
摘要:To achieve efficient nonlinear regression analysis of near-infrared spectra,a near-infrared spectrum regression analysis algorithm based on an improved stacked autoencoder combined with LightGBM is proposed. The algorithm consists of the stacked autoencoder module and the LightGBM module. The hidden layer features obtained from the stacked autoencoder module are sent to the LightGBM module for regression analysis. The structure of the stacked autoencoder module is adaptively determined through a progressive strategy,and the hyperparameters of the LightGBM module are automatically optimized using the Optuna framework. To validate the effectiveness of the method,the reducing sugar,chlorine,potassium,and total nitrogen of tobacco were selected as the research objects,and a model was built using 1 911 tobacco samples. The results were compared with four other near-infrared spectral regression analysis algorithms. Experimental results showed that the average of the predicted models for tobacco reducing sugar,chlorine,potassium,and total nitrogen were 0.911 0,0.056 8 and 0.832 8,respectively,and the prediction accuracy of the proposed method was the best among the five methods. Given equivalent performance on the training set,the proposed method achieves 1%-40% higher prediction accuracy on the test set compared to XGBoost. The improved stacked autoencoder combined with LightGBM demonstrates good component regression analysis ability in near-infrared spectral analysis and can be used to construct chemical composition prediction models for tobacco.
摘要:The evaluation of antioxidant activity of Sargassum fusiforme is of great importance to protect the interests of consumers. In view of the fact that the traditional analytical methods of Sargassum fusiforme are usually time-consuming and laborious,this study established a rapid and efficient method for the evaluation of antioxidant activity of Sargassum fusiforme based on near infrared spectroscopy(NIRS). The antioxidative activity indexes(DPPH free radical scavenging ability,ABTS free radical scavenging ability and FRAP method) of 150 Sargassum fusiforme samples in six batches were determined by ultraviolet-visible spectrophotometry. Quantitative calibration models for four antioxidant activity indexes were established with partial least squares(PLS),and different spectral preprocessing methods and competitive adaptive reweighted sampling(CARS) method were used to optimize the performance of the model. The correlation coefficient of calibration set(RC),correlation coefficient of prediction set(RP),root mean square error of calibration set(RMSEC) and root mean square error of prediction set(RMSEP) were used as the evaluation indicators of the calibration model. The results showed that the prediction accuracies of the three quantitative calibration models were all ideal,with RP and RMSEP of 0.968 and 2.42%,0.967 and 0.73%,0.979 and 3.60 μmol/L,respectively. The study confirmed that the method based on NIRS and CARS-PLS can be successfully used to determine the antioxidant activity of Sargassum fusiforme,which has the advantages of rapid analysis,simple operation,economy and environmental protection,and has certain guiding significance for ensuring the quality of Sargassum fusiforme and improving the quality control of Sargassum fusiforme.
摘要:2,4,6-Trinitrophenol(TNP) is a commonly used nitroaromatic explosive. Excessive use will cause serious pollution to soil and groundwater. TNP not only causes a series of environmental problems,but also has many negative effects on the human body. So far,many analytical methods have been applied to the determination of nitroaromatic explosives,such as high performance liquid chromatography(HPLC),mass spectrometry(MS),and electrochemical methods. However,these methods have some drawbacks,such as high cost,complicated sample pretreatment,and expensive instruments. It is of great significance to develop a simple,sensitive and selective method for the detection of TNP. In order to solve this problem,a rapid detection and analysis method of TNP was established based on the inner filter effect(IFE) using B-doped carbon dots(B-CDs) as fluorescent probes. In this study,B-CDs with fluorescence quantum yield of 51.43% were prepared by one-step hydrothermal method using 3-aminophenylboronic acid(3-APBA) as raw material. The morphology and particle size distribution of B-CDs were observed by transmission electron microscopy(TEM). The functional groups on the surface of B-CDs were investigated by FT-IR spectroscopy. The elemental composition and chemical state of B-CDs were studied by X-ray photoelectron spectroscopy(XPS). The optical properties of B-CDs were investigated by fluorescence spectroscopy and ultraviolet-visible absorption spectroscopy. In addition,the effects of pH,salt concentration and temperature on the fluorescence intensity of B-CDs were studied. It was found that the fluorescence emission peak of the prepared B-CDs overlapped with the ultraviolet-visible absorption peak of TNP. According to the fluorescence lifetime results,it was judged that there was an internal filtering effect between the two. The pH 6.0 and room temperature were selected as the optimal experimental conditions. Under the optimal experimental conditions,the fluorescence intensity of B-CDs decreased regularly in the range of 0.5-100 μmol/L TNP concentration. The TNP concentration showed a good linear relationship with the quenching degree lg(I0/I),and the linear equation was lg(I0/I)= 0.01c+0.022 86(r2 = 0.999 78). The detection limit was calculated to be 86 nmol/L according to the 3σ rule. The method was successfully applied to the determination of TNP in environmental water samples. The spiked recoveries of the actual samples were 95.1%-110%,and the relative standard deviation(RSD) was in the range of 1.0%-3.9%. The TNP analysis method based on IFE mechanism is simple,sensitive and selective.
