Login In
2022 Volume 50 Issue 5
2022, 50(5): 653-665
doi: 10.19756/j.issn.0253-3820.210897
Abstract:
With the rapid development of nanotechnology and laser technology, surface-enhanced Raman scattering (SERS) technology has flourished with a great leap. As an analysis and detection technology for fast, nondestructive, and ultra-sensitive response to the fingerprint information of the target molecule, SERS technology has been widely applied in the field of food detection, environmental monitoring and clinical diagnosis. Fabrication of SERS substrate is the committed step of achieving the ultra-sensitive detection in various fields using SERS technology. At present, the SERS activity, homogeneity, and other properties of SERS substrates which are constructed by single noble metal nanomaterials through complex and time-consuming methods cannot fit the demand of the point-of-care detection in various fields. Therefore, more and more research scholars focus on the development of simple and rapid methods to fabrication of multi-functional composite SERS substrates and application of these composite SERS substrates into the field of food detection, environmental monitoring and clinical diagnosis. This article mainly reviews the preparation of precious metal composite SERS substrates and their applications in the past years, discusses and analyzes the function and application advantages of multi-functional composite SERS substrates. The forecast of multi-functional composite SERS substrate is also provided at the end of this article.
With the rapid development of nanotechnology and laser technology, surface-enhanced Raman scattering (SERS) technology has flourished with a great leap. As an analysis and detection technology for fast, nondestructive, and ultra-sensitive response to the fingerprint information of the target molecule, SERS technology has been widely applied in the field of food detection, environmental monitoring and clinical diagnosis. Fabrication of SERS substrate is the committed step of achieving the ultra-sensitive detection in various fields using SERS technology. At present, the SERS activity, homogeneity, and other properties of SERS substrates which are constructed by single noble metal nanomaterials through complex and time-consuming methods cannot fit the demand of the point-of-care detection in various fields. Therefore, more and more research scholars focus on the development of simple and rapid methods to fabrication of multi-functional composite SERS substrates and application of these composite SERS substrates into the field of food detection, environmental monitoring and clinical diagnosis. This article mainly reviews the preparation of precious metal composite SERS substrates and their applications in the past years, discusses and analyzes the function and application advantages of multi-functional composite SERS substrates. The forecast of multi-functional composite SERS substrate is also provided at the end of this article.
2022, 50(5): 666-679
doi: 10.19756/j.issn.0253-3820.210570
Abstract:
The deep-sea material circulation process has a great impact on human life. The establishment of fast, accurate and sensitive deep-sea in situ detection technology has important application value for detecting resources and protecting the environment. Mass spectrometry has the characteristics of fast detection speed, high sensitivity, and qualitative and quantitative detection of unknown substances. It can well capture the dynamic changes of chemical substances in the ocean and is very suitable for in-situ analysis of deep seas. This article reviewed recent researches on underwater mass spectrometry in situ analysis technology, summarized the development status and difficulties of the technology, and described the structural characteristics and limitations of the existing underwater mass spectrometry in situ analysis system. The future application prospects of the technology were also briefly described.
The deep-sea material circulation process has a great impact on human life. The establishment of fast, accurate and sensitive deep-sea in situ detection technology has important application value for detecting resources and protecting the environment. Mass spectrometry has the characteristics of fast detection speed, high sensitivity, and qualitative and quantitative detection of unknown substances. It can well capture the dynamic changes of chemical substances in the ocean and is very suitable for in-situ analysis of deep seas. This article reviewed recent researches on underwater mass spectrometry in situ analysis technology, summarized the development status and difficulties of the technology, and described the structural characteristics and limitations of the existing underwater mass spectrometry in situ analysis system. The future application prospects of the technology were also briefly described.
2022, 50(5): 680-691
doi: 10.19756/j.issn.0253-3820.210750
Abstract:
Resolving power and sensitivity are two important parameters to characterize the performance of high field asymmetric waveform ion mobility spectrometry (FAIMS). To simultaneously improve the resolving power and sensitivity of flat plate FAIMS, a hollow needle-ring ion source for inert gas enhanced discharge is proposed in this work. At standard atmospheric pressure, inert gases helium and argon are introduced into the needle-ring ion source to improve the ionization efficiency of the ion source and achieve effective ionization of VOCs. Helium and argon gas with gas flow rates of 0.2, 0.3 and 0.4 L/min were added at a nitrogen flow rate of 1.8 L/min and a radio frequency voltage (RF) of 300 V, respectively. Compared with pure nitrogen, the signal intensities of acetone, ethanol and ethyl acetate were increased by 19.07, 17.26 and 10.85 times, respectively, after passing helium, and 4.86, 13.37 and 4.63 times, respectively, after passing argon, and the mixture of helium, argon and nitrogen resulted in multiple ion peaks in the FAIMS spectrum. The results showed that both helium and argon could improve both resolving power and sensitivity, and that helium was more effective than argon. Mass spectrometry experiments and penning ionization theory analysis showed that the main ions produced by ionization were monomeric and dimeric ions. This study provided new ideas and methods to improve the resolving power and sensitivity of FAIMS systems.
