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1.
Cotinine, the main metabolite of nicotine in human body, is widely used as a biomarker for assessment of direct or passive exposure to tobacco smoke. A method for molecularly imprinted solid-phase extraction (MISPE) of cotinine from human urine has been investigated. The molecularly imprinted polymer (MIP) with good selectivity and affinity for cotinine was synthesized using cotinine as the template molecule, methacrylic acid as the functional monomer, and ethylene glycol dimethacrylate as the cross-linker. The imprinted polymer was evaluated for use as a SPE sorbent, in tests with aqueous standards, by comparing recovery data obtained using the imprinted form of the polymer and a non-imprinted form (NIP). Extraction from the aqueous solutions resulted in more than 80% recovery. A range of linearity for cotinine between 0.05 and 5 μg mL−1 was obtained by loading 1 mL blank urine samples spiked with cotinine at different concentrations in acetate buffer of pH 9.0, and by using double basic washing and acidic elution. The intra-day coefficient of variation (CV) was below 7% and inter-day CV was below 10%. This investigation has provided a reliable MISPE–HPLC method for determination of cotinine in human urine from both active smokers and passive smokers. Figure  相似文献   

2.
Hydrophilic molecularly imprinted polymers(MIPs) were prepared using tetracycline as template,methacrylic acid as monomer and glycidilmethacrylate as pro-hydrophilic co-monomer.Compared with common MIPs,the imprinting effect and adsorption amounts of hydrophilic MIPs for tetracycline(TC) were greatly improved in water media.Furthermore,the electrochemical sensor fabricated by modifying hydrophilic MIPs on glassy carbon electrode was developed for the determination of TC in foodstuff samples.  相似文献   

3.
佟育奎  胡月  夏琴飞  黄玮  田苗苗 《色谱》2017,35(3):291-301
建立了磁性分子印迹聚合物固相萃取与高效液相色谱联用同时检测环境水中4种氟喹诺酮类抗生素的研究方法。分别利用扫描电子显微镜、透射电子显微镜、X-射线衍射、傅里叶红外光谱、振动样品磁强计对合成的磁性分子印迹聚合物进行表征,对影响吸附实验的参数(包括吸附剂用量、吸附和解析时间、洗脱液种类、样品pH值)进行了考察和优化。在最佳的实验条件下,4种氟喹诺酮类抗生素的方法检出限为4.1~21.3 μg/L,方法定量限为13.7~71.0 μg/L,样品加标回收率为70.6%~103.6%。该方法快速、灵敏,能够满足环境水样中氟喹诺酮类抗生素的残留检测要求。  相似文献   

4.
Water-compatible pefloxacin-imprinted monoliths synthesized in a water-containing system were used for the selective extraction of fluoroquinolones (FQs). The MIP monolith was synthesized by using methacrylic acid as the functional monomer, di(ethylene glycol) dimethacrylate as a cross-linker and methanol–water (10:3, v/v) as the porogenic solvent. The ability of the derivated MIP for selective recognition of FQs (ciprofloxacin, difloxacin, danofloxacin and enrofloxacin) and quinolones (flumequine, and oxolinic acid) was evaluated. The derivated monolith showed high selectivity and was able to distinguish between FQs and quinolones. A simple rapid and sensitive method using polymer monolith microextraction (PMME) based on the MIP monolith combined with HPLC with fluorescence detection was developed for the determination of four FQs from milk samples. Owing to the unique porous structure and flow-through channels in the network skeleton of the MIP monolith, phosphate buffer diluted milk samples were directly supplied to PMME; allowing non-specific bound proteins and other biological matrix to be washed out, and FQs to be selectively enriched. The limit of detection of the method was 0.4–1.6 ng/mL and recovery was 92.4–98.2% with relative standard deviations less than 5.9%.  相似文献   

