Electrochemical Methods for the Analysis of Trace Tin Concentrations-Review.

Tin determination allows for the monitoring of pollution and assessment of the impact of human activities on the environment. The determination of tin in the environment is crucial for the protection of human health and ecosystems, and for maintaining sustainability. Tin can be released into the environment from various sources, such as industry, transportation, and electronic waste. The concentration of tin in the environment can be determined by different analytical methods, depending on the form of tin present and the purpose of the analysis. The choice of an appropriate method depends on the type of sample, concentration levels, and the available instrumentation. In this paper, we have carried out a literature review of electrochemical methods for the determination of tin. Electrochemical methods of analysis such as polarography, voltammetry, and potentiometry can be used for the determination of tin in various environmental samples, as well as in metal alloys. The detection limits and linearity ranges obtained for the determination of tin by different electrochemical techniques are collected and presented. The influence of the choice of base electrolyte and working electrode on signals is also presented. Practical applications of the developed tin determination methods in analyzing real samples are also summarized.

A Journey from the Drops of Mercury to the Mysterious Shores of the Brain: The 100-Year Adventure of Voltammetry.

Voltammetry, which is at the core of electroanalytical chemistry, is an analytical method that investigates and evaluates the current-potential relationship obtained at a given working electrode. If it is used dropping mercury as working electrode, the method is called as polarography. The current year 2022 marks the 100th anniversary of the discovery of polarography by Czech Jaroslav Heyrovský. He received the Nobel Prize in Chemistry in 1959 for this discovery and his contribution to the scientific world. A hundred years, within the endless existence of the universe is maybe nothing. A hundred years, in the history of mankind is a line, maybe a short paragraph. But, in science, a hundred years can lead to very significant advances in a field and often to the birth and establishment of an entirely new scientific discipline. Indeed, in the last hundred years, the design and use of new electrochemical devices, depending on the progress in microelectronics and computer technologies, has almost revolutionized voltammetry. Besides these developments, due to the fact that the redox (oxidation/reduction) process is very basic for living organisms; the voltammetry, especially with the beginning of the 21st century, has started to be used as a very powerful tool in neuroscience to solve the mystery of the brain (the basic problems of biomolecules with physiological and genetic importance in brain tissue). This review article is an overview of the 100-year history and fascinating development of voltammetry from Heyrovský to the present.

The Biochemical Assessment of Mitochondrial Respiratory Chain Disorders.

Mitochondrial respiratory chain (MRC) disorders are a complex group of diseases whose diagnosis requires a multidisciplinary approach in which the biochemical investigations play an important role. Initial investigations include metabolite analysis in both blood and urine and the measurement of lactate, pyruvate and amino acid levels, as well as urine organic acids. Recently, hormone-like cytokines, such as fibroblast growth factor-21 (FGF-21), have also been used as a means of assessing evidence of MRC dysfunction, although work is still required to confirm their diagnostic utility and reliability. The assessment of evidence of oxidative stress may also be an important parameter to consider in the diagnosis of MRC function in view of its association with mitochondrial dysfunction. At present, due to the lack of reliable biomarkers available for assessing evidence of MRC dysfunction, the spectrophotometric determination of MRC enzyme activities in skeletal muscle or tissue from the disease-presenting organ is considered the 'Gold Standard' biochemical method to provide evidence of MRC dysfunction. The purpose of this review is to outline a number of biochemical methods that may provide diagnostic evidence of MRC dysfunction in patients.

Polarography Can Successfully Quantify Heavy Metals in Dentistry.

Background and Objectives: Due to the nutritional and behavioral patterns of children, their teeth can be a good indicator of heavy metal uptake from over the years. To determine the amount of Zn, Cu, Cd, and Pb accumulated in the body, primary teeth of children in Zanjan, Iran, were examined with a polarography device. Materials and Methods: Samples were collected from dentistry clinics of Zanjan, Iran, and were prepared for acid digestion, and then were analyzed by a polarography device for determining the concentration of lead, copper, zinc, and cadmium. Results: Data were analyzed by a t-independent test to compare different groups (p < 0.05). Based on the results obtained from this study, the mean concentrations of zinc, lead, copper, and cadmium were 245, 7.66, 5.33, and 0.0879 µg/g, respectively, which shows that the amount of each of the four elements was more than the amounts that have been reported for different countries. The results showed no significant difference between age, tooth type, and jaw groups. Conclusions: We conclude that primary teeth are an important biological indicator to evaluate the concentration of heavy elements in the human body. The high concentrations of these elements in the primary teeth analyzed in this study could be attributed to the high concentrations of these elements in the environment of Zanjan.

