A new and selective sorbent for molecularly imprinted solid-phase extraction (MISPE) was developed and applied for the determination
of residues of fenitrothion (FNT) in tomatoes, using HPLC coupled to photodiode array detection (HPLC-DAD). Using FNT as the
template molecule, methacrylic acid as the functional monomer, ethylene glycol dimethacrylate as the cross-linker, toluene
as the porogenic solvent, and bulk polymerization as the synthetic method, a molecularly imprinted polymer (MIP) was synthesized.
In order to choose the medium which promotes the best molecular recognition of FNT by the MIP, the adsorption of FNT by the
MIP was studied in different media containing acetonitrile and toluene. Besides FNT, three structurally related compounds
were used to evaluate the selectivity of the FNT-molecularly imprinted polymer. The MIP exhibited the highest selective rebinding
to FNT. The method developed was validated, using fortified blank tomato samples. The extraction efficiency was 96%. The limits
of detection and quantitation were 0.050 and 0.130 μg g−1, respectively. The intra-day precision was 5.9% and the inter-day precision 8.1%. The accuracy was higher than 89% for a
concentration level around the maximum residue limit of 0.5 μg g−1. 相似文献
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
A selective molecularly imprinted solid-phase extraction (MISPE) for indomethacin (IDM) from water samples was developed.
Using IDM as template molecule, acrylamide (AM) or methacrylic acid (MAA) as functional monomer, ethylene dimethacrylate (EDMA)
as crosslinker, and bulk or suspension polymerization as the synthetic method, three molecularly imprinted polymers (MIPs)
were synthesized and characterized with a rebinding experiment. It was found that the MIP of AM-EDMA produced by bulk polymerization
showed the highest binding capacity for IDM, and so it was chosen for subsequent experiments, such as those testing the selectivity
and recognition binding sites. Scatchard analysis revealed that at least two kinds of binding sites formed in the MIP, with
the dissociation constants of 7.8 μmol L−1 and 127.2 μmol L−1, respectively. Besides IDM, three structurally related compounds — acemetacin, oxaprozin and ibuprofen — were employed for
selectivity tests. It was observed that the MIP exhibited the highest selective rebinding to IDM. Accordingly, the MIP was
used as a solid-phase extraction sorbent for the extraction and enrichment of IDM in water samples. The extraction conditions
of the MISPE column for IDM were optimized to be: chloroform or water as loading solvent, chloroform with 20% acetonitrile
as washing solution, and methanol as eluting solvent. Water samples with or without spiking were extracted by the MISPE column
and analyzed by HPLC. No detectable IDM was observed in tap water and the content of IDM in a river water sample was found
to be 1.8 ng mL−1. The extraction efficiencies of the MISPE column for IDM in spiked tap and river water were acceptable (87.2% and 83.5%,
respectively), demonstrating the feasibility of the prepared MIP for IDM extraction.
Figure Molecularly imprinted polymer-based solid-phase extraction for indomethacin 相似文献
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
Six molecularly imprinted polymers (MIPs) of erythromycin (ERY) were prepared by noncovalent bulk polymerization using methacrylic
acid (MAA) as the functional monomer. On the basis of binding analysis, the MIPs with 1:2 optimum ratio of template to MAA
were selected for subsequent scanning electron microscopy and Brunauer–Emmett–Teller analyses, which indicated that the MIPs
had more convergent porous structures than the nonimprinted polymers. The equilibrium binding experiments showed that the
binding sites of MIPs were heterogeneous, with two dissociation constants of 0.005 and 0.63 mg mL−1, respectively. Furthermore, the performance of the MIPs as solid-phase extraction (SPE) sorbents was evaluated, and the selectivity
analysis showed that the MIPs could recognize ERY with moderate cross-reactivity for other macrolides. The overall investigation
of molecularly imprinted SPE for cleanup and enrichment of the ERY in pig muscle and tap water confirmed the feasibility of
utilizing the MIPs obtained as specific SPE sorbents for ERY extraction in real samples.