5.
Molecularly imprinted polymers (MIPs) were prepared by precipitation polymerization using tebuconazole (TBZ) as a template. Frontal chromatography and selectivity experiments were used to determine the binding capabilities and binding specificities of different MIPs. The polymer that had the highest binding selectivity and capability was used as the solid-phase extraction (SPE) sorbent for the direct extraction of TBZ from different biological and environmental samples (cabbage, pannage, shrimp, orange juice and tap water). The extraction protocol was optimized and the optimum conditions were: conditioning with 5 mL methanol:acetic acid (9:1), 5 mL methanol and 5 mL water respectively, loading with 5 mL aqueous samples, washing with 1.2 mL acetonitrile (ACN):phosphate buffer (5:5, pH3), and eluting with 3 mL methanol. The MIPs were able to selectively recognize, effectively trap and preconcentrate TBZ over a concentration range of 0.5–15 μmol/L. The intraday and interday RSDs were less than 9.7% and 8.6%, respectively. The limit of quantification was 0.1 μmol/L. Under optimum conditions, the MISPE recoveries of spiked cabbage, pannage, shrimp, orange juice and tap water were 62.3%, 75.8%, 71.6%, 89% and 93.9%, respectively. MISPE gave better HPLC separation efficiencies and higher recoveries than C18 SPE and strong cation exchange (SCX) SPE. Figure HPLC analysis of spiked pannage after MISPE (A) and after C18 SPE (B). HQ (1), E3 (2), p-NP (3), FTF (4), TBZ (5), PNZ (6), HXZ (7) Electronic supplementary material Supplementary material is available in the online version of this article at and is accessible for authorized users.  相似文献   

6.
This work describes an on-line molecularly imprinted solid-phase extraction (MISPE) method for spectrophotometric determination of nicotine in urine samples of smokers. This method is based on manganese (VII) to manganese (VI) reduction in an alkaline medium, promoted by nicotine. Two wash solutions (1:4 (v/v) acetonitrile:sodium hydroxide - pH 11.4, and nitric acid - pH 2.5) were employed to circumvent interferences. Aqueous solutions containing nicotine plus different possible concomitants (cotinine, anabasine, norcotinine and caffeine) were tested individually. The analytical calibration curve was prepared in urine samples collected from non-smokers and spiked with nicotine standard from 1.1 to 60 μmol L−1 (r2 > 0.998). The limit of quantification and the analytical frequency were 1.1 μmol L−1 and 11 h−1, respectively. The precision, evaluated using 3, 10 and 30 μmol L−1 nicotine in urine, was 10, 10 and 4% (intra-day precision) and 12, 13 and 5% (inter-day precision), respectively. Accuracy was checked through high performance liquid chromatography and the results did not present significant differences at the 95% confidence level according to the Student's t-test.  相似文献   

7.
An analytical methodology for the analysis of four polar organophophorus pesticides (monocrotophos, mevinphos, phosphamidon, omethoate) in water and soil samples incorporating a molecularly imprinted solid-phase extraction (MISPE) process using a monocrotophos-imprinted polymer was developed. Binding study demonstrated that the polymer showed excellent affinity and high selectivity to monocrotophos. The MISPE procedure including the clean-up step to remove any interferences was optimized. The accuracy and selectivity of the MISPE process developed were verified using a non-imprinted (blank) polymer and a classical ENVI-18 cartridge as the SPE matrix during control experiments. The use of MISPE improved the accuracy and precision of the GC method and lowered the limit of detection. The recoveries of four polar organophosphorus pesticides (OPPs) extracted from 1 L of river water at a 100 ng/L spike level were in the range of 77.5-99.1%. The recoveries of organophosphorus pesticides extracted from a 5-g soil sample at the 100 microg/kg level were in the range of 79.3-93.5%. The limit of detection varied from 10 to 32 ng/L in water and from 12 to 34 microg/kg in soil samples. The molecularly imprinted polymer (MIP) enabled the selective extraction of four organophosphorus pesticides successfully from water and soil samples, demonstrating the potential of molecularly imprinted solid-phase extraction for rapid, selective, and cost-effective sample pretreatment.  相似文献   