摘要:In this study,somatostatin trisulfide was generated by the reaction of somatostatin with sodium thiosulfate(Na2S2O3),and then freeze-dried after purified by high pressure preparation liquid chromatography. The exact mass,peptide sequence and trisulfide bond assignment were detected by high resolution mass spectrum. The results showed that somatostatin trisulfide was generated by reaction of somatostatin with Na2S2O3 when the molar ratio was 1∶2,and reacted in a 60 ℃ water bath for 1 h. The purity of somatostatin trisulfide was greater than 95% after purified,desalinated and freeze-dried. It was analyzed by mass spectrometry. The m/z of[M+2H]2+ was 835.353 9 and[M+3H]3+ was 557.236 9,the peptide sequence was A-G-C-K-N-F-F-W-K-T-F-T-S-C,and the trisulfide bond was Cys(3)-Cys(14),which were consistent with theoretical structure of somatostatin trisulfide. The research provided a basis for quality research of somatostatin.
关键词:somatostatin trisulfide;high pressure preparation liquid chromatography;purification;mass spectrometry analysis;quality research
摘要:In this study,three ligands were used to synthesize a kind of perovskite nanocrystals core-shell structure with a very thin shell layer that nanocrystals cannot be completely coated with this core-shell. Compared with the original perovskite nanocrystals,the core-shell structure of the perovskite quantum dots has better stability,and also has pores that can contact with related metal ions,so that the fluorescence of the quantum dots can be quenched,so as to achieve the purpose of detecting heavy metal ions. The perovskite nanocrystalline core-shell structure prepared in this study can sensitively detect copper and mercury ions,and the theoretical detection limit of Cu2+ can reach 0.60 nmol/L,while the theoretical detection limit of Hg2+ can reach 0.64 nmol/L. This study is of great significance for the development of novel fluorescence detection agents for quantum dots.
关键词:perovskite nanocrystals;core-shell structure;heavy metal ion detection;fluorescence detection agents
摘要:In this paper,a novel fluorescent probe with D-π-A structure(1) was synthesized by a one-step reaction using 1,2,3,3-tetramethyl-3H-indolium iodide as an electron acceptor and indole as an electron donor for the detection of drug-induced viscosity changes in cells. The structure of the fluorescent probe was characterized by nuclear magnetic hydrogen spectroscopy(1H NMR),nuclear magnetic carbon spectroscopy(13C NMR) and electrospray ionization mass spectrometry(ESI-MS). The optical properties of the probe and the feasibility of response viscosity(η) were measured by fluorescence spectroscopy. The probe was added to different ratios of water-glycerol system,the fluorescence intensity(I) of probe increased gradually with the increasing ratio of glycerol. When the ratio of glycerol was 90%,the fluorescence intensity of the probe was enhanced by about 100 times compared with the pure water system. The analysis using the Förster-Hoffmann equation showed a good linear relationship between lgI and lgη(r2 = 0.998 0),and the lowest detection limit of the probe for viscosity was 1.167 cP,indicating the probe has good sensitivity to viscosity response and has the potential for quantitative viscosity detection. The probe did not respond to other active molecules,and the fluorescence intensity was little affected by organic solvents with small viscosity,and only had a better response to glycerol with large viscosity,which fully indicates that the probe degree has an excellent specificity to viscosity. The fluorescence of the probe both in the aqueous solution and the water-glycerol(90%) solution did not change significantly after 60 min keeping at room temperature. The fluorescence intensities of the probe both in aqueous solution and the water-glycerol(90%) solution were almost unchanged in the pH range of 4.0-9.0,which indicated that the probe has good photostability and pH stability. The probe had a low effect on cell viability within the experimental range,indicating that the probe has good biocompatibility. In addition,only weak fluorescence was observed after HeLa cells were co-incubated with the probe solution for 30 min. In contrast,after the probe solution was co-incubated with HeLa cells which were stimulated with rotenone and carbonyl cyanide chlorophenylhydrazone(CCCP) for 30 min,a significant increase in cell fluorescence brightness could be observed,indicating that the probe can effectively detect changes in viscosity in the cell microenvironment. All the above results indicate that the probe has the advantages of good stability,specificity and biocompatibility as a viscosity-responsive probe,and has excellent potential for biological applications.
