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1.
Molecules ; 29(15)2024 Aug 04.
Article in English | MEDLINE | ID: mdl-39125099

ABSTRACT

A binary system of uridine-5'-diphosphoglucuronic acid with copper (II) ions was studied. Potentiometric studies in aqueous solutions using computer data analysis were carried out. The pH of dominance, the overall stability constants (logß), and the equilibrium constants of the formation reaction (logKe) were determined for each complex compound formed in the studied system. Spectroscopic studies were carried out to determine the mode of coordination in the compounds studied. Cytotoxicity and metabolic activity tests of the compounds obtained showed an increase in the biological activity of the complexes tested against the free ligand. The current research may contribute to the knowledge of complex compounds of biomolecules found in the human body and may also contribute to the characterization of a group of complex compounds with potential anticancer properties.


Subject(s)
Coordination Complexes , Copper , Thermodynamics , Copper/chemistry , Humans , Coordination Complexes/chemistry , Hydrogen-Ion Concentration , Potentiometry , Antineoplastic Agents/chemistry , Antineoplastic Agents/pharmacology , Cell Line, Tumor
2.
ACS Sens ; 9(8): 3870-3876, 2024 Aug 23.
Article in English | MEDLINE | ID: mdl-39115965

ABSTRACT

Ion-selective electrodes (ISEs) have widespread use in the fields of clinical and environmental analyses. Tetrahydrofuran (THF) is the most used solvent for the preparation of modern ISEs, equipped with ion-selective membranes (ISMs). Until now, the influence of impurities in THF toward potentiometric instability of ion-selective membrane based ISEs was probably associated with the presence of either residual water or peroxide. To address this issue, most literature recommends redistilling THF prior to use in the preparation of the potentiometric membranes. Current study reveals that the actual THF impurity that is responsible for potential instability in the ISM includes products from the oxidation of THF, which contains the hydroxyl group and possibly carbonyl group with a boiling point of above 200 °C. The density functional theory calculation supported pathway of the chemical reaction of THF oxidation, hence, the chemical structure of the uncertain impurities was predicted. The underlying reason for the deteriorating potential stability of the ISEs is proposed as the significant hydrophilicity of these impurities that affect the partitioning of the ion sensing components in the membrane, thus enhancing the leaching of the membrane components from the membrane phase. This finding explains why redistillation of aged THF is advised.


Subject(s)
Furans , Furans/chemistry , Ion-Selective Electrodes , Oxidation-Reduction , Membranes, Artificial , Potentiometry , Density Functional Theory
3.
Anal Biochem ; 695: 115657, 2024 Dec.
Article in English | MEDLINE | ID: mdl-39216634

ABSTRACT

In this study, a new potentiometric sensor was developed for the determination of the local anesthetic drug procaine in pharmaceutical samples. Procaine (Pr)-Tetraphenlyborate (TPB) ion-pair was synthesized and used as a sensor material. Potentiometric sensors using the synthesized ion pair (Pr-TPB), poly(vinyl chloride) (PVC) and o-nitrophenyloctyl ether (o-NPOE) in different proportions were prepared and their performance properties were tested. Among the prepared sensors, the best potentiometric response characteristics were obtained with the sensor composition Pr-TPB:PVC:o-NPOE in the ratio of 6.0:32.0:62.0 (w/w %). The new procaine sensor developed in the present study had a near-Nernstian behavior of 54.1 ± 3.3 mV/per decade and a low detection limit of 3.18 × 10-5 mol L-1 in the concentration range of 1.0 × 10-1-1.0 × 10-4 mol L-1. Additionally, the sensor had a response time of less than 10 s and could work in a wide pH range for two different concentration values without being affected by pH changes. Finally, the new procaine potentiometric sensor was used to detect procaine in injection samples and successfully determined procaine concentrations with high recoveries.


