Label-free and highly-sensitive detection of calcium ions using a silicon-on-sapphire light-addressable potentiometric sensor.

BACKGROUND: Ionic calcium (Ca2+) plays a crucial role in maintaining normal physiological and biochemical functions within the human body. Detecting the concentration of Ca2+ is of utmost significance for various purposes, including disease screening, cellular metabolism research, and evaluating drug effectiveness. However, current detection approaches such as fluorescence and colorimetry face limitations due to complex labeling techniques and the inability to track changes in Ca2+ concentration. In recent years, extensive research has been conducted in this field to explore label-free and efficient approaches. RESULTS: In this study, a novel light-addressed potentiometric sensor (LAPS) using silicon-on-sapphire technology, has been successfully developed for Ca2+ sensing. The Ca2+-sensitive LAPS achieved a wide-range detection of Ca2+, ranging from 10-2 M to 10-7 M, with an impressive detection limit of 100 nM. These advancements are attributed to the ultra-thin silicon layer, silicon dioxide layer, and solid-state silicon rubber sensitive membrane around 6 µm. Furthermore, the sensor demonstrated the ability to dynamically monitor fluctuations in Ca2+ concentration ranging from 10-9 M to 10-2 M within a solution. Its remarkable selectivity, specificity, and long-term stability have facilitated its successful application in the detection of Ca2+ in human serum and urine. SIGNIFICANCE AND NOVELTY: This work presents a Ca2+-sensitive sensor that combines a low detection limit and a wide detection range. The development represents the emergence of a label-free and rapid Ca2+ detection tool with immense prospects in home-based health monitoring, community disease screening, as well as cellular metabolism, and drug screening evaluations.

A trimodal detection paper chip for undisclosed drug "sibutramine" in nutraceuticals.

Nutraceuticals are promoted and marketed with the stated label of being natural as well as safe herbal products. In order to enhance their effectiveness, nutraceuticals are usually adulterated with undeclared constituents. Slimming herbs may contain sibutramine (SBT) which is an FDA-banned ingredient due to its fatal outcomes. This current work's aim is to design a trimodal sensor for SBT detection in different herbal slimming formulations. Screen-printed silver and multi-walled carbon nanotube inks were employed for the potentiometric sensor. The sensor was designed to fill a reaction well in which a carbon dot-silver nanoparticle pair was applied for fluorimetric and colorimetric purposes. The trimodal sensor was designed to fit an 8 mm 2-pin LED strip connector. Potentiometric measurement took place upon application of one sample aliquot then the optical reaction proceeded next in a specified zone for optical detection. These multiple detection mechanisms achieved the required selectivity for SBT determination in the presence of other slimming products' additives. This trimodal sensor satisfied World Health Organization standards for point-of-care devices demonstrating the suggested device as a dynamic part for rapid on-site detection of undisclosed SBT.

A regenerable electrochemical sensor for electro-inactive cyclovirobuxine D detection in biological samples.

Based on the pKa determination of cyclovirobuxine D (CVB-D) using the method of potentiometry, we predicted the ionization state of CVB-D at physiological pH. Thus, by taking advantage of the ionization state and consequent non-covalent interactions between protonated CVB-D and deprotonated polymerized bromothymol blue (poly-BTB) under physiological conditions, we developed a simple and reusable electrochemical sensor that contains a poly-BTB/SWNT-modified electrode for electro-inactive CVB-D detection in biological fluids using poly-BTB as both the recognition unit and the electrochemical probe. Upon being immersed in the solution of CVB-D, the poly BTB-based electrode shows a current decrease due to the interaction-driven binding of CVB-D on the electrode surface. The current decrease in the electrochemical sensor toward CVB-D concentration shows a linear relationship in the dynamic ranges of 0.01-1 µM and 1-50 µM with a detection limit of 1.65 nM based on 3σ. The sensor can be easily regenerated through the removal of the binding of CVB-D from the electrode surface by highly negatively charged heparin, and it presents high repeatability with an RSD of less than 4.0% for seven measurements. In animal experiments, the electrochemical sensor was selective and sensitive for CVB-D determination in plasma and liver homogenates. The electrochemical sensor is readily accessible, robust, and cost-effective and holds good promise for more applications in biological and clinical fields associated with CVB-D using less technically demanding and simple operating procedures.

A new potentiometric PVC membrane sensor for the determination of DPPH radical scavenging activity of plant extracts.

