Charge transport in electrospinning of polyelectrolyte solutions.

This study elucidates the electrical charge transport during electrospinning of weak polyelectrolyte (poly(acrylic acid) (PAA)) solutions by employing current emission measurements. With pH variation, the PAA ionization degree could be controlled from uncharged at low pH to weakly charged at intermediate solution pH. Electrospinning neutral poly(vinylpyrrolidone) (PVP) as a reference polymer solution confirmed established current-flow rate scaling relationships as shown by De La Mora and Loscertales (1994), I ∼ (γKQ)ν, independent of the applied electric field polarity, where ν = 0.5, K is the conductivity, γ is the surface tension, Q is the flow rate, and I is the current. Similarly, the uncharged PAA did not display any polarity dependence, yet ν ≈ 0.8. Negatively charged PAA, however, showed a marked deviation in the current-flow rate behavior, which was affected by the applied electric field polarity. In the case of negative polarity, ν = 0.99, whereas for a positive polarity ν = 0.68. Similarly, the voltage required for stable cone-jet electrospinning of charged PAA was significantly higher in the negative polarity configuration for all tested flow rates (300-1600 µL h-1). As opposed to merely surface charges typically considered when electrospinning leaky dielectric fluids, as suggested by Melcher and Taylor (1969), our results suggest that the measured current is also affected by volumetric charges from charged PAA in the bulk of the jet. The proposed additional charge transport might affect the orientational order within PE-based nanofibers and their diameter.

Electrically Mediated Static Contact Angle and Hysteresis of Polyelectrolyte Solutions.

Manipulating a droplet by electrowetting-on-dielectric (EWOD) is vital in various fields ranging from industrial applications to life sciences. As of now, EWOD research has focused primarily on aqueous electrolytes and ionic liquids. This paper investigates the electrowetting behavior of weak polyelectrolyte solutions containing poly(acrylic acid) (PAA). The study reveals distinct wetting behavior of weakly and fully charged PAA droplets controlled by their solution pH. Under an applied electric field, strongly ionized PAA wets more effectively than weakly charged PAA. The electrowetting hysteresis of fully ionized PAA droplets was also higher than that of weakly charged droplets. The reason may be the suppression of retraction flow near the contact line. In this thin region, the electric field aligns the stretched polymer chains perpendicular to the dielectric surface, thus affecting the bulk rheological properties. The results reveal how charge-connectivity and polyelectrolyte conformation under an external electric field can control the electrowetting gain and the hysteresis. This previously unexplored electrowetting mechanism of polyelectrolyte solutions might help order and manipulate biological polyelectrolytes, such as deoxyribonucleic acid (DNA), polypeptides, and glycosaminoglycans.

Thermoregulation of Hydrogel Spatiotemporal Mechanics by Exploiting the Folding-Unfolding Characteristics of Globular Proteins.

The incorporation of proteins into hydrogel networks has the potential to enhance bioactivity and biocompatibility. In this work, we report on the fabrication of a polymer-protein hydrogel consisting of polymethacrylamide (PMAAm) and bovine serum albumin (BSA). The hydrogel was prepared by in situ polymerization of methacrylamide in the presence of BSA at elevated temperatures. Due to its specific interactions between corresponding functional groups, BSA acts as a cross-linker of polymer chains. Hydrogel with optimized composition and preparation conditions (BSA/methacrylamide ratio and synthesis temperature) demonstrated excellent mechanical properties. Due to the presence of side amide groups in PMAAm, the energy barrier required for heat-induced transformation of globular BSA structures into unfolded linear structures decreased, causing a significant shift in the transition temperature. This transition led to a steep and substantial strengthening of the two-component hydrogel. After compressive and shear deformation, the hydrogel restored damaged structure and demonstrated superior fatigue resistance. Compared to BSA that is globular, it was found that BSA in its unfolded state has a much greater impact on the mechanical properties of the hydrogel.

Injectable Hydrogels Based on Inter-Polyelectrolyte Interactions between Hyaluronic Acid, Gelatin, and Cationic Cellulose Nanocrystals.