Resolving power and sensitivity are two important parameters to characterize the performance of high field asymmetric waveform ion mobility spectrometry (FAIMS). To simultaneously improve the resolving power and sensitivity of flat plate FAIMS, a hollow needle-ring ion source for inert gas enhanced discharge is proposed in this work. At standard atmospheric pressure, inert gases helium and argon are introduced into the needle-ring ion source to improve the ionization efficiency of the ion source and achieve effective ionization of VOCs. Helium and argon gas with gas flow rates of 0.2, 0.3 and 0.4 L/min were added at a nitrogen flow rate of 1.8 L/min and a radio frequency voltage (RF) of 300 V, respectively. Compared with pure nitrogen, the signal intensities of acetone, ethanol and ethyl acetate were increased by 19.07, 17.26 and 10.85 times, respectively, after passing helium, and 4.86, 13.37 and 4.63 times, respectively, after passing argon, and the mixture of helium, argon and nitrogen resulted in multiple ion peaks in the FAIMS spectrum. The results showed that both helium and argon could improve both resolving power and sensitivity, and that helium was more effective than argon. Mass spectrometry experiments and penning ionization theory analysis showed that the main ions produced by ionization were monomeric and dimeric ions. This study provided new ideas and methods to improve the resolving power and sensitivity of FAIMS systems.
2022, 50(5): 692-700
doi: 10.19756/j.issn.0253-3820.210477
Abstract:
An ultrasensitive ratiometric electrochemical biosensor was developed for detection of BCR/ABL fusion gene relied on Prussian blue (PB) and thionine (Thi) as double signals. Exonucleases Ⅲ (Exo Ⅲ)-assisted target recycling and hybrid chain reaction (HCR) signal amplification strategies were applied. Above all, the PB film was formed on the electrode surface by controlled potential electrolysis. Exo Ⅲ-assisted target recycling was operated onto the hairpin DNA, which included the specific recognition fragment of BCR/ABL fusion genes according to target DNA-triggered exonuclease reaction, and release of the hairpin fragment. The released hairpin fragments were captured on PB film-modified electrode for further amplification of HCR signal with Help-DNA, AD1 and AD2, which induced the formation of a typical linear DNA concatamers with Y-shaped structure. The formed concatamers were bound with Thi based on electrostatic interaction for second important electrochemical response. The signal ratio (IT/IP) of Thi and PB showed an excellent linearity with BCR/ABL fusion gene (lg(IT/IP)=1.094 × lgC+0.1557) in the concentration range of 1 pmol/L-100 nmol/L with a detection limit (S/N=3) of 0.19 pmol/L. The developed ratiometric genosensor provided a simple and feasible strategy for diagnosis and prognosis of chronic myeloid leukemia (CML).
An ultrasensitive ratiometric electrochemical biosensor was developed for detection of BCR/ABL fusion gene relied on Prussian blue (PB) and thionine (Thi) as double signals. Exonucleases Ⅲ (Exo Ⅲ)-assisted target recycling and hybrid chain reaction (HCR) signal amplification strategies were applied. Above all, the PB film was formed on the electrode surface by controlled potential electrolysis. Exo Ⅲ-assisted target recycling was operated onto the hairpin DNA, which included the specific recognition fragment of BCR/ABL fusion genes according to target DNA-triggered exonuclease reaction, and release of the hairpin fragment. The released hairpin fragments were captured on PB film-modified electrode for further amplification of HCR signal with Help-DNA, AD1 and AD2, which induced the formation of a typical linear DNA concatamers with Y-shaped structure. The formed concatamers were bound with Thi based on electrostatic interaction for second important electrochemical response. The signal ratio (IT/IP) of Thi and PB showed an excellent linearity with BCR/ABL fusion gene (lg(IT/IP)=1.094 × lgC+0.1557) in the concentration range of 1 pmol/L-100 nmol/L with a detection limit (S/N=3) of 0.19 pmol/L. The developed ratiometric genosensor provided a simple and feasible strategy for diagnosis and prognosis of chronic myeloid leukemia (CML).
2022, 50(5): 701-710
doi: 10.19756/j.issn.0253-3820.221008
Abstract:
An analytical method based on amplification refractory mutation system-real time fluorescence-quantitative polymerase chain reaction (ARMS-qPCR) was developed for detection of gene mutation PTENR130* mutation in thyroid cancer. Allele-specific and reference primers for the PTENR130* mutation were designed for allele-specific and reference amplification of each sample at the same time, and the ΔCt value was obtained by Ct-allele-specific value minus Ct-reference value to analyze the variant allele frequency (VAF). The ARMS-qPCR method could detect VAF as low as 0.01%, with a linear range of 0.1% to 90% VAF, and could identify PTEN mutations in genomic DNA as low as 4 copies. This method successfully detected 5 cases of mutation with VAF>0.1% in 24 thyroid tumor samples. In addition, the ARMS-qPCR method also showed good detection performance for PTENR130* mutant spiked plasma samples under the electrochemical enrichment, indicating clinical practicability and the potential to detect trace PTENR130* mutation in complex samples.
An analytical method based on amplification refractory mutation system-real time fluorescence-quantitative polymerase chain reaction (ARMS-qPCR) was developed for detection of gene mutation PTENR130* mutation in thyroid cancer. Allele-specific and reference primers for the PTENR130* mutation were designed for allele-specific and reference amplification of each sample at the same time, and the ΔCt value was obtained by Ct-allele-specific value minus Ct-reference value to analyze the variant allele frequency (VAF). The ARMS-qPCR method could detect VAF as low as 0.01%, with a linear range of 0.1% to 90% VAF, and could identify PTEN mutations in genomic DNA as low as 4 copies. This method successfully detected 5 cases of mutation with VAF>0.1% in 24 thyroid tumor samples. In addition, the ARMS-qPCR method also showed good detection performance for PTENR130* mutant spiked plasma samples under the electrochemical enrichment, indicating clinical practicability and the potential to detect trace PTENR130* mutation in complex samples.