In this study, a simple, fast, stable and low-cost potentiometric determination method is recommended for the evaluation of 1,1-diphenyl-1-picrylhydrazil radical (DPPH•) scavenging activity, which is one of the antioxidant activity tests. For this purpose, a new type of solid-state-contact potentiometric polyvinyl chloride (PVC) membrane sensor was developed. Gallic acid compound, which is sensitive to the DPPH•, was used as the active ingredient in the membrane structure of the sensor. The potentiometric behavior of the developed DPPH•-selective PVC membrane sensor was characterized. The detection limit of the developed sensor was obtained as 2.3 µg/mL. The sensor can measure at low volumes with its high selectivity. The measurement results obtained were in accordance with the results of the spectroscopic method in the literature. The developed DPPH•-selective PVC membrane sensor was quickly dipped directly into the plant extracts and successfully used in test measurements of DPPH• scavenging activity.

Deferoxamine B: A Natural, Excellent and Versatile Metal Chelator.

Deferoxamine B is an outstanding molecule which has been widely studied in the past decade for its ability to bind iron and many other metal ions. The versatility of this metal chelator makes it suitable for a number of medicinal and analytical applications, from the well-known iron chelation therapy to the most recent use in sensor devices. The three bidentate hydroxamic functional groups of deferoxamine B are the centerpiece of its metal binding ability, which allows the formation of stable complexes with many transition, lanthanoid and actinoid metal ions. In addition to the ferric ion, in fact, more than 20 different metal complexes of deferoxamine b have been characterized in terms of their chemical speciation in solution. In addition, the availability of a terminal amino group, most often not involved in complexation, opens the way to deferoxamine B modification and functionalization. This review aims to collect and summarize the available data concerning the complex-formation equilibria in solutions of deferoxamine B with different metal ions. A general overview of the progress of its applications over the past decade is also discussed, including the treatment of iron overload-associated diseases, its clinical use against cancer and neurodegenerative disorders and its role as a diagnostic tool.

t-Butyl calixarene/Fe2O3@MWCNTs composite-based potentiometric sensor for determination of ivabradine hydrochloride in pharmaceutical formulations.

Ivabradine hydrochloride (IVB) has shown high medical importance as it is a medication for lowering the heart rate for the symptomatic chronic heart failure and symptomatic management of stable angina pectoralis. The high dose of IVB may cause severe and prolonged bradycardia, uncontrolled blood pressure, headache, and blurred vision. In this study, a highly sensitive carbon-paste electrode (CPEs) was constructed for the potentiometric determination of IVB in pharmaceutical formulations. t-Butyl calixarene (t-BCX) was used as an ionophore due to its ability to mask IVB in the cavity via multiple H-bonding at the lower rim, as estimated quantitatively by the sandwich membrane method (Log ßILn = 8.62). Besides, the use of multi-walled carbon nanotubes decorated with Fe2O3 nanoparticles (Fe2O3@MWCNTs) as an additive for the paste electrode significantly improved the detection limit of the sensor up to 36 nM, with Nernstian response of 58.9 mV decade-1 in the IVB linear dynamic range of 10-3-10-7 M in aqueous solutions. The constructed sensors showed high selectivity against interfering species that may exist in physiological fluids or pharmaceutical formulations (e.g. Na+, K+, NH4+, Ca2+, Mg2+, Ba2+, Fe3+, Co2+, Cr3+, Sr2+, glucose, lactose, maltose, glycine, dopamine, and ascorbic acid). The sensors were successfully employed for IVB determination in the pharmaceutical formulations (Savapran®).

Contact hybrid potentiometric method for on-site and in situ estimation of the antioxidant activity of fruits and vegetables.

A new version of the hybrid potentiometric method (HPM) for evaluating the antioxidant activity (AOA) of fruits and vegetables, which we called contact (CHPM), is proposed. A screen-printed electrode pair coated by a membrane impregnated with a mediator serves as a sensor system. The potential shift, which is observed when the sensor system is exposed to the sample slice is used as a source of information. CHPM provides reproducible and correct results: relative standard deviation does not exceed 8.4% and recovery of model antioxidant at close to 100%. The AOA values of fruits and vegetables found by CHPM are in the range of 1-21 µmol-eq/g. Correlation between the AOA of slices and suspensions is found. The proposed CHPM can be used in on-site and in situ formats.

Uranium biosorption mechanism model of protonated Saccharomyces cerevisiae.

