Fabrication of a molecularly imprinted polymer-based electrochemical sensor for the selective assay of antipsychotic drug clozapine and performance comparison with LC-MS/MS.

Clozapine (CLO) is an atypical antipsychotic drug indicated for the treatment of schizophrenia. The treatment effectiveness of CLO is better than that of other atypical antipsychotics, and it has the advantage of being able to determine its effectiveness by measuring its concentration in the patient's blood. Thus, sensitive, selective, and accurate determination of CLO in blood is highly significant for treatment monitoring. This study describes the design and fabrication of a molecularly imprinted polymer (MIP)-based electrochemical sensor for CLO determination. This is the first MIP-based electrochemical application in the literature for CLO determination. Employing the thermal polymerization approach, the MIP was formed on the glassy carbon electrode (GCE) using CLO as the template, trans-3-(3-Pyridyl)acrylic acid (3,3-TA) as the functional monomer, and the support of zinc oxide nanoparticles (ZnO NPs). Elaborate characterizations in terms of surface morphology and electrochemistry were performed via scanning electron microscopy (SEM), cyclic voltammetry (CV), and electrochemical impedance spectroscopy (EIS) methods. An indirect approach was employed to determine CLO in standard solution, real human biological samples, and tablet formulation, using 5 × 10-3 M [Fe(CN)6]3-/4- solution as the redox probe. The limit of detection (LOD) values for the standard solution and serum sample were calculated as 2.9 × 10-11 M and 6.01 × 10-12 M, respectively. These values and recovery studies confirmed the sensor's sensitivity and feasibility. The measurements in the presence of similarly structured compounds (olanzapine and quetiapine fumarate) verified the sensor's superior selectivity. Moreover, the developed sensor's performance was compared and verified using an LC-MS/MS method using the student's t-test and F-test.

Monitoring of Specific Phytoestrogens by Dedicated Electrochemical Sensors: A Review.

Phytoestrogens are non-steroidal estrogens produced from plants that can bind with the human body's estrogenic receptor site and be used as a substitute for maintaining hormonal balance. They are mainly classified as flavonoids, phenolic acids, lignans, stilbenes, and coumestans; some are resocyclic acids of lactones, which are mycotoxins and not natural phytoestrogen. Phytoestrogens have many beneficial medicinal properties, making them an important part of the daily diet. Electrochemical sensors are widely used analytical tools for analysing various pharmaceuticals, chemicals, pollutants and food items. Electrochemical sensors provide an extensive platform for highly sensitive and rapid analysis. Several reviews have been published on the importance of the biological and medicinal properties of phytoestrogens. However, this review provides an overview of recent work performed through electrochemical measurements with electrochemical sensors and biosensors for all the classes of phytoestrogens done so far since 2019.

Development of a molecularly imprinted polymer-based electrochemical sensor with metal-organic frameworks for monitoring the antineoplastic drug vismodegib.

A novel and robust electrochemical sensing tool for the determination of vismodegib (VIS), an anticancer drug, has been developed by integrating the selective recognition capabilities of molecularly imprinted polymer (MIP) and the sensitivity enhancement capability of metal-organic framework (MOF). Prior to this step, the electrochemical behavior of VIS was investigated using a bare glassy carbon electrode (GCE). It was observed that in 0.5 M H2SO4 solution as electrolyte, VIS has an oxidation peak around 1.3 V and the oxidation mechanism is diffusion controlled. The determination of VIS in a standard solution using a bare GCE showed a linear response in the concentration range from 2.5 µM to 100 µM, with a limit of detection (LOD) of 0.75 µM. Since sufficient sensitivity and selectivity could not be achieved with bare GCE, a MIP sensor was developed in the next step of the study. For this purpose, the GCE surface was first modified by drop casting with as-synthesized Co-MOF. Subsequently, a MIP network was synthesized via a thermal polymerization approach using 2-acrylamido-2-methylpropanesulfonic acid (AMPS) as monomer and VIS as template. MOFs are ideal electrode materials due to their controllable and diverse morphologies and modifiable surface properties. These characteristics enable the development of MIPs with more homogeneous binding sites and high affinity for target molecules. Integrating MOFs could help the performance of sensors with the desired stability and reproducibility. Electrochemical analysis revealed an observable enhancement of the output signal by the incorporation of MOF molecules, which is consistent with the sensitivity-enhancing role of MOF by providing more anchoring sites for the attachment of the polymer texture to the electrode surface. This MOF-MIP sensor exhibited impressive linear dynamic ranges ranging from 0.1 to 1.0 pM for VIS, with detection limits in the low picomolar range. In addition, the MOF-MIP sensor offers high accuracy, selectivity and precision for the determination of VIS, with no interference observed from complex media of serum samples. Additionally, in this study, Analytical GREEnness metric (AGREE), Analytical GREEnness preparation (AGREEprep) and Blue Applicability Grade Index (BAGI) were used to calculate the green profile score.

