Design and performance of some microflow-cell potentiometric transducers

The paper presents and compares the design of three potentiometric transducers: ion-selective field effect transistor (ISFET), solid-state Ag/AgCl electrode and miniaturized classical Ag/AgCl electrode. The reported transducers were fabricated using different, less or more complicated and expensive, technologies. The transducers were constructed to be compatible with the sensor housing of the flow-cell, designed previously. Moreover, the back-side contact structures of the two planar devices, where electrical connectors and the sensing layer are on the opposite sides, facilitated their application in the flow analysis. Exemplary potassium-selective microsensors based on developed transducers were prepared, applying plasticized PVC and polysiloxane membranes containing valinomycine. The determined microsensor performances allowed comparison of their usefulness for multiparameter flow analysis.     

Towards advanced chemical microsensors-an overview

The paper presents design and performance of miniaturized chemical sensors based on silicon transducers: ion-sensitive field effect transistor (ISFET) and solid-state electrode (SSE). The sensors were fabricated as back-side contact structures, which facilitate their mounting in a flow-cell. The role of an intermediate layer between the transducer and the ion-selective membrane is discussed. Various polymeric matrices were used to manufacture microsensors: polysiloxanes, polyacrylates (polymethacrylates), polyurethanes.     

Screen-printed reference electrodes for potentiometric measurements

A convenient and reliable method for large-scale production of miniaturized, planar, all-solid-state reference electrodes is reported. All elements of the Ag/AgCl/KCl reference half-cell i.e. layer of Ag/AgCl (inner electrode), immobilized electrolyte (junction) and encapsulation are fabricated by means of screen-printing technology. The use of pastes cured in low temperature allows fabrication on low-cost, plastic, flexible foils. The developed reference electrodes exhibit good long-term stability. Continuous operation life-time exceeds one week. Storage stability is longer than 9 months. pH, chlorides as well as other halide anions, typical buffer components, alkaline and heavy metal cations, complexing ligands and redox agents, do not influence the potential of the reference electrodes. The developed reference electrodes are compatible with strip potentiometric sensors fabricated in the same format. Examples of analytical applications of the reference electrodes with various screen-printed sensors are demonstrated.     

The recognition of beer with flow-through sensor array based on miniaturized solid-state electrodes

Flow-through electronic tongue based on miniaturized solid-state potentiometric sensors has been developed. A simple technique, i.e. membrane solution casting on the surface of the planar Au transducers was applied for the preparation of classical ion-selective and partially selective microelectrodes, introduced in the flow-through sensor array. The performance of the designed electronic tongue was tested in the qualitative analysis of various brands of beer. Samples of the same brand of beer but with different manufacture dates, originating from different manufacture lots, have been applied in the studies. The combination of PLS and ANN techniques allowed the discrimination between different brands of beer with 83% of correct classifications.     

A Polymer-Based All-Solid-State Internal Reference System for pH Glass Electrodes – Performance and Charge Transfer

An all-solid-state internal reference system for pH glass electrodes employing polypyrrole (PPy)-Nafion® composites is described. pH sensors based on this reference system are characterised at 23±3°C. The observed characteristics of the resulting all-solid-state sensors, i.e. slope and linearity of the calibration plot, response behaviour, and signal stability, are very promising, and the differences with respect to the parameters of conventional liquid filled sensors are negligible. The values of the zero potential point, which differ from those of conventional pH glass electrodes, could be controlled within limits via the composition of the PPy-Nafion composite.The excellent sensor performance observed seems to be the consequence of a reversible charge transfer between the ion-conducting membrane, the mixed conducting PPy-Nafion interlayer, and the metal wire. A first discussion of the mechanism of this charge transfer is given.     

Effect of interferents present in the internal solution or in the conducting polymer transducer on the responses of ion-selective electrodes

The effect of interferents present on the opposite side of the Pb²⁺-selective membrane has been studied for both internal solution and all-solid-state sensors with a conducting polymer (CP) transducer. For interferents with moderate selectivity coefficients (sodium cations) present in the internal solution or in the CP transducer phase, super-Nernstian responses were obtained. For sensors containing strongly discriminated interferents (lithium ions), however, responses typical of conventional electrodes are observed, despite the low activity of primary ions on the opposite side of the membrane. This effect is attributed to hindered incorporation of interfering ions into the membrane, which also impairs the long term stability of the potential. Because of the relatively small absolute amounts of interferents in the transducer of all-solid-state sensors, their exchange for primary ions occurs quickly. Thus, transformation of the sensor to one with a micromolar detection limit and high potential stability is observed.      

