Molecularly Imprinted Polymer Research Articles

Innovative Solid-Phase Extraction Strategies for Improving the Advanced Chromatographic Determination of Drugs in Challenging Biological Samples

In the past few decades, considerable scientific strides have been made in the subject of drug analysis in human biological samples. However, the risk caused by incorrect drug plasma levels in patients still remains an important concern. This review paper attempts to investigate the advances made over the last ten years in common sample preparation techniques (SPT) for biological samples based on solid sorbents, including solid-phase extraction (SPE) and solid-phase micro-extraction (SPME), and in particular in the field of molecularly imprinted polymers (MIPs), including non-stimuli-responsive and stimuli-responsive adsorbents. This class of materials is known as ‘smart adsorbents’, exhibiting tailored responses to various stimuli such as magnetic fields, pH, temperature, and light. Details are provided on how these advanced SPT are changing the landscape of modern drug analysis in their coupling with liquid chromatography-mass spectrometry (LC-MS) analytical techniques, a general term that includes high-performance liquid chromatography (HPLC) and ultra-high performance liquid chromatography (UHPLC), as well as any variation of MS, such as tandem (MS/MS), multiple-stage (MSn), and high-resolution (HRMS) mass spectrometry. Some notes are also provided on coupling with less-performing techniques, such as high-performance liquid chromatography with ultraviolet (HPLC-UV) and diode array detection (HPLC-DAD) detection. Finally, we provide a general review of the difficulties and benefits of the proposed approaches and the future prospects of this research area.

Plant-based zinc nanoflowers assisted molecularly imprinted polymer for the design of an electrochemical sensor for selective determination of abrocitinib

The first electrochemical sensor application in the literature is described for the sensitive and selective determination of the selective Janus kinase (JAK)-1 inhibitor abrocitinib (ABR). ABR is approved by the U.S. Food and Drug Administration (FDA) for the treatment of atopic dermatitis. The molecularly imprinted polymer (MIP)-based sensor was designed to incorporate zinc nanoflower (ZnNFs)-graphene oxide (GO) conjugate (ZnNFs@GO), synthesized from the root methanolic extract (RME) of the species Alkanna cappadocica Boiss. et Bal. to improve the porosity and effective surface area of the glassy carbon electrode (GCE). Furthermore, the MIP structure was prepared using ABR as a template molecule, 4-aminobenzoic acid (4-ABA) as a functional monomer, and other additional components. Scanning electron microscopy (SEM), X-ray diffraction (XRD), and Fourier transform infrared spectroscopy (FTIR) were used to characterize the surface and structure of the synthesized nanomaterial and MIP-based surface. Among the electrochemical methods, cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) were preferred for detailed electrochemical characterization, and differential pulse voltammetry (DPV) was preferred for all other electrochemical measurements using 5.0 mM [Fe(CN)6]3–/4– solution as the redox probe. The MIP-based sensor, which was the result of a detailed optimization phase, gave a linear response in the 1.0 × 10–13 – 1.0 × 10–12 M range in standard solution and serum sample. The obtained limit of detection (LOD) and limit of quantification (LOQ) values and recovery studies demonstrated the sensitivity, accuracy, and applicability of the sensor. Selectivity, the most important feature of the MIP-based sensor, was verified by imprinting factor calculations using ibrutinib, ruxolitinib, tofacitinib, zonisamide, and acetazolamide.Graphical

Raman spectroscopy‐based molecularly imprinted polymer sensor for sensitive detection of lysophosphatidic acid in serum

