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1.
Anal Chem ; 2020 Jun 26.
Artigo em Inglês | MEDLINE | ID: mdl-32588617

RESUMO

We present an epidermal patch for glucose analysis in sweat incorporating for the first time pH and temperature correction according to local dynamic fluctuations in sweat during on-body tests. This sort of correction is indeed the main novelty of the paper, being crucial toward reliable measurements in every sensor based on an enzymatic element whose activity strongly depends on pH and temperature. The results herein reported for corrected glucose detection during on-body measurements are supported by a two-step validation protocol: with the biosensor operating off- and on-bodily, correlating the results with UV-vis spectrometry and/or ion chromatography. Importantly, the wearable device is a flexible skin patch that comprises a microfluidic cell designed with a sweat collection zone coupled to a fluidic channel in where the needed electrodes are placed: glucose biosensor, pH potentiometric electrode and a temperature sensor. The glucose biosensor presents a linear range of response within the expected physiological levels of glucose in sweat (10-200 µM), and the calibration parameters are dynamically adjusted to any change in pH and temperature during the sport practice by means of a new "correction approach". In addition, the sensor displays a fast response time, appropriate selectivity, and excellent reversibility. A total of 9 validated on-body tests are presented: the outcomes revealed a great potential of the wearable glucose sensor toward the provision of reliable physiological data linked to individuals during sport activity. In particular, the developed "correction approach" is expected to impact into the next generation of wearable devices that digitalize physiological activities through chemical information in a trustable manner for both sport and healthcare applications.

2.
Analyst ; 145(9): 3188-3210, 2020 May 07.
Artigo em Inglês | MEDLINE | ID: mdl-32239016

RESUMO

The monitoring of ammonium ion concentration has gained the attention of researchers from multiple fields since it is a crucial parameter with respect to environmental and biomedical applications. For example, ammonium is considered to be a quality indicator of natural waters as well as a potential biomarker of an enzymatic byproduct in key physiological reactions. Among the classical analytical methods used for the detection of ammonium ions, potentiometric ion-selective electrodes (ISEs) have attracted special attention in the scientific community because of their advantages such as cost-effectiveness, user-friendly features, and miniaturization ability, which facilitate easy portable measurements. Regarding the analytical performance, the key component of ISEs is the selective receptor, labelled as an ionophore in ISE jargon. Indeed, the preference of an ionophore for ammonium amongst other ions (i.e., selectivity) is a factor that primarily dictates the limit of detection of the electrode when performing measurements in real samples. A careful assessment of the literature for the last 20 years reveals that nonactin is by far the most employed ammonium ionophore to date. Despite the remarkable cross-interference of potassium over the ammonium response of nonactin-based ISEs, analytical applications comprising water quality assessment, clinical tests in biological fluids, and sweat monitoring during sports practice have been successfully researched. Nevertheless, there is evident difficulty in the determination of close-to-micromolar levels of ammonium in real samples with a significant potassium background level (i.e., millimolar concentration). This fact has fostered the search for a large variety of ammonium ionophores over the years, which are critically inspected herein. Overall, we provide an easily readable state of the art accompanied by a comprehensive description of other types of ammonium electrodes, including commercially available units. We conclude that newer breakthroughs are still required in the field to reach the desired analytical applications.

3.
Biosens Bioelectron ; 151: 112002, 2020 Mar 01.
Artigo em Inglês | MEDLINE | ID: mdl-31999596

RESUMO

Herein, an isothermal padlock probe-based assay for the simple and portable detection of pathogens coupled with a glucose oxidase (GOx)-based electrochemical readout is reported. Infectious diseases remain a constant threat on a global scale, as in recurring pandemics. Rapid and portable diagnostics hold the promise to tackle the spreading of diseases and decentralising healthcare to point-of-care needs. Ebola, a hypervariable RNA virus causing fatalities of up to 90% for recent outbreaks in Africa, demands immediate attention for bedside diagnostics. The design of the demonstrated assay consists of a rolling circle amplification (RCA) technique, responsible for the generation of nucleic acid amplicons as RCA products (RCPs). The RCPs are generated on magnetic beads (MB) and subsequently, connected via streptavidin-biotin bonds to GOx. The enzymatic catalysis of glucose by the bound GOx allows for an indirect electrochemical measurement of the DNA target. The RCPs generated on the surface of the MB were confirmed by scanning electron microscopy, and among other experimental conditions such as the type of buffer, temperature, concentration of GOx, sampling and measurement time were evaluated for the optimum electrochemical detection. Accordingly, 125 µg mL-1 of GOx with 5 mM glucose using phosphate buffer saline (PBS), monitored for 1 min were selected as the ideal conditions. Finally, we assessed the analytical performance of the biosensing strategy by using clinical samples of Ebola virus from patients. Overall, this work provides a proof-of-concept bioassay for simple and portable molecular diagnostics of emerging pathogens using electrochemical detection, especially in resource-limited settings.

