Chirality, volume 35, issue 9, pages 625-635

Enantioselective voltammetric sensor based on mesoporous graphitized carbon black Carbopack X and fulvene derivative

Publication typeJournal Article
Publication date2023-03-23
Journal: Chirality
scimago Q2
wos Q2
SJR0.438
CiteScore4.4
Impact factor2.8
ISSN08990042, 1520636X
Catalysis
Organic Chemistry
Drug Discovery
Spectroscopy
Pharmacology
Analytical Chemistry
Abstract

For medicine and pharmaceuticals, the problem of determining and recognizing the enantiomers of biologically active compounds is an actual issue because the enantiomers of the same substance can have different effects on living organisms. This paper describes the development of an enantioselective voltammetric sensor (EVS) based on a glassy carbon electrode (GCE) modified with mesoporous graphitized carbon black Carbopack X (CpX) and a fulvene derivative (1S,4R)‐2‐cyclopenta‐2,4‐dien‐1‐ylidene‐1‐isopropyl‐4‐methylcyclohexane (CpIPMC) for recognition and determination of tryptophan (Trp) enantiomers. Synthesized CpIPMC was characterized by 1H and 13C nuclear magnetic resonance (NMR), chromatography–mass spectrometry, and polarimetry. The proposed sensor platform was studied by Fourier‐transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), cyclic voltammetry (CV), and electrochemical impedance spectroscopy (EIS). Using the square‐wave voltammetry (SWV), it was established that the developed sensor is an effective chiral platform for the quantitative determination of Trp enantiomers, including in a mixture and in biological fluids like urine and blood plasma, with adequate precision and recovery ranged from 96% to 101%.

Yarkaeva Y., Maistrenko V., Dymova D., Zagitova L., Nazyrov M.
Electrochimica Acta scimago Q1 wos Q1
2022-11-01 citations by CoLab: 16 Abstract  
• To AMX determination, sensors based on molecular imprinted PANI and PMOA were developed. • PANI and PMOA were obtained through electrochemical polymerization. • The interaction energy of AMX-PMOA complex is greater than AMX-PANI complex. • PMOA based MIP-sensor has a higher sensitivity, selectivity, and lower detection limit. • Proposed MIP-sensors determine AMX in urine and blood plasma with high accuracy. In this work, sensors based on molecular imprinted polyaniline (MIPANI) and poly-2-methoxyaniline (MIPMOA) for amoxicillin (AMX) determination were developed and compared with each other. MIPANI and MIPMOA were deposited on the surface of modified by graphene oxide (GO) glassy carbon electrode (GCE) through electrochemical polymerization using cyclic voltammetry, which was carried out in a 1 M sulfuric acid solution containing the corresponding monomer and amoxicillin as a template, followed by removal of the template. Using a scanning electron microscopy and electrochemical impedance spectroscopy, the morphology and electrochemical properties of the modified surface of GCE were studied. The applying PANI and PMOA on the GCE/GO surface leads to a decrease in [Fe(CN) 6 ] 3-/4− currents. The electron transfer resistance on PMOA sensor (62 ± 4 Ω) is lower than on PANI sensor (71 ± 5 Ω). The areas of the electroactive surface of GCE/GO/PANI and GCE/GO/PMOA are 6.64 ± 0.12 mm 2 and 7.75 ± 0.14 mm 2 , respectively. After the removal of the AMX, the electron transfer rate increases due to the formation of pores in the polymers through which [Fe(CN) 6 ] 3-/4− ions penetrate. Using FTIR spectroscopy, it was shown that amoxicillin is incorporated into both polymer films. In this case, the binding of AMX to PMOA is stronger, which is confirmed by quantum chemical modeling. The optimal conditions for analysis were selected: the number of polymerization cycles was 7, the template concentration was 1 mM, and the pH of the analyzed solution was 7.00. Square wave voltammograms MIPANI and MIPMOA sensors show a pronounced electrooxidation peak, which are linear over the AMX concentration range of 1.0 × 10 −5 – 5.0 × 10 −3 and 5.0 × 10 −6 – 5.0 × 10 −3 M with detection limits of 2.6 × 10 −6 and 6.1 × 10 −7 M, respectively. It is shown that the MIPMOA sensor exhibits higher sensitivity and selectivity to AMX than MIPANI sensor, as well as high accuracy in determining AMX in urine and blood plasma.
