Trace-level sensing of dopamine in real samples using molecularly imprinted polymer-sensor

Induced-fit responsive dopamine (DA) imprinted polymer, poly (melamine-co-chloranil), was used as a suitable coating material for the modification of a hanging mercury drop electrode. The zwitterionic conformation of the imprinted polymer responded differential pulse, cathodic stripping voltammetric current, without any false-positive or false-negative contributions of non-specific sorptions, in aqueous environment of complex matrices. The limit of detection (3σ) of dopamine was found to be as low as 0.148 ng mL⁻¹, by the proposed sensor that could be considered a sensitive marker of dopamine depletion in Parkinson's disease (PD).     

Selective solid-phase extraction of bio- and environmental samples using molecularly imprinted polymers

Of the many applications of molecular imprinting in analytical separation science, the one with highest potential of soon being used in routine analysis is that of solid-phase extraction. Already several examples of selective pre-concentration of biological and environmental samples have been reported. The interest in imprinted extraction sorbents originates from the high selectivities and affinities obtainable, properties which can be qualitatively and quantitatively pre-determined for a particular analyte and separation by the imprinting process. This review summarises work published on molecular imprinted solid-phase extraction and discusses some imprinted-sorbent specific method development issues.     

Application of molecularly imprinted polymers to solid-phase extraction of analytes from real samples

A review is presented of recent developments in the use of molecularly imprinted polymers (MIPs) as selective materials for solid-phase extraction. Compared with traditional sorbents, MIPs can not only concentrate but also selectively separate the target analytes from real samples, which is crucial for the quantitatively determination of analytes in complex samples. Consequently, as one of the most effective sorbents, MIPs have been successfully applied to the pretreatment of analytes in foods, drugs, and biological and environmental samples in the past five years.     

Application of molecularly imprinted polymers to solid-phase extraction of analytes from real samples

A review is presented of recent developments in the use of molecularly imprinted polymers (MIPs) as selective materials for solid-phase extraction. Compared with traditional sorbents, MIPs can not only concentrate but also selectively separate the target analytes from real samples, which is crucial for the quantitatively determination of analytes in complex samples. Consequently, as one of the most effective sorbents, MIPs have been successfully applied to the pretreatment of analytes in foods, drugs, and biological and environmental samples in the past five years.     

Characterization of molecularly imprinted polymer nanoparticles by photon correlation spectroscopy

We follow template‐binding induced aggregation of nanoparticles enantioselectively imprinted against (S)‐propranolol, and the non‐imprinted ones, using photon correlation spectroscopy (dynamic light scattering). The method requires no separation steps. We have characterized binding of (R,S)‐propranolol to the imprinted polymers and determined the degree of non‐specificity by comparing the specific binding with the results obtained using non‐imprinted nanoparticles. Using (S)‐propranolol as a template for binding to (S)‐imprinted nanoparticle, and (R)‐propranolol as a non‐specific control, we have determined range of concentrations where chiral recognition can be observed. By studying aggregation induced by three analytes related to propranolol, atenolol, betaxolol, and 1‐amino‐3‐(naphthalen‐1‐yloxy)propan‐2‐ol, we were able to determine which parts of the template are involved in the specific binding, discuss several details of specific adsorption, and the structure of the imprinted site. Copyright © 2014 John Wiley & Sons, Ltd.     

Selective solid-phase extraction using molecularly imprinted polymer for analysis of methamidophos in water and soil samples

An analytical methodology for the analysis of methamidophos in water and soil samples incorporating a molecularly imprinted solid-phase extraction process using methamidophos-imprinted polymer was developed. Binding study demonstrated that the polymer exhibited excellent affinity and high selectivity to the methamidophos. Evidence was also found by FT-IR analysis that hydrogen bonding between the CO(2)H in the polymer cavities and the NH(2) and P=O of the template was the origin of methamidophos recognition. The use of molecularly imprinted solid-phase extraction improved the accuracy and precision of the GC method and lowered the limit of detection. The recovery of methamidophos extracted from a 10.0 g soil sample at the 100 ng/g spike level was 95.4%. The limit of detection was 3.8 ng/g. The recovery of methamidophos extracted from 100 mL tap and river water at 1 ng/mL spike level was 96.1% and 95.8%, and the limits of detection were 10 and 13 ng/L respectively. These molecularly imprinted solid-phase extraction procedures enabled selective extraction of polar methamidophos successfully from water and soil samples, demonstrating the potential of molecularly imprinted solid-phase extraction for rapid, selective, and cost-effective sample pretreatment.     

