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A novel electrochemical cell design in a vertically stacked configuration is presented. Through a layered structure using a top macroporous working electrode, a polyelectrolyte, and a bottom metallic conductor a standalone electrochemical cell with an internal reference electrode is built. This sensor allows monitoring an electrochemical property of an external solution with only one electrode in direct contact with the sample. Using paper-based platinum electrode for the porous top electrode and Nafion as polyelectrolyte material, the self-powered detection of hydrogen peroxide is performed. The system can be operated in multiple modes. In a capacitive way, the open circuit potential is measured. Alternatively, in a self-powered current mode, the system emulates a fuel cell. Additionally, a potential-current switched mode is also demonstrated. Because of this unique design and operational features this sensor is considered as an electrochemical pixel. To further demonstrate the advantages of this device, the detection of glucose is performed by building an array of sensors using a single back (reference) electrode and multiple working electrodes. These results lay the groundwork for the development of a new generation of simple and low cost biochemical sensors and electrochemical sensing arrays.
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Técnicas Biosensibles , Polielectrolitos , Técnicas Biosensibles/métodos , Electrodos , Peróxido de Hidrógeno , Porosidad , Técnicas Electroquímicas/métodosRESUMEN
Systematic errors in the calix [4] pyrrole-based potentiometric detection of creatinine have been observed in heavy smokers. This work further characterizes the interactions between the nicotinium cation and the cavitand as well as the resulting interference produced during the potentiometric detection. It is found that the nicotinium cation binds the electronic rich aromatic cavity defined by the pyrrole rings of the receptor's cone conformation with an estimated binding constant higher than 10-4 M-1 in methylene chloride. On the other hand, the creatininium cation is preferentially included in the hydrophobic aromatic cavity of the ionophore by establishing hydrogen bond interactions with the pyrrole NHs groups. Potentiometric calibrations confirmed the detection of the nicotinium cation at neutral and acidic pH, respectively. Due to the lower pka of creatinine, a methodology to quantify creatinine in presence of nicotine by using an array of three sensors at two pH values is proposed. A partial least squares regression was performed and reported recoveries of 103% with a standard deviation of 20%. The improved determination of creatinine was therefore discussed. This approach represents a step forward in the development of effective approaches to improve the measurement of creatinine in decentralized settings.
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Nicotina , Pirroles , Cationes , Creatinina , Potenciometría/métodosRESUMEN
The growing demand for tools to generate chemical information in decentralized settings is creating a vast range of opportunities for potentiometric sensors, since their combination of robustness, simplicity of operation and cost can hardly be rivalled by any other technique. In previous works, we have shown that the mixed potential of a Pt electrode can be controlled with analytical purposes using a coating of Nafion, thus providing a way to develop a potentiometric biosensor for glucose. Unfortunately, the linear range of this device did not match the relevant clinical range for glucose in blood. This work presents a novel strategy to control the mixed potential that allows the development of a potentiometric biosensor for the direct detection of glucose in whole, undiluted blood without any sample pretreatment. By changing the ionomer, the analytical response can be tuned, shifting the linear range while keeping the sensitivity. Aquivion, a polyelectrolyte from the same family as Nafion, is used to stabilize the mixed potential of a platinized paper-based electrode, to entrap the enzyme and to reduce the interference from negatively charged species. Factors affecting the generation of the signal and the principle of detection are discussed. Optimization of the biosensor composition was achieved with particular focus on the characterization of the linear range and sensitivity. The accurate measurement of blood sugar levels in a single drop of whole blood with excellent recovery is presented.
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Técnicas Biosensibles , Electrodos , Glucosa , Glucosa Oxidasa , PotenciometríaRESUMEN
BACKGROUND: It is vital for frontline emergency physicians to immediately recognize the signs and symptoms of measles to initiate appropriate therapy and prevent spread to the health care team and other patients. OBJECTIVE: This review serves as a clinically practical updated reference for when the differential diagnosis includes measles. DISCUSSION: Measles is a highly contagious illness that classically presents with a rash, fever, cough, coryza, and conjunctivitis. Cases in the United States since 2000 have been attributed mainly to travelers who are infected abroad and then spread the illness to small, susceptible populations within the United States. Complications from measles are relatively common and can be associated with significant morbidity and mortality. Clinical suspicion should be confirmed with laboratory testing, which is most commonly a serum immunoglobulin M. The management of measles is mainly supportive. Patients that require more aggressive management include those who are pregnant, immunocompromised, or unvaccinated. Treatment may consist of the measles vaccine, intravenous immunoglobulin, vitamin A, and even ribavirin. Additionally, special precautions are required by hospital workers to help prevent the spread of the virus, which include N-95 masks and patient isolation in an airborne infection isolation room. CONCLUSION: Emergency physicians must be readily able to identify, contain patients with suspected measles, and determine who will need further medical management for this potentially life-threatening illness. As this public health crisis evolves, novel ways of screening for and reporting cases of measles is needed.
