Search

The global spread of COVID-19 as well as the worsening air pollution throughout the world have brought tremendous attention to the development of materials that can efficiently capture particulate matter. We suggest that the high porosity of electrospun filters composed of nanofibers could provide minimal obstruction to air flow, while their high tortuosity and surface area-to-volume ratio present an excellent platform to capture particulates. In this study, the removal of nanoscale particles via in-house fabricated cellulose nanofilters is significantly enhanced by chemically functionalizing the fibers' surface via the deposition of the bioinspired glue polydopamine (PDA) or the polycation poly(diallyldimethylammonium chloride) (PDADMAC). The effects of filter packing density, layering thickness, and chemistry on their performance, i.e., their filtration efficiency, most penetrating particle size (MPPS), particle fractional penetration percent, and performance in a high relative humidity environment, were investigated. When evaluated in an extremely hazardous environment (PM concentration ∼2000 μg m-3), the filtration efficiency, pressure drop, and quality factor for the cellulose nanofilters were measured to be >98.0%

We designed and synthesized epoxy-encapsulated microparticles with core-shell structures via suspension polymerization to enable high-efficiency, room-temperature cold spray processing. The soft core of the microparticles was comprised of a thermoset resin, diglycidyl ether of bisphenol A (DGEBA), which was optionally blended with the thermoplastic, poly(butyl acrylate); the protective shell was formed using polyurea. The composition, morphology, and thermal behavior of the microparticles were investigated. An inverse relationship between deposition efficiency and particle size was demonstrated by varying the surfactant concentration that was used during particle synthesis. We also determined that the microparticles that had pure resin as the core had the lowest viscosity, exhibited a decrease in the critical impact velocity required for adhesion, had the best flowability, and yielded a dramatic increase in deposition efficiency (56%). We have demonstrated that our in-house synthesized particles can form homogeneous, smooth, and fully coalesced coatings using room-temperature cold spray.

The COVID-19 pandemic has revealed the importance of the detection of airborne pathogens. Here, we present composite air filters featuring a bioinspired liquid coating that facilitates the removal of captured aerosolized bacteria and viruses for further analysis. We tested three types of air filters: commercial polytetrafluoroethylene (PTFE), which is well known for creating stable liquid coatings, commercial high-efficiency particulate air (HEPA) filters, which are widely used, and in-house-manufactured cellulose nanofiber mats (CNFMs), which are made from sustainable materials. All filters were coated with omniphobic fluorinated liquid to maximize the release of pathogens. We found that coating both the PTFE and HEPA filters with liquid improved the rate at which Escherichia coli was recovered using a physical removal process compared to uncoated controls. Notably, the coated HEPA filters also increased the total number of recovered cells by 57%. Coating the CNFM filters did not improve either the rate of release or the total number of captured cells. The most promising materials, the liquid-coated HEPA, filters were then evaluated for their ability to facilitate the removal of pathogenic viruses via a chemical removal process. Recovery of infectious JC polyomavirus, a nonenveloped virus that attacks the central nervous system, was increased by 92% over uncoated controls; however, there was no significant difference in the total amount of genomic material recovered compared to that of controls. In contrast, significantly more genomic material was recovered for SARS-CoV-2, the airborne, enveloped virus, which causes COVID-19, from liquid-coated filters. Although the amount of infectious SARS-CoV-2 recovered was 58% higher, these results were not significantly different from uncoated filters due to high variability. These results suggest that the efficient recovery of airborne pathogens from liquid-coated filters could improve air sampling efforts, enhancing biosurveillance and global pathogen early warning.