Determination of digoxin in serum samples using a flow-through fluorosensor based on a molecularly imprinted polymer

This work describes the development of a competitive flow-through FIA assay for digoxin using a molecularly imprinted polymer (MIP) as the recognition phase. In previous work, a number of non-covalent imprinted polymers were synthesised by “bulk” polymerisation. The digoxin binding and elution characteristics of these MIPs were then evaluated to obtain a highly selective material for integration into a sensor. The optimum MIP was synthesised by photo-initiated polymerisation of a mixture containing digoxin, MAA, EDGMA and AIBN in acetonitrile. The bulk polymer was ground and sieved and the template removed by Soxhlet extraction in MeOH/ACN. The MIP was packed into a flow cell and placed in a spectrofluorimeter to integrate the reaction and detection systems. The physical and chemical variables involved in digoxin determination by the sensor (nature and concentration of solution, flow rates, etc.) were optimised. Binding with the non-imprinted polymer (NIP) was also analysed. The new fluorosensor showed high selectivity and sensitivity, a detection limit of 1.7 × 10⁻² μg l⁻¹, and high reproducibility (R.S.D. of 1.03% and 1.77% for concentrations of 1.0 × 10⁻³ and 4.0 × 10⁻³ mg l⁻¹, respectively). Selectivity was tested by determining the cross-reactivity of several compounds with structures analogous to digoxin. Under the assay conditions used, in which the potential interfering compounds were in concentrations 100 times higher than that of the analyte, no interference was recorded. The proposed fluorosensor was successfully used to determine digoxin concentration of human serum samples.     

Solid-phase extraction of tramadol from plasma and urine samples using a novel water-compatible molecularly imprinted polymer

In this study, a novel method is described for the determination of tramadol in biological fluids using molecularly imprinted solid-phase extraction (MISPE) as the sample clean-up technique combined with high-performance liquid chromatography (HPLC). The water-compatible molecularly imprinted polymers (MIPs) were prepared using methacrylic acid as functional monomer, ethylene glycol dimethacrylate as cross-linker, chloroform as porogen and tramadol as template molecule. The novel imprinted polymer was used as a solid-phase extraction (SPE) sorbent for the extraction of tramadol from human plasma and urine. Various parameters affecting the extraction efficiency of the polymer have been evaluated. The optimal conditions for the MIP cartridges were studied. The MIP selectivity was evaluated by checking several substances with similar molecular structures to that of tramadol. The limit of detection (LOD) and limit of quantification (LOQ) for tramadol in urine samples were 1.2 and 3.5 μg L⁻¹, respectively. These limits for tramadol in plasma samples were 3.0 and 8.5 μg L⁻¹, respectively. The recoveries for plasma and urine samples were higher than 91%.     

Controlling size and uniformity of molecularly imprinted nanoparticles using auxiliary template

Molecularly imprinted nanomaterials are gaining substantial importance. As a simple and efficient synthetic method, precipitation polymerization has been used to prepare uniform molecularly imprinted microspheres for numerous template compounds. Despite of its general applicability, the difficulty of obtaining uniform particles for some difficult templates by precipitation polymerization has been reported. In this work, we attempted to produce uniform atrazine-imprinted nanoparticles using propranolol as an auxiliary template under standard precipitation polymerization condition. When propranolol was added in the prepolymerization mixture for atrazine imprinting, it displayed a significant effect on particle size and size distribution of atrazine-imprinted polymers. The molecular binding characteristics of the molecularly imprinted polymer (MIP) nanoparticles were found to be dependent on the relative ratios of the two templates. Under an optimal template propranolol-atrazine ratio of 1:3 mol/mol, very uniform imprinted nanoparticles (d(H) =?106?nm) with a polydispersity index of 0.07 were obtained. The loading of the auxiliary template (propranolol) could be reduced to as low as 5% without sacrificing the uniformity of the MIP nanoparticles. The uniform MIP nanoparticles could be easily encapsulated into polyethylene terephthalate nanofibers using a simple electrospinning technique. The composite nanofibers containing the MIP nanoparticles maintained specific molecular binding capability for both atrazine and propranolol.     

Separation and sensing based on molecular recognition using molecularly imprinted polymers

Molecular recognition-based separation and sensing systems have received much attention in various fields because of their high selectivity for target molecules. Molecular imprinting has been recognized as a promising technique for the development of such systems, where the molecule to be recognized is added to a reaction mixture of a cross-linker(s), a solvent(s), and a functional monomer(s) that possesses a functional groups(s) capable of interacting with the target molecule. Binding sites in the resultant polymers involve functional groups originating from the added functional monomer(s), which can be constructed according to the shape and chemical properties of the target molecules. After removal of the target molecules, these molecularly imprinted complementary binding sites exhibit high selectivity and affinity for the template molecule. In this article, recent developments in molecularly imprinted polymers are described with their applications as separation media in liquid chromatography, capillary electrophoresis, solid-phase extraction, and membranes. Examples of binding assays and sensing systems using molecularly imprinted polymers are also presented.     