Subject(s)
Anesthetics, Local , Polyvinyl Chloride , Potentiometry , Procaine , Procaine/analysis , Potentiometry/methods , Anesthetics, Local/analysis , Polyvinyl Chloride/chemistry , Tetraphenylborate/chemistry , Hydrogen-Ion Concentration , Limit of Detection , Ethers
4.
Lab Chip ; 24(17): 4096-4104, 2024 08 20.
Article in English | MEDLINE | ID: mdl-39086302

ABSTRACT

Electrochemical sensors provide an affordable and reliable approach towards the detection and monitoring of important biological species ranging from simple ions to complex biomolecules. The ability to miniaturize electrochemical sensors, coupled with their affordability and simple equipment requirements for signal readout, permits the use of these sensors at the point-of-care where analysis using non-invasively obtainable biofluids is receiving growing interest by the research community. This paper describes the design, fabrication, and integration of a 3D printed Mg2+ potentiometric sensor into a 3D printed microfluidic device for the quantification of Mg2+ in low-sample volume biological fluids. The sensor employs a functionalized 3D printable photocurable methacrylate-based ion-selective membrane affixed to a carbon-mesh/epoxy solid-contact transducer for the selective determination of Mg2+ in sweat, saliva and urine. The 3D printed Mg2+ ion-selective electrode (3Dp-Mg2+-ISE) provided a Nernstian response of 27.5 mV per decade with a linear range of 10 mM to 39 µM, covering the normal physiological and clinically relevant levels of Mg2+ in biofluids. 3Dp-Mg2+-ISEs selectively measure Mg2+ over other biologically present cations - sodium, potassium, calcium, ammonium - as well as provide high stability in the analytical signal with a drift of just 13 µV h-1 over 10 hours. Comparison with poly(vinylchloride)-based Mg2+-ISEs showed distinct advantages to the use of 3Dp-Mg2+-ISEs, with respect to stability, resilience towards biofouling and importantly providing a streamlined and rapid approach towards mass production of selective and reliable sensors. The miniaturization capabilities of 3D printing coupled with the benefits of microfluidic analysis (i.e., low sample volumes, minimal reagent consumption, automation of multiple assays, etc.), provides exciting opportunities for the realization of the next-generation of point-of-care diagnostic devices.


Subject(s)
Lab-On-A-Chip Devices , Magnesium , Printing, Three-Dimensional , Magnesium/chemistry , Humans , Potentiometry/instrumentation , Equipment Design , Microfluidic Analytical Techniques/instrumentation , Ion-Selective Electrodes , Saliva/chemistry
5.
Food Chem ; 456: 139971, 2024 Oct 30.
Article in English | MEDLINE | ID: mdl-38876060

ABSTRACT

A novel approach for simultaneous detection of iron and potassium via a smartphone-based potentiometric method is proposed in this study. The screen printed electrodes were modified with carbon black nanomaterial and ion selective membrane including zinc (II) phtalocyanine as the ionophore. The developed Fe3+-selective electrode and K+-selective electrode exhibited detection limits of 1.0 × 10-6 M and 1.0 × 10-5 M for Fe3+ and K+ ions, respectively. The electrodes were used to simultaneously detect Fe3+ and K+ ions in apple juice, skim milk, soybean and coconut water samples with recovery values between 90%-100.5%, and validated against inductively coupled plasma-optical emission spectrometry. Due to the advantageous characteristics of the sensors and the portability of Near Field Communication potentiometer supported with a smartphone application, the proposed method offers sensitive and selective detection of iron and potassium ions in food and beverage samples at the point of need.


Subject(s)
Beverages , Iron , Potassium , Smartphone , Potassium/analysis , Beverages/analysis , Iron/analysis , Potentiometry/instrumentation , Potentiometry/methods , Milk/chemistry , Animals , Limit of Detection , Food Analysis/instrumentation , Food Analysis/methods , Fruit and Vegetable Juices/analysis
6.
Sci Rep ; 14(1): 11526, 2024 05 21.
Article in English | MEDLINE | ID: mdl-38773136

ABSTRACT

This paper reports on the development of a flexible-wearable potentiometric sensor for real-time monitoring of sodium ion (Na+), potassium ion (K+), and pH in human sweat. Na0.44MnO2, polyaniline, and K2Co[Fe(CN)6] were used as sensing materials for Na+, H+ and K+ monitoring, respectively. The simultaneous potentiometric Na+, K+, and pH sensing were carried out by the developed sensor, which enables signal collection and transmission in real-time to the smartphone via a Wi-Fi access point. Then, the potentiometric responses were evaluated by a designed android application. Na+, K+, and pH sensors illustrated high sensitivity (59.7 ± 0.8 mV/decade for Na+, 57.8 ± 0.9 mV/decade for K+, and 54.7 ± 0.6 mV/pH for pH), excellent stability, and good batch-to-batch reproducibility. The results of on-body experiments demonstrated that the proposed platform is capable of real-time monitoring of the investigated ions.