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Sarampión , Médicos , Brotes de Enfermedades , Femenino , Fiebre , Humanos , Inmunoglobulina M , Sarampión/diagnóstico , Sarampión/epidemiología , Sarampión/prevención & control , Vacuna Antisarampión , EmbarazoRESUMEN
The use of a Pt electrode coated with a layer of Nafion has been described in previous works as an attractive way to perform the potentiometric detection of hydrogen peroxide. Despite of the attractive features of this approach, the nature of the non-Nernstian response of this system was not properly addressed. In this work, using a mixed potential model, the open circuit potential of the Pt electrode is shown to be under kinetic control of the oxygen reduction reaction (ORR). It is proposed that hydrogen peroxide acts as an oxygenated species that blocks free sites on the Pt surface, interfering with the ORR. Therefore, the effect of the polyelectrolyte coating can be understood in terms of the modulation of the factors that affects the kinetics of the ORR, such as an increase of the H+ concentration, minimization of the effect of the spectator species, etc. Because of the complexity and the lack of models that accurately describe systems with practical applications, this work is not intended to provide a mechanistic but rather a phenomenological view on problem. A general framework to understand the factors that affect the potentiometric response is provided. Experimental evidence showing that the use of polyelectrolyte coatings are a powerful way to control the mixed potential open new ways for the development of robust and simple potentiometric sensors.
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The fabrication and performance of a wearable paper-based chemiresistor for monitoring perspiration dynamics (sweat rate and sweat loss) are detailed. A novel approach is introduced to measure the amount of aqueous solution in the order of microliters delivered to the sensor by monitoring a linear change in resistance along a conducting paper. The wearable sensor is based on a single-walled carbon nanotubes and surfactant (sodium dodecylbenzenesulfonate) nanocomposite integrated within cellulose fibers of a conventional filter paper. The analytical performance and the sensing mechanism are presented. Monitoring sweat loss in the human body while exercising is demonstrated using the integration of a wireless reader and a user-friendly interface. By addressing the barriers of cost, simplicity, and the truly in situ demanding measurements, this unique wearable sensor is expected to serve in the future in many different applications involving the on-body detection of biofluids, such as a monitoring tool of dehydration levels for athletes as well as a tool for enhancing the sport performance by providing an accurate recovery of the hydration status in daily exercises.
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Bencenosulfonatos/química , Técnicas Biosensibles/métodos , Nanotubos/química , Sudor/fisiología , HumanosRESUMEN
Creatinine is a metabolite present in urine, and its concentration is used to diagnose and monitor kidney performance. For that reason, the development of new sensors to analyze this metabolite and obtain accurate results in a short period of time is necessary. An optical disposable sensor for monitoring creatinine levels in urine is described. The system, based on a new aryl-substituted calix[4]pyrrole synthetic receptor, has an unusual coextraction scheme. Due to the low p Ka values of creatininium (p Ka 4.8), a careful selection of a lipophilic pH indicator that works in acid medium is required. The sensor components were optimized, and the new sensor displays a good response time to creatinine (approximately 3 min) over a wide dynamic range (from 1 × 10-5 to 1 × 10-2 M). Moreover, the optical selectivity coefficients obtained for creatinine over common cations present in urine meet the requirements for real sample measurements. With a good sensor-to-sensor reproducibility (RSD, 5.1-6.9% in the middle of the range), this method provides a simple, quick, cost-effective, and selective alternative to the conventional methodology based on Jaffé's reaction.
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Creatinina/orina , Ionóforos/química , Dispositivos Ópticos , Urinálisis/instrumentación , Calibración , Humanos , Concentración de Iones de Hidrógeno , Límite de Detección , Membranas ArtificialesRESUMEN
A new biosensor for monitoring glucose levels in beverages is presented. The measurements are performed using potentiometric detection. Working electrodes are made using platinised paper as support and a biocompatible polymeric membrane made of a mixture of polyvinyl alcohol and chitosan containing glucose oxidase as the recognition layer. The system is based on the detection of the hydrogen peroxide generated by an enzymatic reaction performed in a highly sensitive, selective and simple way. The biosensors display suitable analytical performance (sensitivity -119.6⯱â¯6.4â¯mV/dec in the 0.03-1.0â¯mM range with a limit of detection of 0.02â¯mM). Determination of glucose in commercial orange juices is presented. These results were validated against conventional standard methods, showing good accuracy and fast analytical response. The methodology presented herein does not require complex samples treatment, offering an alternative to conventional methods, particularly for determinations performed with minimal expertise and without a laboratory infrastructure.