Zou J., Zhao G., Zhao G., Yu J.
Coordination Chemistry Reviews scimago Q1 wos Q1
2022-11-01 citations by CoLab: 38 Abstract  
• The basic principle of rational design of electrochemical chiral sensor for sensing is summarized. • Preparation of doped electrodes and their recognition performance for chiral enantiomers are summarized. • Construction of modified electrodes and their recognition performances are discussed. • The challenges and scientific prospects of new generation of modifiers in electrochemical chiral sensing are proposed. Chiral recognition, especially rendering specificity in biomolecular recognition, is a basic property of many biomolecules. Being closely related to the chirality of biomolecules, it has been regarded as one of the most important areas in biological and medical sciences due to the different effects in biological systems. Based on the possible interactions between chiral selectors and the enantiomers, various methods including chromatographic techniques such as gas or liquid chromatography, electromigration techniques such as capillary electrophoresis and so on were developed for the chiral separation and recognition of different optical isomers. Recently, chemical sensors and biosensors have been gradually designed and developed for the analysis of chiral compounds. Based on the difference in electrical response to different isomers, chiral identifications can be successfully implemented. Major successes in enantiomer recognition based on electrochemical analysis are reviewed. The research data available for highly enantio -selective recognition are categorized into several subgroups according to specific topics and critically discussed for the period since 1994, and the latest techniques for electrochemical chiral recognition of enantiomers were also reviewed. Simultaneously, a brief conclusive summary and future perspectives are presented, and the challenges and scientific prospects of the newest generation of electrode modifiers in electrochemical sensing are also proposed.
Ji J., Qu L., Wang Z., Li G., Feng W., Yang G.
Microchemical Journal scimago Q1 wos Q1
2022-04-01 citations by CoLab: 25 Abstract  
This study describes a facile strategy to synthesize the electrochemical chiral recognition tryptophan sensor based on carboxymethyl cellulose (CMC) and copper ions-complexed hydroxypropyl-β-cyclodextrin (HP-β-CD) in the presence of MWCNTs (GCE/MWCNTs/CMC-CD-Cu). Compared with D-Trp, the higher electrochemical signal of L-Trp was ascribed to the stronger affinity for L-type tryptophan, and the oxidation peak current ratio (I L /I D ) of DPV could be reached at 2.2 under the optimal experimental conditions. • A facile electrochemical chiral sensor (GCE/MWCNTs/CMC-CD-Cu) for Trp isomer was designed. • The oxidation peak current ratio (I L /I D ) of DPV could be reached at 2.2 under the optimal experimental conditions. • The stronger affinity for L-Trp leads to a higher electrochemical signal than D-Trp. • The sensor can achieve quantitative analysis of tryptophan enantiomers and has lower detection limit for L-Trp (0.81 μM) and D-Trp (1.9 μM). • The electrochemical chiral sensor could be utilized to analyze the amount of D-Trp in the enantiomer mixture solutions. The development of facile and convenient sensors for the chiral recognition of enantiomers is of great significance for medical and life science. Herein, a sensitive electrochemical sensor for the chiral recognition of tryptophan (Trp) enantiomers was developed based on the assembly of cellulose grafted with hydroxypropyl-β-cyclodextrins (CMC-CD), multi-walled carbon nanotubes (MWCNTs) and copper ions on the surface of a GCE. The morphologies and electrochemical behaviors of the prepared electrode (GCE/MWCNTs/CMC-CD-Cu) were characterized by differential pulse voltammetry (DPV), FT-IR, XPS, cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). The oxidation peak current ratio (I L /I D ) of DPV could be reached at 2.2 under the optimal experimental conditions. Compared with D-Trp, the higher electrochemical signal of L-Trp was ascribed to the stronger affinity for L-type tryptophan. Additionally, the as-prepared chiral sensor was successfully utilized to analyze the amount of D-Trp in the racemic mixture.
Chen F., Niu X., Yang X., Pei H., Guo R., Liu N., Mo Z.
