Invasive electrochemical impedance spectroscopy with phase delay for experimental atherosclerosis phenotyping.

Distinguishing quiescent from rupture-prone atherosclerotic lesions has significant translational and clinical implications. Electrochemical impedance spectroscopy (EIS) characterizes biological tissues by assessing impedance and phase delay responses to alternating current at multiple frequencies. We evaluated invasive 6-point stretchable EIS sensors over a spectrum of experimental atherosclerosis and compared results with intravascular ultrasound (IVUS), molecular positron emission tomography (PET) imaging, and histology. Male New Zealand White rabbits (n = 16) were placed on a high-fat diet, with or without endothelial denudation via balloon injury of the infrarenal abdominal aorta. Rabbits underwent in vivo micro-PET imaging of the abdominal aorta with 68Ga-DOTATATE, 18F-NaF, and 18F-FDG, followed by invasive interrogation via IVUS and EIS. Background signal-corrected values of impedance and phase delay were determined. Abdominal aortic samples were collected for histology. Analyses were performed blindly. EIS impedance was associated with markers of plaque activity including macrophage infiltration (r = .813, p = .008) and macrophage/smooth muscle cell (SMC) ratio (r = .813, p = .026). Moreover, EIS phase delay correlated with anatomic markers of plaque burden, namely intima/media ratio (r = .883, p = .004) and %stenosis (r = .901, p = .002), similar to IVUS. 68Ga-DOTATATE correlated with intimal macrophage infiltration (r = .861, p = .003) and macrophage/SMC ratio (r = .831, p = .021), 18F-NaF with SMC infiltration (r = -.842, p = .018), and 18F-FDG correlated with macrophage/SMC ratio (r = .787, p = .036). EIS with phase delay integrates key atherosclerosis features that otherwise require multiple complementary invasive and non-invasive imaging approaches to capture. These findings indicate the potential of invasive EIS to comprehensively evaluate human coronary artery disease.

Electrochemical impedance spectroscopy unmasks high-risk atherosclerotic features in human coronary artery disease.

Coronary plaque rupture remains the prominent mechanism of myocardial infarction. Accurate identification of rupture-prone plaque may improve clinical management. This study assessed the discriminatory performance of electrochemical impedance spectroscopy (EIS) in human cardiac explants to detect high-risk atherosclerotic features that portend rupture risk. In this single-center, prospective study, n = 26 cardiac explants were collected for EIS interrogation of the three major coronary arteries. Vessels in which advancement of the EIS catheter without iatrogenic plaque disruption was rendered impossible were not assessed. N = 61 vessels underwent EIS measurement and histological analyses. Plaques were dichotomized according to previously established high rupture-risk parameter thresholds. Diagnostic performance was determined via receiver operating characteristic areas-under-the-curve (AUC). Necrotic cores were identified in n = 19 vessels (median area 1.53 mm2) with a median fibrous cap thickness of 62 µm. Impedance was significantly greater in plaques with necrotic core area ≥1.75 mm2 versus <1.75 mm2 (19.8 ± 4.4 kΩ vs. 7.2 ± 1.0 kΩ, p = .019), fibrous cap thickness ≤65 µm versus >65 µm (19.1 ± 3.5 kΩ vs. 6.5 ± 0.9 kΩ, p = .004), and ≥20 macrophages per 0.3 mm-diameter high-power field (HPF) versus <20 macrophages per HPF (19.8 ± 4.1 kΩ vs. 10.2 ± 0.9 kΩ, p = .002). Impedance identified necrotic core area ≥1.75 mm2, fibrous cap thickness ≤65 µm, and ≥20 macrophages per HPF with AUCs of 0.889 (95% CI: 0.716-1.000) (p = .013), 0.852 (0.646-1.000) (p = .025), and 0.835 (0.577-1.000) (p = .028), respectively. Further, phase delay discriminated severe stenosis (≥70%) with an AUC of 0.767 (0.573-0.962) (p = .035). EIS discriminates high-risk atherosclerotic features that portend plaque rupture in human coronary artery disease and may serve as a complementary modality for angiography-guided atherosclerosis evaluation.

