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Analytical Chemistry Feb 2024Redox potentiometry has emerged as a new platform for in vivo sensing, with improved neuronal compatibility and strong tolerance against sensitivity variation caused by...
Redox potentiometry has emerged as a new platform for in vivo sensing, with improved neuronal compatibility and strong tolerance against sensitivity variation caused by protein fouling. Although enzymes show great possibilities in the fabrication of selective redox potentiometry, the fabrication of an enzyme electrode to output open-circuit voltage () with fast response remains challenging. Herein, we report a concept of novel enzymatic galvanic redox potentiometry (GRP) with improved time response coupling the merits of the high selectivity of enzyme electrodes with the excellent biocompatibility and reliability of GRP sensors. With a glucose biosensor as an illustration, we use flavin adenine dinucleotide-dependent glucose dehydrogenase as the recognition element and carbon black as the potential relay station to improve the response time. We find that the enzymatic GRP biosensor rapidly responds to glucose with a good linear relationship between and the logarithm of glucose concentration within a range from 100 μM to 2.65 mM. The GRP biosensor shows high selectivity over O and coexisting neurochemicals, good reversibility, and sensitivity and can in vivo monitor glucose dynamics in rat brain. We believe that this study will pave a new platform for the in vivo potentiometric biosensing of chemical events with high reliability.
Topics: Potentiometry; Reproducibility of Results; Glucose Oxidase; Electrodes; Glucose; Oxidation-Reduction; Glucose 1-Dehydrogenase; Biosensing Techniques
PubMed: 38361229
DOI: 10.1021/acs.analchem.4c00185 -
Critical Reviews in Analytical Chemistry 2024Khellin is the key furanocoumarin of L. (Lam.) that exhibits various biological properties. This unique natural product has inspired the discovery of two first-in-class... (Review)
Review
Khellin is the key furanocoumarin of L. (Lam.) that exhibits various biological properties. This unique natural product has inspired the discovery of two first-in-class drugs, amiodarone and sodium cromoglycate. A wide range of analytical methods were generated while translating khellin scaffold into clinically used drugs; however, they have never been reviewed and critically assessed. The present review aims to review and evaluate the analytical techniques for the natural products, khellin, visnagin, and their inspired drugs, amiodarone and sodium cromoglycate. High-performance liquid chromatography (HPLC) is the extensively used technique in most analytical methods reported for these compounds; however, other techniques including the fluorimetry, luminescence spectrophotometry, potentiometry, voltammetry, FT-Raman spectroscopy, and ELISA were also employed. The review will be helpful for further basic and translational research on furanochromone and related scaffolds.
Topics: Biological Products; Amiodarone; Cromolyn Sodium; Humans; Khellin; Chromatography, High Pressure Liquid
PubMed: 35776740
DOI: 10.1080/10408347.2022.2094198 -
Biological Trace Element Research Aug 2024High fluoride exposures can lead to adverse effects such as dental and bone fluorosis, as well as endocrine and cognitive developmental problems. Water is the main...
High fluoride exposures can lead to adverse effects such as dental and bone fluorosis, as well as endocrine and cognitive developmental problems. Water is the main dietary source of this ion, although significant concentrations have also been detected in other beverages widely consumed by the population such as soft drinks. A total of 200 soft drink samples (60 flavoured, 70 extracts, 60 fruit juice and 10 soft drinks) were analysed by fluoride ion selective potentiometry. A consumption of 330 mL was estimated for exposure assessment and subsequent F-risk assessment by soft drink consumption. The highest average concentration was found in extract soft drinks (2.45 ± 1.15 mg/L), followed by flavoured (1.71 ± 2.29 mg/L) and carbonated soft drinks (1.38 ± 0.40 mg/L), while the lowest was found in fruit juice soft drinks (1.09 ± 0.62 mg/L). The flavours with the highest concentration were tea-melon and tea-passion fruit with 3.66 ± 0.40 and 3.17 ± 0.56 mg/L respectively and the lowest was lemon flavour with 0.69 mg/L. The contribution of these beverages, considering the UL (Upper level) reference values set by EFSA (European Food Safety Authority) are between 3.28-41.78%, depending on age group and sex.
Topics: Fluorides; Humans; Carbonated Beverages; Dietary Exposure; Fruit and Vegetable Juices; Female
PubMed: 37922070
DOI: 10.1007/s12011-023-03937-0 -
ACS Sensors Jul 2023Potentiometric ion-selective electrodes (ISEs) have broad applications in personalized healthcare, smart agriculture, oil/gas exploration, and environmental monitoring....
