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Herein we introduce a novel water-based graphite ink modified with multiwalled carbon nanotubes, designed for the development of the first wearable self-powered biosensor enabling alcohol abuse detection through sweat analysis. The stencil-printed graphite (SPG) electrodes, printed onto a flexible substrate, were modified by casting multiwalled carbon nanotubes (MWCNTs), electrodepositing polymethylene blue (pMB) at the anode to serve as a catalyst for nicotinamide adenine dinucleotide (NADH) oxidation, and hemin at the cathode as a selective catalyst for H2O2 reduction. Notably, alcohol dehydrogenase (ADH) was additionally physisorbed onto the anodic electrode, and alcohol oxidase (AOx) onto the cathodic electrode. The self-powered biosensor was assembled using the ADH/pMB-MWCNTs/SPG||AOx/Hemin-MWCNTs/SPG configuration, enabling the detection of ethanol as an analytical target, both at the anodic and cathodic electrodes. Its performance was assessed by measuring polarization curves with gradually increasing ethanol concentrations ranging from 0 to 50 mM. The biosensor demonstrated a linear detection range from 0.01 to 0.3 mM, with a detection limit (LOD) of 3 ± 1 µM and a sensitivity of 64 ± 2 µW mM-1, with a correlation coefficient of 0.98 (RSD 8.1%, n = 10 electrode pairs). It exhibited robust operational stability (over 2800 s with continuous ethanol turnover) and excellent storage stability (approximately 93% of initial signal retained after 90 days). Finally, the biosensor array was integrated into a wristband and successfully evaluated for continuous alcohol abuse monitoring. This proposed system displays promising attributes for use as a flexible and wearable biosensor employing biocompatible water-based inks, offering potential applications in forensic contexts.
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The successful synthesis of La-doped CoFe LDH@rGO nanocomposite is reported combining the advantages of LDH and rGO and shows promising performances in electrochemical sensors. The structure of the obtained nanocomposite was investigated using Fourier transform infrared spectroscopy (FTIR), X-ray diffraction pattern (XRD), and field emission scanning electron microscope images (FE-SEM). Then, it was directly utilized to construct a carbon paste electrode (CPE) for urea detection. The electrochemical performance of the sensor was evaluated by various electrochemical methods. The La-CoFe LDH@rGO electrode exhibited excellent electrocatalytic properties, including a wide linear working range of 0.001-23.5 mM, very high sensitivity of 1.07 ± 0.023 µA µM-1 cm-2, a low detection limit of 0.33 ± 0.11 µM, and rapid response time of 5 s towards urea detection at the working potential of 0.4 V. Furthermore, the sensor displayed a high selectivity in different matrices, appropriate reproducibility, and long shelf life without activity loss during 3 months of storage under ambient conditions. Further tests were performed on serum and milk samples to confirm the capability of the proposed sensor for practical applications, demonstrating a reasonable recovery of 94.8 to 102% with an RSD value below 3%. Consequently, the synergistic effect of each component led to the good electrocatalytic activity of the modified electrode towards urea.
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A ratiometric electrochemical immunosensor is proposed for simultaneous detection of cellular-myelocytomatosis oncoprotein (C-myc) and B-cell lymphoma 2 (Bcl-2) via the potential-resolved strategy. It relied on multi-role co-loaded alloy composites (CLACs) and poly(3,4-ethylenedioxythiophene) (PEDOT)-graphene oxide (GO)-multiwalled carbon nanotubes (MWCNTs) (PGM) modified electrodes. CLACs with good catalytic and enzyme-like properties were synthesized in one step by loading tetramethylbenzidine (TMB) or methylene blue (MB) into Pt-Pd alloy and used as label materials. After immunological reactions, CLACs showed distinguishable dual differential pulse voltammetry signals at - 0.26 V and 0.38 V, corresponding to C-myc and Bcl-2, and the PGM had an electrochemical signal at 1.2 V, which could be used as a reference signal to construct a ratiometric sensor. CLACs had a satisfactory synergistic effect with the PGM, and eventually achieved quadruple signal amplification. Thus, benefiting from multiple magnification and ratiometric self-calibration functions, sensitive detections of C-myc and Bcl-2 were achieved, with detection limits as low as 0.5 and 2.5 pg mL-1, respectively. Additionally, when the designed method was applied to blood samples from lymphoma patients, results consistent with the ELISA kit were obtained. This will open avenues for constructing multiple protein detection sensors.