Further understanding absorption uranium mechanism of the regenerational biosorbent is very interesting in application of the biosorbent. The regeneration adsorbent of Saccharomyces cerevisiae biomass was made by hydrochloric acid. Using it to absorb uranium at low constant pH(2.50), accompanied with proton releasing the ratio almost 1:2 which is to be analyzed in this paper. The type and amount of functional groups in the biomass such as carboxyl, amino, phosphoryl were determined by Potentiometric titrations and FTIR analysis. Chemical modification showed that the contribution of functional groups to uranium adsorption was carboxyl, phosphoryl and amino in turn. Analysis of SEM-EDX and staining microscopy showed that uranium on the surface of cells did not exist in the form of precipitation at lower pH 2.98, but at higher pH 4.52. The effects of phosphorus release and pH on uranium species was analyzed by MINTEQ software 3.0. Based on the above boundary conditions of the model construction, a multi-site of functional groups model equation of ion exchange absorption mechanism was built in which the final uranium ion concentration and pH as functions. It could well describe the exchange equilibrium of proton with uranium ion at pH2.50 to pH4.00.

Rapid electroanalytical procedure for sesamol determination in real samples.

In this study, the development of an electroanalytical assay based on square wave voltammetry technique for determining sesamol (Ses) in sesame oil samples is described. The influence of various factors such as pH of the supporting electrolyte, its composition, and SW (square wave) parameters was studied. Linearity of the peak current depended on the concentration of Ses in the range from 3.0 to 140.0 µmol L-1 with a limit of detection of 0.71 µmol L-1. Furthermore, the cyclic voltammetric behavior of Ses and the effects of scan rate and pH on the peak current and peak potential of Ses were determined. Moreover, the electrode process was found to be diffusion-controlled. The proposed methodology was successfully applied for determining Ses in commercial sesame oil samples. The obtained results were in good agreement with the results from the HPLC-UV reference method.

Potentiometric method of plant microsuspensions antioxidant activity determination.

This paper focuses on the development of a simple, fast and reliable technique of sample preparation to be employed as part of potentiometric measurements of plant total antioxidant activity (AOA). Plant extracts and plant microsuspensions were analysed. The conditions for obtaining plant extracts were chosen: they exhibited the highest antioxidant activity at +80 °C and extraction time 20 min. A higher degree of dispersion of the analysed samples was accompanied by an increase in AOA of extracts and microsuspensions. The microsuspension enhanced effect results from the fact that antioxidants contained in both liquid and solid fractions are involved in the zone of a signal-generating reaction. The analysis of plant microsuspensions reduces the duration of AOA assessment. Comparison of the results of antioxidant activity of black and green tea microsuspensions with the results of the analysis of extracts prepared by a certified method showed no difference.

Determination of Carbonyl Functional Groups in Bio-oils by Potentiometric Titration: The Faix Method.

Carbonyl compounds present in bio-oils are known to be responsible for bio-oil property changes upon storage and during upgrading. Specifically, carbonyls cause an increase in viscosity (often referred to as 'aging') during storage of bio-oils. As such, carbonyl content has previously been used as a method of tracking bio-oil aging and condensation reactions with less variability than viscosity measurements. Additionally, carbonyls are also responsible for coke formation in bio-oil upgrading processes. Given the importance of carbonyls in bio-oils, accurate analytical methods for their quantification are very important for the bio-oil community. Potentiometric titration methods based on carbonyl oximation have long been used for the determination of carbonyl content in pyrolysis bio-oils. Here, we present a modification of the traditional carbonyl oximation procedures that results in less reaction time, smaller sample size, higher precision, and more accurate carbonyl determinations. While traditional carbonyl oximation methods occur at room temperature, the Faix method presented here occurs at an elevated temperature of 80 °C.

Phosphoryl Transfer Processes Promoted by a Trifunctional Calix[4]arene Inspired by DNA Topoisomerase I.

The cone-calix[4]arene derivative (1H3)2+, decorated at the upper rim with two guanidinium units and a phenolic hydroxyl in an ABAH functionalization pattern, effectively promotes the cleavage of the DNA model compound bis(p-nitrophenyl) phosphate (BNPP) in 80% DMSO solution at pH values in the range 8.5-12.0. The pH dependence of the kinetics was found to be fully consistent with the results of the potentiometric titration of the triprotic acid (1H3)2+. At pH 9.5, the rate enhancement of p-nitrophenol liberation from BNPP relative to background hydrolysis is 6.5 × 104-fold at 1 mM concentration of the calix[4]arene derivative. Experimental data clearly point to the effective cooperation of the three active units and to the involvement of the phenolate moiety as a nucleophile in the phosphoryl transfer step. Subsequent liberation of a second equivalent of p-nitrophenol from the phosphorylated calixarene intermediate is conceivably promoted by the "built-in" guanidine/guanidinium catalytic dyad.

