Automatic analytical approach for the determination of 12 illicit drugs and nicotine metabolites in wastewater using on-line SPE-UHPLC-MS/MS

In this study,we developed a novel on-line solid phase extraction(SPE)-ultra-high-performance liquid chromatography tandem mass spectrometry(UHPLC-MS/MS)-based analytical method for simultaneously quantifying 12 illicit drugs and metabolites(methamphetamine,amphetamine,morphine,codeine,6-monoacetylmorphine,benzoylecgonine,3,4-methylenedioxymethamphetamine,3,4-methylenedioxyamphetamine,cocaine,ketamine,norketamine,and methcathinone)and cotinine(COT)in wastewater samples.The analysis was performed by loading 2 m L of the sample onto an Oasis hydrophilic-lipophilic balance cartridge and using a cleanup step(5%methanol)to eliminate interference with a total run time of 13 min.The isotope-labeled internal standard method was used to quantify the target substances and correct for unavoidable losses and matrix effects during the on-line SPE process.Typical analytical characteristics used for method validation were sensitivity,linearity,precision,repeatability,recovery,and matrix effects.The limit of detection(LOD)and limit of quantification(LOQ)of each target were set at 0.20 ng/L and 0.50 ng/L,respectively.The linearity was between 0.5 ng/L and250 ng/L,except for that of COT.The intra-and inter-day precisions were<10.45%and 25.64%,respectively,and the relative recovery ranged from 83.74%to 162.26%.The method was used to analyze various wastewater samples from 33 cities in China,and the results were compared with the experimental results of identical samples analyzed using off-line SPE.The difference rate was between 19.91%and-20.44%,and the error range could be considered acceptable.These findings showed that on-line SPE is a suitable alternative to off-line SPE for the analysis of illicit drugs in samples.

On-line SPE-UPLC-MSMS快速检测水中痕量微囊藻毒素-LR

建立了测定水中痕量微囊藻毒素-LR的On-line SPE-UPLC-MSMS分析方法,该方法的工作曲线的相关系数均大于0.99、方法的精密度都≤18.3%、加标回收率均在80%—100%之间,检出限为3.5ng/L。方法具有快速、灵敏,且操作性强等特点。

STRONGLY CONVERGENT INERTIAL FORWARD-BACKWARD-FORWARD ALGORITHM WITHOUT ON-LINE RULE FOR VARIATIONAL INEQUALITIES

This paper studies a strongly convergent inertial forward-backward-forward algorithm for the variational inequality problem in Hilbert spaces.In our convergence analysis,we do not assume the on-line rule of the inertial parameters and the iterates,which have been assumed by several authors whenever a strongly convergent algorithm with an inertial extrapolation step is proposed for a variational inequality problem.Consequently,our proof arguments are different from what is obtainable in the relevant literature.Finally,we give numerical tests to confirm the theoretical analysis and show that our proposed algorithm is superior to related ones in the literature.

Quantitative determination of cyclophosphamide in rat plasma using an on-line SPE HPLC-DAD

A rapid and simple liquid chromatography method with on-line solid phase extraction was developed and validated for the quantitative determination of cyclophosphamide in rat plasma.The plasma sample was first extracted on an Acclaim？ Polar Advantage II C18 guard column（PA II C18,10 mm×4.6 mm,5 μm）,which was also the on-line Extraction Cartridge SPE column,by washing with 100% H2O for 1 min.The extracted sample was then eluted onto a PA II C18 column（150 mm×4.6 mm,5 μm） and separated by isocratic elution with acetonitrile-water（40：60,v/v）.The mobile phase was run at a flow rate of 1.0 mL/min,and the UV detector was set at 195 nm.Retention time of cyclophosphamide was 4.3 min and the total run-time was 6 min.The linear range of the standard curve was from 1.0 to 200 μg/mL（r2 = 0.9999）,and the limits of quantification and detection were 1.0 μg/mL（RSD10%,n = 5） and 0.3 μg/mL（RSD13%,n = 5）,respectively.Both intra-and inter-day variations were less than 5.6%.The developed method can be used for the therapeutic drug monitoring of cyclophosphamide in the clinic.

