Micropatterned Polymer Nanoarrays with Distinct Superwettability for a Highly Efficient Sweat Collection and Sensing Patch.

Wearable sweat sensor offers a promising means for noninvasive real-time health monitoring, but the efficient collection and accurate analysis of sweat remains challenging. One of the obstacles is to precisely modulate the surface wettability of the microfluidics to achieve efficient sweat collection. Here a facile initiated chemical vapor deposition (iCVD) method is presented to grow and pattern polymer nanocone arrays with distinct superwettability on polydimethylsiloxane microfluidics, which facilitate highly efficient sweat transportation and collection. The nanoarray is synthesized by manipulating monomer supersaturation during iCVD to induce controlled nucleation and preferential vertical growth of fluorinated polymer. Subsequent selective vapor deposition of a conformal hydrogel nanolayer results in superhydrophilic nanoarray floor and walls within the microchannel that provide a large capillary force and a superhydrophobic ceiling that drastically reduces flow friction, enabling rapid sweat transport along varied flow directions. A carbon/hydrogel/enzyme nanocomposite electrode is then fabricated by sequential deposition of highly porous carbon nanoparticles and hydrogel nanocoating to achieve sensitive and stable sweat detection. Further encapsulation of the assembled sweatsensing patch with superhydrophobic nanoarray imparts self-cleaning and water-proof capability. Finally, the sweat sensing patch demonstrates selective and sensitive glucose and lactate detection during the on-body test.

Fabrication and Characterization of Flexible and Miniaturized Humidity Sensors Using Screen-Printed TiO2 Nanoparticles as Sensitive Layer.

This paper describes the fabrication and the characterization of an original example of a miniaturized resistive-type humidity sensor, printed on flexible substrate in a large-scale manner. The fabrication process involves laser ablation for the design of interdigitated electrodes on PET (Poly-Ethylene Terephthalate) substrate and a screen-printing process for the deposition of the sensitive material, which is based on TiO2 nanoparticles. The laser ablation process was carefully optimized to obtain micro-scale and well-resolved electrodes on PET substrate. A functional paste based on cellulose was prepared in order to allow the precise screen-printing of the TiO2 nanoparticles as sensing material on the top of the electrodes. The current against voltage (I-V) characteristic of the sensor showed good linearity and potential for low-power operation. The results of a humidity-sensing investigation and mechanical testing showed that the fabricated miniaturized sensors have excellent mechanical stability, sensing characteristics, good repeatability, and relatively fast response/recovery times operating at room temperature.

Electrolyte-induced aggregation of zein protein nanoparticles in aqueous dispersions.

Ion specific effects on the charging and aggregation features of zein nanoparticles (ZNP) were studied in aqueous suspensions by electrophoretic and time-resolved dynamic light scattering techniques. The influence of mono- and multivalent counterions on the colloidal stability was investigated for positively and negatively charged particles at pH values below and above the isoelectric point, respectively. The sequence of the destabilization power of monovalent salts followed the prediction of the indirect Hofmeister series for positively charged particles, while the direct Hofmeister series for negatively charged ones assumed a hydrophobic character for their surface. The multivalent ions destabilized the oppositely charged ZNPs more effectively and the aggregation process followed the Schulze-Hardy rule. For some multivalent ions, strong adsorption led to charge reversal resulting in restabilization of the suspensions. The experimental critical coagulation concentrations (CCCs) could be well-predicted with the theory developed by Derjaguin, Landau, Verwey and Overbeek indicating that the aggregation processes were mainly driven by electrical double layer repulsion and van der Waals attraction. The ion specific dependence of the CCCs is owing to the modification of the surface charge through ion adsorption at different extents. These results are crucial for drug delivery applications, where inorganic electrolytes are present in ZNP samples.

Investigation of Silk Fibroin/Poly(Acrylic Acid) Interactions in Aqueous Solution.

Silk fibroin (SF) is a protein with many outstanding properties (superior biocompatibility, mechanical strength, etc.) and is often used in many advanced applications (epidermal sensors, tissue engineering, etc.). The properties of SF-based biomaterials may additionally be tuned by SF interactions with other (bio)polymers. Being a weak amphoteric polyelectrolyte, SF may form polyelectrolyte complexes (PECs) with other polyelectrolytes of opposite charge, such as poly(acrylic acid) (PAA). PAA is a widely used, biocompatible, synthetic polyanion. Here, we investigate PEC formation between SF and PAA of two different molecular weights (MWs), low and high, using various techniques (turbidimetry, zeta potential measurements, capillary viscometry, and tensiometry). The colloidal properties of SF isolated from Bombyx mori and of PAAs (MW, overlap concentration, the influence of pH on zeta potential, adsorption at air/water interface) were determined to identify conditions for the SF-PAA electrostatic interaction. It was shown that SF-PAA PEC formation takes place at different SF:PAA ratios, at pH 3, for both high and low MW PAA. SF-PAA PEC's properties (phase separation, charge, and surface activity) are influenced by the SF:PAA mass ratio and/or the MW of PAA. The findings on the interactions contribute to the future development of SP-PAA PEC-based films and bioadhesives with tailored properties.

Study of vitamin E microencapsulation and controlled release from chitosan/sodium lauryl ether sulfate microcapsules.

