This paper reported a new analytical method for the simultaneous determination of seven benzotriazole ultraviolet absorbers and seven antibacterial agents in textiles. After ultrasonic extraction for the textile sampl...This paper reported a new analytical method for the simultaneous determination of seven benzotriazole ultraviolet absorbers and seven antibacterial agents in textiles. After ultrasonic extraction for the textile samples in methanol, the solutions were analyzed by ultra-high performance liquid chromotagraphy/orbitrap high resolution mass spectrometry (UPLC/Orbitrap HRMS). It showed that a good chromatographic separation for these target compounds was achieved by a Hypersil GOLD column (100 mm × 2.1 mm × 1.9 μm) with a gradient elution of methanol and 0.1% aqueous formic acid solution (containing 0.5 mmol/L ammonium acetate). Triclosan and 4-chloro-3,5-dimethyl phenol (PCMX) were detected by the orbitrap HRMS in an electrospray ionization (ESI) negative mode while the other twelve target compounds were detected by orbitrap HRMS in ESI positive mode. Full scan experiment was performed over the range from m/z 100 to m/z 500. These target compounds were routinely detected with mass accuracy below 2 × 10-6 (2 ppm) at the optimized conditions. The results showed that the limits of detection (LODs) were in the range from 0.1 to 0.3 μg/kg. The blank samples were spiked at three levels and their average recoveries varied from 80.5% to 96.3% while the relative standard deviation (RSD) changed from 3.2% to 9.9%. The present method was also applied for the determination of those ultraviolet absorbers and antibacterial agents in the commercial textiles.展开更多
This study established a method using gas chromatography-electrostatic field Orbitrap high-resolution mass spectrometry(Orbitrap GC-MS)for the simultaneous determination of 70 organic pollutants across 4 categories:or...This study established a method using gas chromatography-electrostatic field Orbitrap high-resolution mass spectrometry(Orbitrap GC-MS)for the simultaneous determination of 70 organic pollutants across 4 categories:organochlorine pesticides(OCPs),polycyclic aromatic hydrocarbons(PAHs),polychlorinated biphenyls(PCBs),and phthalates(PAEs)in infant cereal-based supplementary foods.Techniques integrating cryogenic centrifugation and lipid and protein adsorbent(LPAS)purification were employed.The precise mass numbers of target compounds were determined by Orbitrap GC-MS in full-scan mode(Full MS),which effectively minimized matrix interferences in these foods.Method validation on rice flour samples demonstrated that the 70 compounds exhibited excellent linearity within their respective mass concentration ranges,with correlation coefficients all exceeding 0.995.The detection limits for this method ranged 0.10–1.00μg/kg,while the quantification limits varied 0.3–3.0μg/kg,meeting the established detection requirements.The average spike recovery of the 70 compounds at 3 spiked levels(5,20,and 100μg/kg)ranged 75.3%–119.3%,with relative standard deviations ranging 1.8%–10.8%.Both inter-day and intra-day precision demonstrated relative standard deviation values below 15%.This method was applied to analyze 100 samples of commercial infant cereal-based supplementary food,revealing the presence of PAEs and PAHs in 12.0%of the samples.Notably,no OCPs or PCBs were detected.The detected concentrations of benzo[a]pyrene(Ba P)and dibutyl phthalate(DBP)were(4.2±0.1)and(1.8±0.3)μg/kg,respectively.This method is straightforward,highly sensitive,and suitable for the rapid screening and confirmation of 70 organic pollutants in infant cereal-based supplementary foods.展开更多
Developing a chiral material as versatile and universal chiral stationary phase(CSP) for chiral separation in diverse chromatographic techniques simultaneously is of great significance.In this study,we demonstrated fo...Developing a chiral material as versatile and universal chiral stationary phase(CSP) for chiral separation in diverse chromatographic techniques simultaneously is of great significance.In this study,we demonstrated for the first time that a chiral metal-organic cage(MOC),[Zn_(6)M_(4)],as a universal chiral recognition material for both multi-mode high-performance liquid chromatography(HPLC) and capillary gas chromatography(GC) enantioseparation.Two novel HPLC CSPs with different bonding arms(CSP-A with a cationic imidazolium bonding arm and CSP-B with an alkyl chain bonding arm) were prepared by clicking of functionalized chiral MOC [Zn_(6)M_(4)] onto thiolated