Dynamic three-phase microextraction as a sample preparation technique prior to capillary electrophoresis

Dynamic three-phase (liquid-liquid-liquid) microextraction was developed for capillary electrophoresis. Four aromatic amines as model compounds were extracted from 4-mL aqueous samples adjusted to basic condition (donor solution) through a small volume of organic solvent impregnated in a hollow fiber, which was held by the needle of a conventional syringe, and retracted into a 5-microL acidic acceptor solution inside the syringe. A renewable organic film and aqueous sample plug were formed inside the hollow fiber with the repeated movement of the syringe plunger enabled by a programmable syringe pump. This is believed to be the first reported instance of a semiautomated dynamic liquid-liquid-liquid microextraction (LLLME) procedure. Following this microextraction, the 5-microL acceptor solution was analyzed by capillary zone electrophoresis (CE). This new technique provided approximately 140-fold enrichment in 20 min. Utilizing 4-chloroaniline as internal standard, dynamic LLLME could provide good reproducibility (<4.0%). In addition, this method allowed the direct transfer of extracted analytes to a CE system for analysis.     

Two-step liquid-liquid-liquid microextraction of nonsteroidal antiinflammatory drugs in wastewater

A simple and novel two-step liquid-liquid-liquid microextraction technique combined with reversed-phase HPLC has been developed for the determination of the nonsteroidal antiinflammatory drugs ibuprofen and 2-(4-chlorophenoxy)-2-methylpropionic acid in wastewater samples. In the first step, the analytes were extracted from an acidified sample (donor solution) into 1-octanol immobilized in the pores of 10 pieces of polypropylene hollow fiber and further into a basic acceptor phase inside the hollow fiber channels. This first extraction step, using 0.01 M NaOH as the acceptor phase and 0.1 M HCl within the donor phase, had a 100% relative recovery with an enrichment factor of 100-fold. The extract in the first step was then adjusted to acidic condition with HCl. It now represented the donor phase for the second step of the extraction, using a single piece of hollow fiber, with 2 microL of 0.01 M NaOH solution as the acceptor phase. This analyte-enriched acceptor phase was subsequently withdrawn into a microsyringe and directly injected into an HPLC system for analysis. With this two-step microextraction, sensitivity enhancement of >15,000-fold could be obtained. Detection limits of < or =100 ng/L could be achieved for both compounds. The method was applied to the analysis of wastewater.     

Dynamic liquid-liquid-liquid microextraction with automated movement of the acceptor phase

A new dynamic liquid-liquid-liquid microextraction procedure, with the automated movement of acceptor phase (LLLME/AMAP) to facilitate mass transfer, was developed in this study. Four compounds, 3-nitrophenol, 4-nitrophenol, 3,4-dinitrophenol, and 2,4-dichlorophenol, were used as model compounds to be preconcentrated from water samples. The extraction involved filling a 2-cm length of hollow fiber with 4 muL of acceptor solution using a conventional microsyringe, followed by impregnation of the pores of the fiber wall with 1-octanol. The fiber was then immersed in 4 mL of aqueous sample solution. The analytes in the sample solution were extracted into the organic solvent and then back-extracted into the acceptor solution. During extraction, the acceptor phase was repeatedly moved in and out of the hollow fiber channel and the syringe controlled by a syringe pump. Separation and quantitative analyses were then performed by using high-performance liquid chromatography. The results indicated that up to 400-fold enrichment of the analytes could be obtained under the optimized conditions. The enrichment factors were two times those of static liquid-liquid-liquid microextraction. Good repeatabilities (RSD values below 9.30%) were obtained. The calibration linear range was from 10 to 1000 ng/mL with the square of the correlation coefficient (r2) >0.9916. Detection limits were in the range of 0.45-0.98 ng/mL. In addition, as compared with the previously reported dynamic three-phase microextraction in which there was no relative movement between the acceptor and the organic phase (which is not conducive to effective mass transfer), this new method shows much higher extraction efficiency. All these results suggest that this new dynamic LLLME/AMAP technique could be a better alternative to the previous LLLME for the extraction of analytes from aqueous samples.     