Potential benefit of microencapsulation is its ability to deliver and protect incorporated ingredients such as vitamin E. Microcapsule wall properties can be changed by adding of coss-linking agents that are usually considered toxic for application. The microcapsules were prepared by a spray-drying technique using coacervation method, by depositing the coacervate formed in the mixture of chitosan and sodium lauryl ether sulfate to the oil/water interface. All obtained microcapsules suspensions had slightly lower mean diameter compared to the starting emulsion (6.85 ± 0.213 µm), which shows their good stability during the drying process. The choice and absence of cross-linking agents had influence on kinetics of vitamin E release. Encapsulation efficiency of microcapsules without cross-linking agent was 73.17 ± 0.64 %. This study avoided the use of aldehydes as cross-linking agents and found that chitosan/SLES complex can be used as wall material for the microencapsulation of hydrophobic active molecules in cosmetic industry.

Chitosan/Sodium Dodecyl Sulfate Complexes for Microencapsulation of Vitamin E and Its Release Profile-Understanding the Effect of Anionic Surfactant.

Microencapsulation of bioactive substances is a common strategy for their protection and release rate control. The use of chitosan (Ch) is particularly promising due to its abundance, biocompatibility, and interaction with anionic surfactants to form complexes of different characteristics with relevance for use in microcapsule wall design. In this study, Ch/sodium dodecyl sulfate (SDS) microcapsules, without and with cross-linking agent (formaldehyde (FA) or glutaraldehyde (GA)), were obtained by the spray drying of vitamin E loaded oil-in-water emulsion. All of the microcapsules had good stability during the drying process. Depending on the composition, their product yield, moisture content, and encapsulation efficiency varied between 11-34%, 1.14-1.62%, and 94-126%, respectively. SEM and FTIR analysis results indicate that SDS as well as cross-linkers significantly affected the microcapsule wall properties. The profiles of in vitro vitamin E release from the investigated microcapsules fit with the Korsmeyer-Peppas model (r2 > 0.9). The chemical structure of the anionic surfactant was found to have a significant effect on the vitamin E release mechanism. Ch/SDS coacervates may build a microcapsule wall without toxic crosslinkers. This enabled the combined diffusion/swelling based release mechanism of the encapsulated lipophilic substance, which can be considered favorable for utilization in food and pharmaceutical products.

Interactions of zein and zein/rosin nanoparticles with natural polyanion gum arabic.

The objective of this study was to investigate interactions of zein (Z) and zein/rosin (Z/R) nanoparticles with gum arabic (GA), at different pH. Nanoparticles were firstly prepared by antisolvent precipitation of biopolymers from aqueous ethanol solutions. Nanoparticles suspensions were then dialyzed against water in order to remove ethanol and other impurities, and water suspensions of zein and zein/rosin nanoparticles were obtained. It was shown that composition of nanoparticles affects their surface charge density. Zeta potential of nanoparticles was positive without GA and changed to negative after addition of GA, at all pH tested. SEM analysis proved both Z and Z/R nanoparticles to be spherical and in size around 200 nm. The effect of addition of GA on particle size was determined using dynamic light scattering method. It was found that addition of GA increases size of nanoparticles at pH = 4 and pH = 5.5, from 150 - 220 nm to 250 - 320 nm. However, at pH = 3 it causes aggregation process, and diameter of particles increases up to few micrometres. Isothermal titration calorimetry was used to measure enthalpy changes in reaction between Z or Z/R nanoparticles and GA. Results showed that reaction between GA and Z or Z/R NPs is exothermic at each pH tested, except for Z NPs at pH = 3, where it was endothermic. At presented pHs, Z/R NPs were less charged compared to Z NPs, and their surface get saturated with GA molecules more rapidly. Z NPs showed greater enthalpy change in reaction with GA, compared to Z/R NPs.

Influence of polymer-surfactant interactions on o/w emulsion properties and microcapsule formation.

The aim of this work was to investigate the influence of interactions between 1.00%w/w hydroxypropylmethyl cellulose (HPMC) and the anionic surfactant sodium dodecylsulfate (SDS) on the properties of 20%w/w sunflower oil/water emulsion and the corresponding microcapsules obtained by spray drying technique. On the basis of the viscosity and rheological measurements, particle size and particle size distribution, and stability assessment, it was concluded that the emulsion characteristics depend strongly on the interaction mechanism. Significant increase in viscosity and non-Newtonian thixotropic behavior was observed in the SDS concentration range from 0.15 to 1.00%w/v, corresponding to HPMC-SDS interactions in the continuous phase. In the interaction region, a three-dimensional network is formed in the continuous phase by intermolecular binding of SDS molecules to the adjacent HPMC chains, which contributes to increase in the viscosity and thixotropic properties. The mean diameter of emulsion particles, d(vs), decreases with increase in SDS concentration, but emulsion stability depends on the adsorption layer structure, i.e. HPMC-SDS interactions. The HPMC/SDS complex adsorbed at the o/w interface makes the layer more compact, enhancing thus emulsion stability. Microcapsules, obtained in the form of powder by spray drying of emulsions, have good redispersibility in water, but their stability changes depending on the HPMC-SDS interaction mechanism, i.e., the HPMC/SDS complex forms a more compact layer that is resistant to breaking during the drying process. The highest encapsulation efficiency was found in the interaction region.