The present work dealt with the development of physically cross-linked injectable hydrogels with potential applications in tissue engineering. The hydrogels were composed of a ternary mixture of a polyanion and a polyampholyte, hyaluronic acid (HA) and gelatin, respectively, bridged by cationic cellulose nanocrystals (cCNCs). A 3D network is formed by employing attractive electrostatic interactions and hydrogen bonding between these components under physiological conditions. The hydrogels demonstrated low viscosity at high stresses, enabling easy injection, structural stability at low stresses (<15 Pa), and nearly complete structure recovery within several minutes. Increasing the cCNC content (>3%) reduced hydrogel swelling and decelerated the degradation in phosphate-buffered saline as compared to that in pure HA and HA-gelatin samples. Biological evaluation of the hydrogel elutions showed excellent cell viability. The proliferation of fibroblasts exposed to elutions of hydrogels with 5% cCNCs reached ∼200% compared to that in the positive control after 11 days. Considering these results, the prepared hydrogels hold great potential in biomedical applications, such as injectable dermal fillers, 3D bioprintable inks, or 3D scaffolds to support and promote soft tissue regeneration.

Personalized Reusable Face Masks with Smart Nano-Assisted Destruction of Pathogens for COVID-19: A Visionary Road.

The Coronavirus disease 2019 (COVID-19) emergency has demonstrated that the utilization of face masks plays a critical role in limiting the outbreak. Healthcare professionals utilize masks all day long without replacing them very frequently, thus representing a source of cross-infection for patients and themselves. Nanotechnology is a powerful tool with the capability to produce nanomaterials with unique physicochemical and antipathogen properties. Here, how to realize non-disposable and highly comfortable respirators with light-triggered self-disinfection ability by bridging bioactive nanofiber properties and stimuli-responsive nanomaterials is outlined. The visionary road highlighted in this Concept is based on the possibility of developing a new generation of masks based on multifunctional membranes where the presence of nanoclusters and plasmonic nanoparticles arranged in a hierarchical structure enables the realization of a chemically driven and on-demand antipathogen activities. Multilayer electrospun membranes have the ability to dissipate humidity present within the mask, enhancing the wearability and usability. The photothermal disinfected membrane is the core of these 3D printed and reusable masks with moisture pump capability. Personalized face masks with smart nano-assisted destruction of pathogens will bring enormous advantages to the entire global community, especially for front-line personnel, and will open up great opportunities for innovative medical applications.

Synthesis of an Effective Flame-Retardant Hydrogel for Skin Protection Using Xanthan Gum and Resorcinol Bis(diphenyl phosphate)-Coated Starch.

We report on the production of a flame-resistant xanthan gum (XG)-based hydrogel formulation, which could be directly applied onto the skin for protection against burning projectiles. The hydrogel cream represents an efficient use of XG and starch, both of which are biodegradable, reusable natural materials and are also GRAS-certified. The flame-retardant agent resorcinol bis(diphenyl phosphate) (RDP) was shown to be nontoxic to cells in vitro when adsorbed directly onto the starch delivery vehicle. Three hydrogel formulations were studied, the pure XG hydrogel, commercial FireIce hydrogel, and RDP-XG/RDP-starch hydrogel. After application of a direct flame for 150 s, the RDP-XG/RDP-starch hydrogel produced a thick char layer, which was easily removed, showing undamaged chicken skin and tissue underneath. In contrast, complete burning of skin and tissue was observed on untreated control samples and those covered with FireIce and pure XG hydrogels. The thermal protective performance test was also performed, where the heat transfer was measured as a function of time for all three hydrogels. The RDP-XG/RDP-starch hydrogel was able to prolong the protection time before obtaining a second-degree burn for 103 s, which is double that for FireIce and triple that for the pure XG hydrogel. The model proposed involves endothermic reactions, producing char and burning "cold", as opposed to simply relying on the adsorbed water in the hydrogel for burn protection.

