Presented here is a sensing membrane consisting of a modified merocyanine photoacid polymer and a calcium ionophore in plasticized poly(vinyl chloride). This membrane is shown to actively exchange protons with calcium ions when switched ON after illumination at 470 nm, and the exchange can be followed by UV–vis spectroscopy. The sensing membrane shows no response in the ON state when calcium ions are absent. The limit of detection of the sensor is 5.0 × 10–4 M with an upper detection limit of 1.0 M. Thus, we demonstrate for the first time the use of a visible light activated, lipophilic photoacid polymer in an ion-sensing membrane for calcium ions, which highly discriminates potassium, sodium, and magnesium ions.
Amplified potentiometric transduction of DNA hybridization based on using liposome ‘nanocarriers’ loaded with the signaling ions is reported. The liposome-amplified potentiometric bioassay involved the duplex formation, followed by the capture of calcium-loaded liposomes, asurfactant-induced release and highly-sensitive measurements of the calcium signaling ions using a Ca2+ ion-selective electrode (ISE). The high loading yield of nearly one million signaling ions per liposome leads to sub-fmol DNA detection limits. Factors affecting the ion encapsulation efficiency and signal amplification are evaluated and discussed. The influence of the surfactant lysing agent is also examined. Such use of ‘green’ calcium signaling ions addresses the inherent toxicity of Agand CdS nanoparticle tags used in previous potentiometric bioassays. The new strategy was applied for the detection of low levels of E. coli bacteria. It could be readily extended to trace measurements of other important biomolecules in connection to different biorecognition events. The attractive analytical performance makes liposomes a useful addition to the armory of potentiometric bioassays.
The concept of locally heated polymeric membrane potentiometric sensors is introduced here for the first time. This is accomplished in an all solid state sensor configuration, utilizing poly(3-octylthiophene) as the intermediate layer between the ion-selective membrane and underlying substrate that integrates the heating circuitry. Temperature pulse potentiometry (TPP) gives convenient peak-shaped analytical signals and affords an additional dimension with these sensors. Numerous advances are envisioned that will benefit the field. The heating step is shown to give an increase in the slope of the copper-selective electrode from 31 to 43 mV per 10-fold activity change, with a reproducibility of the heated potential pulses of 1% at 10 μM copper levels and a potential drift of 0.2 mV/h. Importantly, the magnitude of the potential pulse upon heating the electrode changes as a function of the copper activity, suggesting an attractive way for differential measurement of these devices. The heat pulse is also shown to decrease the detection limit by half an order of magnitude.
Here, we report on a highly sensitive potentiometric detection of DNA hybridization. The new assay uses a low-volume solid-contact silver ion-selective electrode (Ag+-ISE) to monitor the depletion of silver ions induced by the biocatalytic reaction of the alkaline-phosphatase enzyme tag. The resultant potential change of the Ag+-ISE, thus, serves as the hybridization signal. Factors affecting the potentiometric hybridization response have been optimized to offer a detection limit of 50 fM (0.2 amol) DNA target. The new potentiometric assay was applied successfully to the monitoring of the 16S rRNA of E. coli pathogenic bacteria to achieve a low detection limit of 10 CFU in the 4 μL sample. Such potentiometric transduction of biocatalytically induced metallization processess holds great promise for monitoring various bioaffinity assays involving common enzyme tags.
The modification of electrodes with gold nanoparticles results in an increased electrode surface area, enhanced mass transport, and improved catalytic properties. We have extended this approach to indium tin oxide (ITO) electrodes to obtain optically transparent gold nanorod-modified electrodes which display enhanced electrochemical capabilities and have the additional advantage of showing a tunable surface plasmon resonance. The procedures for attaining high surface coverage (15 gold nanorods per square Âµm) of such electrodes were optimized, and the potential-dependent surface plasmon resonance was studied under controlled electrical potential. In an exemplary sensor application, we demonstrate the detection of mercury via potential-dependent formation of an Au-Hg amalgam
Herein, we present different functionalized meta-stable photoacids in ion-sensors to tune the equilibrium response time. As a proof of concept, two new meta-stable photoacids were synthesized, one contains an ether group and the other has an ester functional group. These functionalized meta-stable photoacids were elucidated in solution of ethanol and in ion-sensing films via pH and kinetic studies. In comparison from our previous work, the response time was reduced from hours to minutes by utilizing an ether functional group in the meta-stable photoacid.