8.
Molecularly imprinted polymers (MIPs) were prepared using bisphenol A (BPA) as a template by precipitation polymerization. The polymer that had the highest binding selectivity and ability was used as solid-phase extraction (SPE) sorbents for direct extraction of BPA from different biological and environmental samples (human serum, pig urine, tap water and shrimp). The extraction protocol was optimized and the optimum conditions were as follows: conditioning with 5 mL methanol–acetic acid (3:1), 5 mL methanol, 5 mL acetonitrile and 5 mL water, respectively, loading with 5 mL aqueous samples, washing with 1 mL acetonitrile, and eluting with 3 mL methanol. MIPs can selectively recognize, effectively trap and preconcentrate BPA over a concentration range of 2–20 μM. Recoveries ranged from 94.03 to 105.3 %, with a relative standard deviation lower than 7.9 %. Under the optimal condition, molecularly imprinted SPE recoveries of spiked human serum, pig urine, tap water and shrimp were 65.80, 82.32, 76.00 and 75.97 %, respectively, when aqueous samples were applied directly. Compared with C18 SPE, a better baseline, better high-performance liquid chromatography separation efficiency and higher recoveries were achieved after molecularly imprinted SPE.   相似文献   

9.
We aim to develop novel photoresponsive surface molecularly imprinted polymer (SIMP) microspheres, an SiO2‐SIMP, for the photocontrolled extraction of uric acid from biological samples. The SiO2‐SMIP was prepared on silica microspheres by surface polymerization and characterized by using scanning electron microscopy, transmission electron microscopy, FTIR spectroscopy, thermogravimetric analysis, nitrogen adsorption–desorption analysis, and UV‐visible spectroscopy. The SiO2‐SMIP microspheres showed a photocontrolled uptake and release of uric acid in NaH2PO4 buffer upon alternate irradiation at 365 and 440 nm. The SiO2‐SMIP microspheres were able to photocontrollably extract uric acid from complicated biological samples for concentration analysis with no significant interference encountered and it exhibited very good recognition ability and fast binding kinetics toward uric acid.  相似文献   

10.
A broad selective molecularly imprinted polymers-based solid phase extraction (MISPE) for levonorgestrel (LNG) from water samples was developed. Using LNG as a template molecule, acrylamide (AA) as functional monomer, ethylene glycol dimethacrylate (EGDMA) as linking agent and bulk polymerisation as a synthetic method, the molecularly imprinted polymers (MIPs) were synthesised and characterised. The MIPs displayed a high specific rebinding for LNG with the imprinting factor of 3.71. The Scatchard analysis showed that there was at least one class of binding site for LNG formed in the MIPs with the dissociation constant of 8.046?µg?mL?1. The results of selectivity testing indicated that the MIPs also exhibited high cross-reactivity with structurally related compounds (estrone, methylprednisolone and ethinyl estradiol), but no recognition with non-structurally related compound (indomethacin), suggesting that the MIPs could be used as a broad recognition absorbent. MISPE column was prepared by packing MIPs particles into a common SPE cartridge. The MISPE extraction conditions including loading, washing and eluting solutions were carefully optimised. Water samples spiked with LNG were extracted by MISPE column and detected by high-performance liquid chromatography. The recoveries were found to be 79.97?~?132.79% with relative standard deviations (RSD) of 1.92?~?10.43%, indicating the feasibility of the prepared MIPs for LNG extraction.  相似文献   

11.
This work demonstrates the synthesis and characterization of core‐shell magnetic molecularly imprinted polymers based on surface imprinting using methacryloyl chloride as a functional monomer for the selective extraction of imidacloprid (template) from apple fruit. The characterization analysis results ensured the successful synthesis of the magnetic molecularly imprinted polymers owing to their heterogeneous structure and good magnetic properties. An isothermal binding test was assessed with a pseudo‐second‐order kinetic model, and the kinetic results fit well to the Freundlich isothermal model. The polymers exhibited an adsorption capacity of 5.75 mg/g for the target analyte with a good selective extraction ability. In addition, the polymers can be reused several times without significant performance loss. The molecularly imprinted polymers showed good performance in the analysis of spiked apple sample with a linear range of 0.05–1.0 mg/L, a limit of detection of 0.048 mg/L and a limit of quantification of 0.146 mg/L (S/N = 3/10). The recoveries of the samples were 77.66–96.57% and their respective relative standard deviations were 3.36–0.45%. All the results indicated that the proposed method provided good selective extraction, as qualifying the analytical standards.  相似文献   