The XT-tube extractor: a hollow fiber-based supported liquid membrane extractor for bioanalytical sample preparation

A new supported liquid membrane extractor for bioanalytical sample preparation is presented. The extractor consists of a polypropylene hollow fiber mounted inside a PTFE tube by means of a cross-connector and a tee-connector. All parts are commercially available, inexpensive, and easily assembled. An organic solvent in the pores of the fiber forms a liquid membrane that separates the sample, which is pumped along the outside of the fiber, from the acceptor phase, which is pumped inside. The length of the hollow fiber may easily be varied to meet different demands on extractive surface and extract volumes. To test the system, the strongly acidic plasticizer/flame retardant metabolite diphenyl phosphate ester (DPhP), with a pKa value of 0.26, was extracted from urine. DPhP was protonated using 4 M hydrochloric acid and extracted into an acceptor phase at pH 9. Thirty extractions were made with the same liquid membrane without any decrease in extraction efficiency and with a relative standard deviation <7%. An analyte concentration enrichment of 5-10 times was achieved in the extraction step, giving a limit of detection (S/N = 3) of 0.014 microg/mL with LC/ESI-MS and 0.18 microg/mL with CE-UV. The effects on extraction efficiency using different sample pH, organic solvents, sample flow rates, and lengths of the fiber were evaluated.     

Sample preparation using a miniaturized supported liquid membrane device connected on-line to packed capillary liquid chromatography

A miniaturized supported liquid membrane device has been developed for sample preparation and connected on-line to a packed capillary liquid chromatograph. The device consists of hydrophobic polypropylene hollow fiber, inserted and fastened in a cylindrical channel in a Kel-F piece. The pores of the fiber are filled with an organic solvent, in this study 6-undecanone, thus forming a liquid membrane. The sample is pumped on the outside of the hollow fiber (donor), and the analytes are selectively enriched and trapped in the fiber lumen (acceptor). With this approach, the volume of the acceptor solution can be kept as low as 1-2 μL. This stagnant acceptor solution is then transferred through capillaries attached to the fiber ends to the LC system. The system was tested with a secondary amine (bambuterol), as a model substance in aqueous standard solutions as well as in plasma. The best extraction efficiency in aqueous solution, with an acceptor volume of 1.9 μL, was 32.5% at a donor flow rate of 2.5 μL/min. At flow rates above 20 μL/min, the concentration enrichment per time unit was approximately constant, at 0.9 times/min, i.e., 9 times enrichment in about 10 min. The overall repeatability (RSD) for spiked plasma samples was ～4% (n = 12). Linear calibration curves of peak area versus bambuterol concentration were obtained for both aqueous standard solutions and spiked plasma samples. The detection limit for bambuterol in plasma, after 10 min of extraction at a flow rate of 24 μL/min, was 80 nM.     

几种中空纤维膜对氧气,环氧丙烷透过性的比较

为选定适合气－固－液三相生物反应过程膜反应器中的膜材料，采用氧电极测试了几各收集到的聚砜、聚丙烯及聚氟乙烯中空纤维膜对氧气的通透性，其中的聚丙烯中空纤维适于做膜生物反应器中的透气膜，同时还测定了聚砚、聚偏氟乙和聚丙烯腈地水溶液中环氧丙烷的通透性，在实验条件下它们之间的差异不大。     

超声技术结合小波分析在线监测中空纤维膜污染及其可视化研究

采用超声时域反射法和小波分析技术在线监测单根内压式聚醚砜中空纤维微滤膜(ID/OD为0.8 mm/1.2 mm)处理2.4 g/L高岭土污水时的初期污染情况.结果显示:小波谱图能够提供中空纤维膜内部结构和污染过程的清晰2D和3D图片,实现了膜污染在线监测过程的可视化.随着污染的进行,膜通量不断下降,小波谱图上中空纤维膜断面上部和下部的信号持续时间在时间区域内发生了有序移动.小波谱图的这种有序变化与污染物在膜表面的沉积以及污染层的生长有关.SEM观察显示,污染420 min后中空纤维膜内腔下表面形成的污染层比内腔上表面的污染层厚.这与通过小波谱图信号持续时间变化计算得出的污染层厚结果一致.     