silica via thiol-ene click chemistry.Meanwhile,a capillary GC column statically coated with the chiral MOC [Zn_(6)M_(4)] was also fabricated.The results showed that the chiral MOC exhibits excellent enantioselectivity not only in normal phase HPLC(NP-HPLC) and reversed phase(RP-HPLC) but also in GC,and various racemates were well separated,including alcohols,diols,esters,ketones,ethers,amines,and epoxides.Importantly,CSP-A and CSP-B are complementary to commercially available Chiralcel OD-H and Chiralpak AD-H columns in enantioseparation,which can separate some racemates that could not be or could not well be separated by the two widely used commercial columns,suggesting the great potential of the two prepared CSPs in enantioseparation.This work reveals that the chiral MOC is potential versatile chiral recognition materials for both HPLC and GC,and also paves the way to expand the potential applications of MOCs.展开更多
Metal organic framework(MOF) assembled with coordination bonds has the disadvantage of poor stability that limits its application in the field of stationary phase,while covalent organic framework(COF)assembled through...Metal organic framework(MOF) assembled with coordination bonds has the disadvantage of poor stability that limits its application in the field of stationary phase,while covalent organic framework(COF)assembled through covalent bonds exhibits excellent structural stability.It has been shown that the stationary phases prepared by combining MOF and COF can make up for the poor stability of MOF@SiO_(2),and the MOF/COF composites have superior chromatographic separation performance.However,the traditional methods for preparing COF/MOF based stationary phases are generally solvent thermal synthesis.In this study,a green and low-cost synthesis method was proposed for the preparation of MOF/COF@SiO_(2) stationary phase.Firstly,COF@SiO_(2) was prepared in a choline chloride/ethylene glycol based deep eutectic solvent(DES).Secondly,another acid-base tunable DES prepared by mixing p-toluenesulfonic acid(PTSA)and 2-methylimidazole in different proportions was introduced as the reaction solvent and reactant for rapid synthesis of MOF/COF@SiO_(2).Compared with the toxic transition metal-based MOFs selected in most previous studies,a lightweight and non-toxic S-zone metal(calcium) based MOF was employed in this study.PTSA and calcium will form the calcium/oxygen-containing organic acid framework in acidic DES,which assembles with terephthalic acid dissolved in basic DES to form MOF.The strong hydrogen bonding effect of DES can facilitate rapid assembly of Ca-MOF.The obtained Ca-MOF/COF@SiO_(2) can be used for multi-mode chromatography to efficiently separate multiple isomeric/hydrophilic/hydrophobic analytes.The synthesis method of Ca-MOF/COF@SiO_(2) is green and mild,especially the use of acid-base tunable DES promotes the rapid synthesis of non-toxic Ca-MOF/COF@silica composites,which offers an innovative approach of greenly synthesizing novel MOF/COF stationary phases and extends their applications in the field of chromatography.展开更多
文摘This paper reported a new analytical method for the simultaneous determination of seven benzotriazole ultraviolet absorbers and seven antibacterial agents in textiles. After ultrasonic extraction for the textile samples in methanol, the solutions were analyzed by ultra-high performance liquid chromotagraphy/orbitrap high resolution mass spectrometry (UPLC/Orbitrap HRMS). It showed that a good chromatographic separation for these target compounds was achieved by a Hypersil GOLD column (100 mm × 2.1 mm × 1.9 μm) with a gradient elution of methanol and 0.1% aqueous formic acid solution (containing 0.5 mmol/L ammonium acetate). Triclosan and 4-chloro-3,5-dimethyl phenol (PCMX) were detected by the orbitrap HRMS in an electrospray ionization (ESI) negative mode while the other twelve target compounds were detected by orbitrap HRMS in ESI positive mode. Full scan experiment was performed over the range from m/z 100 to m/z 500. These target compounds were routinely detected with mass accuracy below 2 × 10-6 (2 ppm) at the optimized conditions. The results showed that the limits of detection (LODs) were in the range from 0.1 to 0.3 μg/kg. The blank samples were spiked at three levels and their average recoveries varied from 80.5% to 96.3% while the relative standard deviation (RSD) changed from 3.2% to 9.9%. The present method was also applied for the determination of those ultraviolet absorbers and antibacterial agents in the commercial textiles.
