Electrochemical modification of polypyrrole films for imparting hemocompatible properties to hemosorbent

A method of production of hemosorbent based on thermally expanded graphite is developed. The method involves the electropolymerization of pyrrole on rolled thermally expanded graphite and subsequent cyclic electrochemical doping of polypyrrole film with Cl^? anions. The method enables one to produce a hemosorbent with an open-circuit potential, which is necessary for its biocompatibility.     

Stretchable Electrochemical Sensor for Real‐Time Monitoring of Cells and Tissues

Stretchable electrochemical sensors are conceivably a powerful technique that provides important chemical information to unravel elastic and curvilinear living body. However, no breakthrough was made in stretchable electrochemical device for biological detection. Herein, we synthesized Au nanotubes (NTs) with large aspect ratio to construct an effective stretchable electrochemical sensor. Interlacing network of Au NTs endows the sensor with desirable stability against mechanical deformation, and Au nanostructure provides excellent electrochemical performance and biocompatibility. This allows for the first time, real‐time electrochemical monitoring of mechanically sensitive cells on the sensor both in their stretching‐free and stretching states as well as sensing of the inner lining of blood vessels. The results demonstrate the great potential of this sensor in electrochemical detection of living body, opening a new window for stretchable electrochemical sensor in biological exploration.     

Simulation of detoxication processes on ideally polarizable porous carbon materials

The hemosorbents made of carbon materials, which are used for hemosorption detoxication, should be indifferent toward blood. Therefore, in the course of hemosorption, it is important to avoid the Faradaic processes, which can change the blood composition. The probability of Faradaic processes depends on the open-circuit potential of activated carbon. This dependence is studied by simulating the detoxication processes. In order to obtain various open-circuit potentials, which are reached after switching-off polarization, the adsorption of cupric ions and t-butanol on the preliminarily polarized hemosorbent (AG-3 activated carbon) is studied. The effective number of electrons, which are transferred in an elementary adsorption act, is determined. The conditions, under which the Faradaic process does or does not proceed, are found.     

Measurements of platinum electrode potential in blood and blood plasma and serum

The method of electrochemical pretreatment of platinum electrode with the goal of standardizing the initial state of electrode surface and its open-circuit potential (OCP) in the blood and other biological media is proposed. The platinum electrode potential is measured in 0.14 M Na₂SO₄ aqueous solution, in the blood and blood plasma and serum. By the examples of OCP measured in the blood serum of patients with acute poisoning, acute cerebral pathology and patients treated by the method of hyperbaric oxygenation, it was found that the values of blood serum OCP were different for studied pathological states and healthy people.     

A selective sorbent for removing bacterial endotoxins from blood

Synthetic ligands carrying a positive charge and capable of selective binding of bacterial endotoxins are covalently immobilized on surfaces of domestic hemosorbent Styrosorb-514 based on hypercrosslinked polystyrene. It is shown that the resulting sorbent aimed at treating sepsis exceeds imported specific hemosorbent in Toraymyxin? columns in removing lipopolysaccharides, and can be used in domestically-produced Desepta columns.     

Der Mensch,ein elektrisches Wesen

The cells of our body, and the organelles within the cells, are surrounded by a biological membrane. The membranes are composed of a lipid bilayer which has no conductivity for the electric current. Across most biological membranes of living cells exists an electric tension or an electrochemical potential. All expressions of human life require energy which is supplied by the molecule ATP. The chemical energy of ATP originates from “cold combustion" of nutrients in mitochondria, accompanied by the intermediate formation of an electrochemical potential. The ATP‐synthase uses the energy of the potential to form ATP. If the tension across the membrane exceeds a certain value, deleterious oxygen radicals are formed. High ATP‐values prevent the formation of oxygen radicals by inhibition of cytochrome c oxidase, the last step of cell respiration. During stress situations of the organism this ATP‐inhibition is switched off so that the electric tension increases and oxygen radicals are produced. These have been shown to cause multiple degenerative diseases.     