2021-04-03 citations by CoLab: 11 Abstract  
A nanocomposite was synthesized from reduced graphene oxide (rGO), polyaniline (PANI), and carboxymethyl cellulose (CMC) as the initial materials by in situ polymerization. The substrate rGO provides many active sites for in situ polymerization of aniline and self-assembly of CMC. Scanning electron microscopy, X-ray diffraction, thermogravimetry, Raman, Infrared Spectroscopy, and X-ray photoelectron spectroscopies were used to characterize the morphology, electronic structure, and composition of different materials. The nanocomposite was used to modify a glassy carbon electrode (GCE) to obtain a sensor for chiral electrochemical recognition of tryptophan enantiomers. Their electrochemical properties and recognition abilities were investigated using cyclic voltammetry and differential pulse voltammetry, and the final consequence demonstrated that the modified GCE could well distinguish l-tryptophan and d-tryptophan. The enantiomeric selectivity is 2.26. The GCE was successfully used for the recognition of d-tryptophan and l-tryptophan in spiked serum and urine samples.
Moein M.M.
Talanta scimago Q1 wos Q1
2021-03-01 citations by CoLab: 56 Abstract  
Since chiral recognition mechanism based on molecularly imprinted polymers immerged, it has assisted countless chemical and electrochemical analytical sample preparation techniques. It has done this by enhancing the enatioseparation abilities of these techniques. The preparation and optimization of chiral molecularly imprinted polymers (CMIPs) are two favored methods in the separation and sensor fields. This review aims to present an overview of advances in the preparation and application of CMIPs in analytical approaches in different available formats (eg. column, monolithic column, cartridge, membrane, nanomaterials, pipette tip and stir bar sorptive) over the last decade. In addition, progress in the preparation and development of CMIPs-based sensor fields have been also discussed. Finally, the main application challenges of CMIPs are also summarily explained, as well as upcoming prospects in the field. • Chiral molecularly imprinted polymers (CMPs) can offer enormous potential in enatioseparation field. • The last decade advances for the preparation of CMIPs in different formats are detailed. • The recent progress on CMIPs in sensor field are reviewed. • Factors affecting the CMIPs performance are commented. • The main challenges and upcoming prospects in CMIPs field are discussed.
Zagitova L.R., Maistrenko V.N., Yarkaeva Y.A., Zagitov V.V., Zilberg R.A., Kovyazin P.V., Parfenova L.V.
2021-01-01 citations by CoLab: 30 Abstract  
To achieve satisfactory recognition and determination of tryptophan (TRP) enantiomers a chiral voltammetric sensor based on carbon black paste electrode (CBPE) containing Carboblack C powder and 3-neomenthylindene (NMI) chiral selector is developed in this work. A possible recognition mechanism as well as chiral selectivity have been explained using the molecular dynamics simulation. It was shown that 3-neomenthylindene attracts to TRP enantiomers via Van der Waals and π-π-stacking interactions. Compared with D-TRP, the sensor indicates favorable chiral recognition towards L-TRP with a selectivity coefficient of 1.34. The higher response signal of L-TRP than D-TRP is due to the energetically more favorable interaction of 3-neomenthylindene with L-TRP, which is confirmed by a change in the total energy of the system. CBPE modified by NMI was characterized by cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), scanning electron microscopy (SEM), and Fourier transform infrared spectroscopy (FT-IR). The electrochemical and analytical characteristics of the sensor and conditions of the voltammogram registration were studied by differential pulse voltammetry (DPV). It was found that the oxidation of TRP enantiomers on CBPE/NMI is the diffusion-controlled process. The experimental results indicate a linear correlation between the peak currents of TRP enantiomers and their concentration in the range from 2.5 μM to 0.3 mM, leading to a detection limit of 1.71 μM and 2.23 μM for L- and D-TRP, respectively. The practical capabilities of the proposed sensor were demonstrated by analyzing human urine and blood plasma with satisfactory recoveries ranging from 95.2% to 99.0%. L-TRP was recognized in dietary supplements using projection to latent structures discriminant analysis. The present sensor also can detect the enantiomeric composition based on current signals with the different total concentrations of the mixture. The selectivity, stability, and reproducibility of the proposed sensor were studied as well.
Maistrenko V.N., Zil’berg R.A.
