scholarly journals Electrochemical Sensing of Interactions between DNA and Charged Macrocycles

Chemosensors ◽  
2021 ◽  
Vol 9 (12) ◽  
pp. 347
Author(s):  
Tatjana Kulikova ◽  
Pavel Padnya ◽  
Igor Shiabiev ◽  
Alexey Rogov ◽  
Ivan Stoikov ◽  
...  

In this work, we investigated aggregation of native DNA and thiacalix[4]arene derivative bearing eight terminal amino groups in cone configuration using various redox probes on the glassy carbon electrode. It was shown that sorption transfer of the aggregates on the surface of the electrode covered with carbon black resulted in changes in electrostatic interactions and diffusional permeability of the surface layer. Such changes alter the signals of ferricyanide ion, methylene green and hydroquinone as redox probes to a degree depending on their specific interactions with DNA and own charge. Inclusion of DNA in the surface layer was independently confirmed by scanning electron microscopy, electrochemical impedance spectroscopy and experiments with doxorubicin as a model intercalator. Thermal denaturing of DNA affected the charge separation on the electrode interface and the signals of redox probes. Using hydroquinone, less sensitive to electrostatic interactions, made it possible to determine from 10 pM to 1.0 nM doxorubicin (limit of detection 3 pM) after 10 min incubation. Stabilizers present in the commercial medications did not alter the signal. The DNA sensors developed can find future application in the assessment of the complexes formed by DNA and macrocycles as delivery agents for small chemical species.

Chemosensors ◽  
2022 ◽  
Vol 10 (1) ◽  
pp. 33
Author(s):  
Anastasia Goida ◽  
Yurii Kuzin ◽  
Vladimir Evtugyn ◽  
Anna Porfireva ◽  
Gennady Evtugyn ◽  
...  

A highly sensitive electrochemical DNA sensor for detection of the chemotherapeutic drug idarubicin mediated by Methylene blue (MB) has been developed. DNA from fish sperm has been immobilized at the electropolymerized layers of Azure B. The incorporation of MB into the DNA layers substantially increased the sensor sensitivity. The concentration range for idarubicin determination by cyclic voltammetry was from 1 fM to 0.1 nM, with a limit of detection (LOD) of 0.3 fM. Electrochemical impedance spectroscopy (EIS) in the presence of a redox probe ([Fe(CN)6]3−/4−) allowed for the widening of a linear range of idarubicin detection from 1 fM to 100 nM, retaining LOD 0.3 fM. The DNA sensor has been tested in various real and artificial biological fluids with good recovery ranging between 90–110%. The sensor has been successfully used for impedimetric idarubicin detection in medical preparation Zavedos®. The developed DNA biosensor could be useful for the control of the level of idarubicin during cancer therapy as well as for pharmacokinetics studies.


Molecules ◽  
2018 ◽  
Vol 23 (10) ◽  
pp. 2688 ◽  
Author(s):  
Jingheng Ning ◽  
Long Liu ◽  
Xin Luo ◽  
Min Wang ◽  
Donglin Liu ◽  
...  

Human epidermal growth factor receptor 2 (HER2) is a key tumor marker for several common and deadly cancers. It is of great importance to develop efficient detection methods for its over-expression. In this work, an electrochemical impedance spectroscopy (EIS) method adjustable by anionic porphyrin for HER2 gene detection has been proposed, based on the impedance difference between multi-walled carbon nanotubes (MWCNTs) and DNA. The interesting finding herein is that with the addition of anionic porphyrin, i.e., meso-tetra(4-sulfophenyl)-porphyrin (TSPP), the impedance value obtained at a glass carbon electrode (GCE) modified with MWCNTs and a single stranded DNA (ssDNA), the probe DNA that might be assembled tightly onto MWCNTs through π-π stacking interaction, gets a slight decrease; however, the impedance value from a GCE modified with MWCNTs and a double stranded DNA (dsDNA), the hybrid of the probe DNA with a target DNA, which might be assembled loosely onto MWCNTs for the screening effect of phosphate backbones in dsDNA, gets an obvious decrease. The reason may be that on the one hand, being rich in negative sulfonate groups, TSPP will try to push DNA far away from CNTs surface due to its strong electrostatic repulsion towards DNA; on the other hand, rich in planar phenyl or pyrrole rings, TSPP will compete with DNA for the surface of CNTs since it can also be assembled onto CNTs through conjugative interactions. In this way, the “loosely assembled” dsDNA will be repelled by this anionic porphyrin and released off CNTs surface much more than the “tightly assembled” ssDNA, leading to a bigger difference in the impedance value between dsDNA and ssDNA. Thus, through the amplification effect of TSPP on the impedance difference, the perfectly matched target DNA could be easily determined by EIS without any label. Under the optimized experimental conditions, this electrochemical sensor shows an excellent linear response to target DNA in a concentration range of 2.0 × 10−11–2.0 × 10−6 M with a limit of detection (LOD) of 6.34 × 10−11 M (S/N = 3). This abnormally sensitive electrochemical sensing performance resulting from anionic porphyrin for DNA sequences specific to HER2 gene will offer considerable promise for tumor diagnosis and treatment.