A total analytical system featuring a novel solid-liquid extraction chamber for solid sample flow analysis.

In this work, a total flow analysis system based on a novel solid-liquid extraction chamber is presented. This strategy enables all the main experimental procedures for the analysis of a solid sample to be performed automatically: enrichment of the liquid extract, sample treatment, filtration of the liquid extract from the solid sample, directing the extract towards detection, and finally cleansing of the chamber for the following solid sample to be analyzed. The chamber designed to be incorporated in the flow manifold presents two main features: it accommodates stirring bars for enhancing the extraction process, and it presents replaceable solid sample containers (a spare part of the solid-liquid extraction chamber) to easily replace the solid sample and therefore enhance sample analysis throughput. The chamber performance was assessed using two different solid samples, an ion exchanger resin and vegetable samples, focussing on proton and nitrate ion extraction, respectively. The main figures of merit achieved were relative standard deviation (RSD) and relative error values below 7 % for all determinations. The determination rate for vegetable samples was ca. 12 samples h-1. The proposed strategy may be exploited to perform automatically the analysis of solid samples as it embodies a simple automatic strategy of a very important but time-consuming and laborious analytical operation. Graphical abstract TAS for solid liquid extraction and nitrate potentiometric determination of vegetable samples.

Exploring bitterness of traditional Chinese medicine samples by potentiometric electronic tongue and by capillary electrophoresis and liquid chromatography coupled to UV detection.

Instrumental bitterness assessment of traditional Chinese herbal medicine (TCM) preparations was addressed in this study. Three different approaches were evaluated, high-performance liquid chromatography coupled to UV detector (HPLC), capillary electrophoresis coupled to UV detector (CE) and a potentiometric multisensor system - electronic tongue (ET). Most studies involving HPLC and CE separations use these as selective instruments for quantification of individual substances. However we employed these techniques to provide chromatographic or electrophoretic sample profiles. These profiles are somewhat analogous to the profiles produced by the ET. Profiles from all instruments were then related to professional sensory panel evaluations using projections on latent structures (PLS) regression. It was found that all three methods allow for bitterness assessment in TCM samples in terms of human sensory panel with root mean squared errors of prediction ca. 0.9 within bitterness scale from 0 (no bitterness) to 6 (maximal bitterness).

Rapid determination of trace level copper in tea infusion samples by solid contact ion selective electrode.

A new solid contact copper selective electrode with a poly (vinyl chloride) (PVC) membrane consisting of o-xylylenebis(N,N-diisobutyldithiocarbamate) as ionophore has been prepared. The main novelties of constructed ion selective electrode concept are the enhanced robustness, cheapness, and fastness due to the use of solid contacts. The electrode exhibits a rapid (< 10 seconds) and near-Nernstian response to Cu2+ activity from 10-1 to 10-6 mol/L at the pH range of 4.0-6.0. No serious interference from common ions was found. The electrode characterizes by high potential stability, reproducibility, and full repeatability. The electrode was used as an indicator electrode in potentiometric titration of Cu(II) ions with EDTA and for the direct assay of tea infusion samples by means of the calibration graph technique. The results compared favorably with those obtained by the atomic absorption spectroscopy (AAS).

Quantitative determination of fucoidan using polyion-sensitive membrane electrodes.

The use of polyanion and polycation-sensitive membrane electrodes to detect five different preparations of fucoidan is described. Unlike linear polyanionic molecules previously measured with polymer membrane-based electrochemical sensors, fucoidans from marine brown algae are all highly branched, sulfated polysaccharides with varying charge densities and structures, depending on the species of seaweed, method of extraction used and extent of purification. When tridodecylmethylammonium (TDMA) was used as the ion-exchanger, a large, non-equilibrium EMF response was observed over a concentration range of 0.5-50 µg mL(-1) fucoidan. Fucoidan was also measured by titration with polycationic protamine, using a dinonylnaphthalene sulfonate (DNNS)-doped membrane electrode as the potentiometric endpoint detector. Potentiometric titration was used to determine the binding ratio between protamine and fucoidan at the neutralization endpoint for each fucoidan preparation. This binding ratio was then used to successfully determine the fucoidan content of commercially available nutritional supplements. Fucoidan was also measured in undiluted blood serum, demonstrating that this method may be applicable for measuring fucoidan for clinical applications.