Electrical Impedance Spectroscopy with Bacterial Biofilms: Neuronal-like Behavior.

Negative capacitance at low frequencies for spiking neurons was first demonstrated in 1941 (K. S. Cole) by using extracellular electrodes. The phenomenon subsequently was explained by using the Hodgkin-Huxley model and is due to the activity of voltage-gated potassium ion channels. We show that Escherichia coli (E. coli) biofilms exhibit significant stable negative capacitances at low frequencies when they experience a small DC bias voltage in electrical impedance spectroscopy experiments. Using a frequency domain Hodgkin-Huxley model, we characterize the conditions for the emergence of this feature and demonstrate that the negative capacitance exists only in biofilms containing living cells. Furthermore, we establish the importance of the voltage-gated potassium ion channel, Kch, using knock-down mutants. The experiments provide further evidence for voltage-gated ion channels in E. coli and a new, low-cost method to probe biofilm electrophysiology, e.g., to understand the efficacy of antibiotics. We expect that the majority of bacterial biofilms will demonstrate negative capacitances.

Impact of Solvent Electrostatic Environment on Molecular Junctions Probed via Electrochemical Impedance Spectroscopy.

The electrostatic environment around nanoscale molecular junctions modulates charge transport; solvents alter this environment. Methods to directly probe solvent effects require correlating measurements of the local electrostatic environment with charge transport across the metal-molecule-metal junction. Here, we measure the conductance and current-voltage characteristics of molecular wires using a scanning tunneling microscope-break junction (STM-BJ) setup in two commonly used solvents. Our results show that the solvent environment induces shifts in molecular conductance, which we quantify, but more importantly we find that the solvent also impacts the magnitude of current rectification in molecular junctions. By incorporating electrochemical impedance spectroscopy into the STM-BJ setup, we measure the capacitance of the dipole layer formed at the metal-solvent interface and show that rectification can be correlated with solvent capacitance. These results provide a method of quantifying the impact of the solvent environment and a path toward improved environmental control of molecular devices.

Photothermal Enhancement of Prussian Blue Cathodes for Li-Ion Batteries.

Photoenhanced batteries, where light improves the electrochemical performance of batteries, have gained much interest. Recent reports suggest that light-to-heat conversion can also play an important role. In this work, we study Prussian blue analogues (PBAs), which are known to have a high photothermal heating efficiency and can be used as cathodes for Li-ion batteries. PBAs were synthesized directly on a carbon collector electrode and tested under different thermally controlled conditions to show the effect of photothermal heating on battery performance. Our PBA electrodes reach temperatures that are 14% higher than reference electrodes using a blue LED, and a capacity enhancement of 38% was achieved at a current density of 1600 mA g-1. Additionally, these batteries show excellent cycling stability with a capacity retention of 96.6% in dark conditions and 94.8% in light over 100 cycles. Overall, this work shows new insights into the effects leading to improved battery performance in photobatteries.

Machine learning assisted analysis of equivalent circuit usage in electrochemical impedance spectroscopy applications.

Electrical equivalent circuits are a widely applied tool with which electrical processes can be rationalized. There is a wide-ranging selection of fields from bioelectrochemistry to batteries to fuel cells making use of this tool. Enabling meta-analysis on the similarities and differences in the used circuits will help to identify commonly used circuits and aid in evaluating the underlying physics. We present a method and an implementation that enables the conversion of circuits included in scientific publications into a machine-readable form for generating machine learning datasets or circuit simulations.

Electrical impedance spectroscopy detects skin barrier dysfunction in childhood atopic dermatitis.

