Potentiometric Results Research Articles

Solid Contact Microfabricated Electrode for Point-of-Care Electrochemical Determination of a Parasitic Infection Managing Medication Based on a Transducer Layer Prussian Blue Analogue Decorated with Multi-Walled Carbon Nanotubes

Point-of-care diagnostics (POC), often known as on-site testing has evolved as a quick and accurate methodology for analyzing and therapeutic monitoring of drugs. The aim of this study is to provide cost-effective, simple, portable, reliable, and ecofriendly methodology for determination of Tinidazole (TD); potentiometric sensors are found to be an ideal fit for achieving these goals. An advanced microfabricated ion selective electrode is provided employing two-steps procedure. The first is selecting the most selective ionophore for TD determination while the second is to improve the stability and detection limit upon doping the nanoparticles as ion to electron transducer layer between the microfabricated copper electrode and the ion selective media as it can decrease potential drift from 8.0 to ∼1.0 mV h−1. Nernstian potentiometric results were obtained for TD in range of concentration 1.0 × 10−3 to 1.0 × 10−8 M, its slope was −57.43 mV/decade with lower detection limits 2.55 × 10−9 M. Essential values of the adopted sensor are fast and stable response time (9 ± 2 s). The provided potentiometric approach succeeds to asses TD in its pure and pharmaceutical forms, furthermore in different biological fluids with satisfactory results.

All-Solid-State PVC-Membrane Cu(II)-Selective Potentiometric Microsensor Based on a Novel Calix[4]arene Derivative

In this study, 25,27-dihydroxy-26,28-bis(ethoxycarbonylbutyoxy)-5,11,17,23-p-tert-butylcalix[4]arene was used as an ionophore for the preparation of a novel all-solid-state type microsensor to make a selective potentiometric response towards Cu(II) ions. The optimum membrane composition of the microsensor was determined as 2% (w/w) ionophore, 67% (w/w) bis (2-ethylhexyl) sebacate (DOS), 30% (w/w) polyvinylchloride (PVC), and 1%(w/w) potassium tetrakis 4-chlorophenyl borate (KTpClPB). The Cu(II)-selective microsensor exhibited a highly selective Nernstian response of 31.3±2.1 mV slope (R2: 0.997) with a short response time (15 s) over the concentration range of 10−5 to 10−1 mol L−1 of Cu(II) ions for 8 weeks with no significant difference in potentials. The microsensor was effectively performed in the pH range of 5.0–8.0, with low detection limit as 7.63×10−7 mol L−1, and a temperature range of 15−40 °C. The prepared microsensor was successfully used both as an indicator electrode in the potentiometric titration of Cu(II) ions with EDTA and also in the determination of the Cu(II) content of environmental water samples. When the potentiometric results were compared with ICP-OES, they were found to be in good agreement with ICP-OES results at a 95% confidence level.

The Role of the Unbinding Cycle on the Coordination Abilities of the Bi-Cyclopeptides toward Cu(II) Ions.

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.

Development of potentiometric immunosensor for determination of live attenuated Varicella Vaccine: Potency and stability studies

Determination of Varicella vaccine's potency; containing live attenuated strain (Oka) of Varicella Zoster virus, has been limited to in vitro cell culture methods. In this study, a label free potentiometric biosensor has been developed for the first time and optimized to determine the content of varicella zoster virus. A passive ion-flux sensing platform has been developed using an anti-varicella monoclonal antibody and tetrabutyl ammonium bromide as a marker ion. The immunosensor has been optimized with respect to membrane diameter and concentration of the immobilized antibody. Linearity was achieved over a concentration range of 2.5–3.2 log PFU/dose with a LOD of 1.9 log PFU/dose. Potentiometric results were compared to the plaque-forming assay using the cell culture technique. The developed immunosensor was superior with respect to analysis time and cost without affecting critical analytical performance characteristics. Furthermore, in order to evaluate the stability indicating ability of the immunosensor, the effect of pH and temperature was investigated. Vaccine samples were subjected to forced degradation conditions; pH and elevated temperatures. Stability results showed the ability of immunosensor to differentiate between intact and degraded viral content. This would demonstrate the reliability of the immunosensor for evaluating the efficacy and stability of the vaccine.

Potentiometric determination of mebeverine hydrochloride antispasmodic drug based on molecular docking with different ionophores host-guest inclusion as a theoretical study.