Synergistic Effect of Two Organogelators for the Creation of Bio-Based, Shape-Stable Phase-Change Materials.

Two organogelators of different chemistry (a fatty acid derivative and a bis-urea derivative), as well as their blends, were used to impart shape stability to a bio-based phase-change material (PCM) bearing a near-ambient phase-transition temperature. Characterization of the individual gelators and their blends revealed their ability to immobilize the PCM by forming a continuous fibrillar network. The fibrils formed by the fatty acid derivative were helical, while the bis-urea derivative formed smooth fibrils. Also, the bis-urea derivative formed a continuous network at a lower critical concentration than the fatty acid derivative. At each fixed concentration, the bis-urea derivative yielded gels with higher thermal stability than the fatty acid derivative. The two gelators blended in certain ratios demonstrated a strong synergistic effect, providing gels with a significantly higher modulus (∼20-fold) and yield stress (∼1.5-fold) than each gelator individually. PCM gelation did not significantly affect its thermal behavior, however, affected its crystalline morphology. The gelled PCM displayed stacked structures, consisting of alternating pure PCM layers separated by layers formed by gelator fibrils. The phase diagram of the triple system comprising both gelators and PCM demonstrated either single or double gelation behavior depending on the composition. These findings may provide guidelines for the development of novel, shape-stable PCMs, which could be of potential use in various thermal energy storage applications.

Structural Arrest and Phase Transition in Glassy Nanocellulose Colloids.

From drying blood to oil paint, the developing of a glassy phase from colloids is observed on a daily basis. Colloidal glass is solid soft matter that consists of two intertwined phases: a random packed particle network and a fluid solvent. By dispersing charged rod-like cellulose nanoparticles into a water-ethylene glycol cosolvent, here we demonstrate a new kind of colloidal glass with a high liquid crystalline order, namely, two general superstructures with nematic and cholesteric packing states are preserved and jammed inside the glass matrix. During the glass formation process, structural arrest and phase transition occur simultaneously at high particle concentrations, yielding solid-like behavior as well as a frozen liquid crystal texture that is because of caging of the charged colloids through neighboring long-ranged repulsive interactions.

Controlled Assembly of Nanocellulose-Stabilized Emulsions with Periodic Liquid Crystal-in-Liquid Crystal Organization.

Colloidal particles combined with a polymer can be used to stabilize an oil-water interface forming stable emulsions. Here, we described a novel liquid crystal (LC)-in-LC emulsion composed of a nematic oil phase and a cholesteric or nematic aqueous cellulose nanocrystal (CNC) continuous phase. The guest oil droplets were stabilized and suspended in liquid-crystalline CNCs, inducing distortions and topological defects inside the host LC phase. These emulsions exhibited anisotropic interactions between the two LCs that depended on the diameter-to-pitch ratio of suspended guest droplets and the host CNC cholesteric phase. When the ratio was high, oil droplets were embedded into a cholesteric shell with a concentric packing of CNC layers and took on a radial orientation of the helical axis. Otherwise, discrete surface-trapped LC droplet assemblies with long-range ordering were obtained, mimicking the fingerprint configuration of the cholesteric phase. Thus, the LC-in-LC emulsions presented here define a new class of ordered soft matter in which both nematic and cholesteric LC ordering can be well-manipulated.

Tunable pH-Responsive Chitosan-Poly(acrylic acid) Electrospun Fibers.

The macromolecular organization in system composed of anionic poly(acrylic acid) (PAA) and cationic chitosan (Cs), with different degrees of deacetylation (DD), under extensive elongational flow, is described. Cs/PAA nanofibers were obtained, and polyelectrolyte complexation only occurred when fibers were immersed in fluid media of a certain pH. Assembled polyelectrolytes complexes formed a pH-triggered system, as demonstrated by reversible change of the swelling degree, by 3 orders of magnitude, and a change on the elastic modulus, by 2 orders of magnitude. Both the swelling degree and the elastic modulus proved sensitive to the DD of Cs. Rheological measurements showed that increased DD of Cs resulted in a decrease in viscosity of both pure Cs and precursor Cs/PAA solutions, attributed to repulsive interactions between ionized amino groups in Cs. At the same time, a DD-dependent change in balance between hydrogen bonding and ion-dipole interactions between the components in Cs/PAA, was responsible for the more pronounced viscosity decrease in these solutions.

