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1.
Mitotane is a cytotoxic drug used in the treatment of inoperable adrenocortical carcinoma, it inhibits steroidogenesis as well, and therefore monitoring the level of steroid hormones in patients treated with mitotane is a crucial point of therapy. Hence, we have developed a simple, fast, and efficient electrophoretic method combined with reverse polarity sweeping as online preconcentration technique and dispersive liquid–liquid microextraction for the simultaneous determination of mitotane, its main metabolite DDA, and five steroid hormones (progesterone, testosterone, epitestosterone, cortisol, and corticosterone) in urine samples. In addition, a new sample matrix consisting of β-CD2SDS1 complexes for a high hydrophobic compounds solubilization was developed. Approach based on the application of β-cyclodextrin and SDS complex of a ratio 2:1 allowed for hydrodynamic injection into the capillary of a solution containing both mitotane and other analytes. The detection limits of the analytes for the reverse polarity sweeping-dispersive liquid–liquid microextraction method were found to be in the range of 1.5–3 ng/mL, which were approximately 1000 times lower than in the conventional hydrodynamic injection (5 s, 0.5 psi) without any preconcentration procedure. All analytes were completely resolved in less than 13 min by uncoated silica capillary with an inner diameter of 75 μm (ID) × 60 cm. Electrophoretic separation was performed in reverse polarity with a voltage of –25 kV with a background electrolyte (BGE) consisting of 100 mM SDS, 25% ACN, 25 mM phosphate buffer (pH 2.5), and 7 mM β-cyclodextrin.  相似文献   
2.
王雨晨  王延梅 《色谱》2020,38(9):1022-1027
毛细管电泳作为一种常见的液相分离技术,因其分析速度快、分离效率高、样品消耗量少等特点,在蛋白质分离分析领域有广泛应用。然而,常用的熔融硅毛细管容易吸附蛋白质,导致电渗流不稳定,分离结果重现性变差;此外,商用毛细管电泳中常用的紫外检测器由于光程短,使得毛细管电泳的检测灵敏度往往不能达到低丰度蛋白质的直接分析要求。因此寻找能够阻止蛋白质吸附、同时能够提高检测灵敏度的涂层是毛细管电泳分离分析蛋白质的重要课题之一。聚(2-甲基-2-噁唑啉)(PMOXA)作为一种类肽类亲水性聚合物,具有与抗蛋白质吸附聚合物聚乙二醇类似的亲水性、抗蛋白质吸附性和生物相容性,而且其类肽结构使之具有较聚乙二醇更好的稳定性,因此近年来在生物质传递、药物载体和阻抗蛋白质吸附等领域得到越来越多的应用。该文主要从两个方面对聚(2-甲基-2-噁唑啉)在毛细管电泳中的应用进行了阐述。一是利用多巴胺作为黏合层将其涂覆在毛细管内壁作为抗蛋白质吸附涂层,这种涂层不仅能成功分离多种蛋白质的混合物(如溶菌酶、细胞色素C、核糖核酸酶A和α-胰凝乳蛋白酶原A),而且在定量检测奶粉中三聚氰胺、乳铁蛋白的过程中,能阻抗其他蛋白质的非特异性吸附,提高了毛细管电泳对奶粉中三聚氰胺、乳铁蛋白的检测效率。二是将其与具有刺激响应性的聚合物(如聚丙烯酸)构成二元混合刷涂层,在一定的pH和离子强度条件下,涂层可吸附目标蛋白质(如牛血清白蛋白、溶菌酶),在另一pH和离子强度条件下可将吸附的目标蛋白质全部释放,同时在释放过程中,处于涂层表面的聚(2-甲基-2-噁唑啉)会进一步阻止蛋白质的吸附,释放的蛋白质在电渗流和电泳的双重作用下快速迁移,到达检测器的蛋白质瞬时浓度大大增加,使目标蛋白质得到富集,目标蛋白质的检测信号得到放大,从而达到了提高低丰度蛋白质检测灵敏度的目的。此外,该文还对聚(2-甲基-2-噁唑啉)在毛细管电泳分离蛋白质中的未来发展趋势进行了展望。  相似文献   
3.
An efficient and fast dispersive magnetic solid phase extraction method was developed using MIL‐101(Cr)/poly (mercaptobenzothiazole)@magnetite nanoparticles for the preconcentration and determination of nitrophenols in river and rain water samples. High‐performance liquid chromatography‐Ultraviolet instrument was applied for the analysis of target nitrophenols. The effect of several variables on the extraction performance was explored via design of experiment approach. Limits of detection and linear dynamic ranges were attained in the range of 0.05–0.10 µg/L and 0.2–250 µg/L, respectively. The enrichment factors were in the range of 317–363. The precision (n = 3) of dispersive magnetic solid phase extraction method was in the range of 5.3–6.8%. Eventually, the method was utilized for the analysis of target nitrophenols in river and rain water samples.  相似文献   
4.
