Reducing Ice Adhesion to Polyelectrolyte Surfaces by Counterion-Mediated Nonfrozen Hydration Water.

Hydrophilic anti-icing coatings can be energy-effective passive solutions for combating ice accretion and reducing ice adhesion. However, their underlying mechanisms of action remain inferential and are ill-defined from a molecular perspective. Here, we systematically investigate the influence of the counterion identity on the shear ice adhesion strength to cationic polymer coatings having quaternary alkyl ammonium moieties as chargeable groups. Temperature-dependent molecular information on the hydrated polymer films is obtained using total internal reflection (TIR) Raman spectroscopy, complemented with differential scanning calorimetry (DSC) and ellipsometry. Ice adhesion measurements show a pronounced counterion-specific behavior with a sharp increase in adhesion at temperatures that depend on the anion identity, following the order Cl- < F- < SCN- < Br- < I-. Linked to the freezing of hydration water, the specific ordering results from differences in ion pairing and the amount of water present within the polymer film. Moreover, similar effects can be promoted by varying the cross-linking density in the coating while keeping the anion identity fixed. These findings shed new light on low ice adhesion mechanisms and may inspire novel approaches for improved anti-icing coatings.

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.

Self-Cross-Linkable Chitosan-Alginate Complexes Inspired by Mussel Glue Chemistry.

In this study, mussel-inspired chemistry, based on catechol-amine reactions, was adopted to develop self-cross-linkable chitosan-alginate (Chi-Alg) complexes. To do so, the biopolymers were each substituted with ∼20% catechol groups (ChiC and AlgC), and then four complex combinations (Chi-Alg, ChiC-Alg, Chi-AlgC, ChiC-AlgC) were prepared at the surface and in bulk solution. Based on QCM-D and lap shear adhesion tests, the complex with catechol only on Chi (ChiC-Alg) did not show a significant variation from the control complex (Chi-Alg). Conversely, the complexes with catechol on alginate (Chi-AlgC and ChiC-AlgC) rendered a self-cross-linking property and enhanced cohesive properties.

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.

Fibrin Adsorption on Cardiovascular Biomaterials and Medical Devices.

Medical devices that are inserted in blood vessels always risk eliciting thrombosis, and the surface properties of such devices are thus of major importance. The initiating step for surface-induced pathological coagulation has been associated with adsorption of fibrinogen protein on biomaterial surfaces and subsequent polymerization into an insoluble fibrin clot. This issue gives rise to an inherent challenge in biomaterial design as varied surface materials must fulfill specialized roles while also minimizing thrombotic complications from spontaneous fibrin(ogen) recruitment. We have aimed to characterize the thrombogenic properties of state-of-the-art cardiovascular biomaterials and medical devices by quantifying the relative surface-dependent adsorption and formation of fibrin followed by analysis of the resulting morphologies. We identified stainless steel and amorphous fluoropolymer as comparatively preferable biomaterials based on their low fibrin(ogen) recruitment, in comparison to other metallic and polymeric biomaterials, respectively. In addition, we observed a morphological trend that fibrin forms fiber structures on metallic surfaces and fractal branched structures on polymeric surfaces. Finally, we used vascular guidewires as clotting substrates and found that fibrin adsorption depends on parts of the guidewire that are exposed, and we correlated the morphologies on uncoated guidewires with those formed on raw stainless-steel biomaterials.

Fibrin formation and fractal organization at cationic, anionic, and zwitterionic polymer coated interfaces.

Biomaterial-associated thrombosis remains a persistent challenge whenever medical devices are inserted in blood vessels. The issue is principally addressed by the development of antithrombogenic coatings that prevent the formation of blood clots, e.g. by limiting adsorption of fibrin - the core protein network of a clot. Charged polymers (i.e. polyelectrolytes and zwitterionic polymers) show potential as coating materials for medical devices, and we here investigate these polymer coatings in the context of biomaterial-associated thrombosis. Our findings indicate that fibrin polymerization can yield a surface-dependent distribution of fractal-like branched structures and amorphous aggregates, with surface-induced fibrin formation dominating for anionic polymer interfaces and recruitment of bulk-formed fibrin dominating for cationic polymer interfaces. In addition, we identify coatings containing zwitterionic sulfobetaine groups as promising candidates for antithrombogenic biomaterials.