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.

Current Analytical Methods for the Sensitive Assay of New-Generation Ovarian Cancer Drugs in Pharmaceutical and Biological Samples.

Ovarian cancer, which affects the female reproductive organs, is one of the most common types of cancer. Since this type of cancer has a high mortality rate from gynaecological cancers, the scientific community shows great interest in studies on its treatment. Chemotherapy, radiotherapy, and surgical treatment methods are used in its treatment. In the absence of targeted treatments in these treatment methods, side effects occur in patients, and patients show resistance to the drug. In addition, the underlying causes of ovarian cancer are still not fully known. The scientific world thinks that genetic factors, environmental conditions, and consumed foods may cause this cancer. The most important factor in the treatment of ovarian cancer is early diagnosis. Therefore, the drugs used in the treatment of ovarian cancer are platinum-based anticancer drugs. In addition to these drugs, the most preferred treatment method recently is targeted treatment approaches using poly(adenosine diphosphate ribose) polymerase (PARP) inhibitors. In this review, studies on the sensitive analysis of the treatment methods of these new-generation drugs used in the treatment of ovarian cancer have been comprehensively examined. In addition, the basic features, structural aspects, and biological data of analytical methods used in treatments with new-generation drugs are explained. Analytical studies carried out in the literature in recent years aim to show future developments in how these new-generation drugs are used today and to guide future studies by comprehensively examining and explaining the structure-activity relationship, mechanism of action, toxicity, and pharmacokinetic studies. Finally, in this study, the methods used in the analysis of drugs used in the treatment of ovarian cancer and the studies conducted between 2015 and 2023 were discussed in detail.

Investigation of Health Effects of Major Phenolic Compounds in Foods: Extraction Processes, Analytical Approaches and Applications.

The escalating costs of healthcare services and a growing awareness of personal health responsibilities have led individuals to explore natural methods alongside conventional medicines for health improvement and disease prevention. The aging global population is experiencing increased health needs, notably related to conditions like diabetes, heart disease, and hypertension. Lifestyle-related diseases, poor dietary habits, and sedentary lifestyles underscore the importance of foods containing nutrients that can aid in preventing and managing these diseases. Phenolic compounds, a fundamental group of phytochemicals, are prominent in the chemical diversity of the natural world and are abundant in functional foods. Widely distributed in various plant parts, these compounds exhibit important functional and sensory properties, including color, taste, and aroma. Their diverse functionalities, particularly antioxidant activity, play a crucial role in mitigating cellular oxidative stress, potentially reducing damage associated with serious health issues such as cardiovascular disease, neurodegenerative disea23ses, and cancer. Phenolic compounds exist in different forms, some combined with glycosides, impacting their biological effects and absorption. Approximately 8000 polyphenols isolated from plants offer significant potential for natural medicines and nutritional supplements. Therefore, their extraction process and selective and sensitive food determination are very important. This review focuses on the extraction processes, analytical methods, and health effects of major phenolic compounds in foods. The examination encompasses a comprehensive analysis of analytical approaches and their applications in elucidating the presence and impact of these compounds on human health.

Highly selective and sensitive molecularly imprinted sensors for the electrochemical assay of quercetin in methanol extracts of Rubus sanctus and Fragaria vesca.