Figure Schematic diagram of the preparation and application of the erythromycin imprinted molecularly imprinted polymers
Suquan Song and Aibo Wu contributed equally to this work. 相似文献
A highly selective molecularly imprinted polymer (MIP) for the recognition of the pesticide carbaryl in water has been synthesized
using halogenated bisphenol A compounds as one of the polymeric precursors and carbaryl as the template molecule. On the basis
of the heavy-atom effect, both the brominated and the iodinated MIPs allowed analyte detection by room-temperature-phosphorescence
measurements. In the presence of an oxygen scavenger (sodium sulphite) the halide, included in the polymeric structure, induced
efficient room-temperature phosphorescence of the analyte (once it had been selectively retained by the MIP). The MIP cavity
can be easily regenerated for subsequent sample injections with 2 mL methanol. The optosensing system developed has demonstrated
high selectivity for carbaryl, even in the presence of other luminophores that could be unspecifically adsorbed onto the MIP
surface. Under optimal experimental conditions, the detection limit for the target molecule was 4 μg/L (3-mL sample injection
volume), and the linear range extended up to 1 mg/L of the analyte. Good reproducibility was achieved (a relative standard
deviation of 3% was obtained for ten replicates of 150 μg/L carbaryl). The synthesized sensing material showed good stability
for at least 3 months after preparation. Finally, the applicability to carbaryl determination in real samples was evaluated
through the successful determination of the pesticide in spiked mineral and tap water samples.
Figure Schematic diagram of carbaryl recognition process by an halogenated molecularly imprinted polymer for room temperature phosphorescence
detection of the analyte. 相似文献
A rapid, specific, and sensitive method has been developed using molecularly imprinted polymers (MIPs) as solid-phase extraction
sorbents for extraction of trace tetracycline antibiotics (TCs) in foodstuffs. MIPs were prepared by precipitation polymerization
using tetracycline as the template. Under the optimal condition, the imprinting factors for MIPs were 4.1 (oxytetracycline),
7.0 (tetracycline), 7.4 (chlortetracycline), 7.7 (doxycycline), respectively. Furthermore, the performance of MIPs as solid-phase
extraction sorbents was evaluated and high extraction efficiency of molecularly imprinted solid-phase extraction (MISPE) procedure
was demonstrated. Compared with commercial sorbents, MISPE gave a better cleanup efficiency than C18 cartridge and a higher
recovery than Oasis HLB cartridge. Finally, the method of liquid chromatography–tandem mass spectrometry coupled with molecular-imprinted
solid-phase extraction was validated in real samples including lobster, duck, honey, and egg. The spiked recoveries of TCs
ranged from 94.51% to 103.0%. The limits of detection were in the range of 0.1–0.3 μg kg−1.
Chromatograms obtained by direct injection of the spiked egg extracts (5 × 10-3 mmol L−1) and purification with MISPE 相似文献
In this paper, a highly selective molecularly imprinted polymer (MIP) for tramadol hydrochloride, a drug used to treat moderate
to severe pain, was prepared and its use as solid-phase extraction (SPE) sorbent was demonstrated. The molecularly imprinted
solid-phase extraction procedure followed by high performance liquid chromatography with ultraviolet detector (MISPE-HPLC)
was developed for selective extraction and determination of tramadol in human plasma and urine. The optimal conditions for
molecularly imprinted solid-phase extraction (MISPE) consisted of conditioning with 1 mL methanol and 1 mL of deionized water
at neutral pH, loading of tramadol sample (50 μg L−1) at pH 7.5, washing using 1 mL acetone and elution with 3 × 1 mL of 10% (v/v) acetic acid in methanol. The MIP selectivity
was evaluated by checking several substances with similar molecular structures to that of tramadol. Results from the HPLC
analyses showed that the calibration curve of tramadol (using MIP from human plasma and urine) is linear in the ranges of
6–100 and 3–120 μg L−1 with good precisions (1.9% and 2.9% for 5.0 μg L−1), respectively. The recoveries for plasma and urine samples were higher than 81%.
相似文献
Highly sensitive flow-injection chemiluminescence (CL) combined with molecularly imprinted solid-phase extraction (MISPE)
has been used for determination of 2,4-dichlorophenol (2,4-DCP) in water samples. The molecularly imprinted polymer (MIP)
for 2,4-DCP was prepared by non-covalent molecular imprinting methods, using 4-vinylpyridine (4-VP) and ethylene glycol dimethacrylate
(EGDMA) as the monomer and cross-linker, respectively. 2,4-DCP could be selectively adsorbed by the MIP and the adsorbed 2,4-DCP
was determined by its enhancing effect on the weak chemiluminescence reaction between potassium permanganate and luminol.
The enhanced CL intensity was linear in the range from 1 × 10−7 to 2 × 10−5g mL−1. The LOD (S/N = 3) was 1.8 × 10−8g mL−1, and the relative standard deviation (RSD) was 3.0% (n = 11) for 1.4 × 10−6g mL−1. The proposed method had been successfully applied to the determination of 2,4-DCP in river water.
