Chemical Selectivity of Laser Ion Source for on-Line Mass Separator

Thulium(Tm)atoms are resonantly ionized in a hot tube by stepwise excitations us-ing three dye lasers pumped by a series of copper vapor pulsed at a 10 kHz rate.The chemicalselectivity of the laser ion source is measured as a function of temperature of the tubes made ofTa,Nb-Zr and TaC.The chemical selectivity rises from 50 to 10000 with decreasing tube temp-erature and strongly depends on the tube material.A chemical selectivity of about 10000 withhigh efficiencies is obtained with the Nb-Zr and TaC tubes.Such a laser ion source can be usedin on-line mass separator to obtain isobarically pure ion beams.

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.

Stepped-up development of accelerator mass spectrometry method for the detection of ^(60)Fe with the HI-13 tandem accelerator

The Moon provides a unique environment for investigating nearby astrophysical events such as supernovae.Lunar samples retain valuable information from these events,via detectable long-lived“fingerprint”radionuclides such as^(60)Fe.In this work,we stepped up the development of an accelerator mass spectrometry(AMS)method for detecting^(60)Fe using the HI-13tandem accelerator at the China Institute of Atomic Energy(CIAE).Since interferences could not be sufficiently removed solely with the existing magnetic systems of the tandem accelerator and the following Q3D magnetic spectrograph,a Wien filter with a maximum voltage of±60 kV and a maximum magnetic field of 0.3 T was installed after the accelerator magnetic systems to lower the detection background for the low abundance nuclide^(60)Fe.A 1μm thick Si_(3)N_(4) foil was installed in front of the Q3D as an energy degrader.For particle detection,a multi-anode gas ionization chamber was mounted at the center of the focal plane of the spectrograph.Finally,an^(60)Fe sample with an abundance of 1.125×10^(-10)was used to test the new AMS system.These results indicate that^(60)Fe can be clearly distinguished from the isobar^(60)Ni.The sensitivity was assessed to be better than 4.3×10^(-14)based on blank sample measurements lasting 5.8 h,and the sensitivity could,in principle,be expected to be approximately 2.5×10^(-15)when the data were accumulated for 100 h,which is feasible for future lunar sample measurements because the main contaminants were sufficiently separated.

Microfluidic Analytical System with On-Line Luminol Chemiluminescence Detection Based on Annular Flow of Phase Separation Multiphase Flow

Microfluidic analytical system was developed based on annular flow of phase separation multiphase flow with a ternary water-hydrophilic/hydrophobic organic solvent solution. The analytical system was combined with on-line luminol chemiluminescence detection for catechin analysis. The water (10 mM phosphate buffer, pH 7.3)-acetonitrile-ethyl acetate mixed solution (3:8:4, volume ratio) containing 60 μM luminol and 2 mM hydrogen peroxide as a carrier was fed into the capillary tube (open-tubular fused-silica, 75 μm inner diameter, 110 cm effective length) at a flow rate of 1.0 μL·min-1. The carrier solution showed stable chemiluminescence as a baseline on the flow chart. Eight catechins were detected as negative peaks for their antioxidant potential with different detection times. The system was applied to analyze the amounts of catechin in commercially available green tea beverages.

Development of an automatic measurement system using atmospheric pressure photoionization ultrahigh-resolution mass spectrometry and application for on-line analysis of particulate matter

