Chronopotentiometric Nanopore Sensor Based on a Stimulus-Responsive Molecularly Imprinted Polymer for Label-Free Dual-Biomarker Detection.

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.

Functionalized orthopaedic implant as pH electrochemical sensing tool for smart diagnosis of hardware infection.

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.

Chronopotentiometric sensors for antimicrobial peptide-based biosensing of Staphylococcus aureus.

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.

A novel potentiometric screen-printed electrode based on crown ethers/nano manganese oxide/Nafion composite for trace level determination of copper ion in biological fluids.

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.

Stability Enhancement of Galvanic Redox Potentiometry by Optimizing the Redox Couple in Counterpart Poles.

Potentiometry based on the galvanic cell mechanism, i.e., galvanic redox potentiometry (GRP), has recently emerged as a new tool for in vivo neurochemical sensing with high neuronal compatibility and good sensing property. However, the stability of open circuit voltage (EOC) outputting remains to be further improved for in vivo sensing application. In this study, we find that the EOC stability could be enhanced by adjusting the sort and the concentration ratio of the redox couple in the counterpart pole (i.e., indicating electrode) of GRP. With dopamine (DA) as the sensing target, we construct a spontaneously powered single-electrode-based GRP sensor (GRP2.0) and investigate the correlation between the stability and the redox couple used in the counterpart pole. Theoretical consideration suggests that the EOC drift is minimum when the concentration ratio of the oxidized form (O1) to the reduced form (R1) of the redox species in the backfilled solution is 1:1. The experimental results demonstrate that, compared with other redox species (i.e., dissolved O2 at 3 M KCl, potassium ferricyanide (K3Fe(CN)6), and hexaammineruthenium(III) chloride (Ru(NH3)6Cl3)) used as the counterpart pole, potassium hexachloroiridate(IV) (K2IrCl6) exhibits better chemical stability and outputs more stable EOC. As a result, when IrCl62-/3- with the concentration ratio of 1:1 is used as the counterpart, GRP2.0 displays not only an excellent EOC stability (i.e., 3.8 mV drifting during 2200 s for in vivo recording) but also small electrode-to-electrode variation (i.e., the maximum EOC variation between four electrodes is 2.7 mV). Upon integration with the electrophysiology, GRP2.0 records a robust DA release, accompanied by a burst of neural firing, during the optical stimulation. This study paves a new avenue to stable neurochemical sensing in vivo.

Clofazimine pKa Determination by Potentiometry and Spectrophotometry: Reverse Cosolvent Dependence as an Indicator of the Presence of Dimers in Aqueous Solutions.

The weakly basic antibiotic and anti-inflammatory drug, clofazimine (CFZ), was first described in 1957. It has been used therapeutically, most notably in the treatment of leprosy. However, the compound is extremely insoluble in aqueous media, and, indeed, there is poor consensus about what its intrinsic solubility is since the reported values range from 0.04 to 11 ng/mL. To understand the speciation and solubilization of CFZ as a function of pH, it is of paramount importance to know the true aqueous pKa. However, there is also poor consensus about the value of the pKa (reported measured values range from 6.08 to 9.11). In the present study, we report the determination of the CFZ ionization constant using two independent techniques. A state-of-the-art potentiometric analysis was performed, drawing on titration data in methanol-water solutions (46-75 wt % MeOH) of CFZ, using the bias-reducing consensus of two different procedures of extrapolating the apparent psKa values to zero cosolvent to approximate the true aqueous pKa as 9.43 ± 0.12 (25 °C, I = 0.15 M reference ionic strength). In parallel, spectrophotometric UV/vis titration data were acquired (250-600 nm at different pH) in 10 mM HEPES buffer solutions containing up to 54 wt % MeOH. The alternating least squares (ALS) method was used in the analysis of the absorbance-pH spectra. Uncharacteristically, the cosolvent UV/vis data in our study showed reverse cosolvent dependence (apparent pKa values increased with increasing cosolvent) which could be explained by a dimerization of the free base. The analysis of UV/vis data obtained from 54 wt % MeOH-water solution containing 20 µM CFZ yielded the apparent pKa 9.51 ± 0.17 (I ≈ 0.005 M). To assess whether self-assembly of CFZ was energetically feasible, density functional theory (DFT) calculations were used to study the putative CFZ dimers in aqueous and methanol media. The DFT-optimized geometries and infrared spectra of CFZ dimers using water and methanol as solvents were calculated and analyzed. Based on the lack of negative frequencies in calculated infrared spectra, it was confirmed that optimized geometries correspond to the true energetic minima. Visual analysis of optimized structures indicates the presence of stacking interactions between two CFZ molecules. The protonation site (the imine nitrogen atom) was determined by 1H NMR spectroscopy.

