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Eric Bakker

Publications and source records attributed to Eric Bakker.

At least 19 recordsLinked to original sources
PubMed2006

Potentiometry at trace levels in confined samples: ion-selective electrodes with subfemtomole detection limits.

We explore here for the first time the direct potentiometric detectability of calcium, lead, and silver ions in amounts on the order of 300 attomoles at 100 picomolar concentrations without any preconcentration, analyte recycling, or electrocatalytic signal enhancement. The results presented here place zero-current potentiometry among the most sensitive electrochemical methods available.

Calcium↗
PubMed2006

Calcium pulstrodes with 10-fold enhanced sensitivity for measurements in the physiological concentration range.

Ion-selective electrodes ideally operate on the basis of the Nernst equation, which predicts less than 60- and 30-mV potential change for a 10-fold activity change of monovalent and divalent ions measured at room temperature, respectively. Typical concentration ranges in extracellular fluids are quite narrow for the electrolytes of key importance. A range of 2.2-2.6 mM for calcium ions, for instance, translates into just a 2.2-mV potential change. The direct potentiometric measurement of physiological electrolytes is certainly possible with direct potentiometry and is done routinely in clinical analyzers and handheld measuring devices. It places, however, strong demands on the precision of the reference electrode and requires careful temperature control and frequent calibration runs. In this paper, a robust 10-20-fold sensitivity enhancement for calcium measurements is attained by departing from the classical response mechanism and operating in a non-Nernstian response mode. Stable and reproducible super-Nernstian responses of these so-called pulstrodes in a narrow calcium activity range can be controlled by instrumental means in good agreement with theory. The potentials may be measured during a galvanostatic excitation pulse (mode I) or immediately after it (mode II), under open-circuit conditions. Subtraction of the potentials, sampled at different times during a single pulse, allows one to obtain a sensitive differential peak-shaped signal at a critical and fully adjustable analyte activity range. Calcium pulstrodes based on the diamide ionophore AU-1 were characterized and applied to the measurement in model physiological liquids. Super-Nernstian responses exceeding 700 mV/decade were observed in a physiological range of calcium concentration. Such remarkable sensitivity of the pulstrodes, complemented with the well-documented high selectivity of these potentiometric sensors, may provide a significant increase in the accuracy and precision of electrolyte measurements in clinical analysis.

Biosensing Techniques↗
PubMed2006

Solid contact potentiometric sensors for trace level measurements.

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 x 10(-9) M), potassium (10(-7) M), and iodide (10(-8) M) are presented. The developed electrodes exhibited a good response time and excellent reproducibility.

Calibration↗
PubMed2005

Ion-selective supported liquid membranes placed under steady-state diffusion control.

Supported liquid membranes are used here to establish steady-state concentration profiles across ion-selective membranes rapidly and reproducibly. This opens up new avenues in the area of nonequilibrium potentiometry, where reproducible accumulation and depletion processes at ion-selective membranes may be used to gain valuable analytical information about the sample. Until today, drifting signals originating from a slowly developing concentration profile across the ion-selective membrane made such approaches impractical in zero current potentiometry. Here, calcium- and silver-selective membranes were placed between two identical aqueous electrolyte solutions, and the open circuit potential was monitored upon changing the composition of one solution. Steady state was reached in approximately 1 min with 25-microm porous polypropylene membranes filled with bis(2-ethylhexyl) sebacate doped with ionophore and lipophilic ion exchanger. Ion transport across the membrane resulted on the basis of nonsymmetric ion-exchange processes at both membrane sides. The steady-state potential was calculated as the sum of the two membrane phase boundary potentials, and good correspondence to experiment was observed. Concentration polarizations in the contacting aqueous phases were confirmed with stirring experiments. It was found that interferences (barium in the case of calcium electrodes and potassium with silver electrodes) induce a larger potential change than expected with the Nicolsky equation because they influence the level of polarization of the primary ion (calcium or silver) that remains potential determining.

Diffusion↗
PubMed2005

Response characteristics of a reversible electrochemical sensor for the polyion protamine.