BACKGROUND: Skin barrier dysfunction is associated with the development of atopic dermatitis (AD), however methods to assess skin barrier function are limited. We investigated the use of electrical impedance spectroscopy (EIS) to detect skin barrier dysfunction in children with AD of the CARE (Childhood AlleRgy, nutrition, and Environment) cohort. METHODS: EIS measurements taken at multiple time points from 4 months to 3-year-old children, who developed AD (n = 66) and those who did not (n = 49) were investigated. Using only the EIS measurement and the AD status, we developed a machine learning algorithm that produces a score (EIS/AD score) which reflects the probability that a given measurement is from a child with active AD. We investigated the diagnostic ability of this score and its association with clinical characteristics and age. RESULTS: Based on the EIS/AD score, the EIS algorithm was able to clearly discriminate between healthy skin and clinically unaffected skin of children with active AD (area under the curve 0.92, 95% CI 0.85-0.99). It was also able to detect a difference between healthy skin and AD skin when the child did not have active AD. There was no clear association between the EIS/AD score and the severity of AD or sensitisation to the tested allergens. The performance of the algorithm was not affected by age. CONCLUSIONS: This study shows that EIS can detect skin barrier dysfunction and differentiate skin of children with AD from healthy skin and suggests that EIS may have the ability to predict future AD development.

Household laundry detergents disrupt barrier integrity and induce inflammation in mouse and human skin.

BACKGROUND: Epithelial barrier impairment is associated with many skin and mucosal inflammatory disorders. Laundry detergents have been demonstrated to affect epithelial barrier function in vitro using air-liquid interface cultures of human epithelial cells. METHODS: Back skin of C57BL/6 mice was treated with two household laundry detergents at several dilutions. Barrier function was assessed by electric impedance spectroscopy (EIS) and transepidermal water loss (TEWL) measurements after the 4 h of treatments with detergents. RNA sequencing (RNA-seq) and targeted multiplex proteomics analyses in skin biopsy samples were performed. The 6-h treatment effect of laundry detergent and sodium dodecyl sulfate (SDS) was investigated on ex vivo human skin. RESULTS: Detergent-treated skin showed a significant EIS reduction and TEWL increase compared to untreated skin, with a relatively higher sensitivity and dose-response in EIS. The RNA-seq showed the reduction of the expression of several genes essential for skin barrier integrity, such as tight junctions and adherens junction proteins. In contrast, keratinization, lipid metabolic processes, and epidermal cell differentiation were upregulated. Proteomics analysis showed that the detergents treatment generally downregulated cell adhesion-related proteins, such as epithelial cell adhesion molecule and contactin-1, and upregulated proinflammatory proteins, such as interleukin 6 and interleukin 1 beta. Both detergent and SDS led to a significant decrease in EIS values in the ex vivo human skin model. CONCLUSION: The present study demonstrated that laundry detergents and its main component, SDS impaired the epidermal barrier in vivo and ex vivo human skin. Daily detergent exposure may cause skin barrier disruption and may contribute to the development of atopic diseases.

Selective Perchlorate Sensing Using Electrochemical Impedance Spectroscopy with Self-Assembled Monolayers of semiaza-Bambusurils.

In the last two decades, perchlorate salts have been identified as environmental pollutants and recognized as potential substances affecting human health. We describe self-assembled monolayers (SAMs) of novel semiaza-bambus[6]urils (semiaza-BUs) equipped with thioethers or disulfide (dithiolane) functionalities as surface-anchoring groups on gold electrodes. Cyclic voltammetry (CV) with Fe(CN)6 3-/4- as a redox probe, together with X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM) and ellipsometry, were employed to characterize the interactions at the interface between the anchoring groups and the metal substrate. Data showed that the anion receptors' packing on the gold strongly depends on the anchoring group. As a result, SAMs of BUs with lipoic amide side chains show a concentration-dependent layer thickness. The BU SAMs are extremely stable on repeated electrochemical potential scans and can selectively recognize perchlorate anions. Our electrochemical impedance spectroscopy (EIS) studies indicated that semiaza-BU equipped with the lipoic amide side chains binds perchlorate (2-100 mM) preferentially over other anions such as F- , Cl- , I- , AcO- , H2 PO4 - , HPO4 2- , SO4 2- , NO2 - , NO3 - , or CO3 2- . The resistance performance is 10 to 100 times more efficient than SAMs containing all other tested anions.