4.
Anal Chem ; 92(4): 3315-3323, 2020 02 18.
Artigo em Inglês | MEDLINE | ID: mdl-31971373

RESUMO

Herein, thin-layer potentiometry combined with ion-exchange membranes as barriers for charged interferences is demonstrated for the analytical detection of creatinine (CRE) in undiluted human urine. Briefly, CRE diffuses through an anion-exchange membrane (AEM) from a sample contained in one fluidic compartment to a second reservoir, containing the enzyme CRE deiminase. There, CRE reacts with the enzyme, and the formation of ammonium is dynamically monitored by potentiometric ammonium-selective electrodes. This analytical concept is integrated into a lab-on-a-chip microfluidic cell that allows for a high sample throughput and the operation under stop-flow mode, which allows CRE to passively diffuse across the AEM. Conveniently, positively charged species (i.e., potassium, sodium, and ammonium, among others) are repelled by the AEM and never reach the ammonium-selective electrodes; thus, possible interference in the response can be avoided. As a result, the dynamic potential response of the electrodes is entirely ascribed to the stoichiometric formation of ammonium. The new CRE biosensor exhibits a Nernstian slope, within a linear range of response from 1 to 50 mM CRE concentration. As expected, the response time (15-60 min) primarily depends on the CRE diffusion across the AEM. CRE analysis in urine samples displayed excellent results, without requiring sample pretreatment (before the introduction of the sample in the microfluidic chip) and with high compatibility with development into a potential point-of-care clinical tool. In an attempt to decrease the analysis time, the presented analytical methodology for CRE detection is translated into an all-solid-state platform, in which the enzyme is immobilized on the surface of the ammonium-selective electrode and with the AEM on top. While more work is necessary in this direction, the CRE sensor appears to be promising for CRE analysis in both urine and blood.

5.
Anal Chem ; 91(23): 14951-14959, 2019 12 03.
Artigo em Inglês | MEDLINE | ID: mdl-31691565

RESUMO

Here, we provide the first experimental evidence of proton release from polyaniline (PANI) films subjected to anodic potentials at environmental pHs. We conducted an extensive characterization of unpolarized/polarized PANI films-synthesized by traditional sequential voltammetric scanning-by using spectroelectrochemistry, synchrotron radiation-X-ray photoelectron spectroscopy, near edge X-ray absorption fine structure, and potentiometric pH sensing in the vicinity of the PANI layer. This new insight enables the utilization of PANI as a proton pump, which is actively tuned through an electrochemical pulse, so as to controllably acidify well-confined thin layer samples. Furthermore, we demonstrate the analytical significance of this system by measuring the alkalinity of artificial and natural water samples by using two faced planar PANI electrodes, one working as a proton source and the other one as pH electrode. Finally, the impact of this approach is 2-fold: (i) all-solid-state electrode materials may be used with devisible consequences in miniaturized and implementable submersible probes, and (ii) rapid determination of alkalinity as compared to traditional approaches together with a versatility in pH adjustment in any kind of sample, among other applications.

6.
Angew Chem Int Ed Engl ; 58(52): 19027-19033, 2019 Dec 19.
Artigo em Inglês | MEDLINE | ID: mdl-31617301

RESUMO

Water-splitting photoanodes based on semiconductor materials typically require a dopant in the structure and co-catalysts on the surface to overcome the problems of charge recombination and high catalytic barrier. Unlike these conventional strategies, a simple treatment is reported that involves soaking a sample of pristine BiVO4 in a borate buffer solution. This modifies the catalytic local environment of BiVO4 by the introduction of a borate moiety at the molecular level. The self-anchored borate plays the role of a passivator in reducing the surface charge recombination as well as that of a ligand in modifying the catalytic site to facilitate faster water oxidation. The modified BiVO4 photoanode, without typical doping or catalyst modification, achieved a photocurrent density of 3.5 mA cm-2 at 1.23 V and a cathodically shifted onset potential of 250 mV. This work provides an extremely simple method to improve the intrinsic photoelectrochemical performance of BiVO4 photoanodes.