Subject(s)
Potassium , Potentiometry , Sodium , Sweat , Wearable Electronic Devices , Humans , Hydrogen-Ion Concentration , Potentiometry/methods , Potentiometry/instrumentation , Sodium/analysis , Sweat/chemistry , Potassium/analysis , Biosensing Techniques/instrumentation , Biosensing Techniques/methods , Wireless Technology/instrumentation , Smartphone , Reproducibility of Results
7.
Molecules ; 29(10)2024 May 08.
Article in English | MEDLINE | ID: mdl-38792059

ABSTRACT

Bicyclic peptides have attracted the interest of pharmaceutical companies because of their remarkable properties, putting them on a new path in medicine. Their conformational rigidity improves proteolytic stability and leads to rapid penetration into tissues via any possible route of administration. Moreover, elimination of renal metabolism is of great importance, for example, for people with a history of liver diseases. In addition, each ring can function independently, making bicyclic peptides extremely versatile molecules for further optimization. In this paper, we compared the potentiometric and spectroscopic properties studied by UV-vis, MCD, and EPR of four synthetic analogues of the bi-cyclic peptide c(PKKHP-c(CFWKTC)-PKKH) (BCL). In particular, we correlated the structural and spectral properties of complexes with coordinating abilities toward Cu(II) ions of MCL1 (Ac-PKKHPc(CFWKTC)PKKH-NH2) that contains the unbinding cycle and N- and C-terminal linear parts with two histidine residues, one per part; two monocyclic ligands containing one histidine residue, both in the N-terminal position, i.e., MCL2 (Ac-PKKHPc(CFWKTC)PKKS-NH2) and in the C-terminal position, i.e., MCL3 (Ac-PKKSPc(CFWKTC)PKKH-NH2), respectively; and the linear structure LNL (Ac-PKKHPSFWKTSPKKH-NH2). Potentiometric results have shown that the bicyclic structure promotes the involvement of the side chain imidazole donors in Cu(II) binding. On the other hand, the results obtained for the mono-cyclic analogues lead to the conclusion that the coordination of the histidine moiety as an anchoring group is promoted by its location in the peptide sequence further from the nonbinding cycle, strongly influencing the involvement of the amide donors in Cu(II) coordination.


Subject(s)
Copper , Peptides, Cyclic , Copper/chemistry , Peptides, Cyclic/chemistry , Coordination Complexes/chemistry , Ligands , Ions/chemistry , Potentiometry
8.
Analyst ; 149(11): 3085-3096, 2024 May 28.
Article in English | MEDLINE | ID: mdl-38712737

ABSTRACT

In the orthopaedic surgery field, the use of medical implants to treat a patient's bone fracture is nowadays a common practice, nevertheless, it is associated with possible cases of infection. The consequent hardware infection can lead to implant failure and systemic infections, with prolonged hospitalization, time-consuming rehabilitation treatments, and extended antibiotic therapy. Hardware infections are strictly related to bacterial adhesion to the implant, leading to infection occurrence and consequent pH decreasing from physiological level to acid pH. Here, we demonstrate the new strategy to use an orthopaedic implant functionalized with iridium oxide film as the working electrode for the potentiometric monitoring of pH in hardware infection diagnosis. A functional investigation was focused on selecting the implant material, namely titanium, titanium alloy, and stainless steel, and the component, namely screws and implants. After selecting the titanium-based implant as the working electrode and a silver wire as the reference electrode in the final configuration of the smart sensing orthopaedic implant, a calibration curve was performed in standard solutions. An equation equal to y = (0.76 ± 0.02) - (0.068 ± 0.002) x, R2 = 0.996, was obtained in the pH range of 4-8. Subsequently, hysteresis, interference, matrix effect, recovery study, and storage stability were investigated to test the overall performance of the sensing device, demonstrating the tremendous potential of electrochemical sensors to deliver the next generation of smart orthopaedic implants.


