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Sensor Issues

Can Calibration-Free Sensors Be Realized?
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Department of Inorganic and Analytical Chemistry, University of Geneva, Quai E.-Ansermet 30, 1211 Geneva 4, Switzerland
*E-mail: [email protected]
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ACS Sensors

Cite this: ACS Sens. 2016, 1, 7, 838–841
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https://doi.org/10.1021/acssensors.6b00247
Published June 22, 2016

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Abstract

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This opinion piece describes progress and issues regarding the realization of calibration-free chemical sensors for analysis in aqueous systems. A special focus of the discussion is on electrochemical methodologies, given that they are the most established. Calibration-free sensors are clearly possible, but require a multipronged approach for maximizing robustness that include the optimization of sensing materials and the use of the most adequate readout methodologies.

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A long lasting focus of modern chemical sensor research has been to move the measurement out of the traditional laboratory and as close as possible to the site of interest. Indeed, clinical measurements of key blood parameters are today routinely performed at the point of care. Glucose measurements are achieved by millions of people in the comfort of their own home with hand-held electrochemical biosensor devices. Remote environmental sensing is today a reality, even though the number of accessible analytes is still limited.
The promise for a chemical sensor to work autonomously for long periods of time, without the need for sample preparation and without (re)calibration, remains a key selling point for research in this area. Recent work has aimed at realizing very low cost, paper-based sensing systems that can be put into the hands of low skilled operators while maintaining meaningful results. (1) In the environmental sensing area, an important direction has been the development of large, autonomously operating sensor networks that provide a real time chemical map to visualize environmental contaminations and for the localization of plumes. (2)
Only if chemical sensors can operate with the ease and robustness demanded by the application will these directions truly become successful and have the potential to have a significant impact to our world. In this context, calibration-free sensors are primarily understood as being maintenance-free, i.e., comprising a sufficiently robust system that can be precalibrated in the factory, and used as is. This opinion piece focuses on the issues regarding calibration-free chemical sensors, with a special focus on electrochemical methodologies, since this is where most progress has historically been made.

What Error Can One Tolerate?

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The question of the required out of the box accuracy of different sensor systems must be answered by the anticipated analytical problem. An environmental contamination might increase the basal concentration by many orders of magnitude, depending on incident and type of released chemical. Moreover, the readout of a large sensor network benefits from knowledge of the behavior of neighboring sensors and of the time evolution of the signal, which can all be used to distinguish random fluctuations from an event that can be traced across numerous sensor points. (3) Calibration requirements are clearly less stringent with such systems.
For glucose biosensors, the target range for diabetic patients is 4.0–9.0 mM, about a factor 2 in concentration, while glucose test strips should be able to measure in the range of 1–30 mM. The measure of success with glucose sensors is the location of a point on an Clarke Error Grid, and therefore concentration dependent, but an error of less than 20% is typically considered acceptable. (4)
On the other hand, the normal range for blood electrolytes is much narrower, for potassium 3.5–5.0 mM, a 43% change in concentration, and for sodium 136–145 mM, a mere 7% change. (5) As explained in a recent review on clinical diagnostics of electrolytes, (5) a measurement must distinguish the electrolyte level sufficiently to allow for a meaningful diagnosis.

A Challenging Case Study: Clinical Diagnostics of Blood Electrolytes

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Given the above numbers, arguably the most challenging routine analytical sensing application in terms of required precision and accuracy is the assessment of blood electrolytes. Clinical analyzers achieve the required analytical figures of merit by careful termperature control and frequent intermittent washing and one point calibration steps and are automated, but not maintenance or calibration-free.
An early study by Rumpf et al. demonstrated the absolute measurement of potassium and sodium levels in serum by ion-selective electrodes using a highly symmetrical measurement cell; see Figure 1. (6) The authors did not achieve a maintenance-free measurement, since high flow rates of the reference electrolyte and intermittent cleaning steps were required to renew the two reference electrodes and the side of the sensing membrane exposed to the biological fluids. But measurements without prior calibration were demonstrated, with errors of 0.02 mM for potassium and 1.4 mM for sodium (tolerable errors: 0.10 and 0.5 mM, respectively). Indeed, the signal from a symmetrical cell containing a reference solution of known composition carries information and can be considered an internal one step calibration.

Figure 1

Figure 1. Symmetrical measuring cell for the sensing of potassium and sodium ions in undiluted serum without prior calibration. (6) Two reference electrodes with free-flowing liquid junctions were used in this arrangement. While this approach was not maintenance-free, a residual error of just a fraction of a millivolt was found.

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This sensing approach is similar to the Kodak Ektachem electrolyte sensor (today the Johnson & Johnson Vitros system), (7) which uses thick film technology in a highly symmetrical arrangement where the signal is generated from applying the sample and a reference solution to the chip. Recent work on paper based ion-selective electrodes equally aimed to use a cell of high symmetry in which the sample and a reference solution were applied to two different zones on the paper (no interdevice repeatabilities were reported). (1) In other work, mass fabricated all solid state ion sensors have been shown to give out of the box reproducibilities of just 0.2 mV at millimolar sample concentrations (2b) and demonstrating “fit for purpose” environmental trace detection as well, (8) suggesting that these systems can be batch calibrated.
While this looks great, adsorption and surface fouling by biological, macromolecular and chemical constituents of the sample are today still major practical limitation to achieve maintenance-free sensors that are free of signal drift. (5) Important efforts in materials durability and compatibility with complex samples have been achieved, for example with hydrophilic surface coatings (9) and nitric oxide release strategies for active biocompatibility control on appropriate sensing materials. (10)
Unfortunately, liquid junction reference electrodes are fundamentally unattractive choices for achieving maintenance-free electrochemical sensors. Recently, important progress has been made in introducing fundamentally sound reference elements that no longer require a liquid junction, which tends to be the major source of error in potentiometric experiments. While not yet established in clinical diagnostics applications, a most promising candidate appears to be based on Kakiuchi’s ionic liquid reference electrode. (11) Rather than relying on a liquid junction potential between the sample and a salt solution, the potential at this film is based on equilibrium partitioning of an ionic liquid between the film and the sample. Buhlmann has recently explored this new type of reference electrode in paper based electrochemical sensing devices with promising results. (1) The future will show whether this exciting direction will eventually result in sensors with dramatically improved robustness.