The scientific community has continued to pay particular attention to potentiometric sensors based on ion-selective membrane sensors as an energy-efficient, easy-to-use method suitable for microfabrication. To this end, potentiometric ion-selective sensors were used as an alternative green analytical instrument. Three distinct sensors relying on various ionophores were built and assessed. A cationic exchanger, tetra phenyl borate, was used in the polyvinyl chloride polymeric plasticized matrix using di octyl phthalate, where α, β, and γ cyclodextrins were utilized as ionophores. A comparative potentiometric analysis was carried out using three ion-selective sensor designs: α, β, and γ cyclodextrins sensors. β-Cyclodextrin significantly reduced the detection limit and improved the discriminative performance of mebeverine hydrochloride (MBV) in the pharmaceutical dosage form over α- and γ-cyclodextrins in the presence of other interfering chemicals. Additionally, a significant connection was made between the practical perspective and a theoretical investigation based on computational research. Nernstian potentiometric results for the optimum sensor were obtained for MBV in the range of concentrations 1.0 × 10-2 to 1.0 × 10-6 M, its slope was -58.70 ± 0.12 mV per decade with lower detection limits 4.50 × 10-7 M. This computational molecular docking investigation clarified that the binding sites and modes were in good agreement with the experiment results. This investigation was applied to expect the interaction between MBV and the proposed sensors to ensure which ionophores were the best for MBV.

Selective recognition of neurotransmitters in aqueous solution by hydroxyphenyl aza-scorpiand ligands.

The synthesis, acid-base behaviour and anion recognition of neurotransmitters (dopamine, tyramine and serotonin) in aqueous solution of different aza-scorpiand ligands functionalized with hydroxyphenyl and phenyl moieties (L1-L3 and L4, respectively) have been studied by potentiometry, NMR, UV-Vis and fluorescence spectroscopy and isothermal titration calorimetry (ITC). The analysis of the potentiometric results shows the selective recognition of serotonin at physiological pH (Keff = 8.64 × 104) by L1. This selectivity has an entropic origin probably coming from a fine pre-organization of the interacting partners. Thus, the complementarity of the receptor and the substrate allows the reciprocal formation of hydrogen bonds, π-π and cation-π interactions, stabilizing the receptors and slowing the rate of oxidative degradation, and satisfactory results are obtained at acidic and neutral pH values. NMR and molecular dynamics studies reveal the rotation blockage in the neurotransmitter side chain once complexed with L1.

Enthalpy profile of pH-induced flocculation and redispersion of polyacrylic acid-coated nanoparticles in protic ionic liquid, N,N-diethylethanolammonium trifluoromethanesulfonate

Maghemite nanoparticles coated with polyacrylic acid (pAA) were dispersed in the protic ionic liquid, diethylethanolammonium trifluoromethanesulfonate (DEEAH+⋅TfO−), and the thermodynamics of particle dispersion was studied by means of potentiometric and calorimetric titrations over the entire accessible pH range. As previously reported, the domain of colloidal stability is divided into two pH regions, mildly acidic and basic, separated by a flocculation domain at an intermediate pH. In this study, solvent DEEAH+⋅TfO− was first characterized in terms of the thermodynamic parameters of two reference reactions: autoprotolysis and ionization of acetic acid. A negative autoprotolysis entropy is obtained due to hydrogen-bond formation between the neutralized solvent cation, DEEA, and the neighboring cation DEEAH+. This suggests that the solvent structure is reinforced by the formation of neutral species, being an opposite trend to both ethylammonium nitrate and water. Second, the ionization and flocculation of pAA-coated nanoparticles (CNps) in the ionic liquid were examined. The potentiometric results could be modeled using a simple pAA ionization, independent of the aggregation state over the entire pH range. However, the calorimetric titration detected extra heat generation in an acidic condition prior to flocculation, in addition to an ionization enthalpy of pAA of 30 kJ/mol. This exothermic contribution is attributed to a change in the solvation process of CNps in the ionic liquid. Herein, we propose a model in which different types of solvation in the acidic and basic domains are sufficient to ensure colloidal stability, while aggregation unfolds between the switching pH.