7.
ACS Sens ; 4(9): 2524-2535, 2019 09 27.
Artigo em Inglês | MEDLINE | ID: mdl-31448593

RESUMO

We present the most complete study to date comprising in vitro cytotoxicity tests of ion-selective membranes (ISMs) in terms of cell viability, proliferation, and adhesion assays with human dermal fibroblasts. ISMs were prepared with different types of plasticizers and ionophores to be tested in combination with assays that focus on the medium-term and long-term leaching of compounds. Furthermore, the ISMs were prepared in different configurations considering (i) inner-filling solution-type electrodes, (ii) all-solid-state electrodes based on a conventional drop-cast of the membrane, (iii) peeling after the preparation of a wearable sensor, and (iv) detachment from a microneedle-based sensor, thus covering a wide range of membrane shapes. One of the aims of this study, other than the demonstration of the biocompatibility of various ISMs and materials tested herein, is to create an awareness in the scientific community surrounding the need to perform biocompatibility assays during the very first steps of any sensor development with an intended biomedical application. This will foster meeting the requirements for subsequent on-body application of the sensor and avoiding further problems during massive validations toward the final in vivo use and commercialization of such devices.

8.
Anal Chem ; 91(13): 8644-8651, 2019 07 02.
Artigo em Inglês | MEDLINE | ID: mdl-31194514

RESUMO

Herein, the reproducibility and a double validation of on-body measurements provided by new wearable potentiometric ion sensors (WPISs) is presented. Sweat collected during sport practice was first analyzed using the developed device, the pH-meter, and ion chromatography (IC) prior to on-body measurements (off-site validation). Subsequently, the accuracy of on-body measurements accomplished by the WPISs was evaluated by comparison with pH-meter readings and IC after collecting sweat (every 10-12.5 min) during sport practice. The developed device contains sensors for pH, Cl-, K+, and Na+ that are embedded in a flexible sampling cell for sweat analysis. The electrode array was fabricated employing MWCNTs (as an ion-to-electron transducer) and stretchable materials that have been exhaustively characterized in terms of analytical performance, presenting Nernstian slopes within the expected physiological range of each ion analyte (Cl-, 10-100 mM; K+, 10-10 mM; and Na+, 10-100 mM and pH, 4.5-7.5), drift suitable for midterm exercise practice (0.3 ± 0.2 mV h-1), fast response time, adequate selectivity for sweat measurements, and excellent reversibility. Besides that, the designed sampling cell avoids any sweat contamination and evaporation issues while supplying a passive sweat flow encompassing specifically the individual's perspiration. The interpretation of ion concentration profiles may permit the identification of personal dynamic patterns in sweat composition while practicing sport.

9.
Biosens Bioelectron ; 130: 110-124, 2019 Apr 01.
Artigo em Inglês | MEDLINE | ID: mdl-30731344

RESUMO

The importance of knowing creatinine levels in the human body is related to the possible association with renal, muscular and thyroid dysfunction. Thus, the accurate detection of creatinine may indirectly provide information surrounding those functional processes, therefore contributing to the management of the health status of the individual and early diagnosis of acute diseases. The questions at this point are: to what extent is creatinine information clinically relevant?; and do modern creatinine (bio)sensing strategies fulfil the real needs of healthcare applications? The present review addresses these questions by means of a deep analysis of the creatinine sensors reported in the literature over the last five years. There is a wide range of techniques for detecting creatinine, most of them based on optical readouts (20 of the 33 papers collected in this review). However, the use of electrochemical techniques (13 of the 33 papers) is recently emerging in alignment with the search for a definitive and trustworthy creatinine detection at the point-of-care level. In this sense, biosensors (7 of the 33 papers) are being established as the most promising alternative over the years. While creatinine levels in the blood seem to provide better information about patient status, none of the reported sensors display adequate selectivity in such a complex matrix. In contrast, the analysis of other types of biological samples (e.g., saliva and urine) seems to be more viable in terms of simplicity, cross-selectivity and (bio)fouling, besides the fact that its extraction does not disturb individual's well-being. Consequently, simple tests may likely be used for the initial check of the individual in routine analysis, and then, more accurate blood detection of creatinine could be necessary to provide a more genuine diagnosis and/or support the corresponding decision-making by the physician. Herein, we provide a critical discussion of the advantages of current methods of (bio)sensing of creatinine, as well as an overview of the drawbacks that impede their definitive point-of-care establishment.