12.
Qu S  Wang X  Tong C  Wu J 《Journal of chromatography. A》2010,1217(52):8205-8211
A new molecularly imprinted polymer (MIP) targeting to quinolones (Qs) and tetracyclines (TCs) was synthesized using itaconic acid (ITA) and ciprofloxacin (CIP) as a functional monomer and template molecule, respectively. Factors affecting the overall performance of MIP were investigated, and the results showed that Fe(3+) ion play a vital role in the formation of MIP with high molecular imprinting effect. Meanwhile, the chelating ability of monomer, species of template molecule, as well as the molar ratio of monomer and template also contribute to the performance of the obtained MIP. Cyclic voltammetry verified that, with the participation of Fe(3+) ions, a ternary complex of ITA-Fe(3+)-CIP could be formed before polymerization. Compared with conventional MIP prepared from commonly used monomer, methacrylic acid (MAA), the new MIP show significantly enhanced molecular imprinting effect and higher capacity for specific adsorption of target compounds as revealed by static and dynamic binding experiments. The MIP was successfully used as solid-phase extraction (SPE) adsorbent for enriching a broad spectrum of antibiotics containing beta-diketone structure from surface water sample. HPLC detection showed that high recovery rate (78.6-113.6%) was found in these spiked antibiotics, whereas recovery rate for the non structurally related drugs, epinephrine (EP) and dopamine (DOPA), was very low (4.7-7.6%) on the MIP cartridges. The results demonstrate that the MIP prepared by the strategy proposed in this work, could specifically target to a series of structurally related antibiotics containing beta-diketone structure.  相似文献   

13.
A hydrophobic ionic liquid modified thermoresponsive molecularly imprinted monolith was synthesized using N‐isopropylacrylamide as a thermoresponsive monomer and a long‐chain hydrophobic ionic liquid as an auxiliary modification monomer. The ionic‐liquid‐modified thermoresponsive molecularly imprinted polymer was characterized by scanning electron microscopy and Fourier transform infrared spectroscopy. When the column temperature was 50°C, the synthesized monolithic column was successfully applied to the selective separation of homologue tanshinones within 7 min and eluted only by water (mobile phase) (theoretical plates more than 1.00 × 105 per meter). The negative Gibbs free energy (≤–2.37) values showed that the transfer of the tanshinones from the mobile phase to the stationary phase on this monolithic column was a thermodynamically spontaneous process. Good linearity of the five tanshinones by thermoresponsive monolith was obtained in the range of 0.100–25.0 μg/mL. The limit of detection (S/N = 3) and limit of quantitation (S/N = 10) were less than 0.0390 and 0.0630 μg/mL, respectively, with a relative standard deviation of <4.8%. In this proposed thermoresponsive chromatography method, the separation of homologue analytes can be achieved by changing the column temperature, and the use of water as the mobile phase would decrease the economic cost and organic pollution.  相似文献   

14.
Curcumin widely exists in food, and rapid selective and accurate detection of curcumin have great significance in chemical industry. In this experiment, a new magnetic biocompatibility molecularly imprinted polymer was prepared with nontoxic and biocompatible Zein to adsorb curcumin selectively. The polymer has high biocompatibility, good adsorption capacity, and specific adsorption for curcumin. Combined with portable electrochemical workstations, the polymer can be used to detect curcumin rapidly and cost‐effectively. Using curcumin as a template and Zein as the crosslinking agent, the polymers were synthesized on the surface of Fe3O4 particles for solid phase extraction. The experimental results showed that the polymer reached large adsorption capacity (32.12 mg/g) with fast kinetics (20 min). The adsorption characteristic of the polymer followed the Langmuir isotherm and pseudo‐second‐order kinetic models. Hexacyanoferrate was used as electrochemical probe to generate signals, and the linear range was 5–200 µg/mL for measuring curcumin. The experimental analysis showed that the polymer was an ideal material for selective accumulation of curcumin from complex samples. This approach has been successfully applied to the determination of curcumin in food samples with electrochemical detection, indicating that this is a feasible and practical technique.  相似文献   

