Recognition and Sensing of Creatinine.

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.

Chloride-selective electrodes based on "two-wall" aryl-extended calix[4]pyrroles: combining hydrogen bonds and anion-π interactions to achieve optimum performance.

The performance of chloride-selective electrodes based on "two-wall" aryl-extended calix[4]pyrroles and multiwall carbon nanotubes is presented. The calix[4]pyrrole receptors bear two phenyl groups at opposite meso-positions. When the meso-phenyl groups are decorated with strong electron-withdrawing substituents, attractive anion-π interactions may exist between the receptor's aromatic walls and the sandwiched anion. These anion-π interactions are shown to significantly affect the selectivity of the electrodes. Calix[4]pyrrole, bearing a p-nitro withdrawing group on each of the meso-phenyl rings, afforded sensors that display anti-Hofmeister behavior against the lipophilic salicylate and nitrate anions. Based on the experimental data, a series of principles that help in predicting the suitability of synthetic receptors for use as anion-specific ionophores is discussed. Finally, the sensors deliver excellent results in the direct detection of chloride in bodily fluids.

Analysis of risk factors for hydrocephalus development in newborn infants with germinal matrix hemorrhage.

AIM: The aim of this study was to analyze risk factors for the development of hydrocephalus in newborn infants with germinal matrix (GM) hemorrhage. METHODS: The study comprised 271 patients admitted to Carlos Haya University Hospital in Malaga with GM hemorrhage. The following data were recorded: gestational age, gender, twin birth, head circumference at birth, weight at birth, and Papile grade. Severe obstetrical (abruption, chorioamnionitis, pregnancy-induced hypertension, tocolytic treatment) and neonatal disorders (respiratory distress syndrome, neonatal infection, coagulation disorder, patent ductus arteriosus, necrotizing enterocolitis) were also recorded. Symptomatic hydrocephalus was diagnosed in the event of a progressive increase in head circumference and ventricular indices requiring shunting. RESULTS: Of the 271 patients, 139 (51%) developed posthemorrhagic ventriculomegaly; 47 patients (17%) developed symptomatic hydrocephalus and needed shunt implantation. We found a significant relationship between the development of symptomatic hydrocephalus and Papile grade, lower gestational age, lower birth weight, twin birth, and neonatal infection. CONCLUSION: Awareness of risk factors for the development of hydrocephalus in newborn infants with GM hemorrhage should be emphasized in order to enable an early diagnosis of ventriculomegaly and symptomatic hydrocephalus and thus make a correct therapeutic decision.

Carbon nanotube-based aptasensors for the rapid and ultrasensitive detection of bacteria.

In this paper we present a new generation of potentiometric biosensors based on carbon nanotubes (transducer layer of the biosensor) and aptamers (sensing layer of the biosensor) for the ultralow and selective detection of microorganisms. We show that with these aptasensors we were able to detect a few CFU of the target bacteria almost in real-time, both in buffered and in real samples.

Ventriculoperitoneal shunt as a primary neurosurgical procedure in newborn posthemorrhagic hydrocephalus: report of a series of 47 shunted patients.

PURPOSE: Intraventricular hemorrhage is the most common cause of infantile acquired hydrocephalus. Our objective is to determine if the implantation of ventriculoperitoneal shunt in posthemorrhagic hydrocephalus as a primary and definitive neurosurgical treatment, with no previous temporary procedures, would decrease complication rates with good functional outcomes. METHODS: Two hundred seventy-one patients with germinal matrix hemorrhage were diagnosed at the Carlos Haya Hospital between 2003 and 2010. Forty-seven patients underwent ventriculoperitoneal shunt after developing symptomatic hydrocephalus. The minimum weight required for shunt implantation was 1,500 g. We recorded complications related to the surgical procedure and analyzed functional state with a self-developed four-grade scale. RESULTS: One hundred thirty-nine (51.3 %) patients with intraventricular hemorrhage developed ventricular dilatation, but only 47 patients (17.34 %) needed shunting. In seven cases, temporary neurosurgical procedures were performed, but in all of them, this was followed by ventriculoperitoneal shunt implantation. The infection rate was 4.25 %, and shunt obstruction rate was 4.25 %. More than 80 % of patients were classified as good or excellent functional state. Mean follow-up period was 38.75 months (SD, 27.09; range, 1-102 months). CONCLUSIONS: Ventriculoperitoneal shunting as a primary neurosurgical treatment in posthemorrhagic hydrocephalus would decrease surgical morbidity with good functional outcome.