We describe here in detail the first reversible electrochemical sensors for the polyion protamine. Potentiometric sensors were proposed in recent years, mainly for the determination of the polyions heparin and protamine. Such potentiometric polyion sensors functioned on the nonequilibrium extraction of polyions into a hydrophobic membrane phase via ion pairing with lipophilic ion exchangers. This made it difficult to design sensors that operate in a truly reversible fashion. The reversible sensors described here utilize the same basic response mechanism as their potentiometric counterparts, but the processes of extraction and ion stripping are now fully controlled electrochemically. Spontaneous polyion extraction is avoided by using membranes containing highly lipophilic electrolytes that possess no ion-exchange properties. Reversible extraction of polyions is induced if a constant current pulse of fixed duration is applied across the membrane, followed by a baseline potential pulse. The key theoretical response principles of this new class of polyion sensors are discussed here and compared to those of its classical potentiometric counterpart. The electrochemical sensing system is characterized in terms of optimal working conditions, membrane composition, selectivity, and influence of sample stirring and organic-phase diffusion coefficient on the response characteristics. Excellent potential stability and reversibility of the sensors are observed, and measurements of heparin concentration in whole blood samples via protamine titration are demonstrated.

Biosensing Techniques↗
PubMed2005

Fiber-optic microsensor array based on fluorescent bulk optode microspheres for the trace analysis of silver ions.

An optical microsensor array is described for the rapid analysis of silver ions at low parts per trillion levels. Because the ionophore o-xylylenebis(N,N-diisobutyldithiocarbamate) (Cu-I) was reevaluated and shown to exhibit excellent selectivity for silver ions, ion-selective electrode (ISE) membranes were optimized and found to exhibit the lowest reported detection limit so far (3 x 10(-10) M). A corresponding Ag+-selective fluorescent optical microsensor array for the rapid sensing of trace level Ag+ was then developed. It was fabricated using plasticized PVC-based micrometer-scale fluorescent microspheres that were produced via a sonic particle casting device. They contained 156 mmol/kg Cu-I, 10 mmol/kg 9-(diethylamino)-5-[4-(15-butyl-1,13-dioxo-2,14-dioxanodecyl) phenylimino]benzo[a]phenoxazine (chromoionophore VII, ETH 5418), 2.3 mmol/kg 1,1' '-dioctadecyl-3,3,3',3'-tetramethylindocarbocyanine perchlorate (internal reference dye), and 14 mmol/kg sodium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate and were deposited onto the etched distal end of a 3200-microm-diameter optical fiber bundle. The microarray was characterized by fluorescence spectroscopy in samples containing 10(-12)-10(-8) M AgNO3 at pH 7.4, with selectivity characteristics comparable to the corresponding ISEs. The response time of the microsensor array was found to be less than 15 min for 10(-9) M AgNO3, which is drastically shorter than earlier data on optode films (8 h) and corresponding ISEs (30 min). A detection limit of 4 x 10(-11) M for Ag+ was observed, lower than any previously reported optode or silver-selective ISE. The microsensor array was applied for measurement of free silver levels in buffered pond water samples.

Calibration↗
PubMed2005

Potentiometric sensors for trace-level analysis.

This review summarizes recent progress in the development and application of potentiometric sensors with limits of detection (LODs) in the range 10(-8)-10(-11) M. These LODs relate to total sample concentrations and are defined according to a definition unique to potentiometric sensors. LODs calculated according to traditional protocols (three times the standard deviation of the noise) yield values that are two orders of magnitude lower. We are targeting this article at analytical chemists who are non-specialists in the development of such sensors so that this technology may be adopted by a growing number of research groups to solve real-world analytical problems.We discuss the unique response features of potentiometric sensors and compare them to other analytical techniques, emphasizing that the choice of the method must depend on the problem of interest. We discuss recent directions in sensor design and development and present a list of 23 sensors with low LODs, with references. We give recent examples where potentiometric sensors have been used to solve trace-level analytical problems, including the speciation of lead and copper ions in drinking water, the measurement of free copper in sea water, and the uptake of cadmium ions by plant roots as a function of their speciation.