Fragmentation of Hydrophilic Guidewire Coatings During Neuroendovascular Therapy.

PURPOSE: Cerebral polymer coating embolism from intravascular devices may cause serious complications after endovascular therapy (EVT) for neurovascular diseases. Although polymer fragments are often created during endovascular procedures, exact mechanisms of their formation, especially if of small size, are largely unknown. METHODS: In this study eight microguidewires (Asahi Chikai 200 cm (Asahi Intecc, Aichi, Japan), Asahi Chikai Black (Asahi Intecc), Fathom™ (Boston Scientific, Marlborough, MA, USA), Hybrid (Balt Extrusion, Montmorency, France), Radifocus® Guide Wire GT (Terumo, Leuven, Belgium), Synchro2® (Stryker, Kalamazoo, MI, USA), Transend™ EX (Boston Scientific), and Traxcess™ (MicroVention®, Tustin, CA, USA)) frequently used during EVT were investigated ex vivo using their dedicated metal or plastic insertion tools to assess for coating delamination after backloading of the microguidewires. RESULTS: Backloading caused damage to the coating of all microguidewires especially when the main body of the guidewires was bent in front of the insertion tool. All studied microguidewires produced microscopic filamentous and/or band-like coating fragments. Few larger irregular fragments were observed, but also very small fragments measuring 1-3 µm in diameter were found. Spectroscopic measurements of polymer fragments and microguidewires identified various polymers. CONCLUSION: Backloading of polymer-coated microguidewires during EVT should be minimized if possible. More stable hydrophilic coatings on microguidewires and less traumatic insertion tools are desirable.

Influence of Ionic Strength and Specific Ion Effects on Polyelectrolyte Multilayer Films with pH-Responsive Behavior.

Layer-by-layer assembled multilayer films have shown great potential for different applications owing to their responsive behavior. Herein, we systematically investigated the effects of composition, salt concentration, and ion specificity on the pH responsiveness of covalently crosslinked chitosan and alginate dialdehyde multilayer films. The changes in film swelling were measured using ellipsometry from low (0.01 mM) to high (3 M) salt (NaCl or NaSCN) concentrations at pH 3, 6, and 9. The swelling responses to increasing ionic strength matched the swelling responses observed for polyzwitterionic and weak monocomponent polyelectrolyte films and depended on the multilayer composition, pH, and ion specificity. Finally, we used the ellipsometric data to demonstrate that the pH responsiveness of such multilayer films, as measured using a quartz crystal microbalance with dissipation monitoring, strongly depends on the ionic condition under which the responses were measured. We thus show that erroneous conclusions about the pH responsiveness of polyelectrolyte multilayer films can be easily obtained if the ionic environment of the application does not closely resemble the ionic condition under which the pH responsiveness is tested.

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.

Engineered substrates incapable of induction of chondrogenic differentiation compared to the chondrocyte imprinted substrates.

It is well established that surface topography can affect cell functions. However, finding a reproducible and reliable method for regulating stem cell behavior is still under investigation. It has been shown that cell imprinted substrates contain micro- and nanoscale structures of the cell membrane that serve as hierarchical substrates, can successfully alter stem cell fate. This study investigated the effect of the overall cell shape by fabricating silicon wafers containing pit structure in the average size of spherical-like chondrocytes using photolithography technique. We also used chondrocyte cell line (C28/I2) with spindle-like shape to produce cell imprinted substrates. The effect of all substrates on the differentiation of adipose-derived mesenchymal stem cells (ADSCs) has been studied. The AFM and scanning electron microscopy images of the prepared substrates demonstrated that the desired shapes were successfully transferred to the substrates. Differentiation of ADSCs was investigated by immunostaining for mature chondrocyte marker, collagen II, and gene expression of collagen II, Sox9, and aggrecan markers. C28/I2 imprinted substrate could effectively enhanced chondrogenic differentiation compared to regular pit patterns on the wafer. It can be concluded that cell imprinted substrates can induce differentiation signals better than engineered lithographic substrates. The nanostructures on the cell-imprinted patterns play a crucial role in harnessing cell fate. Therefore, the patterns must include the nano-topographies to have reliable and reproducible engineered substrates.