Potentiometric ion-selective electrodes (ISEs) have broad applications in personalized healthcare, smart agriculture, oil/gas exploration, and environmental monitoring. However, high-precision potentiometric sensing is difficult with field-deployed sensors due to time-dependent voltage drift and the need for frequent calibration. In the laboratory setting, these issues are resolved by repeated calibration by measuring the voltage response at multiple standard solutions at a constant temperature. For field-deployed sensors, it is difficult to frequently interrupt operation and recalibrate with standard solutions. Moreover, the constant surrounding temperature constraint imposed by the traditional calibration process makes it unsuitable for temperature-varying field use. To address the challenges of traditional calibration for field-deployed sensors, in this study, we propose a novel in situ calibration approach in which we use natural/external temperature variation in the field to obtain the time-varying calibration parameters, without having to relocate the sensors or use any complex system. We also develop a temperature-supervised monitoring method to detect the drift of the sensor during operation. Collectively, the temperature-based drift monitoring and in situ calibration methods allow us to monitor the drift of sensors and correct them periodically to achieve high-precision sensing. We demonstrate our approach in three testbeds: (1) under controlled temperature variation in the lab, (2) under natural temperature variation in a greenhouse, and (3) in the field to monitor nitrate activity of an agricultural site. In the laboratory study, we validate that the calibration parameters of printed nitrate ISEs can be reproduced by our proposed calibration process; therefore, it can serve as an alternative to traditional calibration processes. In the greenhouse, we show the use of natural temperature variation to calibrate the sensors and detect the drift in a fixed concentration nitrate solution. Finally, we demonstrate the use of the method to monitor the nitrate activity of an agricultural field within 10% of laboratory-based measurements (i.e., a sensitivity of 0.03 mM) for a period of 22 days. The findings highlight the prospect of temperature-based calibration and drift monitoring for high-precision sensing with field-deployed ISEs.
Topics: Nitrates; Calibration; Temperature; Ion-Selective Electrodes; Potentiometry
PubMed: 37350462
DOI: 10.1021/acssensors.3c00735 -
Journal of Inorganic Biochemistry Dec 2023Mixed-ligand complexes of cobalt(II) with two bioligands, viz. 2-picolinehydroxamic acid and the reduced Schiff base N-(2-hydroxybenzyl)phenylalanine, were studied in...
Equilibria in the aqueous system of cobalt(II) based on 2-picolinehydroxamic acid and N-(2-hydroxybenzyl)phenylalanine and its ability to inhibit the propagation of cancer cells.
Mixed-ligand complexes of cobalt(II) with two bioligands, viz. 2-picolinehydroxamic acid and the reduced Schiff base N-(2-hydroxybenzyl)phenylalanine, were studied in aqueous solution by potentiometry and UV-Vis spectroscopic analysis. The coordination mode of the complexes and their stability were determined and compared to their parent species. Stacking interactions between the rings present in the ligands influence the stability of the complexes. Also, UV-Vis spectroscopy revealed that the stacking interactions affected the intercalation of DNA and mixed-ligand complexes. The in vitro anticancer activity of the free ligand 2-picolinehydroxamic acid and the complexes was tested against cervical and gastric human adenocarcinoma epithelial cell lines. At concentrations of 0.06 and 0.11 mM, the mixed-ligand structures showed the ability to reduce gastric cancer cells with no inhibitory effect on mouse fibroblasts. The cytotoxic effect was accompanied by damage to the cell nuclei, which may confirm that the complexes demonstrate effective binding to DNA. No determination of minimal inhibitory and bactericidal/fungicidal concentrations against the test organisms was possible at higher complex concentrations due to precipitation.
Topics: Animals; Mice; Humans; Cobalt; Coordination Complexes; Ligands; Phenylalanine; DNA; Schiff Bases; Copper; Neoplasms
PubMed: 37806005
DOI: 10.1016/j.jinorgbio.2023.112389 -
Scientific Reports Nov 2023Multiple electrolyte disorders, including sodium, potassium and calcium disorders, have been associated with hypertension in pregnancy. Most of these studies failed to...