Relationships between correlated spikes, oxygen and LFP in the resting-state primate.

Resting-state functional MRI (rsfMRI) provides a view of human brain organization based on correlation patterns of blood oxygen level dependent (BOLD) signals recorded across the whole brain. The neural basis of resting-state BOLD fluctuations and their correlation remains poorly understood. We simultaneously recorded oxygen level, spikes, and local field potential (LFP) at multiple sites in awake, resting monkeys. Following a spike, the average local oxygen and LFP voltage responses each resemble a task-driven BOLD response, with LFP preceding oxygen by 0.5 s. Between sites, features of the long-range correlation patterns of oxygen, LFP, and spikes are similar to features seen in rsfMRI. Most of the variance shared between sites lies in the infraslow frequency band (0.01-0.1 Hz) and in the infraslow envelope of higher-frequency bands (e.g. gamma LFP). While gamma LFP and infraslow LFP are both strong correlates of local oxygen, infraslow LFP explains significantly more of the variance shared between correlated oxygen signals than any other electrophysiological signal. Together these findings are consistent with a causal relationship between infraslow LFP and long-range oxygen correlations in the resting state.

Evaluation of Interactions of Selected Olivacine Derivatives with DNA and Topoisomerase II.

Olivacine and ellipticine are model anticancer drugs acting as topoisomerase II inhibitors. Here, we present investigations performed on four olivacine derivatives in light of their antitumor activity. The aim of this study was to identify the best antitumor compound among the four tested olivacine derivatives. The study was performed using CCRF/CEM and MCF-7 cell lines. Comet assay, polarography, inhibition of topoisomerase II activity, histone acetylation, and molecular docking studies were performed. Each tested compound displayed interaction with DNA and topoisomerase II, but did not cause histone acetylation. Compound 2 (9-methoxy-5,6-dimethyl-1-({[1-hydroxy-2-(hydroxymethyl)butan-2-yl]amino}methyl)-6H-pyrido[4,3-b]carbazole) was found to be the best candidate as an anticancer drug because it had the highest affinity for topoisomerase II and caused the least genotoxic damage in cells.

Determination of Oxidative Phosphorylation Complexes Activities.

Mitochondria possess a genome that codes for proteins, in the same fashion as the nuclear genome. However, the small, circular mitochondrial DNA (mtDNA) molecule has a reduced base pair content, for it can only code for 2 rRNA, 22 tRNA molecules, and 13 proteins, all of them part of the mitochondrial respiratory chain. As such, all of the other mitochondrial components derive from nuclear genome. This separation leads to a requirement for a well-tuned coordination between both genomes, in order to produce fully functional mitochondria. A vast number of pathologies have been demonstrated to involve, to some extent, alterations in mitochondrial function that, no doubt, can be caused by alterations to the respiratory chain activity. As such, several methods and techniques have been developed to assess both content and function of mitochondrial proteins, in order to help understand mitochondrial involvement on the pathogenesis of disease. In this chapter, we will address some of these methods, with the main focus being on isolated mitochondria.

Analytic and chemometric assessments of the native probiotic bacteria and inulin effects on bioremediation of lead salts.

BACKGROUND: Lead (Pb2+ ) is one of the most toxic heavy metals and can be found in various quantities in the environment. The five native probiotic bacteria and inulin were used to assess in vitro lead nitrate and lead acetate binding capacities, as well as removal potentials. RESULTS: The highest decrease in media pH was seen for samples containing a combination of Lactobacillus paracasei IRBC-M 10784, lead nitrate and inulin (5.30 ± 0.012). The presence of inulin in the environment accelerated decreases in the pH of all samples with no significance. In all groups, lead nitrate-containing samples included maximum pH decreases. From the highest to the lowest, the ability of lead removal was linked to Lactobacillus acidophilus PTCC-1932 (88.48%), Bifidobacterium bifidum BIA-7 (85.32%), Bifidobacterium lactis BIA-6 (85.24%), Lactobacillus rhamnosus IBRC-M 10782 (83.18%) and L. paracasei IRBC-M 10784 (80.66%). Most species included the highest decrease in lead nitrate. Fourier-transform infrared spectroscopy (FTIR) analysis demonstrated that various functional groups (hydroxyl, carboxylic, carbonyl, amino and amide binds) on the bacterial cell wall were involved in lead ion binding during incubation. Principal component analysis of the FTIR results showed differences with respect to treated groups and control groups. CONCLUSION: The results obtained in the present study reveal that the simultaneous use of native probiotics and inulin can be an effective and safe approach for removing various toxic substances, especially Pb. © 2021 Society of Chemical Industry.