In this work, five different types of membranes were developed responsible to anion-selective electrodes. The membranes were based on tri-caprylyl-trimethyl-ammonium chloride (Aliquat-336S) supported on poly(ethylene-co-vinyl-acetate) copolymer (EVA). The sensors were prepared by solubilizing the copolymer with the appropriate exchanger in chloroform, without using of any plasticizers. The ion-selective electrodes prepared using these membranes show the utility for anions determinations in the concentration range between 10−5 and 10−1 mol l−1 in the steady-state. The membrane performance was also evaluated in FIA system using tubular electrode for salicylate and iodide. In FIA system, the electrode exhibited nernstian response for salicylate in the concentration range of 2.5×10−3 and 1.0×10−1, while for iodide from 5.0×10−4 up to 1.0×10−1 mol l−1. The systems were employed for the salicylate and iodide determination in pharmaceutical samples obtaining a relative deviation of 1.6%, when compared to the reference method.
The development of an amperometric sensor for the determination of reduced glutathione (GSH) is described. The sensor is based on tetrathiafulvalene–tetracyanoquinodimethane (TTF–TCNQ) incorporated into the graphite powder/Nujol oil matrix. The electrooxidation of GSH was monitored amperometrically at 200 mV versus SCE (saturated calomel electrode). The amperometric response of the sensor was linearly proportional to the GSH concentration between 20 and 300 μmol l−1, in 0.1 mol l−1phosphate buffer (pH 8.0), containing 0.1 mol l−1 KCl and 0.5 mmol l−1 Na2H2EDTA, as supporting electrolyte.
The detection limit, considering signal/noise ratio equal three, was 4.2 μmol l−1 for GSH and the repeatability obtained as relative standard deviation was of 5.1% for a series of 10 successive measurements.
In the present work, a simultaneous determination of calcium and potassium in coconut water samples using a flow-injection system with tubular ion-selective electrodes (ISEs) in series is described. The samples were injected into a 0.1 mol L−1 HEPES (pH=6.0) carrier solution, using an injection volume of 100 μL and a flow of 2.0 mL min−1 in the FIA system. The electrodes developed exhibited nernstian response for calcium and potassium in the concentration range between 1.0×10−5 and 1.0×10−1 mol L−1 with detection limits of 5.6×10−6 mol L−1 for calcium and 9.5×10−6 mol L−1 for potassium. And no significant interference between both ions was observed. The flow-injection analysis (FIA) system with tubular ISEs was suitable for the simultaneous calcium and potassium on-line monitoring. The determination of potassium presented good results when compared to the reference method. And the recovery results were 95±1% for calcium and 102±2% for potassium, showing a good evidence of the accuracy of the method.
This paper gives an overview of the newest developments of polymeric membrane ion-selective electrodes. A short essence of the underlying theory is given, emphasizing how the electromotive force may be used to assess binding constants of the ionophore, and how the selectivity and detection limit are related to the basic membrane processes. The recent developments in lowering the detection limits of ISEs are described, including recent approaches of developing all solid state ISEs, and breakthroughs in detecting ultra-small quantities of ions at low concentrations. These developments have paved the way to use potentiometric sensors as in ultra-sensitive affinity bioanalysis in conjunction with nanoparticle labels. Recent results establish that potentiometry compares favorably to electrochemical stripping analysis. Other new developments with ion-selective electrodes are also described, including the concept of backside calibration potentiometry, controlled current coulometry, pulsed chronopotentiometry, and localized flash titration with ion-selective membranes to design sensors for the direct detection of total acidity without net sample perturbation. These developments have further opened the field for exciting new possibilities and applications.
This paper describes a simple and inexpensive procedure to produce thin-films of poly(dimethylsiloxane). Such films were characterized by a variety of techniques (ellipsometry, nuclear magnetic resonance, atomic force microscopy, and goniometry) and used to investigate the adsorption kinetics of three model proteins (fibrinogen, collagen type-I, and bovine serum albumin) under different conditions. The information collected from the protein adsorption studies was then used to investigate the adhesion of human dermal microvascular endothelial cells. The results of these studies suggest that these films can be used to model the surface properties of microdevices fabricated with commercial PDMS. Moreover, the paper provides guidelines to efficiently attach cells in BioMEMS devices.
As shown recently, the interference problem typical of ion-selective electrodes can be dealt with via smart arrays adjusted by blind source separation methods. In this letter, we resume this study and show that such an approach can be applied even when faced with a limited number of samples acquired through flow-injection analysis.
A new platform of ion-selective optode is presented here to detect cations under thermodynamic equilibrium via ratiometric analysis. This novel platform utilizes a ‘one of a kind’ visibile light-induced metastable photoacid as a reference ion indicator to achieve activatable and controllable sensors. These ion-selective optodes were studied in terms of its stability, sensitivity, selectivity, and theoretical aspects.