Quercetin (QUE) is a powerful antioxidant and one of the common phenolic compounds found in plants, vegetables, and fruits, which has shown many pharmacological activities. The complex nature of the matrix in which QUE is found and its importance and potential uses in diverse applications force the researchers to develop selective and sensitive sensors. In the present work, a novel molecularly imprinted polymer (MIP)-based electrochemical sensor was fabricated for the selective and sensitive determination of the QUE in plant extracts and food supplements. Tryptophan methacrylate (TrpMA) was chosen as the functional monomer, whereas the photopolymerization (PP) method was applied using a glassy carbon electrode (GCE). Electrochemical and morphological characterizations of the developed sensor (TrpMA@QUE/MIP-GCE) were performed using cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), and scanning electron microscopy (SEM). The linear range of the developed sensor was determined to be in the range of 1.0-25 pM, while the limit of detection (LOD) was calculated to be 0.235 pM. In conclusion, The TrpMA@QUE/MIP-GCE sensor might be classified as a promising platform for selective and sensitive determination of QUE not only in plant extracts but also in commercial food supplements because of its reliability, reproducibility, repeatability, stability, and fast response time.

A novel electrochemical sensor based on a molecularly imprinted polymer for highly selective and sensitive determination of rutin from herbal supplements and plant extracts.

Rutin (RUT), a natural flavonoid with various beneficial pharmacological actions such as cardioprotective, antioxidant, anti-inflammatory, neuroprotective, etc., is found in the content of many plants that are consumed daily. Due to the healthful effects, RUT is also included in the composition of various herbal supplement samples. Therefore, it is highly important to develop a sensor with high selectivity and sensitivity to determine RUT in complex samples. In this study, it was aimed to take advantage of the cheap, easy, and sensitive nature of electrochemistry and, in addition, to improve the selectivity. For this purpose, the functional monomer selected in the fabricated molecularly imprinted polymer (MIP) was N-methacryloyl-L-aspartic acid (MA-Asp) while photopolymerization (PP) was applied as the polymerization route. After completing critical optimization steps, the developed sensor (MA-Asp@RUT/MIP-GCE) was characterized electrochemically and morphologically. As a result of analytical performance evaluation in standard solution, the linear response of the sensor was found in the concentration range between 1 and 10 pM with a detection limit of 0.269 pM. The recovery studies from plant extract and commercial herbal supplement samples emphasized accuracy and applicability. In imprinting factor studies figuring out quite good selectivity, molecules with a structure similar to RUT were selected as competitors to prove the affinity of the sensor against RUT. Consequently, the MA-Asp@RUT/MIP-GCE sensor offers a more sensitive and selective method thanks to its indirect analysis approach and also stands out with the diversity of its real sample application compared to other available studies.

The Effect of Polymerization Techniques on the Creation of Molecularly Imprinted Polymer Sensors and Their Application on Pharmaceutical Compounds.

Molecularly imprinted polymers (MIPs) have become more prevalent in fabricating sensor applications, particularly in medicine, pharmaceuticals, food quality monitoring, and the environment. The ease of their preparation, adaptability of templates, superior affinity and specificity, improved stability, and the possibility for downsizing are only a few benefits of these sensors. Moreover, from a medical perspective, monitoring therapeutic medications and determining pharmaceutical compounds in their pharmaceutical forms and biological systems is very important. Additionally, because medications are hazardous to the environment, effective, quick, and affordable determination in the surrounding environment is of major importance. Concerning a variety of performance criteria, including sensitivity, specificity, low detection limits, and affordability, MIP sensors outperform other published technologies for analyzing pharmaceutical drugs. MIP sensors have, therefore, been widely used as one of the most crucial techniques for analyzing pharmaceuticals. The first part of this review provides a detailed explanation of the many polymerization techniques that were employed to create high-performing MIP sensors. In the subsequent section of the review, the utilization of MIP-based sensors for quantifying the drugs in their pharmaceutical preparation, biological specimens, and environmental samples are covered in depth. Finally, a critical evaluation of the potential future research paths for MIP-based sensors clarifies the use of MIP in pharmaceutical fields.

Development of a molecularly imprinted polymer-based electrochemical sensor for the selective detection of nerve agent VX metabolite ethyl methylphosphonic acid in human plasma and urine samples.