Increasing Robustness with Enzyme Biosensors

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But what about amperometric chemical sensors, such as enzyme biosensors? Enzymes denature over time, and moreover, any direct contact of electrodes with complex samples is known to result in surface fouling. It is possible to achieve adequate robustness by controlling the rate limiting step and minimizing electrode fouling. With enzyme biosensors, a diffusion limiting membrane is placed between enzyme layer and sample. (12) Besides helping to achieve adequate selectivity, the resulting current remains diffusion limited at all times and even a substantial loss of enzyme activity will not result in a deterioration of the signal. The membrane also serves to protect the active electrode surface from direct contact with the sample and hence minimizes fouling. Today, amperometric glucose sensors are mass fabricated and a subset of the sensor strips factory calibrated to describe the response of the entire batch. (4)
Direct film coatings onto electrodes (without enzyme) may also result in robust amperometric sensors for the detection of electrically neutral drug molecules (such as propofol) that can easily partition into a hydrophobic film and react at the underlying electrode, (13) although calibration-free sensors were not the aim of the study.
As typical polymeric permeation membranes exclude ionic and bulky interferences, antifouling coatings for the electrochemical detection of ionic analytes must follow alternative strategies. For example, hydrogel coatings have been demonstrated to be attractive in this regard since they act as size exclusion membranes to keep macromolecular and colloidal interferences away from the membrane. (14) As they are less effective as diffusion limiting membranes, thicker coatings (hundreds of micrometers) are needed to ensure that the ions are sourced from within the gel during measurement, thereby minimizing effects of mass transport fluctuations in the contacting sample. Note that low molecular weight interferences (such as surfactants) may still permeate across the gel and can therefore result in chemical interference and/or electrode fouling.

Using Robust Methodologies: From Amperometry to Coulometry

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Still, further progress will likely remain limited if one continues to use detection principles that are highly sensitive to chemical changes of the sensing surface. Despite the important advances described above, amperometry is an inherently kinetic technique and the signal remains very sensitive to fluctuations in temperature and other processes that influence the kinetics of the rate limiting step. On the other hand, direct potentiometry gives a signal that is dependent on the logarithm of the ion activity change, which places important demands on the tolerable error in potential. Let us therefore step back in time to the 1830s with Michael Faraday, who in an electrolysis experiment measured the mass of deposited metal and the corresponding amount of charge. (15) The latter was measured by the volume of gas (hydrogen or oxygen, depending on the direction of current flow) produced from an acidified water solution (the so-called volta-electrometer, later voltameter or coulometer). This allowed him, without prior calibration, to relate amount (number of moles) to the charge passed across the cell, which formed the basis for Faraday’s first law of electrolysis (the second law simply states that chemical and electrochemical equivalences are the same). This was an alternative and infinitely more elegant manner of determining the molar mass of metals than the laborious procedures developed earlier by Berzelius. Sadly, Berzelius did not appear capable of understanding Faraday’s approach and apparently made sure to use his influence to suppress its acceptance within the wider scientific community during his lifetime.
We realize now that Faraday’s early experiments were very close in spirit to today’s aspirations by the sensor community for simple, low cost devices that show an easily visualized analog signal (here, volume of produced gas or mass of plated metal) and that require no calibration (by using coulometry)!
Indeed, conceptual improvements of glucose biosensors, while allowing for a significant reduction in sample size, have been achieved with an exhaustive, coulometric sensing mode. (16) If the sample glucose level can be quantitatively and selectively depleted by the biosensor, the current may be integrated to give total charge, which is related to the amount of analyte by Faraday’s law. To reduce analysis time, the sample layer thickness should normally not exceed that of the diffusion layer (typically less than 100 μm). If, and only if, the entire current can be ascribed to the reaction of interest (excellent selectivity and nearly 100% coulometric efficiency) and the sample volume is fixed by a suitable microfluidic channel, one may achieve a calibration-free sensor.
Can such a device still be called a sensor? Perhaps not in the strictest sense, since the sample solution is altered by the measurement. But if this perturbation involves only a very small portion of the total sample that can easily be replenished by diffusion or fluidic delivery, perturbation is no more severe than with other amperometric sensors where the composition of the diffusion layer close to the electrode is altered in a similar way.
A thin layer coulometric glucose biosensor (FreeStyle) by Abbott/Therasens is commercially established and requires a sample volume of just 300 nL. (16) A subcutaneously implantable glucose monitoring system has also been developed based on the technology, although a calibration step is here still required to correct for matrix effects.
Coulometric sensors with thin layer sample layers are also promising for the detection of ionic species. In one recent example, shown in Figure 2, the three halides chloride, bromide and iodide were detected with high precision by exhaustive oxidative plating onto a silver electrode. (17) The thin layer sample was defined by the space between the silver electrode and a Donnan exclusion cation-exchange membrane, outside of which was an electrolyte solution and the reference/counter electrode. Interdevice reproducibility was found to be 2.5% (N = 6), even though the cells were made by hand. Note that a comparable reproducibility in direct potentiometry would need to ensure variations of less than 0.5 and 0.3 mV for monovalent and divalent ions, respectively. This is already quite difficult.

Figure 2

Figure 2. Thin layer coulometric halide detection as a more robust readout principle compared to potentiometry. Top: experimental arrangement and relevant reactions. (17) Shown here is the exhaustive anodic deposition of chloride onto a silver element, while the countercation migrates across a Donnan exclusion cation-exchange membrane into the outer solution. There, reduction at the counter electrode results in a dissolution of halide ions. Bottom: when interrogated with a linear potential sweep at an appropriate scan rate, the integrated current gives the total charge, which is translated to concentration with Faraday’s law.

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One can also make use of the coulometric thin layer sample concept to electrochemically deliver ions. This may result in a family of sensing concepts that essentially behave the same way as volumetric titrations, but without the hassle of taking aliquots, preparing standards and doing the volumetric delivery. In one such recent example, a total alkalinity sensor was developed that delivers hydrogen ions by electrochemical control across a pH responsive polymeric membrane of high mobility. (18) A pH probe placed directly opposite across the thin layer sample gap of ca. 100 μm measures the resulting pH. No pumps or moving parts were required to achieve this coulometric alkalinity probe. While the interdevice reproducibility for this system has not yet been rigorously characterized, mass fabrication should result in excellent repeatabilities, as demonstrated by the earlier work of van der Schoot et al., (19) who developed a dynamically operating alkalinity probe that was fully mass produced.