Nanomaterials ◽  
2020 ◽  
Vol 10 (7) ◽  
pp. 1368 ◽  
Author(s):  
Sathish Panneer Selvam ◽  
Somasekhar R. Chinnadayyala ◽  
Sungbo Cho ◽  
Kyusik Yun

An rGO-Ag@SiO2 nanocomposite-based electrochemical sensor was developed to detect etidronic acid (EA) using the differential pulse voltammetric (DPV) technique. Rapid self-assembly of the rGO-Ag@SiO2 nanocomposite was accomplished through probe sonication. The developed rGO-Ag@SiO2 nanocomposite was used as an electrochemical sensing platform by drop-casting on a gold (Au) printed circuit board (PCB). Cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) confirmed the enhanced electrochemical active surface area (ECASA) and low charge transfer resistance (Rct) of the rGO-Ag@SiO2/Au PCB. The accelerated electron transfer and the high number of active sites on the rGO-Ag@SiO2/Au PCB resulted in the electrochemical detection of EA through the DPV technique with a limit of detection (LOD) of 0.68 μM and a linear range of 2.0–200.0 μM. The constructed DPV sensor exhibited high selectivity toward EA, high reproducibility in terms of different Au PCBs, excellent repeatability, and long-term stability in storage at room temperature (25 °C). The real-time application of the rGO-Ag@SiO2/Au PCB for EA detection was investigated using EA-based pharmaceutical samples. Recovery percentages between 96.2% and 102.9% were obtained. The developed DPV sensor based on an rGO-Ag@SiO2/Au PCB could be used to detect other electrochemically active species following optimization under certain conditions.


Author(s):  
Chanakarn Sanguarnsak ◽  
Kiattisak Promsuwan ◽  
Jenjira Saichanapan ◽  
Asamee Soleh ◽  
Kasrin Saisahas ◽  
...  

Abstract A new electrode material of phosphorus-doped multi-walled carbon nanotubes (P-MWCNTs) was developed as an electrochemical sensing element for amitriptyline (AMT). P-MWCNTs were hydrothermally synthesized and drop casted on a glassy carbon electrode (P-MWCNTs/GCE). The P-MWCNTs were morphologically, chemically and structurally characterized. The electrochemical characteristics of the P-MWCNTs/GCE were investigated by cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), and adsorptive stripping voltammetry (AdSV). The P-MWCNTs increased electron transfer at the GCE and the electrochemical conductivity of the electrode. Electrocatalytic activity toward the oxidation of AMT was excellent. In the optimal voltammetric condition, the P-MWCNTs/GCE produced linear ranges of 0.50 to 10 µg mL-1 and 10 to 40 µg mL-1. The limit of detection (LOD) and limit of quantification (LOQ) were 0.15 µg mL-1 (0.54 µM) and 0.52 µg mL-1 (1.80 µM), respectively. The developed sensor displayed good repeatability, reproducibility and specificity. The sensor successfully quantified AMT in pharmaceutical tablets, giving results consistent with spectrophotometric analysis. The sensor achieved recoveries from 98±2% to 101±5% from spiked urine samples. The proposed sensor could be applied to determine AMT in pharmaceutical and urine samples for forensic toxicology.


2021 ◽  
Vol 11 (1) ◽  
Author(s):  
B. Chakraborty ◽  
A. Das ◽  
N. Mandal ◽  
N. Samanta ◽  
N. Das ◽  
...  