Electrochemical sensing of heavy metals in biological media: A review

Trace metals are required in the body as they play a significant role in several biochemical processes. Moreover, certain heavy metals are beneficial at appropriate levels. Copper (Cu), for example, is essential for red blood cell formation, bone strength, and infant growth. Despite these fundamental roles, Cu can become toxic at high levels. Other heavy metals such as lead (Pb), cadmium (Cd), manganese (Mn), and mercury (Hg), have been identified to cause acute and chronic health complications. For these reasons, rapid, real-time quantification of such metals in biological media is of interest to improving human health outcomes. Electrochemical methods offer numerous advantages, such as portability, capability to be miniaturized, low cost, and ease-of-use. In this review, we examine recent developments in electrochemical sensing for the detection of heavy metals in biological media. To meet the requirements for inclusion in this review, the electrochemical sensor must have been evaluated in biological media (blood, serum, sweat, saliva, urine, brain tissue/cells). Several applications are explored to examine recent advancements in electrochemical sensing within these matrices. Addressing the challenges through materials, device, and system innovations, it is expected that electrochemical sensing of heavy metals in biological media will facilitate future diagnoses and treatments in healthcare.     

Biophysical measurement of red blood cells by laboratory on print circuit board chip

Microfluidic impedance pulse sensor has emerged as an easily handled and low‐cost platform in the electrical analysis of biological cells. In the conventional method, impedance sensor demanded expensive patterning metal electrodes on the substrate, which are directly in touch with electrolytes in order to measure the microfluidic channel impedance change. In this article, a cost‐effective microfluidic impedance sensor built upon a dielectric film coated printed circuit board is introduced. Impedance electrodes are protected by a dielectric film layer from electrochemical erosion between electrodes and electrolyte. Human red blood cells from adult and neonatal were utilized to demonstrate the feasibility of the proposed device in the electroanalysis of biological cells.     

Open micro-fluidic system for atomic force microscopy-guided in situ electrochemical probing of a single cell

Ultra-sharp nano-probes and customized atomic force microscopy (AFM) have previously been developed in our laboratory for in situ sub-cellular probing of electrochemical phenomena in living plant cells during their photosynthesis. However, this AFM-based electrochemical probing still has numerous engineering challenges such as immobilization of the live cells, compatibility of the immobilization procedure with AFM manipulation of the probe, maintenance of biological activity of the cells for an extended time while performing the measurements, and minimization of electrochemical noise. Thus, we have developed an open micro-fluidic channel system (OMFC) in which individual cells can be immobilized in micro-traps by capillary flow. This system affords easy AFM access and allows for maintenance of the cells in a well-defined chemical environment, which sustains their biological activity. The use of micro-channels for making the electrochemical measurements significantly reduces parasitic electrical capacitances and allows for current detection in the sub-pico-ampere range at high signal bandwidths. The OMFC was further studied using simulation packages for optimal design conditions. This system was successfully used to measure light-dependent oxidation currents of a few pico-amperes from the green alga Chlamydomonas reinhardtii.     

Single tungsten nanowires as pH sensitive electrodes

The electrochemical potentials of tungsten nanowire samples, covered with their own oxide, were measured in dependence of the pH value. The samples were prepared by selective etching of a directionally solidified eutectic NiAl–W alloy. Directional solidification in a Bridgman-type crystal growth furnace yields nanostructured two-phase materials. Electrochemical processing allows selective etching of the phases exposing the nanoscale structures. In this work, pointed samples with a single wire 200 nm in diameter protruding from the tip were produced. Subsequently the tungsten oxide layer on these single nanowires was electrochemically modified to optimize their pH sensing capabilities. The method has a potential for further downsizing since the wire diameter and exposed length can be controlled by the process parameters during solidification and during electrochemical processing. The advantages of these nanowire pH probes along with possible applications such as the pH measurement in ultra small cavities and other small systems of interest such as corrosion pits and biological cells are discussed.     

DNA-based electrochemical biosensors for monitoring of bis-indoles as potential antitumoral agents, chemistry, X-ray crystallography

Facile and practical electrochemical DNA bioassay, X-ray diffraction analysis, synthesis and 1H and 13C NMR data of the 5,5'-disubstituted-3,3'-methanediyl-bis-indoles are reported. On the basis of electrochemical measurements we have hypothesized that the analyzed bis-indoles have an effect on human tumor cells due to DNA binding at adenine-thymidine deoxynucleotides rich region in a concentration/substituent dependent manner. Interesting N-H...pi and hydrogen-bonding intermolecular interactions were observed which may differentiate their biological features. The 5,5'-dimethoxy-3,3'-methanediyl-bis-indole (2) was found to reduce considerably the growth of cancer cell lines HOP-92 (lung), A498 (renal) and MDA-MB-231/1TCC (breast). The results indicate that title compounds could be interesting as potential antitumoral chemotherapeutics.     