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Técnicas Biossensoriais , Nanotubos de Carbono , Humanos , Imunoensaio , Ligas , CalibragemRESUMO
Sunset Yellow FCF (SY FCF) is one of the widely used synthetic azo dyes in the food industry whose content has to be controlled for safety reasons. Electrochemical sensors are a promising tool for this type of task. A voltammetric sensor based on a combination of tin and cerium dioxide nanoparticles (SnO2-CeO2 NPs) with surfactants has been developed for SY FCF determination. The synergetic effect of both types of NPs has been confirmed. Surfactants of various natures (sodium lauryl sulfate (SLS), Brij® 35, and hexadecylpyridinium bromide (HDPB)) have been tested as dispersive media. The best effects, i.e., the highest oxidation currents of SY FCF, have been observed in the case of HDPB. The sensor demonstrates a 4.5-fold-higher electroactive surface area and a 38-fold-higher electron transfer rate compared to the bare glassy carbon electrode (GCE). The electrooxidation of SY FCF is an irreversible, two-electron, diffusion-driven process involving proton transfer. In differential pulse mode in Britton-Robinson buffer (BRB) pH 2.0, the sensor gives a linear response to SY FCF from 0.010 to 1.0 µM and from 1.0 to 100 µM with an 8.0 nM detection limit. The absence of an interferent effect from other typical food components and colorants has been shown. The sensor has been tested on soft drinks and validated with the standard chromatographic method.
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Manganese(II) complexes with phenanthroline derivatives modified with different substituents were synthesized and incorporated into Nafion layers covering the surfaces of glassy carbon electrodes and were studied electrochemically. Formal potentials and apparent diffusion coefficients were calculated and discussed. The suitability for electrocatalytic oxidation of ascorbic acid and glycolic acid was examined. The surfaces of modified electrodes were characterized using atomic force microscopy.
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Carbono , Polímeros de Fluorcarboneto , Fenantrolinas , Carbono/química , Manganês , Eletroquímica , EletrodosRESUMO
Increased evidence has documented a direct association between Ciprofloxacin (CFX) intake and significant disruption to the normal functions of connective tissues, leading to severe health conditions (such as tendonitis, tendon rupture and retinal detachment). Additionally, CFX is recognized as a potential emerging pollutant, as it seems to impact both animal and human food chains, resulting in severe health implications. Consequently, there is a compelling need for the precise, swift and selective detection of this fluoroquinolone-class antibiotic. Herein, we present a novel graphene-based electrochemical sensor designed for Ciprofloxacin (CFX) detection and discuss its practical utility. The graphene material was synthesized using a relatively straightforward and cost-effective approach involving the electrochemical exfoliation of graphite, through a pulsing current, in 0.05 M sodium sulphate (Na2SO4), 0.05 M boric acid (H3BO3) and 0.05 M sodium chloride (NaCl) solution. The resulting material underwent systematic characterization using scanning electron microscopy/energy dispersive X-ray analysis, X-ray powder diffraction and Raman spectroscopy. Subsequently, it was employed in the fabrication of modified glassy carbon surfaces (EGr/GC). Linear Sweep Voltammetry studies revealed that CFX experiences an irreversible oxidation process on the sensor surface at approximately 1.05 V. Under optimal conditions, the limit of quantification was found to be 0.33 × 10-8 M, with a corresponding limit of detection of 0.1 × 10-8 M. Additionally, the developed sensor's practical suitability was assessed using commercially available pharmaceutical products.