硬弹性聚丙烯中空纤维的形成

通过应力场下聚丙烯熔体结晶制备出硬弹性聚丙烯中空纤维 .利用对样品弹性回复率及力学性能测试等手段 ,研究了硬弹性聚丙烯中空纤维的形成 .结果表明 :纺丝温度下降、熔体拉伸比增加及热处理等均有利于硬弹性聚丙烯中空纤维的形成 ,聚丙烯原料的分子量、纺丝冷却条件等对硬弹性的形成也有影响 .所制备的硬弹性中空纤维具有典型的应力 -应变行为 .     

Equilibrium sampling through membranes of freely dissolved chlorophenols in water samples with hollow fiber supported liquid membrane

The freely dissolved concentration (C(free)) of pollutants is generally believed to be bioavailable and thus responsible for toxic effects. The C(free) of organic weak acids and bases consists of a dissociated and a nondissociated fraction. By using chlorophenols as model compounds, a negligible-depletion extraction technique, equilibrium sampling through membranes (ESTM), was developed for the measurement of the nondissociated part of the C(free). Polypropylene hollow fiber membranes (280-microm i.d., 50-microm wall thickness, 0.1-microm pore size, 15-cm length) were impregnated with undecane in the pores in the fiber wall as liquid membrane and filled with buffer solution in the lumen as acceptor. Then, the hollow fiber membranes were placed into the sample (donor) for an equilibrium extraction after sealing the two ends. The chlorophenol concentrations in the acceptor were then determined by direct injection into a HPLC system. Finally, the C(free) of the nondissociated and the dissociated species of a chlorophenol were calculated based on its measured concentration in the acceptor, its pK(a) value, and the measured pH in sample and acceptor. Theoretically calculated distribution coefficients (D = 8-970) agree well with the experimental enrichment factors (E(e(max)) = 6-1124), and the equilibration time was observed to increase with increasing distribution coefficients (hours to days). The freely dissolved concentration of five chlorophenols, with a wide range of pK(a) (4.9-9.2) and log K(ow) (2.35-5.24), were successfully determined in model solutions of humic acids and at low-ppb levels in river and leachate water.     

Coupling fiber optics to a permeation liquid membrane for heavy metal sensor development

We present the first sensing system for metal ions based on the combination of separation/preconcentration by a permeation liquid membrane (PLM) and fluorescence detection with an optical fiber. As a model, a system for the detection of Cu(II) ions was developed. The wall of a polypropylene hollow fiber serves as support for the permeable liquid membrane. The lumen of the fiber contains the strip solution in which Cu(II) is accumulated. Calcein, a fluorochromic dye, acts as stripping agent and at the same time as metal indicator. The quenching of the calcein fluorescence upon metal accumulation in the strip phase is detected with a multimode optical fiber, which is incorporated into the lumen. Fluorescence is excited with a blue LED and detected with a photon counter. Taking advantage of the high selectivity and sensitivity of PLM preconcentration, a detection limit for Cu(II) of approximately 50 nM was achieved. Among five tested heavy metal ions, Pb(II) was the only major interfering species. The incorporation of small silica optical fibers into the polypropylene capillary allows for real-time monitoring of the Cu(II) accumulation process.     

超声波-减压膜蒸馏组合技术处理甲基橙溶液的研究

将超声波与减压膜蒸馏技术相结合,采用聚丙烯(PP)中空纤维膜,研究了超声波促进作用下减压膜蒸馏法处理高浓度甲基橙溶液的分离性能.实验结果表明,超声波有利于减轻减压膜蒸馏过程的膜污染,提高分离性能;进料甲基橙溶液浓度600 mg/L时,超声波提高减压膜蒸馏过程的膜通量达44.87%;同时,超声波-减压膜蒸馏组合技术较减压膜蒸馏过程有更大的COD去除率.     