AbstractLysophosphatidic acid (LPA) has significant potential as a biomarker for diagnosis of ovarian cancer in female patients because it is present throughout all phases of the illness. Regrettably, there is not a clinically useful test for this biomarker yet. In this work, an ultra‐detection of LPA molecule by Raman spectroscopy‐based molecularly imprinted polymer (MIP) in serum samples is reported. β‐CD was synthesized to facilitate the collection of Raman spectroscopy and combined with MIP to denote it as β‐CD‐MIP for the adsorption of LPA with high sensitivity and selectivity. Linear regression model in serum samples shows peaks at 1100 and 1116 cm−1, respectively. A satisfactory linear fit was seen with LPA concentration log I = 3.7 log C + 1255.74 and with spiked serum log I = 4.6 log C + 327.22, respectively. The literature survey suggests the threshold LPA level in healthy person is 1.50 μM/L whereas the LPA level rises in patients with benign ovarian cancer tumor as 7.90 μM/L. This LPA level rises to 16.99 μM/L in ovarian cancer patients. On the basis of the band intensity, the limit of detection of the β‐CD‐MIP sensor for LPA was recorded as 0.003 μM/L. The binding constant of β‐CD‐MIP for LPA in serum was 0.031–0.003 μM/L, respectively. β‐CD‐MIP gel was optimized, characterized, and successfully applied on spiked serum samples. The findings of this research show that this substrate has a lot of potential for ultradetection of trace amounts of LPA molecule from the serum samples. The MIP sensor is robust, recyclable, efficient, and selective.

Molecularly Imprinted Polymer Biosensor Based on Nitrogen-Doped Electrochemically Exfoliated Graphene/Ti3 CNTX MXene Nanocomposite for Metabolites Detection.

Rapid and accurate quantification of metabolites in different bodily fluids is crucial for a precise health evaluation. However, conventional metabolite sensing methods, confined to centralized laboratory settings, suffer from time-consuming processes, complex procedures, and costly instrumentation. Introducing the MXene/nitrogen-doped electrochemically exfoliated graphene (MXene@N-EEG) nanocomposite as a novel biosensing platform in this work addresses the challenges associated with conventional methods, leveraging the concept of molecularly imprinted polymers (MIP) enables the highly sensitive, specific, and reliable detection of metabolites. To validate our biosensing technology, we utilize agmatine as a significant biologically active metabolite. The MIP biosensor incorporates electrodeposited Prussian blue nanoparticles as a redox probe, facilitating the direct electrical signaling of agmatine binding in the polymeric matrix. The MXene@N-EEG nanocomposite, with excellent metal conductivity and a large electroactive specific surface area, effectively stabilizes the electrodeposited Prussian blue nanoparticles. Furthermore, increasing the content of agmatine-imprinted cavities on the electrode enhances the sensitivity of the MIP biosensor. Evaluation of the designed MIP biosensor in buffer solution and plasma samples reveals a wide linear concentration range of 1.0 nM-100.0 μM (R2 = 0.9934) and a detection limit of 0.1 nM. Notably, the developed microfluidic biosensor offers low cost, rapid response time to the target molecule (10 min of sample incubation), good recovery results for detecting agmatine in plasma samples, and acceptable autonomous performance for on-chip detection. Moreover, its high reliability and sensitivity position this MIP-based biosensor as a promising candidate for miniaturized microfluidic devices with the potential for scalable production for point-of-care applications.

Preparation of a Molecularly Imprinted Polymer on Polyethylene Terephthalate Platform Using Reversible Addition-Fragmentation Chain Transfer Polymerization for Tartrazine Analysis via Smartphone

This work describes the preparation of a molecularly imprinted polymer (MIP) platform on polyethylene terephthalate (MIP-PET) via RAFT polymerization for analyzing tartrazine using a smartphone. The MIP-PET platform was characterized using Fourier transform infrared (FTIR) techniques, Raman Spectroscopy, X-ray photoelectron spectroscopy (XPS), and confocal microscopy. The optimal pH and adsorption time conditions were determined. The adsorption capacity of the MIP-PET plates with RAFT treatment (0.057 mg cm−2) was higher than that of the untreated plates (0.028 mg cm−2). The kinetic study revealed a pseudo-first-order model with intraparticle diffusion, while the isotherm study indicated a fit for the Freundlich model. Additionally, the MIP-PET demonstrated durability by maintaining its adsorption capacity over five cycles of reuse without significant loss. To quantify tartrazine, images were captured using a smartphone, and the RGB values were obtained using the ImageJ® free program. A partial least squares regression (PLS) was performed, obtaining a linear range of 0 to 7 mg L−1 of tartrazine. The accuracy of the method was 99.4% (4.97 ± 0.74 mg L−1) for 10 samples of 5 mg L−1. The concentration of tartrazine was determined in two local soft drinks (14.1 mg L−1 and 16.5 mg L−1), with results comparable to the UV–visible spectrophotometric method.