Conclusions and Outlook

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Recent years have seen significant progress with optimized materials and methodologies to make maintenance-free electrochemical sensors a real possibility. In many instances, the recording of fluctuations with time, or the identification of point sources with large arrays are more important than absolute values, which places lesser requirements on the accuracy of sensor outputs. In all cases, however, one must ask: what is the intended application? Obviously, a sensor should be evaluated in view of that application, using adequate materials that are compatible with the matrix of interest. Moreover, there exist analytical methodologies, such as exhaustive coulometry, that are inherently more robust than others. This should be taken into account from the start of the research to achieve the important goal of sensors that no longer need to be calibrated in the field. This is in fact the answer to the question of what error can one tolerate? In all cases the answer is, the system must be as good as required and only that good!

Author Information

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  • Corresponding Author
    • Eric Bakker - Department of Inorganic and Analytical Chemistry, University of Geneva, Quai E.-Ansermet 30, 1211 Geneva 4, Switzerland;  Email: [email protected]
    • Notes
      The authors declare no competing financial interest.

    Acknowledgment

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    The author thanks the Swiss National Science Foundation and the European Union (FP7-GA 614002-SCHeMA project).

    References

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    This article references 19 other publications.

    1. 1
      Hu, J.; Ho, K. T.; Zou, X. U.; Smyrl, W. H.; Stein, A.; Buhlmann, P. All-Solid-State Reference Electrodes Based on Colloid-Imprinted Mesoporous Carbon and Their Application in Disposable Paper- based Potentiometric Sensing Devices Anal. Chem. 2015, 87, 2981– 2987 DOI: 10.1021/ac504556s
      Google Scholar
      There is no corresponding record for this reference.
    2. 2
      (a) Cantor, R. S.; Ishida, H.; Janata, J. Sensing Array for Coherence Analysis of Modulated Aquatic Chemical Plumes Anal. Chem. 2008, 80 (4) 1012– 1018 DOI: 10.1021/ac701880w
      Google Scholar
      There is no corresponding record for this reference.
      (b) Radu, A.; Anastasova, S.; Fay, C.; Diamond, D.; Bobacka, J.; Lewenstam, A. Low Cost, Calibration-Free Sensors for In Situ Determination of Natural Water Pollution Sensors 2010 IEEE 2010, 1487– 1490 DOI: 10.1109/ICSENS.2010.5690357
      Google Scholar
      There is no corresponding record for this reference.
    3. 3
      Nakamoto, T.; Ishida, H. Chemical Sensing in Spatial/Temporal Domains Chem. Rev. 2008, 108, 680– 704 DOI: 10.1021/cr068117e
      Google Scholar
      3
      Chemical sensing in spatial/temporal domains
      Nakamoto, Takamichi; Ishida, Hiroshi
      Chemical Reviews (Washington, DC, United States) (2008), 108 (2), 680-704CODEN: CHREAY; ISSN:0009-2665. (American Chemical Society)
      A review. In this paper, the authors described the aspect of chem. sensing in spatial and time domains and then reviewed the sensing related to both domains. Although sensing technol. for chem. signals is not matured in comparison with that for phys. signals, that technol. is gradually proceeding. In the study of spatial domain, the gas distribution can be measured using a homogeneous sensor array. Two types of sensor arrays, such as sparse and packed sensor arrays, are available. The sparse sensor array can show the global behavior of the plume, whereas the packed one reveals the local detailed behavior of the plume. The optical method is also useful to obtain the plume image. An attempt to make the plume generated in a virtual environment, where people perceive sensory stimuli even if they do not stay in the actual environment, is also introduced. Next, a signal in time domain is described. Since the temporal information sometimes includes useful information for discriminating among the vapors, the technique to know the sensor dynamics such as time const. is studied. Frequency anal. is helpful when the useful information is hidden in the temporal data changing irregularly due to the turbulence. Then the sensing in both spatial and time domains is described. The straightforward method to understand the combination of both domains is to observe change in spatial distribution with time. Another approach is to see the correlation of signal features in time domain with several locations. The frequency anal. of the signals also provides us with useful information about an odor-source location. It is an important task for us to fully understand the plume behavior in both spatial and time domains and to establish the measurement method of capturing its behavior. Moreover, a sensor dynamics model is required because a sensor response does not follow the speed of the plume change. A systematic approach including algorithms will become more important as well as the improvement of chem.-sensor capability itself. The current technol. is not sufficient to find the toxic or explosive substance immediately. However, the appropriate combination of sensors with signal-processing techniques will make this a field in progress.
      >> More from SciFinder ®
      https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD1cXhtVaisLw%253D&md5=bae7c2b788ee31d927d63fb52db7d46f
    4. 4
      Heller, A.; Feldman, B. Electrochemical Glucose Sensors and Their Applications in Diabetes Management Chem. Rev. 2008, 108, 2482– 2505 DOI: 10.1021/cr068069y
      Google Scholar
      4
      Electrochemical Glucose Sensors and Their Applications in Diabetes Management
      Heller, Adam; Feldman, Ben
      Chemical Reviews (Washington, DC, United States) (2008), 108 (7), 2482-2505CODEN: CHREAY; ISSN:0009-2665. (American Chemical Society)
      A review with major subsections entitled Scope, Roots and Fundamentals, Electrochem. Monitoring of the Glucose Concn. by Its GOx [glucose oxidase]-Catalyzed O2-Oxidn., Central Lab. and Desktop Glucose-Analyzers, Home Blood-Glucose Monitors Used by Self-Monitoring Diabetic People, and Diabetes Management Based on Frequent or Continuous Amperometric Monitoring of Glucose.
      >> More from SciFinder ®
      https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD1cXls1Skt7g%253D&md5=5bb7a9aa6916509bb19bfe51a7e8df1d
    5. 5
      Lewenstam, A. Routines and Challenges in Clinical Application of Electrochemical Ion-Sensors Electroanalysis 2014, 26, 1171– 1181 DOI: 10.1002/elan.201400061
      Google Scholar
      5
      Routines and Challenges in Clinical Application of Electrochemical Ion-Sensors
      Lewenstam, Andrzej