Biofouling is a serious problem in ultrafiltration (UF) membrane applications. Modifying the surface of membranes with low molecular weight, commercially available antibacterial chemistries is an excellent strategy to mitigate biofouling. Herein, we report a new strategy to impart antibacterial and anti-biofouling behavior without changing the support membrane's size selectivity and pure water permeance (PWP). To this end, a strong antibacterial agent, cetyltrimethylammonium bromide (CTAB), was codeposited with dopamine onto commercial polyethersulfone (PES) UF membranes in the presence of nitrogen (N

In this study, we provide the first demonstration that aqueous complex coacervates can be electrospun into chemically robust polyelectrolyte complex (PEC) fiber mats. PECs form due to electrostatic complexation between oppositely charged polymers. Here, we exploit the ability of salt to plasticize PECs, thus enabling the electrospinning of solid fibers. Electrospinning solutions were composed of a pair of strong polyelectrolytes, poly(4-styrenesulfonic acid, sodium salt) and poly(diallyldimethylammonium chloride) using potassium bromide as the plasticizing salt. We systematically investigated the effect of salt concentration and electrospinning apparatus parameters on fiber formation. Electrospun PEC fiber mats were stable over a wide range of pH values, ionic strength conditions, and many organic solvents. This study demonstrates that the electrospinning of aqueous complex coacervates can generate chemically robust, free-standing PEC fiber mats while circumventing the reliance on organic solvents, the challenge of working with entangled polyelectrolytes in solution, and the need to chemically cross-link the as-spun fibers. These PEC fiber mats hold potential in applications where environmentally benign fiber mats are imperative, such as tissue engineering scaffolds and water purification technologies.

Dysfunction of the intestinal mucus barrier causes disorders such as ulcerative colitis and Crohn’s disease. The function of this essential barrier may be affected by the periodically changing luminal environment. We hypothesized that the pH and ion concentration in mucus control its porosity, molecular permeability, and the penetration of microbes. To test this hypothesis, we developed a scalable method to extract porcine small intestinal mucus (PSIM). The aggregation and porosity of PSIM were determined using rheometry, spectrophotometry, and microscopy. Aggregation of PSIM at low pH increased both the elastic (G′) and viscous (G″) moduli, and it slowed the transmigration of pathogenic Salmonella. Molecular transport was dependent on ion concentration. At moderate concentrations, many microscopic aggregates (2–5 μm in diameter) impeded diffusion. At higher concentrations, PSIM formed aggregate islands, increasing both porosity and diffusion. This in vitro model could lead to a better understanding of mucus barrier functions and improve the treatment of intestinal diseases.

Developing an engineerable chemical reaction that is triggerable for simultaneous chemical bond formation and cleavage by external cues offers tunability and orthogonality which is highly desired in many biological and materials applications. Here, we present a chemical switch that concurrently captures these features in response to chemically and biologically abundant and important cues, viz., thiols and amines. This thiol/amine-triggerable chemical switch is based on a Triggerable Michael Acceptor (TMAc) which bears good leaving groups at its β-position. The acceptor undergoes a “trigger-to-release” process where thiol/amine addition triggers cascaded release of leaving groups and generates a less activated acceptor. The newly generated TMAc can be further reversed to liberate the original thiol/amine by a second nucleophile trigger through a “trigger-to-reverse” process. Within the small molecular volume of the switch, we have shown five locations that can be engineered to achieve tunable “trigger-to-release” kinetics and tailored reversibility. The potential of the engineerable bonding/debonding capability of the chemical switch is demonstrated by applications in cysteine-selective and reversible protein modification, universal self-immolative linkers, and orthogonally addressable hydrogels., A triggerable Michael acceptor (TMAc) with programmable reactivity and reversibility for simultaneous coupling and decoupling has been developed for selective protein modification, self-immolative linker and orthogonally addressable hydrogel.

Antifouling membranes that offer excellent operational lifetimes are critical technologies needed to meet the growing demand for clean water. In this study, we demonstrate antifouling membranes featuring an ultrathin oil layer that stayed immobilized on the surface and in the pore walls of poly(vinylidene fluoride) membranes for multiple cycles of operation at industrially relevant transmembrane pressures. An optimized quantity of a commercial Krytox oil with either a low (K103) or a high viscosity (K107) was infused onto the active surface and into the pores of membranes with a 0.45 μm pore size. The presence of the oil layer was qualitatively confirmed using crystal violet staining and variable pressure scanning electron microscopy. Using a dead-end stirred cell, a consistent pure water permeance value of 3000 L m

Herein, we report a controllable pathway to accelerate the polymerization kinetics of dopamine using ultrasound as a trigger. The use of ultrasound was demonstrated to dramatically accelerate the slow liquid phase reaction kinetics and increase the deposition rate of the polydopamine coating on the surface of polymeric membranes.