Ultrasensitive detection of chlortetracycline in animal-origin food using molecularly imprinted electrochemical sensor based on SnS2/ZnCo-MOF and AuNPs

The chlortetracycline (CTC) residue in food poses a threat to human health. Therefore, developing sensitive, convenient and selective analytical methods for CTC detection is crucial. This study innovatively uses tin disulfide/bimetallic organic framework (SnS2/ZnCo-MOF) nanocomposites in conjunction with gold nanoparticles (AuNPs) to co-modify a glassy carbon electrode (GCE). Further, a molecularly imprinted polymer (MIP)-based electrochemical sensing platform Au-MIP/SnS2/ZnCo-MOF/Au/GCE (AZG) was fabricated for selective CTC detection. SnS2/ZnCo-MOF enhanced the stability and surface area of the AZG sensor. The presence of AuNPs facilitated electron transport between the probe and the electrode across the insulating MIP layer. The fixation of AuNPs and MIP via electropolymerization enhanced the selective recognition of this sensor and amplified its output signal. The AZG sensor demonstrated a wide linear detection range (0.1–100 μM), low detection limit (0.072 nM), and high sensitivity (0.830 μA μM−1). It has been used for detecting CTC in animal-origin food with good recovery (96.08%–104.60%).

Self-powered sandwich-type dual-mode sensor built on open bipolar electrode

Here, we developed a self-powered bipolar electrode (SP-BPE) based dual-mode sensor with electrochromic (EC) and photoelectrochemical (PEC) techniques for the visualized and sensitive detection of bisphenol A (BPA). An open BPE with the molecularly imprinted polymers (MIPs) modified electron injection area and the Prussian blue (PB) coated electrochromic area was fabricated on an indium tin oxide (ITO) glass. A kind of Zr-based metal-organic framework (UiO-66) coated TiO2 heterojunction (TiO2@UiO-66) was used for aptamer (Apt) immobilization and electron generation. BPA was selectively accumulated by MIPs, and subsequently recognized TiO2@UiO-66-Apt quantitatively, resulting in the formation of MIPs/BPA/Apt-TiO2@UiO-66 “sandwich” structure. Under UV-light, electrons were generated from the captured TiO2@UiO-66. For EC visualization measurements, electrons were injected into the PB film, causing a color change without an external power source. The extent of color change was proportional to the number of generated electrons, which correlated with the amount of captured BPA within a concentration range of 10−6–10−11 M. This allowed for the semi-quantification of BPA by naked eyes. For PEC detection, the BPE was used as the working electrode in a three-electrode system. The generated photocurrents signals could be digitally output for BPA with the concentrations ranging from 10−5 to 10−11 M. The SP-BPE sensors showed low background signal, improved selectivity and anti-interference abilities, and have demonstrated excellent performance in quantitative BPA analysis in water samples. They are particularly useful in scenarios where traditional power sources are limited or unavailable, and they offer opportunities for sustainable and environmentally friendly target detection.

Research Progress on Molecularly Imprinted Materials for the Screening and Identification of Organic Pollutants

Organic pollutants, distinguished by their persistence and bioaccumulation in the environment, pose significant ecological and health threats that surpass those of traditional pollutants. Crucial to understanding their environmental behavior, health risks, and mitigation strategies, is the screening and identification of these pollutants. This process indispensably employs functional materials, among which molecularly imprinted polymers (MIPs) prove to be particularly advantageous because of their specific recognition capabilities and extensive application range. This review presents cutting-edge techniques and strategies for the fabrication of MIPs, including surface imprinting techniques and dummy molecular strategies. It encapsulates the last five years’ advancements in MIP research within the domains of sample pretreatment, as well as optical and electrochemical sensing analysis. The objective of this discourse is to potentially foster the evolution of MIP technology and establish the groundwork for its transition from lab-scale to commercial production.