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Bebidas/análisis , Técnicas Biosensibles/economía , Técnicas Biosensibles/métodos , Citrus sinensis/química , Equipos Desechables , Glucosa/análisis , Papel , Técnicas Biosensibles/instrumentación , Quitosano/química , Costos y Análisis de Costo , Electrodos , Enzimas Inmovilizadas/química , Enzimas Inmovilizadas/metabolismo , Glucosa/química , Glucosa Oxidasa/química , Peróxido de Hidrógeno/química , Límite de Detección , Factores de TiempoRESUMEN
Despite predictions of their widespread application in healthcare and environmental monitoring, electrochemical sensors are yet to be distributed at scale, instead remaining largely confined to R&D labs. This contrasts sharply with the situation for physical sensors, which are now ubiquitous and seamlessly embedded in the mature ecosystem provided by electronics and connectivity protocols. Although chemical sensors could be integrated into the same ecosystem, there are fundamental issues with these sensors in the three key areas of analytical performance, usability, and affordability. Nevertheless, advances are being made in each of these fields, leading to hope that the deployment of automated and user-friendly low-cost electrochemical sensors is on the horizon. Here, we present a brief survey of key challenges and advances in the development of distributed electrochemical sensors for liquid samples, geared towards applications in healthcare and wellbeing, environmental monitoring, and homeland security. As will be seen, in many cases the analytical performance of the sensor is acceptable; it is usability that is the major barrier to commercial viability at this moment. Were this to be overcome, the issue of affordability could be addressed. Graphical Abstract á .
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Plant mitochondrial and chloroplast genomes encode essential proteins for oxidative phosphorylation and photosynthesis. For proper cellular function, plant organelles must ensure genome integrity. Although plant organelles repair damaged DNA using the multi-enzyme Base Excision Repair (BER) pathway, the details of this pathway in plant organelles are largely unknown. The initial enzymatic steps in BER produce a 5'-deoxyribose phosphate (5'-dRP) moiety that must be removed to allow DNA ligation and in plant organelles, the enzymes responsible for the removal of a 5'-dRP group are unknown. In metazoans, DNA polymerases (DNAPs) remove the 5'-dRP moiety using their intrinsic lyase and/or strand-displacement activities during short or long-patch BER sub-pathways, respectively. The plant model Arabidopsis thaliana encodes two family-A DNAPs paralogs, AtPolIA and AtPolIB, which are the sole DNAPs in plant organelles identified to date. Herein we demonstrate that both AtPolIs present 5'-dRP lyase activities. AtPolIB performs efficient strand-displacement on a BER-associated 1-nt gap DNA substrate, whereas AtPolIA exhibits only moderate strand-displacement activity. Both lyase and strand-displacement activities are dependent on an amino acid insertion that is exclusively present in plant organellar DNAPs. Within this insertion, we identified that residue AtPollB-Lys593 acts as nucleophile for lyase activity. Our results demonstrate that AtPolIs are functionally equipped to play a role in short-patch BER and suggest a major role of AtPolIB in a predicted long-patch BER sub-pathway. We propose that the acquisition of insertion 1 in the polymerization domain of AtPolIs was a key component in their evolution as BER associated and replicative DNAPs.
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Proteínas de Arabidopsis/metabolismo , Arabidopsis/enzimología , Dominio Catalítico , Reparación del ADN , ADN Polimerasa Dirigida por ADN/metabolismo , Secuencia de Aminoácidos , Arabidopsis/genética , Arabidopsis/metabolismo , Proteínas de Arabidopsis/química , Daño del ADN , ADN de Cloroplastos/metabolismo , ADN Mitocondrial/metabolismo , ADN de Plantas/metabolismo , ADN Polimerasa Dirigida por ADN/química , Liasas de Fósforo-Oxígeno/metabolismo , Alineación de SecuenciaRESUMEN
A novel low-cost, compact and sensitive paper-based platform for the accurate monitoring of glucose in biological fluids is presented. Paper-based working and reference electrodes are combined to build a whole potentiometric cell, which also fits a sampling module for simple and fast determination of glucose in a single drop of blood. The working electrode is built using a platinized filter paper coated with a Nafion membrane that entraps the enzyme glucose oxidase; the reference electrode is made by casting a polyvinylbutyral-based membrane onto a conductive paper. The system works by detecting the hydrogen peroxide generated as a result of the enzymatic reaction. Selectivity is achieved due to the permselective behaviour of Nafion, while a significant enhancement of the sensitivity is reached by exploiting the Donnan-coupled formal potential. Under optimum conditions, a sensitivity of -95.9 ± 4.8 mV per decade in the 0.3-3 mM range is obtained. Validation of the measurements has been performed against standard methods in human serum and blood. Final integration with a wireless reader allows for truly in situ measurements with a less than 2 minute procedure including a two-point calibration, washing and measurement. This low-cost analytical device opens up new prospects for rapid diagnostic results in non-laboratory settings.