膜蒸馏海水淡化用疏水性钇稳定氧化锆中空纤维膜的制备与表征

采用相转化/高温烧结技术方法制备了多孔钇稳定氧化锆(YSZ)中空纤维膜, 中空纤维膜的外径1.92 mm, 壁厚为0.21 mm。SEM分析表明: 纤维膜为典型的三明治结构, 靠近膜内外表面为指状孔, 中间区域为海绵状层。采用阿基米德法测得其孔隙率为54%。用泡点法测得其平均孔径为0.56 μm。通过表面接枝氟硅烷将其亲水性的表面改变为疏水性。真空式膜蒸馏实验表明YSZ中空纤维膜具有优异的盐水淡化性能。当膜的外侧与温度为80℃、浓度为4wt%的循环盐水接触, 膜的内侧用真空泵抽至4×10³ Pa时, 膜的水渗透通量高达48.3 L/(m²•h), 脱盐率大于99.7%。     

Liquid-phase microextraction as an on-line preconcentration method in capillary electrophoresis

A simple and efficient sample preconcentration method for capillary electrophoresis has been developed using liquid-phase microextraction (LPME). A thin layer of an organic liquid was used to separate a drop of the aqueous acceptor phase hanging at the inlet of a capillary from the bulk aqueous donor phase. The donor-phase pH was 1.0, and the acceptor phase pH was 9.5. This pH difference caused the preconcentration of the acidic compounds, fluorescein and fluorescein isothiocyanate, into the acceptor-phase drop. Enrichment factors of 3 orders of magnitude were obtained with 30-min LPME at 35 degrees C.     

改性聚丙烯中空纤维的纺制工艺与结构性能

经熔融共混纺丝，制得内径约２００μｍ，外径约３００μｍ的ＰＰ－ＣＡＢ中空纤维膜。并采用扫描电镜、Ｘ射线衍射、压汞法、透水法等对改性中空纤维膜成型工艺条件与结构性能进行了研究。     

膜萃取去除水中氯仿的研究

采用煤油－氯仿－水为实验体系,在两种不同型号的的聚丙烯中空纤维膜器中进行了连续逆流膜萃取过程的研究．计算了基于水相的总传质系数Ｋｗ,分析了实测值与计算值之间的偏差．实验结果表明,传质由水相边界层控制,壳程的非理想流动是造成偏差的主要原因．通过计算传质单元高度ｈＨＴＵ及测定萃取前后氯仿水溶液的ＣＯＤ值,证明了中空纤维膜萃取去除水中氯仿的高效性     

On-line microextraction of metal traces for subsequent determination by plasma atomic emission spectrometry using pH peak focusing countercurrent chromatography

Metal ions were highly efficiently enriched by pH peak focusing high-speed countercurrent chromatography. The peak intensity for a 10-mL standard sample in the effluent stream was increased over 100-fold compared to conventional plasma atomic emission spectrometry. Ca, Cd, Cu, Mg, Mn, Ni, and Zn are chromatographically extracted in a basic organic stationary phase containing a complex-forming reagent such as bis(2-ethylhexyl) phosphoric acid. After the sample solution is introduced into the column, metal ions remain around the sharp pH border formed between acidic and basic zones, moving toward the column outlet. Enriched metal ions are finally eluted with the sharp pH border as a highly concentrated peak into a volume of less than 100 microL. We evaluated this method for concentration efficiency in trace determination in tap water using different column diameters.     

Injection port derivatization following ion-pair hollow fiber-protected liquid-phase microextraction for determining acidic herbicides by gas chromatography/mass spectrometry

Injection port derivatization following ion-pair hollow fiber-protected liquid-phase microextraction (LPME) for the trace determination of acidic herbicides (2,4-dichlorobenzoic acid, 2,4-dichlorophenoxyacetic acid, 2-(2,4-dichlorophenoxy)propionic acid, 3,5-dichlorobenzoic acid, 2-(2,4,5-trichlorophenoxy)propionic acid) in aqueous samples by gas chromatography/mass spectrometry (GC/MS) was developed. Prior to GC injection port derivatization, acidic herbicides were converted into their ion-pair complexes with tetrabutylammonium chloride in aqueous samples and then extracted by 1-octanol impregnated in the hollow fiber. Upon injection, ion pairs of acidic herbicides were quantitatively derivatized to their butyl esters in the GC injection port. Thus, several parameters related to the derivatization process (i.e., injection temperature, purge-off time) were evaluated, and main parameters affecting the hollow fiber-protected LPME procedure such as extraction organic solvent, ion-pair reagent type, pH of aqueous medium, concentration of ion-pair reagent, sodium chloride concentration added to the aqueous medium, stirring speed, and extraction time profile, optimized. At the selected extraction and derivatization conditions, no matrix effects were observed. This method proved good repeatability (RSDs <12.3%, n = 6) and good linearity (r2 > or = 0.9939) for spiked deionized water samples for five analytes. The limits of detection were in the range of 0.51-13.7 ng x L(-1) (S/N =3) under GC/MS selected ion monitoring mode. The results demonstrated that injection port derivatization following ion-pair hollow fiber-protected LPME was a simple, rapid, and accurate method for the determination of trace acidic herbicides from aqueous samples. In addition, this method proved to be environmentally friendly since it completely avoided open derivatization with potentially hazardous reagents.     