Subject(s)
Prostheses and Implants , Hydrogen-Ion Concentration , Humans , Iridium/chemistry , Electrodes , Electrochemical Techniques/methods , Electrochemical Techniques/instrumentation , Titanium/chemistry , Prosthesis-Related Infections/diagnosis , Potentiometry/instrumentation , Potentiometry/methods
9.
Anal Methods ; 16(20): 3240-3248, 2024 May 23.
Article in English | MEDLINE | ID: mdl-38726550

ABSTRACT

Currently, Nernstian-response-based polymeric membrane potentiometric sensors using molecularly imprinted polymers (MIPs) as receptors have been successfully developed for determination of organic ionic species. However, the preparation of these MIP receptors usually involves tedious and time-consuming template-removal procedures. Herein, a template-removal-free MIP is proposed and used as a receptor for fabrication of a potentiometric sensor. The proposed methodology not only significantly shortens the preparation time of MIP-based potentiometric sensors but also improves the batch-to-batch reproducibility of these sensors. By using antibiotic vancomycin as a model, the new concept offers a linear concentration range of 1.0 × 10-7 to 1.0 × 10-4 mol L-1 with a detection limit of 2.51 × 10-8 mol L-1. It can be expected that the template-removal-free MIP-based sensing strategy could lay the foundation for simple fabrication of electrochemical sensors without the need for template removal such as potentiometric and capacitive sensors and ion-sensitive field-effect transistors.


Subject(s)
Anti-Bacterial Agents , Molecularly Imprinted Polymers , Potentiometry , Vancomycin , Potentiometry/methods , Potentiometry/instrumentation , Anti-Bacterial Agents/analysis , Molecularly Imprinted Polymers/chemistry , Vancomycin/chemistry , Vancomycin/analysis , Membranes, Artificial , Molecular Imprinting/methods , Limit of Detection , Polymers/chemistry , Reproducibility of Results
10.
BMC Oral Health ; 24(1): 501, 2024 May 09.
Article in English | MEDLINE | ID: mdl-38725023

ABSTRACT

BACKGROUND: Releasing of metal ions might implicate in allergic reaction as a negative subsequent of the corrosion of Stainless Steel (SS304) orthodontic wires. The aim of this study was to evaluate the corrosion resistance of zinc-coated (Zn-coated) SS orthodontic wires. METHODS: Zinc coating was applied on SS wires by PVD method. Electrochemical impedance spectroscopy (EIS), Potentiodynamic polarization tests and Tafel analysis methods were used to predict the corrosion behavior of Zn-coated and uncoated SS wires in both neutral and acidic environments. RESULTS: The values of Ecorr ,icorr and Rct ,which were the electrochemical corrosion characteristics, reported better corrosion behavior of Zn-coated SS wires against uncoated ones in both artificial saliva and fluoride-containing environments. Experimental results of the Tafel plot analyses were consistent with that of electrochemical impedance spectroscopy analyses for both biological solutions. CONCLUSION: Applying Zn coating on bare SS orthodontic wire by PVD method might increase the corrosion resistance of the underlying stainless-steel substrate.


Subject(s)
Dielectric Spectroscopy , Materials Testing , Orthodontic Wires , Saliva, Artificial , Stainless Steel , Zinc , Corrosion , Stainless Steel/chemistry , Zinc/chemistry , Saliva, Artificial/chemistry , Dental Alloys/chemistry , Coated Materials, Biocompatible/chemistry , Fluorides/chemistry , Hydrogen-Ion Concentration , Humans , Surface Properties , Potentiometry
11.
Mikrochim Acta ; 191(6): 356, 2024 05 29.
Article in English | MEDLINE | ID: mdl-38811412

ABSTRACT

Charged antimicrobial peptides can be used for direct potentiometric biosensing, but have never been explored. We report here a galvanostatically-controlled potentiometric sensor for antimicrobial peptide-based biosensing. Solid-state pulsed galvanostatic sensors that showed excellent stability under continuous galvanostatic polarization were prepared by utilizing reduced graphene oxide/poly (3,4-ethylenedioxythiophene): poly (4-styrenesulfonate) (rGO/PEDOT: PSS) as a solid contact. More importantly, the chronopotentiometric sensor can be made sensitive to antimicrobial peptides with intrinsic charge on demand via a current pulse. In this study, a positively charged antimicrobial peptide that can bind to Staphylococcus aureus with high affinity and good selectivity was designed as a model. Two arginine residues with positive charges were linked to the C-terminal of the peptide sequence to increase its potentiometric responses on the electrode. The bacteria binding-induced charge or charge density change of the antimicrobial peptide enables the direct chronopotentiometric detection of the target. Under the optimized conditions, the concentration of Staphylococcus aureus can be determined in the linear range 10-1.0 × 105 CFU mL-1 with a detection limit of 10 CFU mL-1. It is anticipated that such a chronopotentiometric sensing platform is readily adaptable to detect other bacteria by choosing the peptides.


