Measuring the Salt Content of Sweat inside a Sweat-Absorbing Skin Adhesive.

Biofluids contain a wealth of different biomarkers, and their concentrations are indicative of the state of the body. As one of those biofluids, sweat is easily accessible, and its composition can, for example, be related to particular diseases or sports performance. Due to the relatively low sweat flow rates, however, adequate sampling is paramount. Here, we aim to explore the potential use of sweat-absorbing skin adhesives as a sweat sampling system for wearable sensors with a simple construction. Upon absorption of sweat, the electrochemical properties of the skin adhesive are determined by the composition of sweat and the amount of sweat within the skin adhesive (i.e., hydration). Through the incorporation of two polarizable electrodes within the skin adhesive, its electrical properties can be monitored using impedance spectroscopy. Here, the double layer capacitance is used as an indicator of hydration, while the conductance depends on both the ion concentration and hydration (the mobility of ions). By evaluating the conductance as a function of hydration, the ion concentration within an electrolyte solution can be estimated. We demonstrate the concept based on a simple model sensor patch, which is exposed to electrolyte solutions containing various concentrations of NaCl and an artificial sweat solution. Finally, we show that ion concentrations in human sweat can be estimated when the model sensor patch is worn during exercise.

Skin and Artificial Skin Models in Electrical Sensing Applications.

Skin electrical properties play a significant role in recording biopotentials by using electrophysiological sensors. To test and evaluate sensor systems, it is commonly accepted to employ artificial skin models due to complications associated with testing on living tissues. The first goal of this Review is to provide a systematic understanding of the relation between skin structure and skin electrochemical behavior at an appropriate depth for electrophysiological sensing applications through a focus on skin structure, electrochemical properties of skin, and theoretical models (equivalent circuits) representing skin electrochemical behavior. The second goal is to review artificial skin models mimicking the electrochemical properties of skin and to give suggestions for future studies on relevant skin models based on a comparison between the behavior of skin and that of artificial skin models. The Review aims to help the reader to analyze the relation between the structure, elements of the equivalent circuits, and the resulting impedance data for both skin and artificial skin models.

Ion-Specific Antipolyelectrolyte Effect on the Swelling Behavior of Polyzwitterionic Layers.

In this study, we systematically investigate the interactions between mobile ions generated from added salts and immobile charges within a sulfobetaine-based polyzwitterionic film in the presence of five salts (KCl, KBr, KSCN, LiCl, and CsCl). The sulfobetaine groups contain quaternary alkylammonium and sulfonate groups, giving the positive and negative charges. The swelling of the zwitterionic film in the presence of different salts is compared with the swelling behavior of a polycationic or polyanionic film containing the same charged groups. For such a comparative study, we design cross-linked terpolymer films with similar thicknesses, cross-link densities, and charge fractions, but with varying charged moieties. While the addition of salt in general leads to a collapse of both cationic and anionic films, the presence of specific types of mobile anions (Cl-, Br-, and SCN-) considerably influences the swelling behavior of polycationic films. We attribute this observation to a different degree of ion-pair formations between the different types of anionic counterions and the immobile cationic quaternary alkylammonium groups in the films where highly polarizable counterions such as SCN- lead to a high degree of ion pairing and less polarizable counterions, such as Cl-, cause a low degree of ion pairing. Conversely, we do not observe any substantial effect of varying the type of cationic counterions (K+, Li+, and Cs+), which we assign to the lack of ion pairing between the weakly polarizable cations and the immobile anionic sulfonate groups in the films. In addition, we observe that the zwitterionic films swell with increasing ionic strength and the degree of swelling is anion dependent, which is in agreement with previous reports on the "antipolyelectrolyte effect". Herein, we explain this ion-specific swelling behavior with the different cation and anion abilities to form ion pairs with quaternary alkylammonium and sulfonate in the sulfobetaine groups.

Antimicrobial PDMS Surfaces Prepared through Fast and Oxygen-Tolerant SI-SARA-ATRP, Using Na2SO3 as a Reducing Agent.

Poly(dimethylsiloxane) (PDMS) is an attractive, versatile, and convenient material for use in biomedical devices that are in direct contact with the user. A crucial component in such a device is its surface in terms of antimicrobial properties preventing infection. Moreover, due to its inherent hydrophobicity, PDMS is rather prone to microbial colonization. Thus, developing an antimicrobial PDMS surface in a simple, large-scale, and applicable manner is an essential step in fully exploiting PDMS in the biomedical device industry. Current chemical modification methods for PDMS surfaces are limited; therefore, we present herein a new method for introducing an atom transfer radical polymerization (ATRP) initiator onto the PDMS surface via the base-catalyzed grafting of [(chloromethyl)phenylethyl]trimethoxysilane to the PDMS. The initiator surface was grafted with poly[2-(dimethylamino)ethyl methacrylate] (PDMAEMA) brushes via a surface-initiated supplemental activator and reducing agent ATRP (SI-SARA-ATRP). The use of sodium sulfite as a novel reducing agent in SI-SARA-ATRP allowed for polymerization during complete exposure to air. Moreover, a fast and linear growth was observed for the polymer over time, leading to a 400 nm thick polymer layer in a 120 min reaction time. Furthermore, the grafted PDMAEMA was quaternized, using various alkylhalides, in order to study the effect on surface antimicrobial properties. It was shown that antimicrobial activity not only depended highly on the charge density but also on the amphiphilicity of the surface. The fast reaction rate, high oxygen tolerance, increased antimicrobial activity, and the overall robustness and simplicity of the presented method collectively move PDMS closer to its full-scale exploitation in biomedical devices.

How Dissociation of Carboxylic Acid Groups in a Weak Polyelectrolyte Brush Depend on Their Distance from the Substrate.

A weak polyelectrolyte brush is composed of a layer of polyacids or polybases grafted by one end of their chains to a substrate surface. For such brush layers immersed in an aqueous solution, the dissociation behavior of the acidic or basic groups and the structural and physical properties of the brush layer will thus be strongly dependent on the environmental conditions. For a polyacid brush layer consisting of, e.g., poly(acrylic acid), this means that the chains in the brush layer will be charged at high pH and uncharged at low pH. However, theoretical scaling laws not only foresee the structural changes occurring in response to the pH-induced dissociation behavior but also how the dissociation behavior of the brush layer depends on the ionic strength of the aqueous solution and the density of acidic groups within the brush layer. We have herein employed spectroscopic ellipsometry and a quartz crystal microbalance with dissipation monitoring (QCM-D) to experimentally evaluate the theoretically predicted dissociation and structural behavior of PAA brushes. Spectroscopic ellipsometry allows us to study the brush thickness as a function of pH and ionic strength, while QCM-D gives us an opportunity to investigate the swelling behavior of PAA brushes at various penetration depths of propagating acoustic waves. Our studies show that the dissociation degree of the carboxylic acid groups in a PAA brush increases with increasing distance from the substrate. Moreover, the ionic strength enhances carboxylic acid dissociation, such that a higher ionic strength leads to a narrower distribution and higher average dissociation degree. In conclusion, our results provide an experimental verification of the theoretically predicted gradient in the degree of dissociation of the acid groups in weak polyacid brush layers and shows that at a pH value equal to approximately the average pKa value of the brush, the state of the acid groups varies from being almost uncharged to almost fully dissociated depending on the ionic strength and vertical position in the brush.