All-solid-state reference electrodes based on conducting polymers

A novel construction of solution free (pseudo)reference electrodes, compatible with all-solid-state potentiometric indicator electrodes, has been proposed. These electrodes use conducting polymers (CP): polypyrrole (PPy) or poly(3,4-ethylenedioxythiophene) (PEDOT). Two different arrangements have been tested: solely based on CP and those where the CP phase is covered with a poly(vinyl chloride) based outer membrane of tailored composition. The former arrangement was designed to suppress or compensate cation- and anion-exchange, using mobile perchlorate ions and poly(4-styrenesulfonate) or dodecylbenzenesulfonate anions as immobilized dopants. The following systems were used: (i) polypyrrole layers doped simultaneously by two kinds of anions, both mobile and immobilized in the polymer layer; (ii) bilayers of polypyrrole with anion exchanging inner layer and cation-exchanging outer layer; (iii) polypyrrole doped by surfactant dodecylbenzenesulfonate ions, which inhibit ion exchange on the polymer/solution interface. For the above systems, recorded potentials have been found to be practically independent of electrolyte concentration. The best results, profound stability of potentials, have been obtained for poly(3,4-ethylenedioxythiophene) or polypyrrole doped by poly(4-styrenesulfonate) anions covered by a poly(vinyl chloride) based membrane, containing both anion- and cation-exchangers as well as solid potassium chloride and silver chloride with metallic silver. Differently to the cases (i)-(iii) these electrodes are much less sensitive to the influence of redox and pH interferences. This arrangement has been also characterized using electrochemical impedance spectroscopy and chronopotentiometry.     

Flow injection analysis of potassium using an all-solid-state potassium-selective electrode as a detector

The concentration of potassium was determined by a combination of flow injection analysis (FIA) with an all-solid-state potassium sensor detection. The all-solid-state potassium-selective electrode possessing long-term potential stability was fabricated by coating an electroactive polypyrrole/poly(4-styrenesulfonate) film electrode with a plasticized poly(vinyl chloride) membrane containing valinomycin. The simple FIA system developed in this laboratory demonstrated sensitivity identical to that in the batch system and achieved considerably rapid assay (150 samples h⁻¹). Analyses of soy sauce and control serum samples by this FIA system yielded results in good agreement with those obtained by conventional measurements.     

Element profiles in galvanostatically polarized K+-selective all-solid-state sensors with poly(vinyl chloride)-based membranes

The influence of galvanostatic polarization on ion concentration profiles in all-solid-state ion-selective sensors was studied. As a model system K⁺-selective electrode with poly(vinyl chloride)-based membrane, ionophore–valinomycin and polypyrrole doped by chloride ions as ion-to-electron transducer was selected. The ion exchanger—a typical component of ion-selective membrane—was replaced by lipophilic salt: tetradodecylammonium tetrakis(4-chlorophenyl) borate to avoid spontaneous extraction of potassium ions. Potassium, sodium, and chlorine distribution within the sensor phases were studied using laser ablation micro-sampling followed by inductively coupled plasma mass spectrometry measurements. The experiments revealed accumulation of potassium ions in course of cathodic galvanostatic polarization, with concentration decreasing by moving inside the ion-selective membrane. The surface content of K⁺ ions was found to be linearly dependent on applied current. Influence of sequential anodic galvanostatic polarization or open circuit conditioning applied after cathodic polarization revealed only limited recovery of the initial concentration profiles in the membrane.     

Chemical Reactivity of Polypyrrole and Its Relevance to Polypyrrole Based Electrochemical Sensors

One of the most frequently used conducting polymers, polypyrrole, can take part in chemical processes with typical components of ambient media: oxygen, acids, bases, redox reactants, water, and organic vapors; it can also incorporate nonreactive ions and surfactants from solutions. The influence of such processes on changes of the polymer structure, composition and on possible degradation is analyzed. The benefits and disadvantages of such processes for analytical characteristic of polypyrrole based electrochemical sensors are considered. This discussion is focused on potentiometric ion sensors, where polypyrrole is either a receptor membrane or an ion‐to‐electron transducer placed between a solid state electrode support and a typical ion‐selective membrane.     