2022, 50(5): 711-719
doi: 10.19756/j.issn.0253-3820.210856
Abstract:
The roles of various signaling molecules in myocardial remodeling (MR) in vivo and in vitro were investigated and the mechanisms based on the combination of various detection techniques was explored in this study. First, the in vivo MR model of Wistar rat was established using isoprenaline (Iso). AngiotensinⅡ (AngⅡ) induced proliferation of neonatal rat myofibroblasts (myoFbs) and thus set up the MR model in vitro. Further, Western blot was applied to detection of the expression of PKCα (protein kinase Ca, PKCα) in vivo, while methyl thiazolyl tetrazolium (MTT) assay was adopted for detection of myoFbs proliferation in vitro. Iso increased both the content of hydroxyproline (Hyp) and the expression of PKCα in myocardial tissue significantly. At the same time, it was found that AngⅡ (10-7 mol/L) promoted the proliferation of myoFbs significantly. Immunocytochemical staining and laser confocal microscopy were used to detect expression and content of p-PKCα, extracellular signal regulating protein kinase (ERKl/2) and reactive oxygen species (ROS) induced by AngⅡ in myoFbs. The results showed that the formation of MR was related to the increase of expression of ROS, p-PKCα and p-ERKl/2.
The roles of various signaling molecules in myocardial remodeling (MR) in vivo and in vitro were investigated and the mechanisms based on the combination of various detection techniques was explored in this study. First, the in vivo MR model of Wistar rat was established using isoprenaline (Iso). AngiotensinⅡ (AngⅡ) induced proliferation of neonatal rat myofibroblasts (myoFbs) and thus set up the MR model in vitro. Further, Western blot was applied to detection of the expression of PKCα (protein kinase Ca, PKCα) in vivo, while methyl thiazolyl tetrazolium (MTT) assay was adopted for detection of myoFbs proliferation in vitro. Iso increased both the content of hydroxyproline (Hyp) and the expression of PKCα in myocardial tissue significantly. At the same time, it was found that AngⅡ (10-7 mol/L) promoted the proliferation of myoFbs significantly. Immunocytochemical staining and laser confocal microscopy were used to detect expression and content of p-PKCα, extracellular signal regulating protein kinase (ERKl/2) and reactive oxygen species (ROS) induced by AngⅡ in myoFbs. The results showed that the formation of MR was related to the increase of expression of ROS, p-PKCα and p-ERKl/2.
2022, 50(5): 720-727
doi: 10.19756/j.issn.0253-3820.210740
Abstract:
A sensitive and simple method was developed for detection of manganese superoxide dismutase (MnSOD) DNA using exonuclease Ⅲ assisted signal amplification technique and gold substrate capture cycle strategy. This strategy relied on three major steps in the experiment. First, the hairpin probe labeled with fluorophore was opened by MnSOD DNA. Second, with the help of exonuclease Ⅲ, the hairpin probe was partially hydrolyzed to release MnSOD DNA and residual hairpin probe fragments labeled with fluorophore. The released MnSOD DNA could be recycled and continued to hybridize with the complete hairpin probe. And third, the reaction solution contained a large number of residual hairpin probe fragments labeled with fluorophore, which could be hybridized with capture probe modified on gold substrate, and then transferred to a new tube solution for fluorescence detection. Based on this principle, the method for MnSOD DNA detection was constructed, with detection limit of about 0.42 pmol/L. The method was also applied to the detection of MnSOD DNA in lysates of HeLa, Jurkat and Ramos cells, with recoveries ranging from 90.2% to 111.2%. This method could effectively eliminate the influence of background interference and matrix effect, and provide a new promising paradigm in developing universal methods for detection of short DNA.
A sensitive and simple method was developed for detection of manganese superoxide dismutase (MnSOD) DNA using exonuclease Ⅲ assisted signal amplification technique and gold substrate capture cycle strategy. This strategy relied on three major steps in the experiment. First, the hairpin probe labeled with fluorophore was opened by MnSOD DNA. Second, with the help of exonuclease Ⅲ, the hairpin probe was partially hydrolyzed to release MnSOD DNA and residual hairpin probe fragments labeled with fluorophore. The released MnSOD DNA could be recycled and continued to hybridize with the complete hairpin probe. And third, the reaction solution contained a large number of residual hairpin probe fragments labeled with fluorophore, which could be hybridized with capture probe modified on gold substrate, and then transferred to a new tube solution for fluorescence detection. Based on this principle, the method for MnSOD DNA detection was constructed, with detection limit of about 0.42 pmol/L. The method was also applied to the detection of MnSOD DNA in lysates of HeLa, Jurkat and Ramos cells, with recoveries ranging from 90.2% to 111.2%. This method could effectively eliminate the influence of background interference and matrix effect, and provide a new promising paradigm in developing universal methods for detection of short DNA.
2022, 50(5): 728-738
doi: 10.19756/j.issn.0253-3820.210827
Abstract:
Capillary electrophoresis (CE) has been considered as an efficient method for aptamer screening due to its high separation efficiency, less sample consumption and low screening cost. In this study, an aptamer screening method was established for virginiamycin M1 (VGM-M1) based on capillary electrophoresis-systematic evolution of ligands by exponential enrichment (CE-SELEX). The initial ssDNA library was mixed and incubated with VGM-M1, and the conjugate was separated and collected by capillary electrophoresis-ultraviolet detection (CE-UV). The next sub-library ssDNA was obtained by polymerase chain reaction (PCR) amplification and single stranded DNA (ssDNA) preparation. After four rounds of screening, the first 10 candidate aptamer sequences with high enrichment were obtained, and the first 4 candidate aptamer sequences with the highest enrichment were selected for affinity and specificity evaluation. The VGM-M1 aptamer Seq 1 with the highest affinity and the strongest specificity was obtained, and its equilibrium constant value (Kd) was 49 nmol/L. The aptamer Seq 1 was modified to obtain optimized candidate aptamer sequences and their affinity and specificity were evaluated. The results showed that the modified aptamer Seq 1-1 had the highest affinity and specificity, and its Kd was as low as 45 nmol/L. Competitive enzyme-linked aptamer visual detection method was used to detect VGM-M1, and the minimum detection limit was as low as 51 ng/mL, which was far below the maximum residue limit of 100 ng/mL for VGM-M1. Further standard addition and recovery experiments were carried out on VGM-M1 in milk, and the recoveries reached 97.8%.8-103.2%. The above research results showed that the aptamer Seq 1-1 screened by CE-SELEX could specifically recognize VGM-M1 and could be applied to the detection of VGM-M1 in real samples.