SPE-GC-FPD法测定三七中甲基对硫磷残留量

目的:为更好地控制三七质量,拟建立三七中甲基对硫磷的GC-FPD检测方法。方法:采用超声提取固相萃取法、GC-FPD检测。结果:方法回收率在62.52%~118.49%,精密度RSD为3.597%,标准偏差符合检测要求,满足农药残留检测的要求。

Sequential injection spectrophotometric determination of nanomolar nitrite in seawater by on-line preconcentration with HLB cartridge

The unstable state of nitrite results in its very low concentration in seawater, which is below the limit of detection （LOD） of conventional techniques of analysis. Some sensitivity-enhanced methods have been proposed for the determination of nitrite at nanomolar level to illustrate the role of nitrite in the marine nitrogen cycle. However, most of previous reports are not widely accepted, because of their complexity and cost equipment or intensive labor requirement. In this study, a simple automatic system for the determination of nanomolar level nitrite using on-line preconcentration with spectrophotometric detection was described..An Oasis HLB cartridge was adopted to quantitatively enrich the pink-colored azo compound, formed from nitrite via Griess reaction. The cartridge was rinsed with water and ethanol （volume fraction is 55%, the same below）, in turn, then eluted by an eluent containing 50% ethanol and 0.25 M（mol/dm^3） H2SO4, and determined at 543 nm with a 2 cm path-length flow cell. Under the optimized experimental conditions, the calibration curve showed a good linearity in the range of 1.4 85.7 aM, and the LOD （3a） was estimated to be 0.5 nM. The relative standard deviations of 7 measurements were 4.0% and 1.0% for the samples spiked at 7.1 and 28.6 nM, respectively. The recoveries for the different natural water samples were between 92.2%-108.4%. Each HLB cartridge could be reused for at least 50 times. As compared with other SPE methods, the advantages of this method included the free of interference from salinity variation and less sample consuming. The results of the application of the proposed method to natural water showed good agreement with liquid waveguide capillary cell detection method.

SPE-UPLC-MS/MS同时测定食品中24种酸性工业染料

建立了固相萃取-超高效液相色谱串联质谱法同时测定食品中24种酸性工业染料的分析方法。样品经氨水乙醇溶液(氨水:无水乙醇:水=2:7:1,v/v/v)提取,提取液氮吹浓缩至1 mL,加入10 mL 5%甲醇水溶液,弱阴离子交换固相萃取柱(Agela Cleanert PWAX)富集净化,氮吹复溶后,Agilent ZORBAX Eclipse RRHD C_(18)(3.0 mm×150 mm,1.8μm)色谱柱分离,流动相采用乙腈和10 mmol/L乙酸铵溶液进行梯度洗脱,电喷雾离子源负离子进行电离,多反应监测模式(MRM)下测定,外标法定量。结果表明,24种酸性工业染料在20~300 ng/mL范围内,相关系数r均大于0.999;方法检出限为10μg/kg,定量限为25μg/kg;在25、100、250μg/kg三个不同加标水平下的回收率为91.0%~112.7%,相对标准偏差(n=6)为0.42%~4.39%。采用该方法对市售的豆制品、调味品、水产品、肉制品各40批次进行测定,2批次卤肉样品中检出酸性橙Ⅱ,含量分别为138±2.8μg/kg和179±3.7μg/kg;2批次香肠样品中检出红2G,含量分别为320±8.6μg/kg和230±6.2μg/kg。该方法灵敏、快速、准确,适用于食品中24种酸性工业染料的定性定量测定。

One-step Eco-friendly Fabrication of Antibacterial Polyester Via On-line Amination Reaction by Melt Coextrusion