基金funded by National Key Research and Development Program for Young Scientists of China(2022YFF1102900)Hebei Province High-level Talent Funding Project(C20221009)。
文摘This study established a method using gas chromatography-electrostatic field Orbitrap high-resolution mass spectrometry(Orbitrap GC-MS)for the simultaneous determination of 70 organic pollutants across 4 categories:organochlorine pesticides(OCPs),polycyclic aromatic hydrocarbons(PAHs),polychlorinated biphenyls(PCBs),and phthalates(PAEs)in infant cereal-based supplementary foods.Techniques integrating cryogenic centrifugation and lipid and protein adsorbent(LPAS)purification were employed.The precise mass numbers of target compounds were determined by Orbitrap GC-MS in full-scan mode(Full MS),which effectively minimized matrix interferences in these foods.Method validation on rice flour samples demonstrated that the 70 compounds exhibited excellent linearity within their respective mass concentration ranges,with correlation coefficients all exceeding 0.995.The detection limits for this method ranged 0.10–1.00μg/kg,while the quantification limits varied 0.3–3.0μg/kg,meeting the established detection requirements.The average spike recovery of the 70 compounds at 3 spiked levels(5,20,and 100μg/kg)ranged 75.3%–119.3%,with relative standard deviations ranging 1.8%–10.8%.Both inter-day and intra-day precision demonstrated relative standard deviation values below 15%.This method was applied to analyze 100 samples of commercial infant cereal-based supplementary food,revealing the presence of PAEs and PAHs in 12.0%of the samples.Notably,no OCPs or PCBs were detected.The detected concentrations of benzo[a]pyrene(Ba P)and dibutyl phthalate(DBP)were(4.2±0.1)and(1.8±0.3)μg/kg,respectively.This method is straightforward,highly sensitive,and suitable for the rapid screening and confirmation of 70 organic pollutants in infant cereal-based supplementary foods.
基金supported by the National Natural Science Foundation of China (Nos.22064020,22364022,and 22174125)the Applied Basic Research Foundation of Yunnan Province (Nos.202101AT070101 and 202201AT070029)。
文摘Developing a chiral material as versatile and universal chiral stationary phase(CSP) for chiral separation in diverse chromatographic techniques simultaneously is of great significance.In this study,we demonstrated for the first time that a chiral metal-organic cage(MOC),[Zn_(6)M_(4)],as a universal chiral recognition material for both multi-mode high-performance liquid chromatography(HPLC) and capillary gas chromatography(GC) enantioseparation.Two novel HPLC CSPs with different bonding arms(CSP-A with a cationic imidazolium bonding arm and CSP-B with an alkyl chain bonding arm) were prepared by clicking of functionalized chiral MOC [Zn_(6)M_(4)] onto thiolated silica via thiol-ene click chemistry.Meanwhile,a capillary GC column statically coated with the chiral MOC [Zn_(6)M_(4)] was also fabricated.The results showed that the chiral MOC exhibits excellent enantioselectivity not only in normal phase HPLC(NP-HPLC) and reversed phase(RP-HPLC) but also in GC,and various racemates were well separated,including alcohols,diols,esters,ketones,ethers,amines,and epoxides.Importantly,CSP-A and CSP-B are complementary to commercially available Chiralcel OD-H and Chiralpak AD-H columns in enantioseparation,which can separate some racemates that could not be or could not well be separated by the two widely used commercial columns,suggesting the great potential of the two prepared CSPs in enantioseparation.This work reveals that the chiral MOC is potential versatile chiral recognition materials for both HPLC and GC,and also paves the way to expand the potential applications of MOCs.
基金supported by National Natural Science Foundation of China (Nos.21906124,32302202)Natural Science Foundation of Hubei Province (No.2017CFB220)Natural Science Foundation of Shandong Province (No.ZR2023MH278)。
文摘Metal organic framework(MOF) assembled with coordination bonds has the disadvantage of poor stability that limits its application in the field of stationary phase,while covalent organic framework(COF)assembled through covalent bonds exhibits excellent structural stability.It has been shown that the stationary phases prepared by combining MOF and COF can make up for the poor stability of MOF@SiO_(2),and the MOF/COF composites have superior chromatographic separation performance.However,the traditional methods for preparing COF/MOF based stationary phases are generally solvent thermal synthesis.In this study,a green and low-cost synthesis method was proposed for the preparation of MOF/COF@SiO_(2) stationary phase.Firstly,COF@SiO_(2) was prepared in a choline chloride/ethylene glycol based deep eutectic solvent(DES).Secondly,another acid-base tunable DES prepared by mixing p-toluenesulfonic acid(PTSA)and 2-methylimidazole in different proportions was introduced as the reaction solvent and reactant for rapid synthesis of MOF/COF@SiO_(2).Compared with the toxic transition metal-based MOFs selected in most previous studies,a lightweight and non-toxic S-zone metal(calcium) based MOF was employed in this study.PTSA and calcium will form the calcium/oxygen-containing organic acid framework in acidic DES,which assembles with terephthalic acid dissolved in basic DES to form MOF.The strong hydrogen bonding effect of DES can facilitate rapid assembly of Ca-MOF.The obtained Ca-MOF/COF@SiO_(2) can be used for multi-mode chromatography to efficiently separate multiple isomeric/hydrophilic/hydrophobic analytes.The synthesis method of Ca-MOF/COF@SiO_(2) is green and mild,especially the use of acid-base tunable DES promotes the rapid synthesis of non-toxic Ca-MOF/COF@silica composites,which offers an innovative approach of greenly synthesizing novel MOF/COF stationary phases and extends their applications in the field of chromatography.