Assuntos
Técnicas Biossensoriais , Creatinina/isolamento & purificação , Técnicas Eletroquímicas , Rim/química , Creatinina/química , Diagnóstico Precoce , Humanos , Rim/patologia , Sistemas Automatizados de Assistência Junto ao Leito
10.
Sensors (Basel) ; 19(2)2019 Jan 17.
Artigo em Inglês | MEDLINE | ID: mdl-30658434

RESUMO

Wearable potentiometric sensors have received considerable attention owing to their great potential in a wide range of physiological and clinical applications, particularly involving ion detection in sweat. Despite the significant progress in the manner that potentiometric sensors are integrated in wearable devices, in terms of materials and fabrication approaches, there is yet plenty of room for improvement in the strategy adopted for the sample collection. Essentially, this involves a fluidic sampling cell for continuous sweat analysis during sport performance or sweat accumulation via iontophoresis induction for one-spot measurements in medical settings. Even though the majority of the reported papers from the last five years describe on-body tests of wearable potentiometric sensors while the individual is practicing a physical activity, the medical utilization of these devices has been demonstrated on very few occasions and only in the context of cystic fibrosis diagnosis. In this sense, it may be important to explore the implementation of wearable potentiometric sensors into the analysis of other biofluids, such as saliva, tears and urine, as herein discussed. While the fabrication and uses of wearable potentiometric sensors vary widely, there are many common issues related to the analytical characterization of such devices that must be consciously addressed, especially in terms of sensor calibration and the validation of on-body measurements. After the assessment of key wearable potentiometric sensors reported over the last five years, with particular attention paid to those for medical applications, the present review offers tentative guidance regarding the characterization of analytical performance as well as analytical and clinical validations, thereby aiming at generating debate in the scientific community to allow for the establishment of well-conceived protocols.


Assuntos
Tecnologia Biomédica/instrumentação , Técnicas Biossensoriais/instrumentação , Potenciometria/instrumentação , Dispositivos Eletrônicos Vestíveis , Eletroquímica , Humanos , Iontoforese
11.
Anal Chem ; 91(2): 1578-1586, 2019 01 15.
Artigo em Inglês | MEDLINE | ID: mdl-30543102

RESUMO

A new analytical all-solid-state platform for intradermal potentiometric detection of potassium in interstitial fluid is presented here. Solid microneedles are modified with different coatings and polymeric membranes to prepare both the potassium-selective electrode and reference electrode needed for the potentiometric readout. These microneedle-based electrodes are fixed in an epidermal patch suitable for insertion into the skin. The analytical performances observed for the potentiometric cell (Nernstian slope, limit of detection of 10-4.9 potassium activity, linear range of 10-4.2 to 10-1.1, drift of 0.35 ± 0.28 mV h-1), together with a fast response time, adequate selectivity, and excellent reproducibility and repeatability, are appropriate for potassium analysis in interstitial fluid within both clinical and harmful levels. The potentiometric response is maintained after several insertions into animal skin, confirming the resiliency of the microneedle-based sensor. Ex vivo tests based on the intradermal detection of potassium in chicken and porcine skin demonstrate that the microneedle patch is suitable for monitoring potassium changes inside the skin. In addition, the dimensions of the microneedles modified with the corresponding layers necessary to enhance robustness and provide sensing capabilities (1000 µm length, 45° tip angle, 15 µm thickness in the tip, and 435 µm in the base) agree with the required ranges for a painless insertion into the skin. In vitro cytotoxicity experiments showed that the patch can be used for at least 24 h without any side effect for the skin cells. Overall, the developed concept constitutes important progress in the intradermal analysis of ions related to an electrolyte imbalance in humans, which is relevant for the control of certain types of diseases.