This study focuses on the detection of ethyl methyl phosphonic acid (EMPA), a metabolite of the banned organophosphorus nerve agent VX. We developed an electrochemical sensor utilizing the molecularly imprinted polymer (MIP) based on 4-aminobenzoic acid (4-ABA) and tetraethyl orthosilicate for the selective detection of EMPA in human plasma and urine samples. The 4-ABA@EMPA/MIP/GCE sensor was constructed by a thermal polymerization process on a glassy carbon electrode and sensor characterization was performed by cyclic voltammetry and electrochemical impedance spectroscopy. The 4-ABA@EMPA/MIP/GCE sensor demonstrated impressive linear ranges 1.0 × 10-10 M-2.5 × 10-9 M for the standard solution, 1.0 × 10-10 M-2.5 × 10-9 M for the urine sample, and 1.0 × 10-10 M-1 × 10-9 M of EMPA for the plasma sample with outstanding detection limits of 2.75 × 10-11 M (standard solution), 2.11 × 10-11 M (urine), and 2.36 × 10-11 M (plasma). The sensor exhibited excellent recovery percentages ranging from 99.86 to 101.30% in urine samples and 100.62 to 101.08% in plasma samples. These findings underscore the effectiveness of the 4-ABA@EMPA/MIP/GCE as a straightforward, highly sensitive, and selective interface capable of detecting the target analyte EMPA in human plasma and urine samples.

The sensor applications for prostate and lung cancer biomarkers in terms of electrochemical analysis.

Prostate and lung cancers are the most common types of cancer and affect a large part of the population around the world, causing deaths. Therefore, the rapid identification of cancer can profoundly impact reducing cancer-related death rates and protecting human lives. Significant resources have been dedicated to investigating new methods for early disease detection. Cancer biomarkers encompass various biochemical entities, including nucleic acids, proteins, sugars, small metabolites, cytogenetic and cytokinetic parameters, and whole tumor cells in bodily fluids. These tools can be utilized for various purposes, such as risk assessment, diagnosis, prognosis, treatment efficacy, toxicity evaluation, and predicting a return. Due to these versatile and critical purposes, there are widespread studies on the development of new, sensitive, and selective approaches for the determination of cancer biomarkers. This review illustrates the significant lung and prostate cancer biomarkers and their determination utilizing electrochemical sensors, which have the advantage of improved sensitivity, low cost, and simple analysis. Additionally, approaches such as improving sensitivity with nanomaterials and ensuring selectivity with MIPs are used to increase the performance of the sensor. This review aims to overview the most recent electrochemical biosensor applications for determining vital biomarkers of prostate and lung cancers in terms of nanobiosensors and molecularly imprinted polymer (MIP)-based biosensors.

Designing an electrochemical sensor based on ZnO nanoparticle-supported molecularly imprinted polymer for ultra-sensitive and selective detection of sorafenib.

BACKGROUND: Sorafenib (SOR) is a multikinase inhibitor anticancer drug that is used in treating non-small cell lung cancer. In this work, we focused on developing nanomaterial-supported smart porous interfaces by following the molecular imprinting approach for the selective determination of SOR. Determination-based studies in the literature for SOR are limited, and they are chromatographic techniques-based; hence, there is a need in the literature to elaborate the selective and sensitive analysis/monitoring of SOR in both biological and pharmaceutical samples with more studies. RESULTS: The results showed that adding ZnO NPs enhanced the signal five times compared to the solo molecularly imprinted polymer (MIP). Under the optimized conditions, ZnO/AMPS@MIP-GCE showed a linear response in the concentration range between 1.0 × 10-12 and 1.0 × 10-11 M with LOD and LOQ values of 2.25 × 10-13 M and 7.51 × 10-13 M, respectively, in the serum sample. The selectivity study was conducted against common cations, anions, and compounds such as dopamine, paracetamol, ascorbic acid, and uric acid. Also, the imprinting factor (IF) analysis was performed on selected drug substances having structural similarities to SOR and the relative IF values of regorafenib, leflunomide, teriflunomide, nilotinib, axitinib, and dasatinib indicated the selectivity of the developed sensor for SOR. Finally, ZnO/AMPS@MIP-GCE was implemented to determine SOR in the spiked commercial human serum samples and tablet dosage form with bias% between -0.43 and + 0.66. SIGNIFICANCE AND NOVELTY: This study is the first electrochemical study for the determination of SOR, and thanks to the ZnO NPs supported MIP sensor, it stands out in terms of both high sensitivity and superior selectivity. Also, this designed sensor provides controlled orientation of the template and complete removal of templates in a one-step process, allowing extremely low detection and quantification limits.