Low sugar jellies of berry fruits: the impact of low vs. high temperature regime on their chemical composition and antioxidativity.

This study focuses on the impact of low and high temperature regimes on the chemical composition and antioxidativity of low sugar berry fruits jellies. High quality fruits (strawberry, raspberry and blackberry) were collected from Western Serbia region, quite well recognised both nationally and internationally due to an extremely well developed practice in growing berry fruits. The obtained results have clearly indicated the importance of low temperature regime for enriched contents of both total phenolics and anthocyanins followed by an enhanced antioxidativity. Rubus fruticosus L. Cacak Thornless cultivar, the only autochthonous berry fruit variety screened herein, may be firmly recommended as a raw material for industrial production of low sugar blackberry jellies with exceptional characteristics. This innovative procedure of preparing berry fruit jellies have encompassed the application of low temperature regime (55 °C), lower content of sugar (40%), seeds separation from jellies followed by no use of pectin throughout the whole process.

Polarography as a technique of choice for the evaluation of total antioxidant activity: The case study of selected Coprinus Comatus extracts and quinic acid, their antidiabetic ingredient.

This study was focused on in vitro screening of the total antioxidant activity of the selected extracts of the mushroom Coprinus comatus and quinic acid, one of their antidiabetic ingredients, by an uncommon electrochemical assay. Indeed, direct current (DC) polarographic HydroxoPerhydroxo Mercury(II) Complex (HPMC) assay based on decrease of anodic limiting current originating from HPMC formation in alkaline solutions of hydrogen peroxide at potential of mercury dissolution, observed upon gradual addition of antioxidants, was applied herein for the estimation of the natural products' antioxidativity. Quinic acid was found to exhibit most promising antioxidant potential (4.0 ± 0.2%µL-1) being ≈ 2-fold more active than the screened C. comatus extract samples. Actually, such a finding puts some light on the antioxidativity of cyclic polyols, well understimated class of organic compounds, compared to aromatic (poly)phenolics. As a low cost, easy-to handle and accurate this polarographic assay may be thoroughly recommended for much broader use. [Formula: see text].

Review of Electroanalytical-Based Approaches for the Determination of Benzodiazepines.

The benzodiazepine class of drugs are characterised by a readily electrochemically reducible azomethine group. A number are also substituted by other electrochemically active nitro, N-oxide, and carbonyl groups, making them readily accessible to electrochemical determination. Techniques such as polarography, voltammetry, and potentiometry have been employed for pharmaceutical and biomedical samples, requiring little sample preparation. This review describes current developments in the design and applications of electrochemical-based approaches for the determination of the benzodiazepine class of drugs form their introduction in the early 1960s to 2019. Throughout this period, state-of-the-art electroanalytical techniques have been reported for their determination. Polarography was first employed focused on mechanistic investigations. Subsequent studies showed the adsorption of many the benzodiazepines at Hg electrodes allowed for the highly sensitive technique of adsorptive stripping voltammetry to be employed. The development and introduction of other working electrode materials such as carbon led to techniques such as voltammetry to become commonly reported, and the modification of these electrodes has now become the most commonly employed approach using molecularly imprinting and nanotechnology.

Ammonia as a substrate-water analogue in photosynthetic water oxidation: Influence on activation barrier of the O2-formation step.