Design of molecularly imprinted polymers (MIP) using computational methods: A review of strategies and approaches

AbstractThis paper focuses on the computationally assisted design of molecularly imprinted polymers (MIP), emphasizing the selected strategies and chosen methods of approach. In summary, this paper provides an overview of the MIP fabrication procedure, focusing on key factors and challenges, where the fabrication of MIP includes a step‐by‐step process with extensive experimental procedures. This brings challenges in optimizing experimental conditions, such as the selection of monomer, cross‐linker, and their relevant molar ratios to the template and solvent. Next, the principles of computational methods are elucidated to explore their potential applicability in solving the challenges. The computational approach can tackle the problems and optimize the MIP's design. Finally, the atomistic, quantum mechanical (QM), and combined methods in the recent research studies are overviewed with stress on strategies, analyses, and results. It is demonstrated that optimization of pre‐polymerization mixture by employing simulations significantly reduces the trial‐and‐error experiments. Besides, higher selectivity and sensitivity of MIP are observed. The polymerization and resulting binding sites by computational methods are considered. Several models of binding sites are formed and analyzed to assess the affinities representing the sensitivity and selectivity of modeled cavities. Combined QM/atomistic methods showed more flexibility and versatility for realistic modeling with higher accuracy. This methodological advancement aligns with the principles of green chemistry, offering cost‐effective and time‐efficient solutions in MIP design.This article is categorized under: Structure and Mechanism > Molecular Structures Structure and Mechanism > Computational Materials Science Molecular and Statistical Mechanics > Molecular Interactions

Reagent-Free Lactate Detection Using Prussian Blue and Electropolymerized-Molecularly Imprinted Polymers-Based Electrochemical Biosensors.

Sweat lactate, a promising biomarker for assessing physical performance and health conditions, calls for noninvasive, convenient, and affordable detection methods. This study leverages molecularly imprinted polymers (MIPs) as a synthetic biorecognition element for lactate detection due to their affordability and high stability. Traditional MIPs-based electrochemical sensors often require external redox probes such as ferricyanide/ferrocyanide in the solution to signal the binding between analytes and MIPs, which restricts their applicability. To address this, our study introduces an innovative approach utilizing a layer of Prussian blue (PB) nanoparticles as the internal redox probe on screen-printed carbon electrodes (SPCE), followed by a layer of electropolymerized MIP (eMIP) for molecular recognition, enabling reagent-free lactate detection. The real-time growth of eMIP and the processes of template elution and lactate rebinding were examined and validated using electrochemical surface plasmon resonance (EC-SPR) spectroscopy. The sensor's performance was thoroughly investigated using Differential Pulsed Voltammetry (DPV) and Electrochemical Impedance Spectroscopy (EIS) with samples spiked in 0.1 M KCl solution and artificial sweat. The developed sensors demonstrated a fast and selective response to lactate, detecting concentrations from 1 to 35 mM with a Limit of Detection (LOD) of 0.20 mM, defined by a signal-to-noise ratio of 3 in the DPV measurements. They also exhibited excellent reproducibility, reusability, and a shelf life of up to 10 months under ambient conditions. These eMIP/PB/SPCE-based lactate sensors show considerable potential as point-of-care (POC) devices for sweat lactate detection, and the technology could be adapted for reagent-free detection of a broad spectrum of molecules.

High selectivity and anti-interference molecularly imprinted polymer based on spheroidal carbonized polymer dots for effective sulfadiazine sodium removal

Although several methods for enhancing the selectivity of molecularly imprinted polymers (MIPs) have been reported, their effects on complex substrates remain unsatisfactory. In this study, a customised 1-vinyl-3-hydroxyethylimidazolium tetrafluoroborate ionic liquid with a vinyl double bond polymerizable unit and an F-atom recognition unit was employed as a precursor carbon source to prepare unique spherical carbonised polymer dots (CPDs-F) through an incomplete carbonisation process using the one-step hydrothermal method. Then used it as a novel functional monomer, sulfadiazine sodium (SDS), as a template to synthesize the SDS-imprinted material CPDs-F@MIP in aqueous media. The results indicated that the obtained CPDs-F@MIP exhibited excellent selectivity for the template, with an imprinting factor of up to 6.39, surpassing that of the MIPs prepared with chain functional monomers 2.12–4.76 times. The selective adsorption of the template molecule, SDS (selectivity coefficient: approximately 2.615–43.149), was not significantly influenced by the coexistence of contaminants with various structural characteristics. The maximum adsorption capacity reached 61.06 mg g−1. After at least twenty applications, the adsorption capability of CPDs-F@MIP did not decrease significantly. Finally, the prepared CPDs-F@MIP were used as solid-phase extraction adsorbents in combination with high-performance liquid chromatography, and the anti-interference ability and selective adsorption performance of CPDs-F@MIP in six actual water samples were investigated. Additionally, an accurate, reliable method for detecting SDS in environmental water and poultry food was established (limit of detection of 0.2 μg L−1, and the recoveries ranged from 91.79 % to 111.32 %). Imprinting materials prepared using spherical functional monomers significantly enhance their selective recognition ability in complex media and provide new ideas for the preparation and application of novelty imprinting materials with superior performance.