Subject(s)
Biosensing Techniques , Graphite , Potentiometry , Staphylococcus aureus , Biosensing Techniques/methods , Graphite/chemistry , Potentiometry/methods , Antimicrobial Peptides/chemistry , Antimicrobial Peptides/pharmacology , Limit of Detection , Polymers/chemistry , Bridged Bicyclo Compounds, Heterocyclic/chemistry , Bridged Bicyclo Compounds, Heterocyclic/pharmacology , Electrodes
12.
Anal Chim Acta ; 1306: 342615, 2024 Jun 01.
Article in English | MEDLINE | ID: mdl-38692795

ABSTRACT

The Caco-2 cells were used as intestinal epithelial cell model to illustrate the hyperuricemia (HUA) mechanism under the co-culture of the imbalanced intestinal microbiome in this work. The uric acid (UA) concentration in the HUA process was monitored, and could be up to 425 µmol/L at 8 h co-cultured with the imbalanced intestinal microbiome. Single-cell potentiometry based on ion-selective microelectrode was used to study extracellular calcium change, which is hypothesized to play an important role in the UA excretion. The potential signal of the calcium in the extremely limited microenvironment around single Caco-2 cell was recorded through the single-cell analysis platform. The potential signal of sharp decrease and slow increase followed within a few seconds indicates the sudden uptake and gradually excretion process of calcium through the cell membrane. Moreover, the value of the potential decrease increases with the increase of the time co-cultured with the imbalanced intestinal microbiome ranging from 0 to 8 h. The Ca2+ concentration around the cell membrane could decrease from 1.3 mM to 0.4 mM according to the potential decrease of 27.0 mV at the co-culture time of 8 h. The apoptosis ratio of the Caco-2 cells also exhibits time dependent with the co-culture of the imbalanced intestinal microbiome, and was 39.1 ± 3.6 % at the co-culture time of 8 h, which is much higher than the Caco-2 cells without any treatment (3.9 ± 2.9 %). These results firstly provide the links between the UA excretion with the apoptosis of the intestinal epithelial cell under the interaction of the imbalanced intestinal microbiome. Moreover, the apoptosis could be triggered by the calcium signaling.


Subject(s)
Gastrointestinal Microbiome , Single-Cell Analysis , Single-Cell Analysis/instrumentation , Single-Cell Analysis/methods , Caco-2 Cells , Humans , Microelectrodes , Coculture Techniques/instrumentation , Coculture Techniques/methods , Calcium/analysis , Carbon Fiber , Intestines/microbiology , Potentiometry/instrumentation , Adenosine/analysis , Apoptosis
13.
Int J Mol Sci ; 25(10)2024 May 14.
Article in English | MEDLINE | ID: mdl-38791410

ABSTRACT

Bacillus subtilis ferredoxin:NADP+ oxidoreductase (BsFNR) is a thioredoxin reductase-type FNR whose redox properties and reactivity with nonphysiological electron acceptors have been scarcely characterized. On the basis of redox reactions with 3-acetylpyridine adenine dinucleotide phosphate, the two-electron reduction midpoint potential of the flavin adenine dinucleotide (FAD) cofactor was estimated to be -0.240 V. Photoreduction using 5-deazaflavin mononucleotide (5-deazaFMN) as a photosensitizer revealed that the difference in the redox potentials between the first and second single-electron transfer steps was 0.024 V. We examined the mechanisms of the reduction of several different groups of non-physiological electron acceptors catalyzed by BsFNR. The reactivity of quinones and aromatic N-oxides toward BsFNR increased when increasing their single-electron reduction midpoint redox potentials. The reactivity of nitroaromatic compounds was lower due to their lower electron self-exchange rate, but it exhibited the same trend. A mixed single- and two-electron reduction reaction was characteristic of quinones, whereas reactions involving nitroaromatics proceeded exclusively via the one-electron reduction reaction. The oxidation of FADH• to FAD is the rate-limiting step during the oxidation of fully reduced FAD. The calculated electron transfer distances in the reaction with nitroaromatics were close to those of other FNRs including the plant-type enzymes, thus demonstrating their similar active site accessibility to low-molecular-weight oxidants despite the fundamental differences in their structures.