Journal of Analytical Chemistry scimago Q3 wos Q4
2020-12-19 citations by CoLab: 17 Abstract  
The review presents exhaustive information for the last 5 years on the trends and methods of research, development, and application of enantioselective voltammetric sensors on the basis of new chiral materials for the recognition of enantiomers of biologically active and medicinal compounds. Enantioselective sensors on the basis of chiral Cu, Au, Ag, Pt, and Pd nanoparticles and single crystals, mesoporous metals with molecular imprints, single-wall carbon nanotubes, smart polymers, metal–organic frameworks and supramolecular assemblies, and chiral ionic liquids are considered. Examples of the recognition and determination of enantiomers in various samples and analytical characteristics of the proposed sensors are given. Problems and prospects of using enantioselective voltammetric sensors for the chiral recognition of optically active compounds are discussed.
Niu X., Yang X., Li H., Liu J., Liu Z., Wang K.
Microchimica Acta scimago Q1 wos Q1
2020-11-27 citations by CoLab: 75 Abstract  
Chirality is a universal phenomenon in nature and an essential attribute of life systems. Chiral recognition has very important research value in many fields. Amino acids and other chiral molecules are the basic components of human body. Understanding the configuration of chiral molecules is beneficial not only to the development of life science, but also to the development of chiral recognition. Compared with other traditional chiral recognition methods, electrochemical methods have the advantages of rapid detection, simple operation, low price, and high sensitivity, which has been widely concerned. In this review, we present an overview of chiral materials in a view of various chiral selectors, including amino acids and their derivatives, proteins, polysaccharides, chiral ligand exchange compounds, chiral cavity compounds (such as cyclodextrin, cucurbituril, calixarene, crown ether), and chiral ionic liquids, which were applied for the recognition of chiral molecules. Besides the chiral recognition mechanisms, some critical challenges and outlooks in the field of electrochemical chiral sensing interfaces are also discussed.
Ashwin B.C., Shanmugavelan P., Muthu Mareeswaran P.
2020-09-29 citations by CoLab: 13 Abstract  
The electrochemical behaviour of the host–guest complexes formed by cyclodextrin, calixarene and cucurbiturils host molecules with simple organic guest molecules and their applications using electrochemical studies are discussed in detail in this review. The change in the redox behaviour of the individual molecules upon complexation and the unique properties of the complexes formed are elaborated. The methodology and various electrochemical techniques used for the investigation of these host–guest are categorised with respect to the analytical methods. The electrochemical behaviour upon binding of host with guest and their applications are analysed in detail. The applications are ranging from simple molecular detection to sensing of toxicants, pollutants and biomolecules. The identification of cancer cells and discrimination of chiral molecules are the noteworthy application of these supramolecular electrochemical sensing systems. The aspects discussed in this review could help to extend the electrochemical applications of host–guest systems to utilize them in the highly important applications like cancer detection and pollutant detection.
Bernardo-Bermejo S., Sánchez-López E., Castro-Puyana M., Marina M.L.
2020-03-01 citations by CoLab: 164 Abstract  
The implications of chirality in different environments are already well known and reported extensively in the literature. Capillary Electrophoresis, a separation technique that only requires few nanoliters of sample, has demonstrated its potential for chiral analysis in the past years. The aim of this article is to provide an overview on the fundamentals and characteristics of Chiral Capillary Electrophoresis as well as the main advances and trends in this topic. Special attention is paid to the most recent technological and methodological developments achieved mainly in the most employed separation mode (Electrokinetic Chromatography). The most noteworthy and recent applications reported on the enantiomeric separation and determination of compounds in pharmaceutical, food, biomedical, environmental or forensic samples will also be critically overviewed. The characteristics of the developed methodologies will be detailed in Tables and future trends will also be discussed.
Zilberg R.A., Maistrenko V.N., Zagitova L.R., Guskov V.Y., Dubrovsky D.I.