An ultra-selective and non-enzymatic colorimetric sensor based on imprinted polymer for ephedrine assay in urine samples

A novel non-enzymatic, rapid, and portable molecularly imprinted polymer (MIP)-based colorimetric sensor was developed for ephedrine (EPD) assay in urine samples. The EPD-imprinted polymer was provided via the precipitation polymerization method and applied to fabricate an EPD colorimetric sensor utilizing the carbon disulfide and Cu2+ reagents. The calibration curve for different concentrations of EPD was obtained using the captured images on a cell smartphone and associated RGB data. Some effective parameters including pH of the EPD extraction, time of data collection after adding the reagents, and reagents sequence were investigated and optimized. The selectivity of the sensor was studied using different similar structural compounds, which proved the favorable capability of this method for the selective determination of EPD. This sensor platform with a relatively wide linear calibration range (1-100μM), and the detection limit of 0.6μM represents the efficient, reliable, and easy approach for EPD assay in urine samples.

An Innovative Approach for Tailoring Molecularly Imprinted Polymers for Biosensors—Application to Cancer Antigen 15-3

This work presents a novel approach for tailoring molecularly imprinted polymers (MIPs) with a preliminary stage of atom transfer radical polymerization (ATRP), for a more precise definition of the imprinted cavity. A well-defined copolymer of acrylamide and N,N′-methylenebisacrylamide (PAAm-co-PMBAm) was synthesized by ATRP and applied to gold electrodes with the template, followed by a crosslinking reaction. The template was removed from the polymer matrix by enzymatic/chemical action. The surface modifications were monitored via electrochemical impedance spectroscopy (EIS), having the MIP polymer as a non-conducting film designed with affinity sites for CA15-3. The resulting biosensor exhibited a linear response to CA15-3 log concentrations from 0.001 to 100 U/mL in PBS or in diluted fetal bovine serum (1000×) in PBS. Compared to the polyacrylamide (PAAm) MIP from conventional free-radical polymerization, the ATRP-based MIP extended the biosensor’s dynamic linear range 10-fold, improving low concentration detection, and enhanced the signal reproducibility across units. The biosensor demonstrated good sensitivity and selectivity. Overall, the work described confirmed that the process of radical polymerization to build an MIP material influences the detection capacity for the target substance and the reproducibility among different biosensor units. Extending this approach to other cancer biomarkers, the methodology presented could open doors to a new generation of MIP-based biosensors for point-of-care disease diagnosis.

Chronopotentiometric Nanopore Sensor Based on a Stimulus-Responsive Molecularly Imprinted Polymer for Label-Free Dual-Biomarker Detection.

The development of sensors for detection of biomarkers exhibits an exciting potential in diagnosis of diseases. Herein, we propose a novel electrochemical sensing strategy for label-free dual-biomarker detection, which is based on the combination of stimulus-responsive molecularly imprinted polymer (MIP)-modified nanopores and a polymeric membrane chronopotentiometric sensor. The ion fluxes galvanostatically imposed on the sensing membrane surface can be blocked by the recognition reaction between the target biomarker in the sample solution and the stimulus-responsive MIP receptor in the nanopores, thus causing a potential change. By using two external stimuli (i.e., pH and temperature), the recognition abilities of the stimulus-responsive MIP receptor can be effectively modulated so that dual-biomarker label-free chronopotentiometric detection can be achieved. Using alpha fetoprotein (AFP) and prostate-specific antigen (PSA) as model biomarkers, the proposed sensor offers detection limits of 0.17 and 0.42 ng/mL for AFP and PSA, respectively.