Information on binding and rearrangement of pivotal water molecules could support understanding of light-driven water oxidation at the catalytic Mn4CaO5 cluster of photosystem II (PSII). To address this point, the binding of ammonia (NH3)-a possible substrate-water analogue-has been investigated and discussed in the context of putative reaction mechanisms. By time-resolved detection of O2 formation after light-flash excitation, we discriminate three NH3/NH4+ binding sites jointly characterized by a Km value around 25 mM (of NH4+), but differing in their influence on the O2-formation step. At 100 mM NH4Cl (pH 7.5), we observe (1) a PSII fraction with complete inhibition of O2-formation, (2) fast O2-formation with a time constant of 1.7 ms at 20 °C (Fast-PSII), and (3) slow O2-formation with a time constant of 36 ms at 20 °C (Slow-PSII). For the Fast-PSII, we determine an activation enthalpy of 223 ±â€¯11 meV. Activation enthalpy and entropy of the Fast-PSII are essentially identical to the corresponding figures in the absence NH3/NH4+ binding. For the Slow-PSII, the activation enthalpy is 323 ±â€¯11 meV and thus significantly increased, whereas the activation entropy remains essentially unchanged. We conclude: (1) The fully-inhibitory binding site could relate to bound NH3 replacing one of the two substrate-water molecules. (2) The Fast-PSII may relate to NH3/NH4+ binding in the S2-state of PSII followed by unbinding before onset of the OO bond formation step, but also more intricate mechanisms are not excluded. (3) In the Slow-PSII, NH3/NH4+ binding increases the energetic barrier of the OO bond formation step significantly.

Isolation of mitochondrial subpopulations from skeletal muscle: Optimizing recovery and preserving integrity.

AIM: The subsarcolemmal (SSM) and interfibrillar (IFM) mitochondria in skeletal muscle appear to have distinct biochemical properties affecting metabolism in health and disease. The isolation of mitochondrial subpopulations has been a long-time challenge while the presence of a continuous mitochondrial reticulum challenges the view of distinctive SSM and IFM bioenergetics. Here, a comprehensive approach is developed to identify the best conditions to separate mitochondrial fractions. METHODS: The main modifications to the protocol to isolate SSM and IFM from rat skeletal muscle were: (a) decreased dispase content and homogenization speed; (b) trypsin treatment of SSM fractions; (c) recentrifugation of mitochondrial fractions at low speed to remove subcellular components. To identify the conditions preserving mitochondrial function, integrity, and maximizing their recovery, microscopy (light and electron) were used to monitor effectiveness and efficiency in separating mitochondrial subpopulations while respiratory and enzyme activities were employed to evaluate function, recovery, and integrity. RESULTS: With the modifications described, the total mitochondrial yield increased with a recovery of 80% of mitochondria contained in the original skeletal muscle sample. The difference between SSM and IFM oxidative capacity (10%) with complex-I substrate was significant only with a saturated ADP concentration. The inner and outer membrane damage for both subpopulations was <1% and 8%, respectively, while the respiratory control ratio was 16. CONCLUSION: Using a multidisciplinary approach, conditions were identified to maximize SSM and IFM recovery while preserving mitochondrial integrity, biochemistry, and morphology. High quality and recovery of mitochondrial subpopulations allow to study the relationship between these organelles and disease.

Graphene Quantum Dots Protect against Copper Redox-Mediated Free Radical Generation and Cardiac Cell Injury.

In this work, we investigated the effects of graphene quantum dots (GQDs) on copper redox-mediated free radical generation and cell injury. Using electron paramagnetic resonance (EPR) spectrometry in conjunction with 5,5-dimethyl-1-pyrroline N-oxide (DMPO) as a spin trap, we found that GQDs at a concentration as low as 1 µg/ml significantly inhibited Cu(II)/H2O2-mediated hydroxyl radical formation. GQDs also blocked Cu(II)-catalyzed nucleophilic addition of H2O to DMPO to form a DMPO-OH adduct in the absence of H2O2, suggesting a potential for GQDs to inhibit copper redox activity. Indeed, we observed that the presence of GQDs prevented H2O2-mediated reduction of Cu(II) to Cu(I) though GQDs themselves also caused the reduction of Cu(II) to Cu(I). To further investigate the effects of GQDs on copper redox activity, we employed the Cu(II)/hydroquinone system in which copper redox activity plays an essential role in the oxidation of hydroquinone to semiquinone radicals with consequent oxygen consumption. Using oxygen polarography as well as EPR spectrometry, we demonstrated that the presence of GQDs drastically blocked the oxygen consumption and semiquinone radical formation resulting from the reaction of Cu(II) and hydroquinone. These results suggested that GQDs suppressed free radical formation via inhibiting copper redox activity. Lastly, using cultured human cardiomyocytes, we demonstrated that the presence of GQDs also protected against Cu(II)/H2O2-mediated cardiac cell injury as indicated by morphological changes (e.g., cell shrinkage and degeneration). In conclusion, our work shows, for the first time, the potential for using GQDs to counteract copper redox-mediated biological damage.