摘要:Positively charged polydienyl dimethyl ammonium chloride(PDDA) and the negatively charged CdS quantum dots(CdS QDs) were adsorbed on the surface of graphene oxide(GO) in order to prepare the graphene-PDDA-quantum dots complex. And modify this complex onto the surface of the electrode. Then capture DNA(cDNA) was assembled on the surface of quantum dots by amide bond,and chloramphenicol aptamer(Apt) was hybridized with cDNA to construct the sensing interface. Finally,hemin embedded in the DNA chain is used to catalyze the oxidation of hydrogen peroxide,resulting in the consumption of co-reactant H2O2 and the decrease of luminous intensity of quantum dots. In the presence of chloramphenicol(CAP),Apt DNA will bind to CAP and detach from the electrode surface,resulting in an increase in the luminous intensity of quantum dots,thus achieving sensitive and specific detection. In the CAP concentration range of 1.0×10-10-1.0×10-6 mol/L,the sensor has a good detection signal,the ECL intensity is linearly correlated with the logarithm of CAP concentration,and the detection limit is 3×10-11 mol/L. The sensor has excellent repeatability,stability and specificity. Finally,the sensor has been applied to the determination of CAP residues in real milk samples with satisfactory results. The rapid and simple sensor detection technology of CAP will have a good application prospect in the fields of food safety and environmental monitoring.
摘要:To develop a new paper chip preparation technology to produce high-precision paper-based microfluidic chips,this paper proposes a new preparation method based on maskless lithography. The effects of exposure and development on the hydrophobic strength and liquid flow in the hydrophobic region were investigated using the surface contact angle of the hydrophobic pattern and the liquid flow in the microfluidic channel as evaluation criterias. The results showed that the contact angle of the hydrophobic region of the paper chip prepared with an exposure time of only 2 s could reach to 100.56°,with a clear distinction between the hydrophilic and hydrophobic regions. The minimum achievable hydrophilic channel and hydrophobic barrier widths were(68±5) μm and(104±9) μm,respectively. The paper-based chip was used for the detection of nitrite,and there was a good correlation between concentration of the solution and color intensity in the color development zone,with a linear equation of Y=3.450X+34.83 and r2=0.977 0. The preparation of paper chips based on maskless lithography without making a mask version greatly reduces the cost and time of chip fabrication,and shows a simple process and high chip accuracy,which could provide an effective means for the development,production,and application of paper chips.
摘要:The method was developed to analyze the metabolic products of ofloxacin in muscle,colon,liver,kidney,ileum and gut content of mice,with an ultra-high performance liquid chromatography-quadrupole time-of-flight mass spectrometry(UHPLC-Q-TOF MS). Metabolomics and feature-based molecular networking(FBMN) technology were used for data processing based on precise molecular weight. With the aid of the Human Metabolome Database(HMDB),two metabolic products of ofloxacin in mice were identified by metabolomics software of Progenesis QI,that is,N-oxidation product and pefloxacin,and the other three metabolic products,which are decarboxylation products,N-dealkylation products after decarboxylation,and ring-opening decarboxylation products after deamination,were identified by FBMN. The developed method can analyze the metabolic products of ofloxacin in mice with rapid,accurate and no standards. It has a broad application in analyzing other metabolic products.
关键词:ofloxacin;metabolites;high resolution mass spectrometry;FBMN;mice
摘要:A quantitative determination method for the separation of all-trans retinol,13-cis-retinol and α-tocopherol chiral isomers in infant formula was established by online solid phase extraction and two-dimensional liquid chromatography technique. After sample was purified by divinylbenzene and N-vinylpyrrolidone macroporous copolymer(HLB) online solid phase extraction column,retinol and four tocopherols were eluted to the first-dimensional high performance liquid chromatography with pentafluorophenyl packing column(PFP) by switching valve,and the total retinol and four tocopherol isomers were separated in the first-dimensional column. The total retinol and α-tocopherol were cut sequentially into the second-dimensional column by the trap column and the central switching valve,then the separation of all-trans and 13-cis-retinol isomers was realized in the chiral column(CND) coated with 3,5-dimethylphenylcarbamate,and the separation of d and l chiral isomers of α-tocopherol was realized at the same time. All of the compounds are detected by ultraviolet and fluorescent detectors with external standard quantification. The linear range was 0.1-5.0 mg/L for all-trans retinol and 13-cis-retinol,1.0-30.0 mg/L for d- and l-α-tocopherol with correlation coefficients more than 0.999,and the quantitation limits of all-trans retinol,13-cis-retinol,d- and l-α-tocopherol were 53 μg/100 g,56 μg/100 g,290 μg/100 g,and 340 μg/100 g respectively. Recoveries at low,medium and high spiked concentrations were between 90.9%-106%,with relative standard deviations(RSD) not more than 2.8%. The method could meet the regular analysis of retinol and α-tocopherols in milk-based infant formula,and also the exact evaluation of their bioavailability after considering relative bioactive factor for each.