Endoscopic third ventriculostomy: can we predict success during surgery?

Endoscopic third ventriculostomy (ETV) is widely used as an alternative technique for hydrocephalus treatment. ETV success or failure may be influenced by numerous factors. In this study, we have analyzed preoperative and intraoperative risk factors and suggest an intraoperative scale to predict etV failure. Fifty-one patients (27 adults and 24 children) underwent an etV at Carlos Haya University Hospital, Malaga. Intraoperative video records were assessed and the following intraoperative findings were recorded: (1) abnormal ventricular anatomy, (2) intraoperative incident, (3) Liliequist membrane opening in a second endoscopic maneuver, (4) thickened or scarred membranes in the subarachnoid space, (5) absence or "weakness" of pulsation of third ventricle floor at etV completion, and (6) floppy premammillary membrane that needs edge coagulation. An intraoperative scale ranging from 0 to 6 points was performed. A significant relation was found between a higher result on the prognosis scale and etV failure (p < 0.0001). An absence or weakness of pulsation of the third ventricle floor at etV completion was significantly related to etV failure (p < 0.0001). The presence of thickened or scarred membranes in the subarachnoid space was significantly related to etV failure (p < 0.04) as well as the Liliequist membrane opening in a second endoscopic maneuver (p < 0.008). Intraoperative factors should be taken into account for prediction of etV success. More studies with larger case series are needed to determine the influence of all intraoperative factors over etV success.

A potassium sensor based on non-covalent functionalization of multi-walled carbon nanotubes.

Non-covalent functionalization of multi-walled carbon nanotubes (MWCNTs) by a pyrene based benzo-18-crown-6 ether 1 leads to nanostructure assemblies that play both the role of an ion-to-electron transducer and a selective recognition element in solid-contact ion-selective-electrodes (SC-ISEs). The high loading capacity (36 wt%) as well as the suitable dispersion character of the MWCNT hybrid in the ion-selective membrane (ISM) confirmed the benefit of this approach over the covalent one. The sensor has been applied successfully to the detection of potassium. Nernstian response (56.9 ± 0.9 mV per decade) was obtained (10(-5) and 10(-2) M K(+)) and the selectivity pattern was not altered by the immobilization of the ionophore on the MWCNTs. Leakage of the ionophore from the polymeric matrix is therefore avoided while the sensor construction was simplified and the analytical performances were maintained.

Potentiometric sensors using cotton yarns, carbon nanotubes and polymeric membranes.

A simple and generalized approach to build electrochemical sensors for wearable devices is presented. Commercial cotton yarns are first turned into electrical conductors through a simple dyeing process using a carbon nanotube ink. These conductive yarns are then partially coated with a suitable polymeric membrane to build ion-selective electrodes. Potentiometric measurements using these yarn-potentiometric sensors are demonstrated. Examples of yarns that can sense pH, K(+) and NH4(+) are presented. In all cases, these sensing yarns show limits of detection and linear ranges that are similar to those obtained with lab-made solid-state ion-selective electrodes. Through the immobilization of these sensors in a band-aid, it is shown that this approach could be easily implemented in a wearable device. Factors affecting the performance of the sensors and future potential applications are discussed.

A novel miniaturized radiofrequency potentiometer tag using ion-selective electrodes for wireless ion sensing.

Instrumental approaches to remotely and wirelessly monitoring chemical species are increasingly needed. Together with the electronic developments, efforts to optimize and validate the performance of these new devices are required. In this work, the analytical performance of a recently developed potentiometer-radiofrequency tag connected to ion-selective electrodes is evaluated. This credit card sized and extremely low power consumption device yield results that are comparable to those obtained with more sophisticated, lab-based tools. Advantages such as portability and autonomy, together with unique features, such as the ability to be read through the walls in a closed vessel are demonstrated. Future perspectives opened by this new generation of devices, such as their use in wearable devices and in decentralized settings are discussed.