Heavy metals and arsenic content in water along the southern Caspian coasts in Iran.

Due to the importance of pollution monitoring in marine ecosystems and lack of a coherent and systematic investigation of heavy metal ions along the southern shores of the Caspian Sea, in the present study, the amount of these metals and As ions in coastal waters along its 780-km-long coast in Iran have been studied. Heavy metals (cobalt, nickel, copper, zinc, cadmium, mercury, lead) and a poisonous metalloid (arsenic) were selected in 59 sampling stations and determined using differential pulse polarography method. The multivariate statistical tools were applied to describe and interpret the experimental data. The overall mean concentrations of studied metals (in microgram per liter; µg L-1) in the samples were found in the order Zn (10.9) > Ni (7.4) > Cu (5.5) > Pb (1.9) > Hg (1.4) > As (1.3) > Co (1.1) > Cd (0.2). The results when compared with reported international standards confirmed that the sampled waters do contain some of these elements above the suggested maximum permissible limits. Hg and Cu were detected in 54.2 and 72.9% of the samples, almost all above the permissible limits. Ni, Zn, Pb, and Co were detected in 100, 96.6, 93.2, and 88.1%, respectively, while 8.5, 22.0, 3.4, and 1.7% were above the permissible limits. Cd and As were present in 61 and 93% of the samples, and their concentrations were higher than the rate presented by Russian System of Management Chemicals (RSMC). In addition, spatial distribution of heavy metal concentrations showed that Gorgan Bay is an ecosystem serving as a filter, trapping natural and anthropogenic materials that are brought from industrial, commercial, and urbanized areas. The multivariate data analysis reveals that Caspian Sea is contaminated by both anthropogenic as well as pedo-geochemical sources.

Real-time multiparameter study of mitochondrial functions: Instrumental and analytical approaches.

In modern biomedical science, a descriptive study is no longer the major focus of many fields. More researchers are now seeking approaches that will help them obtain maximum information from a single sample or model, which will allow them to make more detailed conclusions than previously about mechanisms that underlie certain phenomena. Clearly, simultaneous measurement of multiple parameters will provide more useful information compared to that which can be assessed through parallel studies with multiple single-parameter measurements. Mitochondria are actively involved in the regulation of a number of biochemical processes that are vitally important for normal cell functioning. Dysregulation of cell metabolism occurs under multiple pathological conditions. While changes in mitochondrial and cellular functioning are related to each other, understanding of the details of most mechanisms underlying these relationships are still unknown. It would be appropriate to have an instrument that will help to uncover sequences of events and temporal links among the parameters that involve functional mitochondrial and cellular integration. The current review is focused on the analysis of these technological limitations, and, based on the combined approach, provides hypothetical suggestion on how possibly to create such an instrument.

Polarographic study on the presence of antibiotics in food.

EU and Italian laws dealing for the presence of antibiotics or, more in general, drags in food established limits for different kinds of food. Suitable rules exist about the medical treatment of cattle in relation to the production of milk and meat. The adoption of a procedure to check the respect of the law limits is necessary. In this paper, the presence of different classes of antibiotics in milk and in homogenised meat is investigated. Generally, HPLC methods are applied for this purpose. In this paper, the application of polarographic analysis is studied and the results are compared with the chromatographic ones. The comparison is relative to all the phases of analysis including the sample preparation. The results show the advantage of the proposed procedure.

The oxygen-binding properties of hemocyanin from the mollusk Concholepas concholepas.