2020-03-01 citations by CoLab: 25 Abstract  
A chiral electrochemical sensor based on carbon black paste electrode (CBPE), consisting of graphitized carbon black powder Carboblack C modified by nanoclusters of 3,4,9,10-perylenetetracarboxylic acid (PTCA) for the selective recognition and determination of warfarin (WA) enantiomers is described in this work. The spontaneous appearance of two-dimensional space group during self-assembly by an external induction of PTCA nanoclusters provides their chirality. It was found that the CBPE modified by PTCA afforded specific interaction with WA enantiomers and acted as a chiral selector, which affected the current and peak potential change. CBPE modified by PTCA was characterized by cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS) and scanning electron microscopy (SEM). The electrochemical and analytical characteristics of the sensor, and conditions of the voltammogram registration were studied by differential pulse voltammetry (DPV). The experimental results indicate a linear correlation between the peak current of warfarin enantiomers and their concentration in the range from 5 μM to 0.16 mM, leading to a detection limit of 3.09 μM and 4.02 μM for R- and S-WA, respectively. The potential ability of proposed electrode for WA enantiomer determinations has been evaluated by analyzing human urine and blood plasma with a recovery ranging from 97.1% to 102.9%. The present sensor can determine ratio of WA isomer's in enantiomeric mixture.
Tashiro S., Shionoya M.
Accounts of Chemical Research scimago Q1 wos Q1
2020-01-23 citations by CoLab: 88 Abstract  
Molecular recognition is one of the fundamental events in biological systems, as typified by enzymes that enable highly efficient and selective catalytic reactions through precise recognition of substrate(s) and cofactor(s) in the binding pockets. Chemists therefore have long been inspired by such excellent molecular systems to develop various synthetic receptors with well-defined binding sites. Their effort is currently being devoted to the construction of not only molecular receptors but also self-assembled host compounds possessing connected cavities (pores) in the crystalline frameworks to rationally design functional porous materials capable of efficiently adsorbing molecules or ions at binding sites on the pore walls. However, it is still challenging to design multiple distinct binding sites that are precisely arranged in an identical framework, which is currently one of the most important targets in this field to realize elaborate molecular systems beyond natural enzymes.In this Account, we provide an overview of porous crystals with well-defined molecular recognition sites. We first show several strategies for arranging macrocyclic binding sites in crystalline frameworks such as metal-organic frameworks, porous molecular crystals, and covalent organic frameworks. Porous metal-macrocycle frameworks (MMFs) that we have recently developed are then described as a new type of porous crystals with well-defined multiple distinct binding sites. The MMF-1 crystal, which was developed first and is composed of four stereoisomers of helical PdII3-macrocycle complexes, has one-dimensional channels with dimensions of 1.4 nm × 1.9 nm equipped with enantiomeric pairs of five distinct binding sites. This structural feature of MMF-1 therefore allows for site-selective and asymmetric arrangement of not only single but also multiple guest molecules in the crystalline channels based on molecular recognition between the guests and the multiple binding sites. This characteristic was also exploited to develop a heterogeneous catalyst by non-covalently immobilizing an organic acid on the pore surface of MMF-1 to conduct size-specific catalytic reactions. In addition, adsorption of a photoreactive substrate in MMF was found to switch the photoreaction pathway to cause another reaction with the aid of photoactivated PdII centers arranged on the pore walls. Furthermore, the dynamic, transient process of molecular arrangement incorporated in MMF-1 has been successfully visualized by single-crystal X-ray diffraction analysis. The formation of homochiral MMF-2 composed of only (P)- or (M)-helical PdII3-macrocycle complexes is also described. Thus, macrocycle-based porous crystals with a complex structure such as MMFs are expected to serve as novel porous materials that have great potential to mimic or surpass enzymes by utilizing well-defined multiple binding sites capable of spatially arranging a catalyst, substrate, and effector for highly selective and allosterically tunable catalytic reactions, which can be also visualized by crystallographic analysis because of their crystalline nature.
Zhang C., Woolfork A.G., Suh K., Ovbude S., Bi C., Elzoeiry M., Hage D.S.
2020-01-01 citations by CoLab: 40 Abstract  
Affinity capillary electrophoresis (ACE) is a separation technique that combines a biologically-related binding agent with the separating power and efficiency of capillary electrophoresis. This review will examine several classes of binding agents that have been used in ACE and applications that have been described for the resulting methods in clinical or pharmaceutical analysis. Binding agents that will be considered are antibodies, aptamers, lectins, serum proteins, carbohydrates, and enzymes. This review will also describe the various formats in which each type of binding agent has been used in CE, including both homogeneous and heterogeneous methods. Specific areas of applications that will be considered are CE-based immunoassays, glycoprotein/glycan separations, chiral separations, and biointeraction studies. The general principles and formats of ACE for each of these applications will be examined, along with the potential advantages or limitations of these methods.