      Electroanalysis (2014), 26 (6), 1171-1181CODEN: ELANEU; ISSN:1040-0397. (Wiley-VCH Verlag GmbH & Co. KGaA)
      A review. This review provides information on application of potentiometric ion-sensors in routine clin. anal. The text comprises sensor design, way-of-use, conventions and practical recommendations, and elements of IS response theory. An instrument producer point of view, based on direct industrial involvement of the author, is emphasized.
      >> More from SciFinder ®
      https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2cXmtVCnsbg%253D&md5=4e258632aeb8cfce8b7c408dcd7fdeee
    6. 6
      Rumpf, G.; Spichiger-Keller, U.; Bühler, H.; Simon, W. Calibration-Free Measurement of Sodium and Potassium in Undiluted Serum with an Electrically Symmetric Measuring System Anal. Sci. 1992, 8, 553– 559 DOI: 10.2116/analsci.8.553
      Google Scholar
      6
      Calibration-free measurement of sodium and potassium in undiluted human serum with an electrically symmetric measuring system
      Rumpf, G.; Spichiger-Keller, U.; Buehler, H.; Simon, W.
      Analytical Sciences (1992), 8 (4), 553-9CODEN: ANSCEN; ISSN:0910-6340.
      The limitations of ion-selective electrodes (ISEs) presently in use mainly concern the stability of the calibration values. By applying optimal membrane technols. and optimized ref. electrodes, a perfectly sym. measuring system including a sym. ISE membrane was developed. Thus, stable std. potentials of the cell assembly, both before and after serum contact, as well as theor. slopes of the electrode response were obtained. Results of calibration-free assays of K+ and Na+ concns. in aq. calibration solns. and in undild. human serum are presented. The precision required is fully met for K+ measurements in aq. solns. and in sera of the normal as well as pathol. concn. range. In addn., the precision of Na+ assays in aq. calibration solns. and in serum samples of the normal concn. range is close to the required values.
      >> More from SciFinder ®
      https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaK38XlsVKns7o%253D&md5=b8c7a64750ff53002e598ece2287e7c5
    7. 7
      Curme, H.; Rand, R. N. Early history of Eastman Kodak Ektachem Slides and Instrumentation Clin. Chem. 1997, 43 (9) 1647– 1652
      Google Scholar
      7
      Early history of Eastman Kodak Ektachem slides and instrumentation
      Curme, Henry; Rand, Royden N.
      Clinical Chemistry (Washington, D. C.) (1997), 43 (9), 1647-1652CODEN: CLCHAU; ISSN:0009-9147. (American Association for Clinical Chemistry)
      The early history of Eastman Kodak Ektachem slides and instrumentation is described, beginning in 1970.
      >> More from SciFinder ®
      https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaK2sXmtVyitLg%253D&md5=8b5f3ff52e6fe43becaa48c5386ec93c
    8. 8
      Anastasova, S.; Radu, A.; Matzeu, G.; Zuliani, C.; Mattinen, U.; Bobacka, J.; Diamond, D. Disposable Solid-Contact Ion-Selective electrodes for Environmental Monitoring of Lead with ppb Limit-of-Detection Electrochim. Acta 2012, 73, 93– 97 DOI: 10.1016/j.electacta.2011.10.089
      Google Scholar
      There is no corresponding record for this reference.
    9. 9
      Pawlak, M.; Grygolowicz-Pawlak, E.; Crespo, G. A.; Mistlberger, G.; Bakker, E. PVC-based Ion-Selective Electrodes with Enhanced Biocompatibility by Surface Modification with ″Click″ Chemistry Electroanalysis 2013, 25, 1840– 1846 DOI: 10.1002/elan.201300212
      Google Scholar
      There is no corresponding record for this reference.
    10. 10
      Ren, H.; Coughlin, M. A.; Major, T. C.; Aiello, S.; Rojas Pena, A.; Bartlett, R. H.; Meyerhoff, M. E. Improved in Vivo Performance of Amperometric Oxygen (PO2) Sensing Catheters via Electrochemical Nitric Oxide Generation/Release Anal. Chem. 2015, 87 (16) 8067– 8072 DOI: 10.1021/acs.analchem.5b01590
      Google Scholar
      There is no corresponding record for this reference.
    11. 11
      Zhang, L.; Miyazawa, T.; Kitazumi, Y.; Kakiuchi, T. Ionic Liquid Salt Bridge with Low Solubility of Water and Stable Liquid Junction Potential Based on a Mixture of a Potential-Determining Salt and a Highly Hydrophobic Ionic Liquid Anal. Chem. 2012, 84 (7) 3461– 3464 DOI: 10.1021/ac203425u
      Google Scholar
      There is no corresponding record for this reference.
    12. 12
      Chen, T.; Friedman, K. A.; Lei, I.; Heller, A. In Situ Assembled Mass-Transport Controlling Micromembranes and Their Application in Implanted Amperometric Glucose Sensors Anal. Chem. 2000, 72 (16) 3757– 3763 DOI: 10.1021/ac000348c
      Google Scholar
      12
      In Situ Assembled Mass-Transport Controlling Micromembranes and Their Application in Implanted Amperometric Glucose Sensors
      Chen, Ting; Friedman, Keith A.; Lei, Ian; Heller, Adam
      Analytical Chemistry (2000), 72 (16), 3757-3763CODEN: ANCHAM; ISSN:0003-2700. (American Chemical Society)
      Micromembranes were assembled by sequentially chemisorbing polyanions and polycations on miniature (5 × 10-4 cm2) enzyme electrodes. The sequential chemisorption process allowed the simultaneous tailoring of their sensitivity, dynamic range, drift, and selectivity. When assembled on tips of 250-μm-diam. gold wires coated with redox polymer-"wired" glucose oxidase, they allowed tailoring of the glucose electrodes for >2 nA/mM sensitivity; 0-30 mM dynamic range; drift of ≤5% per 24 h at 37 °C at 15 mM glucose concn.; and ≤5% current increment by the combination of 0.1 mM ascorbate, 0.2 mM acetaminophen, and 0.5 mM urate. The membranes also retained transition metal ions that bound to and damaged the redox polymer "wiring" the enzyme. The electrodes were tested in the jugular veins and in the intrascapular s.c. region of anesthetized and heparinized nondiabetic Sprague-Dawley rats, in which rapid changes of glycemia were forced by i.v. injections of glucose and insulin. After one-point in vivo calibration of the electrodes, all of the 152 data points were clin. accurate when it was assumed that after insulin injection the glycemia in the s.c. fluid lags by 9 min behind that of blood withdrawn from the insulin-injected vein.
      >> More from SciFinder ®
      https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD3cXks1ehtr0%253D&md5=73ff0531d1ad07b4ee0d6834dfeccb65
    13. 13
      Kivlehan, F.; Chaum, E.; Lindner, E. Propofol Detection and Quantification in Human Blood: the Promise of Feedback Controlled, Closed-Loop Anesthesia Analyst 2015, 140, 98– 106 DOI: 10.1039/C4AN01483A
      Google Scholar
      There is no corresponding record for this reference.
    14. 14
      Tercier-Waeber, M.-L.; Confalonieri, F.; Koudelka-Hep, M.; Dessureault-Rompré, J.; Graziottin, F.; Buffle, J. Gel-Integrated Voltammetric Microsensors and Submersible Probes as Reliable Tools for Environmental Trace Metal Analysis and Speciation Electroanalysis 2008, 20, 240– 258 DOI: 10.1002/elan.200704067