Proton transfer and regulation across chemical interfaces by small-molecule assemblies.

We report on measurements and control of proton gradient across interfaces of water and dichloroethane. Such interfaces are interesting as mimics of biological membranes. We use impedance spectroscopy to quantify interfacial proton gradient and identify proton transfer modes. We quantify proton movement using reciprocal of time constant (τ-1 ) acquired from electrochemical impedance modeling. We show that proton gradient across interfaces of water/dichloroethane and τ-1 correlate with the aqueous phase pH, changing from ca. 1 s-1 at pH 1 to 0.2 s-1 at pH 7. τ-1 changes in the presence of proton shuttling fat-soluble molecules. Dinitrophenol acts as a pH activated proton coupler which is active at around neutral pH and inert at pH <4. However, quinone type cofactors change the interfacial proton transport when activated by redox reactions with ferrocene type molecules, such as decamethyl ferrocence (DMFc). Quinone type cofactors show distinct features in their impedance response assigned to a proton coupled electron transfer (PCET) process, different from the uncoupled proton transfer activity of dinitrophenol. The observed PCET reaction significantly changes τ-1 . We use τ-1 as a proton transport descriptor. In particular, CoQ10 -DMFc shows a τ-1 of 3.5 s-1 at pH 7, indicating how small-molecule assemblies change proton availability.

Electrochemical investigation of an anticancer drug 5-Fluorouracil in the presence of Theophylline using low-cost and disposable poly(GLY) modified pencil graphite electrode.

Herein this study, a facile, efficient and disposable electrochemical sensor has been prepared by electropolymerization of glycine (poly(GLY)) on the surface of pencil graphite electrode (PGE). The surface topology of the equipped poly(GLY) modified pencil graphite electrode (poly(GLY)/PGE) and bare pencil graphite electrode (BPGE) has been characterized by the scanning electron microscopy (SEM) combined with energy dispersive x-ray analysis (EDX) and charge transfer behaviour was measured by electron impedance spectroscopy (EIS) method. The voltammetric behaviour of anticancer, 5-fluorouracil (5-FU) in the presence of theophylline (THP) has been carried out in 0.1 M phosphate buffer solution (PBS) of physiological pH 7.0 using different techniques such as cyclic voltammetry (CV), linear sweep voltammetry (LSV) and differential pulse voltammetry (DPV). The proposed poly(GLY)/PGE shows augmented peak current for 5-FU at lower potential side over the BPGE due to the electrocatalytic behaviour of modifier layers wrapped on the electrode surface. The kinetic behaviour of 5-FU at modified electrode surface was studied by varying different parameters such as pH, scan rate and concentration study in 0.1 M PBS used as a supporting electrolyte. The limit of detection (LOD) for 5-FU was attained using DPV method with different concentrations (1.0-13.0 µM) and it was found to be 0.012 µM. The possible electrochemical reaction of 5-FU was proposed and it was incorporated by two electrons and two protons mechanism at modified electrode surface. The voltammetric response of poly(GLY)/PGE towards the determination of 5-FU was unaffected in the presence of some excipients in addition to the remarkable stability and reproducibility. The applicability of the proposed sensor has been performed by real sample investigation of 5-FU with a substantial percentage of recovery results in all optimized conditions.

Measurement of microRNA-106b as a gastric cancer biomarker based on Zn-BTC MOF label-free genosensor.