The role of polymer-solvent interactions in polyvinyl-alcohol dispersions of multi-wall carbon nanotubes: from coagulant to dispersant.

Dispersion of carbon nanotubes in solutions of polyvinyl-alcohol is required for solution casting of composite materials with improved interfacial adhesion where chains adsorbed on the nanotubes serve in the dual role of dispersant and compatible "connector" to the polyvinyl-alcohol matrix. Yet polyvinyl-alcohol is known to induce coagulation of nanotubes in aqueous solutions and thus far, it has not been used for dispersing pristine nanotubes. Here, we report that non-fully hydrolyzed (80-90%) polyvinyl-alcohol can be used for the preparation of stable, surfactant-free, dispersions of multi-wall carbon nanotubes in ethanol-water mixtures (of at least 50 vol% ethanol). Cryo-TEM imaging and rheological measurements of stable, long-lived dispersions reveal the formation of random networks of suspended tubes, with an averaged mesh size of ∼500 nm, indicating that the individual tubes do not aggregate or coagulate. We hypothesize that the polyvinyl-acetate sequences found in non-fully hydrolyzed polymers swell in the presence of ethanol, leading to the formation of a long-ranged steric (entropic) repulsion among polymer-decorated nanotubes. The unexpected role of the polyvinyl-acetate sequences along with a detailed dispersion mechanism are described.

Raman scattering from single WS2 nanotubes in stretched PVDF electrospun fibers.

Inorganic WS2 nanotubes (INT-WS2) were embedded into sub-µm polyvinylidene fluoride-co-hexafluropropylene (PVDF-HFP) electrospun fibers. In this report we explore the Raman scattering spectroscopy from a single nanotube during stretching of individual nanocomposite fibers. Red shifts of up to ∼4.7 cm-1 for A1g and E WS2 bands were found before reaching the "tearing point" of the fibers. These shifts may correlate with up to ∼2.8% of the WS2 nanotube elongation. Moreover, the absence of the A1g and E bands' broadening, as well as the nonappearance of the E shear mode in the nanotube Raman spectra, suggest the stretching of the nanotubes as a whole (including inner layers). These results point to the excellent adhesion of the nanotubes' surface to the polymer and to the effective load transfer from the polymer to the WS2 nanotube. In order to elucidate the nature of interaction between the polymer and the nanofiller, we modeled the deformation of composite fibers using an elastic lattice spring model (LSM). The results of the model are fully consistent with our interpretation.

Structural Transition in Liquid Crystal Bubbles Generated from Fluidic Nanocellulose Colloids.

The structural transition in micrometer-sized liquid crystal bubbles (LCBs) derived from rod-like cellulose nanocrystals (CNCs) was studied. The CNC-based LCBs were suspended in nematic or chiral nematic liquid-crystalline CNCs, which generated topological defects and distinct birefringent textures around them. The ordering and structure of the LCBs shifted from a nematic to chiral nematic arrangement as water evaporation progressed. These packed LCBs exhibited a specific photonic cross-communication property that is due to a combination of Bragg reflection and bubble curvature and size.

Rheological Properties and Electrospinnability of High-Amylose Starch in Formic Acid.