AbstractDeveloping point-of-care (PoC) diagnostic platforms for carcinoembryonic antigen detection is essential. However, thefew implementations of transferring the signal amplification strategies in electrochemical sensing on paper-based platforms are not satisfactory in terms of detection limit (LOD). In the quest for pushing down LOD, majority of the research has been targeted towards development of improved nanostructured substrates for entrapping more analyte molecules and augmenting the electron transfer rate to the working electrode. But, such approaches have reached saturation. This paper focuses on enhancing the mass transport of the analyte towards the sensor surface through the application of an electric field, in graphene-ZnO nanorods heterostructure. These hybrid nanostructures have been deposited on flexible polyethylene terephthalate substrates with screen printed electrodes for PoC application. The ZnO nanorods have been functionalized with aptamers and the working sensor has been integrated with smartphone interfaced indigenously developed low cost potentiostat. The performance of the system, requiring only 50 µl analyte has been evaluated using electrochemical impedance spectroscopy and validated against commercially available ELISA kit. Limit of detection of 1 fg/ml in human serum with 6.5% coefficient of variation has been demonstrated, which is more than three orders of magnitude lower than the existing attempts on PoC device.


2021 ◽  
Vol 12 (1) ◽  
Author(s):  
Pattan-Siddappa Ganesh ◽  
Ganesh Shimoga ◽  
Seok-Han Lee ◽  
Sang-Youn Kim ◽  
Eno E. Ebenso

Abstract Background A simple and simultaneous electrochemical sensing platform was fabricated by electropolymerization of allura red on glassy carbon electrode (GCE) for the interference-free detection of dihydroxy benzene isomers. Methods The modified working electrode was characterized by electrochemical and field emission scanning electron microscopy methods. The modified electrode showed excellent electrocatalytic activity for the electrooxidation of catechol (CC) and hydroquinone (HQ) at physiological pH of 7.4 by cyclic voltammetric (CV) and differential pulse voltammetric (DPV) techniques. Results The effective split in the overlapped oxidation signal of CC and HQ was achieved in a binary mixture with peak to peak separation of 0.102 V and 0.103 V by CV and DPV techniques. The electrode kinetics was found to be adsorption-controlled. The oxidation potential directly depends on the pH of the buffer solution, and it witnessed the transfer of equal number of protons and electrons in the redox phenomenon. Conclusions The limit of detection (LOD) for CC and HQ was calculated to be 0.126 μM and 0.132 μM in the linear range of 0 to 80.0 μM and 0 to 110.0 μM, respectively, by ultra-sensitive DPV technique. The practical applicability of the proposed sensor was evaluated for tap water sample analysis, and good recovery rates were observed. Graphical abstract Electrocatalytic interaction of ALR/GCE with dihydroxy benzene isomers.


Sensors ◽  
2021 ◽  
Vol 21 (6) ◽  
pp. 1929
Author(s):  
Alexander Rodríguez ◽  
Francisco Burgos-Flórez ◽  
José D. Posada ◽  
Eliana Cervera ◽  
Valtencir Zucolotto ◽  
...  

Neuronal damage secondary to traumatic brain injury (TBI) is a rapidly evolving condition, which requires therapeutic decisions based on the timely identification of clinical deterioration. Changes in S100B biomarker levels are associated with TBI severity and patient outcome. The S100B quantification is often difficult since standard immunoassays are time-consuming, costly, and require extensive expertise. A zero-length cross-linking approach on a cysteamine self-assembled monolayer (SAM) was performed to immobilize anti-S100B monoclonal antibodies onto both planar (AuEs) and interdigitated (AuIDEs) gold electrodes via carbonyl-bond. Surface characterization was performed by atomic force microscopy (AFM) and specular-reflectance FTIR for each functionalization step. Biosensor response was studied using the change in charge-transfer resistance (Rct) from electrochemical impedance spectroscopy (EIS) in potassium ferrocyanide, with [S100B] ranging 10–1000 pg/mL. A single-frequency analysis for capacitances was also performed in AuIDEs. Full factorial designs were applied to assess biosensor sensitivity, specificity, and limit-of-detection (LOD). Higher Rct values were found with increased S100B concentration in both platforms. LODs were 18 pg/mL(AuES) and 6 pg/mL(AuIDEs). AuIDEs provide a simpler manufacturing protocol, with reduced fabrication time and possibly costs, simpler electrochemical response analysis, and could be used for single-frequency analysis for monitoring capacitance changes related to S100B levels.