Portable Device for Potentiometric Determination of Antioxidant Capacity.

For the first time, a prototype of a portable device for the potentiometric determination of antioxidant capacity based on a new measurement principle is proposed. A feature of the approach is the use of an electrochemical microcell with separated spaces and two identical electrodes with immobilized reagents. An antioxidant solution is introduced into one half-cell, and the antioxidants interact with the reagents. The other half-cell contains only reagents. The potential difference between the electrodes is due to the change in the ratio of the oxidized and reduced form of the reagents, which occurs as a result of the reaction with the antioxidants in one of the half-cells and is related to their concentration. The range of linearity of the microcell with immobilized reagents is 40-4000 µM-eq, and the limit of detection is 20 µM-eq. The device was successfully tested in the analysis of standard antioxidant solutions. The recoveries were (92-113)%, and the relative standard deviation did not exceed 15%. A good correlation was found between the data obtained by the approach and the potentiometric method in a macrocell for fruit juice analysis. Pearson's coefficient for the obtained experimental data was 0.9955. The proposed portable device is promising and can be used in field conditions.

Prospective of Agro-Waste Husks for Biogenic Synthesis of Polymeric-Based CeO2/NiO Nanocomposite Sensor for Determination of Mebeverine Hydrochloride.

BACKGROUND: The remarkable properties of nickel oxide (NiO) and cerium oxide (CeO2) nanostructures have attracted considerable interest in these nanocomposites as potential electroactive materials for sensor construction. METHODS: The mebeverine hydrochloride (MBHCl) content of commercial formulations was determined in this study using a unique factionalized CeO2/NiO-nanocomposite-coated membrane sensor. RESULTS: Mebeverine-phosphotungstate (MB-PT) was prepared by adding phosphotungstic acid to mebeverine hydrochloride and mixing with a polymeric matrix (polyvinyl chloride, PVC) and plasticizing agent o-nitrophenyl octyl ether. The new suggested sensor showed an excellent linear detection range of the selected analyte at 1.0 × 10-8-1.0 × 10-2 mol L-1 with regression equation EmV = (-29.429 ± 0.2) log [MB] + 347.86. However, the unfunctionalized sensor MB-PT displayed less linearity at 1.0 × 10-5-1.0 × 10-2 mol L-1 drug solution with regression equation EmV = (-26.603 ± 0.5) log [MB] + 256.81. By considering a number of factors, the applicability and validity of the suggested potentiometric system were improved following the rules of analytical methodological requirements. CONCLUSION: The created potentiometric technique worked well for determining MB in bulk substance and in medical commercial samples.

Ionophore-Based Polymeric Sensors for Potentiometric Assay of the Anticancer Drug Gemcitabine in Pharmaceutical Formulation: A Comparative Study.

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), ß-cyclodextrin (sensor 2), and γ-cyclodextrin (sensor 3) as ionophores. The three sensors were prepared by incorporating the ionophores with o-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 × 10-6 to 1.0 × 10-2 mol L-1 and 9.0 × 10-6 to 1.0 × 10-2 mol L-1 and 8.0 × 10-6 to 1.0 × 10-2 mol L-1 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 × 10-6, 2.2 × 10-6, and 2.7 × 10-6 mol L-1. 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.

An Analytical Protocol for the Differentiation and the Potentiometric Determination of Fluorine-Containing Fractions in Bovine Milk.

Free fluoride ions are effective in combating caries in children, and their supplementation in milk has been widely used worldwide for this purpose. Furthermore, it is known that ionic fluoride added to milk is distributed among its components, but little is known about their quantitative relationships. This is likely due to the absence of an analytical protocol aimed at differentiating and quantifying the most important forms of fluorine present in milk. For the first time, a comprehensive protocol made up of six potentiometric methods devoted to quantifying the most important fractions of fluorine in milk (i.e., the free inorganic fluoride, the inorganic bonded fluorine, the caseins-bonded fluorine, the whey-bonded fluorine, the lipid-bonded fluorine, and the total fluorine) has been developed and tested on real samples. Four of the six methods of the procedure are original, and all have been validated in terms of limit of detection and quantification, precision, and trueness. The data obtained show that 9% of all fluorine was in ionic form, while 66.3% of total fluorine was bound to proteins and lipids, therefore unavailable for human absorption. Beyond applications in dental research, this protocol could be extended also to other foods, or used in environmental monitoring.