Journal Article↗
PubMed2005

Shifting the Measuring Range of Chloride Selective Electrodes and Optodes Based on the Anticrown Ionophore [9]Mercuracarborand-3 by the Addition of 1-Decanethiol.

Ion-selective electrodes and optodes based on the anticrown ionophore mercuracarborand-3 (MC-3) exhibit excellent selectivity to halide ions but suffer from a low upper detection limit because of very strong complexation in the sensing phase. In this work, we have successfully improved the upper detection limit and widened the working range of chloride selective electrode based on MC-3 by introducing 1-decanethiol into the membrane cocktail. With an assumed 1:2 stoichiometry between chloride and MC-3 the apparent complex formation constant was reduced from log beta = 13.4 as reported for the membrane without the addition of 1-decanethiol to log beta = 12.13, log beta = 10.84 and log beta = 5.67 with the addition of a 1:1, 1:2 and 1:4 molar ratio of 1-decanethiol to MC-3. Besides these values, obtained with the sandwich membrane method, similar shifts in the measuring range of thin optode film responses to lower chloride concentrations were observed as well. The selectivity of the modified membrane was found to be very good, with hydroxide and the other halides: bromide and iodide, as the main interferences. Based on these results, corresponding iodide selective electrodes were prepared that showed a near-Nernstian iodide slope, rather than a cationic slope as observed without thiol additive.Jonoselektywne elektrody i optody stosujace antykoronowy jonofor [9]merkuracarborand-3 (MC-3) charakteryzuja sie doskonała selektywnościa w stosunku do jonów halogenków lecz wskutek silnego kompleksowania w fazie receptora maja ograniczony zakres górnej granicy oznaczalności. W przedstawionej pracy poszerzono zakres stosowalności dzieki wprowadzeniu 1-dekanotiolu do membrany zawierajacej MC-3. Przy załozonej stechiometrii kompleksu chlorek-MC-3 równej 1:2 stała tworzenia kompleksu została obnizona, z wartości log beta = 13,4 (w przypadku membrany bez dodatku 1-dekanotiolu) do wartości log beta = 12,13; log beta = 10,84 i log beta = 5,67 (po dodaniu 1-dekanotiolu) dla stosunków molowych stezeń-1-dekanotiol:MC-3 wynoszacych odpowiednio 1:1, 1:2 i 1:4. Ponadto oprócz tych danych otrzymanych metoda warstwowej membrany, podobne przesuniecie zakresu pomiarowego obserwowano w przypadku małych stezeń chlorków dla cienkowarstwowej optody. Selektywnoś ć modyfikowanej membrany była dobra, przy czym głównymi interferentami były jony bromkowe, jodkowe i wodorotlenkowe. W oparciu o te wyniki skonstruowano elektrode czuła na jony jodkowe, charakteryzujaca sie nachyleniem anionowym charakterystyki bliskim Nernstowskiemu, a nie kationowym wykazywanym w nieobecności tiolu.

Journal Article↗
PubMed2004

Dynamic diffusion model for tracing the real-time potential response of polymeric membrane ion-selective electrodes.

A numerical solution for the prediction of the time-dependent potential response of a polymeric-based ion-selective electrode (ISE) is presented. The model addresses short- and middle-term potential drifts that are dependent on changes in concentration gradients in the aqueous sample and organic membrane phase. This work has important implications for the understanding of the real-time response behavior of potentiometric sensors with low detection limits and with nonclassical super-Nernstian response slopes. As a model system, the initial exposure of membranes containing the well-examined silver ionophore O,O' '-bis[2-(methylthio)ethyl]-tert-butylcalix[4]arene was monitored, and the large observed potential drifts were compared to theoretical predictions. The model is based on an approximate solution of the diffusion equation for both aqueous and organic diffusion layers using a numerical scheme (finite difference in time and finite elements in space). The model may be evaluated on the basis of experimentally available parameters and gives time-dependent information previously inaccessible with a simpler steady-state diffusion model. For the cases studied, the model gave a very good correlation with experimental data, albeit with lower than expected diffusion coefficients for the organic phase. This model may address numerous open questions regarding the response time and memory effects of low-detection-limit ion-selective electrodes and for other membrane electrodes where ion fluxes are relevant.

