Soft nanofluidics governing minority ion exclusion in charged hydrogels.

We investigate ionic partition of negatively charged molecular probes into also negatively charged, covalently crosslinked alginate hydrogels. The aim is to delimit the domain of validity of the major nanoelectrostatic models, and in particular to assess the influence of hydrogel chain mobility on ionic partition. We find that the widely used Gibbs-Donnan model greatly overestimates exclusion of the co-ion probes used. For low molecular weight probes, a much better fit is obtained by taking into account the electrostatics in the nanometric gel pores by means of the Poisson-Boltzmann framework; the fit is improved slightly when taking into account alginate chain mobility. For high molecular weight probes, we find it essential to take into account local gel deformation due to electrostatic repulsion between the flexible gel strands and the probe. This is achieved by combining Poisson-Boltzmann simulations with heterogeneous pore size distribution given by the Ogston model, or more simply and precisely, by applying a semi-empirical scaling law involving the ratio between Debye length and pore size.

Sweat Biomarker Sensor Incorporating Picowatt, Three-Dimensional Extended Metal Gate Ion Sensitive Field Effect Transistors.

Ion sensitive field effect transistors (ISFETs) form a very attractive solution for wearable sensors due to their capacity for ultra-miniaturization, low power operation, and very high sensitivity, supported by complementary metal oxide semiconductor (CMOS) integration. This paper reports for the first time, a multianalyte sensing platform that incorporates high performance, high yield, high robustness, three-dimensional-extended-metal-gate ISFETs (3D-EMG-ISFETs) realized by the postprocessing of a conventional 0.18 µm CMOS technology node. The detection of four analytes (pH, Na+, K+, and Ca2+) is reported with excellent sensitivities (58 mV/pH, -57 mV/dec(Na+), -48 mV/dec(K+), and -26 mV/dec(Ca2+)) close to the Nernstian limit, and high selectivity, achieved by the use of highly selective ion selective membranes based on postprocessing integration steps aimed at eliminating any significant sensor hysteresis and parasitics. We are reporting simultaneous time-dependent recording of multiple analytes, with high selectivities. In vitro real sweat tests are carried out to prove the validity of our sensors. The reported sensors have the lowest reported power consumption, being capable of operation down to 2 pW/sensor. Due to the ultralow power consumption of our ISFETs, we achieve and report a final four-analyte passive system demonstrator including the readout interface and the remote powering of the ISFET sensors, all powered by an radio frequency (RF) signal.

Three-Dimensional Integrated Ultra-Low-Volume Passive Microfluidics with Ion-Sensitive Field-Effect Transistors for Multiparameter Wearable Sweat Analyzers.

Wearable systems could offer noninvasive and real-time solutions for monitoring of biomarkers in human sweat as an alternative to blood testing. Recent studies have demonstrated that the concentration of certain biomarkers in sweat can be directly correlated to their concentrations in blood, making sweat a trusted biofluid candidate for noninvasive diagnostics. We introduce a fully on-chip integrated wearable sweat sensing system to track biochemical information at the surface of the skin in real time. This system heterogeneously integrates, on a single silicon chip, state-of-the-art ultrathin body (UTB) fully depleted silicon-on-insulator (FD-SOI) ISFET sensors with a biocompatible microfluidic interface, to deliver a "lab-on-skin" sensing platform. A full process for the fabrication of this system is proposed in this work and is demonstrated by standard semiconductor fabrication procedures. The system is capable of collecting small volumes of sweat from the skin of a human and posteriorly passively driving the biofluid, by capillary action, to a set of functionalized ISFETs for analysis of pH level and Na+ and K+ concentrations. Drop-casted ion-sensing membranes on different sets of sensors on the same substrate enable multiparameter analysis on the same chip, with small and controlled cross-sensitivities, whereas a miniaturized quasireference electrodes set a stable analyte potential, avoiding the use of a cumbersome external reference electrode. The progress of lab-on-skin technology reported here can lead to autonomous wearable systems enabling real-time continuous monitoring of sweat composition, with applications ranging from medicine to lifestyle behavioral engineering and sports.

Facile fabrication of nanofluidic diode membranes using anodic aluminium oxide.

Active control of ion transport plays important roles in chemical and biological analytical processes. Nanofluidic systems hold the promise for such control through electrostatic interaction between ions and channel surfaces. Most existing experiments rely on planar geometry where the nanochannels are generally very long and shallow with large aspect ratios. Based on this configuration the concepts of nanofluidic gating and rectification have been successfully demonstrated. However, device minimization and throughput scaling remain significant challenges. We report here an innovative and facile realization of hetero-structured Al(2)O(3)/SiO(2) (Si) nanopore array membranes by using pattern transfer of self-organized nanopore structures of anodic aluminum oxide (AAO). Thanks to the opposite surface charge states of Al(2)O(3) (positive) and SiO(2) (negative), the membrane exhibits clear rectification of ion current in electrolyte solutions with very low aspect ratios compared to previous approaches. Our hetero-structured nanopore arrays provide a valuable platform for high throughput applications such as molecular separation, chemical processors and energy conversion.