Plasma electrochemistry: potential measured at boron doped diamond and platinum in gaseous electrolyte

Premixed hydrogen/oxygen flame doped with ionisable alkali metals was considered as a dilute electrolyte. Two identical premixed flames which were in physical contact, served as a two compartment flame electrolyte cell. Five different electrochemical cells were studied, each containing a different combination of three alkali metals, Li, K and Cs. Pairs of boron doped diamond (BDD) and platinum electrodes were used to measure the overall zero current cell potential. The total potential measured across the cell was shown to be the sum of the mixed potential, dependent on the identity of ionised species present in the flame, and the diffusion potential originating at the junction between the two flames. Classical kinetic molecular theory and electrochemical theory of mixed potentials have been applied to account for the potential difference measured across these gas phase electrochemical cells. The relative merits of both models are discussed in the context of the experimental results obtained.     

Review: electrochemical studies on some metal complexes having anti-cancer activities

Cancer is a leading cause of death worldwide. Since the discovery of cisplatin, a platinum-based anti-cancer metallodrug, research on metal-based compounds and complexes as potential anti-cancer agents has gained importance in modern medical and chemical sciences. Electrochemical techniques provide useful complements to other analytical methods of analysis such as UV–vis and fluorescence spectroscopy. Since the redox active metal complexes are not amenable to spectroscopic techniques either due to weak absorption bands or overlap of electronic transitions with those of DNA, they can potentially be studied via electrochemical techniques. Due to the resemblance between the electrochemical and biological redox reactions, the application of electrochemical measurements of metal-based anti-cancer drugs is a highly sensitive method. Cyclic voltammetry is a versatile technique to investigate redox activities during drug–DNA interactions. Variations in peak potentials and peak currents of a cyclic voltammogram during a redox reaction resulting from intercalation or electrostatic interactions can be used to determine equilibrium constants (K) and the number of base pair sites. This review is focused on some electrochemical studies of potential metal-based anti-cancer drug candidate?DNA interactions and the correlation between binding studies and anti-cancer activities.     

Cerium oxide nanofiber–based electrochemical immunosensor for detection of sepsis in biological fluid

Sepsis causes life-threatening complications with the highest burden of death and medical expenses in hospitals worldwide. Despite the progression of targeted therapies for sepsis, the challenge of early diagnosis of sepsis-related biomarkers remains. The analysis of the TNF-α and sTREM-1 in biological fluids provides essential information for effective treatments. In this work, we report developing an electrochemical immunosensor for the rapid detection of TNF-α and sTREM-1 proteins in human plasma samples. First, using the electrospinning process, cerium oxide nanofibers were synthesized. Subsequently, the antibodies corresponding to the targeted proteins are immobilized onto the surface-functionalized working electrodes using NHS/EDC chemistry. The proposed immunosensor’s performance in a biological fluid was assessed using an analytical electrochemistry approach. The limit of detection for the electrochemical immunosensors was 0.51 and 0.41 pg/mL for TNF-α and sTREM-1, respectively, with high selectivity and sensitivity for the use as a point of care device.

     

Liquid chromatography with electrochemical detection for the determination of choline and acetylcholine in plasma and red blood cells. Failure to detect acetylcholine in blood of humans and mice

An assay is described for the measurement of choline in plasma and red blood cells using liquid chromatography, an enzyme reactor and electrochemical detection after a simple sample pretreatment. The intra-assay coefficient of variation for choline was 6.2 and 3.8% in plasma and in red blood cells, respectively. Using this method we have re-investigated the presence of acetylcholine in blood constituents. We were not able to demonstrate acetylcholine with a limit of detection of 10 pmol per ml of plasma or per ml of red blood cells.     