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Glucemia/análisis , Glucosa Oxidasa/metabolismo , Potenciometría/instrumentación , Tecnología Inalámbrica/instrumentación , Diseño de Equipo , Glucosa Oxidasa/química , Humanos , Peróxido de Hidrógeno/análisis , Peróxido de Hidrógeno/metabolismo , Límite de Detección , Modelos Lineales , Papel , Potenciometría/métodos , Reproducibilidad de los ResultadosRESUMEN
A novel paper-based potentiometric sensor with an enhanced response for the detection of glucose in biological fluids is presented. The electrode consists on platinum sputtered on a filter paper and a Nafion membrane to immobilize the enzyme glucose oxidase. The response obtained is proportional to the logarithm of the concentration of glucose, with a sensitivity of -119±8mV·decade-1, a linear range that spans from 10-4M to 10-2.5 M and a limit of detection of 10-4.5 M of glucose. It is shown that Nafion increases the sensitivity of the technique while minimizing interferences. Validation with human serum samples shows an excellent agreement when compared to standard methods. This approach can become an interesting alternative for the development of simple and affordable devices for point of care and home-based diagnostics.
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Técnicas Biosensibles , Glucosa Oxidasa/química , Glucosa/aislamiento & purificación , Enzimas Inmovilizadas/química , Humanos , Papel , Platino (Metal)/química , PotenciometríaRESUMEN
The optimization, analytical characterization and validation of a novel ion-selective electrode for the highly sensitive and selective determination of creatinine in urine is presented. A newly synthesized calix[4]pyrrole-based molecule is used as an ionophore for the enhanced recognition of creatininium cations. The calculation of the complex formation constants in the polymeric membrane with creatininium, potassium and sodium confirms the strong selective interactions between the ionophore and the target. The optimization of the potentiometric sensor presented here yields an outstanding analytical performance, with a linear range that spans from 1µM to 10mM and limit of detection of 10-6.2M. The calculation of the selectivity coefficients against most commonly found interferences also show significant improvements when compared to other sensors already reported. The performance of this novel sensor is tested by measuring creatinine in real urine samples (N=50) and comparing the values against the standard colorimetric approach (Jaffé's reaction). The results show that this sensor allows the fast and accurate determination of creatinine in real samples with minimal sample manipulation.
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Calixarenos/química , Creatinina/orina , Electrodos de Iones Selectos , Porfirinas/química , Potenciometría/instrumentación , Técnicas Biosensibles/instrumentación , Diseño de Equipo , Humanos , Ionóforos/química , Límite de Detección , Membranas Artificiales , Modelos MolecularesRESUMEN
A textile-based wearable multi-ion potentiometric sensor array is described. The printed flexible sensors operate favorably under extreme mechanical strains (that reflect daily activity) while offering attractive real-time noninvasive monitoring of electrolytes such as sodium and potassium.
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Potasio/metabolismo , Sodio/metabolismo , Textiles , Humanos , Monitoreo Fisiológico/instrumentación , Monitoreo Fisiológico/métodos , Potenciometría/instrumentación , Potenciometría/métodosRESUMEN
Current methods for creatinine quantification suffer from significant drawbacks when aiming to combine accuracy, simplicity, and affordability. Here, an unprecedented synthetic receptor, an aryl-substituted calix[4]pyrrole with a monophosphonate bridge, is reported that displays remarkable affinity for creatinine and the creatininium cation. The receptor works by including the guest in its deep and polar aromatic cavity and establishing directional interactions in three dimensions. When incorporated into a suitable polymeric membrane, this molecule acts as an ionophore. A highly sensitive and selective potentiometric sensor suitable for the determination of creatinine levels in biological fluids, such as urine or plasma, in an accurate, fast, simple, and cost-effective way has thus been developed.
