Non-Enzymatic Phenylboronic Acid-Based Optode Membrane for Glucose Monitoring in Serums of Diabetic Patients and in the Culture Medium of Human Embryos.

Monitoring glucose levels is important not only for diabetics, but also for tracking embryonic development in human embryo culture media. In this study, an optochemical sensor (glucose-selective polymer membrane) was fabricated for the determination of glucose in serum from diabetic patients and the culture media of human embryos. The optode membranes were formulated using polyvinyl chloride (PVC) as the polymer matrix and 4',5'-dibromofluorescein octadecyl ester (ETH 7075) as the chromoionophore. The sensitivity of the optode membranes was optimized using two different plasticizers (tricresyl phosphate-TCP and nitrophenyloctyl ether-NOPE) and three ionophores (nitrophenylboronic acid-NPBA, trifluorophenyboronic acid-TFPBA, 4'-nitrobenzo-15-crown-5) and tested for glucose detection. The best optode membrane was formulated from 49.5% PVC, 49.5% TCP, 1% NPBA, and 1% ETH 7075. It showed a linear dynamic range of 10-3 M to 10-1 M, with a detection limit of 9 × 10-4 M and a response time of 2 min. The detection mechanism involves H-bonding between NPBA and glucose, which was confirmed by Fourier transform infrared (FTIR) and nuclear magnetic resonance (NMR). The reaction also involves the formation of boronate esters in basic media with deprotonation of the chromoionophore (ETH 7075), leading to a decrease in UV-Vis absorbance at λmax = 530 nm. The membrane optode was used for glucose determination in synthetic culture medium, commercial embryo culture medium (GLOBAL® TOTAL® W/HEPES), and serum from normal and diabetic patients, showing good accuracy and precision of the optode.

Ionophore-modified polyaniline-based optode for the determination of hydrogen sulfite levels in beverages, wastewater, and soil.

Sulfite is a very important species, affecting human health, plant and animal life, and environmental sustainability. In this study, for the first time, an ionophore-based ion-selective optode was constructed for hydrogen sulfite determination in beverages, such as Birell® and Sprite®, water, and soil samples; instead of normal pH-chromoionophores, polyaniline film was precipitated on a glass slide and used for the transduction of the sensation mechanism. The ionophore-modified polyaniline-based optode incorporated thiourea derivative as an ionophore and tridodecyl methyl ammonium chloride as an ion-exchanger. The optode film was prepared in situ with a modified chemical polymerization method, and it was characterized using atomic force microscopy (AFM), scanning electron microscopy (SEM), and X-ray diffraction (XRD); also, FTIR spectroscopy was performed for the film before and after interaction with hydrogen sulfite for mechanism elucidation. The optode was applied in the hydrogen sulfite concentration range of 10-1 to 10-5 M with a low detection limit of 8.0 × 10-6 M and minimum interference of other interfering species, such as salicylate, iodide, and sulphide. The response mechanism was due to the ion-exchange of hydrogen sulfite with the anion exchanger, followed by the molecular recognition between thiourea ionophore and hydrogen sulfite, with concomitant redox reaction via the protonation of the polyaniline that causes a decrease in absorbance at 685 nm. The optode was applied successfully for the determination of hydrogen sulfite in real beverages, Birell® and Sprite® without any pretreatment steps. Also, it was applied successfully for the environmental monitoring of hydrogen sulfite in real wastewater and soil samples.

Molecularly-imprinted polymer-base bulk optode for the determination of ivabradine hydrochloride in Procoralan®.