Wattanakit C., Kuhn A.
Chemistry - A European Journal scimago Q1 wos Q2
2019-12-30 citations by CoLab: 22 Abstract  
The concept of encoding molecular information in bulk metals has been proposed over the past decade. The structure of various types of molecules, including enantiomers, can be imprinted in achiral substrates. Typically, to encode metals with chiral information, several approaches, based on chemical and electrochemical concepts, can be used. In this Minireview, recent achievements with respect to the development of such materials are discussed, including the entrapment of chiral biomolecules in metals, the chiral imprinting of metals, as well as the combination of imprinting with nanostructuring. The features and potential applications of these designer materials, such as chirooptical properties, enantioselective adsorption and separation, as well as their use for asymmetric synthesis will be presented. This will illustrate that the development of molecularly encoded metal structures opens up very interesting perspectives, especially in the frame of chiral technologies.
Salikhov R., Zilberg R., Mullagaliev I., Salikhov T., Teres Y., Bulysheva E., Ostaltsova A.
Current Nanomedicine scimago Q4
2025-02-01 citations by CoLab: 0 Abstract  
Aim: Currently, developing composite and nanocomposite materials based on natural polymers is attracting the growing attention of scientists. In particular, chitosan succinamide, a modified biopolymer, has good biocompatibility, biodegradability, and electrical conductivity, allowing it to be used as a functional material for creating various electronic devices, including sensors for use in medicine and pharmaceuticals. Composite sensors based on chitosan deriva-tives have found application for the recognition and determination of enantiomers of tryptophan, tyrosine, naproxen, and propranolol in human urine and blood plasma in tablet forms of drugs without a preliminary active substance. Methods: This article discusses the studies on composite and nanocomposite thin-film structures based on chitosan succinamide obtained using various fillers, such as graphene oxide, single-walled carbon nanotubes, and carbon adsorbents. Result: The studies used cyclic voltammetry, electrochemical impedance spectroscopy, and atom-ic force microscopy. The results created field-effect transistors based on the films in question as the transport layer. Conclusion: The mobility of charge carriers was estimated, and the following values were ob-tained: μ(SCTS) = 0.173cm2/V·s; μ(SCTS-GO) = 0.509 cm2/V·s; μ(SCTS-CP) = 0.269 cm2/V·s; μ(SCTS-CB) = 0.351cm2/V·s; μ(SCTS-SWCNT) = 0.713 cm2/V·s.
Nazyrov M.I., Perfilova Y.A., Abdullin Y.R., Kovyazin P.V., Maistrenko V.N.
2024-12-22 citations by CoLab: 0 Abstract  
To recognize and determine the enantiomers of clopidogrel, a sensor system based on a glassy carbon electrode modified with Carbopack X mesoporous carbon black and cyclopentadiene derivatives – (1S)-2-cyclopenta-2,4-dien-1-yl-1,7,7-trimethylbicyclo[2.2.1]heptane; (1S, 2S, 4R)-2-cyclopenta-1,3-dien-1-yl-1-isopropyl-4-methylcyclohexane; 9-[(1S,2S,5R)-2-isopropyl-5-methylcyclohexyl]-9H-fluorene. Due to the unique properties of Carbopack X, such as large surface area and high conductivity, it was possible to obtain a mechanically stable and sensitive sensor layer that firmly retains chiral selector molecules on its surface. The morphological, electrochemical and analytical properties of the obtained sensors were studied by scanning electron microscopy, electrochemical impedance spectroscopy, cyclic and differential pulse voltammetry. The determination of clopidogrel enantiomers in biological fluids has been carried out; linear dependences of oxidation peak currents on their concentration in solution for all sensors are preserved in the concentration range from 1 × 10–6 to 5 × 10–4 M. The sensors are cross-sensitized, which allowed combining them into a sensor system with high enantioselectivity and sensitivity towards clopidogrel enantiomers. With the proposed sensor system, the probability of correctly recognizing samples increases compared to single sensors. In all cases, the content of R-clopidogrel in the mixture is correctly determined with a relative error not exceeding 9% and a degree of discovery ranging from 96 to 102%.