On-line chemical characterization of atmospheric particulate matter(PM)with soft ionization technique and ultrahigh-resolution Mass Spectrometry(UHRMS)provides molecular information of organic constituents in real time.Here we describe the development and application of an automatic measurement system that incorporates PM_(2.5)sampling,thermal desorption,atmospheric pressure photoionization,and UHRMS analysis.Molecular formulas of detected organic compounds were deducted from the accurate(±10 ppm)molecular weights obtained at a mass resolution of 100,000,allowing the identification of small organic compounds in PM_(2.5).Detection efficiencies of 28 standard compounds were determined and we found a high sensitivity and selectivity towards organic amines with limits of detection below 10 pg.As a proof of principle,PM_(2.5)samples collected off-line in winter in the urban area of Beijing were analyzed using the Ionization Module and HRMS of the system.The automatic system was then applied to conduct on-line measurements during the summer time at a time resolution of 2 hr.The detected organic compounds comprised mainly CHON and CHN compounds below 350 m/z.Pronounced seasonal variations in elemental composition were observed with shorter carbon backbones and higher O/C ratios in summer than that in winter.This result is consistent with stronger photochemical reactions and thus a higher oxidation state of organics in summer.Diurnal variation in signal intensity of each formula provides crucial information to reveal its source and formation pathway.In summary,the automatic measurement system serves as an important tool for the on-line characterization and identification of organic species in PM_(2.5).

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.

Effect of inlet area on the performance of a two-stage cyclone separator

The cyclone separator is an important separation device.This paper presents a new type of embedded two-stage cyclone,which includes a 2 nd-stage cyclone(internal traditional cyclone)with multiple inlets and a 1 st-stage cyclone(outer cylinder)that unifies the 2 nd-stage cyclone inlets into one inlet.The Taguchi experimental method was used to study the two-stage cyclone separator’s inlet area on its performance.Studies have shown that the increase of the 1 st-stage cyclone inlet area and the increase in the number of 2 nd-stage cyclone inlets(N)positively affect reducing the pressure drop and a negative effect on efficiency.It is recommended to use 2 S(the original 1 st-stage cyclone inlet area)of the 1 st-stage cyclone inlet area and 2 N of the 2 nd-stage cyclone inlets when separating fine particles.Compared with a traditional cyclone,the pressure drop is reduced by 1303 Pa,the mass separation efficiency(Eq)is increased by 0.56%,and the number separation efficiency(En)is increased by 2.05%.When separating larger particles,it is recommended to use 2 S of the 1 st-stage cyclone inlet area and 4 N of the 2 nd-stage cyclone inlets.Compared with a traditional cyclone,although Endecreases slightly,the pressure drop is reduced by 3055 Pa,and the Eqis increased by 0.56%.The research results provide new insight into the design of the cyclone.

Stereoselective separation and determination of quizalofopethyl in tobacco by ultra-performance convergence chromatography with tandem mass spectrometry

The purpose of this study was to develop and validate a novel and sensitive method for simultaneous enantiomeric analysis of quizalofop-ethyl in tobacco using ultra-performance converge nee chromatography with tandem mass spectrometry(UPC-MS/MS).Sample preparation prior to UPC^2-MS/MS analysis followed a QuEChERS(quick,easy,cheap,effective,rugged and safe)method.The UPC^2-MS/MS method used an Acquity UPC2 Trefoil CEL2 column with a mobile phase of CO2 and methanol.The injection volume was 2 μL and run-time was 6 min with the mobile phase running at 2.0 mL/min flow rate.Column temperature,auto back pressure regulator pressure(ABPR),and modifier solvent were optimized for separation efficiency.Under the optimal conditio ns,the recoveries for all the ena ntiomers were 81.3%-94.8% with relative standard deviations(RSD)less than 5.0% at 0.1,1.0 and 2.0 mg/kg levels,respectively.Good coefficients of determination(R^2≥0.993 7)were achieved for all the studied enantiomers in the tobacco over the concentration range of 10-250 ng/mL.The limits of detection(LODs)varied from 0.02 mg/kg to 0.04 mg/kg,and the limits of quantification(LOQs)were ≤ 0.13 mg/kg.The results confirm that the proposed method is green,convenient and reliable for the enantioselective determination of the enantiomers of quizalofop-ethyl in tobacco.