IVH may be administered orally twice per day for treating heart failure, sinus rhythm, heart-related chest pain and angina pectoris, and its overdose may cause problems such as blurred vision, uncontrolled blood pressure, prolonged bradycardia, and others. A molecularly imprinted polymer-based bulk optode, miptode, was constructed for the determination of ivabradine hydrochloride (IVH) in its pharmaceutical preparation Procoralan®. The molecularly-imprinted polymers (MIPs) were prepared in different ratios, and MIP3 had the highest imprinting factor (1.6) as an ionophore in the miptode preparation. The miptode was prepared using weight ratios of 30% PVC polymer, 62% nitrophenyl octyl ether (NPOE) plasticizer, 6% MIP3 ionophore, 1% tetraphenyl borate derivative (TPB) ion-exchanger, and 1% ETH7075 chromoionophore; this miptode exhibited an absorbance increase at 530 nm in the concentration range of 10-2-10-5 M with a detection limit of 3.1 µM using Tris-HCl buffer of pH 7.2. The miptode was imaged using AFM, and showed the dissolution of all components except MIP particles which exhibited restricted solubility. However, the incorporation of MIP3 as an ionophore improved the selectivity coefficient over the interfering species that may exist in the pharmaceutical formulation to an extent that was not reported before; e.g. coefficients of IVH over sodium, magnesium, and glucose were improved by 5, 4 and 2 orders, when compared to the previous sensor that operated with the molecular interaction mechanism. The selectivity improvement in miptode is due to the Key-Lock fitting (host-guest molecular recognition) between the MIP particles and the template IVH molecule which is transduced with the ion-exchange process of the chromoionophore. The miptode has a response time of 1-2 minutes, and a reliable lifetime of two months. The miptode was applied successfully for the determination of IVH in the pharmaceutical preparation Procoralan® with recovery values of 89-99.8% with low standard deviations of <1.2.

Molecularly Imprinted Electrochemical Sensor-Based Fe2O3@MWCNTs for Ivabradine Drug Determination in Pharmaceutical Formulation, Serum, and Urine Samples.

Ivabradine hydrochloride (IVR) is a medically important drug because of its ability to lower the heart rate. Techniques reported for IVR determination were expensive, laborious, besides being of poor selectivity. In this study, iron oxide @ carbon nanotube (Fe2O3@MWCNTs) nanocomposite and molecularly imprinted polymer (MIP) were synthesized and used in the fabrication of carbon paste electrodes (CPEs) for the potentiometric detection of IVR in biological and pharmaceutical samples. CPEs of the best sensor were formulated from graphite (41 wt%) as a carbon source, MIP (3 wt.%) as an ionophore, Fe2O3@MWCNTs (5 wt%) as a modifier, and nitrophenyl octyl ether (NPOE, 51 wt.%) as a conductive oil so-called plasticizer. The best sensor exhibits a Nernstian slope (response) of 56 mV decade-1 within the IVR concentration range from 1.0 × 10-3 M to 9.8 × 10-8 M with high selectivity against interfering species (ascorbic, maltose, glucose, lactose, dopamine, glycine) over those reported earlier. The use of Fe2O3@MWCNTs together with MIP in the electrode formulation was found to improve the limit of detection (LOD) from 630 to 98 nM along with high reversibility, a short response time of 30 s, and a good lifetime of more than 2 weeks. The sandwich membrane (SMM) method was used to quantify the H-bonding complexing strength of the MIP binding sites for IVR with Log ß ILn = 11.33. The constructed sensors were successfully applied for the IVR determination in blood serum, urine, and commercial formulations (Savapran®) with high sensitivity.

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®).

PVC membrane, coated-wire, and carbon-paste ion-selective electrodes for potentiometric determination of galantamine hydrobromide in physiological fluids.

We report on highly-sensitive ion-selective electrodes (ISEs) for potentiometric determining of galantamine hydrobromide (GB) in physiological fluids. Galantamine hydrobromide (GB) was selected for this study due to its previous medical importance for treating Alzheimer's disease. Three different types of ISEs were investigated: PVC membrane electrode (PVCE), carbon-paste electrode (CPE), and coated-wire electrode (CWE). In the construction of these electrodes, galantaminium-reineckate (GR) ion-pair was used as a sensing species for GB in solutions. The modified carbon-paste electrode (MCPE) was prepared using graphene oxide (MCPE-GO) and sodium tetrakis (trifluoromethyl) phenyl borate (MCPE-STFPB) as ion-exchanger. The potentiometric modified CPEs (MCPE-GO and MCPE-STFPB) show an improved performance in term of Nernstian slope, selectivity, response time, and response stability compared to the unmodified CPE. The prepared electrodes PVCE, CWE, CPE, MCPE-GO and MCPE-STFPB show Nernstian slopes of 59.9, 59.5, 58.1, 58.3 and 57.0 mV/conc. decade, and detection limits of 5.0 × 10-6, 6.3 × 10-6, 8.0 × 10-6, 6.0 × 10-6 and 8.0 × 10-6 mol L-1, respectively. The prepared ISEs also show high selectivity against cations (i.e. Na+, K+, NH4+, Ca2+, Al3+, Fe3+), amino acids (i.e. glycine, L-alanine alanine), and sugars (i.e. fructose, glucose, maltose, lactose). The prepared ISEs are applicable for determining GB in spiked serums, urines, and pharmaceutical preparations, using a standard addition and a direct potentiometric method. The fast response time (<10 s), long lifetime (1-5 weeks), reversibility and stability of the measured signals facilitate the application of these sensors for routine analysis of the real samples.