Protein detection with potentiometric aptasensors: a comparative study between polyaniline and single-walled carbon nanotubes transducers.

A comparison study on the performance characteristics and surface characterization of two different solid-contact selective potentiometric thrombin aptasensors, one exploiting a network of single-walled carbon nanotubes (SWCNTs) and the other the polyaniline (PANI), both acting as a transducing element, is described in this work. The molecular properties of both SWCNT and PANI surfaces have been modified by covalently linking thrombin binding aptamers as biorecognition elements. The two aptasensors are compared and characterized through potentiometry and electrochemical impedance spectroscopy (EIS) based on the voltammetric response of multiply charged transition metal cations (such as hexaammineruthenium, [Ru(NH3)6](3+)) bound electrostatically to the DNA probes. The surface densities of aptamers were accurately determined by the integration of the peak for the reduction of [Ru(NH3)6](3+) to [Ru(NH3)6](2+). The differences and the similarities, as well as the transduction mechanism, are also discussed. The sensitivity is calculated as 2.97 mV/decade and 8.03 mV/decade for the PANI and SWCNTs aptasensors, respectively. These results are in accordance with the higher surface density of the aptamers in the SWCNT potentiometric sensor.

Paper-based ion-selective potentiometric sensors.

A new approach to develop ultra low-cost, robust, rugged, and disposable potentiometric sensors is presented. A suspension of carbon nanotubes in a water-surfactant mixture (carbon nanotubes ink) is applied on conventional filter papers to turn them into conductive papers, which are then used as a substrate to build ion-selective electrodes. The electrodes are made by drop casting a membrane on a small circular area of the conductive paper. In this way, the carbon nanotubes act as both electric conductors and ion-to-electron transducers of the potentiometric signal. Electrodes for sensing K(+), NH(4)(+), and pH were built and tested using this approach, and the results were compared with classical solid-state ion selective electrodes using carbon nanotubes as transducers and glassy carbon as a substrate. In all cases, the analytical performance (sensitivity, linear ranges, limits of detection, selectivity, etc.) of these disposable paper electrodes was similar to that obtained for the more conventional type of ion-selective-electrodes. This opens new avenues for very low-cost platforms for generation of chemical information.

Disposable planar reference electrode based on carbon nanotubes and polyacrylate membrane.

In this technical note, we report a new all-solid-state planar reference electrode based on single-walled carbon nanotubes and photocured poly(n-butylacrylate) (poly(nBA)) membrane containing the Ag/AgCl/Cl(-) ion system. Single-walled carbon nanotubes functionalized with octadecylamide (SWCNT-ODA) and deposited by drop-casting onto a disposable screen-printed electrode are an excellent all-solid-state transducer. The novel potentiometric planar reference electrode shows low potential variability (calibration slopes inferior to 2 mV/dec) for a wide range of chemical species (i.e., ions, small molecules, proteins) in a wide calibration range, redox pairs, changes in pH, and changes in ambient light. Potentiometric medium-term signal stability (-0.9 ± 0.2 mV/h) and electrochemical impedance characterization confirm the correct solid contact between the SWCNT-ODA layer and photocured poly(nBA) membrane. Overall, the materials used and the simple fabrication by screen-printing and drop-casting enable a high throughput and highly parallel and cost-effective mass manufacture of the new disposable reference electrode. Moreover, the reference electrode has a long shelf life, a characteristic that can be of special interest in decentralized and multiplexing potentiometric analysis.

Potentiometric strip cell based on carbon nanotubes as transducer layer: toward low-cost decentralized measurements.

In this study, we developed a potentiometric planar strip cell based on single-walled carbon nanotubes that aims to exploit the attributes of solid-contact ion-selective electrodes for decentralized measurements. That is, the ion-selective and reference electrodes have been simultaneously miniaturized onto a plastic planar substrate by screen-printing and drop-casting techniques, obtaining disposable strip cells with satisfactory performance characteristics (i.e., the sensitivity is 57.4 ± 1.3 mV/dec, the response time is ≤30 s within the linear range from log a(K+) = -5 to -2, and the limit of detection is -6.5), no need of maintenance during long dry storage, quick signal stabilization, and light insensitivity in short-term measurements. We also show how the new potentiometric strip cell makes it possible to perform decentralized and rapid determinations of ions in real samples, such as saliva or beverages.