The work is dedicated to develop a one-step eco-friendly method to prepare antibacterial polyethylene terephthalate(PET).We report a one-step eco-friendly method to manufacture antibacterial PET via on-line amination reaction by melt coextrusion.Beside evenly mixing of poly(hexamethylene guanidine)(PHMG)and PET in the melt coextrusion procedure,the amination reaction also occurred between PHMG and PET under high temperature(230-270℃).The antibacterial ability of composite PET showed obvious PHMG concentration dependence,and antibacterial activity reached more than 99%when PHMG content was 2.5 wt%.Moreover,LIVE/DEAD fluorescence test further confirmed that the composite PET could kill bacteria quickly and efiectively(within 30 min);while negligible cytotoxicity was observed to HSF and HUVEC cells.Onestep eco-friendly fabrication of composite antibacterial PET was accomplished by on-line melt coextrusion.The composite antibacterial PET has potential use in multiple fields to combat with pathogenic including textiles,packaging materials,decoration materials and biomedical devices,etc.

Rapid analysis of fifteen sulfonamide residues in pork and fish samples by automated on-line solid phase extraction coupled to liquid chromatography–tandem mass spectrometry

The aim of this work was to develop an automated on-line solid phase extraction(SPE)with liquid chromatography-tandem mass spectrometry method for the detection of fifteen sulfonamides in pork and fish samples.Samples were extracted with 0.2%formic acid acetonitrile solution,purified by on-line SPE device with HLB column,then separated by XBridge C18 column,using 0.1%formic acid solution and acetonitrile as the mobile phase.Mass spectrometric data was acquired under multiple reaction monitoring(MRM)mode using positive ionization electrospray.Internal standard method was used in the quantification,good linear relationship was got in range of 0.1–100 ng/mL and correlation coefficient was higher than 0.9990.The limits of detection were in the range of 0.125–2.00g/kg and the limits of quantitation were in the range of 0.250–5.00g/kg.Recoveries of the method were in range of 78.3%–99.3%,relative standard deviation were lower than 10%.The method was simple,sensitivity,and could be used for routine supervision and analysis of fifteen sulfonamides in pork and fish.

On-line monitoring of dissolved gas-in-oil with FTIR spectra

To overcome the disadvantages of conventional DGA (dissolved gas-in-oil)analysis using gas chromatography and other electrochemical sensors, initial researches werecompleted to realize on-line monitoring of dissolved gas-in-oil of power transformers using FTIR(Fourier Transform InfraRed) spectroscopy. Gas cell method is used to determine the characteristicabsorption peaks of each diagnostic gas; simple and novel devices and procedures were designed inorder to get measurable samples and spectra of mixed diagnostic gases with known concentration aretaken using long optical path gas cell. The range of wavelength is estimated to be 3.0-13.9 mum fromexperimental spectra data. Hence the corresponding sampling frequency range should be in 536-4288Hz and usable optical materials are suggested. It is concluded that a resolution of 10 cm^(-1) maywell satisfy the monitoring of all diagnostic gases and water content except hydrogen, and thelowest detection limit may be as low as 2Xl0^(-8) to acetylene with a 2.4-meter-long optical length.

QuEChERS与SPE前处理方法结合GC-MS/MS同时测定8种果蔬中21种农药残留的对比研究

利用气相色谱-三重四极杆质谱法(GC-MS/MS)对比研究固相萃取(SPE)和QuEChERS 2种前处理方法在果蔬中21种农药残留的检测效果。以番茄、黄瓜、胡萝卜、油麦菜、橙、梨、桃、西瓜为基质,分别从定量限、线性关系、回收率、精密度等方面进行比较。结果表明:SPE法和QuEChERS法的21种农药残留基质标准曲线:在0.1~2.0μg/mL范围内线性关系良好(r>0.999),定量限均为0.009 mg/kg。在0.009~0.09 mg/kg加标水平下,SPE法回收率为88.7%~91.9%,相对标准偏差为1.56%~3.72%;QuEChERS法回收率为94.9%~97.4%,相对标准偏差为1.54%~4.17%。QuEChERS法可针对不同果蔬的特性添加不同的净化物质,净化过程具有更高的灵活性,且回收率均优于SPE法。