Direct output of electrical signals from LSPR sensors on the basis of plasmon-induced charge separation.

Potentiometric and conductometric sensors based on localized surface plasmon resonance were developed. The sensors can be applied to coloured and turbid samples because light need not pass through the sample solution.

Standard addition flow method for potentiometric measurements at low concentration levels: application to the determination of fluoride in food samples.

A standard addition method was implemented by using a flow manifold able to perform automatically multiple standard additions and in-line sample treatment. This analytical strategy was based on the in-line mixing of sample and standard addition solutions, using a merging zone approach. The flow system aimed to exploit the standard addition method to quantify the target analyte particularly in cases where the analyte concentration in the matrix is below the lower limit of linear response of the detector. The feasibility of the proposed flow configuration was assessed through the potentiometric determination of fluoride in sea salts of different origins and different types of coffee infusions. The limit of quantification of the proposed manifold was 5×10(-6) mol L(-1), 10-fold lower than the lower limit of linear response of the potentiometric detector used. A determination rate of 8 samples h(-1) was achieved considering an experimental procedure based on three standard additions per sample. The main advantage of the proposed strategy is the simple approach to perform multiple standard additions, which can be implemented with other ion selective electrodes, especially in cases when the primary ion is below the lower limit of linear response of the detector.

Degradation behavior of biodegradable Fe35Mn alloy stents.

This article reports a degradation study that was done on stent prototypes made of biodegradable Fe35Mn alloy in a simulated human coronary arterial condition. The stent degradation was observed for a short-term period from 0.5 to 168 h, which simulates the early period of stenting procedure. Potentiodynamic polarization and electrochemical impedance spectroscopy were used to quantify degradation rate and surface property of the stents. Results showed that signs of degradation were visible on both crimped and expanded stents after 1 h of test, mostly located on the stent's curvatures. The degradation rate of stent was higher compared to that of the original alloy, indicating the surface altering effect of stent fabrication processing to degradation. A single oxide layer was formed and detected as a porous structure with capacitive behavior. Expanded stents exhibited lower polarization resistance compared to the nonexpanded ones, indicating the cold work effect of expansion procedure to degradation.

Electrochemical corrosion and surface analyses of a ni-cr alloy in bleaching agents.

PURPOSE: The aim of this study was to evaluate the corrosion behavior of a Ni-Cr dental casting alloy subjected to 10% hydrogen peroxide (HP) and 10% carbamide peroxide (CP) bleaching solutions and to determine the composition of the surface oxide layer formed on the alloy specimens. MATERIALS AND METHODS: Ten cylindrical specimens (4 mm in diameter × 25 mm in height) were cast from a Ni-Cr alloy (Wiron 99) and divided into two groups (n = 5). A potentiodynamic polarization test was used to compare the corrosion rates of specimens in HP and CP (pH = 6.5). Before cyclic polarization tests, all alloy specimens were allowed to reach a steady open circuit potential (Ecorr ) for a period of 1 hour. Then tests were initiated at 100 mV versus standard calomel electrode (SCE) below Ecorr and scanned at a rate of 1 mV/s in the anodic direction until reaching 1000 mV over the Ecorr value. The scan then was reversed back to the Ecorr of the specimens. The open circuit potentials (Ecorr ) and the current densities (Icorr ) were determined using the anodic Tafel regions extrapolating from the curves. Differences in Ecorr and Icorr were determined using one-way ANOVA (α = 0.05). In addition, corrosion rates were calculated from these curves. Before and after polarization tests, a scanning electron microscope (SEM) examination accompanied by energy dispersive X-ray spectroscopy (EDS) was used to analyze the surface morphology. The surface characterization of the passive film formed on alloy specimens was also performed by using X-ray photoelectron spectroscopy (XPS). RESULTS: In this study, bleaching agents had an effect on the anodic process for two groups. Although no statistical difference was identified between the groups for both corrosion parameters, results indicated that the effect of CP on the corrosion behavior was less than that of HP. These results agreed with the SEM observations. XPS data showed that oxide layers formed on all groups contained mainly Cr2 O3 , NiO, and MoO3 , and the amounts of oxides formed on CP-treated specimens were higher than HP treated ones. Also, molybdenum rates were increased with CP application compared to HP. CONCLUSIONS: The comparison of the effects of the two bleaching agents at 10% showed that the alloy suffered less corrosion with CP than HP. This result was also confirmed by the SEM and XPS data. The presence of Mo on the oxide layer affected the oxide layer, leading to lower corrosion rates.