Fabrication of bimetallic microfluidic surface-enhanced Raman scattering sensors on paper by screen printing

Au–Ag bimetallic microfluidic, dumbbell-shaped, surface enhanced Raman scattering (SERS) sensors were fabricated on cellulose paper by screen printing. These printed sensors rely on a sample droplet injection zone, and a SERS detection zone at either end of the dumbbell motif, fabricated by printing silver nanoparticles (Ag NPs) and gold nanoparticles (Au NPs) successively with microscale precision. The microfluidic channel was patterned using an insulating ink to connect these two zones and form a hydrophobic circuit. Owing to capillary action of paper in the millimeter-sized channels, the sensor could enable self-filtering of fluids to remove suspended particles within wastewater without pumping. This sensor also allows sensitive SERS detection, due to advantageous combination of the strong surface enhancement of Ag NPs and excellent chemical stability of Au NPs. The SERS performance of the sensors was investigated by employing the probe rhodamine 6G, a limit of detection (LOD) of 1.1 × 10⁻¹³ M and an enhancement factor of 8.6 × 10⁶ could be achieved. Moreover, the dumbbell-shaped bimetallic sensors exhibited good stability with SERS performance being maintained over 14 weeks in air, and high reproducibility with less than 15% variation in spot-to-spot SERS intensity. Using these dumbbell-shaped bimetallic sensors, substituted aromatic pollutants in wastewater samples could be quantitatively analyzed, which demonstrated their excellent capability for rapid trace pollutant detection in wastewater samples in the field without pre-separation.     

A novel hydrogen peroxide sensor based on Ag nanoparticles electrodeposited on chitosan-graphene oxide/cysteamine-modified gold electrode

A novel strategy to fabricate a hydrogen peroxide sensor based on Ag nanoparticles electrodeposited on chitosan-graphene oxide nanocomposites/cysteamine-modified gold (Au) electrode was reported. The chitosan-graphene oxide nanocomposites were first assembled on a cysteamine-modified Au electrode to produce chitosan-graphene oxide/cysteamine/Au electrode. Then Ag nanoparticles were electrodeposited on the modified Au electrode and formed Ag nanoparticles/chitosan-graphene oxide/cysteamine/Au electrode. The chitosan-graphene oxide nanocomposites and the electrodeposited Ag nanoparticles were characterized by atomic force microscopy and scanning electron microscopy. The results showed the Ag nanoparticles were uniformly dispersed on the chitosan-graphene oxide/cysteamine/Au electrode. The cyclic voltammagrams and amperometric method were used to evaluate electrocatalytic properties of the Ag nanoparticles/chitosan-graphene oxide/cysteamine/Au electrode. The results showed that the modified electrode displayed good electrocatalytic activity to the reduction of hydrogen peroxide with a detection limit of 0.7 μM hydrogen peroxide based on a signal-to-noise ratio of 3. The sensor has good reproducibility, wide linear range, and long-term stability.     

Ag@Au core/shell triangular nanoplates with dual enzyme-like properties for the colorimetric sensing of glucose

Due to the serious harm of diabetes to human health, development of sensitive assays for glucose level is of high significance for early prevention and treatment of diabetes. Currently, most conventional enzyme-based glucose sensors suffer from high cost and low stability due to the inherent defects of natural enzymes. Herein, we develop a pure nanozyme-based glucose detection method using Ag@Au core/shell triangular nanoplates (TNPs), which combines glucose oxidase (GOD)- and horseradish peroxidase (HRP)-like activities of the Au shell and inherent plasmonic properties of Ag TNPs. The sensing mechanism is based on the fact that the Au shell possessed GOD-like activity, enabling the oxidation of glucose to produce H₂O₂, which can further etch the silver core, leading to the decrease of absorbance at 800 nm and the color change from blue to colorless. Compared with the previous nanozymes-based glucose sensors, our method avoids the use of enzymes and organic chromogenic agent. Moreover, the stability of the Ag@Au core/shell TNPs is much better than that of Ag TNPs due to the protection by the coating of the Au shell. This method was successfully applied to the detection of urine samples from patients with diabetes, indicating its practical applicability for real sample analysis.     