Subject(s)
Bacillus subtilis , Ferredoxin-NADP Reductase , Oxidation-Reduction , Ferredoxin-NADP Reductase/metabolism , Ferredoxin-NADP Reductase/chemistry , Bacillus subtilis/enzymology , Xenobiotics/metabolism , Xenobiotics/chemistry , Flavin-Adenine Dinucleotide/metabolism , Flavin-Adenine Dinucleotide/chemistry , Bacterial Proteins/metabolism , Bacterial Proteins/chemistry , Potentiometry , Oxidants/chemistry , Quinones/metabolism , Quinones/chemistry , Electron Transport
14.
Mikrochim Acta ; 191(6): 313, 2024 05 08.
Article in English | MEDLINE | ID: mdl-38717608

ABSTRACT

Copper levels in biological fluids are associated with Wilson's, Alzheimer's, Menke's, and Parkinson's diseases, making them good biochemical markers for these diseases. This study introduces a miniaturized screen-printed electrode (SPE) for the potentiometric determination of copper(II) in some biological fluids. Manganese(III) oxide nanoparticles (Mn2O3-NPs), dispersed in Nafion, are drop-casted onto a graphite/PET substrate, serving as the ion-to-electron transducer material. The solid-contact material is then covered by a selective polyvinyl chloride (PVC) membrane incorporated with 18-crown-6 as a neutral ion carrier for the selective determination of copper(II) ions. The proposed electrode exhibits a Nernstian response with a slope of 30.2 ± 0.3 mV/decade (R2 = 0.999) over the linear concentration range 5.2 × 10-9 - 6.2 × 10-3 mol/l and a detection limit of 1.1 × 10-9 mol/l (69.9 ng/l). Short-term potential stability is evaluated using constant current chronopotentiometry (CP) and electrochemical impedance spectroscopy (EIS). A significant improvement in the electrode capacitance (91.5 µF) is displayed due to the use of Mn2O3-NPs as a solid contact. The presence of Nafion, with its high hydrophobicity properties, eliminates the formation of the thin water layer, facilitating the ion-to-electron transduction between the sensing membrane and the conducting substrate. Additionally, it enhances the adhesion of the polymeric sensing membrane to the solid-contact material, preventing membrane delamination and increasing the electrode's lifespan. The high selectivity, sensitivity, and potential stability of the proposed miniaturized electrode suggests its use for the determination of copper(II) ions in human blood serum and milk samples. The results obtained agree fairly well with data obtained by flameless atomic absorption spectrometry.


Subject(s)
Copper , Crown Ethers , Electrodes , Fluorocarbon Polymers , Limit of Detection , Manganese Compounds , Oxides , Potentiometry , Copper/chemistry , Fluorocarbon Polymers/chemistry , Oxides/chemistry , Manganese Compounds/chemistry , Humans , Potentiometry/instrumentation , Potentiometry/methods , Crown Ethers/chemistry , Graphite/chemistry
15.
Int J Biol Macromol ; 268(Pt 1): 131598, 2024 May.
Article in English | MEDLINE | ID: mdl-38621570

ABSTRACT

The present work demonstrates the correlation between structure, properties, and self-sensing protocols of in situ prepared ferric oxide doped grafted copolymer composite, comprised of ferric oxide, chitosan, and polypyrrole (α-Fe2O3-en-CHIT-g-PPy) for residual ibuprofen present in natural and artificial samples. The chemical structure, morphology, functionality, and physio-mechanical properties of the composite were determined by Fourier transform infrared spectrometer (FT-IR), Raman spectra, X-ray diffraction (XRD), Scanning electron microscope (SEM), X-ray photoelectron spectroscopy (XPS), Two probe method, and standard ASTM techniques to explore sensing nature. The results confirm the evolution of axially aligned structure against 110 planes of α-Fe2O3 and chemically functionalized expanded polymer matrix during in-situ chemical polymerization of pyrrole, with better porosity, interactivity, and improved electrical conductivity i.e. 7.32 × 10-3 S cm-1. Further, a thin film of prepared composite coated on an ITO glass plate was explored for potentiometric sensing of ibuprofen (IBU) present in artificial and natural samples without the use of any additional energy sources. The observed sensing parameters are the sensing ranging 0.5 µM to 100.0 µM, sensitivity 2.5081 mV µM-1 cm-2, response time 50 s, recovery time 10 s, and stability for 60 days. The sensing mechanism of the IBU sensor and effective charge transfer in the electrode was also discussed based on changes in IR spectra of the electrode recorded before and after sensing due to surface oxidation of IBU due to the presence of iron and doping effect of iron oxide in the composite.