Urinary biomonitoring of fuel ether oxygenates using a needle trap device packed with a novel molecularly imprinted polymer surface modified Zeolite Y

This study introduces an innovative needle trap device (NTD) featuring a molecularly imprinted polymer (MIP) surface-modified Zeolite Y. The developed NTD was integrated with gas chromatography-flame ionization detector (GC-FID) and employed for analysis of fuel ether oxygenates (methyl tert‑butyl ether, MTBE, ethyl tert‑butyl ether, ETBE, and tert‑butyl formate, TBF) in urine samples. To optimize the key experimental variables including extraction temperature, extraction time, salt concentration, and stirring speed, a central composite design-response surface methodology (CCD-RSM) was employed. The optimal values for extraction in the study were found to be 51.2 °C extraction temperature, 46.2 min extraction time, 27 % salt concentration, and 620 rpm stirring speed. Under the optimized conditions, the calibration curves demonstrated excellent linearity within the range of 0.1–100 μg L−1, with correlation coefficients (R2) exceeding 0.99. The limits of detection (LODs) for MTBE, ETBE, and TBF were obtained 0.06, 0.08, and 0.09 μg L−1, respectively. Moreover, the limits of quantification (LOQs) for MTBE, ETBE, and TBF were obtained 0.18, 0.24, and 0.27 μg L−1, respectively. The enrichment factor was also found to be in the range of 98–129.The NTD-GC-FID procedure demonstrated a high extraction efficiency, making it a promising tool for urinary biomonitoring of fuel ether oxygenates with improved sensitivity and selectivity compared to current methods.

Preparation of styrene-based imprinted polymer for the adsorption of hazardous bromocresol green dye: Equilibrium, kinetics and thermodynamics study

In this study, styrene was used as a functional monomer for the production of molecularly imprinted polymer (MIP) via free radical  polymerization method, using bromocresol green dye (BCG) as template. A non-imprinted polymer (NIP), that excluded the template,  was also synthesized. Both polymers were applied for the removal of BCG from aqueous medium. The synthesized polymers were  characterized with Fourier transform infrared spectroscopy, scanning electron microscopy, and X-ray powder diffraction spectroscopic  techniques. The effect of operating variables, such as pH, contact time, initial dye concentration and process temperature, on the efficiencies of the polymers in removing the dye were evaluated. Equilibrium time of BCG adsorption onto the  MIP was reached within  40 min, with adsorption capacity of 49.68 mg g-1 . The adsorption process followed the pseudo-second-order kinetic and Freundlich  isotherm models, while chemisorption mechanism was predicted. The adsorption process was spontaneous and exothermic in nature,  with DH values of -140.03 and -25.01 kJ/mol-1 recorded for BCG removal by MIP and NIP, respectively. The styrene-based MIP showed  good mechanical stability, and retained up to about 99% of its adsorption capacity after six sequential cycles of   regeneration.  Comparatively, the MIP (99.81mg g-1 ) performed considerably better than its NIP (59.00 mg g-1 ) analogue in the removal of BCG from  aqueous medium, thus affirming the potentials of the molecular imprinting technique in the production of efficient adsorbents for  adsorption of toxic dyes from industrial effluents. 

Molecularly Imprinted Electrochemical Sensor Based on α-Cyclodextrin Inclusion Complex and MXene Modification for Highly Sensitive and Selective Detection of Alkylresorcinols in Whole Wheat Foods.

Authenticating whole wheat foods poses a significant challenge for both the grain industry and consumers. Alkylresorcinols (ARs), serving as biomarkers of whole wheat, play a crucial role in assessing the authenticity of whole wheat foods. Herein, we introduce a novel molecularly imprinted electrochemical sensor with modifications involving a molecularly imprinted polymer (MIP) and MXene nanosheets, enabling highly sensitive and selective detection of ARs. Notably, we specifically chose 5-heneicosylresorcinol (AR21), the predominant homologue in whole wheat, as the template molecule. α-Cyclodextrin and acrylamide served as dual functional monomers, establishing a robust multiple interaction between the MIP and AR21. As a result, the sensor exhibited a wide linear range of 0.005 to 100 μg·mL-1 and a low detection limit of 2.52 ng·mL-1, demonstrating exceptional selectivity and stability. When applied to commercial whole wheat foods, the assay achieved satisfactory recoveries and accuracy, strongly validating the practicality and effectiveness of this analytical technique.