Rapid detection of Aspergillus flavus in rice using biofunctionalized carbon nanotube field effect transistors.

In the present study, we have used carbon nanotube field effect transistors (FET) that have been functionalized with protein G and IgG to detect Aspergillus flavus in contaminated milled rice. The adsorbed protein G on the carbon nanotubes walls enables the IgG anti-Aspergillus antibodies to be well oriented and therefore to display full antigen binding capacity for fungal antigens. A solution of Tween 20 and gelatine was used as an effective blocking agent to prevent the non-specific binding of the antibodies and other moulds and also to protect the transducer against the interferences present in the rice samples. Our FET devices were able to detect at least 10 µg/g of A. flavus in only 30 min. To evaluate the selectivity of our biosensors, Fusarium oxysporum and Penicillium chrysogenum were tested as potential competing moulds for A. flavus. We have proved that our devices are highly selective tools for detecting mycotoxigenic moulds at low concentrations in real samples.

Solid-state reference electrodes based on carbon nanotubes and polyacrylate membranes.

A novel potentiometric solid-state reference electrode containing single-walled carbon nanotubes as the transducer layer between a polyacrylate membrane and the conductor is reported here. Single-walled carbon nanotubes act as an efficient transducer of the constant potentiometric signal originating from the reference membrane containing the Ag/AgCl/Cl(-) ions system, and they are needed to obtain a stable reference potentiometric signal. Furthermore, we have taken advantage of the light insensitivity of single-walled carbon nanotubes to improve the analytical performance characteristics of previously reported solid-state reference electrodes. Four different polyacrylate polymers have been selected in order to identify the most efficient reservoir for the Ag/AgCl system. Finally, two different arrangements have been assessed: (1) a solid-state reference electrode using photo-polymerised n-butyl acrylate polymer and (2) a thermo-polymerised methyl methacrylate:n-butyl acrylate (1:10) polymer. The sensitivity to various salts, pH and light, as well as time of response and stability, has been tested: the best results were obtained using single-walled carbon nanotubes and photo-polymerised n-butyl acrylate polymer. Water transport plays an important role in the potentiometric performance of acrylate membranes, so a new screening test method has been developed to qualitatively assess the difference in water percolation between the polyacrylic membranes studied. The results presented here open the way for the true miniaturisation of potentiometric systems using the excellent properties of single-walled carbon nanotubes.

Nanostructured materials in potentiometry.

Potentiometry is a very simple electrochemical technique with extraordinary analytical capabilities. It is also well known that nanostructured materials display properties which they do not show in the bulk phase. The combination of the two fields of potentiometry and nanomaterials is therefore a promising area of research and development. In this report, we explain the fundamentals of potentiometric devices that incorporate nanostructured materials and we highlight the advantages and drawbacks of combining nanomaterials and potentiometry. The paper provides an overview of the role of nanostructured materials in the two commonest potentiometric sensors: field-effect transistors and ion-selective electrodes. Additionally, we provide a few recent examples of new potentiometric sensors that are based on receptors immobilized directly onto the nanostructured material surface. Moreover, we summarize the use of potentiometry to analyze processes involving nanostructured materials and the prospects that the use of nanopores offer to potentiometry. Finally, we discuss several difficulties that currently hinder developments in the field and some future trends that will extend potentiometry into new analytical areas such as biology and medicine.

Potentiometric online detection of aromatic hydrocarbons in aqueous phase using carbon nanotube-based sensors.