Stimuli-responsive Membranes： Smart Tools for Controllable Mass-transfer and Separation Processes

As emerging artificial biomimetic membranes, smart or intelligent membranes that are able to respond to environmental stimuli are attracting ever-increasing interests from various fields. Their permeation properties including hydraulic permeability and diffusional permeability can be dramatically controlled or adjusted self-regulatively in response to small chemical and/or physical stimuli in their environments. Such environmental stimuli-responsive smart membranes could find myriad applications in numerous fields ranging from controlled release to separations. Here the trans-membrane mass-transfer and membrane separation is introduced as the beginning to initiate the requirement of smart membranes, and then bio-inspired design of environmental stimuli-responsive smart membranes and four essential elements for smart membranes are introduced and discussed. Next, smart membrane types and their applications as smart tools for controllable mass-transfer in controlled release and separations are reviewed. The research topics in the near future are also suggested.

Method Development of Enantiomer Separations by Affinity Capillary Electrophoresis,Cyclodextrin Electrokinetic Chromatography and Capillary Electrophoresis-Mass Spectrometry

Capillary electrophoresis (CE) has become a powerful tool for enantiomer separations during the last decade. Since 1993, the author has investigated enantiomer separations by affinity capillary electrophoresis (affinity CE) with some proteins and by cyclodextrin electrokinetic chromatography (CDEKC) with some charged cyclodextrins (CDs). Many successful enantiomer separations are demonstrated from our study in this review article. In the enantiomer separations by affinity CE, the deterioration of detection sensitivity was observed under high concentration of the protein in running solutions. The partial filling technique was practically useful to solve the serious problem. It allowed operation at high protein concentrations, such as 500 μmol/L, without the detection problem. Charged CDs had several advantages for the enantiomer separations over neutral ones. Strong electrostatic interactions between a charged CD and oppositely charged analytes should be effective for the formation of the complex. A large difference in electrophoretic mobility between the free analyte and the inclusion complex should also enhance the enantiomeric resolution. In CE mass spectrometry (CE MS), the partial filling technique was applied to avoid the introduction of nonvolatile chiral selectors into the CE MS interface. By replacing the nonvolatile electrolytes in the running buffer by volatile ones, the separation conditions employed in CE with the UV detection method could be transferred to CE MS.

Results of the Main Phase of Ion Separation in the Process of Plasma-Optical Mass Separation

This paper presents separation results of a mixture of nitrogen, argon and krypton ions in the process of plasma-optical mass separation on the POMS-E-3 separator model. We determined the behavior of the separation with a change in the value of magnetic field induction in the azimuthator and in the degree of compensation of the spatial charge in ion flows. An analysis is performed for experimental data by correlation with the results of a theoretical study and numerical experiments. The objectives of future experiments are outlined.

Analysis of non-ionized substance losses in experiments on plasma mass separation

Plasma mass separation requires a lot of diagnostic techniques that not only demonstrate the separation effect but also show the efficiency of the process.During the test experiments,plasma flux to be separated may contain neutral particles that avoid the separation process due to their insensitivity to electromagnetic field.We present the diagnostics of the lost substance in experiments on plasma mass separation.The obtained data of the diagnostics helps determine the law of particle evaporation from the plasma source.We show that neutral flux is unable to distort the result of separation diagnostics.The presented approach can be used in experiments aimed at enhancing the separation effect and achieving target productivity for industry applications.

Separation and analysis of six fractions in low temperature coal tar by column chromatography

