Chemosensory performance of molecularly imprinted fluorescent conjugated polymer materials

Fluorescent conjugated polymers are an attractive basis for the design of low detection limit sensing devices owing to their intrinsic signal amplification capability. A simple and universal method to rationally control or fine-tune the chemodetection selectivity of conjugated polymer materials toward a desired analytical target would further benefit their applications. In a quest of such a method we investigated a general approach to cross-linked molecularly imprinted fluorescent conjugated polymer (MICP) materials that possess an intrinsic capability for signal transduction and have potential to enhance selectivity and sensitivity of sensor devices based on conjugated polymers. To study these capabilities, we prepared an MICP material for the detection of 2,4,6-trinitrotoluene and related nitroaromatic compounds. We found the imprinting effect in this material to be based on analyte shape/size recognition being substantial and generally overcoming other competing thermodynamically determined trends. The described molecularly imprinted fluorescent conjugated polymers show remarkable air stability and photostability, high fluorescence quantum yield, and reversible analyte binding and therefore are advantageous for sensing applications due to the ability to "preprogram" their detection selectivity through a choice of an imprinted template.     

Molecularly imprinted polymers for chemical agent detection in multiple water matrices

In the past few years concerns over the possibility of terrorist actions against domestic and military water supplies has become paramount. Antibodies, peptides, and enzymes have been used as molecular recognition elements in chemical sensors; however, such devices often have storage and operational stability issues that limits their success. Molecularly imprinted polymers (MIPs), have been successfully demonstrated an alternative in pesticide applications [A.L. Jenkins, R. Yin, J.J. Jensen, Analyst 126 (2001) 798-802]. The MIP materials possess selective molecular recognition properties that are complementary to the analyte in the shape and positioning of functional groups. These polymers have high selectivity and affinity constants while maintaining excellent thermal and mechanical stability. In this study, direct imprinting of chemical agents EA2192, VX, sarin, and soman (the “G” agents), was performed and the limits of detection calculated. The ability of these sensors to work in various water matrices including tap, deionized and reverse osmosis water with residual chlorine was also evaluated. Typical detection limits for these MIP sensors are approximately 50 ppt with wide linear dynamic ranges (ppt-ppm). Sensor response time is approximately 15 min.     

State‐of‐the‐art applications of cyclodextrins as functional monomers in molecular imprinting techniques: a review

As a versatile tool in separation science, cyclodextrins and their derivatives, known as emerging functional monomers, have been used extensively in molecular imprinting techniques. The attributes of cyclodextrins and their derivatives are widely known to form host–guest inclusion complex processes between the polymer and template. The exploitation of the imprinting technique could produce a product of molecularly imprinted polymers, which are very robust with long‐term stability, reliability, cost‐efficiency, and selectivity. Hence, molecularly imprinted polymers have gained popularity in chemical separation and analysis. Molecularly imprinted polymers containing either cyclodextrin or its derivatives demonstrate superior binding effects for a target molecule. As noted in the previous studies, the functional monomers of cyclodextrins and their derivatives have been used in molecular imprinting for selective separation with a wide range of chemical compounds, including steroidals, amino acids, polysaccharides, drugs, plant hormones, proteins, pesticides, and plastic additives. Therefore, the main goal of this review is to illustrate the exotic applications of imprinting techniques employing cyclodextrins and their derivatives as single or binary functional monomers in synthesizing molecularly imprinted polymers in areas of separation science by reviewing some of the latest studies reported in the literature.     

Recent advances in molecular imprinting technology: current status, challenges and highlighted applications

Molecular imprinting technology (MIT) concerns formation of selective sites in a polymer matrix with the memory of a template. Recently, molecularly imprinted polymers (MIPs) have aroused extensive attention and been widely applied in many fields, such as solid-phase extraction, chemical sensors and artificial antibodies owing to their desired selectivity, physical robustness, thermal stability, as well as low cost and easy preparation. With the rapid development of MIT as a research hotspot, it faces a number of challenges, involving biological macromolecule imprinting, heterogeneous binding sites, template leakage, incompatibility with aqueous media, low binding capacity and slow mass transfer, which restricts its applications in various aspects. This critical review briefly reviews the current status of MIT, particular emphasis on significant progresses of novel imprinting methods, some challenges and effective strategies for MIT, and highlighted applications of MIPs. Finally, some significant attempts in further developing MIT are also proposed (236 references).     