Surfaces made of entangled networks of single-walled carbon nanotubes (SWCNTs) display a strong adsorption affinity for aromatic hydrocarbons. Adsorption of these compounds onto the walls of SWCNTs changes the electrical characteristics of the SWCNT-solution interface. Using these features, we have developed a potentiometric sensor to detect neutral aromatic species. Specifically, we can detect online aromatic hydrocarbons in industrial coolant water. Our chromatographic results confirm the adsorption of toluene onto the walls of carbon nanotubes, and our impedance spectroscopy data show the change in the double layer capacitance of the carbon nanotube-solution interface upon addition of toluene, thus confirming the proposed sensing mechanism. The sensor showed a toluene concentration dependent EMF response that follows the shape of an adsorption isotherm and displayed an immediate response to the presence of toluene with a detection limit of 2.1 ppm. The sensor does not respond to other nonaromatic hydrocarbons that may coexist with aromatic hydrocarbons in water. It shows a qualitative sensitivity and selectivity of 100% and 83%, respectively, which confirms its ability to detect aromatic hydrocarbons in aqueous solutions. The sensor showed an excellent ability to immediately detect the presence of toluene in actual coolant water. Its operational characteristics, including its fast response, low cost, portability, and easy use in online industrial applications, improve those of current chromatographic or spectroscopic techniques.

Real-time potentiometric detection of bacteria in complex samples.

Detecting and identifying pathogen bacteria is essential to ensure quality at all stages of the food chain and to diagnose and control microbial infections. Traditional detection methods, including those based on cell culturing, are tedious and time-consuming, and their further application in real samples generally implies more complex pretreatment steps. Even though state-of-the-art techniques for detecting microorganisms enable the quantification of very low concentrations of bacteria, to date it has been difficult to obtain successful results in real samples in a simple, reliable, and rapid manner. In this Article, we demonstrate that the label-free detection and identification of living bacteria in real samples can be carried out in a couple of minutes and in a direct, simple, and selective way at concentration levels as low as 6 colony forming units/mL (CFU) in complex matrices such as milk or 26 CFU/mL in apple juice where the pretreatment step of samples is extremely easy. We chose Escherichia coli ( E. coli ) CECT 675 cells as a model organism as a nonpathogenic surrogate for pathogenic E. coli O157:H7 to test the effectiveness of a potentiometric aptamer-based biosensor. This biosensor uses single-walled carbon nanotubes (SWCNT) as excellent ion-to-electron transducers and covalently immobilized aptamers as biorecognition elements. The selective aptamer-target interaction significantly changes the electrical potential, thus allowing for both interspecies and interstrain selectivity and enabling the direct detection of the target. This technique is therefore a powerful tool for the immediate identification and detection of microorganisms. We demonstrate the highly selective detection of living bacteria with an immediate linear response of up to 10(4) CFU/mL. The biosensor can be easily built and used, is regenerated without difficulty, and can be used at least five times with no loss in the minimum amount of detected bacteria.

Determination of calcium ion in sap using carbon nanotube-based ion-selective electrodes.

A new reduced-size solid-state electrode using carbon nanotubes as the transducing layer has been developed for the direct determination of Ca(2+) in sap, overcoming problems encountered by commercial ISEs analysing real complex samples. We show that this solid-contact ISE, which can be easily miniaturized, can be used directly in diluted real samples without any other pretreatment. The performance parameters of the new ISE include a Nernstian slope and excellent stability, good coefficients of selectivity, range of linearity (10(-5) to 10(-2.5) M) and limit of detection (10(-6.2) M), thus making it an excellent tool for determining Ca(2+) in a wide range of plant species.

Solid-contact potentiometric aptasensor based on aptamer functionalized carbon nanotubes for the direct determination of proteins.

A facile, solid-contact selective potentiometric aptasensor exploiting a network of single-walled carbon nanotubes (SWCNT) acting as a transducing element is described in this work. The molecular properties of the SWCNT surface have been modified by covalently linking aptamers as biorecognition elements to the carboxylic groups of the SWCNT walls. As a model system to demonstrate the generic application of the approach, a 15-mer thrombin aptamer interacts with thrombin and the affinity interaction gives rise to a direct potentiometric signal that can be easily recorded within 15 s. The dynamic linear range, with a sensitivity of 8.0 mV/log a(Thr) corresponds to the 10(-7)-10(-6) M range of thrombin concentrations, with a limit of detection of 80 nM. The aptasensor displays selectivity against elastase and bovine serum albumin and is easily regenerated by immersion in 2 M NaCl. The aptasensor demonstrates the capacity of direct detection of the recognition event avoiding the use of labels, mediators, or the addition of further reagents or analyte accumulation.