AgI-Ag2O-V2O5 glasses as ion-to-electron transducers for the construction of all-solid-state microelectrodes

A method for the fabrication of ion-selective all-solid-state microelectrodes is presented. The ion-to-electron transduction process takes place into the transducer material. In this approach, AgI-Ag₂O-V₂O₅ glasses, which exhibit ionic and electrical conductivity are applied as ion-to-electron transducers of polymeric membrane microelectrodes. All-solid-state electrodes based on potassium-sensitive poly(vinyl chloride) membranes, deposited directly on the surface of glass composites, exhibited theoretical responses. Their selectivity and durability were comparable to planar microelectrodes containing an internal electrolyte immobilized in the intermediate hydrogel layer. The only disadvantage of the proposed structures was their limited reproducibility. Moreover, it was found that the unmodified AgI-Ag₂O-V₂O₅ glasses can be applied as ion-sensitive membrane of solid-state microelectrodes for the determination of Ag⁺ and I⁻ ions.     

Effect of dissolved CO2 on the potential stability of all-solid-state ion-selective electrodes.

The influence of dissolved CO2 on the potentiometric responses of all-solid-state ion-selective electrodes (ISEs) was systematically examined with four different types of electrodes fabricated by pairing pH-sensitive and pH-insensitive metal electrodes (Pt and Ag/AgCl, respectively) with pH-sensitive and pH-insensitive ion-selective membranes (H+-selective membrane based on tridodecylamine and Na+-selective membrane based on tetraethyl calix[4]arenetetraacetate, respectively). The experimental results clearly showed that the carbonic acid formed by the diffused CO2 and water vapor at the membrane/metal electrode interface varies the phase boundary potentials both at the inner side of the H+-selective membrane (deltaE(in)mem) and at the metal electrode surface (deltaEelec). The potential changes, deltaE(in)mem and deltaEelec, occurring at the facing boundaries, are opposite in their sign and result in a canceling effect if both the membrane and metal surface are pH-sensitive. Consequently, the H+-selective membrane coated on a pH-sensitive electrode (Pt) tends to exhibit a smaller CO2 interference than that on a pH-insensitive electrode (Ag/AgCl). When the all-solid-state Na+ and K+ ISEs were fabricated with both pH-insensitive metal electrode and ion-selective membrane, they did not suffer from CO2 interference. It was also confirmed that plasticization of the PVC leads to increased CO2 permeation. Various types of intermediate layers were examined to reduce the CO2 interference problem in the fabrication of H+-selective all-solid-state ISEs. The results indicated that the H+-selective electrode needs an intermediate layer that maintains a constant pH unless the carbonic acid formation at the interfacial area is effectively quenched.     

Planar micro sensors for in vivo myocardial pH measurements

Potentiometric responses of microelectronically fabricated planar pH sensors based on both TDDA or ETH 5294 proton neutral carriers, in aminated PVC matrix, were evaluated with respect to main analytical parameters (linear ranges, slopes, reproducibility of potential measurements, potential drift and membrane resistance). In order to increase the electrode life time, increased amounts of membrane material were applied on the Ag/AgCl-poly-HEMA active spots of the polyimide substrate. The electrodes were implanted into an in situ porcine beating heart preparation at a midmyocardial depth in order to monitor H(+) concentration changes during the course of coronary artery occlusion.     

Ion-Selective Microchemical Sensors with Reduced Preconditioning Time. Membrane Biostability Studies and Applications in Blood Analysis

Abstract

Progress on solution of two general problems regarding the use of in vivo planar microchemical sensors is reported. These are issues of short term and long term response stability. Reduction of preconditioning time (hydration period), i.e., the time needed by the planar microchemical sensors based on Kapton® substrate to achieve the optimal analytical performances, has been achieved. By storing the electrodes in containers with humid atmospheres (100% humidity) their short time responses, e.g. measured potential, when placed in samples to be analyzed, are practically constant after one minute of immersion. The electrode sensitivity, potential reproducibility and membrane resistance of both pH and K⁺ sensors were evaluated and compared before and after placing them in whole blood samples for specified periods of time. Blood serum samples were successfully assayed and the results compared with those obtained with a pH glass electrode and a blood gas analyzer, respectively. The long term stability of the membranes for in vivo use was investigated by determination of cell adhesion and membrane biostability (at 14 days of subcutaneous implantation in rats) using scanning electron microscopy.     