Development of a quantum dot molecularly imprinted polymer sensor for fluorescence detection of atrazine

Atrazine is a common agricultural pesticide which has been reported to occur widely in surface drinking water, making it an environmental pollutant of concern. In the quest for developing sensitive detection methods for pesticides, the use of quantum dots (QDs) as sensitive fluorescence probes has gained momentum in recent years. QDs have attractive and unique optical properties whilst coupling of QDs to molecularly imprinted polymers (MIPs) has been shown to offer excellent selectivity. Thus, the development of QD@MIPs based fluorescence sensors could provide an alternative for monitoring herbicides like atrazine in water. In this work, highly fluorescent CdSeTe/ZnS QDs were fabricated using the conventional organometallic synthesis approach and were then encapsulated with MIPs. The CdSeTe/ZnS@MIP sensor was characterized and applied for selective detection of atrazine. The sensor showed a fast response time (5 min) upon interaction with atrazine and the fluorescence intensity was linearly quenched within the 2–20 mol L^?1 atrazine range. The detection limit of 0.80 × 10^?7 mol L^?1 is comparable to reported environmental levels. Lastly, the sensor was applied in real water samples and showed satisfactory recoveries (92–118%) in spiked samples, hence it is a promising candidate for use in water monitoring.     

Separation and screening of compounds of biological origin using molecularly imprinted polymers

Molecularly imprinted polymers (MIPs) represent a new class of materials possessing high selectivity and affinity for the target molecule. Since their discovery in 1972, molecularly imprinted polymers have attracted considerable interest from bio- and chemical laboratories to pharmaceutical institutes. They have been utilized as sensors, catalysts, sorbents for solid-phase extraction, stationary phase for liquid chromatography, mimics of enzymes, receptors and antibodies. Among which, the application of molecularly imprinted polymers for molecular recognition-based separation and screening of compounds has undergone rapid extension and received much attention in recent years. This article mainly focuses on the separation and screening of certain pharmacophoric compounds of interests from biological origin using molecular imprinting technology. Examples of extraction and recognition of active components as anti-tumors or anti-Hepatitis C virus inhibitors from Chinese traditional herbs using molecularly imprinting technology are particularized in this article. Comparison between the screening effect based on MIPs and that based on antibodies is also represented. Consequently the merits and demerits of these two technologies are highlighted.     

Composite of CdTe quantum dots and molecularly imprinted polymer as a sensing material for cytochrome c

A newly designed molecularly imprinted polymer (MIP) material was fabricated and successfully utilized as recognition element to develop a quantum dots (QDs) based MIP-coated composite for selective recognition of the template cytochrome c (Cyt). The composites were synthesized by sol-gel reaction (imprinting process). The imprinting process resulted in an increased affinity of the composites toward the corresponding template. The fluorescence of MIP-coated QDs was stronger quenched by the template versus that of non-imprinted polymer (NIP)-coated QDs, which indicated the composites could recognize the corresponding template. The results of specific experiments further exhibited the recognition ability of the composites. Under optimum conditions, the linear range for Cyt is from 0.97 μM to 24 μM, and the detection limit is 0.41 μM. The new composites integrated the high selectivity of molecular imprinting technology and fluorescence property of QDs and could convert the specific interactions between imprinted cavities and corresponding template to the obvious changes of fluorescence signal. Therefore, a simple and selective sensing system for protein recognition has been realized.     

DNA detection system using molecularly imprinted polymer as the gel matrix in electrophoresis

To develop a simple and inexpensive method for DNA detection, we prepared a molecularly imprinted polymer (MIP) for recognizing a specific double-stranded DNA (dsDNA) sequence and used it in an electrophoretic gel matrix. The MIP gel has many binding sites that are complementary in size, shape, and arrangement of functional groups of the target dsDNA sequence. During MIP gel electrophoresis (MIPGE), migration of the target dsDNA should be hindered by the capture effect of the binding sites in the MIP gel. This was confirmed by observation of deviations from the linear relationship between the migration distances of the DNA standard size markers in the polyacrylamide gel and those in the MIP gel. The migration distances of nontarget dsDNA maintained a linear relationship, however. In addition, the sequence selectivity of dsDNA in this method was investigated by using the Ha-ras gene and its point mutants. Except for A.T to T.A base pair substitution, mutant dsDNA (for example, substitution from A.T to C.G and from G.C to T.A) could be distinguished from the target (wild-type) dsDNA. Although some improvement in A.T (T.A) base pair distinction is still needed, this study is the first to demonstrate detection of a specific dsDNA sequence with MIPs and, as such, opens up a new realm for practical applications of MIPs.     