High-Performance Nucleic Acid Sensors for Liquid Biopsy Applications

Circulating tumour nucleic acids (ctNAs) are released from tumours cells and can be detected in blood samples, providing a way to track tumors without requiring a tissue sample. This “liquid biopsy” approach has the potential to replace invasive, painful, and costly tissue biopsies in cancer diagnosis and management. However, a very sensitive and specific approach is required to detect relatively low amounts of mutant sequences linked to cancer because they are masked by the high levels of wild-type sequences. This review discusses high-performance nucleic acid biosensors for ctNA analysis in patient samples. We compare sequencing- and amplification-based methods to next-generation sensors for ctDNA and ctRNA (including microRNA) profiling, such as electrochemical methods, surface plasmon resonance, Raman spectroscopy, and microfluidics and dielectrophoresis-based assays. We present an overview of the analytical sensitivity and accuracy of these methods as well as the biological and technical challenges they present.     

Electrochemical Aptasensors for Biological and Chemical Analyte Detection

Aptamers are short length, single-stranded DNA or RNA affinity molecules which interact with any desired targets such as biomarkers, cells, biological molecules, drugs or chemicals with high sensitivity. They have been extensively employed for medical applications due to having more advantages than the antibodies such as easier preparation and modification, higher stability, lower batch-to-batch variability and cost. Moreover, aptamers can be easily integrated efficiently with sensors, biosensors, actuators and other devices. In this review article, different applications of aptamers for biological and chemical molecules detection within the scope of electrochemical methods were presented with recent studies. In addition, the present status and future perspectives for highly-effective aptasensors for specific and selective analyte detection were discussed. As in stated throughout the review, combining of extraordinary properties of aptamers with the electrochemical-based biosensors could have improved the sensitivity of the assay and reduced limit of detection.     

Electrochemical Detection of Superoxide Anion Released by Living Cells by Manganese(III) Tetraphenyl Porphine as Superoxide Dismutase Mimic

Superoxide anion, one of the most active reactive oxygen species, is associated with the development of many diseases. So monitoring superoxide anion in living cells is of great significance for the pathological research of many diseases. In this work, a new non-enzymatic sensor for the detection of superoxide anion(O₂^·-) was developed, which was fabricated by the nanocomposites composed of manganese(III) tetraphenyl porphine(MnTPP) as super-oxide dismutase mimic and electrochemical reduced graphene oxide(ERGO) as electrode support material to modify the glassy carbon electrode(GCE). The electrochemical behavior of the fabricated electrode(MnTPP/ERGO/GCE) was performed by electrochemical impedance spectroscopy(EIS) and cyclic voltammetry(CV), which revealed that MnTPP/ERGO/GCE possessed good catalytic ability to the electrochemical reduction of O₂^·-. The MnTPP/ERGO/GCE showed excellent electroanalysis performance towards O₂^·- using the technique of differential pulse voltammetry(DPV) with a linear relationship in the range of 0.2-110.0 μmol/L, a sensitivity of 445 μA·L·mmol^-1·cm^-2 and a detection limit of 0.039 μmol/L(S/N=3). The real-time monitoring of O₂^·- from MCF-7 breast cancer cells stimulated by zymosan was realized in this work, which indicates that the MnTPP/ERGO/GCE hold potential application for electrochemical quantification of superoxide anions in biological applications.     

A Simple Electrochemical Aptamer Cytosensor for Direct Detection of Chronic Myelogenous Leukemia K562 Cells

A simple and rapid electrochemical aptamer cytosensor has been developed for direct detection of chronic myelogenous leukemia (CML) K562 cells based on a specific aptamer and a biotin conjugated concanavalin A (bio‐ConA) detection probe. The K562 cell could be specifically recognized by T2‐KK1B10 capture aptamer pre‐immobilized on gold modified electrode surface. Then, bio‐ConA was added in the reaction to identify K562 cell surface mannose, resulting in an aptamer‐K562 cell‐bio‐ConA sandwich complex. Finally, streptavidin conjugated alkaline phosphatase (ST‐ALP) combined with the bio‐ConA to catalyze α‐naphthyl (α‐NP) phosphate to form α‐naphthol which is highly electroactive at an operating voltage of 180 mV (vs. Ag/AgCl). Under optimum conditions, the DPV signals were proportional to the logarithm of K562 cell from 1×10² to 1×10⁷ cells mL⁻¹ with a detection limit of 79 cells mL⁻¹. The cytosensor also exhibited high selectivity, stability and reproducibility. When applied to detect K562 cells in human blood samples, recoveries between 79.6 %–93.3 % were obtained, indicating the developed biosensor would be a potential alternative tool for CML K562 cell detection in real biological samples.