12.
ACS Appl Mater Interfaces ; 10(48): 41146-41154, 2018 Dec 05.
Artigo em Inglês | MEDLINE | ID: mdl-30412378

RESUMO

Cellulose nanofibers (CNFs) have recently attracted a lot of attention in sensing because of their multifunctional character and properties such as renewability, nontoxicity, biodegradability, printability, and optical transparency in addition to unique physicochemical, barrier, and mechanical properties. However, the focus has exclusively been devoted toward developing two-dimensional sensing platforms in the form of nanopaper or nanocellulose-based hydrogels. To improve the flexibility and sensing performance in situ, for example, to detect biomarkers in vivo for early disease diagnostics, more advanced CNF-based structures are needed. Here, we developed porous and hollow, yet robust, CNF-based microcapsules using only the primary plant cell wall components, CNF, pectin, and xyloglucan, to assemble the capsule wall. The fluorescein isothiocyanate-labeled dextrans with MW of 70 and 2000 kDa could enter the hollow capsules at a rate of 0.13 ± 0.04 and 0.014 ± 0.009 s-1, respectively. This property is very attractive because it minimizes the influence of mass transport through the capsule wall on the response time. As a proof of concept, glucose oxidase (GOx) enzyme was loaded (and cross-linked) in the microcapsule interior with an encapsulation efficiency of 68 ± 2%. The GOx-loaded microcapsules were immobilized on a variety of surfaces (here, inside a flow channel, on a carbon-coated sensor or a graphite rod) and glucose concentrations up to 10 mM could successfully be measured. The present concept offers new opportunities in the development of simple, more efficient, and disposable nanocellulose-based analytical devices for several sensing applications including environmental monitoring, healthcare, and diagnostics.


Assuntos
Técnicas Biossensoriais , Celulose/química , Enzimas Imobilizadas/química , Glucose Oxidase/química , Glucose/análise , Nanofibras/química , Dextranos/química , Fluoresceína-5-Isotiocianato/análogos & derivados , Fluoresceína-5-Isotiocianato/química , Porosidade
13.
Biosens Bioelectron ; 99: 70-76, 2018 Jan 15.
Artigo em Inglês | MEDLINE | ID: mdl-28738230

RESUMO

Fluorinated tripodal compounds were recently reported to be efficient transmembrane transporters for a series of inorganic anions. In particular, this class of receptors has been shown to be suitable for the effective complexation of chloride, nitrate, bicarbonate and sulfate anions via hydrogen bonding. The potentiometric properties of urea and thiourea-based fluorinated tripodal receptors are explored here for the first time, in light of the need for reliable sensors for chloride monitoring in undiluted biological fluids. The ion selective electrode (ISE) membranes with tren-based tris-urea bis(CF3) tripodal compound (ionophore I) were found to exhibit the best selectivity for chloride over major lipophilic anions such as salicylate ( [Formula: see text] ) and thiocyanate ( [Formula: see text] ). Ionophore I-based ISEs were successfully applied for chloride determination in undiluted human serum as well as artificial serum sample, the slope of the linear calibration at the relevant background of interfering ions being close to Nernstian (49.8±1.7mV). The results of potentiometric measurements were confirmed by argentometric titration. Moreover, the ionophore I-based ISE membrane was shown to exhibit a very good long-term stability of potentiometric performance over the period of 10 weeks. Nuclear magnetic resonance (NMR) titrations, potentiometric sandwich membrane experiments and density functional theory (DFT) computational studies were performed to determine the binding constants and suggest 1:1 complexation stoichiometry for the ionophore I with chloride as well as salicylate.


Assuntos
Técnicas Biossensoriais , Cloretos/isolamento & purificação , Ionóforos/química , Ânions/química , Cloretos/química , Halogenação , Humanos , Ligação de Hidrogênio , Concentração de Íons de Hidrogênio , Membranas Artificiais , Potenciometria , Tiocianatos/química
14.
Talanta ; 177: 191-196, 2018 Jan 15.
Artigo em Inglês | MEDLINE | ID: mdl-29108575

RESUMO

A heterogeneous pH buffer based on a colloidal emulsion containing ion-exchanger and lipophilic base is described that can be integrated into hydrogels without affecting their ion-exchange properties. Each sphere works on the basis of reversible ion-exchange of hydrogen ions with solution cations, acting as a pH buffer while staying removed from solution in the nonpolar core of the spheres. The ion-exchange mechanism is supported by titration experiments in aqueous emulsion, showing that the nature and concentration of the exchanging solution cations influences the buffer action, with increasing lipophilicity moving the equilibrium to lower pH values. Agarose gels with entrapped pH buffer emulsions and mounted in a transport cell are shown by zero current potentiometry to exhibit negligible permselective properties above an ionic strength of 1mM, a behavior no different from unmodified agarose, with an observed ion-exchanger concentration of 7mM in dry agarose. This suggests that such pH buffers do not give rise to substantial ion-exchange properties of the gel material. In a first attempt to control the pH in the vicinity of an electrode surface by this approach, the emulsion was entrapped in an agarose gel in direct contact with a pH electrode, demonstrating the ability to buffer such gel films.