Comparative MIP sensor technique: photopolymerization or thermal polymerization for the sensitive determination of anticancer drug Regorafenib in different matrixes.

Regorafenib (REG) is a diphenylurea derivative oral multikinase inhibitor. It plays an important role in the treatment of colorectal cancer, metastatic gastrointestinal stromal tumors, and hepatocellular carcinoma. Molecularly imprinted polymer (MIP) based glassy carbon electrodes (GCE) were fabricated using photopolymerization (PP) and thermal polymerization (TP) methods. The characterizations of the proposed sensors were investigated by electrochemical techniques, Fourier transform infrared spectroscopy (FT-IR), and scanning electron microscopy (SEM). Several parameters were studied in detail for the optimum conditions of MIP-based sensors, such as dropping volume, photopolymerization and thermal polymerization durations, removal medium and time, and rebinding time. Both sensors' analytical validation and electroanalytical performance comparison were made in different REG concentrations ranging between 0.1 nM and 2.5 nM in standard solution and commercial human serum samples. The limit of detection (LOD) of PP-REG@MIP/GCE and TP-REG@MIP/GCE were 9.13 × 10-12 M and 1.44 × 10-11 M in standard solutions and 2.04 × 10-11 M and 2.02 × 10-11 M in serum samples, respectively. The applicability of the proposed sensors was tested using commercial human serum samples and pharmaceutical form of REG with high recovery values (PP-REG@MIP/GCE and TP REG@MIP/GCE sensors, 99.56-101.59%, respectively). The selectivity of the sensor for REG was investigated in the presence of similar molecules: Sorafenib, Sunitinib, Nilotinib, and Imatinib. The developed techniques and sensors checked the possible biological compounds and ions' effects and storage stability.

A molecularly imprinted polymer-based electrochemical sensor for the determination of tofacitinib.

Tofacitinib citrate (TOF) is a Janus kinase-3 inhibitor used for rheumatoid arthritis treatment. In this study, a molecularly imprinted polymer (MIP)-based sensor was produced using acrylamide as the functional monomer via photopolymerization technique for the electrochemical determination of TOF. This study is the first one to explain the electrochemical determination of TOF with a highly selective MIP-based sensor. The surface characterization of the MIP-based sensor was performed with scanning electron microscopy and energy-dispersive X-ray spectroscopy methods, and it was expanded with electrochemical characterization by cyclic voltammetry and electrochemical impedance spectroscopy (EIS) methods. TOF determination was performed using differential pulse voltammetry (DPV) and EIS methods in standard solution and spiked serum sample in the linear range between 1×10-11 M and 1×10-10 M. Very low limit of detection and limit of quantification values were found, confirming the sensitivity of the sensor. Recovery analysis with spiked serum and tablet samples verified the sensor's accuracy and applicability using DPV and EIS methods. The selectivity of the sensor was confirmed with imprinting factor and interference studies, and the sensor performance was controlled using non-imprinted polymer for comparison at every step.

A Comprehensive Overview of Sensors Applications for the Diagnosis of SARS-CoV-2 and of Drugs Used in its Treatment.

During the COVID-19 process, determination-based analytical chemistry studies have had a major place at every stage. Many analytical techniques have been used in both diagnostic studies and drug analysis. Among these, electrochemical sensors are frequently preferred due to their high sensitivity, selectivity, short analysis time, reliability, ease of sample preparation, and low use of organic solvents. For the determination of drugs used in the SARS-CoV-2, such as favipiravir, molnupiravir, ribavirin, etc., electrochemical (nano)sensors are widely used in both pharmaceutical and biological samples. Diagnosis is the most critical step in the management of the disease, and electrochemical sensor tools are widely preferred for this purpose. Diagnostic electrochemical sensor tools can be biosensor-, nano biosensor-, or MIP-based sensors and utilize a wide variety of analytes such as viral proteins, viral RNA, antibodies, etc. This review overviews the sensor applications in SARS-CoV-2 in terms of diagnosis and determination of drugs by evaluating the most recent studies in the literature. In this way, it is aimed to compile the developments so far by shedding light on the most recent studies and giving ideas to researchers for future studies.