In this work, a binary-mixed-brushes-coated (BBC) capillary with switchable protein adsorption/desorption properties was developed and applied for on-line preconcentration of proteins. Firstly, amine-terminated poly(2-methyl-2-oxazoline) (PMOXA-NH2) and thiolterminated poly(acrylic acid) (PAA-SH) were synthesized by using cationic ring-opening polymerization (CROP) and reversible addition fragmentation chain transfer (RAFT) polymerization, respectively. Then, the BBC capillary based on poly(2-methyl-2-oxazoline) (PMOXA) and poly(acrylic acid) (PAA) was prepared by sequentially grafting of PMOXA-NH2 and PAA-SH onto fused-silica capillary inner surface through poly(dopamine) (PDA) as an anchor. The obtained PMOXA/PAA coating formed on the capillary or capillary's raw material was characterized in terms of the thickness, surface chemical composition by using scanning electron microscope (SEM) and X-ray photoelectron spectrum (XPS). The switchable protein adsorption/desorption performance of the BBC capillary was investigated by using fluorescence microscope under di erent solutions with certain pH and ionic strength(I). The results showed that bovine serum albumin (BSA) could be adsorbed on BBC capillary at pH=5.0 (I=10-5 mol/L), and then the adsorbed BSA could be released at pH=9.0 (I=0.1 mol/L). This switchable protein adsorption/desorption property of coated capillary was then used to preconcentrate proteins on-line for increasing the detection sensitivity of BSA in capillary electrophoresis (CE). With this method, a sensitivity enhancement factor (SEF) more than 5000 for BSA detection was obtained.  相似文献   
5.
The present work describes the development and validation of a sensitive method for the determination of traces of diverse groups of pharmaceuticals and endocrine disruptors in surface water. Thirty-seven substances have been selected, including 10 pesticides, 6 hormonal steroids and assimilates, 12 pharmaceuticals, 5 alkylphenols, 1 chlorophenol and 3 other well-known human contaminants, 1 UV filter and 2 plasticisers. An automated online solid-phase extraction (SPE) is directly coupled to liquid chromatography–tandem mass spectrometry. Different SPE columns have been tested, and the injection volume has been optimised. The developed analytical methodology is based on the direct injection of 2.5 mL of water sample acidified at pH 1.6 on an Oasis HLB loading column (20 × 2.1 mm) with 5-µm particles. Then, the chromatographic separation is achieved on a Kinetex XB C18 (100 × 2.1 mm; 1.7 µm) column, and the quantification is realised in multiple-reaction monitoring mode. The online SPE step warrants minimal sample handling, low solvent consumption, high sample throughput, saving time and costs. This method allows the quantification of the target analytes in the lower ng/L concentration range, with limits of quantification (LQs) between 100 pg/L and 10 ng/L, 26 compounds having LQ lower than 1 ng/L. The monitoring of two selected MS/MS transitions for each compound allows the reliable confirmation of positive findings even at the LQ level. The developed and validated methodology has been applied to the analysis of various real samples from two French rivers. Twelve target compounds have been detected in the environmental samples, and the major pollutants are pharmaceuticals usually used by humans (paracetamol, carbamazepine, oxazepam, ketoprofen, trimethoprim). The pesticides atrazine and carbendazim have been ubiquitously detected in real samples too. Metronidazole, sulfamethoxazole and diuron were also frequently quantified in the water samples.  相似文献   
6.
A novel method for the online extraction and preconcentration of four sulfonamides was developed using column switching liquid chromatography. Sulfadiazine, sulfathiazole, sulfamethoxypyridazine and sulfamethoxazole were analysed in water samples and preconcentrated in a C18 guard column. Suitable validation parameters were obtained, such as precision, accuracy and relative recovery, in accordance with the validation guidelines of the Food and Drug Administration. Low limits of detection (0.05–0.09 µg L?1) and quantification (0.30 µg L?1, for all of them) were obtained. The quadratic polynomial model was used to adjust the calibration data, and the coefficients of determination were higher than 0.999 for all the analytes. The method was shown to be robust to the assayed parameters according to Youden’s test. The proposed method was successfully used to determine sulfonamides in 11 different fish farming water samples, in which sulfadiazine (0.732 µg L?1), sulfamethoxazole (0.531 µg L?1), sulfathiazole (0.546–1.856 µg L?1) and sulfamethoxypyridazine (0.369–1.509 µg L?1) were found.  相似文献   
7.