15.
Anal Chem ; 89(6): 3508-3516, 2017 03 21.
Artigo em Inglês | MEDLINE | ID: mdl-28194968

RESUMO

To understand the rate determining processes during the equilibration of poly(3,4-ethylenedioxythiophene):polystyrenesulfonate-based (PEDOT(PSS)-based) solid contact (SC) ion-selective electrodes (ISEs), the surfaces of Pt, Au, and GC electrodes were coated with 0.1, 1.0, 2.0, and 4.0 µm thick galvanostatically deposited PEDOT(PSS) films. Next, potential vs time transients were recorded with these electrodes, with and without an additional potassium ion-selective membrane (ISM) coating, following their first contact with 0.1 M KCl solutions. The transients were significantly different when the multilayered sensor structures were assembled on Au or GC compared to Pt. The differences in the rate of equilibration were interpreted as a consequence of differences in the hydrophilicity of PEDOT(PSS) in contact with the substrate electrode surfaces based on X-ray photoelectron spectroscopy (XPS) and synchrotron radiation-XPS (SR-XPS) analysis of 10-100 nm thick PEDOT(PSS) films. The influence of the layer thickness of the electrochemically deposited PEDOT(PSS)-films on the hydrophilicity of these films has been documented by contact angle measurements over PEDOT(PSS)-coated Au, GC, and Pt electrode surfaces. This study demonstrates that it is possible to minimize the equilibration (conditioning) time of SC ISEs with aqueous solutions before usage by optimizing the thickness of the SC layer with a controlled ISM thickness. PEDOT(PSS)-coated Au and GC electrodes exhibit a significant negative potential drift during their equilibration in an aqueous solution. By coating the PEDOT(PSS) surface with an ISM, the negative potential drift is compensated by a positive potential drift related to the hydration of the ISM and activity changes at the PEDOT(PSS)|ISM interface. The potential drifts related to activity changes in the ISM have been determined by a novel adaptation of the "sandwich membrane" method.

16.
Anal Chem ; 89(1): 571-575, 2017 01 03.
Artigo em Inglês | MEDLINE | ID: mdl-28105834

RESUMO

We report on a novel approach for in-line sample acidification that results in a significant improvement in the limit of detection of potentiometric anion-selective electrodes aiming at determining nutrients in natural waters. The working principle of the developed acidification module relies on the cation-exchange process between the sample and an ion-exchange Donnan exclusion membrane in its protonated form. The resulting in-line acidification of natural waters with millimolar sodium chloride level (freshwater, drinking water, and aquarium water, as well as dechloridized seawater) decreases the pH down to ∼5. By using the acidification module, the limit of detection of nitrite-selective electrodes significantly improves by more than 2 orders of magnitude with respect to that observed at environmental pH. The originality of the proposed flow cell lies in the possibility to adjust the pH of the sample by modifying its exposure time with the membrane by varying the volumetric flow rate. Facile coupling with a detection technique of choice, miniaturized configuration and simple implementation for long-term monitoring with submersible probes for environmental analysis are possible analytical configurations. This approach was here successfully applied for the potentiometric detection of nitrite in aquarium and dechloridized seawater samples.


Assuntos
Nitritos/análise , Potenciometria/métodos , Poluentes Químicos da Água/análise , Água/química , Concentração de Íons de Hidrogênio , Miniaturização , Pressão
17.
Anal Chem ; 89(1): 586-594, 2017 01 03.
Artigo em Inglês | MEDLINE | ID: mdl-27976858