15.
Since natural pigments are lost during the processing of beverages such as pomegranate juice, carmoisine, as an adulterant, is often added into the pure juice to improve color characteristics. In this study, molecularly imprinted polymers, as an adsorbent of carmoisine, were synthesized using acrylamide, methacrylic acid, and 4‐vinylpyridine as functional monomers and then they were evaluated in terms of the separation and detection of carmoisine. Experiments on the batch adsorption of carmoisine 10 ppm stock solution revealed a better binding capacity for the 4‐vinylpyridine‐based polymer in comparison to methacrylic acid and acrylamide polymers. The complexation of carmoisine with the 4‐vinylpyridine‐based polymer was confirmed by Fourier transform infrared spectroscopy. The synthesized polymer exerted a high thermal degradation point and average diameter of polymer particles were obtained to be 0.2 μm by dynamic light scattering analysis. This work showed that detection of pomegranate juice adulteration with carmoisine is not necessarily difficult, time consuming or expensive with selective separation techniques such as molecularly imprinted polymers.  相似文献   

16.
In this paper we describe, for the first time, a molecularly imprinted polymer (MIP) for the antibiotic amoxicillin (AMX), synthesised by a noncovalent molecular imprinting approach and used to extract AMX selectively from urine samples. The MIP was applied as a molecularly selective sorbent in molecularly imprinted SPE (MISPE) in an off-line mode, where it showed useful cross-selectivity for a structurally related antibiotic, cephalexin (CPX). By using a MISPE protocol, the MIP was able to selectively extract both AMX and CFX from 5 mL of water spiked with 10 mg/L with recoveries of 75 and 78% for AMX and CFX, respectively. When applied to real samples (urine) at clinically relevant concentrations, recoveries from 2 mL of human urine spiked with 20 mg/L decreased slightly to 65 and 63% for AMX and CFX, respectively. To demonstrate further the selectivity of the MIP obtained, a comparison with commercially available SPE cartridges was performed. Improvements in the retention of both AMX and CFX on the MIP were obtained relative to the commercially available cartridges, and the MISPE extracts were considerably cleaner, due to molecularly selective analyte binding by the MIP.  相似文献   

17.
Porous molecularly imprinted polymer membranes and polymeric particles   总被引:1,自引:0,他引:1  
Porous free-standing molecularly imprinted polymer membranes were synthesised by the method of in situ polymerisation using the principle of synthesis of interpenetrating polymer networks and tested in solid-phase extraction of triazine herbicides from aqueous solutions. Atrazine-specific MIP membranes were obtained by the UV-initiated co-polymerisation of methacrylic acid, tri(ethylene glycol) dimethacrylate, and oligourethane acrylate in the presence of a template (atrazine). Addition of oligourethane acrylate provided formation of the highly cross-linked MIP in a form of a free-standing 60 μm thick flexible membrane. High water fluxes through the MIP membranes were achieved due to addition of linear polymers (polyethylene glycol Mw 20,000 and polyurethane Mw 40,000) to the initial mixture of monomers before the polymerization. As a result, typical semi-interpenetrating polymer networks (semi-IPNs) have been formed, where the cross-linked polymer was represented by the atrazine-specific molecularly imprinted polymer, while the linear one was represented by polyethylene glycol/polyurethane. Extraction of the linear polymers from the fully formed semi-IPNs resulted in formation of large pores in the membrane structure. At the same time, extraction of the template molecules lead to formation of the sites in the polymeric network, which in shape and arrangement of functional groups are complementary to atrazine. Reference polymeric membranes were prepared from the same mixture of monomers but in the absence of the template. Recognition properties of the MIP membranes were estimated in solid-phase extraction by their ability to selective re-adsorbtion of atrazine from 10−8 to 10−4 M aqueous solutions. The imprinting effect was demonstrated for both types of the MIP membranes and the influence of the type of the linear compound on their recognition properties was estimated. The recognition properties of the MIP membranes were compared to those of the MIP particles of the same composition. Morphology of the MIP membranes was investigated using the SEM microscopy. High fluxes of the developed membranes together with high affinity and adsorption capability make them an attractive alternative to MIP particles in separation processes.  相似文献   