Starch derivatives, such as starch-esters, are commonly used as alternatives to pure starch due to their enhanced mechanical properties. However, simple and efficient processing routes are still being sought out. In the present article, we report on a straightforward method for electrospinning high-amylose starch-formate nanofibers from 17 wt % aqueous formic acid (FA) dispersions. The diameter of the electrospun starch-formate fibers ranged from 80 to 300 nm. The electrospinnability window between starch gelatinization and phase separation was determined using optical microscopy and rheological studies. This window was shown to strongly depend on the water content in the FA dispersions. While pure FA rapidly gelatinized starch, yielding solutions suitable for electrospinning within a few hours at room temperature, the presence of water (80 and 90 vol % FA) significantly delayed gelatinization and dissolution, which deteriorated fiber quality. A complete destabilization of the electrospinning process was observed in 70 vol % FA dispersions. Optical micrographs showed that FA induced a disruption of starch granule with a loss of crystallinity confirmed by X-ray diffraction. As a result, starch fiber mats exhibited a higher elongation at break when compared to brittle starch films.

Living Composites of Electrospun Yeast Cells for Bioremediation and Ethanol Production.

The preparation of composites of living functional cells and polymers is a major challenge. We have fabricated such "living composites" by preparation of polymeric microtubes that entrap yeast cells. Our approach was the process of coaxial electrospinning in which a core containing the yeast was "spun" within a shell of nonbiodegradable polymer. We utilized the yeast Candida tropicalis, which was isolated from olive water waste. It is particularly useful since it degrades phenol and other natural polyphenols, and it is capable of accumulating ethanol. The electrospun yeast cells showed significant activity of bioremediation of phenol and produced ethanol, and, in addition, the metabolic processes remained active for a prolonged period. Comparison of electrospun cells to planktonic cells showed decreased cell activity; however, the olive water waste after treatment by the yeast was no longer toxic for Escherichia coli, suggesting that detoxification and prolonged viability and activity may outweigh the reduction of efficiency.

Electrospinning polyelectrolyte complexes: pH-responsive fibers.

Fibers were electrospun from a solution comprised of oppositely charged polyelectrolytes, in efforts to achieve highly confined macromolecular packaging. A stoichiometric ratio of poly(allylamine hydrochloride) and poly(acrylic acid) solution was mixed in an ethanol-water co-solvent. Differential scanning calorimetry (DSC) analysis of electrospun fibers demonstrated no indication of glass transition, Tg. Infrared spectroscopy (FTIR) analysis of the fibers as a function of temperature, demonstrated an amidation process at lower temperature compared to cast film. Polarized FTIR indicated a preference of the functional groups to be perpendicular to the fiber axis. These results imply formation of mixed phase fibers with enhanced conditions for intermolecular interactions, due to the highly aligned and confined assembly of the macromolecules. The tunable intermolecular interactions between the functional groups of the polyelectrolytes, impact pH-driven, reversible swelling-deswelling of the fibers. The degree of ionization of PAA at pH 5.5 and pH 1.8 varied from 85% to 18%, correspondingly, causing transformation of ionic interactions to hydrogen bonding between the functional groups. The chemical change led to a massive water diffusion of 500% by weight and to a marked increase of 400% in fiber diameter, at a rate of 0.50 µm s(-1). These results allow for manipulation and tailoring of key fiber properties for tissue engineering, membranes, and artificial muscle applications.

Albumin fiber scaffolds for engineering functional cardiac tissues.

In recent years attempts to engineer contracting cardiac patches were focused on recapitulation of the myocardium extracellular microenvironment. We report here on our work, where for the first time, a three-dimensional cardiac patch was fabricated from albumin fibers. We hypothesized that since albumin fibers' mechanical properties resemble those of cardiac tissue extracellular matrix (ECM) and their biochemical character enables their use as protein carriers, they can support the assembly of cardiac tissues capable of generating strong contraction forces. Here, we have fabricated aligned and randomly oriented electrospun albumin fibers and investigated their structure, mechanical properties, and chemical nature. Our measurements showed that the scaffolds have improved elasticity as compared to synthetic electrospun PCL fibers, and that they are capable of adsorbing serum proteins, such as laminin leading to strong cell-matrix interactions. Moreover, due to the functional groups on their backbone, the fibers can be chemically modified with essential biomolecules. When seeded with rat neonatal cardiac cells the engineered scaffolds induced the assembly of aligned cardiac tissues with high aspect ratio cardiomyocytes and massive actinin striation. Compared to synthetic fibrous scaffolds, cardiac cells cultured within aligned or randomly oriented scaffolds formed functional tissues, exhibiting significantly improved function already on Day 3, including higher beating rate (P = 0.0002 and P < 0.0001, respectively), and higher contraction amplitude (P = 0.009 and P = 0.003, respectively). Collectively, our results suggest that albumin electrospun scaffolds can play a key role in contributing to the ex vivo formation of a contracting cardiac muscle tissue.