RESUMO

Voltammetric thin layer (∼200 nm) ionophore-based polymeric films of defined ion-exchange capacity have recently emerged as a promising approach to acquire multi-ion information about the sample, in analogy to performing multiple potentiometric measurements with individual membranes. They behave under two different regimes that are dependent on the ion concentration. A thin layer control (no mass transport limitation of the polymer film or solution) is identified for ion concentrations of >10 µM, in which case the peak potential serves as the readout signal, in analogy to a potentiometric sensor. On the other hand, ion transfer at lower concentrations is chiefly controlled by diffusional mass transport from the solution to the sensing film, resulting in an increase of peak current with ion concentration. This concentration range is suitable for electrochemical ion transfer stripping analysis. Here, the transition between the two mentioned scenarios is explored experimentally, using a highly silver-selective membrane as a proof-of-concept under different conditions (variation of ion concentration in the sample from 0.1 µM to 1 mM, scan rate from 25 mV s-1 to 200 mV s-1, and angular frequency from 100 rpm to 6400 rpm). Apart from experimental evidence, a numerical simulation is developed that considers an idealized conducting polymer behavior and permits one to predict experimental behavior under diffusion or thin-layer control.

18.
Anal Chem ; 89(1): 595-602, 2017 01 03.
Artigo em Inglês | MEDLINE | ID: mdl-27976860

RESUMO

This work reports on a semiempirical treatment that allows one to rationalize and predict experimental conditions for thin-layer ionophore-based films with cation-exchange capacity read out with cyclic voltammetry. The transition between diffusional mass transport and thin-layer regime is described with a parameter (α), which depends on membrane composition, diffusion coefficient, scan rate, and electrode rotating speed. Once the thin-layer regime is fulfilled (α = 1), the membrane behaves in some analogy to a potentiometric sensor with a second discrimination variable (the applied potential) that allows one to operate such electrodes in a multianalyte detection mode owing to the variable applied ion-transfer potentials. The limit of detection of this regime is defined with a second parameter (ß = 2) and is chosen in analogy to the definition of the detection limit for potentiometric sensors provided by the IUPAC. The analytical equations were validated through the simulation of the respective cyclic voltammograms under the same experimental conditions. While simulations of high complexity and better accuracy satisfactorily reproduced the experimental voltammograms during the forward and backward potential sweeps (companion paper 1), the semiempirical treatment here, while less accurate, is of low complexity and allows one to quite easily predict relevant experimental conditions for this emergent methodology.

19.
Chem Commun (Camb) ; 52(62): 9703-6, 2016 Aug 11.
Artigo em Inglês | MEDLINE | ID: mdl-27405722

RESUMO

This paper presents the first direct spectroscopic evidence for double layer or capacitive charging of carbon nanomaterial-based solid contacts in all-solid-state polymeric ion-selective electrodes (ISEs). Here, we used synchrotron radiation-X-ray photoelectron spectroscopy (SR-XPS) and SR valence band (VB) spectroscopy in the elucidation of the charging mechanism of the SCs.

20.
Anal Chem ; 88(13): 6939-46, 2016 07 05.
Artigo em Inglês | MEDLINE | ID: mdl-27266678

RESUMO

We report on the limiting conditions for ion-transfer voltammetry between an ion-exchanger doped and plasticized poly(vinyl chloride) (PVC) membrane and an electrolyte solution that was triggered via the oxidation of a poly(3-octylthiophene) (POT) solid-contact (SC), which was unexpectedly related to the thickness of the POT SC. An electropolymerized 60 nm thick film of POT coated with a plasticized PVC membrane exhibited a significant sodium transfer voltammetric signal whereas a thicker film (180 nm) did not display a measurable level of ion transfer due to a lack of oxidation of thick POT beneath the membrane film. In contrast, this peculiar phenomenon was not observed when the POT film was in direct contact with an organic solvent-based electrolyte. This evidence is indicative of three key points: (i) the coated membrane imposes a degree of rigidity to the system, which restricts the swelling of the POT film and its concomitant p-doping; (ii) this phenomenon is exacerbated with thicker POT films due to an initial morphology (rougher comprising a network of large POT nanoparticles), which gives rise to a diminished surface area and electrochemical reactivity in the POT SC; (iii) the rate of sodium transfer is higher with a thin POT film due to a smoother surface morphology made up of a network of smaller POT nanoparticles with an increased surface area and electrochemical reactivity. A variety of techniques including cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), ellipsometry, scanning electron microscopy (SEM), atomic force microscopy (AFM), and synchrotron radiation-X-ray photoelectron spectroscopy (SR-XPS) were used to elucidate the mechanism of the POT thickness/POT surface roughness dependency on the electrochemical reactivity of the PVC/POT SC system.

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