Due to the late detection of stomach cancer, this cancer usually causes high mortality. The development of an electrochemical genosensor to measure microRNA 106b (miR-106b), as a gastric cancer biomarker, is the aim of this effort. In this regard, first, 1,3,5-benzenetricarboxylate (BTC) metal-organic frameworks (Zn-BTC MOF) were self-assembled on the glassy carbon electrode and then the probe (ssDNA) was immobilized on it. The morphology Zn-BTC MOF was characterized by SEM, FT-IR, Raman and X-Ray techniques. Zn-BTC MOF as a biosensor substrate has strong interaction with ssDNA. Quantitative measurement of miR-106b was performed by electrochemical impedance spectroscopy (EIS). To perform this measurement, the difference of the charge transfer resistances (ΔRct) of Nyquist plots of the ssDNA probe modified electrode before and after hybridization with miR-106b was obtained and used as an analytical signal. Using the suggested genosensor, it is possible to measure miR-106b in the concentration range of 1.0 fM to 1.0 µM with a detection limit of 0.65 fM under optimal conditions. Moreover, at the genosensor surface, miR-106b can be detected from a non-complementary and a single base mismatch sequence. Also, the genosensor was used to assess miR-106b in a human serum sample and obtained satisfactory results.

A novel ACE2-Based electrochemical biosensor for sensitive detection of SARS-CoV-2.

SARS-CoV-2 emerged in late 2019 and quickly spread globally, resulting in significant morbidity, mortality, and socio-economic disruptions. As of now, collaborative global efforts in vaccination and the advent of novel diagnostic tools have considerably curbed the spread and impact of the virus in many regions. Despite this progress, the demand remains for low-cost, accurate, rapid and scalable diagnostic tools to reduce the influence of SARS-CoV-2. Herein, the angiotensin-converting enzyme 2 (ACE2), a receptor for SARS-CoV-2, was immobilized on two types of electrodes, a screen-printed gold electrode (SPGE) and a screen-printed carbon electrode (SPCE), to develop electrochemical biosensors for detecting SARS-CoV-2 with high sensitivity and selectivity. This was achieved by using 1H, 1H, 2H, 2H-perfluorodecanethiol (PFDT) and aryl diazonium salt serving as linkers for SPGEs and SPCEs, respectively. Once SARS-CoV-2 was anchored onto the ACE2, the interaction of the virus with the redox probe was analyzed using electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV). Aryl diazonium salt was observed as a superior linker compared to PFDT due to its consistent performance in the modification of the SPCEs and effective ACE2 enzyme immobilization. A distinct pair of redox peaks in the cyclic voltammogram of the biosensor modified with aryl diazonium salt highlighted the redox reaction between the functional groups of SARS-CoV-2 and the redox probe. The sensor presented a linear relationship between the redox response and the logarithm of SARS-CoV-2 concentration, with a detection limit of 1.02 × 106 TCID50/mL (50% tissue culture infectious dose). Furthermore, the biosensor showed remarkable selectivity towards SARS-CoV-2 over H1N1virus.

Can Electrochemical Impedance Spectroscopy be Replaced by Direct Current Techniques in Battery Diagnosis?

Electrochemical impedance spectroscopy (EIS), a conventional and alternating-current-(AC)-based technique for impedance measurement, is commonly used in battery diagnosis. However, it requires expensive equipment and demanding operating conditions and is complex and model-dependent in data analysis. Recently, novel direct current (DC) analytics have emerged as an alternative to EIS. They are simple yet powerful, being capable of revealing impedance information that traditionally could only be obtained through EIS and determining Li-ion diffusion coefficient. Besides, a complete EIS spectrum can be predicted based on constant current charging curves in the support of machine learning methods. This work highlights the similarities and discrepancies between DC techniques and EIS in the electrochemical analysis of Li-ion batteries. Looking ahead, DC techniques may be a promising substitute for EIS in future battery diagnosis, requiring simplified equipment while offering a deep understanding of battery impedance and its underlying electrochemical processes.