分子印迹-电化学发光技术研究进展

分子印迹-电化学发光技术具有分子印迹技术的高选择性及电化学发光技术的高灵敏性,以及发光易于调控、稳定性好、便于微型化和仪器操作简单等优点,已被广泛地应用于重金属检测、免疫传感技术、基因传感技术、酶传感技术、食品安全与药物分析等领域。该文结合本实验室的研究工作介绍了分子印迹电化学发光传感器的原理和构建思路。在此基础上,着重介绍了分子印迹电化学发光技术在食品安全与药物分析中的应用,并对其今后的研究趋势进行了展望。     

分子印迹-仿生传感器的研究进展

分子印迹技术是制备具有选择性分子识别能力聚合物(分子印迹聚合物)的新兴化学合成技术。分子印迹聚合物的一个重要应用是在生物传感器中取代生物分子作为识别元件,研制耐受性强、低成本的分子印迹仿生传感器。综述了分子印迹技术的基本原理及其在仿生传感器方面的应用研究现状,并对分子印迹仿生传感器的发展前景进行了评述。引用文献24篇。     

Nanotemplating for two-dimensional molecular imprinting

A new 2D molecular imprinting technique based on nanotemplating and soft-lithography techniques is reported. This technique allows the creation of target-specific synthetic recognition sites on different substrates using a uniquely oriented and immobilized template and the attachment of a molecularly imprinted polymer on a substrate. The molecularly imprinted polymer was characterized by AFM, fluorescence microscopy, and ATR-FTIR. We evaluated the rebinding ability of the sites with theophylline (the target molecule). The selectivity of the molecularly imprinted polymer was determined for the theophylline-caffeine couple. The molecularly imprinted polymer exhibited selectivity for theophylline, as revealed by competitive rebinding experiments. Fluorescence microscopy experiments provided complementary proof of the selectivity of the molecularly imprinted polymer surfaces toward theophylline. These selective molecularly imprinted polymers have the potential for chemical sensor applications. Because of its 2D nature, this novel chemical sensor technology can be integrated with many existing high-sensitivity multichannel detection technologies.     

Bovine serum albumin surface imprinted polymer fabricated by surface grafting copolymerization on zinc oxide rods and its application for protein recognition

A novel bovine serum albumin (BSA) surface imprinted polymer based on ZnO rods was synthesized by surface grafting copolymerization. It exhibited an excellent recognition performance to bovine serum albumin. The adsorption capacity and imprinting factor of bovine serum albumin could reach 89.27 mg/g and 2.35, respectively. Furthermore, the fluorescence property of ZnO was used for tracing the process of protein imprinting and it implied the excellent optical sensing property of this material. More importantly, the hypothesis that the surface charge of carrier could affect the imprinting process was confirmed. That is, ZnO with positive surface charge could not only improve the recognition specificity of binding sites to template proteins (pI < 7), but also deteriorate the bindings between sites and non‐template proteins (pI > 7). It was also important that the reusability of ZnO@BSA molecularly imprinted polymers was satisfactory. This implied that the poor mechanical/chemical stability of traditional zinc oxide sensors could be solved by the introduction of surface grafting copolymerization. These results revealed that the ZnO@BSA molecularly imprinted polymers are a promising optical/electrochemical sensor element.     

Electrochemical sensing with electrodes modified with molecularly imprinted polymer films

This article summarises our work on the development of voltammetric sensors based on molecularly imprinted polymers. Several recognition elements and integration strategies were used:1.membranes electropolymerised at the electrode surface; 2.casting of polymeric membranes by drop-coating a solution of pre-formed polymer (polyphosphazene) and template in a low-boiling-point solvent on to the electrode surface; 3.preparation of composite membranes containing conductive material (graphite or carbon black), acrylic-type molecularly imprinted polymers (small particle size), and PVC as binder; and 4.in-situ polymerisation of a thin layer of acrylic imprinted polymer deposited on the electrode surface by spin coating.All the options evaluated offer the possibility of controlling electrode characteristics such as hydrophobic/hydrophilic character, permeability, or film thickness, which are essential for obtaining good sensor performance.     

A two‐step strategy to visually identify molecularly imprinted polymers for tagged proteins

A practical and relatively simple method to identify molecularly imprinted polymers capable of binding proteins via the molecular tagging (epitope‐like) approach has been developed. In our two‐step method, we first challenge a previously obtained anti‐tag molecularly imprinted polymer with a small molecule including the said tag of choice (a biotin derivative as shown here or other) connected to a linker bound to a second biotin moiety. An avidin molecule partially decorated with fluorescent labels is then allowed to bind the available biotin derivative associated with the polymer matrix. At the end of this simple process, and after washing off all the low‐affinity binding molecules from the polymer matrix, only suitable molecularly imprinted polymers binding avidin through its previously acquired small molecule tag (or epitope‐like probe, in a general case) will remain fluorescent. For confirmation, we tested the selective performance of the anti‐biotin molecularly imprinted polymer binding it to biotinylated alkaline phosphatase. Residual chemical activity of the enzyme on the molecularly imprinted polymer solid support was observed. In all cases, the corresponding nonimprinted polymer controls were inactive.     