Nitrogen doped nano porous graphene was used as an efficient sorbent in solid‐phase extraction process for simultaneous separation and pre‐concentration of metal ions lead (II), cadmium(II), and chromium(III)) in biological samples. Ultrasonic assisted in‐syringe dispersive micro solid phase extraction coupled with micro sampling atomic absorption spectrometry was utilized for the determination of metal ions. Nitrogen doped nano porous graphene was synthesized as a nano sorbent by chemical vapour deposition method. Methane and aniline were used as carbon and nitrogen sources. The characterization of sorbent was performed by field emission scanning electron microscope, transmission electron microscopy, atomic force microscope, fourier transform infrared, chemical element analysis and raman analysis. Effective parameters on the extraction efficiency such as pH, sorbent dosage, eluent volume and eluent concentration were optimized by central composite design and desirability function. Experimental results indicate that the optimal conditions for this extraction were pH = 6.4, 1.42 mg of sorbent, 100 μL of eluent, and 0.84 mol L‐1 of eluent concentration. The detection limits are as low as 1.5, 0.3 and 0.9 μg L‐1 for lead, cadmium, and chromium, respectively. The intra‐day precisions were 3.6, 4.38 and 2.94 and Inter‐day precision were 4.83, 5.26 and 4.52 for lead, cadmium, and chromium, respectively. Method performance was investigated by determination of mentioned heavy metals in complicated biological matrixes such as human plasma, urine and saliva samples with good recoveries.  相似文献   
8.
In this study, a novel sorbent material bearing a bis(aldimine) group was designed and successfully synthesized by covalently bonding a 2-[N,N′-bis(salicylaldimine)]aminoethyl amine ligand to the silica gel surface that was characterized by carbon, hydrogen, and nitrogen elemental analysis, thermogravimetric analysis, and the Fourier transform infrared spectroscopy technique. The sorbent was used for the online solid-phase extraction (SPE) of Cd(II), Cu(II), and Co(II) ions for their determination at trace concentration levels by flame atomic absorption spectrometry. The effective factors for the online SPE such as the pH and the flow rate of the sample solution, and type, volume, and flow rate of eluent were investigated. The concentration levels of Cd(II), Cu(II), and Co(II) were measured in certified reference materials including Virginia tobacco leaves (CTA-VTL-2) and water-trace elements (NWTM-15.2) to validate this method. The metal levels in environmental water were determined by this method, and the values were checked by spiking and recovery experiments and independent analysis by inductively coupled plasma-mass spectrometry. The adsorption capacities of the sorbent were found to be 41.2, 31.6, and 25.6?mg/g for Cd(II), Cu(II), and Co(II), respectively. This method was also successfully used for the determination of Cd(II), Cu(II), and Co(II) concentrations in rice and molasses.  相似文献   
9.
A procedure has been proposed for the separation and preconcentration of trace amounts of thallium. It is based on the adsorption of thallium ions onto organo nanoclay loaded with 1-(2-pyridylazo)-2-naphthol (PAN). Thallium ions were quantitatively retained on the column in the pH range of 3.5–6.0, whereas quantitative desorption occurs with 5.0?mL of 5% ascorbic acid and thallium was determined by flame atomic absorption spectrometry. Linearity was maintained between 0.66?ng?mL?1–15.0?µg?mL?1?in initial solution. Detection limit was 0.2?ng?mL?1?in initial solution and preconcentration factor was 150. Eight replicate determinations of 2.0?µg?mL?1 of thallium in final solution gave a relative standard deviation of ±1.48%. Various parameters have been studied, such as the effect of pH, breakthrough volume and interference of a large number of anions and cations and the proposed method was used to determine thallium ions in water and standard samples. Determination of thallium ions in standard sample showed that the proposed method has good accuracy.  相似文献   
10.
A preconcentration method by adsorption of cadmium on a niobium wire was developed for the environmental waters, followed by electrothermal atomic absorption spectrometry with a tungsten tube atomizer. After the preconcentration, the niobium wire was directly inserted into the tungsten tube atomizer. In the preconcentration (adsorption) process of cadmium, the optimal immersing time was 60?s. The effects of large amounts of concomitants on the preconcentration of cadmium were evaluated. When 103–104 fold excess of matrix elements existed in aqueous solution at pH 4 and 9, the cadmium response was profoundly affected by the matrix elements. However, the cadmium absorption signal was not significantly influenced at pH 7. Therefore, pH 7 was selected for the application into the real environmental samples. Under the optimal conditions, the detection limit (3S/N) for cadmium by the niobium wire preconcentration method was 7.0?pg?mL?1 and the relative standard deviation was 6.8%. The method with preconcentration on a niobium wire was applied to the determination of cadmium in water and proved to be sensitive, simple and convenient. Because this preconcentration method can be utilized in the in situ treatment of trace cadmium in environmental water samples, it was unnecessary to carry the water samples to the analytical work place. The technique was shown to be useful for the determination of cadmium in environmental water samples at 0.1–1?µg?L?1 levels.  相似文献   
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