      Google Scholar
      14
      Gel-integrated voltammetric microsensors and submersible probes as reliable tools for environmental trace metal analysis and speciation
      Tercier-Waeber, Mary-Lou; Confalonieri, Fabio; Koudelka-Hep, Milena; Dessureault-Rompre, Jacynthe; Graziottin, Flavio; Buffle, Jacques
      Electroanalysis (2008), 20 (3), 240-258CODEN: ELANEU; ISSN:1040-0397. (Wiley-VCH Verlag GmbH & Co. KGaA)
      This article gives a review of the anal. and environmental criteria which must be considered and the relevant specific developments needed for direct, reliable voltammetric measurements of trace metal speciation in environmental systems. In particular, this article will focus on the tools which enable remote, long-term in situ measurements. The development of such tools is a challenging task. The strategies that can be used to achieve this goal are described for the development of innovative and versatile gel-integrated voltammetric microsensors, micro-/mini-integrated anal. systems, and submersible probes. The advantages of these new tools with respect to selectivity, sensitivity, reliability, spatial and temporal resoln. of data, and thus efficient environmental monitoring of the biogeochem. cycle of trace metals are demonstrated by providing examples of measurements made in various aquatic samples in lab. (water, soils, solid-liq. interface) and in situ in fresh and seawaters.
      >> More from SciFinder ®
      https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD1cXkvVyls7Y%253D&md5=27887476279f47b2ce8605fa26e3555a
    15. 15
      Ehl, R. G.; Ihde, A. J. Faraday’s Electrochemical Laws and the Determination of Equivalent Weights J. Chem. Educ. 1954, 31, 226– 232 DOI: 10.1021/ed031p226
      Google Scholar
      15
      Faraday's electrochemical laws and the determination of equivalent weights
      Ehl, Rosemary G.; Ihde, Aaron J.
      Journal of Chemical Education (1954), 31 (), 226-32CODEN: JCEDA8; ISSN:0021-9584.
      Historical.
      >> More from SciFinder ®
      https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaG2cXktFWktg%253D%253D&md5=9a4e9e9b545f1cc5b8e1313048391aab
    16. 16
      Heller, A.; Feldman, B. Electrochemistry in Diabetes Management Acc. Chem. Res. 2010, 43, 963– 973 DOI: 10.1021/ar9002015
      Google Scholar
      16
      Electrochemistry in Diabetes Management
      Heller, Adam; Feldman, Ben
      Accounts of Chemical Research (2010), 43 (7), 963-973CODEN: ACHRE4; ISSN:0001-4842. (American Chemical Society)
      A review. In this Account, the authors describe the founding of TheraSense, now a major part of Abbott Diabetes Care, and the development of two products that have improved the lives of people with diabetes. The first, a virtually painless microcoulometer (300 nL vol.), the FreeStyle blood glucose monitoring system, was approved by the FDA and became available in 2000. In 2009, this system was used in more than one billion blood assays. The second, the enzyme-wiring based, s.c.-implanted FreeStyle Navigator continuous glucose monitoring system, was approved by the FDA and became available in the United States in 2008. The strips of the FreeStyle blood glucose monitoring system comprise a printed parallel plate coulometer, with a 50 μm gap between two facing printed electrodes, a carbon electrode and a Ag/AgCl electrode.
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    17. 17
      Cuartero, M.; Crespo, G. A.; Ghahraman Afshar, M.; Bakker, E. Exhaustive Thin-Layer Cyclic Voltammetry for Absolute Multianalyte Halide Detection Anal. Chem. 2014, 86, 11387– 11395 DOI: 10.1021/ac503344f
      Google Scholar
      17
      Exhaustive Thin-Layer Cyclic Voltammetry for Absolute Multianalyte Halide Detection
      Cuartero, Maria; Crespo, Gaston A.; Ghahraman Afshar, Majid; Bakker, Eric
      Analytical Chemistry (Washington, DC, United States) (2014), 86 (22), 11387-11395CODEN: ANCHAM; ISSN:0003-2700. (American Chemical Society)
      Water anal. is one of the greatest challenges in the field of environmental anal. In particular, seawater anal. is often difficult because a large amt. of NaCl may mask the detn. of other ions, i.e., nutrients, halides, and carbonate species. The authors demonstrate here the use of thin-layer samples controlled by cyclic voltammetry to analyze water samples for chloride, bromide, and iodide. The fabrication of a microfluidic electrochem. cell based on a Ag/AgX wire (working electrode) inserted into a tubular Nafion membrane is described, which confines the sample soln. layer to <15 μm. By increasing the applied potential, halide ions present in the thin-layer sample (X-) are electrodeposited on the working electrode as AgX, while their resp. counterions are transported across the perm-selective membrane to an outer soln. Thin-layer cyclic voltammetry allows one to obtain sepd. peaks in mixed samples of these three halides, finding a linear relation between the halide concn. and the corresponding peak area from ∼10-5 to 0.1M for bromide and iodide and from 10-4 to 0.6M for chloride. This technique was successfully applied for the halide anal. in tap, mineral, and river water as well as seawater. The proposed methodol. is abs. and potentially calibration-free, as evidenced by an obsd. 2.5% relative std. deviation cell to cell reproducibility and independence from the operating temp.
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    18. 18
      Ghahraman Afshar, M.; Crespo, G. A.; Bakker, E. Thin-Layer Chemical Modulations by a Combined Selective Proton Pump and pH Probe for Direct Alkalinity Detection Angew. Chem. 2015, 127, 8228– 8231 DOI: 10.1002/ange.201500797
      Google Scholar
      There is no corresponding record for this reference.
    19. 19
      van der Schoot, B.; van der Wal, P.; de Rooij, N.; West, S. Titration-on-a-Chip, Chemical Sensor–Actuator Systems from Idea to Commercial Product Sens. Actuators, B 2005, 105, 88– 95 DOI: 10.1016/j.snb.2004.02.058
      Google Scholar
      19
      Titration-on-a-chip, chemical sensor-actuator systems from idea to commercial product
      van der Schoot, Bart; van der Wal, Peter; de Rooij, Nico; West, Steve
      Sensors and Actuators, B: Chemical (2005), 105 (1), 88-95CODEN: SABCEB; ISSN:0925-4005. (Elsevier B.V.)
      A review. The earliest reports of integrated chem. sensor-actuator devices to perform coulometric acid-base titrns. date back almost 20 years. Recently a first com. instrument appeared that allows to perform very rapid, accurate acid-base detns. with a solid-state probe and no need for liq. titrants. This paper reviews some of the early developments and shows the effort that was undertaken to bring this technol. to routine use in the anal. lab. and beyond.
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    • Abstract