Figure Effect of 4-VP content on the ultraviolet spectrum of 2,4-DCP in chloroform 相似文献
We describe a molecularly imprinted polymer (MIP) for the solid-phase extraction of the skin protectant allantoin. The MIP was deposited on the surface of monodisperse silica microspheres possessing acroyl groups on the surface (MH-SiO2). The resulting MIP microspheres (MH-SiO2@MIP) showed a 3.4-fold higher adsorption capacity and a 1.9-fold better selectivity for allantoin than the respective non-imprinted polymer (MH-SiO2@NIP). The monolayer adsorption capacities of the MH-SiO2@MIP and the MH-SiO2@NIP were calculated with the help of the Langmuir model and found to be 6.8 and 1.9 mg•g−1, respectively. Adsorption kinetics fit a pseudo-second order rate mechanism, with an initial adsorption rate of 1.44 for the MH-SiO2@MIP, and of 0.07 mg•g−1•min−1 for the MH-SiO2@NIP. The material can be regenerated, and its adsorption capacity for allantoin remains stable for at least five regeneration cycles. It was successfully used as a sorbent for the selective solid-phase extraction of allantoin from Rhizoma dioscoreae.
A molecularly imprinted polymer (MIP) for the specific retention of neopterin has been developed. A set of 6 polymers was prepared by radical polymerization under different experimental condition using methacrylic acid as functional monomer and ethylene glycol dimethacrylate as crosslinker, with the aim to understand their influence on the efficiency of the MIP. The performance of each MIP was tested in batch experiments via their binding capacity. The MIP prepared in the presence of nickel ions in dimethylsulfoxide-acetonitrile mixture (P4) exhibited the highest binding capacity for neopterin (260 μmol per gram of polymer). A selectivity study with two other pteridines demonstrated the polymer P4 also to possess the best selectivity.
Despite the increasing number of applications of molecularly imprinted polymers (MIP) in analytical chemistry, the synthesis
of polymers with hemin introduced as the catalytic center to mimic the active site of peroxidase remains as a challenge. In
the current work, a new type of molecularly imprinted polymer (MIP) was synthesized with 4-aminophenol (4-APh) as the template
and two monomers: hemin, which acts as the catalytic center, and methacrylic acid (MAA), which is used to build the active
sites. This work shows that MIP successfully mimics peroxidase. For this purpose, a flow injection analysis system coupled
to an amperometric detector was investigated through multivariate analysis. The determination of 4-APh was not affected by
the equimolar presence of structurally similar phenol compounds, including catechol, 4-chloro-3-methylphenol, 2-aminophenol,
guaiachol, chloroguaiachol and 2-cresol, thus highlighting the good performance of the imprinted polymer. Under the optimized
experimental conditions, an analytical curve covering a wide linear response range from 0.8 up to 500 μmol L−1 (r > 0.999) was obtained, and the method gave satisfactory precisions (n = 8), as evaluated via the relative standard deviation (RSD), of 4.1 and 3.2% for solutions of 4-APh of 50 and 500 μmol L−1, respectively. Recoveries of 96–111% from water samples (tap water and river water) spiked with 4-APh were achieved, thus
illustrating the accuracy of the proposed system.
Figure Schematic presentation of the synthesis of the MIP 相似文献
A molecularly imprinted polymer (MIP) has been synthesized by a thermo-polymerization method using methacrylic acid (MAA) as functional monomer, ethylene glycol dimethacrylate (EGDMA) as cross-linker, acetonitrile as porogenic solvent, and 17β-estradiol as template. The MIP showed obvious affinity for 17β-estradiol in acetonitrile solution, which was confirmed by absorption experiments. After optimization of molecularly imprinted solid-phase extraction (MISPE) conditions, three structurally related estrogenic compounds (17β-estradiol, estriol, and diethylstilbestrol) were used to evaluate the selectivity of the MIP cartridges. The MIP cartridges exhibited highly selectivity for E2, the recoveries were 84.8 ± 6.53% for MIPs and 19.1 ± 1.93% for non-imprinted polymer (NIP) cartridges. The detection and quantification limits correspond to 0.023 and 0.076 mg L−1. Furthermore, the MISPE methods were used to selectively extract E2 from fish and prawn tissue prior to HPLC analysis. This MISPE-HPLC procedure could eliminate all matrix interference simultaneously and had good recoveries (78.3-84.5%). 相似文献
A β-estradiol receptor binding mimic was synthesised using molecular imprinting. Bulk polymers and spherical polymer nanoparticles
based on methacrylic acid and ethylene glycol dimethacrylate as the functional monomer and crosslinker, respectively, were
prepared in acetonitrile. The selectivity was evaluated by radioligand binding assays. The imprinted polymers were very specific
to β-estradiol since the control polymers bound virtually none of the radioligand. The bulk polymer was then employed to screen
endocrine disrupting chemicals. Structurally related steroids like α-estradiol, estrone and ethynylestradiol showed, respectively,
14.0, 5.0 and 0.7% of relative binding to the β-estradiol polymer, whereas most unrelated chemicals did not bind at all. These
results are compared to those obtained with a bioassay using stably transfected yeast cells in culture bearing the human estrogen
receptor. The receptor was activated by several estrogen-like chemicals and to a lesser extent by some structurally related
chemicals.