Molecularly Imprinted Polymers Combined with Electrochemical Sensors for Food Contaminants Analysis

Detection of relevant contaminants using screening approaches is a key issue to ensure food safety and respect for the regulatory limits established. Electrochemical sensors present several advantages such as rapidity; ease of use; possibility of on-site analysis and low cost. The lack of selectivity for electrochemical sensors working in complex samples as food may be overcome by coupling them with molecularly imprinted polymers (MIPs). MIPs are synthetic materials that mimic biological receptors and are produced by the polymerization of functional monomers in presence of a target analyte. This paper critically reviews and discusses the recent progress in MIP-based electrochemical sensors for food safety. A brief introduction on MIPs and electrochemical sensors is given; followed by a discussion of the recent achievements for various MIPs-based electrochemical sensors for food contaminants analysis. Both electropolymerization and chemical synthesis of MIP-based electrochemical sensing are discussed as well as the relevant applications of MIPs used in sample preparation and then coupled to electrochemical analysis. Future perspectives and challenges have been eventually given.     

Monodisperse restricted access material with molecularly imprinted surface for selective solid‐phase extraction of 17β‐estradiol from milk

In this study, novel monodisperse restricted access media‐molecularly imprinted polymers were successfully prepared by surface initiated reversible addition‐fragmentation chain transfer polymerization using monodisperse crosslinked poly (glycidyl methacrylate‐co‐ethylene glycol dimethacrylate) microspheres as the carrier and acryloyl chloride‐modified β‐cyclodextrin as the hydrophilic functional monomer. The surface morphology, protein exclusion, and adsorption properties of the molecularly imprinted polymers were investigated. The results show that the material has excellent monodispersity and hydrophilicity, and simultaneously exhibit high adsorption capacity, fast binding kinetics, high selectivity, and significant thermal stability. The molecularly imprinted polymers as dispersive solid‐phase extraction adsorbent combined with reversed‐phase high‐performance liquid chromatography was used to selectively enrich, separate, and analyze trace 17β‐estradiol in milk samples. The recovery of 17β‐estradiol is 88–95% with relative standard deviation of <4%, and the limits of detection and quantification of this method are 2.08 and 9.29 µg/L, respectively. The novel restricted access media‐molecularly imprinted polymer adsorbents provide an effective method for the selective extraction and detection of 17β‐estradiol directly from complex samples.     

Recent advances and applications of molecularly imprinted polymers in solid‐phase extraction for real sample analysis

Sample pretreatment is essential for the analysis of complicated real samples due to their complex matrices and low analyte concentrations. Among all sample pretreatment methods, solid‐phase extraction is arguably the most frequently used one. However, the majority of available solid‐phase extraction adsorbents suffer from limited selectivity. Molecularly imprinted polymers are a type of tailor‐made artificial antibodies and receptors with specific recognition sites for target molecules. Using molecularly imprinted polymers instead of conventional adsorbents can greatly improve the selectivity of solid‐phase extraction, and therefore molecularly imprinted polymer‐based solid‐phase extraction has been widely applied to separation, clean up and/or preconcentration of target analytes in various kinds of real samples. In this article, after a brief introduction, the recent developments and applications of molecularly imprinted polymer‐based solid‐phase extraction for determination of different analytes in complicated real samples during the 2015‐2020 are reviewed systematically, including the solid‐phase extraction modes, molecularly imprinted adsorbent types and their preparations, and the practical applications of solid‐phase extraction to various real samples (environmental, food, biological, and pharmaceutical samples). Finally, the challenges and opportunities of using molecularly imprinted polymer‐based solid‐phase extraction for real sample analysis are discussed.     

基于磁性分子印迹聚合物的电化学传感器的研究进展

分子印迹聚合物与磁性纳米材料结合,制备成磁性分子印迹纳米敏感膜,这样做不仅可以发挥分子印迹聚合材料的优势,而且磁性纳米粒子可有效提高电化学传感器的灵敏度、稳定性以及生物相容性等。近年来将磁性分子印迹纳米敏感膜应用于电化学传感器制备成的磁性分子印迹电化学传感器得到了较快的发展。本文就近5年来磁性分子印迹电化学传感器敏感膜所用的磁性材料、敏感膜制备方法以及磁性分子印迹电化学传感器在环境、食品以及临床方面的应用进行了综述总结。     

分子印迹技术在样品前处理中的应用

分子印迹聚合物具有选择性高、稳定性好及制备简单的特点,可用于生物、医药、环境样品等复杂基体中痕量分析物的高选择性分离与富集,因此在样品前处理中的应用特别引人关注.本文介绍了分子印迹技术的基本原理,综述了分子印迹技术在样品前处理中应用的研究进展.     