Preparation of ion-selective electrodes (ISEs) often requires long and complicated conditioning protocols limiting their application as tools for in-field measurements. Herein, we eliminated the need for electrode conditioning by loading the membrane cocktail directly with primary ion solution. This proof of concept experiment was performed with iodide, silver, and sodium selective electrodes. The proposed methodology significantly shortened the preparation time of ISEs, yielding functional electrodes with submicromolar detection limits. Moreover, it is anticipated that this approach may form the basis for the development of miniaturized all-solid-state ion-selective electrodes for in situ measurements.
Halogen functionalization of the edges of the graphene sheets can improve processability, add new properties, and enhance its interactions with other materials. Through functionalization, improved materials can be realized. Typically, halogenated graphenes are produced from pure or reactive halogen sources. Current approaches present significant safety challenges. By generating reactive dichlorine monoxide (Cl2O) in situ, a chlorinated graphene with the nominal composition C17Cl2OH can be realized safely and scalably. Chlorinated graphene can be used as a precursor for an array of functionalized materials by mechanically driven solid-state metathesis reactions. For example, nearly 75% of the chlorine in chlorinated graphene can be exchanged with fluorine by using the safer fluorine-containing compound ammonium fluoride (NH4F) as a reagent. A material with the composition C34Cl3F(OH)2 is realized. Preliminary work shows that F–graphene has oxygen reduction properties and Cl–graphene can improve existing zinc–air fuel cells. A scalable production of chlorinated and fluorinated graphenes and graphites will accelerate their adoption in fuel cells, batteries, polymer composites, and catalysts.
For over a decade, the incidence of Huanglongbing (HLB) has grown at an alarming rate, affecting citrus crops worldwide. Current methods of nutrient therapy have little to no effect in alleviating symptoms of HLB, and scarce research has been put forth towards non-destructive tools for monitoring zinc transport in citrus plants. Here, we have developed and characterized a solid contact micro-ion-selective electrode (SC-μ-ISE) for the determination of zinc transport in sour orange seedlings using a non-invasive microelectrode ion flux estimation (MIFE) technique. The SC-μ-ISE displayed a 26.05±0.13 mV decade−1 Nernstian response and a LOD of (3.96±2.09)×10−7 M. Results showed a significant Zn2+ uptake in the leaves and roots of sour orange seedlings when bulk concentrations were higher than 5.99 mM. Above this concentration, a linear relationship between flux and bulk Zn2+ concentration was observed. This relationship suggests passive diffusion may be a key mechanism for Zn transport into plants. Overall, this study is the first to use a Zn2+ SC-μ-ISE for the determination of ion transport processes in plants. This novel tool can be used to further knowledge the effect of nutrient therapy and disease progression on HLB infected citrus plants.
Ion-selective electrodes (ISEs) are an efficient and versatile tool for ion detection. However, portability and applicability for field applications are often limited by the need of a conditioning step, and high cost of the needed bulky reference electrode. Herein, the traditional conditioning protocol of ISEs has been eliminated and a paper-based solid-contact ISE (PBSC-ISE) has been integrated with a paper-based solidcontact reference electrode (PBSC-RE) in a single strip format for on-site analysis. The PBSC-RE is based on the copolymer methyl methacrylate-co-decyl methacrylate (MMA-DMA) (support matrix), combined with ionic liquids (ILs) to create and maintain a stable potential that is un affected by a change in ionic activity. This single-strip ready-to-use sensor yields a Nernstian response towards Na+, K+, and I− ions with submicromolar limits of detection, and is able to be used for multiplex analysis.
A novel method using a micro-ion-selective electrode (micro-ISE) technique was developed for in situ lead monitoring at the water–metal interface of a brass-leaded solder galvanic joint in a prepared chlorinated drinking water environment. The developed lead micro-ISE (100 μm tip diameter) showed excellent performance toward soluble lead (Pb2+) with sensitivity of 22.2 ± 0.5 mV decade–1 and limit of detection (LOD) of 1.22 × 10–6 M (0.25 mg L–1). The response time was less than 10 s with a working pH range of 2.0–7.0. Using the lead micro-ISE, lead concentration microprofiles were measured from the bulk to the metal surface (within 50 μm) over time. Combined with two-dimensional (2D) pH mapping, this work clearly demonstrated that Pb2+ ions build-up across the lead anode surface was substantial, nonuniform, and dependent on local surface pH. A large pH gradient (ΔpH = 6.0) developed across the brass and leaded-tin solder joint coupon. Local pH decreases were observed above the leaded solder to a pH as low as 4.0, indicating it was anodic relative to the brass. The low pH above the leaded solder supported elevated lead levels where even small local pH differences of 0.6 units (ΔpH = 0.6) resulted in about four times higher surface lead concentrations (42.9 vs 11.6 mg L–1) and 5 times higher fluxes (18.5 × 10–6 vs 3.5 × 10–6 mg cm–2 s–1). Continuous surface lead leaching monitoring was also conducted for 16 h.