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      Figure 1

      Figure 1. Symmetrical measuring cell for the sensing of potassium and sodium ions in undiluted serum without prior calibration. (6) Two reference electrodes with free-flowing liquid junctions were used in this arrangement. While this approach was not maintenance-free, a residual error of just a fraction of a millivolt was found.

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      Figure 2

      Figure 2. Thin layer coulometric halide detection as a more robust readout principle compared to potentiometry. Top: experimental arrangement and relevant reactions. (17) Shown here is the exhaustive anodic deposition of chloride onto a silver element, while the countercation migrates across a Donnan exclusion cation-exchange membrane into the outer solution. There, reduction at the counter electrode results in a dissolution of halide ions. Bottom: when interrogated with a linear potential sweep at an appropriate scan rate, the integrated current gives the total charge, which is translated to concentration with Faraday’s law.

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    • References

      This article references 19 other publications.

      1. 1
        Hu, J.; Ho, K. T.; Zou, X. U.; Smyrl, W. H.; Stein, A.; Buhlmann, P. All-Solid-State Reference Electrodes Based on Colloid-Imprinted Mesoporous Carbon and Their Application in Disposable Paper- based Potentiometric Sensing Devices Anal. Chem. 2015, 87, 2981– 2987 DOI: 10.1021/ac504556s
        There is no corresponding record for this reference.
      2. 2
        (a) Cantor, R. S.; Ishida, H.; Janata, J. Sensing Array for Coherence Analysis of Modulated Aquatic Chemical Plumes Anal. Chem. 2008, 80 (4) 1012– 1018 DOI: 10.1021/ac701880w
        There is no corresponding record for this reference.
        (b) Radu, A.; Anastasova, S.; Fay, C.; Diamond, D.; Bobacka, J.; Lewenstam, A. Low Cost, Calibration-Free Sensors for In Situ Determination of Natural Water Pollution Sensors 2010 IEEE 2010, 1487– 1490 DOI: 10.1109/ICSENS.2010.5690357
        There is no corresponding record for this reference.
      3. 3
        Nakamoto, T.; Ishida, H. Chemical Sensing in Spatial/Temporal Domains Chem. Rev. 2008, 108, 680– 704 DOI: 10.1021/cr068117e
        3
        Chemical sensing in spatial/temporal domains
        Nakamoto, Takamichi; Ishida, Hiroshi
        Chemical Reviews (Washington, DC, United States) (2008), 108 (2), 680-704CODEN: CHREAY; ISSN:0009-2665. (American Chemical Society)
        A review. In this paper, the authors described the aspect of chem. sensing in spatial and time domains and then reviewed the sensing related to both domains. Although sensing technol. for chem. signals is not matured in comparison with that for phys. signals, that technol. is gradually proceeding. In the study of spatial domain, the gas distribution can be measured using a homogeneous sensor array. Two types of sensor arrays, such as sparse and packed sensor arrays, are available. The sparse sensor array can show the global behavior of the plume, whereas the packed one reveals the local detailed behavior of the plume. The optical method is also useful to obtain the plume image. An attempt to make the plume generated in a virtual environment, where people perceive sensory stimuli even if they do not stay in the actual environment, is also introduced. Next, a signal in time domain is described. Since the temporal information sometimes includes useful information for discriminating among the vapors, the technique to know the sensor dynamics such as time const. is studied. Frequency anal. is helpful when the useful information is hidden in the temporal data changing irregularly due to the turbulence. Then the sensing in both spatial and time domains is described. The straightforward method to understand the combination of both domains is to observe change in spatial distribution with time. Another approach is to see the correlation of signal features in time domain with several locations. The frequency anal. of the signals also provides us with useful information about an odor-source location. It is an important task for us to fully understand the plume behavior in both spatial and time domains and to establish the measurement method of capturing its behavior. Moreover, a sensor dynamics model is required because a sensor response does not follow the speed of the plume change. A systematic approach including algorithms will become more important as well as the improvement of chem.-sensor capability itself. The current technol. is not sufficient to find the toxic or explosive substance immediately. However, the appropriate combination of sensors with signal-processing techniques will make this a field in progress.
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      4. 4
        Heller, A.; Feldman, B. Electrochemical Glucose Sensors and Their Applications in Diabetes Management Chem. Rev. 2008, 108, 2482– 2505 DOI: 10.1021/cr068069y
        4
        Electrochemical Glucose Sensors and Their Applications in Diabetes Management
        Heller, Adam; Feldman, Ben
        Chemical Reviews (Washington, DC, United States) (2008), 108 (7), 2482-2505CODEN: CHREAY; ISSN:0009-2665. (American Chemical Society)
        A review with major subsections entitled Scope, Roots and Fundamentals, Electrochem. Monitoring of the Glucose Concn. by Its GOx [glucose oxidase]-Catalyzed O2-Oxidn., Central Lab. and Desktop Glucose-Analyzers, Home Blood-Glucose Monitors Used by Self-Monitoring Diabetic People, and Diabetes Management Based on Frequent or Continuous Amperometric Monitoring of Glucose.
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      5. 5
        Lewenstam, A. Routines and Challenges in Clinical Application of Electrochemical Ion-Sensors Electroanalysis 2014, 26, 1171– 1181 DOI: 10.1002/elan.201400061
        5
        Routines and Challenges in Clinical Application of Electrochemical Ion-Sensors
        Lewenstam, Andrzej
        Electroanalysis (2014), 26 (6), 1171-1181CODEN: ELANEU; ISSN:1040-0397. (Wiley-VCH Verlag GmbH & Co. KGaA)
        A review. This review provides information on application of potentiometric ion-sensors in routine clin. anal. The text comprises sensor design, way-of-use, conventions and practical recommendations, and elements of IS response theory. An instrument producer point of view, based on direct industrial involvement of the author, is emphasized.