A new calcium-sensor based on ion-selective conductometric microsensors - membranes and features

Based on the concept of ion-selective conductometric microsensors (ISCOM) a new calcium sensor was developed and characterized. ISCOM have a single probe, all-solid-state construction and do not need a reference electrode. These sensors are amenable to miniaturization and integration in the true sense of integrated circuit and microsystem technologies. The detection is accomplished by measurement of the bulk conductance Gm of a thin polymeric membrane containing an ion-complexing agent, where the magnitude of Gm can be related to the content of the primary ion in the analyzed solution. Thin-film platinum electrodes forming an interdigitated electrode are used as the transducer to detect the conductivity of the polymeric membrane. Optimization of the membrane composition was carried out by testing different types of calcium-ionophores, polymers, and plasticizers. The sensor characteristics have been investigated. The limit of detection is about 10(-7) mol L(-1). The dynamic range is 10(-6)-10(-1) mol L(-1) with a response time of less than 5 s. These parameters are comparable to those of corresponding potentiometric calcium selective electrodes (ISE). The Ca(2+)-ISCOM demonstrates good practical relevant selectivities against typical interfering ions for biomedical and environmental applications.     

Raman scattering of 4-aminobenzenethiol sandwiched between Ag nanoparticle and macroscopically smooth Au substrate: effects of size of Ag nanoparticles and the excitation wavelength

A nanogap formed by a metal nanoparticle and a flat metal substrate is one kind of "hot site" for surface-enhanced Raman scattering (SERS). Accordingly, although no Raman signal is observable when 4-aminobenzenethiol (4-ABT), for instance, is self-assembled on a flat Au substrate, a distinct spectrum is obtained when Ag or Au nanoparticles are adsorbed on the pendent amine groups of 4-ABT. This is definitely due to the electromagnetic coupling between the localized surface plasmon of Ag or Au nanoparticle with the surface plasmon polariton of the planar Au substrate, allowing an intense electric field to be induced in the gap even by visible light. To appreciate the Raman scattering enhancement and also to seek the optimal condition for SERS at the nanogap, we have thoroughly examined the size effect of Ag nanoparticles, along with the excitation wavelength dependence, by assembling 4-ABT between planar Au and a variable-size Ag nanoparticle (from 20- to 80-nm in diameter). Regarding the size dependence, a higher Raman signal was observed when larger Ag nanoparticles were attached onto 4-ABT, irrespective of the excitation wavelength. Regarding the excitation wavelength, the highest Raman signal was measured at 568 nm excitation, slightly larger than that at 632.8 nm excitation. The Raman signal measured at 514.5 and 488 nm excitation was an order of magnitude weaker than that at 568 nm excitation, in agreement with the finite-difference time domain simulation. It is noteworthy that placing an Au nanoparticle on 4-ABT, instead of an Ag nanoparticle, the enhancement at the 568 nm excitation was several tens of times weaker than that at the 632.8 nm excitation, suggesting the importance of the localized surface plasmon resonance of the Ag nanoparticles for an effective coupling with the surface plasmon polariton of the planar Au substrate to induce a very intense electric field at the nanogap.     

Narrow pore-diameter polypyrrole nanotubes

Bulk quantities of electrically conducting nanotubes of polypyrrole having narrow pore diameter (6 nm) can be synthesized rapidly by chemical oxidative polymerization of pyrrole in the presence of stoichiometric amounts of V2O5 nanofibers. The V2O5 nanofibers act as templates for polymerization and yield, as the initial product, polypyrrole nanotubes with pores filled with V2O5. The V2O5 dissolves readily in aq. 1.0 M HCl, yielding hollow polypyrrole nanotubes having conductivity of approximately 2 S/cm. As-synthesized polypyrrole nanotubes spontaneously reduce noble metal ions to the corresponding metal nanoparticles at room temperature without any capping or dispersing agents. For example, 3-5 nm size nanoparticles of Ag, Au, and Pd, etc., deposit readily on the surface of the tubes which then migrate spontaneously to the pore, and, in the case of Ag, coalesce in the core, yielding 4-8 nm diameter coaxial cables of Ag surrounded by a 20-30 nm thick polypyrrole fiber sheath.