Fabrication and Applications of Potentiometric Membrane Sensors Based on Specific Recognition Sites for the Measurement of the Quinolone Antibacterial Drug Gemifloxacin.

Supramolecular gemifloxacin (GF) sensors have been developed. Supramolecular chemistry is primarily concerned with noncovalent intermolecular and intramolecular interactions, which are far weaker than covalent connections, but they can be exploited to develop sensors with remarkable affinity for a target analyte. In order to determine the dose form of the quinolone antibacterial drug gemifloxacin, the current study's goal is to adapt three polyvinylchloride (PVC) membrane sensors into an electrochemical technique. Three new potentiometric membrane sensors with cylindric form and responsive to gemifloxacin (GF) were developed. The sensors' setup is based on the usage of o-nitrophenyl octyl ether (o-NPOE) as a plasticizer in a PVC matrix, ß-cyclodextrin (ß-CD) (sensor 1), γ-cyclodextrin (γ-CD) (sensor 2), and 4-tert-butylcalix[8]arene (calixarene) (sensor 3) as an ionophore, potassium tetrakis (4-chlorophenyl) borate (KTpClPB) as an ion additive for determination of GF. The developed method was verified according to IUPAC guidelines. The sensors under examination have good selectivity for GF, according to their selectivity coefficients. The constructed sensors demonstrated a significant response towards to GF over a concentration range of 2.4 × 10-6, 2.7 × 10-6, and 2.42 × 10-6 mol L-1 for sensors 1, 2, and 3, respectively. The sensors showed near-Nernstian cationic response for GF at 55 mV, 56 mV, and 60 mV per decade for sensors 1, 2, and 3, respectively. Good recovery and relative standard deviations during the day and between days are displayed by the sensors. They demonstrated good stability, quick response times, long lives, rapid recovery, and precision while also exhibiting good selectivity for GF in various matrices. To determine GF in bulk and dose form, the developed sensors have been successfully deployed. The sensors were also employed as end-point indicators for titrating GF with sodium tetraphenyl borate.

Diazotization titrations in pharmacopoeial quality control of medicines and proposals for their revision in the European Pharmacopoeia.

Based on the data in the Ph. Eur., some other newer pharmacopoeias and published experimental papers propose to revise the text of Ph. Eur. 2.5.8. First, it is necessary to specify which of the electrometric methods should be used to indicate the endpoint of diazotization titrations in Ph. Eur. (preferable potentiometry with a platinum indicating electrode). The amount of potassium bromide in the titration solution may be reduced to 1 g, the cooling of the solution before titration may be omitted from the framework procedure, and it may be specified in individual monographs if necessary to obtain accurate and correct results for some medicines. Diazotization titration can be performed in Ph. Eur. and can also be used to determine the content of some other medicines.

Galvanic Redox Potentiometry for Fouling-Free and Stable Serotonin Sensing in a Living Animal Brain.

Serotonin (5-HT) is a major neurotransmitter broadly involved in many aspects of feeling and behavior. Although its electro-activity makes it a promising candidate for electrochemical sensing, the persistent generation of fouling layers on the electrode by its oxidation products presents a hurdle for reliable sensing. Here, we present a fouling-free 5-HT sensor based on galvanic redox potentiometry. The sensor efficiently minimizes electrode fouling as revealed by in situ Raman spectroscopy, ensuring a less than 3 % signal change in a 2 hour continuous experiment, whereas amperometric sensors losing 90 % within 30 min. Most importantly, the sensor is highly amenable for in vivo studies, permitting real-time 5-HT monitoring, and supporting the mechanism associated with serotonin release in brain. Our system offers an effective way for sensing different neurochemicals having significant fouling issues, thus facilitating the molecular-level understanding of brain function.

Deep Learning-Enhanced Potentiometric Aptasensing with Magneto-Controlled Sensors.

Bioelectronic sensors that report charge changes of a biomolecule upon target binding enable direct and sensitive analyte detection but remain a major challenge for potentiometric measurement, mainly due to Debye Length limitations and the need for molecular-level platforms. Here, we report on a magneto-controlled potentiometric method to directly and sensitively measure the target-binding induced charge change of DNA aptamers assembled on magnetic beads using a polymeric membrane potentiometric ion sensor. The potentiometric responses of the negatively charged aptamer, serving as a receptor and reporter, were dynamically controlled and modulated by applying a magnetic field. Based on a potentiometric array, this non-equilibrium measurement technique combined with deep learning algorithms allows for rapidly and reliably classifying and quantifying diverse small molecules using antibiotics as models. This potentiometric strategy opens new modalities for sensing applications.