Understanding the Behavior of Supercapacitor Materials via Electrochemical Impedance Spectroscopy: A Review.

Energy harvesting and energy storage are two critical aspects of supporting the energy transition and sustainability. Many studies have been conducted to achieve excellent performance devices for these two purposes. As energy-storing devices, supercapacitors (SCs) have tremendous potential to be applied in several sectors. Some electrochemical characterizations define the performance of SCs. Electrochemical impedance spectroscopy (EIS) is one of the most powerful analyses to determine the performance of SCs. Some parameters obtained from this analysis include bulk resistance, charge-transfer resistance, total resistance, specific capacitance, response frequency, and response time. This work provides a holistic and comprehensive review of utilizing EIS for SC characterization. Overall, researchers can benefit from this review by gaining a comprehensive understanding of the utilization of electrochemical impedance spectroscopy (EIS) for characterizing supercapacitors (SCs), enabling them to enhance SC performance and contribute to the advancement of energy harvesting and storage technologies.

Exploring the role of impedance spectroscopy in assessing 405 nm laser-induced inactivation of saccharomyces cerevisiae.

Impedance spectroscopy was employed to assess the electrical properties of yeast following 405 nm laser irradiation, exploring the effects of visible, non-ionizing laser-induced inactivation as a more selective and safer alternative for photoinactivation applications compared to the use of DNA targeting, ionizing UV light. Capacitance and impedance spectra were obtained for yeast suspensions irradiated for 10, 20, 30, and 40 min using 100 and 200 mW laser powers. Noticeable differences in capacitance spectra were observed at lower frequencies (40 Hz to 1 kHz), with a significant increase at 40 min for both laser powers. ß-dispersion was evident in the impedance spectra in the frequency range of 10 kHz to 10 MHz. The characteristic frequency of dielectric relaxation steadily shifted to higher frequencies with increasing irradiation time, with a drastic change observed at 40 min for both laser powers. These changes signify a distinct alteration in the physical state of yeast. A yeast spot assay demonstrated a decrease in cell viability with increasing laser irradiation dose. The results indicate a correlation between changes in electrical properties, cell viability, and the efficacy of 405 nm laser-induced inactivation. Impedance spectroscopy is shown to be an efficient, non-destructive, label-free method for monitoring changes in cell viability in photobiological effect studies. The development of impedance spectroscopy-based real-time studies in photoinactivation holds promise for advancing our understanding of light-cell interactions in medical applications.

Compaction of Pressure-Driven Water Treatment Membranes: Real-Time Quantification and Analysis.

Water treatment membranes play crucial roles in applications such as desalination, wastewater treatment, and potable water reuse. In a prior study, we introduced a novel method, combining electrical impedance spectroscopy with dynamic mechanical analysis, to quantify single-layer homogeneous membrane compaction up to 12.5 psi. Now we extend the method's capabilities to quantify real-time compaction of multilayer heterogeneous nanofiltration and reverse osmosis (RO) membranes up to 330 psi. Our findings demonstrate that membrane compaction does not solely occur in the support/backing layer. The air pockets between the polysulfone support and the polyester backing layers, which were not discussed previously, account for up to 18% and 14% of total membrane compaction for the nanofiltration and RO membranes. For the nanofiltration membrane, the majority of compaction (up to 45%) occurs in the void spaces of the backing layer, while for the RO membrane, the majority of compaction (up to 40%) occurs in the solid material of the backing layer. We also confirm, with experimental results, the importance of using compressive testing instead of tensile testing to accurately characterize compaction. Membrane fatigue is characterized by experimental trends including: increasing irrevocable compaction, increasing creep/instantaneous compaction ratios, and increasing strains in hysteresis experiments.

Carbamoylase-based impedimetric electronic tongue for rapid detection of paralytic shellfish toxins.