Gold-modified paper as microfluidic substrates with reduced biofouling in potentiometric ion sensing

Microfluidic sampling media based on paper and its modifications with either gold nanoparticles or sputtered gold were evaluated for potentiometric determination of Na+, K+, and Cl– ions in clinically relevant samples. The measurements were conducted in comparison to other commonly considered microfluidic substrates, i.e. sponge, polyester textile, and polyamide textile. Ion determination was done by using solid-contact ion-selective electrodes based on plasticized PVC membranes for Na+, K+, and Cl– ions and utilizing PEDOT(PSS) or PEDOT(Cl) as the ion-to-electron transducer. The solid-contact ion-selective electrodes and a solid-state reference electrode were placed directly on the substrate into which the sample solution was wicked. Transport of bovine serum albumin (BSA) through the paper substrate was studied by ellipsometry. Modification of the paper substrates by gold nanoparticles (AuNPs) was found to slow down the transport of BSA through the paper, when compared with unmodified paper substrates and when compared with all the other alternative sampling matrices studied. The retention of BSA obtained with AuNP-modified paper substrates significantly improved the accuracy of the potentiometric ion determinations in sweat, saliva, artificial tears, and artificial serum. The potentiometric results were validated by inductively coupled plasma optical emission spectrometry (ICP-OES) and ion chromatography (IC). The study indicates that modification of paper by AuNPs is a feasible approach to reduce biofouling of sensors that are used in the paper-based analysis of clinically relevant samples.

Improving Metal Adsorption on Triethylenetetramine (TETA) Functionalized SBA‐15 Mesoporous Silica Using Potentiometry, EPR and ssNMR

AbstractNanomaterials have received growing attention in the treatment and diagnosis of neurological disorders because the low blood brain barrier permeability hinders the classical pharmacological approach. Metal ion chelators combined with nanoparticles prove effective in the treatment of neurodegeneration and are under extensive studies. Most chelating agents and metallodrugs compete with endogenous molecules for metal coordination, and do not reach the active site. Determining the competition between metallodrugs and endogenous molecules requires knowing the stability constants of formed metal complexes. In this study, for the first time, potentiometric titrations are used to determine metal complex formation constants, and to quantify ligand content in functionalized materials. This new potentiometric approach allows physico–chemical characterization of mesoporous functionalized materials and their metal adsorption capacity in water solution. The potentiometric results are compared with isotherm models obtained by spectroscopic measurements and yield rewarding data fitting. The potentiometric method described here can be extended to different types of nanostructured materials carrying surface ionizable groups.

Nanoestructuras de sílice, con diámetro y distribución de mesoporos variable, modificadas con ácido tungstofosfórico como catalizadores en la síntesis de quinoxalinas

Se sintetizaron catalizadores (SNX#WPA) basados en ácido tungstofosfórico, en soportes de nanoestructuras de sílice (SNX), con distribución de diámetros y tamaños de mesoporos variables. Las SNX se prepararon en medio de octano/agua, usando poliestireno y bromuro de cetiltrimetilamonio como plantillas. Los materiales se caracterizaron por DRX, TEM y adsorción/desorción de nitrógeno. La relación octano/agua influyó tanto en la morfología y el tamaño de las SNX como en la distribución del tamaño de poro. Las SNX obtenidas utilizando relaciones OCT/H2O en el rango de 0,07-0,35, presentan mesoporos pequeños (5-6 nm) y grandes (28-34 nm), generados principalmente por poliestireno. Los mesoporos grandes y su contribución de volumen fueron claramente más altos que en las muestras SN1, SN2 y SN3. La estructura y la morfología de SNX#WPA fueron similares a las de las SNX usadas como soporte. Además, la caracterización de todos los materiales SNX#WPA por FT-IR y 31P NMR indicó la presencia de especies [PW12O40]3− y [H3-XPW12O40](3-X)− sin degradar. Según los resultados de la valoración potenciométrica, los sólidos presentaron sitios ácidos muy fuertes. Se evaluó la actividad de SNX#WPA como catalizadores en la síntesis de quinoxalinas, a partir de lo cual se obtuvieron altos rendimientos, sin formación de subproductos. De ello resultó que los materiales preparados son catalizadores altamente selectivos y reutilizables.