Unconditioned Symmetric Solid-Contact Electrodes for Potentiometric Sensing.

In potentiometric sensing, the preparation of the electrodes preceding a measurement is often the most time-consuming step. Eliminating the conditioning process can significantly speed up the preparation procedure, but it can also compromise the need for proper pre-equilibration of the membrane. We propose here a symmetric setup to address this challenge with an identical indicator and reference elements measured against each other, thereby compensating for potential drift. This strategy allows one to achieve potentiometric measurements using non-conditioned all-solid-state ion-selective electrodes for the detection of nitrate and potassium ions with Nernstian response slopes and detection ranges identical to those of conventional systems. To establish symmetry, a set of solid-contact ion-selective electrodes placed in a reference cell is measured against a set of identical electrodes in a sample cell. By subtracting the potentials between the two cells, potential instabilities not directly relevant to the measuring sample are eliminated, giving minimal potential drifts and stable 5-day potential responses. The E0 value of the nitrate-selective electrodes in the symmetric setup had a standard deviation of just 3 mV for the 5-day period in contrast to 19 mV in the asymmetric system, clearly demonstrating the influence of the conditioning step which is almost eliminated in the former system. During the 20 h potential monitoring experiments, the drift dropped to below 0.3 mV/min in less than 6 min, as opposed to an average time of 35 min for the asymmetric system. The applicability of the proposed setup was successfully demonstrated with the measurement of nitrate in a river water sample, where a potential drift lower than 0.1 mV/min was reached in less than 5 min of first contact with solution.

Highly Selective Potentiometric Sensing of Biologically Relevant Pyrophosphate and Lysophosphatidic Acid Using N-Alkyl/Aryl Ammonium Resorcinarenes/Extended-Resorcinarenes as Ionophores.

The ionophore properties of four kinds of N-alkyl/aryl ammonium resorcinarenes and extended-resorcinarenes were inspected for the first time to fabricate polymeric membrane electrodes for determination of biologically relevant pyrophosphate (PPi) and lysophosphatidic acid (LPA). The proposed ion selective electrodes (ISEs) showed significant preference for PPi and LPA with significant selectivity pattern differences from the Hofmeister series. To gain further insight into the performances of the developed ISEs, the binding constants of ionophore-anion complexes in the plasticized membrane phase were investigated, along with the optimized geometries and calculated electrostatic potential. Nernstian potential responses with good reversibility to target anions can be observed when shifting the optimized membranes in aqueous solutions in the concentration range from 10-6.5 to 10-2.3/10-2.2 M. Moreover, potentiometric sensings of PPi and LPA in mineral water and artificial serum were achieved in low µM concentration range, demonstrating their promising real-world applications. These results provide a promising avenue for the development of polymeric membrane electrodes for biological relevant anions and will broaden the scope of potentiometric sensing.

Multifunctional Molecularly Imprinted Receptor-Based Polymeric Membrane Potentiometric Sensor for Sensitive Detection of Bisphenol A.

Molecularly imprinted polymer (MIP)-based polymeric membrane potentiometric sensors have become an attractive tool for detection of organic species. However, the MIP receptors in potentiometric sensors developed so far are usually prepared by only using single functional monomers. This may lead to low affinities of the MIP receptors due to the lack of diversity of the functional groups, thus resulting in low detection sensitivity of the potentiometric sensors. Additionally, these classical MIP receptors are nonconductive polymers, which are undesirable for the fabrication of an electrochemical sensor. Herein, we describe a novel multifunctional MIP receptor-based potentiometric sensor. The multifunctional MIP receptor is prepared by using two functional monomers, methacrylic acid, and 3-vinylaniline with a dual functionality of both recognition and conduction properties. The poly(aniline) groups are introduced into the methacrylic acid-based MIP by postoxidation of the aniline monomer. Such poly(aniline) groups not only serve as the additional functional groups for selective recognition, but also work as a conducting polymer. The obtained multifunctional MIP receptor shows a high binding capacity and an excellent electron-transfer ability. By using bisphenol A as a model, the proposed multifunctional MIP sensor exhibits a largely improved sensitivity and low noise levels compared to the conventional MIP sensor. We believe that the proposed MIP-based sensing strategy provides a general and facile way to fabricate sensitive and selective MIP-based electrochemical sensors.

Sodium assessment in neonates, infants, and children: a systematic review.