Multiple electrolyte disorders, including sodium, potassium and calcium disorders, have been associated with hypertension in pregnancy. Most of these studies failed to evaluate the combined effect of low and high sodium, potassium, calcium and chloride ion concentrations on hypertension in pregnancy. This study evaluates the combined effect of these ion categories (low, normal, high) on hypertension in pregnancy. Biochemical ion assays and blood pressure measurements were carried out on 1074 apparently healthy pregnant women in late third trimester. Serum potassium, sodium, chloride, and ionised calcium were measured by ion-selective electrode potentiometry, while total plasma calcium was measured by absorption spectrophotometry. Hypertension in pregnancy was defined as systolic blood pressure ≥ 140 mmHg and/or diastolic blood pressure ≥ 90 mmHg. The prevalence of hyponatraemia, hypokalaemia, hypochloraemia, ionised hypocalcaemia and total hypocalcaemia in late pregnancy was 1.30 [0.78-2.18]%, 3.55 [2.60-4.84]%, 1.96 [1.28-2.97]%, 1.49 [0.92-2.21]% and 43.58 [40.64-46.56]%, respectively. Hypernatraemia, hyperkalaemia, hyperchloraemia, ionised hypercalcaemia and total hypercalcaemia were found in 1.49 [0.92-2.41]%, 2.34 [1.59-3.43]%, 4.38 [3.31-5.77]%, 39.94 [37.06-42.90]%, 2.79 [1.96-3.96]% of the participants, respectively. The prevalence of hypertension in pregnancy was 7.17 [5.77-8.87]%. When ion categories were considered in multiple logistic regression, only ionised and total calcium had significant associations with hypertension in pregnancy. Women with ionised hypercalcaemia had lower odds of hypertension in pregnancy (AOR = 0.50 [0.29-0.87], p-value = 0.015), and women with total hypocalcaemia had higher odds of hypertension in pregnancy (AOR = 1.99 [1.21-3.29], p-value = 0.007), compared to women with ionised and total normocalcaemia, respectively. Increasing kalaemia was associated significantly with higher odds of hypertension in pregnancy; however, kalaemia below and above the normal concentrations had no significant association with hypertension. Nonetheless, participants with kalaemia ≤ 3.98 mmol/L, had lower odds of hypertension in pregnancy compared with those with higher kalaemia (OR = 0.40 [0.24-0.66], p-value = 0.0003). Calcium disorders remain the most frequent electrolyte disorders in pregnancy. When normal cut-offs are considered for calcium and other ions, only ionised and total calcium influence the occurrence of hypertension in pregnancy. Kalaemia seems to affect hypertension in pregnancy but primarily within its normal concentrations. Serum electrolyte follow-up is indispensable for a proper pregnancy follow-up.
Topics: Humans; Female; Pregnancy; Calcium; Hypercalcemia; Hypocalcemia; Cameroon; Chlorides; Electrolytes; Hypertension; Sodium; Potassium; Calcium, Dietary
PubMed: 38017060
DOI: 10.1038/s41598-023-47623-6 -
Heliyon Dec 2023In the present paper, three electrodes were prepared with the aim of detecting chromium (III) in pharmaceutical tablets and comparing their capabilities and efficiency....
In the present paper, three electrodes were prepared with the aim of detecting chromium (III) in pharmaceutical tablets and comparing their capabilities and efficiency. At first, N-(pyridine-2-ylcarbamothioyl) benzamide (NP2YCTB) was synthesized and characterized by H NMR, FTIR, and C NMR spectroscopy methods. Then, it is used as a sensing material to prepare three types of chromium potentiometry sensors including solid-state electrodes (SSE), coated wire electrodes (CWE) as asymmetric electrodes, and liquid membrane electrodes (LME) as symmetric electrodes. The responses of all electrodes were Nernstian. Field-emission scanning electron microscopy was utilized to investigate the liquid membrane morphology. The presence of chromium (III) in the membrane was proved using Energy-dispersive X-ray spectroscopy and the coordination of NP2YCTB heteroatoms with chromium (III) was confirmed by Fourier transform infrared spectroscopy. The limit of detection for SSE (3 × 10 mol/L) was enhanced compared with LME (7 × 10 mol/L) and CWE (3 × 10 mol/L). The response time of electrodes was very short so it was about 5-6 s for LME and CWE and 5-8 s for SSE. The sensors were used for the potentiometric determination of chromium (III) in pharmaceutical tablets and in the potentiometric titration of it with EDTA.
PubMed: 38125423
DOI: 10.1016/j.heliyon.2023.e22842 -
Journal of the American Chemical Society Jun 2024Arsenic is highly toxic and a significant threat to human health, but certain bacteria have developed defense mechanisms initiated by As binding to As-sensing proteins...