Diffusion↗
PubMed2004

Pulstrodes: triple pulse control of potentiometric sensors.

Ion-selective electrode membranes based on hydrophobic materials doped with chemically selective host molecules are an attractive sensing technology but normally suffer from a limited sensitivity, given by the Nernst equation, and a direct reliance on the reference electrode potential, which makes miniaturization difficult. These fundamental problems are addressed here by imposing a multipulse electrochemical excitation signal onto ion-selective membranes that lack ion-exchange properties. Current pulses are responsible for the generation of ion fluxes in the direction of the membrane, which give reproducible super-Nernstian response slopes that originate from depletion processes at the membrane surface. Membranes may also be measured at zero current after this pulse, giving super-Nernstian response regions at lower concentrations. Difference potentials obtained from subsequent pulses give about 10-fold higher sensitivities than predicted on the basis of the Nernst equation.

Biosensing Techniques↗
PubMed2004

Elimination of dimer formation in InIIIporphyrin-based anion-selective membranes by covalent attachment of the ionophore.

The spontaneous hydroxy-bridged dimer formation of metalloporphyrins in ion-selective membranes gives rise to a short sensor lifetime (typically days), triggered by solubility problems, the occurrence of a super-Nernstian response slope, and a pH cross response. This dimer formation is eliminated here by covalent attachment of the ionophore to the polymer matrix. Specifically, two different indium(III)porphyrins containing polymerizable groups, the chloride-selective chloro(3-[18-(3-acryloyloxypropyl)-7,12-bis(1-methoxyethyl)-3,8,13,17-tetramethylporphyrin-2-yl]propyl ester)indium(III) and the nitrite-selective Chloro(5-(4-acryloyloxyphenyl)-10,15,20-triphenylporphyrinato)indium(III), were synthesized and copolymerized with methyl methacrylate and decyl methacrylate. The covalent attachment of the ionophore to the polymer matrix indeed prevents the metalloporphyrin from forming dimeric species, as confirmed by UV/visible spectroscopy. The ion-selective membranes with grafted indium porphyrin showed Nernstian response slopes to chloride, nitrite, perchlorate, and thiocyanate anions, with a selectivity comparable to membranes with freely dissolved or underivatized metalloporphyrin. The membranes containing grafted ionophores showed a lifetime of at least two months, apparently since crystallization of the poorly soluble dimeric species may no longer occur. This is one of the first examples where the covalent attachment of an ionophore drastically improves on a number of important sensor characteristics.

Dimerization↗
PubMed2003

Rotating disk potentiometry for inner solution optimization of low-detection-limit ion-selective electrodes.

The extent of optimization of the lower detection limit of ion-selective electrodes (ISEs) can be assessed with an elegant new method. At the detection limit (i.e., in the absence of primary ions in the sample), one can observe a reproducible change in the membrane potential upon alteration of the aqueous diffusion layer thickness. This stir effect is predicted to depend on the composition of the inner solution, which is known to influence the lower detection limit of the potentiometric sensor dramatically. For an optimized electrode, the stir effect is calculated to be exactly one-half the value of the case when substantial coextraction occurs at the inner membrane side. In contrast, there is no stir effect when substantial ion exchange occurs at the inner membrane side. Consequently, this experimental method can be used to determine how well the inner filling solution has been optimized. A rotating disk electrode was used in this study because it provides adequate control of the aqueous diffusion layer thickness. Various ion-selective membranes with a variety of inner solutions that gave different calculated concentrations of the complex at the inner membrane side were studied to evaluate this principle. They contained the well-examined silver ionophore O,O' '-bis[2-(methylthio)ethyl]-tert-butylcalix[4]arene, the potassium ionophore valinomycin, or the iodide carrier [9]mercuracarborand-3. Stir effects were determined in different background solutions and compared to theoretical expectations. Correlations were good, and the results encourage the use of such stir-effect measurements to optimize ISE compositions for real-world applications. The technique was also found to be useful in estimating the level of primary ion impurities in the sample. For an iodide-selective electrode measured in phosphoric acid, for example, apparent iodide impurity levels were calculated as 5 x 10(-10) M.