Local mechanical properties of electrospun fibers correlate to their internal nanostructure.

The properties of polymeric nanofibers can be tailored and enhanced by properly managing the structure of the polymer molecules at the nanoscale. Although electrospun polymer fibers are increasingly exploited in many technological applications, their internal nanostructure, determining their improved physical properties, is still poorly investigated and understood. Here, we unravel the internal structure of electrospun functional nanofibers made by prototype conjugated polymers. The unique features of near-field optical measurements are exploited to investigate the nanoscale spatial variation of the polymer density, evidencing the presence of a dense internal core embedded in a less dense polymeric shell. Interestingly, nanoscale mapping the fiber Young's modulus demonstrates that the dense core is stiffer than the polymeric, less dense shell. These findings are rationalized by developing a theoretical model and simulations of the polymer molecular structural evolution during the electrospinning process. This model predicts that the stretching of the polymer network induces a contraction of the network toward the jet center with a local increase of the polymer density, as observed in the solid structure. The found complex internal structure opens an interesting perspective for improving and tailoring the molecular morphology and multifunctional electronic and optical properties of polymer fibers.

Mechanical Perspective on Increasing Brush Cytology Yield.

Brush cytology is a sampling technique extensively used for mucosal surfaces, particularly to identify malignancies. A sample is obtained by rubbing the brush bristles over the stricture or lesion several times until cells are trapped. Brush cytology detection rate varies, with malignancy confirmed in 15-65% of cases of adenocarcinoma-associated biliary strictures and 44-80% of cases of cholangiocarcinoma. Despite the widespread use of brush cytology, there is no consensus to date defining the optimal biliary brushing parameters for the collection of suspicious lesions, such as the number of passes, brushing rate, and force applied. The aim of this work is to increase the brush cytology diagnostic yield by elucidating the underlying mechanical phenomena. First, the mechanical interactions between the brush bristles and sampled tissue are analyzed. During brushing, mucus and detached cells are transferred to the space between the bristles through the capillary rise and flow eddies. These mass transfer mechanisms and their dependence on mucus rheology as a function of pH, brush displacement rate, and bristle geometry and configuration are examined. Lastly, results from ex vivo brushing experiments performed on porcine stomachs are presented. Clinical practitioners from a variety of disciplines can apply the findings of this study to outline clear procedures for cytological brushing to increase the sensitivity and specificity of the brushings.

A paper-based point-of-care device for the detection of cysteine using gold nanoparticles from whole blood.

We present a colorimetric probe based on polyvinylpyrrolidone-capped gold nanoparticles (PVP-AuNPs) that is sensitive and selective for cysteine (Cys). A microfluidic paper-based analytical device (µ-PAD) with embedded dried PVP-AuNPs at the polyethersulfone (PES) paper surface is used for Cys detection. When thiol molecules attach to PVP-AuNPs in the presence of Cys, they clump together, and this causes the solution's color to shift from red to blue within 5 minutes. The device is capable of detecting Cys levels between 1.0 µM and 50.0 µM with a limit of detection (LOD) of 0.2 µM under optimized conditions. The stability of the µ-PAD was tested for 100 days, demonstrating re-dispersibility to detect Cys levels in blood. Dried PVP-AuNP-µPADs were integrated with blood plasma separation modules for point-of-care (POC) Cys detection. Consequently, the device shows potential as a self-sustaining, quantification platform with a recovery percentage ranging from 98.44 to 111.9 in clinical samples.