Subject(s)
Chitosan , Electrodes , Ferric Compounds , Ibuprofen , Polymers , Potentiometry , Pyrroles , Chitosan/chemistry , Pyrroles/chemistry , Ibuprofen/chemistry , Ibuprofen/analysis , Polymers/chemistry , Ferric Compounds/chemistry , Potentiometry/methods , Spectroscopy, Fourier Transform Infrared
16.
Int J Mol Sci ; 25(8)2024 Apr 17.
Article in English | MEDLINE | ID: mdl-38673999

ABSTRACT

E. coli nitroreductase A (NfsA) is a candidate for gene-directed prodrug cancer therapy using bioreductively activated nitroaromatic compounds (ArNO2). In this work, we determined the standard redox potential of FMN of NfsA to be -215 ± 5 mV at pH 7.0. FMN semiquinone was not formed during 5-deazaflavin-sensitized NfsA photoreduction. This determines the two-electron character of the reduction of ArNO2 and quinones (Q). In parallel, we characterized the oxidant specificity of NfsA with an emphasis on its structure. Except for negative outliers nitracrine and SN-36506, the reactivity of ArNO2 increases with their electron affinity (single-electron reduction potential, E17) and is unaffected by their lipophilicity and Van der Waals volume up to 386 Å. The reactivity of quinoidal oxidants is not clearly dependent on E17, but 2-hydroxy-1,4-naphthoquinones were identified as positive outliers and a number of compounds with diverse structures as negative outliers. 2-Hydroxy-1,4-naphthoquinones are characterized by the most positive reaction activation entropy and the negative outlier tetramethyl-1,4-benzoquinone by the most negative. Computer modelling data showed that the formation of H bonds with Arg15, Arg133, and Ser40, plays a major role in the binding of oxidants to reduced NfsA, while the role of the π-π interaction of their aromatic structures is less significant. Typically, the calculated hydride-transfer distances during ArNO2 reduction are smallwer than for Q. This explains the lower reactivity of quinones. Another factor that slows down the reduction is the presence of positively charged aliphatic substituents.


Subject(s)
Escherichia coli Proteins , Escherichia coli , Nitroreductases , Oxidation-Reduction , Prodrugs , Nitroreductases/metabolism , Nitroreductases/chemistry , Nitroreductases/genetics , Prodrugs/chemistry , Prodrugs/metabolism , Substrate Specificity , Escherichia coli/genetics , Escherichia coli Proteins/metabolism , Escherichia coli Proteins/chemistry , Escherichia coli Proteins/genetics , Potentiometry , Catalysis , Molecular Docking Simulation
17.
J Colloid Interface Sci ; 668: 223-231, 2024 Aug 15.
Article in English | MEDLINE | ID: mdl-38677211

ABSTRACT

The sandwich approach, whereby an antigen is captured by a primary antibody and detected by a secondary antibody, is commonly used to improve the selectivity and sensitivity of enzyme-linked immunosorbent assays (ELISA). This work details the experimental factors that impact the reliable translation of this sandwich approach to two commonly used electronic biosensors, namely potentiometric and impedimetric biosensors. Previous studies have demonstrated the Debye screening limitations associated with potentiometric biosensors. However, the correlation between the ionic strength of the measurement buffer and the impedimetric biosensing response has not been studied. Potentiometric biosensors were able to successfully detect the primary antibody and the target antigen by decreasing the ionic strength of the phosphate buffered saline (PBS) measurement buffer from 1x PBS to 0.01x PBS. However, the secondary antibody used for the selective signal amplification was not reliably detected. Therefore, the sandwich approach is not viable for potentiometric sensing at biologically relevant ionic strengths, due to the Debye screening effect. Alternatively, decreasing the ionic strength of the measurement buffer allowed for the successful translation of the sandwich approach to impedimetric biosensors. Impedimetric biosensing literature typically attributes a measured increase in the charge transfer resistance to an increase in the thickness of the immobilized biolayer. However, this work highlights the influence that both the charge and thickness of the biolayer have on the transport of the redox couple. Decreasing the ionic strength of the measurement buffer lowers the molecular charge screening effect. This permits the transport of a positively charged redox probe through a negatively charged immobilized biolayer via migration and diffusion. The results demonstrate that the use of a buffer at a lower, yet biologically relevant ionic strength allows for the successful translation of the sandwich approach to impedimetric biosensors.