Ion-Selective Electrodes↗
PubMed2003

A copolymerized dodecacarborane anion as covalently attached cation exchanger in ion-selective sensors.

The traditional cation exchangers used in ion-selective electrodes and optodes are tetraphenylborate derivatives, which are generally adequate for most analytical applications but may in some cases suffer from decomposition by acid hydrolysis, oxidants, and light. Recently, halogenated dodecacarboranes were found to be improved cation exchangers in terms of lipophilicity and chemical stability. This forms the basis for the convenient covalent attachment of the cation exchanger to the polymeric backbone of the sensing material. This is a challenge that has not satisfactorily been solved and which is especially important in view of developing ultraminiaturized sensing arrays. Here, a C-derivative of the closo-dodecacarborane anion (CB(11)H(12)(-)) with a polymerizable group was synthesized as a chemically stable cation exchanger. This new derivative was copolymerized with methyl methacrylate and decyl methacrylate (MMA-DMA) to fabricate a plasticizer-free polymer with cation-exchange properties. This polymer could be conveniently blended with traditional plasticized poly(vinyl chloride) or with noncrosslinked methacrylic polymers to give solvent cast films that appear to be clear and homogeneous and that could be doped with ionophores. Optode leaching experiments supported the covalent grafting of the carborane anions. Ion-selective membranes and optode thin films were evaluated in terms of response function, response time, and selectivity. In all cases, the new material exhibited behavior similar to free tetraphenylborate derivative-based membranes. As a result of these studies, an all-polymeric plasticizer-free calcium-selective membrane was fabricated on the basis of the covalently attached carborane, a recently introduced grafted calcium ionophore, and an MMA-DMA polymer matrix. The resulting ion-selective electrodes showed Nernstian response slopes and rapid response times, demonstrating that covalent grafting of all sensing components is a feasible approach to the development of ion sensors.

Algorithms↗
PubMed2003

Reversible electrochemical detection of nonelectroactive polyions.

Selective extraction principles for the recognition of nonelectroactive polyions such as heparin and protamine exist, but the high ionic valency renders the extraction process irreversible. A response principle for the reversible detection of such polyions is proposed here. The extraction of the polyionic analyte to the membrane and its subsequent back-extraction is now controlled electrochemically. The principle is established with a protamine electrode, and excellent stability and reproducibility are demonstrated. This method has important implications for the design of chemical recognition principles for polyionic analytes.

Calibration↗
PubMed2003

Pulsed galvanostatic control of ionophore-based polymeric ion sensors.

This paper describes a pulsed galvanostatic technique to interrogate ion-selective electrodes (ISEs) with no intrinsic ion-exchange properties. Each applied current pulse is followed by a longer baseline potential pulse to regenerate the phase boundary region of the ion-selective membrane. The applied current fully controls the magnitude and sign of the ion flux into the membrane, thus offering instrumental control over an effect that has become very important in ion-selective electrode research in recent years. The resulting chronopotentiometric response curves essentially mimic traditional ISE behavior, with apparently Nernstian response slopes and selectivities that can be described with the Nicolsky equation. Additionally, the magnitude and sign of the current pulse may be used to tune sensor selectivity. Perhaps most important, however, appears to be the finding that the extent of concentration polarization near the membrane surface can be accurately controlled by this technique. A growing number of potentiometric techniques are starting to make use of nonequilibrium principles, and the method introduced here may prove to be very useful to advance these areas of research. The basic characteristics of this pulsed galvanostatic technique are here evaluated with plasticized poly(vinyl chloride) membranes containing the sodium-selective ionophore tert-butyl calix[4]arene tetramethyl ester and a lipophilic inert salt.

Electric Conductivity↗