Interaction of a Weak Acid Cation Exchange Resin (Dowex Mac 3H) with the Belousov‐Zhabotinsky Reaction and Estimation of Metal Ions

AbstractThe work pertains to the study on direct and indirect interaction of a macroporous weak acid cation exchange resin‐Dowex Mac 3H form with Belousov‐Zhabotinsky (BZ) reaction based on malonic acid‐cerium‐bromate‐sulfuric acid system. In the direct mode, the above reaction was perturbed by adding 10% (w/w) of Dowex Mac 3H at three different time intervals, i. e., before the start of induction period, during the induction period and after the commencement of oscillations. This mode of interaction was studied to investigate the effect of heterogeneity on the dynamics of BZ reaction. The indirect interaction of the resin was studied by interacting the resin individually with the optimized metal catalyst for a particular period of time after which the supernatant was used as initial reagent in the otherwise optimized BZ system. The interaction was monitored with respect to the change in oscillatory parameters before and after loading the resin with metal catalyst. The selectivity of the resin towards cerium and iron (ferroin) was studied through the said BZ reaction using potentiometry as the main technique. It was found that resin is more selective towards ferroin. The selectivity of the resin towards the various metal ions was followed by their estimation using UV‐Visible spectrophotometry. The effect of solvents on the ion exchange capacity (IEC) of the resin was also studied through the BZ reaction. Some solvents increased its IEC while others decreased it. The potentiometric results obtained were validated by spectroscopic findings and electrochemical studies.

Synthesis of 12-Membered Tetra-aza Macrocyclic Pyridinophanes Bearing Electron-Withdrawing Groups.

The number of substituted pyridine pyridinophanes found in the literature is limited due to challenges associated with 12-membered macrocycle and modified pyridine synthesis. Most notably, the electrophilic character at the 4-position of pyridine in pyridinophanes presents a unique challenge for introducing electrophilic chemical groups. Likewise, of the few reported, most substituted pyridine pyridinophanes in the literature are limited to electron-donating functionalities. Herein, new synthetic strategies for four new macrocycles bearing the electron-withdrawing groups CN, Cl, NO2, and CF3 are introduced. Potentiometric titrations were used to determine the protonation constants of the new pyridinophanes. Further, the influence of such modifications on the chemical behavior is predicted by comparing the potentiometric results to previously reported systems. X-ray diffraction analysis of the 4-Cl substituted species and its Cu(II) complex are also described to demonstrate the metal binding nature of these ligands. DFT analysis is used to support the experimental findings through energy calculations and ESP maps. These new molecules serve as a foundation to access a range of new pyridinophane small molecules and applications in future work.

Potentiometric microsensor based on ion-imprinted polymer for the trace determination of cesium(I) ions

A cesium potentiometric microsensor based on magnetic ion-imprinted polymer (MIIP) has been developed for Cs(I) sensing. The core-shell structure Cs(I)-MIIP was synthesized by surface-imprinting technique, using functionalized magnetic Fe3O4@SiO2 microspheres, Cs(I) ion and carboxymethyl chitosan as supporter, template and functional monomers respectively. The resultant Cs(I)-MIIP was used as ionophore in the construction of the PVC membrane electrode to obtain a selective potentiometric microsensor toward Cs(I) ions. The fabricated sensor exhibited a highly sensitive Nernstian response (60.2 mV/decade) over the concentration range of 1 × 10−6 to 1 × 10−1 M of Cs(I). The response time of the microsensor was considerably short (less than 3 s) and its detection limit was determined as 3.0 × 10−7 M. The microsensor was effectively performed in the pH range of 4–6, and revealed desirable selectivity over a wide variety of other cations including alkali, alkaline earth and heavy metals. The proposed microsensor was also used for the determination of Cs(I) contents in the environmental water samples. The potentiometric results were in good harmony with the results obtained by the ICP-MS method.

Ternary complex formation of the copper (II)-2,2′-Bipyridine system with some amino acids

In this work we present a stability and speciation study for the formation of binary and ternary metal complexes obtained from the interaction of Cu(II), 2,2’-Bipyridine and the Amino acids: Glycine (HGly), Proline (HPro), α-Alanine (Hα-Ala), β-Alanine (Hβ-Ala), Leucine (HLeu), Isoleucine (HIso), Valine (HVal), Methionine (HMet), Aspartic acid (H2Asp), Glutamic acid (H2Glu), Serine (HSer), Threonine (HThr), Histidine (HHis), Phenylalanine (HPhe), and Tryptophan (HTry), in aqueous solution at 25 °C using 1.0 M KNO3 as the ionic medium. The overall stability constants were established based on the analysis of potentiometric results using the software LETAGROP. The relative stability of the ternary complexes was compared with the corresponding one of the binary complexes. The concentration distribution of various species, formed in aqueous solution, was also evaluated as a function of pH. In addition, the antibacterial properties of some of the ternary complexes were compared using the well-known Kirby-Bauer agar diffusion method. The complexes were in-situ synthetized considering the obtained potentiometric results, and the antibacterial activity was evaluated against Escherichia coli and Staphylococcus aureus, only showing activity against the microorganisms Staphylococcus aureus. These results suggest that Cu(II)-2,2’-Bipyridine-Amino acid complexes have potential as antibacterial agents.