Hyponatremia is a common disorder in childhood. The indirect and the direct potentiometry are currently the most popular techniques employed for sodium assessment, although discrepancies between the two techniques may be > 10 mmol/L. It is known that < 20% of the recently published articles report information about the technique used for sodium analysis, but no data are available on pediatric studies. This study aimed at investigating the laboratory technique employed for sodium measurement in studies conducted in childhood. A systematic literature search in PubMed, Embase, and Web of Science was undertaken to identify articles containing the word "hyponatremia" in the title between 2013 and 2020. Papers with < 10 subjects were excluded. A total of 565 articles were included. Information on the laboratory technique used for sodium analysis was more commonly (p = 0.035) reported in pediatric (n = 15, 28%) than in non-pediatric (n = 81, 16%) reports. The frequency of reports with and without information on the technique for sodium assessment was not different with respect to the study characteristics, the quartile of the journal where the paper was published, the country income setting, and the inclusion of neonates among the 54 pediatric studies.   Conclusion: Most pediatric papers do not report any information on the technique used for sodium analysis. Although international authorities have recommended the implementation of direct potentiometry, a low awareness on this issue is still widespread in pediatric research. What is Known: • Direct potentiometry and indirect potentiometry are currently employed for sodium analysis in blood. • Direct potentiometry is more accurate. What is New: • Less than 30% of pediatric articles provide information on the technique employed for sodium analysis in blood. • Indirect potentiometry is more frequently employed than direct potentiometry in pediatric studies.

The 1,3-Dioctadecyl-1H-imidazol-3-ium Based Potentiometric Surfactant Sensor for Detecting Cationic Surfactants in Commercial Products.

A low-cost and fast potentiometric surfactant sensor for cationic surfactants, based on the new ion-pair 1,3-dioctadecyl-1H-imidazol-3-ium-tetraphenylborate (DODI-TPB), is presented. The new cationic surfactant DODI-Br was synthesized and characterized by NMR, LC-MS, and elemental analysis, and was used for synthesis of the DODI-TPB ionophore. The DODI-TPB surfactant sensor was obtained by implementation of the ionophore in PVC. The sensor showed excellent response characteristics with near-Nernstian slopes to the cationic surfactants DMIC, CPC, CTAB, and Hyamine 1622. The highest voltage responses were obtained for DMIC and CPC (58.7 mV/decade of activity). DMIC had the lowest detection limit (0.9 × 10-6 M) and the broadest useful linear concentration range (1.8 × 10-6 to 1.0 × 10-4 M). An interference study showed remarkable stability. Potentiometric titration curves for the titration of cationic surfactants (DMIC, CPC, CTAB, and Hyamine 1622), with DDS and TPB used as titrants, showed sigmoidal curves with well-defined inflexion points and a broad signal change. The standard addition method was successfully applied with recovery rates from 98.9 to 101.2 at two concentrations. The amount of cationic surfactant found in disinfectants and antiseptics was in good agreement with the referent two-phase titration method and the surfactant sensor on the market. This new surfactant sensor represents a low-cost alternative to existing methods for cationic surfactant detection.

Facile imprinted polymer for label-free highly selective potentiometric sensing of proteins: case of recombinant human erythropoietin.

In the current study, a molecularly imprinted polymer (MIP)-based potentiometric sensor was fabricated for a label-free determination of recombinant human erythropoietin (rhEPO). The MIP sensor was operated under zero current conditions using tetra-butyl ammonium bromide as a marker ion. A highly ordered rhEPO surface imprinted layer was prepared using 3-aminopropyl triethoxysilane and tetraethoxysilane as a monomer and cross-linker, respectively, under mild reaction conditions. A two-fold increase in the signal output was obtained by polymeric surface minimization (0.5 mm) that allowed more pronounced molecular recognition (imprinting factor = 20.1). The proportion of cross-reactivity was examined using different interfering biomolecules. Results confirmed sensor specificity for both structurally related and unrelated proteins. An ~40% decrease in the response was obtained for rhEPO-ß compared to rhEPO-α. The imprinted polymeric surface was evaluated using scanning electron microscopy and Fourier transform infrared spectroscopy. Under the optimal measurement conditions, a linear range of 10.00-1000.00 ng mL-1 (10-10 - 10-8 M) was obtained. The sensor was employed for the determination of rhEPO in different biopharmaceutical formulations. Results were validated against standard immunoassay. Spiked human serum samples were analyzed and the assay was validated. The presence of non-specific proteins did not significantly affect (~8%) the results of our assay. A concentration-dependent linear response was produced in an identical range with detection limit as low as 6.50 ng mL-1 (2.14 × 10-10 M). The facile fabricated MIP sensor offers a cost-effective, portable, and easy to use alternative for biosimilarity assessment and clinical application.