The Power of Carbon Nanotubes on Sensitive Drug Determination Methods.

Nowadays, carbon nanotubes (CNTs) due to their inorganic conducting, semiconducting, and organic π-π stacking properties are becoming innovative materials. CNTs have an adjustable size, large surface area, and other significant chemical properties. Due to their excellent electrical, optical, and mechanical properties, CNTs play an important role in various application fields. In the past decade, many unique intrinsic physical and chemical properties have been intensively explored for pharmaceutical, biological, and biomedical applications. The functionalization of CNTs results in a remarkably reduced cytotoxicity and at the same time increased biocompatibility. The toxicity studies reveal that highly water-soluble and serum stable nanotubes are biocompatible, nontoxic, and potentially useful for biomedical applications. Ultrasensitive drug determination from its dosage form and/or biological samples with carbon nanotubes can be realized after surface modification. The main purpose of this review is to present recent achievements on CNTs which are investigated in electrochemical and chromatographically sensing technologies.

Comparative study of electrochemical-based sensors and immunosensors in terms of advantageous features for detection of cancer biomarkers.

Cancer, becoming increasingly common globally, has a high mortality rate. Despite the much research on diagnosis and treatment methods, the benefits of technological developments, and newly developed sensor devices, cancer is still one of the leading causes of death worldwide. Early detection using powerful and noninvasive tools could be a future focus for prognosis and treatment follow-up. Therefore, electrochemical biosensors can be a strong choice for the detection of cancer biomarkers (such as alpha-fetoprotein, cytochrome c, prostate-specific antigen, myoglobin, carcinoembryonic antigen, alpha-fetoprotein, a cancer antigen, epidermal growth factor receptor, vascular endothelial growth factor, circulating tumor cell, and breast cancer antigen 1/2) due to their advantages such as high sensitivity, excellent selectivity, low cost, short analysis time, and simplicity. Furthermore, electrochemical biosensors are better suited for point-of-care applications due to their mass production and miniaturization ease. This review provides an overview of different electrochemical measurement techniques, bioreceptor surfaces, signal production and amplification, and the integration of electrochemical-modified sensors. Cancer biomarkers based on electrochemical biosensors were given in detail. In addition, studies with MIP-based sensors and immunosensors have been extensively discussed. Integrating electrochemical biosensors with cancer biomarkers was also emphasized as a new research trend. Finally, we provide an overview of current advances in measuring and analyzing cancer biomarkers using electrochemical biosensors and detail current challenges and future perspectives.

Detection of Axitinib Using Multiwalled Carbon Nanotube-Fe2O3/Chitosan Nanocomposite-Based Electrochemical Sensor and Modeling with Density Functional Theory.

In this study, axitinib (AXI), a potent and selective inhibitor of vascular endothelial growth factor receptor (VEGFR) tyrosine kinase and used as a second-generation targeted drug, was investigated electrochemically under optimized conditions using multiwalled carbon nanotubes/iron(III) oxide nanoparticle-chitosan nanocomposite (MWCNT/Fe2O3@chitosan NC) modified on the glassy carbon electrode (GCE) surface. Characterization of the modified electrode was performed using scanning electron microscopy (SEM) and electrochemical impedance spectroscopy (EIS). The adsorptive stripping differential pulse voltammetric (AdSDPV) technique was used for the sensitive, rapid, and precise detection of AXI. The current peak obtained with the MWCNT/Fe2O3@chitosan NC modified electrode was 23 times higher compared to the bare electrode. The developed modified electrode showed excellent electrocatalytic activity in AXI oxidation. Under optimized conditions, the effect of supporting electrolyte and pH was investigated, and 0.1 M H2SO4 was chosen as the electrolyte with the highest peak current for the target analyte. In the concentration range of MWCNT/Fe2O3@chitosan NC/GCE, 6 × 10-9 and 1 × 10-6 M, the limit of detection (LOD) and limit of quantification (LOQ) values were calculated to be 0.904 and 0.0301 pM, respectively. Tablet and serum samples were used for the applicability of the developed sensor, relative standard deviation (RSD) values for all samples were below 2%, and the recovery results were 99.23 and 101.84%, respectively. The MWCNT/Fe2O3@chitosan NC/GCE designed to determine AXI demonstrated the applicability, selectivity, precision, and accuracy of the sensor. The mechanism of electron transfer from the modified GCE surface to the analyte solution is studied via modeling the modified GCE surface by the density functional theory (DFT) method at B3LYP/6-311+g(d,p) and M062X/6-31g(d,p) levels. We observed that the iron oxide nanoparticles play an important role in channeling electron flow from the analyte solution to the MWCNT-coated GCE electrode surface. Adsorption of the nanocomposite material onto the GCE surface occurs via strong electrostatic interactions, including ionic and hydrogen bond formations. During the adsorption-controlled oxidation process of the axitinib, the electrons are transferred via the highest occupied molecular orbital (HOMO) localized on the iron oxide moiety to the lowest unoccupied molecular orbital (LUMO) of the MWCNT/GCE surface.