Development of surface molecular-imprinted electrochemical sensor for palmitic acid with machine learning assistance

Palmitic acid (PA) is a kind of saturated high fatty acid, which is involved in physiological safety and food quality. A surface molecularly imprinted polymer (MIP) electrochemical sensor was prepared on MXene surface using dopamine (DA) as functional monomer. The electrode was modified with gold nanoparticles (AuNPs), ferrocene-graphene oxide-multiwalled carbon nanotubes (Fc-GO-MWCNT) composite to enhance the electroactive area and conductivity. The sensor was characterized by scanning electron microscope (SEM), energy-dispersive X-ray spectroscopy (EDS), electrochemical impedance spectroscopy (EIS) and Differential pulse voltammetry (DPV), respectively. The parameters concerning this assay and various regeneration conditions have been carefully studied. The sensor can detect PA in the range of 1 nM-1 mM (R2 = 0.995), the limit of detection (LOD) is 0.48 nM (S/N = 3), and the limit of quantification (LOQ) is 1.61 nM. The artificial neural network (ANN) model in machine learning is further used to analyze the data collected by the sensor. The results show that the back propagation (BP) neural network in ANN is more suitable for the intelligent analysis of PA. The practicality of the sensor was confirmed by detecting PA in pork samples. This is the first MIP-based electrochemical sensor for PA, and it has great potential in practical applications.

Flexible Dual‐Channel Molecularly Imprinted Electrochemical Sensor for Simultaneously Monitoring Sweat Cortisol and Lactate Levels

While exercise offers significant potential to enhance overall well‐being, unscientific exercise practices often cause exercise fatigue, posing a threat to human health. Flexible sweat sensors have garnered considerable attention owing to their ability to continuously, non‐invasively, and dynamically monitor human health during exercise at the molecular level. Therefore, in this study, we constructed a flexible molecularly imprinted polymer (MIP) sensor for the real‐time monitoring of cortisol and lactate levels in sweat using cortisol or lactate as template molecules and pyrrole (Py) as functional monomer. Prussian blue (PB) was embedded into the MIP as a built‐in redox probe, eliminating the need for an additional probe and facilitating the simultaneous quantification of cortisol and lactate concentrations. Moreover, the MIP‐doped platinum nanoparticles (PtNPs) ehanced the electron transfer capability, further improving the sensitivity of the sensors. The fabricated flexibile cortisol and lactate MIP sensors demonstrated low limits of detection (LOD; 1.07 nM and 1.09 mM, respectively), high sensitivity (0.09 μA lg[nM]‐1 and 1.28 μA lg[nM]‐1), and exceptional stability and selectivity. The flexible MIP sensors could continuously and dynamically monitor changes in sweat cortisol and lactate concentrations, thus contributing to the advancement of next‐generation flexible sweat electrochemical sensors and providing a crucial tool for monitoring exercise fatigue.

In situ detection of dopamine in single living cells by molecularly imprinted polymer-functionalized nanoelectrodes

In situ detection of dopamine (DA) at single-cell level is critical for exploring neurotransmitter-related biological processes and diseases. However, the low content of DA and a variety of distractors with similar oxidation potentials as DA in cells brought great challenges. Here, a sensitive and specific electrochemical nanosensor was proposed for in situ detection of DA in single living cells based on nanodiamond (ND) and molecularly imprinted polymer (MIP)-functionalized carbon fiber nanoelectrode (ND/MIP/CFNE). Due to its excellent electrocatalytic property, ND was modified to the surface of CFNE based on amide bonding. Compared with bare CFNE, ND-modified CFNE can enhance oxidation currents of DA by about 4-fold, improving signal-to-noise ratio and detection sensitivity. MIP was further electropolymerized on the surface of nanoelectrodes to achieve specific capture and recognition of DA, which could avoid the interference of complex matrix and analogs in cells. Taking advantage of the precise positioning capability of a single-cell analyzer and micromanipulator, ND/MIP/CFNE could be precisely inserted into different locations of single cells and monitor oxidation signal of DA. The concentration of DA in the cytoplasm of single pheochromocytoma (PC12) cell was measured to be about 0.4 μM, providing a sensitive and powerful method for single-cell detection. Furthermore, the nanoelectrodes can monitor the fluctuation of intracellular DA under drug stimulation, providing new ideas and methods for new drug development and efficacy evaluation.