新一代单对线以太网NG-SPE技术及在流程工业数据通信中的应用

回顾了流程工业两线制通信技术的发展历程,包括4~20mA,HART,RS-485和新兴的APL/10BASE-T1L单对线以太网通信技术,以及各自的优缺点、面临的问题和后续的演进方向;重点介绍了新一代单对线以太网NG-SPE技术,以及该技术在带宽、距离、节点数和供电四个方面的均衡表现。通过与其他主流单对线技术对比后表明,新一代单对线以太网NG-SPE技术可实现在1km内,通信速率为100Mibit/s的数据传输,15节点接入,点到多点供电,并支持多种线缆和拓扑结构,可应用于流程工业、物联等领域,取代低速总线,利用已有线缆,实现高速远距离总线通信。

On-Line Measurement of the Chemical Oxygen Demand in Wastewater in a Pulp and Paper Mill Using Near Infrared Spectroscopy

Although near infrared (NIR) spectroscopy has been evaluated for numerous applications, the number of actual on-line or even on-site industrial applications seems to be very limited. In the present paper, the attempts to produce online predictions of the chemical oxygen demand (COD) in wastewater from a pulp and paper mill using NIR spectroscopy are described. The task was perceived as very challenging, but with a root mean square error of prediction of 149 mg/l, roughly corresponding to 1/10 of the studied concentration interval, this attempt was deemed as successful. This result was obtained by using partial least squares model regression, interpolated reference values for calibration purposes, and by evenly distributing the calibration data in the concentration space. This work may also represent the first industrial application of online COD measurements in wastewater using NIR spectroscopy.

ON-LINE INSPECTION TECHNIQUES OF MANUFACTURING QUALITY OF ROLLED-STEEL SHEET

On-line measurement of manufaturing quality of rolled steel needs the performances of noncontact, high-responds, high-resolution and high aceuracy. The reccntly developed hardware makes it possible. This paper gives a review of the development of this techniques and introduces four kinds of developed measurement systems. And the future development trends in this field was also discussed.

Cobalt Determination by Means of Flow Injection On-line Sorbent Preconcentration-Flame Atomic Absorption Spectrometry with 1-Nitroso-2-naphthol as a Complexing Reagent

The suitability of 1-nitroso-2-naphthol(NN) as a complexing agent for on-line preconcentration of cobalt eluted on the C_(18) microcolumn by means of the FI-FAAS system was tested. Various parameters affecting the complex formation and its elution were optimized. A 2.3×10^(-3) mol/L reagent solution and the aqueous sample solution acidified with 0.1% (volume fraction) nitric acid were on-line mixed (6.4 mL/min) on a reaction coil set at (65±1)℃ and flowed through the microcolumn for 30 s. The pH of the mixed solution was adjusted to 3—4 with HNO_3(1 mol/L) or NaOH(1 mol/L). The adsorbed complexes in the microcolumn were eluted into the nebulizer of FAAS in 10 s with ethanol acidified with 1% HNO_3(3.0 mL/min). A good precision(1.6% for 100μg/L Co(Ⅱ), n=10), a high enrichment factor 17.2, with detection limit (3σ) 3.2μg/L, and sample throughput (90 h^(-1)) were obtained. The method was applied to the certified reference materials(CRMs), NBS-362 and NBS-364, for the determination of cobalt and the results were in good agreement with the certified values.

Application of on-line quality control for salvianolic acid B by near infrared spectroscopy

OBJECTIVE: To study and establish quality con-trol model of the Salvianolic Acid B by Near In-frared Spectroscopy (NIRS), and to realize on-line quality control of extracting and purifying proc-esses of industrial scale herbal product manu-facturing. METHOD: NIR chromatography was obtained from on-line NIR detection of extract-ing process and purifying process. HPLC analysis was carried out to determine the con-tents of salvianolic acid B. Partial Least Squares Regression (PLS) was used to establish the model between the information between NIRS and HPLC. RESULTS: For extracting model: the optimum Near Infrared (NIR) wavelength range was 9815- 5430cm-1, R=0.9784, RMSEC=0.258;for puri-fying model: the optimum NIR wavelength range was 9815-5430cm-1, R=0.9776, RMSEC=4.02. The average relative error was <5%. CONCLUSION: NIR technique is applicable for on-line quality control in production of salvianolic acid B.