异形聚偏氟乙烯中空纤维膜的研制

利用特殊结构的纺丝喷头,通过溶液相转移法,研制具有异形结构如:一字形多芯、品字形多芯结构的聚偏氟乙烯(PVDF)中空纤维膜.系统研究了纺丝入水距离、异形膜形状对膜形态结构与性能的影响.结果表明:随纺丝入水距离的增大,异形膜的超滤水通量、透气系数、膜蒸馏通量、抗压密系数、断裂强力及破裂压力减小;异形膜中品字形三芯中空纤维膜的断裂强力较单芯中空纤维膜有很大的提高,而且破裂压力和抗压密系数在异形膜中最大,纺丝成形稳定性最佳.     

Sample preparation based on dynamic ion-exchange solid-phase extraction for GC/MS analysis of acidic herbicides in environmental waters

The newly established enrichment technique, dynamic ion-exchange solid-phase extraction (DIE-SPE), was studied for sample preparation for GC/MS analysis of 16 acidic herbicides in environmental waters. C18 bonded silica was the solid-phase material used. The optimal sample pH was weakly acidic to neutral. However, for common tap water and surface water, which run pH 6-9, all the acidic herbicides except for Chloramben could be effectively extracted from a sample of 1,000-mL volume without pH adjustment. The humic acid could be concurrently extracted from water, but most of it was separated from the sample by using 3 mL of 10% methanol in acetone as the eluent, which would completely elute the analytes and leave a large part of the humic acid on the cartridge. The selective elution reduced the interference of humic acid and made the DIE-SPE an effective approach for the analysis of the acidic herbicides in surface water. Comparing DIE-SPE with conventional reversed-phase SPE (RP-SPE), the former gave higher recoveries for the acidic herbicides and was less affected by sample matrixes. A tandem-cartridge system combining RP- and DIE-SPE in sequence was set up for the simultaneous isolation of the acidic herbicides and removal of the interfering substances. Despite some minimal retention on the upper RP-SPE cartridge, most of the acidic herbicides could be extracted on the lower DIE-SPE cartridge with recovery over 80% except for Chloramben (50%), fenoprop (73%), MCPB (67%), and 2,4-DB (70%) when a 500-mL aqueous sample of pH 9.5 was percolated through the tandem-cartridge system. The effectiveness of the system in removing the long carbon chain fatty acids as well as the basic and neutral organic interfering substances from the sample was also demonstrated.     

聚对苯二甲酸乙二醇酯/锡氟磷酸盐玻璃复合材料原位成纤对聚丙烯的增强效果

采用低玻璃化转变温度的锡氟磷酸盐玻璃(Pglass)改性聚对苯二甲酸乙二醇酯(PET),制备低黏度高模量的PET基复合材料(PET/Pglass);以PET/Pglass或PET为成纤相,聚丙烯为基体,利用实验室自主设计的多级拉伸挤出装置,制得原位成纤增强聚丙烯复合材料,并研究成纤相形态及其对复合材料力学性能的影响。结果表明,与PET相比,PET/Pglass在多级拉伸挤出过程中原位成纤更容易,纤维长径比更大,分散更均匀,从而进一步提高聚丙烯的拉伸强度和模量,而且能保持聚丙烯较高的断裂伸长率,表明具有低黏高模的PET/Pglass对聚丙烯的原位成纤增强效果更显著。