Capillary electrophoresis (CE) has been considered as an efficient method for aptamer screening due to its high separation efficiency, less sample consumption and low screening cost. In this study, an aptamer screening method was established for virginiamycin M1 (VGM-M1) based on capillary electrophoresis-systematic evolution of ligands by exponential enrichment (CE-SELEX). The initial ssDNA library was mixed and incubated with VGM-M1, and the conjugate was separated and collected by capillary electrophoresis-ultraviolet detection (CE-UV). The next sub-library ssDNA was obtained by polymerase chain reaction (PCR) amplification and single stranded DNA (ssDNA) preparation. After four rounds of screening, the first 10 candidate aptamer sequences with high enrichment were obtained, and the first 4 candidate aptamer sequences with the highest enrichment were selected for affinity and specificity evaluation. The VGM-M1 aptamer Seq 1 with the highest affinity and the strongest specificity was obtained, and its equilibrium constant value (Kd) was 49 nmol/L. The aptamer Seq 1 was modified to obtain optimized candidate aptamer sequences and their affinity and specificity were evaluated. The results showed that the modified aptamer Seq 1-1 had the highest affinity and specificity, and its Kd was as low as 45 nmol/L. Competitive enzyme-linked aptamer visual detection method was used to detect VGM-M1, and the minimum detection limit was as low as 51 ng/mL, which was far below the maximum residue limit of 100 ng/mL for VGM-M1. Further standard addition and recovery experiments were carried out on VGM-M1 in milk, and the recoveries reached 97.8%.8-103.2%. The above research results showed that the aptamer Seq 1-1 screened by CE-SELEX could specifically recognize VGM-M1 and could be applied to the detection of VGM-M1 in real samples.
2022, 50(5): 739-746
doi: 10.19756/j.issn.0253-3820.210804
Abstract:
A kind of hyperbranched boronate affinity adsorbent was prepared by combination of diboronic acid ligand with polyethyleneimine (PEI) on Fe3O4 microspheres. The optimal adsorption capacity and selectivity was obtained when PEI1800 was employed. The binding affinity of the adsorbent with biomolecules with different couples of cis-diols was investigated. It was shown that the dissociation constant (Kd) between the adsorbent and adenosine was 10-4 mol/L. Compared with previous reports, the binding affinity was improved by 10 times. More interestingly, due to the synergistic binding of boronic acid groups with two or three couples of cis-diols, Kd between the adsorbent and chlorogenic acid, rosmarinic acid, salvianolic acid B and hyperoside was 10-5 mol/L. Compared with adenosine, catechol and dopamine, the binding affinity was further improved by 10 times. Based on the strong binding strength, the adsorbent was applied in the enrichment of catecholamines from human urine and rat serum with high specificity, recovery and sensitivity. The adsorbent was expected to be further applied in the enrichment of nucleosides and glycoproteins in biological samples.
A kind of hyperbranched boronate affinity adsorbent was prepared by combination of diboronic acid ligand with polyethyleneimine (PEI) on Fe3O4 microspheres. The optimal adsorption capacity and selectivity was obtained when PEI1800 was employed. The binding affinity of the adsorbent with biomolecules with different couples of cis-diols was investigated. It was shown that the dissociation constant (Kd) between the adsorbent and adenosine was 10-4 mol/L. Compared with previous reports, the binding affinity was improved by 10 times. More interestingly, due to the synergistic binding of boronic acid groups with two or three couples of cis-diols, Kd between the adsorbent and chlorogenic acid, rosmarinic acid, salvianolic acid B and hyperoside was 10-5 mol/L. Compared with adenosine, catechol and dopamine, the binding affinity was further improved by 10 times. Based on the strong binding strength, the adsorbent was applied in the enrichment of catecholamines from human urine and rat serum with high specificity, recovery and sensitivity. The adsorbent was expected to be further applied in the enrichment of nucleosides and glycoproteins in biological samples.
2022, 50(5): 747-756
doi: 10.19756/j.issn.0253-3820.210764
Abstract:
A novel microwave-assisted graphene oxide/ferroferric oxide/2-methylimidazole zinc salt magnetic solid phase extraction (GO/Fe3O4/ZIF-8-MSPE) method was successfully developed for determination of volatile constituents in lavender using gas chromatography-mass spectrometry (GC-MS). Fe3O4 nanoparticles had the dual effects of magnetic separation and microwave absorption. The effective parameters of GO/Fe3O4/ZIF-8-MSPE were optimized. Under the optimal conditions including 5 mg of GO/Fe3O4/ZIF-8 as adsorbent, ethyl acetate as desorption solvent, microwave power of 600 W and extraction time of 10 min,the limits of detection and limits of quantification were in the ranges of 0.15-0.56 ng and 4.00-4.29 ng, respectively. The developed method was successfully applied to analyze 21 kinds of lavender from two different harvest years (2012 and 2017), and a total of 49 kinds of compounds were identified. The results of principal component analysis (PCA) provided a clear separation between those lavender samples harvested in different years. The results showed that the GO/Fe3O4/ZIF-8-MSPE was a fast, sensitive and simple method for determination of volatile constituents in plant materials.