A semi-covalent molecularly imprinted electrochemical sensor for rapid and selective detection of tiotropium bromide.

Tiotropium bromide (TIO) is a long-acting bronchodilator used in the treatment of chronic obstructive pulmonary disease (COPD) and asthma. Specifically, it is used to prevent patients from worsening breathing difficulties. In this study, a new TIO-imprinted electrochemical sensor was designed to detect TIO in serum and pharmaceutical samples. Methacryloyl-L-histidine-cobalt(II) [MAH-Co(II)] has been used as a metal-chelating monomer for synthesizing selective molecularly imprinted polymer (MIP). MIP film has been developed on glassy carbon electrodes using MAH-Co(II) as the functional monomer, 2-hydroxyethyl methacrylate (HEMA) as the basic monomer, and ethylene glycol dimethacrylate (EGDMA) as the cross-linker in the photopolymerization method. The surface characterization of the developed MAH-Co(II)@MIP/GCE electrochemical sensor was done using scanning electron microscopy (SEM) and Fourier transform infrared spectroscopy (FTIR). Also, the electrochemical behavior of the sensor was provided by differential pulse voltammetry (DPV), cyclic voltammetry (CV), and electrochemical impedance spectroscopy (EIS) techniques. Under optimized experimental conditions, the linearity range was in the range of 10-100 fM, and the limit of detection (LOD) and limit of quantitation (LOQ) values were calculated as 2.73 fM and 9.75 fM, respectively. The MAH-Co(II)@MIP/GCE sensor was used to precisely determine TIO in capsule and commercial serum samples. The results demonstrated that the MIP could specifically recognize TIO compared to structurally related drugs and could be reliably applied to the direct determination of drugs from real samples.

Carbon Nanomaterials-Based Novel Hybrid Platforms for Electrochemical Sensor Applications in Drug Analysis.

Nowadays, the rapid improvements in the medical and pharmaceutical fields increase the diversity and use of drugs. However, problems such as the use of multiple or combined drugs in the treatment of diseases and insensible use of over-the-counter drugs have caused concerns about the side-effect profiles and therapeutic ranges of drugs and environmental contamination and pollution problems due to pharmaceuticals waste. Therefore, the analysis of drugs in various media such as biological, pharmaceutical, and environmental samples is an important topic of discussion. Electrochemical methods are advantageous for sensor applications due to their easy application, low cost, versatility, high sensitivity, and environmentally-friendliness. Carbon nanomaterials such as diamond-like carbon thin films, carbon nanotubes, carbon nanofibers, graphene oxide, and nanodiamonds are used to enhance the performance of the electrochemical sensors with catalytic effects. To further improve this effect, it is aimed to create hybrid platforms by using different carbon nanomaterials together or with materials such as conductive polymers and ionic liquids. In this review, the most used carbon nanoforms will be evaluated in terms of electrochemical characterizations and physicochemical properties. Furthermore, the effect of hybrid platforms developed in the most recent studies on electrochemical sensors will be examined and evaluated in terms of drug analysis studies in the last five years.