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Ciprofloxacina , Grafite , Animais , Humanos , Fluoroquinolonas , Carbono , EletrodosRESUMO
Catecholamines (CAs), which include adrenaline, noradrenaline, and dopamine, are neurotransmitters and hormones that critically regulate the cardiovascular system, metabolism, and stress response in the human body. The abnormal levels of these molecules can lead to the development of various diseases, including pheochromocytoma and paragangliomas, Alzheimer's disease, and Takotsubo cardiomyopathy. Due to their low cost, high sensitivity, flexible detection strategies, ease of integration, and miniaturization, electrochemical techniques have been extensively employed in the detection of CAs, surpassing traditional analytical methods. Electrochemical detection of CAs in real samples is challenging due to the tendency of poisoning electrode. Chemically modified electrodes have been widely used to solve the problems of poor sensitivity and selectivity faced by bare electrodes. There are a few articles that provide an overview of electrochemical detection and efficient enrichment of CAs, but there is a dearth of updates on the role of CAs in the pathogenesis of diseases. Additionally, there is still a lack of systematic synthesis with a focus on modified electrodes for electrochemical detection. Thus, this review provides a summary of the recent clinical pathogenesis of CAs and the modified electrodes for electrochemical detection of CAs published between 2017 and 2022. Moreover, challenges and future perspectives are also highlighted. This work is expected to provide useful guidance to researchers entering this interdisciplinary field, promoting further development of CAs pathogenesis, and developing more novel chemically modified electrodes for the detection of CAs.
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In this work, we conducted a study of the interaction between DNA and favipiravir (FAV). This chemotherapeutic compound is an antiviral drug for the treatment of COVID-19 and other infections caused by RNA viruses. This paper examines the electroanalytical characteristics of FAV. The determined concentrations correspond to therapeutically significant ones in the range of 50-500 µM (R2 = 0.943). We have shown that FAV can be electro-oxidized around the potential of +0.96 V ÷ +0.98 V (vs. Ag/AgCl). A mechanism for electrochemical oxidation of FAV was proposed. The effect of the drug on DNA was recorded as changes in the intensity of electrochemical oxidation of heterocyclic nucleobases (guanine, adenine and thymine) using screen-printed graphite electrodes modified with single-walled carbon nanotubes and titanium oxide nanoparticles. In this work, the binding constants (Kb) of FAV/dsDNA complexes for guanine, adenine and thymine were calculated. The values of the DNA-mediated electrochemical decline coefficient were calculated as the ratio of the intensity of signals for the electrochemical oxidation of guanine, adenine and thymine in the presence of FAV to the intensity of signals for the electro-oxidation of these bases without drug (S, %). Based on the analysis of electrochemical parameters, values of binding constants and spectral data, intercalation was proposed as the principal mechanism of the antiviral drug FAV interaction with DNA. The interaction with calf thymus DNA also confirmed the intercalation mechanism. However, an additional mode of interaction, such as a damage effect together with electrostatic interactions, was revealed in a prolonged exposure of DNA to FAV.
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This paper presents an application for a molybdenum disulfide nanomaterial with multiwalled carbon nanotubes (MoS2@MWCNT/E) in a modified electrode substrate for the detection of uric acid (UA). The modified electrode generates a substantial three-fold increase in the anodic peak current for UA compared to the unmodified MWCNT electrode (MWCNT/E). The MoS2@MWCNT/E surface was characterized by cyclic voltammetry (CV), scanning electron microscopy (SEM), energy-dispersive spectroscopy (EDS) and electrochemical impedance spectroscopy (EIS). The achieved detection limit stood at 0.04 µmol/L, with a relative standard deviation (RSD) of 2.0% (n = 10). The method's accuracy, assessed through relative error and percent recovery, was validated using a urine standard solution spiked with known quantities of UA.