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      6. 6
        Rumpf, G.; Spichiger-Keller, U.; Bühler, H.; Simon, W. Calibration-Free Measurement of Sodium and Potassium in Undiluted Serum with an Electrically Symmetric Measuring System Anal. Sci. 1992, 8, 553– 559 DOI: 10.2116/analsci.8.553
        6
        Calibration-free measurement of sodium and potassium in undiluted human serum with an electrically symmetric measuring system
        Rumpf, G.; Spichiger-Keller, U.; Buehler, H.; Simon, W.
        Analytical Sciences (1992), 8 (4), 553-9CODEN: ANSCEN; ISSN:0910-6340.
        The limitations of ion-selective electrodes (ISEs) presently in use mainly concern the stability of the calibration values. By applying optimal membrane technols. and optimized ref. electrodes, a perfectly sym. measuring system including a sym. ISE membrane was developed. Thus, stable std. potentials of the cell assembly, both before and after serum contact, as well as theor. slopes of the electrode response were obtained. Results of calibration-free assays of K+ and Na+ concns. in aq. calibration solns. and in undild. human serum are presented. The precision required is fully met for K+ measurements in aq. solns. and in sera of the normal as well as pathol. concn. range. In addn., the precision of Na+ assays in aq. calibration solns. and in serum samples of the normal concn. range is close to the required values.
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      7. 7
        Curme, H.; Rand, R. N. Early history of Eastman Kodak Ektachem Slides and Instrumentation Clin. Chem. 1997, 43 (9) 1647– 1652
        7
        Early history of Eastman Kodak Ektachem slides and instrumentation
        Curme, Henry; Rand, Royden N.
        Clinical Chemistry (Washington, D. C.) (1997), 43 (9), 1647-1652CODEN: CLCHAU; ISSN:0009-9147. (American Association for Clinical Chemistry)
        The early history of Eastman Kodak Ektachem slides and instrumentation is described, beginning in 1970.
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      8. 8
        Anastasova, S.; Radu, A.; Matzeu, G.; Zuliani, C.; Mattinen, U.; Bobacka, J.; Diamond, D. Disposable Solid-Contact Ion-Selective electrodes for Environmental Monitoring of Lead with ppb Limit-of-Detection Electrochim. Acta 2012, 73, 93– 97 DOI: 10.1016/j.electacta.2011.10.089
        There is no corresponding record for this reference.
      9. 9
        Pawlak, M.; Grygolowicz-Pawlak, E.; Crespo, G. A.; Mistlberger, G.; Bakker, E. PVC-based Ion-Selective Electrodes with Enhanced Biocompatibility by Surface Modification with ″Click″ Chemistry Electroanalysis 2013, 25, 1840– 1846 DOI: 10.1002/elan.201300212
        There is no corresponding record for this reference.
      10. 10
        Ren, H.; Coughlin, M. A.; Major, T. C.; Aiello, S.; Rojas Pena, A.; Bartlett, R. H.; Meyerhoff, M. E. Improved in Vivo Performance of Amperometric Oxygen (PO2) Sensing Catheters via Electrochemical Nitric Oxide Generation/Release Anal. Chem. 2015, 87 (16) 8067– 8072 DOI: 10.1021/acs.analchem.5b01590
        There is no corresponding record for this reference.
      11. 11
        Zhang, L.; Miyazawa, T.; Kitazumi, Y.; Kakiuchi, T. Ionic Liquid Salt Bridge with Low Solubility of Water and Stable Liquid Junction Potential Based on a Mixture of a Potential-Determining Salt and a Highly Hydrophobic Ionic Liquid Anal. Chem. 2012, 84 (7) 3461– 3464 DOI: 10.1021/ac203425u
        There is no corresponding record for this reference.
      12. 12
        Chen, T.; Friedman, K. A.; Lei, I.; Heller, A. In Situ Assembled Mass-Transport Controlling Micromembranes and Their Application in Implanted Amperometric Glucose Sensors Anal. Chem. 2000, 72 (16) 3757– 3763 DOI: 10.1021/ac000348c
        12
        In Situ Assembled Mass-Transport Controlling Micromembranes and Their Application in Implanted Amperometric Glucose Sensors
        Chen, Ting; Friedman, Keith A.; Lei, Ian; Heller, Adam
        Analytical Chemistry (2000), 72 (16), 3757-3763CODEN: ANCHAM; ISSN:0003-2700. (American Chemical Society)
        Micromembranes were assembled by sequentially chemisorbing polyanions and polycations on miniature (5 × 10-4 cm2) enzyme electrodes. The sequential chemisorption process allowed the simultaneous tailoring of their sensitivity, dynamic range, drift, and selectivity. When assembled on tips of 250-μm-diam. gold wires coated with redox polymer-"wired" glucose oxidase, they allowed tailoring of the glucose electrodes for >2 nA/mM sensitivity; 0-30 mM dynamic range; drift of ≤5% per 24 h at 37 °C at 15 mM glucose concn.; and ≤5% current increment by the combination of 0.1 mM ascorbate, 0.2 mM acetaminophen, and 0.5 mM urate. The membranes also retained transition metal ions that bound to and damaged the redox polymer "wiring" the enzyme. The electrodes were tested in the jugular veins and in the intrascapular s.c. region of anesthetized and heparinized nondiabetic Sprague-Dawley rats, in which rapid changes of glycemia were forced by i.v. injections of glucose and insulin. After one-point in vivo calibration of the electrodes, all of the 152 data points were clin. accurate when it was assumed that after insulin injection the glycemia in the s.c. fluid lags by 9 min behind that of blood withdrawn from the insulin-injected vein.
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      13. 13
        Kivlehan, F.; Chaum, E.; Lindner, E. Propofol Detection and Quantification in Human Blood: the Promise of Feedback Controlled, Closed-Loop Anesthesia Analyst 2015, 140, 98– 106 DOI: 10.1039/C4AN01483A
        There is no corresponding record for this reference.
      14. 14
        Tercier-Waeber, M.-L.; Confalonieri, F.; Koudelka-Hep, M.; Dessureault-Rompré, J.; Graziottin, F.; Buffle, J. Gel-Integrated Voltammetric Microsensors and Submersible Probes as Reliable Tools for Environmental Trace Metal Analysis and Speciation Electroanalysis 2008, 20, 240– 258 DOI: 10.1002/elan.200704067
        14
        Gel-integrated voltammetric microsensors and submersible probes as reliable tools for environmental trace metal analysis and speciation