A novel microwave-assisted graphene oxide/ferroferric oxide/2-methylimidazole zinc salt magnetic solid phase extraction (GO/Fe3O4/ZIF-8-MSPE) method was successfully developed for determination of volatile constituents in lavender using gas chromatography-mass spectrometry (GC-MS). Fe3O4 nanoparticles had the dual effects of magnetic separation and microwave absorption. The effective parameters of GO/Fe3O4/ZIF-8-MSPE were optimized. Under the optimal conditions including 5 mg of GO/Fe3O4/ZIF-8 as adsorbent, ethyl acetate as desorption solvent, microwave power of 600 W and extraction time of 10 min,the limits of detection and limits of quantification were in the ranges of 0.15-0.56 ng and 4.00-4.29 ng, respectively. The developed method was successfully applied to analyze 21 kinds of lavender from two different harvest years (2012 and 2017), and a total of 49 kinds of compounds were identified. The results of principal component analysis (PCA) provided a clear separation between those lavender samples harvested in different years. The results showed that the GO/Fe3O4/ZIF-8-MSPE was a fast, sensitive and simple method for determination of volatile constituents in plant materials.
2022, 50(5): 757-763
doi: 10.19756/j.issn.0253-3820.210493
Abstract:
A rapid, on-site protocol was developed for analysis of 12 kinds of hazardous colorants in textiles using in-syringe air-assisted extraction coupled with a self-made miniaturized linear ion trap mass spectrometer. A custom-made metal hollow needle with a tiny internal diameter enabled the aspiration of a high-speed airflow, resulting in a turbulent vortex and a highly efficient in-syringe extraction. The computational fluid dynamics of the in-syringe air-assisted extraction process was simulated. The extraction solvent, extraction cycle, and spray voltage were optimized. After extraction of target analytes, an electrospray was induced at the needle tip of the syringe, which was subjected to the detection by a miniature mass spectrometer. The limits of detection (LODs) and quantitation (LOQs) for the 12 kinds of colorants were 0.15-2.50 mg/kg and 0.40-6.00 mg/kg, respectively. The recoveries were 80.1%-106.4% with the relative standard deviations of 7.5%-15.6%. The established method was simple and efficient, and could be applied to the rapid and on-site analysis of textile samples.
A rapid, on-site protocol was developed for analysis of 12 kinds of hazardous colorants in textiles using in-syringe air-assisted extraction coupled with a self-made miniaturized linear ion trap mass spectrometer. A custom-made metal hollow needle with a tiny internal diameter enabled the aspiration of a high-speed airflow, resulting in a turbulent vortex and a highly efficient in-syringe extraction. The computational fluid dynamics of the in-syringe air-assisted extraction process was simulated. The extraction solvent, extraction cycle, and spray voltage were optimized. After extraction of target analytes, an electrospray was induced at the needle tip of the syringe, which was subjected to the detection by a miniature mass spectrometer. The limits of detection (LODs) and quantitation (LOQs) for the 12 kinds of colorants were 0.15-2.50 mg/kg and 0.40-6.00 mg/kg, respectively. The recoveries were 80.1%-106.4% with the relative standard deviations of 7.5%-15.6%. The established method was simple and efficient, and could be applied to the rapid and on-site analysis of textile samples.
2022, 50(5): 764-771
doi: 10.19756/j.issn.0253-3820.210910
Abstract:
A high performance liquid chromatography-charge aerosol detector (HPLC-CAD) method for determination of six kinds of bile acids(Glycocholicacid, hyodeoxycholic acid, cholic acid, glycodeoxycholic acid, chenodeoxycholic acid and deoxycholic acid) in Niuhuang Jiedu tablets was developed. The tablet samples were extracted by ultrasonication in 70% methanol and concentrated under nitrogen flow. The separation of bile acids was achieved on an Agilent Poroshell 120 EC C18 column (4.6 mm × 100 mm, 2.7 μm) with gradient elution using methanol and aqueous solution containing 0.1% formic acid and 5 mmol/L ammonium formate. CAD evaporation temperature was set at 55℃ and the power function value (PFV) was 1.35. The linearity ranges were 2.10-972 μg/mL for glycocholic acid, 2.09-1046 μg/mL for hyodeoxycholic acid, 2.05-978 μg/mL for cholic acid, 2.56-1022 μg/mL for glycodeoxycholic acid, 1.25-658 μg/mL for chenodeoxycholic acid and 2.05-1025 μg/mL for deoxycholic acid, respectively. All relative coefficients (R2) were higher than 0.9991. The limits of detection and the limits of quantitation ranged from 0.86 to 1.53 μg/mL and 1.20 to 2.56 μg/mL, respectively. The average recoveries of six kinds of bile acids were in the range of 94.2%-105.3% with RSD ≤ 1.63%. The method was used to determine the real tablet samples, and the results indicated that the contents of six bile acids had an obvious difference among the Niuhuang Jiedu tablets of different manufacturers. The HPLC-CAD method for the determination of six kinds of bile acids was sensitive, accurate and reliable, which could be applied to evaluate the quality of the Niuhuang Jiedu tablets.