加压液体提取-自动SPE-UPLC-MS/MS法检测农业土壤中6种吡啶类农药微量残留

以农业土壤为研究对象,建立采用加压液体提取法将样品中啶氧菌酯、氟啶草酮、吡虫啉、啶酰菌胺、氟啶酰菌胺、啶虫脒6种吡啶类农药提取出来,全自动固相萃取法富集、净化,超高效液相色谱-质谱联用仪定量检测的分析方法。取农业土壤样品,风干、粉碎后,过120目筛,准确称取过筛网后的样品10 g,置萃取池中,加硅藻土20 g,用甲醇:丙酮溶剂(V∶V=1∶1)提取,另取规格为500 mg/12 mL HLB固相萃取小柱,置全自动固相萃取仪中,活化完毕后,设定程序,将上述提取液以20 mL/min的流量,过固相萃取柱,最后用20 mL甲醇-乙腈(V∶V=1∶1)洗脱,收集洗脱液,洗脱液氮吹至近干,加甲醇定容至1 mL,涡旋混匀,上液相色谱-质谱仪定性、定量检测。啶氧菌酯、氟啶草酮、吡虫啉、啶酰菌胺、氟啶酰菌胺、啶虫脒6种吡啶类农药在0.001~5.0μg/mL范围内具有良好的线性,相关系数均大于0.995;检测限分别为0.012、0.009、0.024、0.007、0.013、0.005μg/L。三水平加标回收率均在84.4%~105.2%之间;重复性RSD(n=6)分别为2.0%、3.1%、2.3%、2.2%、1.9%和2.3%。实验结果表明,实验建立的方法具有准确、灵敏等优点,适用于农业土壤中微量吡啶类农药残留的检测。

DETERMINATION OF ANTIMONY IN WATER SAMPLES BY FLOW-INJECTION HYDRIDE GENERATION ATOMIC ABSORPTION SPECTROMETRY WITH ON-LINE ION-EXCHANGE COLUMN PRECONCENTRATION

On-line ion-exchange separation and preconcentration were combined with flow-injection hydride generation atomic absorption spectrometry (HGAAS) to determine ultra-trace amounts of antimony in water samples. Antimony(Ⅲ) was preconcentrated on a micro-column packed with CPG-8Q chelating ion-exchanger using time-based sample loading and eluted by 4 mol l^(-1) HCl directly into the hydride generation AAS system. A detection limit (3σ) of 0.0015μg l^(-1) Sb(Ⅲ) was obtained on the basis of a 20 fold enrichment and with a sampling frequency of 60h^(-1). The precision was 1.0% r.s.d.(n=11) at the 0.5μg l^(-1) Sb(Ⅲ) level. Recoveries for the analysis of antimony in tap water, snow water and sea water samples were in the range 97-102%.

SPE-UFLC-MS法测定医药废水中8种四环素类抗生素

建立了固相萃取-超高速液相色谱质谱(SPE-UFLC-MS)法测定医药废水中8种四环素类抗生素的方法。通过固相萃取条件优化,选择固相Oasis HLB萃取柱、净化剂为30%ZnSO_(4)+20%K_(2)[Fe(CN)_(4)]溶液、稳定剂为1g·L^(-1)的Na_(2)EDTA、萃取pH值为8,获得最佳目标化合物萃取回收率。8种四环素类抗生素的标准曲线线性关系良好(r>0.999),且检出限低于10ng·L^(-1),平均回收率为95.3%~106.9%,相对标准偏差RSD小于8.23%。方法精密度和准确度较好。经实样测试,医药废水的调质池中除地美环素盐酸盐和二甲胺四环素盐酸盐外,其他6种四环素类抗生素均有不同程度检出,可为医药废水抗生素类化合物检测提供借鉴。