Paper-based ion-selective electrodes (ISEs) are simple, flexible, and cost-efficient in comparison to conventional solid-contact ISEs. Yet, paper-based ISEs have poor limits of detection (in the micromolar range) relative to conventional solid-contact ISEs. Here we describe the construction and optimization of ISEs based on commercially available filter paper modified with single-walled carbon nanotubes (SWCNTs), sputtered gold, and conductive polymer poly(3-octylthiophene) to support an ion-selective membrane. The ion-selective membrane presented here is based on the copolymer methyl methacrylate-decyl methacrylate (MMA-DMA). The copolymer MMA-DMA is highly water-repellent and has a low coefficient of diffusion, which makes it particularly suitable for the creation of sensors with high performance in reaching low limits of detection. Three different configurations of the electrodes have been characterized by using contact angle surface analysis, oxygen influence, and testing for the presence of a water layer. Paper-strip ISEs for cadmium, silver, and potassium ions were developed with groundbreaking limits of detection of 1.2, 25.1, and 11.0 nM, respectively. In addition to such low limits of detection, paper-strip ISEs display high selectivity for their ion of interest and high reproducibility.
GSH has a relevant role in human metabolism as an indicator of disease risks. An amperometric sensor for glutathione (GSH) determination is described as an alternative method featuring simple construction procedure and short time analysis.
The developed sensor was used to determine glutathione at low potential using a TTF-TCNQ complex.
The sensor exhibits a linear response range from 5 to 340 micromol/l under applied potential of 200 mV vs. SCE. The sensitivity and detection limit were 90.1 microA l/mmol cm(2) and 0.3 micromol/l, respectively.
When the sensor was tested in hemolysed erythrocyte samples for GSH determination, a good correlation in results was observed between the sensor and the spectrophotometric method. The sensor showed recovery values between 98% and 102%.
We report here for the first time on the use of potentiometry for ultrasensitive nanoparticle-based detection of protein interactions. A silver ion-selective microelectrode is used to detect silver ions oxidatively released from silver enlarged gold nanoparticle labels in a sandwich immunoassay. Since potentiometry is expected to largely maintain its analytical characteristics upon reducing the sample volume, it is anticipated that this approach may form the basis for bioassays with attractive detection limits.
A simple procedure for the development of a range of polymeric ion-selective electrodes (ISEs) with low detection limits is presented. The electrodes were prepared by using a plasticizer-free methyl methacrylate−decyl methacrylate copolymer as membrane matrix and poly(3-octylthiophene) as intermediate layer deposited by solvent casting on gold sputtered copper electrodes as a solid inner contact. Five different electrodes were developed for Ag+, Pb2+, Ca2+, K+, and I-, with detection limits mostly in the nanomolar range. In this work, the lowest detection limits reported thus far with solid contact ISEs for the detection of silver (2.0 × 10-9M), potassium (10-7 M), and iodide (10-8 M) are presented. The developed electrodes exhibited a good response time and excellent reproducibility.
In recent years, ion-selective electrodes based on polymer membranes have been shown to exhibit detection limits that are often in the nanomolar concentration range, and thus drastically lower than traditionally accepted. Since potentiometry is less dependent on scaling laws that other established analytical techniques, their performance in confined sample volumes is explored here. Solid-contact silver-selective microelectrodes, with a sodium-selective microelectrode as a reference, were inserted into a micropipette tip used as a 50-μl sample. The observed potential stabilities, reproducibilities and detection limits were attractive and largely matched that for large 100-ml samples. This should pave the way for further experiments to detecting ultra-small total ion concentrations by potentiometry, especially when used as a transducer after an amplification step in bioanalysis.
This paper describes the recent progress in the development of polymeric membranes for ion-selective electrodes. The importance of knowing the mechanism of potential development in membranes for ion-selective electrodes to reach lower detection limits and improve selectivity are discussed. Recent advances and future trends of research on ion-selective electrodes are also reported.