A high performance liquid chromatography-charge aerosol detector (HPLC-CAD) method for determination of six kinds of bile acids(Glycocholicacid, hyodeoxycholic acid, cholic acid, glycodeoxycholic acid, chenodeoxycholic acid and deoxycholic acid) in Niuhuang Jiedu tablets was developed. The tablet samples were extracted by ultrasonication in 70% methanol and concentrated under nitrogen flow. The separation of bile acids was achieved on an Agilent Poroshell 120 EC C18 column (4.6 mm × 100 mm, 2.7 μm) with gradient elution using methanol and aqueous solution containing 0.1% formic acid and 5 mmol/L ammonium formate. CAD evaporation temperature was set at 55℃ and the power function value (PFV) was 1.35. The linearity ranges were 2.10-972 μg/mL for glycocholic acid, 2.09-1046 μg/mL for hyodeoxycholic acid, 2.05-978 μg/mL for cholic acid, 2.56-1022 μg/mL for glycodeoxycholic acid, 1.25-658 μg/mL for chenodeoxycholic acid and 2.05-1025 μg/mL for deoxycholic acid, respectively. All relative coefficients (R2) were higher than 0.9991. The limits of detection and the limits of quantitation ranged from 0.86 to 1.53 μg/mL and 1.20 to 2.56 μg/mL, respectively. The average recoveries of six kinds of bile acids were in the range of 94.2%-105.3% with RSD ≤ 1.63%. The method was used to determine the real tablet samples, and the results indicated that the contents of six bile acids had an obvious difference among the Niuhuang Jiedu tablets of different manufacturers. The HPLC-CAD method for the determination of six kinds of bile acids was sensitive, accurate and reliable, which could be applied to evaluate the quality of the Niuhuang Jiedu tablets.
2022, 50(5): 772-780
doi: 10.19756/j.issn.0253-3820.210829
Abstract:
A naphthalimide Schiff base fluorescent probe L was designed and synthesized with 4-bromo-1,8-naphthalene dicarboxylic anhydride as raw material. Its structure was characterized by 1H nuclear magnetic resonance (NMR),13C NMR, infrared (IR) spectroscopy and high resolution mass spectrometry (HRMS). In the CH3CN-H2O (75:25, V/V, 20 mmol/L HEPES, pH=7.4) solution, the probe possessed good selectivity and sensitivity to Cu2+ and with a detection limit as low as 0.37 μmol/L. The stoichiometric ratio of L to Cu2+ was 1:1, and the complex L-Cu2+ had high selectivity, good sensitivity, low detection limit of 0.56 μmol/L (0.09 μg/mL) and naked eye recognition for detection of glyphosate by ligand replacement menthod. In addition, the L-Cu2+ was succesfully used in detection of glyphosate in actual water samples, which indicated that the proposed probe had potential application in the field of environmental detection.
A naphthalimide Schiff base fluorescent probe L was designed and synthesized with 4-bromo-1,8-naphthalene dicarboxylic anhydride as raw material. Its structure was characterized by 1H nuclear magnetic resonance (NMR),13C NMR, infrared (IR) spectroscopy and high resolution mass spectrometry (HRMS). In the CH3CN-H2O (75:25, V/V, 20 mmol/L HEPES, pH=7.4) solution, the probe possessed good selectivity and sensitivity to Cu2+ and with a detection limit as low as 0.37 μmol/L. The stoichiometric ratio of L to Cu2+ was 1:1, and the complex L-Cu2+ had high selectivity, good sensitivity, low detection limit of 0.56 μmol/L (0.09 μg/mL) and naked eye recognition for detection of glyphosate by ligand replacement menthod. In addition, the L-Cu2+ was succesfully used in detection of glyphosate in actual water samples, which indicated that the proposed probe had potential application in the field of environmental detection.
2022, 50(5): 781-790
doi: 10.19756/j.issn.0253-3820.210785
Abstract:
By using sophocarpine (SOP) as the guest, and β-cyclodextrin (β-CD), hydroxypropyl-β-cyclodextrin (HP-β-CD), trimethyl-β-cyclodextrin (TM-β-CD), mono-(6-ethanediamine-6- deoxy)-β-cyclodextrin (2N-β-CD) and mono-(6-diethylenetriamine-6- deoxy)-β-cyclodextrin (3N-β-CD) as the host, five host-guest inclusions were prepared by the saturated solution method. The host-guest inclusion complexes were characterized by one-dimensional and two-dimensional nuclear magnetic resonance (1H NMR, 2D NMR), ultraviolet-visible spectroscopy (UV-Vis), X-ray powder diffraction (XRD) and scanning electron microscopy (SEM). The results showed that the host-guest inclusion ratios of the SOP to the five cyclodextrins were all 1:1. After the formation of inclusion complexes, the water solubility and stability of SOP were obviously increased, and the inclusion compounds were more stable under acidic conditions. Nuclear magnetic resonance analysis showed that the D ring of SOP entered its cavity from the narrow side of the CDs, while the C ring of SOP penetrated the cavity of CDs.
By using sophocarpine (SOP) as the guest, and β-cyclodextrin (β-CD), hydroxypropyl-β-cyclodextrin (HP-β-CD), trimethyl-β-cyclodextrin (TM-β-CD), mono-(6-ethanediamine-6- deoxy)-β-cyclodextrin (2N-β-CD) and mono-(6-diethylenetriamine-6- deoxy)-β-cyclodextrin (3N-β-CD) as the host, five host-guest inclusions were prepared by the saturated solution method. The host-guest inclusion complexes were characterized by one-dimensional and two-dimensional nuclear magnetic resonance (1H NMR, 2D NMR), ultraviolet-visible spectroscopy (UV-Vis), X-ray powder diffraction (XRD) and scanning electron microscopy (SEM). The results showed that the host-guest inclusion ratios of the SOP to the five cyclodextrins were all 1:1. After the formation of inclusion complexes, the water solubility and stability of SOP were obviously increased, and the inclusion compounds were more stable under acidic conditions. Nuclear magnetic resonance analysis showed that the D ring of SOP entered its cavity from the narrow side of the CDs, while the C ring of SOP penetrated the cavity of CDs.