Phytotoxins produced by marine microalgae, such as paralytic shellfish toxins (PSTs), can accumulate in bivalve molluscs, representing a human health concern due to the life-threatening symptoms they cause. To avoid the commercialization of contaminated bivalves, monitoring programs were established in the EU. The purpose of this work is the implementation of a PST transforming enzyme-carbamoylase-in an impedimetric test for rapid simultaneous detection of several carbamate and N-sulfocarbamoyl PSTs. Carbamoylase hydrolyses carbamate and sulfocarbamoyl toxins, which may account for up to 90% of bivalve toxicity related to PSTs. Conformational changes of carbamoylase accompanying enzymatic reactions were probed by Fourier transform mid-infrared spectroscopy (FT-MIR) and electrochemical impedance spectroscopy (EIS). Furthermore, a combination of EIS with a metal electrode and a carbamoylase-based assay was employed to harness changes in the enzyme conformation and adsorption on the electrode surface during the enzymatic reaction as an analytical signal. After optimization of the working conditions, the developed impedimetric e-tongue could quantify N-sulfocarbamoyl toxins with a detection limit of 0.1 µM. The developed e-tongue allows the detection of these toxins at concentration levels observed in bivalves with PST toxicity close to the regulatory limit. The quantification of a sum of N-sulfocarbamoyl PSTs in naturally contaminated mussel extracts using the developed impedimetric e-tongue has been demonstrated.

Measurement of Neuropeptide Y in Aptamer-Modified Planar Electrodes.

Electrochemical impedance spectroscopy (EIS) is a powerful technique for studying the interaction at electrode/solution interfaces. The adoption of EIS for obtaining analytical signals in biosensors based on aptamers is gaining popularity because of its advantageous characteristics for molecular recognition. Neuropeptide Y (NPY), the most abundant neuropeptide in the body, plays a crucial role with its stress-relieving properties. Quantitative measurement of NPY is imperative for understanding its role in these and other biological processes. Although aptamer-modified electrodes for NPY detection using EIS present a promising alternative, the correlation between the data obtained and the adsorption process on the electrodes is not fully understood. Various studies utilize the change in charge transfer resistance when employing an active redox label. In contrast, label-free measurement relies on changes in capacitance. To address these challenges, we focused on the interaction between aptamer-modified planar electrodes and their target, NPY. We proposed utilizing -ω*Zimag as the analytical signal, which facilitated the analysis of the adsorption process using an analogous Langmuir isotherm equation. This approach differs from implantable microelectrodes, which adhere to the Freundlich adsorption isotherm. Notably, our method obviates the need for a redox label and enables the detection of NPY at concentrations as low as 20 pg/mL. This methodology demonstrated exceptional selectivity, exhibiting a signal difference of over 20-to-1 against potential interfering molecules.

An impedance labeling free electrochemical aptamer sensor based on tetrahedral DNA nanostructures for doxorubicin determination.

Based on the electrochemical impedance method, a marker-free biosensor with aptamer as a biometric element was developed for the determination of doxorubicin (DOX). By combining aptamer with rigid tetrahedral DNA nanostructures (TDNs) and fixing them on the surface of gold electrode (GE) as biometric elements, the density and directivity of surface nanoprobes improved, and DOX was captured with high sensitivity and specificity. DOX was captured by immobilized aptamers on the GE, which inhibited electron transfer between the GE and [Fe(CN)6]3-/4- in solution, resulting in a change in electrochemical impedance. When the DOX concentration was between 10.0 and 100.0 nM, the aptasensor showed a linear relationship with charge transfer resistance, the relative standard deviation (RSD) ranged from 3.6 to 5.9%, and the detection limit (LOD) was 3.0 nM. This technique offered a successful performance for the determination of the target analyte in serum samples with recovery in the range 97.0 to 99.6% and RSD ranged from 4.8 to 6.5%. This method displayed the advantages of fast response speed, good selectivity, and simple sensor structure and showed potential application in therapeutic drug monitoring.