We here report on the first example of an aptamer-based potentiometric sandwich assay of proteins. The measurements are based on CdS quantum dot labels of the secondary aptamer, which were determined with a novel solid-contact Cd2+-selective polymer membrane electrode after dissolution with hydrogen peroxide. The electrode exhibited cadmium ion detection limits of 100 pM in 100 mL samples and of 1 nM in 200 μL microwells, using a calcium-selective electrode as a pseudoreference electrode. As a prototype example, thrombin was measured in 200 μL samples with a lower detection limit of 0.14 nM corresponding to 28 fmol of analyte. The results show great promise for the potentiometric determination of proteins at very low concentrations in microliter samples.
The use of potentiometric microsensors is demonstrated here for the first time to detect DNA hybridization. Cadmium sulfide nanocrystal labels bound on a secondary oligonucleotide are dissolved and detected with cadmium-selective microelectrodes exhibiting DNA detectionlimits of ca. 2 fmol in a 200 μL sample.
Potentiometric sensors are today sufficiently well understood and optimized to reach ultratrace level (subnanomolar) detection limits for numerous ions. In many cases of practical relevance, however, a high electrolyte background hampers the attainable detection limits. A particularly difficult sample matrix for potentiometric detection is seawater, where the high saline concentration forms a major interfering background and reduces the activity of most trace metals by complexation. This paper describes for the first time a hyphenated system for the online electrochemically modulated preconcentration and matrix elimination of trace metals, combined with a downstream potentiometric detection with solid contact polymeric membrane ion-selective microelectrodes. Following the preconcentration at the bismuth-coated electrode, the deposited metals are oxidized and released to a medium favorable to potentiometric detection, in this case calcium nitrate. Matrix interferences arising from the saline sample medium are thus circumvented. This concept is successfully evaluated with cadmium as a model trace element and offers potentiometric detection down to low parts per billion levels in samples containing 0.5 M NaCl background electrolyte.
We demonstrate the first example of using potentiometry at ion-selective electrodes (ISEs) for probing in real-time monitoring of biometallization processes. A copper ISE is used for real-time monitoring of the NADH-mediated reduction of copper in the presence of gold nanoparticle seeds. Such potentiometric detection of NADH is not susceptible to surface fouling common with analogous amperometric measurements of this co-factor. Biosensing of ethanol is illustrated in the presence of alcohol dehydrogenase and NAD(+), along with potentiometric detection of the NADH product at the copper ISE. The concept can be readily expanded to the monitoring of various biometallization processes in connection to different enzymatic transformations and ISE, and used for ultrasensitive detection of bioaffinity interactions in connection to common enzyme tags.
An electrochemical protocol for real-time monitoring of drug release kinetics from therapeutic nanoparticles (NPs) is described. The method is illustrated for repetitive square-wave voltammetric measurements of the reduction of doxorubicin released from liposomes at a glassy-carbon electrode. Such operation couples high sensitivity down to 20 nM doxorubicin with high speed and stability. It can thus monitor in real time the drug release from NP carriers, including continuous measurements in diluted serum. Such direct and continuous monitoring of the drug release kinetics from therapeutic NPs holds great promise for designing new drug delivery NPs with optimal drug release properties. These NPs can potentially be used to deliver many novel compounds such as marine-life derived drugs and hydrophobic drugs with limited water solubility that are usually difficult to be characterized by traditional analytical tools.
Recent advances in ion-selective electrodes have pushed the detection limits of direct potentiometry to the nanomolar concentration range. Here we present a direct comparison of the sensitivity and selectivity of potentiometric and stripping-voltammetric measurements of cadmium and lead. While both techniques offer a similar sensitivity, the potentiometric method offers higher selectivity in the presence of excess of metal ions (e.g., thallium, tin) that commonly interfere in the stripping-voltammetric operation. Because of the complementary nature of the potentiometric and stripping-voltammetric methods, it is recommended that these techniques will be selected based on the specific analytical problem or used in parallel to provide additional analytical information.
This Communication demonstrates the ability of potentiometric ion-selective electrodes (ISE) to probe the growth dynamics of metal nanoparticles in real-time. The new monitoring capability is illustrated using a solid-contact silver ISE for monitoring the hydroquinone-induced precipitation of silver on gold nanoparticle seeds. Potential-time recordings obtained under different conditions are used to monitor the depletion of the silver ion during the nanoparticle formation and shed useful insights into the growth dynamics of the nanoparticles. Such potentiometric profiles correlate well with the analogous optical measurements. The new real-time electrochemical probing of the particle growth process reflects the direct, rapid and sensitive response of modern ISE to changes in the level of the precipitated metal ion from the bulk solution and holds considerable promise for probing the preparation of different nanoscale materials.