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Creatinina/análisis , Creatinina/sangre , Creatinina/orina , Humanos , Espectroscopía de Protones por Resonancia MagnéticaRESUMEN
Novel membrane-free chemically modified polystyrene microspheres for the optical detection of sulphate in aqueous media are introduced. The working principle of this sensor is based on the surface mass-extraction equilibrium of the target species. This allows overcoming the strong hydration energy penalty, a typical problem for the detection of divalent anions. This optical sensor exhibits both enhanced sensitivity and selectivity, which allows the accurate detection of sulphate in biological samples. To illustrate these features the determination of sulphate in urine is presented.
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The development of a solid-contact potentiometric sensor based on conducting rubbers using a carbon nanotubes ink is described here. Commercial rubbers are turned into conductive ones by a simple and versatile method, i.e. painting an aqueous dispersion of single-walled carbon nanotubes on the polymer surface. On this substrate, both the working ion-selective electrode and the reference electrode are built in order to form an integrated potentiometric cell. As a proof-of-principle, selective potassium electrodes are fully characterized giving comparable performances to conventional electrodes (sensitivity, selectivity, stability, linear range, limit of detection and reproducibility). As an application of the rubber-based electrodes, a bracelet was constructed to measure potassium levels in artificial sweat. Since rubbers are ubiquitous in our quotidian life, this approach offers great promise for the generation of chemical information through daily objects.
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Electroquímica/instrumentación , Tinta , Nanotubos de Carbono/química , Goma/química , Conductividad Eléctrica , Potasio/análisis , Potasio/química , Potenciometría , Propiedades de SuperficieRESUMEN
A new solid-state reference electrode using a polymeric membrane of polyvinyl butyral (PVB), Ag/AgCl and NaCl to be used in decentralized chemical measurements is presented. The electrode is made by drop-casting the membrane cocktail onto a glassy carbon (GC) substrate. A stable potential (less than 1 mV dec(-1)) over a wide range of concentrations for the several chemical species tested is obtained. No significant influence to changes in redox potential, light and pH are observed. The response of this novel electrode shows good correlation when compared with a conventional double-junction reference electrode. Also good long-term stability (90±33 µV/h) and a lifetime of approximately 4 months are obtained. Aspects related to the working mechanisms are discussed. Atomic Force Microscopy (AFM) studies reveal the presence of nanopores and channels on the surface, and electrochemical impedance spectroscopy (EIS) of optimized electrodes show low bulk resistances, usually in the kΩ range, suggesting that a nanoporous polymeric structure is formed in the interface with the solution. Future applications of this electrode as a disposable device for decentralized measurements are discussed. Examples of the utilization on wearable substrates (tattoos, fabrics, etc) are provided.
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A novel approach to monitor Li levels in blood in decentralized (out of the lab) settings is presented. The approach uses a potentiometric cell fully made with filter paper as a support. Electrodes were built using carbon nanotubes ink to create a conductive path and a suitable polymeric membrane. Solid-state ion-selective electrodes for Li and a reference electrode were built and optimized. The results obtained on real samples of serum and whole blood are comparable with those obtained by conventional standard approaches. This platform shows an outstanding performance for the direct, fast and low-cost monitoring of Li levels in blood.
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Litio/sangre , Nanotubos de Carbono/química , Papel , Humanos , Potenciometría/métodosRESUMEN
This article describes the fabrication, characterization and application of an epidermal temporary-transfer tattoo-based potentiometric sensor, coupled with a miniaturized wearable wireless transceiver, for real-time monitoring of sodium in the human perspiration. Sodium excreted during perspiration is an excellent marker for electrolyte imbalance and provides valuable information regarding an individual's physical and mental wellbeing. The realization of the new skin-worn non-invasive tattoo-like sensing device has been realized by amalgamating several state-of-the-art thick film, laser printing, solid-state potentiometry, fluidics and wireless technologies. The resulting tattoo-based potentiometric sodium sensor displays a rapid near-Nernstian response with negligible carryover effects, and good resiliency against various mechanical deformations experienced by the human epidermis. On-body testing of the tattoo sensor coupled to a wireless transceiver during exercise activity demonstrated its ability to continuously monitor sweat sodium dynamics. The real-time sweat sodium concentration was transmitted wirelessly via a body-worn transceiver from the sodium tattoo sensor to a notebook while the subjects perspired on a stationary cycle. The favorable analytical performance along with the wearable nature of the wireless transceiver makes the new epidermal potentiometric sensing system attractive for continuous monitoring the sodium dynamics in human perspiration during diverse activities relevant to the healthcare, fitness, military, healthcare and skin-care domains.