Template synthesized molecularly imprinted polymer nanotube membranes for chemical separations

In this report, we describe the synthesis of a molecularly imprinted polymer (MIP) nanotube membrane, using a porous anodic alumina oxide (AAO) membrane by surface-initiated atom transfer radical polymerization (ATRP). The use of a MIP nanotube membrane in chemical separations gives the advantage of high affinity and selectivity. Furthermore, because the molecular imprinting technique can be applied to different kinds of target molecules, ranging from small organic molecules to peptides and proteins, such MIP nanotube membranes will considerably broaden the application of nanotube membranes in chemical separations and sensors. This report also shows that the ATRP route is an efficient procedure for the preparation of molecularly imprinted polymers. Furthermore, the ATRP route works well in its formation of MIP nanotubes within a porous AAO membrane. The controllable nature of ATRP allows the growth of a MIP nanotube with uniform pores and adjustable thickness. Thus, using the same route, it is possible to tailor the synthesis of MIP nanotube membranes with either thicker MIP nanotubes for capacity improvement or thinner nanotubes for efficiency improvement.     

In-situ polymerized molecularly imprinted polymeric thin films used as sensing layers in surface plasmon resonance sensors: Mini-review focused on 2010–2011

This review provides a short overview of polymeric thin films incorporating molecular imprints within their 3D macromolecular structure as synthetic recognition elements and prepared by in situ polymerization for surface plasmon resonance application. This review starts with a brief reminder of the principle of surface plasmon resonance detection. The second section is focused on molecularly imprinted materials. Bulk and thin film polymer formats can be obtained by free radical polymerization, where the functional monomer interacts specifically with the template and the cross-linker controls the rigidity of the imprinted cavities. Grafting polymerization is presented as a method of choice for covalent attachment of ultra-thin molecularly imprinted films on a surface plasmon resonance metallic substrate. Examples of electropolymerized thin films are also provided. In the rest of this contribution, surface plasmon resonance applications of molecularly imprinted polymers reported mainly over the last two years are presented with respect to the preparation mode. Also, applications of gold nanoparticle/molecularly imprinted polymer composites for the design of surface plasmon resonance-based sensors with enhanced sensitivity due to the phenomenon of localized surface plasmon resonance induced by the presence of gold nanoparticles are summarized.     

An optical reflected device using a molecularly imprinted polymer film sensor

A novel and highly selective optical sensor with molecularly imprinted polymer (MIP) film was fabricated and investigated. The optical sensor head employing a medium finesse molecularly imprinted polymer film has been fabricated and characterised. A blank polymer and formaldehyde imprinted polymer were using methacrylic acid as the functional monomer and the ethylene glycol dimethacrylate as a crosslinker. The transduction mechanism is discussed based on the changes of optical intensity of molecularly imprinted polymer film acting as an optical reflected sensor. Template molecules, which diffused into MIP, could cause film density, and refractive index change, and then induce measurable optical reflective intensity shifts. Based on the reflective intensity shifts, an optical reflection detection of formaldehyde was achieved by illuminating MIP with a laser beam. For the same MIP, the reflective intensity shift was proportional to the amount of template molecule. This optical sensor, based on an artificial recognition system, demonstrates long-time stability and resistance to harsh chemical environments. As the research moves forward gradually, we establish the possibilities of quantitative analysis primly, setting the groundwork to the synthesis of the molecular imprinted optical fiber sensor. The techniques show good reproducibility and sensitivity and will be of significant interest to the MIPcommunity.     

Determination of macrolide antibiotics residues in pork using molecularly imprinted dispersive solid‐phase extraction coupled with LC–MS/MS

A class‐specific macrolide molecularly imprinted polymer was synthesized by precipitation polymerization using tulathromycin as the template and methacrylic acid as the functional monomer. The polymers revealed different specific adsorption and imprinting factor for macrolides with different spatial arrangement of side chains as well as lactonic ring size. And the molecularly imprinted polymer possessed maximum adsorption capacity (54.1 mg/g) and highest imprinting factor (2.4) toward 15‐membered ring azithromycin. On the basis of molecularly imprinted polymer dispersive solid‐phase extraction, a rapid, selective, and reproducible method for simultaneous determination of seven macrolide antibiotics residues in pork was established by using liquid chromatography with tandem mass spectrometry. At spiking levels of 5, 10, 25, and 100 μg/kg, average recoveries of seven macrolides ranged from 68.6 to 95.5% with intraday and interday relative standard deviations below 8%. The limits of detection and limits of quantification were 0.2–0.5 and 0.5–2.0 μg/kg, respectively.     

分子烙印传感器的研究进展

分子烙印技术是制备具有选择性分子识别能力的聚合物的新兴技术,其应用之一是将分子烙印聚合物用作分析化学中化学传感器的识别元件。本文综述了分子烙印技术的原理方法及其在传感器方面的应用,评述了分子烙印传感器的发展方向,展望了其在有机磷化合物检测中的应用前景。