18.
Magnetic molecularly imprinted polymers were prepared using hydrophobic Fe3O4 magnetite as the magnetically susceptible component, oxytetracycline as template molecule, methacrylic acid as functional monomer, and styrene and divinylbenzene as polymeric matrix components. The polymers were applied to the separation of tetracycline antibiotics from egg and tissue samples. The extraction and clean-up procedures were carried out in a single step by blending and stirring the sample, extraction solvent and polymers. The analytes can be transferred from the sample matrix to the polymers directly or through the extraction solvent as medium. When the extraction was complete, the polymers adsorbing the analytes were easily separated from the sample matrix by an adscititious magnet. The analytes eluted from the polymers were determined by liquid chromatography–tandem mass spectrometry. The recoveries ranging from 72.8% to 96.5% were obtained with relative standard deviations in the range of 2.9–12.3%. The limit of detection was less than 0.2 ng g−1. The feasibility of this method was validated by analysis of incurred egg and tissue samples, and the results were compared with those obtained by the classical method in which solvent extraction, centrifugation, and subsequent clean-up and concentration by solid-phase extraction were applied. The proposed method reduced the complicacy of classical method and improved the reliability of method.  相似文献   

19.
Selective polymeric extractants were prepared for preconcentration of Cibacron reactive red dye, a dye that is often applied with Cibacron reactive blue and Cibacron reactive yellow for dyeing of fabrics. The best extractant was fabricated (in chloroform) using methacrylic acid (as monomer), ethylene glycol dimethacrylate (as crosslinker), AIBN (as initiator for polymerization), and red dye as template molecule, with a molar stoichiometric ratio of 8.0:40.0:2.5:0.63, respectively. The structure of the molecularly imprinted polymer (MIP) was robust, and resisted dissolution up to 260 °C. Compared with the un-imprinted polymer, the imprinted product has a large specific surface area which improved its adsorption capacity. The effect of imprinting was obvious from the adsorption capacity measured at pH 4 for red dye (the imprinted molecule), which was increased from 24.0 to 79.3 mg g−1 after imprinting. Equilibrium adsorption studies revealed that the dye-imprinted-polymer enables efficient extraction of red dye even in the presence of blue and yellow dyes which have similar chemical natures to the red dye. The selectivity coefficients S red dye/dye, were 13.9 and 17.1 relative to the yellow and blue dyes, respectively. The MIP was found to be effective for red dye preconcentration, with a preconcentration factor of 100, from tap water and treated textile wastewater. The factors affecting extraction of red dye by the MIP were studied and optimized. Under the optimized extraction conditions, red dye was selectively quantified in the presence of other competing dyes at a concentration of 20 μg L−1 from different water systems with satisfactory recoveries (91–95%) and RSD values (∼5.0%).  相似文献   

20.
We present a facile strategy to prepare the molecularly imprinted polymers layer on the surface of Fe3O4 nanoparticles with core‐shell structure via sol–gel condensation for recognition and enrichment of triclosan. The Fe3O4 nanoparticles were first synthesized by a solvothermal method. Then, template triclosan was self‐assembled with the functional monomer 3‐aminopropyltriethoxysilane on the silica‐coated Fe3O4 nanoparticles in the presence of ethanol and water. Finally, the molecularly imprinted polymers were formed on the surface of silica‐coated Fe3O4 nanoparticles to obtain the product. The morphology, magnetic susceptibility, adsorption, and recognition property of magnetic molecularly imprinted polymers were characterized using transmission electron microscopy, Fourier transform infrared spectroscopy, X‐ray diffractometry, vibrating sample magnetometry, and re‐binding experiments. The magnetic molecularly imprinted polymers showed binding sites with good accessibility, fast adsorption rate, and high adsorption capacity (218.34 μg/g) to triclosan. The selectivity of magnetic molecularly imprinted polymers was evaluated by the rebinding capability of triclosan and two other structural analogues (phenol and p‐chlorophenol) in a mixed solution and good selectivity with an imprinting factor of 2.46 was obtained. The application of triclosan removal in environmental samples was demonstrated.  相似文献   

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