Subject(s)
Biosensing Techniques , Enzyme-Linked Immunosorbent Assay , Biosensing Techniques/methods , Osmolar Concentration , Potentiometry/methods
18.
Anal Chem ; 96(23): 9370-9378, 2024 06 11.
Article in English | MEDLINE | ID: mdl-38683892

ABSTRACT

The development of sensors for detection of biomarkers exhibits an exciting potential in diagnosis of diseases. Herein, we propose a novel electrochemical sensing strategy for label-free dual-biomarker detection, which is based on the combination of stimulus-responsive molecularly imprinted polymer (MIP)-modified nanopores and a polymeric membrane chronopotentiometric sensor. The ion fluxes galvanostatically imposed on the sensing membrane surface can be blocked by the recognition reaction between the target biomarker in the sample solution and the stimulus-responsive MIP receptor in the nanopores, thus causing a potential change. By using two external stimuli (i.e., pH and temperature), the recognition abilities of the stimulus-responsive MIP receptor can be effectively modulated so that dual-biomarker label-free chronopotentiometric detection can be achieved. Using alpha fetoprotein (AFP) and prostate-specific antigen (PSA) as model biomarkers, the proposed sensor offers detection limits of 0.17 and 0.42 ng/mL for AFP and PSA, respectively.


Subject(s)
Biomarkers , Molecularly Imprinted Polymers , Nanopores , Prostate-Specific Antigen , alpha-Fetoproteins , Prostate-Specific Antigen/analysis , Molecularly Imprinted Polymers/chemistry , alpha-Fetoproteins/analysis , Humans , Biomarkers/analysis , Limit of Detection , Electrochemical Techniques/methods , Hydrogen-Ion Concentration , Biosensing Techniques/methods , Potentiometry/methods , Polymers/chemistry , Molecular Imprinting , Temperature
19.
Small ; 20(31): e2311745, 2024 Aug.
Article in English | MEDLINE | ID: mdl-38587168

ABSTRACT

Choline is an essential micronutrient for infants' brain development and health. To ensure that infants receive the needed daily dose of choline, the U.S. Food and Drug Administration (FDA) has set requirements for choline levels in commercialized infant formulas. Unfortunately, not all families can access well-regulated formulas, leading to potential inadequacies in choline intake. Economic constraints or difficulties in obtaining formulas, exacerbated by situations like COVID-19, prompt families to stretch formulas. Accurate measurement of choline in infant formulas becomes imperative to guarantee that infants receive the necessary nutritional support. Yet, accessible tools for this purpose are lacking. An innovative integrated sensor for the periodic observation of choline (SPOOC) designed for at-home quantification of choline in infants' formulas and milk powders is reported. This system is composed of a choline potentiometric sensor and ionic-liquid reference electrode developed on laser-induced graphene (LIG) and integrated into a spoon-like device. SPOOC includes a micro-potentiometer that conducts the measurements and transmits results wirelessly to parents' mobile devices. SPOOC demonstrated rapid and accurate assessment of choline levels directly in pre-consuming infant formulas without any sample treatment. This work empowers parents with a user-friendly tool for choline monitoring promoting informed nutritional decision-making in the care of infants.


Subject(s)
Choline , Infant Formula , Choline/analysis , Choline/chemistry , Infant Formula/chemistry , Humans , Infant , COVID-19 , Graphite/chemistry , Potentiometry/methods
20.
ACS Sens ; 9(5): 2447-2454, 2024 05 24.
Article in English | MEDLINE | ID: mdl-38659329

ABSTRACT

Selective and nondisruptive in vivo neurochemical monitoring within the central nervous system has long been a challenging endeavor. We introduce a new sensing approach that integrates neurocompatible galvanic redox potentiometry (GRP) with customizable phosphorothioate aptamers to specifically probe dopamine (DA) dynamics in live rat brains. The aptamer-functionalized GRP (aptGRP) sensor demonstrates nanomolar sensitivity and over a 10-fold selectivity for DA, even amidst physiological levels of major interfering species. Notably, conventional sensors without the aptamer modification exhibit negligible reactivity to DA concentrations exceeding 20 µM. Critically, the aptGRP sensor operates without altering neuronal activity, thereby permitting real-time, concurrent recordings of both DA flux and electrical signaling in vivo. This breakthrough establishes aptGRP as a viable and promising framework for the development of high-fidelity sensors, offering novel insights into neurotransmission dynamics in a live setting.


Subject(s)
Aptamers, Nucleotide , Brain , Dopamine , Potentiometry , Animals , Aptamers, Nucleotide/chemistry , Dopamine/analysis , Rats , Potentiometry/methods , Potentiometry/instrumentation , Brain/metabolism , Biosensing Techniques/methods , Rats, Sprague-Dawley , Male
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