Figure A molecularly imprinted polymer that was a synthetic receptor for beta-estradiol was used for the screening of endocrine disrupting
chemicals that are structurally related or unrelated to beta-estradiol. The results were compared with the recognition of
the compounds by the biological estrogen receptor expressed in yeast cells. Related steroids like alpha-estradiol, estrone
and ethynylestradiol showed significant binding to the beta-estradiol imprinted polymer, whereas most unrelated chemicals
did not bind. The biological receptor was activated by several estrogen-like chemicals, and to a lesser extent by some structurally
related chemicals 相似文献
Recent efforts in the investigation of chromatographic characterization of molecularly imprinted polymers (MIPs) have focused
mainly on the nature of heterogeneous binding sites. More data on the thermodynamics than on the kinetic features of MIP columns
have been published. The present article addresses the sources of peak broadening and tailing, which are the main drawbacks
often associated with imprinted polymers in chromatography for practical applications. With use of the theory of nonlinear
chromatography, the peak properties of a MIP column, including the retention and peak broadening and tailing, can be well
interpreted. Efforts to improve chromatographic efficiency using MIPs prepared by approaches different from the conventional
method, including covalent imprinting and the format of uniformly sized spherical microbeads, are reviewed and discussed.
This review leads to the conclusion that nonlinear chromatography theory is useful for characterizing chromatographic features
of MIP columns, since a MIP is essentially an affinity-based chromatographic stationary phase. We expect more theoretical
and experimental studies on the kinetic aspects of MIP columns, especially the factors influencing the apparent rate constant,
as well as the analysis of the influences of mobile-phase composition on the chromatographic performance. In addition to revealing
the affinity interaction by molecular recognition, slow nonspecific interactions which may be inherited from the imperfect
imprinting and may be involved in the rebinding of the template to MIPs also need to be characterized.
Figure The peak broadening and tailing associated often with molecularly imprinted polymers (MIPs) in column chromatography for practical
applications can be well characterized by the theory of nonlinear chromatography. 相似文献
Environmental analysis is a potential key application for chemical sensors owing to their inherent ability to detect analytes
on-line and in real time in distributed systems. Operating a chemosensor in a natural environment poses substantial challenges
in terms of ruggedness, long-term stability and calibration. This article highlights current trends of achieving both the
necessary selectivity and ruggedness: one way is deploying sensor arrays consisting of robust broadband sensors and extracting
information via chemometrics. If using only a single sensor is desired, molecularly imprinted polymers offer a straightforward
way for designing artificial recognition materials. Molecularly imprinted polymers can be utilized in real-life environments,
such as water and air, aiming at detecting analytes ranging from small molecules to entire cells.
Figure 相似文献
A magnetized molecularly imprinted polymer (MIP) was prepared via a surface-imprinting technique. An allyl-based deep eutectic solvent was chosen as the functional monomer to obtain the polymer for specific recognition of lysozyme. It was deposited on silica-coated magnetite nanoparticles. The structure of the polymer was confirmed by X-ray diffraction, Fourier transform infrared spectrometry, transmission electron microscopy, thermogravimetric analysis and vibrating sample magnetometry. The maximum binding capacity of the imprinted polymer is found to be 108 mg·g?1, which is higher than that of non-imprinted polymer. Compared to reference proteins such as cytochrome C, bovine hemoglobin and bovine serum albumin, the MIP shows favorable selectivity for lysozyme. Besides, the imprinted polymer can be further used to specifically recognize lysozyme from the protein mixture and chicken egg white. Reusability studies demonstrate that the polymer can be recycled four times without significant loss of adsorption capacity. The LOD of the method is 12.8 μg·mL?1. The relative standard deviations (for n = 3) are 1.38% for precision and 2.76% for repeatability. Its facile synthesis, high adsorption performance and excellent selectivity to capture lysozyme make this polymer an attractive candidate to be applied in biomacromolecular purification.