        Tercier-Waeber, Mary-Lou; Confalonieri, Fabio; Koudelka-Hep, Milena; Dessureault-Rompre, Jacynthe; Graziottin, Flavio; Buffle, Jacques
        Electroanalysis (2008), 20 (3), 240-258CODEN: ELANEU; ISSN:1040-0397. (Wiley-VCH Verlag GmbH & Co. KGaA)
        This article gives a review of the anal. and environmental criteria which must be considered and the relevant specific developments needed for direct, reliable voltammetric measurements of trace metal speciation in environmental systems. In particular, this article will focus on the tools which enable remote, long-term in situ measurements. The development of such tools is a challenging task. The strategies that can be used to achieve this goal are described for the development of innovative and versatile gel-integrated voltammetric microsensors, micro-/mini-integrated anal. systems, and submersible probes. The advantages of these new tools with respect to selectivity, sensitivity, reliability, spatial and temporal resoln. of data, and thus efficient environmental monitoring of the biogeochem. cycle of trace metals are demonstrated by providing examples of measurements made in various aquatic samples in lab. (water, soils, solid-liq. interface) and in situ in fresh and seawaters.
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      15. 15
        Ehl, R. G.; Ihde, A. J. Faraday’s Electrochemical Laws and the Determination of Equivalent Weights J. Chem. Educ. 1954, 31, 226– 232 DOI: 10.1021/ed031p226
        15
        Faraday's electrochemical laws and the determination of equivalent weights
        Ehl, Rosemary G.; Ihde, Aaron J.
        Journal of Chemical Education (1954), 31 (), 226-32CODEN: JCEDA8; ISSN:0021-9584.
        Historical.
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      16. 16
        Heller, A.; Feldman, B. Electrochemistry in Diabetes Management Acc. Chem. Res. 2010, 43, 963– 973 DOI: 10.1021/ar9002015
        16
        Electrochemistry in Diabetes Management
        Heller, Adam; Feldman, Ben
        Accounts of Chemical Research (2010), 43 (7), 963-973CODEN: ACHRE4; ISSN:0001-4842. (American Chemical Society)
        A review. In this Account, the authors describe the founding of TheraSense, now a major part of Abbott Diabetes Care, and the development of two products that have improved the lives of people with diabetes. The first, a virtually painless microcoulometer (300 nL vol.), the FreeStyle blood glucose monitoring system, was approved by the FDA and became available in 2000. In 2009, this system was used in more than one billion blood assays. The second, the enzyme-wiring based, s.c.-implanted FreeStyle Navigator continuous glucose monitoring system, was approved by the FDA and became available in the United States in 2008. The strips of the FreeStyle blood glucose monitoring system comprise a printed parallel plate coulometer, with a 50 μm gap between two facing printed electrodes, a carbon electrode and a Ag/AgCl electrode.
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      17. 17
        Cuartero, M.; Crespo, G. A.; Ghahraman Afshar, M.; Bakker, E. Exhaustive Thin-Layer Cyclic Voltammetry for Absolute Multianalyte Halide Detection Anal. Chem. 2014, 86, 11387– 11395 DOI: 10.1021/ac503344f
        17
        Exhaustive Thin-Layer Cyclic Voltammetry for Absolute Multianalyte Halide Detection
        Cuartero, Maria; Crespo, Gaston A.; Ghahraman Afshar, Majid; Bakker, Eric
        Analytical Chemistry (Washington, DC, United States) (2014), 86 (22), 11387-11395CODEN: ANCHAM; ISSN:0003-2700. (American Chemical Society)
        Water anal. is one of the greatest challenges in the field of environmental anal. In particular, seawater anal. is often difficult because a large amt. of NaCl may mask the detn. of other ions, i.e., nutrients, halides, and carbonate species. The authors demonstrate here the use of thin-layer samples controlled by cyclic voltammetry to analyze water samples for chloride, bromide, and iodide. The fabrication of a microfluidic electrochem. cell based on a Ag/AgX wire (working electrode) inserted into a tubular Nafion membrane is described, which confines the sample soln. layer to <15 μm. By increasing the applied potential, halide ions present in the thin-layer sample (X-) are electrodeposited on the working electrode as AgX, while their resp. counterions are transported across the perm-selective membrane to an outer soln. Thin-layer cyclic voltammetry allows one to obtain sepd. peaks in mixed samples of these three halides, finding a linear relation between the halide concn. and the corresponding peak area from ∼10-5 to 0.1M for bromide and iodide and from 10-4 to 0.6M for chloride. This technique was successfully applied for the halide anal. in tap, mineral, and river water as well as seawater. The proposed methodol. is abs. and potentially calibration-free, as evidenced by an obsd. 2.5% relative std. deviation cell to cell reproducibility and independence from the operating temp.
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      18. 18
        Ghahraman Afshar, M.; Crespo, G. A.; Bakker, E. Thin-Layer Chemical Modulations by a Combined Selective Proton Pump and pH Probe for Direct Alkalinity Detection Angew. Chem. 2015, 127, 8228– 8231 DOI: 10.1002/ange.201500797
        There is no corresponding record for this reference.
      19. 19
        van der Schoot, B.; van der Wal, P.; de Rooij, N.; West, S. Titration-on-a-Chip, Chemical Sensor–Actuator Systems from Idea to Commercial Product Sens. Actuators, B 2005, 105, 88– 95 DOI: 10.1016/j.snb.2004.02.058
        19
        Titration-on-a-chip, chemical sensor-actuator systems from idea to commercial product
        van der Schoot, Bart; van der Wal, Peter; de Rooij, Nico; West, Steve
        Sensors and Actuators, B: Chemical (2005), 105 (1), 88-95CODEN: SABCEB; ISSN:0925-4005. (Elsevier B.V.)
        A review. The earliest reports of integrated chem. sensor-actuator devices to perform coulometric acid-base titrns. date back almost 20 years. Recently a first com. instrument appeared that allows to perform very rapid, accurate acid-base detns. with a solid-state probe and no need for liq. titrants. This paper reviews some of the early developments and shows the effort that was undertaken to bring this technol. to routine use in the anal. lab. and beyond.
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