The low temperature coal tar(CT)is taken as the raw material,and the extraction and column chromatography are used for detailed and accurate characterization in this paper.The n-heptane soluble fraction(CT-HS)and insoluble fraction(CT-HI)were obtained by n-heptane Soxhlet extraction.The extraction rate of CT-HS reached 92.79%(mass),which indicated that there are few heavy compounds in it.Further,different solvents(methylbenzene,benzene,ethyl acetate,methylbenzene-ethanol)were used to elute CT-HS by chromatographic column to obtain five fractions(saturates,aromatics,heteroatoms,phenolics and resins,named CT-SA,CT-AR,CT-HE,CT-PH,CT-RE,respectively).The yields of CTSA,CT-AR,CT-HE,CT-PH,CT-RE are 42.12%,10.43%,2.19%,9.50%and 6.63%(mass),respectively.Gas chromatography-mass spectrometry analysis of eluting components show that alkanes are the main components in CT,followed by polycyclic aromatics,and the corresponding fractions are CT-SA and CT-AR,respectively.The relative content of aliphatics in CT-SA is 76.93%,and the relative content of aromatics in CT-AR is 75.05%.This separation technology effectively separates and enriches different components in CT,and the activation energy required for the pyrolysis process of a single eluting fraction is lower than that of CT,which is expected to provide an important reference for the separation,analysis and conversion of complex oil products such as coal-oil co-processing products,coal tar and other complex heavy carbon oil products.

Recent applications and chiral separation development based on stationary phases in open tubular capillary electrochromatography(2019–2022)

Capillary electrochromatography(CEC)plays a significant role in chiral separation via the double separation principle,partition coefficient difference between the two phases,and electroosmotic flow-driven separation.Given the distinct properties of the inner wall stationary phase(SP),the separation ability of each SP differs from one another.Particularly,it provides large room for promising applications of open tubular capillary electrochromatography(OT-CEC).We divided the OT-CEC SPs developed over the past four years into six types:ionic liquids,nanoparticle materials,microporous materials,biomaterials,non-nanopolymers,and others,to mainly introduce their characteristics in chiral drug separation.There also added a few classic SPs that occurred within ten years as supplements to enrich the features of each SP.Additionally,we discuss their applications in metabolomics,food,cosmetics,environment,and biology as analytes in addition to chiral drugs.OT-CEC plays an increasingly significant role in chiral separation and may promote the development of capillary electrophoresis(CE)combined with other instruments in recent years,such as CE with mass spectrometry(CE/MS)and CE with ultraviolet light detector(CE/UV).

烟草中甲霜灵的手性分离方法差异研究

对比反相液相色谱-串联质谱(RPLC-MS/MS)和超临界流体色谱-串联质谱(SFC-MS/MS)手性分离烟草中甲霜灵的差异。烟草样品经乙腈提取、盐析分层、快速滤过型净化(multi-Plug Filtration Cleanup,m-PFC)柱净化后,分别采用RPLC-MS/MS和SFC-MS/MS进行手性分离。从多个性能参数(分离效率、线性、选择性、回收率、重复性、灵敏度、基质效应等)对两种方法进行了全面比较。采用不同的分离方法,在10~500 ng/mL范围内,甲霜灵的不同异构体均可呈现良好的线性关系(R^(2)≥0.9993)。在各异构体加标浓度为0.1、0.5、2.0 mg/kg水平下,采用不同的分离方法均可获得满意的回收率(88.7%~96.2%)和良好的重复性(RSD<7.0%)。结果表明:RPLC-MS/MS和SFC-MS/MS具有互补性,均适用于手性分离和测定烟草基质中的甲霜灵。

面向深部地热岩体的弹性波逆时偏移成像方法

地热能作为一种清洁能源正受到全世界的日益关注,因此对于深部地热岩体的高精度成像格外重要。传统的弹性波逆时偏移方法是利用耦合纵横波直接成像,从而得到耦合波场的成像结果;然而这种方法可能会出现串扰假象,导致成像结果不够清晰;为了解决这个问题,采用基于解耦的弹性波方程,实现纵横波场的分离;通过利用内积成像条件,对两个典型的干热岩模型进行数值测试。结果表明,相较于耦合波场成像结果,基于解耦方程分离得到的弹性波成像剖面具有更清晰的同相轴,深部能量更加均衡,该方法能够实现对深部地热岩体的高质量成像。