2022, 50(5): 791-800
doi: 10.19756/j.issn.0253-3820.201524
Abstract:
A novel chemometrics coupling technique was proposed for the source apportionment of 11 kinds of polycyclic aromatic hydrocarbons (PAHs) in six topsoils around the steel-industrial region and five nonindustrial topsoils. First, the second-order calibration method based on alternating trilinear decomposition was used to decompose the gas chromatography-mass spectrum-soil sample three-way data array, then component analysis and multiple diagnostic ratios were applied to the source apportionment of 11 kinds of PAHs in the steel-industrial topsoils according to the composition and content of PAHs. The research finding showed that the resolved chromatographic and mass spectral profiles of 11 kinds of PAHs were similar to their actual ones. The found PAHs were less than two kinds, and their total concentrations were less than 25.9 μg/kg in nonindustrial topsoil samples, but the found PAHs were in the range of seven kinds to eleven kinds and total PAHs' concentrations ranged from 249.1 to 2089.1 μg/kg in industrial topsoil samples, and the highest concentration of individual PAH in industrial topsoil samples was 600.4 μg/kg for acenaphthylene. The source of PAHs in these samples mainly came from high temperature combustion of industrial coal, and the combustion and leakage of oil product made a little contribution to the PAHs' pollution to the industrial topsoil. These results demonstrated that the developed method was a simple, fast, accurate and green analytical strategy for identification, quantification and source apportionment of PAHs in actual soil.
A novel chemometrics coupling technique was proposed for the source apportionment of 11 kinds of polycyclic aromatic hydrocarbons (PAHs) in six topsoils around the steel-industrial region and five nonindustrial topsoils. First, the second-order calibration method based on alternating trilinear decomposition was used to decompose the gas chromatography-mass spectrum-soil sample three-way data array, then component analysis and multiple diagnostic ratios were applied to the source apportionment of 11 kinds of PAHs in the steel-industrial topsoils according to the composition and content of PAHs. The research finding showed that the resolved chromatographic and mass spectral profiles of 11 kinds of PAHs were similar to their actual ones. The found PAHs were less than two kinds, and their total concentrations were less than 25.9 μg/kg in nonindustrial topsoil samples, but the found PAHs were in the range of seven kinds to eleven kinds and total PAHs' concentrations ranged from 249.1 to 2089.1 μg/kg in industrial topsoil samples, and the highest concentration of individual PAH in industrial topsoil samples was 600.4 μg/kg for acenaphthylene. The source of PAHs in these samples mainly came from high temperature combustion of industrial coal, and the combustion and leakage of oil product made a little contribution to the PAHs' pollution to the industrial topsoil. These results demonstrated that the developed method was a simple, fast, accurate and green analytical strategy for identification, quantification and source apportionment of PAHs in actual soil.
2022, 50(5): 801-809
doi: 10.19756/j.issn.0253-3820.210798
Abstract:
As an air pollutant, tropospheric ozone (O3) is also a precursor of atmospheric nitrate. Its oxygen isotope abnormal (Δ17O) can be used to trace atmospheric nitrate and other atmospheric chemical processes.This research was based on the passive sampling method, and the O3 in the atmosphere was collected using a passive sampler coated with nitrite. The sampling period was one week. The atmospheric O3 was converted into nitrate on the adsorption filter membrane, the remaining nitrite was removed by adding a certain concentration of sulfamic acid, and then the corresponding concentration of sodium hydroxide was added to neutralize the pH of the solution. Nitrate was converted into N2O by the denitrifying bacteria method, and the produced N2O entered the gold tube at 800℃ to be pyrolyzed into N2 and O2. The δ18O and δ17O values of oxygen were measured and converted to Δ17O (Δ17O=δ17O-0.52δ18O). With the help of international samples with known Δ17O values (USGS34 and USGS35), a Δ17O standard curve was established to convert the Δ17O of real nitrates, and finally converted to the value of Δ17O in atmospheric ozone. The research results showed that adding 0.5 mL of sulfamic acid (1 mol/L) to the reaction and shaking for 15 min could completely remove nitrite without affecting the isotope value of nitrate. The use of 99.999% sodium nitrite could better reduce the blank effect caused by nitrate in the drug, thereby reducing the impact on the isotope value. The content of nitrate generated by O3 conversion should be higher than 6 μg of NO3-N, and the standard deviation of Δ17O measured at this time was 0.29‰ (n=3). This method was used to analyze the passively collected O3 samples in Nanjing spring, and the Δ17O value of O3was 26.59‰±1.41‰, which was consistent with the actively collected value and similar to previous research results. Passive sampling method had many advantages such as low price, good portability and low energy consumption. Its isotope value measurement results showed that the passive sampling was a highly feasible sampling method and could be used in the study of atmospheric O3 oxygen isotope abnormal values.