Dopamine-Assisted Layer-by-Layer Deposition Providing Coatings with Controlled Thickness, Roughness, and Functional Properties.

In this study, dopamine-assisted deposition combined with layer-by-layer assembly was investigated as an efficient method for preparing coatings with tunable thickness, roughness, and functional properties. By this method, one can first benefit from the versatile chemistry of dopamine allowing the co-deposition of various functional materials, for example, polymers, ions, and nanoparticles, within the coating. Moreover, the layer-by-layer approach allows tuning the coating thickness and surface roughness, as well as varying the chemical composition of the coating in the vertical direction. Herein, we demonstrated the benefits of using this method in fabricating both single- and multi-component coatings.

Bioadhesive Tannic-Acid-Functionalized Zein Coating Achieves Engineered Colonic Delivery of IBD Therapeutics via Reservoir Microdevices.

The biggest challenge in oral delivery of anti-inflammatory drugs such as 5-aminosalicylic acid (5-ASA) is to (i) prevent rapid absorption in the small intestine and (ii) achieve localized release at the site of inflammation in the lower gut, i.e., the colon. Here, we present an advanced biopolymeric coating comprising of tannic-acid-functionalized zein protein to provide a sustained, colon-targeted release profile for 5-ASA and enhance the mucoadhesion of the dosage form via a mussel-inspired mechanism. To enable localized delivery and provide high local concentration, 5-ASA is loaded into the microfabricated drug carriers (microcontainers) and sealed with the developed coating. The functionality and drug release profile of the coating are characterized and optimized in vitro, showing great tunability, scalability, and stability toward proteases. Further, ex vivo experiments demonstrate that the tannic acid functionalization can significantly enhance the mucoadhesion of the coating, which is followed up by in vivo investigations on the intestinal retention, and pharmacokinetic evaluation of the 5-ASA delivery system. Results indicate that the developed coating can provide prolonged colonic delivery of 5-ASA. Therefore, the here-developed biodegradable coating can be an eco-friendly substitute to the state-of-the-art commercial counterparts for targeted delivery of 5-ASA and other small molecule drugs.

Stiffness control in dual color tomographic volumetric 3D printing.

Tomographic volumetric printing (TVP) physically reverses tomography to offer fast and auxiliary-free 3D printing. Here we show that wavelength-sensitive photoresins can be cured using visible ([Formula: see text] nm) and UV ([Formula: see text] nm) sources simultaneously in a TVP setup to generate internal mechanical property gradients with high precision. We develop solutions of mixed acrylate and epoxy monomers and utilize the orthogonal chemistry between free radical and cationic polymerization to realize fully 3D stiffness control. The radial resolution of stiffness control is 300 µm or better and an average modulus gradient of 5 MPa/µm is achieved. We further show that the reactive transport of radical inhibitors defines a workpiece's shape and limits the achievable stiffness contrast to a range from 127 MPa to 201 MPa according to standard tensile tests after post-processing. Our result presents a strategy for controlling the stiffness of material spatially in light-based volumetric additive manufacturing.

Polytetrafluoroethylene coating fragments during neuroendovascular therapy: An analysis of two damaged microguidewires.