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PURPOSE: Food forensics is an emerging field and the initial part of this review showcases the toxic effects and the instrumental methods applied for the detection of the most commonly used azo dyes. Electrochemical detection has a lot of advantages and hence the significance of the most important techniques used in the electrochemical detection is discussed. The major part of this review highlights the surface modified electrodes, utilized for the detection of the most important azo dyes to achieve low detection limit (LOD). METHODS: A thorough literature study was conducted using scopus, science direct and other scientific databases using specific keywords such as toxic azo dyes, electrochemical detection, modified electrodes, LOD etc. The recent references in this field have been included. RESULTS: From the published literature, it is observed that with the growing interests in the field of electrochemical techniques, a lot of importance have been given in the area of modifying the working electrodes. The results unambiguously show that the modified electrodes outperform bare electrodes and offer a lower LOD value. CONCLUSION: According to the literature reports it can be concluded that, compared to other detection methods, electrochemical techniques are much dependable and reproducible. The fabrication of the electrode material with the appropriate modifications is the main factor that influences the sensitivity. Electrochemical sensors can be designed to be more sensitive, more reliable, and less expensive. These sensors can be effectively used by toxicologists to detect trace amounts of harmful dyes in food samples.
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In this work, palladium nanoparticles (PdNPs)/p1,5-DAN/ carbon paste electrode (CPE) and p1,5-DAN/CPE sensors have been developed for determination of hydrogen peroxide. Both sensors showed a highly sensitive and selective electrochemical behaviour, which were derived from a large specific area of poly 1,5 DAN and super excellent electroconductibility of PdNPs. PdNPs/p1,5-DAN/CPE exhibited excellent performance over p1,5-DAN/CPE. Thus, it was used for detecting hydrogen peroxide (H2O2) with linear ranges of 0.1 to 250 µM and 0.2 to 300 µM as well as detection limits (S/N = 3) of 1.0 and 5.0 nM for square wave voltammetry (SWV) and cyclic voltammetry (C.V) techniques, respectively. The modified CPE has good reproducibility, adequate catalytic activity, simple synthesis and stability of peak response during H2O2 oxidation on long run that exceeds many probes. Both reproducibility and stability for H2O2 detection are attributable to the PdNPs immobilized on the surface of p1,5-DAN/CPE. The modified CPE was used for determining H2O2 in real specimens with good stability, sensitivity, and reproducibility.
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The aim of this work was to develop an electrochemical approach for the analysis of DNA degradation and fragmentation in apoptotic cells. DNA damage is considered one of the major causes of human diseases. We analyzed the cleavage processes of the circular plasmid pTagGFP2-N and calf thymus DNA, which were exposed to restriction endonucleases (the restriction endonucleases BstMC I and AluB I and the nonspecific endonuclease I). Genomic DNA from the leukemia K562 cell line was used as a marker of the early and late (mature) stages of apoptosis. Registration of direct electrochemical oxidation of nucleobases of DNA molecules subjected to restriction endonuclease or apoptosis processes was proposed for the detection of these biochemical events. Label-free differential pulse voltammetry (DPV) has been used to measure endonuclease activities and DNA damage using carbon nanotube-modified electrodes. The present DPV technique provides a promising platform for high-throughput screening of DNA hydrolases and for registering the efficiency of apoptotic processes. DPV comparative analysis of the circular plasmid pTagGFP2-N in its native supercoiled state and plasmids restricted to 4 and 23 parts revealed significant differences in their electrochemical behavior. Electrochemical analysis was fully confirmed by means of traditional methods of DNA analysis and registration of apoptotic process, such as gel electrophoresis and flow cytometry.
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Layered double hydroxides (LDHs), also named hydrotalcite-like compounds, are anionic clays with a lamellar structure which have been extensively used in the last two decades as electrode modifiers for the design of electrochemical sensors. These materials can be classified into LDHs containing or not containing redox-active centers. In the former case, a transition metal cation undergoing a reversible redox reaction within a proper potential window is present in the layers, and, therefore, it can act as electron transfer mediator, and electrocatalyze the oxidation of an analyte for which the required overpotential is too high. In the latter case, a negatively charged species acting as a redox mediator can be introduced into the interlayer spaces after exchanging the anion coming from the synthesis, and, again, the material can display electrocatalytic properties. Alternatively, due to the large specific surface area of LDHs, molecules with electroactivity can be adsorbed on their surface. In this review, the most significant electroanalytical applications of LDHs as electrode modifiers for the development of voltammetric sensors are presented, grouping them based on the two types of materials.