As an air pollutant, tropospheric ozone (O3) is also a precursor of atmospheric nitrate. Its oxygen isotope abnormal (Δ17O) can be used to trace atmospheric nitrate and other atmospheric chemical processes.This research was based on the passive sampling method, and the O3 in the atmosphere was collected using a passive sampler coated with nitrite. The sampling period was one week. The atmospheric O3 was converted into nitrate on the adsorption filter membrane, the remaining nitrite was removed by adding a certain concentration of sulfamic acid, and then the corresponding concentration of sodium hydroxide was added to neutralize the pH of the solution. Nitrate was converted into N2O by the denitrifying bacteria method, and the produced N2O entered the gold tube at 800℃ to be pyrolyzed into N2 and O2. The δ18O and δ17O values of oxygen were measured and converted to Δ17O (Δ17O=δ17O-0.52δ18O). With the help of international samples with known Δ17O values (USGS34 and USGS35), a Δ17O standard curve was established to convert the Δ17O of real nitrates, and finally converted to the value of Δ17O in atmospheric ozone. The research results showed that adding 0.5 mL of sulfamic acid (1 mol/L) to the reaction and shaking for 15 min could completely remove nitrite without affecting the isotope value of nitrate. The use of 99.999% sodium nitrite could better reduce the blank effect caused by nitrate in the drug, thereby reducing the impact on the isotope value. The content of nitrate generated by O3 conversion should be higher than 6 μg of NO3-N, and the standard deviation of Δ17O measured at this time was 0.29‰ (n=3). This method was used to analyze the passively collected O3 samples in Nanjing spring, and the Δ17O value of O3was 26.59‰±1.41‰, which was consistent with the actively collected value and similar to previous research results. Passive sampling method had many advantages such as low price, good portability and low energy consumption. Its isotope value measurement results showed that the passive sampling was a highly feasible sampling method and could be used in the study of atmospheric O3 oxygen isotope abnormal values.
2022, 50(5): 810-818
doi: 10.19756/j.issn.0253-3820.210837
Abstract:
A method for rapid determination of eight kinds of BPs in fruits and vegetables based on QuEChERS combined with ultra-high performance liquid chromatography-tandem mass spectrometry(UPLC-MS/MS) was developed. The effects of matrix effect (ME) and extraction recovery (RE) on process efficiency (PE) were discussed. Approximately 10.00 g of homogeneous fruit and vegetable samples were accurately weighed, and 10 mL of acetonitrile and 1.0 g of NaAC were added for extraction, respectively. And then, 2 mL of organic phase was taken into a 15-mL centrifuge tube, and the mixed purifier (33 mg PSA, 33 mg GCB and 10 mg C18) was added for purification. After centrifugation, 0.5 mL of supernatant was added into 0.5 mL of methanol aqueous solution (50%, V/V), and the mixture was analyzed by UPLC-MS/MS. The chromatographic separation was performed on a Waters BEH C18 (100 mm × 2.1 mm, 1.7 μm) column using methanol and 0.1 mmol/L ammonium bicarbonate aqueous solution as mobile phase. Quantitative analysis was performed by isotope internal standard method in the modes of electrospray ionization, anion and multiple reaction monitoring. The results showed that the chromatographic separation of eight kinds of BPs could be completed within 8 min with good linearity and correlation coefficients (R2>0.9990). The limits of detection (LODs) and limits of quantification (LOQs) ranged from 0.01 to 0.10 μg/kg and 0.03 to 0.35 μg/kg, respectively. The average recoveries of eight kinds of BPs in different fruits and vegetables were 67.2%-117.8% with relative standard deviations (RSDs) of 0.1%-8.3%. This method was used to detect BPs in fruits and vegetables from Guangyuan city, and it bisphenol A and bisphenol S were found to be the main contaminants with the detection rates of 80.0% and 47.5%, respectively. The concentrations of bisphenol A and bisphenol S ranged from not detected to 31.84 μg/kg and from not detected to 15.75 μg/kg, respectively. This method could rapidly extract, purify and quantitatively detect eight kinds of BPs in fruits and vegetables with the advantages such as simplicity, high sensitivity, low cost and environmental protection, and was suitable for daily mass screening and confirmation of these contaminants in fruits and vegetables.
A method for rapid determination of eight kinds of BPs in fruits and vegetables based on QuEChERS combined with ultra-high performance liquid chromatography-tandem mass spectrometry(UPLC-MS/MS) was developed. The effects of matrix effect (ME) and extraction recovery (RE) on process efficiency (PE) were discussed. Approximately 10.00 g of homogeneous fruit and vegetable samples were accurately weighed, and 10 mL of acetonitrile and 1.0 g of NaAC were added for extraction, respectively. And then, 2 mL of organic phase was taken into a 15-mL centrifuge tube, and the mixed purifier (33 mg PSA, 33 mg GCB and 10 mg C18) was added for purification. After centrifugation, 0.5 mL of supernatant was added into 0.5 mL of methanol aqueous solution (50%, V/V), and the mixture was analyzed by UPLC-MS/MS. The chromatographic separation was performed on a Waters BEH C18 (100 mm × 2.1 mm, 1.7 μm) column using methanol and 0.1 mmol/L ammonium bicarbonate aqueous solution as mobile phase. Quantitative analysis was performed by isotope internal standard method in the modes of electrospray ionization, anion and multiple reaction monitoring. The results showed that the chromatographic separation of eight kinds of BPs could be completed within 8 min with good linearity and correlation coefficients (R2>0.9990). The limits of detection (LODs) and limits of quantification (LOQs) ranged from 0.01 to 0.10 μg/kg and 0.03 to 0.35 μg/kg, respectively. The average recoveries of eight kinds of BPs in different fruits and vegetables were 67.2%-117.8% with relative standard deviations (RSDs) of 0.1%-8.3%. This method was used to detect BPs in fruits and vegetables from Guangyuan city, and it bisphenol A and bisphenol S were found to be the main contaminants with the detection rates of 80.0% and 47.5%, respectively. The concentrations of bisphenol A and bisphenol S ranged from not detected to 31.84 μg/kg and from not detected to 15.75 μg/kg, respectively. This method could rapidly extract, purify and quantitatively detect eight kinds of BPs in fruits and vegetables with the advantages such as simplicity, high sensitivity, low cost and environmental protection, and was suitable for daily mass screening and confirmation of these contaminants in fruits and vegetables.