Zagitova Liana R., Gainanova Svetlana I., Perfilova Yuliya A., Nazyrov Marat I., Abramov Ilya A., Gubaidullin Rinat R.
Microchemical Journal scimago Q1 wos Q1
2024-07-01 citations by CoLab: 2 Abstract  
Enantioselective sensors are potentially in demand at all stages of the production, storage and use of drugs, including identifying impurities of undesirable isomers and improving stereoselective synthesis methods. A key aspect for enantioselective sensors design is the development of appropriate molecular architectures that make it possible to create recognition sites with different affinities for enantiomers. This experimental work proposes a new chiral sensor based on glassy carbon electrode (GCE) modified by graphene oxide (GO) covalent functionalized with pentacyclic triterpenoid betulonic acid (BetA) for voltammetric recognition and determination of propranolol (Prop) enantiomers. Characterization of the materials was carried out using FTIR spectroscopy, scanning electron microscopy and cyclic voltammetry. Differential pulse voltammetry was used for Prop enantiomers recognition and quantification. The potential difference reached 30 mV along with enanitoselectivity coefficient ipS/ipR equal to 1.30. The calculated binding energy for S-Prop/GO-BetA complex is higher by 4.801 kcal moll−1 compared to R-Prop/GO-BetA indicating a more favorable mutual arrangement of molecules. The linear determination range was established as 5.0 × 10-6 ∼ 1.0 × 10-4 mol·L-1 and 1.0 × 10-4 ∼ 4.0 × 10-4 mol·L-1 for both enantiomers. The detection limits were determined to be 3.9⋅10-7 mol·L-1 and 5.0⋅10-7 mol·L-1 for S-Prop and R-Prop, respectively. The standard spike-recovery tests were carried out in human biological fluids with recoveries 97.3 % − 106.9 % for both enantiomers. The proposed sensor was used to determine the ratio of Prop enantiomers in mixture by regression analysis with projection to latent structures (PLS). The purpose was to build a PLS-model based on a calibration set containing a known number of Prop enantiomers and recognize a test set prepared independently. All samples of test set are correctly identified and the RSD did not exceed 8.7 %. GCE modified by covalent functionalized GO with BetA showed better stability compared with noncovalent functionalization in terms of electrode degradation.
Nazyrov M.I., Perfilova Y.A., Abdullin Y.R., Kovyazin P.V., Maistrenko V.N.
Journal of Analytical Chemistry scimago Q3 wos Q4
2024-06-21 citations by CoLab: 0 Abstract  
To recognize and determine clopidogrel enantiomers, a sensor system was developed based on a glassy carbon electrode modified with mesoporous Carbopack X carbon black and cyclopentadiene derivatives (1S)-2-cyclopent-2,4-dien-1-yl-1,7,7-trimethylbicyclo[2.2.1]heptane, (1S,2S,4R)-2-cyclopent-1-en-1-yl-1-isopropyl-4-methylcyclohexane, and 9-[(1S,2S,5R)-2-isopropyl-5-methylcyclohexyl]-9H-fluorene. Because of the unique properties of Carbopack X, such as a large surface area and high conductivity, a mechanically stable and a sensitive sensor layer was obtained, which firmly retains chiral selector molecules on its surface. The morphological, electrochemical, and analytical properties of the obtained sensors were studied using scanning electron microscopy, electrochemical impedance spectroscopy, and cyclic and differential pulse voltammetry. Сlopidogrel enantiomers were determined in biological fluids, and linear dependences of oxidation peak currents on their concentration in solution were maintained for all sensors in the concentration range from 1 × 10–6 to 5 × 10–4 M. The sensors exhibited cross-sensitive properties, enabling them to be combined into a sensor array with high enantioselectivity and sensitivity towards clopidogrel enantiomers. Using the proposed sensor array system increases the probability of correctly identifying samples compared to individual sensors. In all cases, the concentration of R-clopidogrel in a mixture was determined correctly with a relative standard deviation not exceeded 9% and recovery ranged from 96 to 102%.

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