Hemocyanins have highly conserved copper-containing active sites that bind oxygen. However, structural differences among the hemocyanins of various mollusks may affect their physicochemical properties. Here, we studied the oxygen-binding cooperativity and affinity of Concholepas concholepas hemocyanin (CCH) and its two isolated subunits over a wide range of temperatures and pH values. Considering the differences in the quaternary structures of CCH and keyhole limpet hemocyanin (KLH), we hypothesized that the heterodidecameric CCH has different oxygen-binding parameters than the homodidecameric KLH. A novel modification of the polarographic method was applied in which rat liver submitochondrial particles containing cytochrome c oxidase were introduced to totally deplete oxygen of the test solution using ascorbate as the electron donor. This method was both sensitive and reproducible. The results showed that CCH, like other hemocyanins, exhibits cooperativity, showing an inverse relationship between the oxygen-binding parameters and temperature. According to their Hill coefficients, KLH has greater cooperativity than CCH at physiological pH; however, CCH is less sensitive to pH changes than KLH. Appreciable differences in binding behavior were found between the CCH subunits: the cooperativity of CCH-A was not only almost double that of CCH-B, but it was also slightly superior to that of CCH, thus suggesting that the oxygen-binding domains of the CCH subunits are different in their primary structure. Collectively, these data suggest that CCH-A is the main oxygen-binding domain in CCH; CCH-B may play a more structural role, perhaps utilizing its surprising predisposition to form tubular polymers, unlike CCH-A, as demonstrated here using electron microscopy.

Antioxidant efficiency of polyphenols from coffee and coffee substitutes-electrochemical versus spectrophotometric approach.

Antioxidant (AO) capacity of instant, espresso, filter and Turkish/Greek coffee brews, coffee substitutes (roasted chicory root, barley, pea, chickpea, carob and dried fig) and individual compounds (phenolic acids, flavonoids, methylxanthines, N-methyl pyridinium and HMW melanoidins) was assessed using DC polarographic assay based on decrease of anodic current originating from hydroxo-perhydroxo mercury complex formed in alkaline solutions of H2O2 at potential of mercury dissolution, as well as three spectrophotometric assays (DPPH, ABTS and FRAP). A large difference between applied assays ability to recognize various types of individual AOs was noticed. Only according to DC polarographic assay significant AO activity was ascribed to methylxanthines and N-methyl pyridinum. The total content of phenolics (TPC) present in complex samples was determined by FC assay. The highest TPC was ascribed to instant coffees and coffee substitutes while the lowest to decaffeinated filter coffee. Complex samples were grouped based on principal components analysis, phenolics AO coefficient, calculated as the ratio between AO capacity and TPC, and relative AO capacity index (RACI), calculated by assigning equal weight to all applied assays including FC. The highest values of RACI were ascribed to instant coffee brews, followed by substitutes while the lowest to the decaffeinated espresso coffee.

How do low doses of desferrioxamine B and EDTA affect the phytoextraction of metals in sunflower?

The aim of this study was to compare the efficiency of siderophore desferrioxamine B (DFOB) and EDTA in increasing the phytoextraction of metals in sunflower. A 28-day pot experiment was conducted in a metal-contaminated soil supplied with 200µmolkg-1 of DFOB or EDTA. Pore water was collected and pseudo-polarographic analyses were conducted to assess the impact of the two chelators on the mobility and speciation of metals in the liquid phase. Our results showed that DFOB is not an efficient mobilizing agent of divalent metals in soil. Adding DFOB selectively increased the mobility of trivalent metals while the supply of EDTA simultaneously increased the mobility of both trivalent and divalent metals. EDTA significantly reduced the labile fractions of Cd, Cu, (Pb) and Zn measured in the porewater. The labile concentration of Cd and Zn measured in presence of EDTA was even less than that measured in the control. As expected from the pore water analysis, the addition of DFOB did not affect the phytoextraction of any divalent metals. In contrast, the addition of EDTA enhanced Cu and Ni phytoextraction in sunflower 2.0 to 2.8 fold for Cu and 1.3 to 2.3 fold for Ni, depending on the cultivar. This result supports different hypotheses regarding the forms and the related pathways in which metals are taken up in presence of EDTA. Based on the results obtained for Ni, whose uptake is rate limited by its internalization across the cell membrane, the direct uptake of metal-EDTA complexes via the non-selective apoplastic pathway is hypothesized to contribute the most to the overall uptake of metals in presence of EDTA, even added at "low" concentrations.