Direct detection of analyte binding to single molecularly imprinted polymer particles by confocal Raman spectroscopy

We describe the use of Raman spectroscopy to detect and quantify, for the first time, the presence of the imprinting template in single molecularly imprinted polymer microspheres. The polymers were imprinted with the β-blocking drugs propranolol and atenolol, and precipitation polymerization was used to obtain spherical particles of diameters of 200 nm and 1.5 μm. The size of the Raman laser spot being between 1 μm and a few μm, the nanoparticles were used for bulk detection whereas with micrometer-sized particles, quantitative measurements on single particles were possible. The laser power, and consequently the acquisition times, needed to be adapted as a function of the polymer and template used in order to avoid burning. Analyte quantification from Raman spectra is straightforward by determining the peak height of a typical Raman band of the analyte, and by using a typical polymer peak for normalization. Relatively low detection limits down to 1 μM have been reached for the detection of S-propranolol through bulk measurements on MIP nanoparticles.     

Surface plasmon resonance sensor using molecularly imprinted polymer for detection of sialic acid

A surface plasmon resonance (SPR) sensor using a molecularly imprinted polymer-coated sensor chip for the detection of sialic acid was developed. The thinly coated polymer was prepared by co-polymerizing N,N,N-trimethylaminoethyl methacrylate, 2-hydroxyethyl methacrylate and ethyleneglycol dimethacrylate in the presence of p-vinylbenzeneboronic acid ester with sialic acid. The sensor showed a selective response to ganglioside of which sialic acid is located at the non-reducing end and gave a linear relationship from 0.1 to 1.0 mg of ganglioside.     

Preparation and evaluation of a molecularly imprinted polymer for the selective recognition of testosterone--application to molecularly imprinted sorbent assays

Biomimetic testosterone receptors were synthesized via molecular imprinting for use as antibody mimics in immunoassays. As evaluated by radioligand binding assays, imprinted polymers prepared in acetonitrile were very specific for testosterone because the nonimprinted control polymers bound virtually no radiolabeled testosterone. The polymers present an appreciable affinity, with association constants of K(a) = 3.3 x 10(7) M(- 1) (high-affinity binding sites). The binding characteristics of the polymers were also evaluated in aqueous environment to study their viabilities as alternatives to antibodies in molecularly imprinted sorbent assays. Compared with the testosterone-specific antibodies present in commercial kits, our molecularly imprinted polymers are somewhat less sensitive but show a high selectivity.     

In situ synthesis of molecularly imprinted nanoparticles in porous support membranes using high-viscosity polymerization solvents

There is a growing need in membrane separations for novel membrane materials providing selective retention. Molecularly imprinted polymers (MIPs) are promising candidates for membrane functionalization. In this work, a novel approach is described to prepare composite membrane adsorbers incorporating molecularly imprinted microparticles or nanoparticles into commercially available macroporous filtration membranes. The polymerization is carried out in highly viscous polymerization solvents, and the particles are formed in situ in the pores of the support membrane. MIP particle composite membranes selective for terbutylazine were prepared and characterized by scanning electron microscopy and N? porosimetry. By varying the polymerization solvent microparticles or nanoparticles with diameters ranging from several hundred nanometers to 1 μm could be embedded into the support. The permeability of the membranes was in the range of 1000 to 20,000 Lm?2 hr?1 bar?1. The imprinted composite membranes showed high MIP/NIP (nonimprinted polymer) selectivity for the template in organic media both in equilibrium-rebinding measurements and in filtration experiments. The solid phase extraction of a mixture of the template, its analogs, and a nonrelated compound demonstrated MIP/NIP selectivity and substance selectivity of the new molecularly imprinted membrane. The synthesis technique offers a potential for the cost-effective production of selective membrane adsorbers with high capacity and high throughput.     

Enantioselective separation and electrochemical sensing of D- and L-tryptophan at ultratrace level using molecularly imprinted micro-solid phase extraction fiber coupled with complementary molecularly imprinted polymer-fiber sensor

Highly efficient enantioselective separation and quantitative recoveries of D- and L-tryptophan in aqueous and real samples can be achieved, with a monolithic molecularly imprinted polymeric fiber that serves both for micro-solid phase extraction and ultratrace sensing, without any false-positive (non-specific) contribution and cross-reactivity, in the range of 0.15-30.00 ng mL(-1) with detection limit as low as 0.0261 ng mL(-1) (relative standard deviation=0.64%, signal/noise=3). The proposed method combining molecularly imprinted micro-solid phase extraction fiber and a complementary molecularly imprinted polymer-carbon composite fiber sensor is proven to be useful for clinical diagnosis of stress-related diseases caused by acute tryptophan depletion.