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Paracetamol is a non-steroidal,anti-inflammatory drug widely used in pharmaceutical applications for its sturdy,antipyretic and analgesic action.However,an overdose of paracetamol can cause fulminant hepatic necrosis and other toxic effects.Thus,the development of advantageous analytical tools to detect and determine paracetamol is required.Due to simplicity,higher sensitivity and selectivity as well as costefficiency,electrochemical sensors were fully investigated in last decades.This review describes the advancements made in the development of electrochemical sensors for the paracetamol detection and quantification in pharmaceutical and biological samples.The progress made in electrochemical sensors for the selective detection of paracetamol in the last 10 years was examined,with a special focus on highly innovative features introduced by nanotechnology.As the literature is rather extensive,we tried to simplify this work by summarizing and grouping electrochemical sensors according to the by which manner their substrates were chemically modified and the analytical performances obtained.
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RESUMO Um processo eletroanalítico da detecção quantitativa dos íons de zinco bivalente sobre as novas bases de Schiff no modo galvanostático tem sido simulado teoricamente. O respectivo modelo matemático tem sido desenvolvido e analisado mediante a teoria de estabilidade linear e da análise de bifurcações. Foi estabelecido que o sistema é eficiente tanto do ponto de vista eletroanalítico, como do ponto de vista eletrossintético, por ser facilmente estabilizado o estado estacionário. Todavia, o comportamento oscilatorio, neste sistema é mais provável que no caso clássico do desempenho de sensores, baseados em polímeros condutores e outros materiais orgânicos, por haver influências na dupla camada elétrica, causadas pela reação química da formação de complexo.
SUMMARY An electroanalytical process of the quantitative determination of bivalent zinc ions over the novel Schiff bases in galvanostatic mode has been theoretically simulated. The correspondent mathematical model has been developed and analyzed by means of linear stability theory and bifurcation analysis. It was shown that the system is efficient from both electroanalytical and electrosynthetical points of view, as the steady-state is easily stabilized. Nevertheless, the oscillatory behavior in this system is more probable than in the classic case of the sensors, based on conducting polymers and other organic materials, as there are double electric layer influences, caused by complex formation.
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RESUMEN Mediante el análisis mecanístico teórico, ha sido evaluada la posibilidad del empleo del oxihidróxido de vanadio como modificador de electrodo para la detección electroquímica de sacarina. El proceso electroanalítico se realiza a través de un proceso catódico. El modelo matemático correspondiente ha sido analizado mediante la teoría de estabilidad lineal y análisis de bifurcaciones. El análisis del modelo ha mostrado que el oxihidróxido de vanadio puede ser un modificador eficiente para la detección electroquímica de la sacarina en las condiciones del pH suficientemente ácido para mover el proceso, pero insuficiente para disolver el oxihidróxido. Las causas de los comportamientos oscilatorio y monotónico también fueron estipuladas.
SUMMARY By means of the theoretical mechanistic analysis, the possibility of the use of vanadium oxyhydroxide as electrode modifier for saccharin electrochemical determination has been evaluated. The electroanalytical process is realizing by a cathodic route. The correspondent mathematical model has been analyzed by means of the linear stability theory and bifurcation analysis. The analysis of the model has shown that the vanadium oxyhydroxide is an efficient electrode modifier for saccharin electrochemical detection in pH sufficiently low to maintain the process, but insufficiently acidic to dissolve the oxyhydroxide. The causes for the oscillatory and monotonic instabilities have also been derived.
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RESUMEN La posibilidad de usar el oxihidróxido del cobalto en la detección electroquímica de la gabapentina ha sido evaluada, y se sugirió un mecanismo del desempeño del analito y del modificador. Este fue desarrollado y analizado (mediante la teoría de estabilidad lineal y análisis de bifurcaciones) un modelo matemático basado en este mecanismo. La evaluación teórica confirma que el oxihidróxido de cobalto puede ser un modificador eficiente para la detección de la gabapentina, a pesar de la hibridez de su mecanismo de oxidación. La posibilidad y las causas de los comportamientos oscilatorio y monotónico también han sido investigadas.