胺基材料在二氧化碳分离膜领域研究进展

膜法碳捕集是实现双碳目标的重要途径,但受限于材料本身,膜材料的分离性能存在上限。胺基材料可以和CO_(2)发生可逆反应,能够显著提高膜材料的分离性能,常被作为促进传质的载体引入到膜体系。本文介绍了胺基材料促进CO_(2)传质的机理,重点归纳了胺基材料引入到膜体系的4类方法(涂覆法、反应法、接枝法、掺杂法)及制备膜材料的性能,并分析其优势与不足。本文指出胺基材料促进CO_(2)传质机理需要进一步探索,强调开发高胺基密度的膜材料和以更加“牢固”的方式将胺基材料引入膜体系是领域未来需重点发展的方向,利用机器学习提高膜材料设计效率对该领域发展具有指导意义。分析表明真实工况下胺基膜材料的性能稳定性、设备稳定性以及工艺稳定性是值得关注的研究领域,建立完整的胺基膜法CO_(2)捕集技术链仍面临巨大挑战。

多级孔MOF的制备及其吸附分离应用研究进展

金属有机框架材料(MOF)因其具有高比表面积、丰富孔隙率、孔径可调的优点,受诸多学者关注,被认为是用于吸附分离的理想吸附剂。但是在实际应用中,大部分微孔MOF材料在吸附过程中的内在传质速率严重受限,而且构建多级孔的方法一般不具有普遍性。本文介绍了调节剂策略、模板策略、后处理策略等构建多级孔MOF的方法,制备了兼具介孔、大孔的多级孔材料,并结合应用场景评价各方法的优缺点,以获得在相对温和条件下构建孔径可调的多级孔MOF的普适性策略。针对多级孔MOF材料在气体吸附分离领域的应用问题,着重剖析了构建多级孔MOF对CO_(2)气体吸附提升的案例,发现多级孔的构建增加了孔径,提高了MOF的比表面积,提供了额外的孔通道,使气体分子的吸附容量和传质速率得到提升,表明多级孔MOF在气体吸附分离方面有优异的性能。最后讨论了多级孔MOF合成和应用存在的问题,并对多级孔MOF面临的合成过程绿色可重复等挑战进行了展望。

CHPPO工艺氧化液耦合除杂技术的研究与工业应用

异丙苯过氧化氢法(CHPPO)是生产环氧丙烷的绿色新工艺,然而如何从异丙苯氧化液中脱除有机酸和Na+等杂质一直是CHPPO工艺的关键问题。针对现有碱水洗单元洗涤塔设备投资高、占地面积大、传质效果不佳等问题,通过小试和中试实验,开发了基于静态混合和聚结分离的耦合除杂技术,并研究了一系列操作条件对耦合技术分离性能的影响,实现了异丙苯氧化液高效除杂。结果表明,在NaOH溶液浓度为1.5%,碱液用量为氧化液进料量的4%~5%、纯水用量3%~5%、自循环量10%~15%的条件下,处理后的氧化液总酸含量低于10 mg/L,Na+低于0.5 mg/L。此外,耦合除杂技术在某石化工业装置上实现了首次工业应用,处理后的氧化液有机酸含量为33 mg/L、Na^(+)含量为0.4 mg/L,满足环氧化工段对前处理的技术要求,同时减少了5%的碱、水用量,显著增加了装置的绿色属性。该技术为解决氧化液深度净化问题和促进环氧丙烷合成工艺的发展提供了一种极具前景的选择。

基于银型苯基磺酸键合硅胶分离及高分辨质谱分析石油中不同形态含硫化合物

建立一种基于银型苯基磺酸键合硅胶(Ag+-SCX)分离石油中不同形态含硫化合物的方法,分离得到的含硫化合物组分进行甲基化反应和高分辨质谱(HRMS)分析,得到不同形态含硫化合物分子组成。通过模型化合物证明该分离方法的可行性,硫醚类、噻吩类含硫化合物被有效分离。该方法对石油馏分、原油和二次加工油均有良好的适用性,并将其应用于一套原油及其馏分中含硫化合物的分离及分析,详细表征了不同形态含硫化合物在原油和各馏分段的分子组成特点和分布规律。