Arsenic is highly toxic and a significant threat to human health, but certain bacteria have developed defense mechanisms initiated by As binding to As-sensing proteins of the ArsR family. The transcriptional regulator AfArsR responds to As and Sb by coordinating the metalloids with three cysteines, located in a short sequence of the same monomer chain. Here, we characterize the binding of As and Hg to a model peptide encompassing this fragment of the protein via solution equilibrium and spectroscopic/spectrometric techniques (pH potentiometry, UV, CD, NMR, PAC, EXAFS, and ESI-MS) combined with DFT calculations and MD simulations. Coordination of As changes the peptide structure from a random-coil to a well-defined structure of the complex. A trigonal pyramidal AsS binding site is formed with almost exactly the same structure as observed in the crystal structure of the native protein, implying that the peptide possesses all of the features required to mimic the As recognition and response selectivity of AfArsR. Contrary to this, binding of Hg to the peptide does not lead to a well-defined structure of the peptide, and the atoms near the metal binding site are displaced and reoriented in the Hg model. Our model study suggests that structural organization of the metal site by the inducer ion is a key element in the mechanism of the metalloid-selective recognition of this protein.
Topics: Arsenic; Binding Sites; Bacterial Proteins; Metalloids; Density Functional Theory; Molecular Dynamics Simulation; Protein Binding
PubMed: 38820242
DOI: 10.1021/jacs.3c11665 -
ACS Sensors Jul 2023Hydrocarbon (HC) monitoring is necessary for safe and effective operations in industries such as petroleum and gas. In this study, total hydrocarbons can be detected by...
Hydrocarbon (HC) monitoring is necessary for safe and effective operations in industries such as petroleum and gas. In this study, total hydrocarbons can be detected by using yttria-stabilized zirconia (YSZ)-based potentiometric-type gas sensor using MgFeO sensing electrode (SE). The sensor was found to generate a similar response magnitude to those of hydrocarbons that have the same carbon number, irrespective of the type of carbon bond (total hydrocarbon detection). Aside from being capable of detecting total hydrocarbons sensitively and selectively with rapid response time, the sensor using MgFeO-SE also exhibited a linear relationship between sensor responses and carbon number. In addition to that, the developed sensor showed a logarithmically linear relationship between sensor responses and HC concentration in the range 20-700 ppm. These sensing characteristics were confirmed to be reproducible, and sensor responses toward HC were found to be repeatable and gradually decreased with increasing in O concentration in the range of 3-21 vol %.
Topics: Carbon; Electrodes; Hydrocarbons; Potentiometry
PubMed: 37433097
DOI: 10.1021/acssensors.3c00719 -
Molecules (Basel, Switzerland) Nov 2023Gemcitabine is a chemotherapeutic agent used to treat various malignancies, including breast and bladder cancer. In the current study, three innovative selective...
Gemcitabine is a chemotherapeutic agent used to treat various malignancies, including breast and bladder cancer. In the current study, three innovative selective gemcitabine hydrochloride sensors are developed using 4-tert-butylcalix-[8]-arene (sensor 1), β-cyclodextrin (sensor 2), and γ-cyclodextrin (sensor 3) as ionophores. The three sensors were prepared by incorporating the ionophores with -nitrophenyl octyl ether as plasticizer and potassium tetrakis(4-chlorophenyl) borate as ionic additive into a polyvinyl chloride polymer matrix. These sensors are considered environmentally friendly systems in the analytical research. The linear responses of gemcitabine hydrochloride were in the concentration range of 6.0 × 10 to 1.0 × 10 mol L and 9.0 × 10 to 1.0 × 10 mol L and 8.0 × 10 to 1.0 × 10 mol L for sensors 1, 2, and 3, respectively. Over the pH range of 6-9, fast-Nernst slopes of 52 ± 0.6, 56 ± 0.3, and 55 ± 0.8 mV/decade were found in the same order with correlation regressions of 0.998, 0.999, and 0.998, respectively. The lower limits of detection for the prepared sensors were 2.5 × 10, 2.2 × 10, and 2.7 × 10 mol L. The sensors showed high selectivity and sensitivity for gemcitabine. Validation of the sensors was carried out in accordance with the requirements established by the IUPAC, while being inexpensive and easy to use in drug formulation. A statistical analysis of the methods in comparison with the official method showed that there was no significant difference in accuracy or precision between them. It was shown that the new sensors could selectively and accurately find gemcitabine hydrochloride in bulk powder, pharmaceutical formulations, and quality control tests. The ionophore-based sensor shows several advantages over conventional PVC membrane sensor sensors regrading the lower limit of detection, and higher selectivity towards the target ion.
Topics: Drug Compounding; Gemcitabine; Ionophores; Antineoplastic Agents; Polymers; Potentiometry; Polyvinyl Chloride
PubMed: 38005274
DOI: 10.3390/molecules28227552