Cyclodextrin potentiometric sensors based on selective recognition sites for procainamide: Comparative and theoretical study

AbstractPolyvinyl chloride (PVC) membrane sensors were constructed and developed for the determination of procainamide HCl (PR). Three membrane sensors incorporating α-, β- and γ- cyclodextrin (CD) as ionophores with potassium tetrakis (4-chlorophenyl) borate (KTpClPB) as the ion additive, o-nitro phenyl ether (o-NPOE) as the plasticizer and a PVC matrix. The reaction mechanisms were based on inclusion complexes. The developed α- and β- CD sensors exhibited near-Nernstian profile, whereas γ- CD showed a non-Nernstian response. At pH 4 -8, the sensors exhibited a calibration range for PR of 10-3to 10−6, and the detection limits were 2.40 × 10-6, 2.12 × 10-6, 2.40 × 10-6for α-, β- and γ- CD sensors, respectively. Interference was investigated by studying the selectivity coefficient values of the test sensors, which indicated that the methods were free from interference from investigated species. The determination of PR exhibited high recovery and favorable relative standard deviation using the investigated sensors. The sensors were subsequently used for the quantification of PR in a pharmaceutical formulation and the potentiometric results agreed with those of a spectrophotometric method. A molecular docking (MD) study was used to predict the structure of the inclusion complexes of PR (guest) and α- or β- or γ-CD (host). The study results indicated that the formed complexes were stable with sufficient binding energy.

Zinc(II)-selective PVC membrane potentiometric sensor for analysis of Zn2+ in drug sample and different environmental samples

ABSTRACT In this study, a novel potentiometric sensor that is highly selective to Zn2+ ions is described. A highly selective and sensitive all-solid-state poly(vinyl chloride) membrane Zn2+ sensor, using 7,16-dibenzyl-1,4,10,13-tetraoxa-7,16-diazacyclooctadecane as an ionophore, has been prepared. The best performance was obtained with the sensor having a membrane composition of 4.0% ionophore, 33.0% poly(vinyl chloride), 62.0% Bis(2-ethylhexyl) sebacate (BEHS) and 1.0% potassium tetrakis (p-chlorophenyl) borate (KTpClPB). The sensor exhibits a Nernstian slope of 28.0 ± 2.0 mV/decade in a wide linear concentration range of 1.0 × 10−5 to 1.0 × 10−1 M and detection limit of this sensor is 1.17 × 10−6 M. The developed potentiometric sensor showed a relatively fast response time of 5 s, good reproducibility and stability. The proposed sensor revealed good selectivity over a wide variety of other cations. The working pH range of this sensor is 4.0–11.0. The developed zinc(II)-selective sensor was successfully applied to the direct zinc determination in different water samples and drug sample. The potentiometric results for the drug sample was compared with inductively coupled plasma spectrometry. The proposed zinc(II)-selective electrode can be successfully employed as an indicator electrode in potentiometric titration with EDTA.

Antiproliferative activity of copper(II) glutamine complexes with N,N-donor ligands: Synthesis, characterization, potentiometric studies and DNA/BSA interactions

New water soluble copper(II) complexes, - [Cu(phen)(gln)(H2O)]NO3·H2O (1) and [Cu(dmphen)(gln)(H2O)]ClO4 (2) - (phen: 1,10-phenanthroline, dmphen: 4,7-dimethyl-1,10-phenanthroline, gln: l-glutamine), have been synthesized and characterized by CHN analysis, ATR-FT-MIR, ESI-MS and single-crystal X-ray diffraction techniques. Binary and ternary complexes of copper(II) with the selected ligands have been investigated using potentiometric methods in 0.1 M KCl aqueous ionic media at 298.2 K. The protonation constants of the selected ligands and the stability constants of the complexes 1 and 2 have been calculated from the potentiometric data using the “BEST” software package and the potentiometric results have been analyzed using the “SPE” software package. The binding interaction of the complexes with calf thymus DNA (CT-DNA) was investigated by electronic absorption and emission spectroscopic methods revealed that the complexes could interact with CT-DNA via a moderate intercalation mode. The fluorescence quenching mechanism of bovine serum albumin (BSA) by the complexes was analyzed and the binding constant has been calculated. In vitro antiproliferative effect of the complexes was examined on human tumor cell lines (Caco-2, A549 and MCF-7) and healthy cells (BEAS-2B). The complex 2 showed remarkable antiproliferative activity compared to the complex 1 and cisplatin.