Development of ionophore-based nanosphere emulsion incorporating ion-exchanger for complexometric titration of thiocyanate anion.

Ionophore-based ion-exchange nanosphere emulsion was prepared and tested for the determination of thiocyanate. The emulsified nanosphere contained the cationic additive tridodecylmethyl ammonium chloride (TDMAC), the plasticizer, and the ionophore Mn(III)-salophen or Mn(III)-salen. This emulsion was used as titrating agent for thiocyanate complexation with ionophores, which could be transduced using an ion-selective electrode (ISE) as an indicator electrode for the end point detection. The method showed no need for pH control and reliable selectivity, as thiocyanate could be determined in presence of other interfering ions with high accuracy. As well, the emulsion was stable and could be used for approximately couple of weeks. The developed emulsion could be used for the determination of thiocyanate in human saliva with standard deviation <4%. In sum, the proposed method could be used as an alternative for the argentometric titration and would open new avenues for the determination of neutral, anionic, and cationic species without necessity for water soluble ligands or pH control.

Highly selective thiocyanate optochemical sensor based on manganese(III)-salophen ionophore.

We report on the development of optochemical sensor based on Mn(III)-salophen ionophore. The sensor was prepared by embedding the ionophore in a plasticized poly (vinyl chloride) impregnated with the chromoionophore ETH7075. Optical response to thiocyanate occurred due to thiocyanate extraction into the polymer via formation of strong complex with the ionophore and simultaneous protonation of the indicator dye yielding the optical response at 545nm. The developed optochemical sensor exhibited high selectivity for thiocyanate over other anions including the most lipophilic species such as salicylate and perchlorate. For instance, the optical selectivity coefficients, logKSCN,anionopt, were as follow: ClO4-=-5.8; Sal-=-4.0; NO3-˂-6. Further, the thiocyanate optical selectivity obtained using the present optochemical sensor was greatly enhanced in comparison with that obtained using an anion-exchanger based sensor. Also, the optimized optochemical sensor exhibited micro-molar detection limit with 2min response time at pH4.5 using acetate buffer. The reversibility of the optimized sensor was poor due to strong ligation of the thiocyanate to the central Metal ion, log K=14.1, which can be overcome by soaking the optode in sodium hydroxide followed by soaking in buffer solution. The developed sensor was utilized successfully for the determination of thiocyanate in human saliva and in spiked saliva samples.

Development of two reference materials for all trans-retinol, retinyl palmitate, α- and γ-tocopherol in milk powder and infant formula.

Vitamins are important food constituents that can be present in almost every foodstuff. Food quality and safety depends on food surveillance by reliable quantitative analysis enabled by appropriate quality control. Certified matrix reference materials are versatile tools to support quality assurance and control. However, in the case of vitamins, which are important in various foods, there is a lack of matrix reference materials. Two certified reference materials for the determination of all-trans-retinol, retinyl palmitate, and α- and γ-tocopherol in milk powder and infant formula have been developed by the National Institute of Standards, Egypt. This article presents the preparation, characterization, homogeneity, and stability testing as well as statistical treatment of data and certified value assignment. The assignment of the certified values and associated uncertainties in the prepared natural-matrix reference materials were based on the widely used approach of combining data from independent and reliable analytical methods.