SUMMARY The possibility for the use of cobalt (III) oxyhydroxide in gabapentine electrochemical determination has been evaluated. A mechanism for analyte and modifier function has been suggested. A mathematical model based in this mechanism has been developed and analyzed (by means of linear stability theory and bifurcation analysis). The theoretical evaluation confirms that the cobalt (III) oxyhydroxide may be an efficient modifier for gabapentine electrochemical determination, despite of the hybridity of its oxidation mechanism. The possibility and the causes for oscillatory and monotonic instabilities have also been investigated.
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RESUMO O processo da determinação eletroanalítica do fármaco letrozol, assistida pelo compósito VO(OH)-polipirrol, obtido mediante um processo catódico, foi descrito teoricamente. Tanto para a síntese do compósito, como para o processo eletroana-lítico foi sugerido e analisado, mediante a teoria de estabilidade linear e análise de bifurcações, um modelo matemático. Foi mostrado que, ao contrário da eletrossín-tese de polipirrol catódica, iniciada por um composto na solução, o polipirrol resultante tem uma morfologia mais "centrada" aos centros ativos da matriz, dopados pelos cátions VO2+. No entretanto, tanto a síntese do compósito, como o seu desempenho eletroanalítico com o letrozol podem ser considerados eficientes.
SUMMARY The process of the electroanalytical determination of letrozol drug, assisted by the cathodically obtained VO(OH)-Polypyrrole, has been theoretically described. For both the composite synthesis and electroanalytical function a mathematical model has been suggested and analyzed by means of linear stability theory and bifurcation analysis. It was shown that, contrarily to the cathodic polypyrrole electrosynthesis, initiated by a compound in a solution, the resulting cathodic polypyrrole has more "centred" morphology, in the relation to the matrix active centers, doped by VO2+ cations. Nevertheless, either the synthesis of the composite, or its electroanalytical function with letrozole may be considered efficient.
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RESUMO Por meio de uma análise teórica, foi avaliado o desempenho do compósito do oxihidróxido do vanádio trivalente com o polímero do corante alaranjado da acridina, na detecção eletroquímica do fármaco antiparquinsônico entacapona. O processo eletroanalítico é baseado na eletrorredução do fármaco mencionado. Do desenvolvimento e da análise do modelo matemático correspondente, mediante a teoria de estabilidade linear e anáise de bifurcações, foi possível concluir que o compósito pode ser um modificador eficiente para a determinação da entacapona. Os comportamentos oscilatórios e monotônico, neste sistema, também são passíveis de realizar.
SUMMARY By means of a theoretical analysis, the function of trivalent vanadium oxyhydroxyde composite with the polymer of the acridine orange dye for electrochemical evaluation of entacapone antiparkinsonic drug has been evaluated. The electroanalytical process is based on the electrochemical reduction of the mentioned drug. From development and analysis of the correspondent mathematical model by means of linear stability theory and bifurcation analysis, it was possible to conclude that the composite is an efficient electrode modifier for entacapone determination. The oscillatory and monotonic instabilities in this system are also capable to realize.
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RESUMO A possibilidade do uso de um novo derivado de acridina, munido de um grupo doador de elétrons, como modificador de elétrons para a detecção do conteúdo total do ácido gálico em goma de alfarroba tem sido avaliada mediante uma análise teórica. O modelo matemático correspondente foi analisado mediante a teoria de estabilidade linear e análise de bifurcações. Foi mostrado que o derivado fosfazoico da acridina pode servir de modificador eficiente para a detecção eletroanalítica do conteúdo total do ácido gálico em alfarroba. As causas dos comportamentos oscilatório e monotônico também foram detectadas.
SUMMARY The possibility of the use of the novel acridinic derivative, containing an electron donor moiety in the total gallic acid content determination in carob gum has been evaluated by means of a theoretical analysis. The correspondent mathematical model has been analyzed by linear stability theory and bifurcation analysis. It was shown that the phosphazoic acridine derivative may serve as an efficient electrode modifier for electroanalytical determination of the total content of gallic acid in carob. The causes for the oscillatory and monotonic behavior have also been stipulated.