Influence of Extracellular Polymeric Substances on the Adsorption of Cadmium onto Three Bacterial Species

In this study, we measured the effect of EPS on Cd and proton adsorption behaviors by measuring the extent of adsorption onto biomass with and without the EPS removed via a cation exchange resin. We conducted both Cd adsorption experiments and potentiometric titrations of biomass using three common bacterial species: one Gram-positive (Bacillus subtilis) and two Gram-negative (Shewanella oneidensis, Pseudomonas putida) species. The Cd adsorption experiments were conducted as a function of metal loading in order to probe whether environmentally-low metal loadings lead to different adsorption mechanisms and roles for EPS than the higher metal loadings of most previous adsorption studies. We suspended each biomass sample in a solution of dissolved Cd in 0.01 M NaClO4 at metal loadings of 1, 2, 5, and 74 μmol/g. Surface complexation modeling (SCM) was used to determine stability constants for the important Cd-bacteria complexes, and the effect of metal loading on the resulting calculated stability constant values was determined.In general, the measured bulk Cd adsorption behavior is unaffected by EPS removal. However, our potentiometric titration results suggest that EPS removal does alter the distribution of site types, but not the mass-normalized total site concentration within the biomass. SCM suggests that high affinity sulfhydryl sites control Cd binding under low metal loading conditions for B. subtilis and P. putida, and that sulfhydryl sites are present both on the cells and within the EPS for these species. Conversely, the SCM results suggest that Cd-sulfhydryl binding is un-important on the EPS of S. oneidensis.

A novel copper selective sensor based on ion imprinted 2-vinylpyridine polymer

A novel potentiometric Cu2+-selective microsensor has been developed that is based upon ion imprinted 2-vinylpyridine polymer. The polymer was synthesized using Cu(II) ions, 2-vinylpyridine, methacrylic acid, and ethylene glycol dimethacrylate as a template, functional monomer, and cross-linker, respectively. The resultant polymer was used as ionophore to obtain a selective potentiometric response towards Cu(II) ions in the structure of the PVC membrane. The detection limit of the microsensor was determined to be 8.4 × 10−7mol/L, and its response time was considerably short (less than 15 s). The prepared microsensor exhibited a near-Nernstian response for Cu(II) ions over the concentration range of 10−1to 10−6mol/L, with a slope of 28.5 mV per decade over 2 months, and without any considerable divergence in potentials. The microsensor was effectively performed in a pH range between 4.0 and 7.0 and used as an indicator electrode in the potentiometric titration of Cu(II) ions with EDTA. The proposed microsensor has been successfully demonstrated for the determination of copper in a number of environmental water samples. The obtained potentiometric results were in good harmony with the results obtained by the AAS method.

Potentiometric titration data on the enhancement of sorption capacity of surface-modified biosorbents: functional groups scanning method

In the present study, the relationship between the amount of anionic or cationic binding sites and adsorption capacities of biosorbents is discussed through potentiometric titration and mathematical model equations (proton-binding models). The poly(acrylic) acid-modified biomass (PAAB) and polyethylenimine-modified biomass (PEIB) derived from raw biomass (RB) Corynebacterium glutamicum (C. glutamicum) were used as cationic and anionic binding site-enhanced biosorbents, respectively. To obtain the sorption capacities of biomasses for anionic and cationic pollutants, isotherm tests were carried out using Basic Blue 3 (BB3, at pH 9) and Reactive Red 4 (RR4, at pH 2) as model anionic and cationic pollutants, respectively. The maximum sorption capacity (qm) of PAAB was 1.28 times higher than RB for BB3. In the case of PEIB, the sorption capacity was found to be 3.27 times higher than RB for RR4. A quantitative information of functional groups could be estimated by the application of proton-binding models to potentiometric titration results. In addition, the buffering capacities of functional groups were obtained from the parameters of pK models. An increasing ratio of sorption capacities was similar to that of the buffering capacities of modified biosorbents obtained from all conditions of pK models. Therefore, the fact that the sorption capacity of modified biomass can be predicted by comparing it with the buffering capacity of biosorbents was confirmed.