Bacterial attachment and proliferation on surfaces threaten human health and negatively impact the medical, food processing, and marine industries. In this study, we synthetically produced bioinspi...

Electrospun biopolyelectrolyte nanofibers hold potential for use in a range of biomedical applications, but eliminating toxic chemicals involved in their production remains a key challenge. In this study, we successfully electrospun nanofibers from an aqueous complex coacervate solution composed of chitosan and hyaluronic acid. Experimentally, we investigated the effect of added salt and electrospinning apparatus parameters, such as how applied voltage affected fiber formation. We also studied how the addition of alcohol cosolvents affected the properties of the coacervate solution and the resulting nanofibers. Overall, we observed a trade-off in how the addition of salt and alcohol affected the phase behavior and rheology of the coacervates and, consequently, the size of the resulting fibers. While salt served to weaken electrostatic associations within the coacervate and decrease the precursor solution viscosity, the addition of alcohol lowered the dielectric constant of the system and strengthened these interactions. We hypothesize that the optimized concentration of alcohol accelerated the solvent evaporation during the electrospinning process to yield desirable nanofiber morphology. The smallest average nanofiber diameter was determined to be 115 ± 30 nm when coacervate samples were electrospun using an aqueous solvent containing 3 wt % ethanol and an applied voltage of 24 kV. These results demonstrate a potentially scalable strategy to manufacture electrospun nanofibers from biopolymer complex coacervates that eliminate the need for toxic solvents and could enable the use of these materials across a range of biomedical applications.

Antimicrobial biomaterials are critical to aid in the regeneration of oral soft tissue and prevent or treat localised bacterial infections. With the rising trend in antibiotic resistance, there is a pressing clinical need for new antimicrobial chemistries and biomaterial design approaches enabling on-demand activation of antibiotic-free antimicrobial functionality following an infection that are environment-friendly, flexible and commercially-viable. This study explores the feasibility of integrating a bioresorbable electrospun polymer scaffold with localised antimicrobial photodynamic therapy (aPDT) capability. To enable aPDT, we encapsulated a photosensitiser (PS) in polyester fibres in the PS inert state, so that the antibacterial function would be activated on-demand via a visible light source. Fibrous scaffolds were successfully electrospun from FDA-approved polyesters, either poly(epsilon-caprolactone (PCL) or poly[(rac-lactide)-co-glycolide] (PLGA) with encapsulated PS (either methylene blue (MB) or erythrosin B (ER)). The electrospun fibres achieved an ~100 wt.% loading efficiency of PS, which significantly increased their tensile modulus and reduced their average fibre diameter and pore size with respect to PS-free controls. In vitro, PS release varied between a burst release profile to limited release within 100 hours depending on the selected scaffold formulation. Exposure of PS-encapsulated PCL fibres to visible light successfully led to at least a 1 log reduction in E. coli viability after 60 minutes of light exposure whereas PS-free electrospun controls did not inactive microbes. This study successfully demonstrates the significant potential of PS-encapsulated electrospun fibres as photodynamically active biomaterial for antibiotic-free infection control.

Here, we demonstrate the anionic polymerization and the high reactivity of the novel monomer diethyl methylene malonate (DEMM). At room temperature and under atmospheric conditions, water and anionic functional groups (i.e., carboxyl, boronic, and phenol) quickly initiate DEMM. The polymerization of DEMM in water and the final molecular weight of the polymer were both demonstrated to be pH-dependent. Systematically, investigations were conducted to study the conversion rate of DEMM with various functional groups, and the polymerization was verified to occur with anionic groups using a carboxylate-initiated DEMM system. For coating applications, we also investigated a multifunctional derivative monomer called (DEMM)(6) that is an oligomeric polyester of DEMM esterified with butanediol that contains on average six repeat units of reactive DEMM (commercially known as Forza B3000 XP). The incorporation of 15 wt % (DEMM)(6) into latex containing methacrylate acid as a functional monomer yielded cross-linked coatings with a gel content of 76.25 wt % that had a 289% improvement in rub-resistance performance compared to controls (without (DEMM)(6)). This study provides a facile methodology to synthesize cross-linked latex coatings at room temperature.

