High-performance fentanyl molecularly imprinted electrochemical sensing platform designed through molecular simulations.

BACKGROUND: Fentanyl and its derivatives are a type of potent opioid analgesics, with the characteristics of diverse structure, high toxicity, extremely low content, and high fatality rate. Currently, they have become one of the most serious problems in international drug abuse control due to their extensive use in drug production and use. Therefore, the development of a rapid, sensitive, and accurate method for detecting trace fentanyl is of great significance. In this study, in view of its complex structure and trace concentration, a new molecular imprinting electrochemical sensor was developed through molecular simulations followed by experimental validation to detect trace fentanyl. RESULTS: The process consisted of first obtaining the optimal functional monomer and its molar ratio through molecular simulations. The recognition sites of fentanyl-imprinted polymers were predicted to guide the synthesis of imprinted membranes with precision approach to ensure an efficient and accurate reaction process. Reduced graphene oxide (ErGO) was then deposited on glassy carbon electrode surface by electrochemical reduction to yield large numbers of active sites suitable for catalyzing reactions of fentanyl piperidine for promoted efficient electron transfer and amplified sensitivity of the sensor. Accordingly, fentanyl molecularly imprinted film was formed through one-step electropolymerization to yield greatly improved sensing selectivity due to the specific recognition of molecularly imprinted polymer. Under optimal experimental conditions, the fentanyl sensor showed an extended detection range of 3.84 × 10-9 mol L-1-1.72 × 10-6 mol L-1 and a detection limit of 1.28 × 10-9 mol L-1. SIGNIFICANCE: A distinctive feature of this sensor is its molecularly imprinted polymerized membrane, which offers excellent specific recognition, thereby boosting the sensor's selectivity. Throughout the sensor's development process, molecular simulations were employed to steer the synthesis of molecularly imprinted polymers and predict the recognition sites of fentanyl-imprinted polymers. The experimental outcomes proved to align with the simulation data. The final sensor exhibited outstanding selectivity, repeatability, stability, and high sensitivity. The sensor was effectively used to reliably track fentanyl in human serum samples, with acceptable analytical reliability, suggesting its potential for practical applications.

A simple polyarginine membrane electrochemical sensor for the determination of MDMA and MDA.

In this study, a simple electrochemical sensor based on l-arginine membrane (P-L-arg/GCE) was developed for rapid and sensitive detection of MDMA and MDA. A polyarginine membrane was obtained through one-step direct electropolymerization, which provides more reaction sites for the analyte and improves the sensitivity of the sensor. Following the optimized selection parameters, the MDMA detection range was established at 1.0 × 10-7∼3.5 × 10-5 mol L-1, with a detection limit of 3.3 × 10-8 mol L-1. Similarly, the detection range for MDA was established at 1.0 × 10-7∼5.3 × 10-5 mol L-1 with a detection limit of 3.3 × 10-8 mol L-1. Additionally, the potential oxidation mechanism of MDMA and MDA during the REDOX process was analyzed by cyclic voltammetry. Furthermore, the proposed sensor exhibited superior selectivity, excellent reproducibility, and satisfactory stability. The proposed sensors can be used for reliable monitoring of MDMA or MDA in human urine and hair samples, respectively, and it has acceptable analytical reliability and enormous potential for practical applications.

A promising and highly sensitive electrochemical platform for the detection of fentanyl and alfentanil in human serum.

A novel electrochemical method has been developed, based on a covalent organic framework (COF) and reduced graphene oxide (rGO), to detect fentanyl and alfentanil. COF nanomaterials with chrysanthemum morphology obtained by solvothermal reaction contain rich active sites for electrochemical catalytic reaction, thus improving the detection performance of the designed sensor. Reduced graphene oxide improves the sensor's sensitivity due to enhanced electron transfer. Under optimized experimental conditions, the fabricated electrode presents a linear range of 0.02 to 7.26 µM for alfentanil and 0.1 to 6.54 µM for fentanyl, with detection limits of 6.7 nM and 33 nM, respectively. In addition, the sensor possesses excellent selectivity, outstanding reproducibility, and acceptable stability. The proposed sensor is feasible for the reliable monitoring of fentanyl and alfentanil in human serum samples, with acceptable reliability and high potential in real-world applications. Finally, the electrochemical characteristic fingerprint of fentanyl is investigated by studying the electrochemical behavior of alfentanil and fentanyl on the electrode surface.

An electrochemical sensor for direct and sensitive detection of ketamine.

Ketamine is an organic drug with weak electrochemical activity, which makes it difficult to directly detect by electrochemical methods. Herein, an electrochemical sensor, with excellent detection sensitivity, is proposed for direct detection of ketamine based on a weakly conductive poly-L-cysteine molecularly imprinted membrane. Poly-L-cysteine molecularly imprinted membrane sensor (poly-L-Cys-KT-MIM/GCE) is obtained using L-cysteine as a functional monomer and ketamine as a template molecule based on electropolymerization. The green and highly active cysteine is selected as a functional monomer during electropolymerization, which cannot only achieve specific recognition but also improve detection sensitivity. Furthermore, the oxidation mechanism and fingerprint of ketamine on the electrode surface are established by analyzing the corresponding oxidation products using high/resolution mass spectrometry, which will help to promote the application of electrochemistry in the rapid detection of drugs. Under optimal conditions, the as-designed sensor demonstrated a linear response to ketamine within the range of 5.0 × 10-7 to 2.0 × 10-5 mol L-1 and a detection limit of 1.6 × 10-7 mol L-1. The proposed method exhibited excellent performance from the viewpoints of selectivity, sensitivity and stability. Notably, the sensor rendered excellent reliability and could be used for the detection of target analytes in hair and urine samples with high recovery rates.