Cerebral polymer coating embolism from intravascular devices represents a potentially serious complication to endovascular therapy (EVT). We report two cases of neuroendovascular treatment where filamentous polymer fragments were noted possibly due to damage of the surface coating during manipulation and backloading of microguidewires. As the exact origin of the debris was initially not known, microguidewires and fragments were examined with light microscopy, stereomicroscopy, scanning electron microscopy and attenuated-total-reflection Fourier transform infrared spectroscopy. Fragments consisted of polytetrafluoroethylene and silicone oil stemming from the proximal shaft of a standard microguidewire. To our knowledge, this is the first report of polytetrafluoroethylene coating fragments created during EVT. Future studies should assess the mechanism of polymer coating delamination and its potential consequences during EVT including inadvertent fragment migration into the cerebral circulation.

Enhancing the sweat resistance of sunscreens.

BACKGROUND: While sunbathing of performing outdoor sport activities, sunscreens are important for protection of uncovered skin against ultraviolet (UV) radiation. However, perspiration negatively affects the performance of a sunscreen film by weakening its substantivity and uniformity through the activation of two mechanisms, namely sunscreen wash-off and sunscreen redistribution. MATERIAL AND METHODS: We used a perspiring skin simulator to investigate the effect of sunscreen formulation on its efficiency upon sweating. Specifically, we modified the sunscreen formulation by incorporating a hydrophobic film former and adding water-absorbing particles. Sunscreen performance before and after perspiration is assessed by in vitro sun protection factor measurements, direct detection of changes in the sunscreen distribution using UV reflectance imaging, and by coherent anti-Stokes Raman scattering (CARS) microscopy for microscopic characterization of the UV filter relocation. RESULTS: The results show that incorporating a hydrophobic film former can decrease sunscreen wash-off due to sweating, while an excessive amount of film former might negatively affect the sunscreen distribution. The addition of water-absorbing particles, on the other hand, had either a negative or positive impact on the sunscreen substantivity, depending on the particle properties. While the addition of large water-absorbing particles appeared to increase sunscreen redistribution, smaller particles that could form a gel-like structure upon contact with water, appeared to change sunscreen wetting and sweat droplet spreading, thereby decreasing sunscreen wash-off and sunscreen redistribution. CONCLUSIONS: We find that using a combination of hydrophobic film formers, which increase water resistance, and small water-absorbing particles, which change the wetting behavior, can make sunscreen formulations more sweat-resistant and less runny.

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.

In vitro skin model for characterization of sunscreen substantivity upon perspiration.

OBJECTIVE: The resistance of sunscreens to the loss of ultraviolet (UV) protection upon perspiration is important for their practical efficacy. However, this topic is largely overlooked in evaluations of sunscreen substantivity due to the relatively few well-established protocols compared to those for water resistance and mechanical wear. METHODS: In an attempt to achieve a better fundamental understanding of sunscreen behaviour in response to sweat exposure, we have developed a perspiring skin simulator, containing a substrate surface that mimics sweating human skin. Using this perspiring skin simulator, we evaluated sunscreen performance upon perspiration by in vitro sun protection factor (SPF) measurements, optical microscopy, ultraviolet (UV) reflectance imaging and coherent anti-Stokes Raman scattering (CARS) microscopy. RESULTS AND CONCLUSION: Results indicated that perspiration reduced sunscreen efficiency through two mechanisms, namely sunscreen wash-off (impairing the film thickness) and sunscreen redistribution (impairing the film uniformity). Further, we investigated how the sweat rate affected these mechanisms and how sunscreen application dose influenced UV protection upon perspiration. As expected, higher sweat rates led to a large loss of UV protection, while a larger application dose led to larger amounts of sunscreen being washed-off and redistributed but also provided higher UV protection before and after sweating.