关键词:HLB online solid phase extraction;CND-coated chiral separation column;cis and trans-retinol isomers;α-tocopherol chiral isomers;infant formula
摘要:In order to accurately recognize the copy paper found at the crime scene,the“source-manufacturer-brand”three-dimensional characteristics details of them were described and recognized by advanced spectral fusion technology. Spectral data of 200 samples from four sources(Shandong,Henan,Shaanxi and Jiangsu) were collected by microscopic confocal Raman spectroscopy and Fourier transform infrared spectroscopy. The effects of pre-processing methods including Hilbert variation,deconvolution were selected and compared. Principal component analysis was considered to extract characteristic variables. The Bayesian discriminant classification model was built based on different datasets including the single infrared spectra dataset,Raman spectral dataset and three spectral fusion approach datasets. The primary fusion based on the full spectra dataset was selected as the optimal model for recognizing the three-dimensional characteristics details of copy paper by comparing the classification accuracy of different models. It realized the accurate classification of source(96.0%),manufacturer(100%) and brand(92.3%),respectively,which could provid some reference for its application in the field of forensic science.
摘要:Based on the peroxides in oil undergo an redox reaction with 9-octadecylamine iodide (OAmI),and the iodide ions in OAmI readily undergo halide exchange with bromide ions in cesium lead bromide perovskite nanocrystals(CsPbBr3 NCs) and cause the change of fluorescence emission wavelength and fluorescence color of CsPbBr3 NCs, an analytical method for the determination of peroxide number(PON) of traditional Chinese medicinal materials was established according to the fluorescence emission wavelength shift of CsPbBr3 NCs. Additionally,a semi-quantitative fluorescent color chart has been preliminarily created based on the color change of perovskite nanocrystals. It was found that the relative error for this method when detected the PON was around 10% compared with the national standard method. The oxidation degree of the oil seed Chinese herbal medicine could be quickly judged through the color change. A semi-quantitative analysis for the oxidation degree of seed Chinese herbal medicine such as semen armeniacae amarae and peach kernel was established.
关键词:seed Chinese herbal medicine;oil oxidation;peroxide number;fluorescence semi-quantitative method
摘要:Black carbon,which comprises carbon-containing particle produced by the combustion of biomass and fossil fuels,has been recognized as a significant contributor to radiative forcing and global warming,second only to CO2.Consequently,black carbon exerts a substantial influence on global climate and environmental systems.Moreover,the ultra-small particle size of black carbon facilitates its entry into the human body via the respiratory system,posing significant risks to human health due to both the particles themselves and the toxic substances adsorbed on their surface.To investigate the impacts of black carbon on the environment and human health,researchers have devised a range of analytical techniques.Notably,mass spectrometry techniques exhibit exceptional anti-interference capabilities and offer robust qualitative and quantitative analysis performance,rendering it one of the most promising technologies to investigating the environmental effects and health risks associated with black carbon.This article provides a comprehensive review of the principles,technical advantages,and representative applications of mass spectrometry techniques in the analysis of black carbon in complex media.Additionally,the future prospects for the advancement of black carbon analysis technologies was explored.
摘要:Attapulgite is a kind of fibrous silicate clay minerals,which is abundant in China.Attapulgite has the advantages of good mechanical strength,large specific surface area,moderate ion exchange capacity and easy modification. For example,the hydroxyl group on the surface of attapulgite can be used as the modification site for surface functionalization of attapulgite. Through the modification of attapulgite by hydrothermal modification,acid modification,thermal modification and surface functionalization modification,the dispersion as well as electrical conductivity of the material are changed,and the adsorption and catalytic properties of the composite are improved. Therefore,a variety of modified attapulgite and its composite materials could be designed and prepared to expand its application. In this review,the modification methods of attapulgite mentioned above are reviewed,and the research progress of attapulgite and its composites in separation and sensing analysis in recent five years are summarized,including the research progress in separation analysis such as sample pretreatment,chromatographic analysis,adsorption and purification,as well as the research progress of sensor construction such as fluorescence sensing,electrochemical sensing and colorimetric sensing. Finally,the future development trend of attapulgite is summarized and put forward.