In this paper we describe the synthesis of a molecularly imprinted polymer (MIP) by precipitation polymerisation, with barbital as the template molecule, and the application of the barbital MIP as a molecularly selective sorbent in the solid-phase extraction (SPE) of barbiturates from human urine samples. The MIP was synthesised by precipitation polymerisation using 2,6-bis-acrylamidopyridine as the functional monomer and DVB-80 as the cross-linking agent. The spherical MIP particles produced were 4.2 ± 0.4 μm in diameter; a non-imprinted control polymer (NIP) in bead form was 4.8 ± 0.4 μm (mean±standard deviation) in diameter. The particles were packed into a solid-phase extraction cartridge and employed as a novel sorbent in a molecularly imprinted solid-phase extraction (MISPE) protocol. The MIP showed high selectivity for the template molecule, barbital, a feature which can be ascribed to the high-fidelity binding sites present in the MIP which arose from the use of 2,6-bis-acrylamidopyridine as the functional monomer. However, the MIP also displayed useful cross-selectivity for other barbiturates besides barbital. For real samples, the MIP was applied for the extraction of four barbiturates from human urine. However, due to the high urea concentration in this sample which interfere the proper interaction of barbiturates onto the MIP, a tandem system using a commercially available sorbent was developed. 相似文献
We have prepared a hydrophilic molecularly imprinted polymer (MIP) for the hydrophobic compound bisphenol A (BPA) in aqueous solution using 3-acrylamido-N,N,N-trimethylpropan-1-aminium chloride (AMTC) as the functional monomer. Under redox-polymerization conditions, BPA forms an ion-pair with AMTC, which was confirmed by 1H-NMR titration. The imprinting effect in aqueous solution was evaluated by comparison of this material with the corresponding non-imprinted polymer (NIP) and with a control polymer (CP) bearing no AMTC. The MIP showed the highest activity among the three polymers, and the imprinting factors as calculated from the amount of BPA bound to the MIP divided by the amounts bound to NIP and CP, respectively, are 1.8 and 6.0. The MIP was selective for BPA in aqueous solution, while structurally related compounds are not recognized. Such a selectivity for a hydrophobic compound is rarely observed in aqueous medium because non-specific binding of BPA inevitably leads to hydrophobic interaction.
Organophosphorus compounds (OPCs) are used worldwide as, e.g., flame retardants, plasticizers, and pesticides and remaining
stockpiles of OPC nerve agents are present in military arsenals. These OPCs exhibit acute and potential chronic toxicity to
man, the environment, and biota thus emphasizing the need for efficient analytical procedures to monitor potential risk to
health. Therefore, this review discusses LC-MS-based procedures for OPC detection, addressing sample preparation, separation,
ionization, and detection in comprehensive detail. For sample preparation conventional liquid-liquid extraction (LLE) and
diverse solid-phase extraction (SPE) procedures are still used most frequently. Nevertheless, during the last three years
a number of sophisticated novel methods have been introduced. Solid-phase microextraction (SPME), stir-bar-sorptive extraction
(SBSE), membrane-assisted solvent extraction (MASE), and specifically designed molecularly imprinted polymers (MIP) exhibit
high potential for frequent use in the future. Additional emphasis in this review is dedicated to the quite young history
and current progress in ionization and MS detection of OPCs. The number of relevant published LC-MS reports has tripled in
the last five years. This is especially due to the proliferating use of electrospray ionization (ESI), nowadays an indispensable
and reliable tool for LC-MS coupling. LC-MS is becoming an appropriate complementary or replacement method for the more traditional
GC-MS methods, and not only for non-volatile, hydrophilic, and ionic OPCs. The last section of this review covers recent approaches
for verification of OPC poisoning. LC-MS-MS detection of phosphylated peptides generated from inhibited circulating serum
butyrylcholinesterase (BChE) by valuable proteomics techniques enables proof of intoxication on the molecular level. Therefore,
this review gives a comprehensive overview on the status quo of LC-MS-based OPC analysis in respect of both technical progress
and relevant applications.
相似文献