OBJECTIF: La résistance des écrans solaires à la perte de protection contre les ultraviolets (UV) à cause de la transpiration est importante quant à leur efficacité pratique. Cependant, ce point est généralement négligé dans les évaluations de la substantivité des écrans solaires en raison du nombre relativement faible de protocoles bien établis, en comparaison avec ceux pour la résistance à l'eau et l'usure mécanique. MÉTHODES: Dans le but de parvenir à une meilleure compréhension fondamentale du comportement des écrans solaires en cas d'exposition à la sueur, nous avons développé un simulateur de peau transpirante, dont la surface de substrat imite la transpiration de la peau humaine. À l'aide de ce simulateur, nous avons évalué les performances des écrans solaires lors de la transpiration par des mesures in vitro du facteur de protection solaire (FPS), par microscopie optique, par imagerie de la réflectance ultraviolette (UV) et par microscopie cohérente de diffusion Raman anti-Stokes (coherent anti-Stokes Raman scattering, CARS). RÉSULTATS ET CONCLUSION: Les résultats ont montré que la transpiration réduisait l'efficacité de l'écran solaire en raison de deux mécanismes, à savoir le lavage de l'écran solaire (altération de l'épaisseur du film) et la redistribution de l'écran solaire (altération de l'uniformité du film). De plus, nous avons étudié comment le taux de transpiration affectait ces mécanismes et comment la dose d'application d'écran solaire influençait la protection UV en cas de transpiration. Comme l'on pouvait s'y attendre, des taux de sueur plus élevés ont entraîné une perte importante de protection contre les UV, tandis qu'une dose d'application plus importante a conduit à des quantités plus importantes d'écran solaire lavé et redistribué, mais a également fourni une protection contre les UV plus élevée avant et après la transpiration.

Parameterization of the optical constants of polydopamine films for spectroscopic ellipsometry studies.

Bio-inspired polydopamine coatings offer vast possibilities for surface modification of materials. The thickness of such nanometric coatings is usually estimated based on ellipsometry measurements. However, the complex light-absorbing nature of polydopamine is often overlooked when analyzing such data, which can result in inaccurate estimations of the coating thickness as well as the optical properties. In this study, we prepared and characterized three polydopamine coatings where the film thickness and surface roughness are systematically varied. For each case, we developed suitable optical models and showed how an inappropriate optical model can provide inaccurate estimates of the coating properties. AFM height profiles were obtained from scratched areas of each sample to verify the thickness values estimated by ellipsometry. The results confirm that polydopamine coatings, depending on the oxidation conditions, can possess different structural and optical properties, and thus require unique optical models for the ellipsometry analysis.

Cell-imprinted substrates: in search of nanotopographical fingerprints that guide stem cell differentiation.

Cell-imprinted substrates direct stem cell differentiation into various lineages, suggesting the idea of lineage-specific nanotopography. We herein examined the surface topography of five different imprinted cell patterns using AFM imaging and statistical analysis of amplitude, spatial, and hybrid roughness parameters. The results suggest that different cell imprints possess distinguished nanotopographical features.

Water vapor permeation through topical films on a moisture-releasing skin Model.

BACKGROUND: Covering the skin by topical films affects the skin hydration and transepidermal water loss (TEWL). In vivo studies to investigate the water vapor permeation through topical films are complicated, expensive, ethically not preferred, and time- and labor-consuming. The objective of this study was to introduce an in vitro and subject-independent alternative evaluation method to predict the breathability of topical formulations. METHODS: In this study, we developed an in vitro setup to simulate the TEWL values of human skin and investigated the breathability of five polymeric film formers used in topical formulations. Furthermore, a comparative in vivo TEWL study was performed on ten human volunteers with defined areas of skin covered with films of two selected polymers possessing different barrier properties. RESULTS: By employing the in vitro setup, a vinylpyrrolidone/acrylates/lauryl methacrylate copolymer was determined to form the most breathable film, whereas acrylates/octylacrylamide copolymer and shellac films showed the highest barrier properties. The in vivo TEWL study demonstrated the same relative barrier properties for the acrylates/octylacrylamide and polyurethane-64 films, despite a more complex driving force for water vapor permeation due to moisture accumulation on the covered skin surfaces. CONCLUSION: We obtained a good correlation between the in vitro and in vivo results, demonstrating that our model can categorize different polymeric film formers based on their breathability when applied to human skin. This information can aid in selecting suitable film-forming polymers for topical formulations with either breathable or occluding functionalities.