2021 ◽  
Vol 11 (1) ◽  
Author(s):  
K. Chetankumar ◽  
B. E. Kumara Swamy ◽  
S. C. Sharma ◽  
S. A. Hariprasad

AbstractIn this proposed work, direct green 6 (DG6) decorated carbon paste electrode (CPE) was fabricated for the efficient simultaneous and individual sensing of catechol (CA) and hydroquinone (HY). Electrochemical deeds of the CA and HY were carried out by cyclic voltammetry (CV) and differential pulse voltammetry (DPV) at poly-DG6-modfied carbon paste electrode (Po-DG6-MCPE). Using scanning electron microscopy (SEM) studied the surface property of unmodified CPE (UCPE) and Po-DG6-MCPE. The decorated sensor displayed admirable electrocatalytic performance with fine stability, reproducibility, selectivity, low limit of detection (LLOD) for HY (0.11 μM) and CC (0.09 μM) and sensor process was originated to be adsorption-controlled phenomena. The Po-DG6-MCPE sensor exhibits well separated two peaks for HY and CA in CV and DPV analysis with potential difference of 0.098 V. Subsequently, the sensor was practically applied for the analysis in tap water and it consistent in-between for CA 93.25–100.16% and for HY 97.25–99.87% respectively.


2021 ◽  
Vol 0 (0) ◽  
Author(s):  
Magdalena Warczak ◽  
Marianna Gniadek ◽  
Kamil Hermanowski ◽  
Magdalena Osial

Abstract Over the recent decades, conducting polymers have received great interest in many fields including microelectronics, energy conversion devices, and biosensing due to their unique properties like electrical conductivity, stability, and simple synthesis. Modification of conducting polymers with noble metals e.g. gold enhances their properties and opens new opportunities to also apply them in other fields like electrocatalysis. Here, we focus on the synthesis of hybrid material based on polyindole (PIN) nanobrush modified with gold nanoparticles and its application towards electrooxidation of ethanol. The paper presents systematic studies from synthesis to electrochemical sensing applications. For the characterization of PIN–Au composites, scanning electron microscopy and X-ray diffraction analyses were used. The electrocatalytic performance of the proposed hybrid material towards alcohol oxidation was studied in alkaline media by cyclic voltammetry, chronoamperometry, and electrochemical impedance spectroscopy techniques. The results show that PIN–Au hybrid can be employed as an effective and sensitive platform for the detection of alcohols, which makes it a promising material in electrocatalysis or sensors. Moreover, the proposed composite exhibits electrocatalytic activity towards ethanol oxidation, which combined with its good long-term stability opens the opportunity for its application in fuel cells.


2019 ◽  
Vol 16 (22) ◽  
pp. 4485-4496 ◽  
Author(s):  
Ye Tian ◽  
Chao Xue ◽  
Chun-Ying Liu ◽  
Gui-Peng Yang ◽  
Pei-Feng Li ◽  
...  

Abstract. Nitric oxide (NO) is a short-lived compound of the marine nitrogen cycle; however, our knowledge about its oceanic distribution and turnover is rudimentary. Here we present the measurements of dissolved NO in the surface and bottom layers at 75 stations in the Bohai Sea (BS) and the Yellow Sea (YS) in June 2011. Moreover, NO photoproduction rates were determined at 27 stations in both seas. The NO concentrations in the surface and bottom layers were highly variable and ranged from below the limit of detection (i.e., 32 pmol L−1) to 616 pmol L−1 in the surface layer and 482 pmol L−1 in the bottom layer. There was no significant difference (p>0.05) between the mean NO concentrations in the surface (186±108 pmol L−1) and bottom (174±123 pmol L−1) layers. A decreasing trend of NO in bottom-layer concentrations with salinity indicates a NO input by submarine groundwater discharge. NO in the surface layer was supersaturated at all stations during both day and night and therefore the BS and YS were a persistent source of NO to the atmosphere at the time of our measurements. The average flux was about 4.5×10-16 mol cm−2 s−1 and the flux showed significant positive relationship with the wind speed. The accumulation of NO during daytime was a result of photochemical production, and photoproduction rates were correlated to illuminance. The persistent nighttime NO supersaturation pointed to an unidentified NO dark production. NO sea-to-air flux densities were much lower than the NO photoproduction rates. Therefore, we conclude that the bulk of the NO produced in the mixed layer was rapidly consumed before its release to the atmosphere.


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