In this study, we systematically investigated the flux performance of ultrafiltration (UF) membranes functionalized with randomly-accumulated nanofibers. By electrospinning nanofibers from hydrophobic polysulfone (PSf) and hydrophilic cellulose (CL), we were able to explore the role that bulk nanofiber (NF) layer thickness, individual NF diameter, and intrinsic chemistry have on composite membrane flux. Additional parameters that we systematically tested include the molecular weight cut-off (MWCO) of the base membrane (10, 100, and 200 kDa), flow orientation (cross-flow versus dead-end), and the feed solution (hydrophilic water versus hydrophobic oil). Structurally, the crosslinked PSf nanofibers were more robust than the CL nanofibers, which lead to the PSfNF-UF membranes having a greater flux performance. To decouple the structural robustness from the water affinity of the fibers, we chemically modified the PSf fibers to be hydrophilic and indeed, the flux of these new composite membranes featuring hydrophilic crosslinked nanofibers were superior. In summary, the greatest increase in flux performance arises from the smallest diameter, hydrophilic nanofibers that are mechanically robust (crosslinked). We have demonstrated that electrospun nanofiber layers improve the flux performance of ultrafiltration membranes.

Encapsulation technologies are imperative for the safe delivery of live bacteria into the gut where they regulate bodily functions and human health. In this study, we develop alginate-based nanofibers that could potentially serve as a biocompatible, edible probiotic delivery system. By systematically exploring the ratio of three components, the biopolymer alginate (SA), the carrier polymer poly(ethylene oxide) (PEO), and the FDA approved surfactant polysorbate 80 (PS80), the surface tension and conductivity of the precursor solutions were optimized to electrospin bead-free fibers with an average diameter of 167 ± 23 nm. Next, the optimized precursor solution (2.8/1.2/3 wt% of SA/PEO/PS80) was loaded with Escherichia coli (E. coli, 108 CFU mL-1), which served as our model bacterium. We determined that the bacteria in the precursor solution remained viable after passing through a typical electric field (∼1 kV cm-1) employed during electrospinning. This is because the microbes are pulled into a sink-like flow, which encapsulates them into the polymer nanofibers. Upon electrospinning the E. coli-loaded solutions, beads that were much smaller than the size of an E. coli were initially observed. To compensate for the addition of bacteria, the SA/PEO/PS80 weight ratio was reoptimized to be 2.5/1.5/3. Smooth fibers with bulges around the live microbes were formed, as confirmed using fluorescence and scanning electron microscopy. By dissolving and plating the nanofibers, we found that 2.74 × 105 CFU g-1 of live E. coli cells were contained within the alginate-based fibers. This work demonstrates the use of electrospinning to encapsulate live bacteria in alginate-based nanofibers for the potential delivery of probiotics to the gut.

Recent advances in memristive nanocrystal assemblies leverage controllable colloidal chemistry to induce a broad range of defect-mediated electrochemical reactions, switching phenomena, and modulate active parameters. The sample geometry of virtually all resistive switching studies involves thin film layers comprising monomodal diameter nanocrystals. Here we explore the evolution of bipolar and threshold resistive switching across highly ordered, solution-processed nanoribbon assemblies and mixtures comprising BaZrO3 (BZO) and SrZrO3 (SZO) nanocrystals. The effects of nanocrystal size, packing density, and A-site substitution on operating voltage (V-SET and V-TH) and switching mechanism were studied through a systematic comparison of nanoribbon heterogeneity (i.e., BZO-BZO vs BZO-SZO) and monomodal vs bimodal size distributions (i.e., small-small and small-large). Analysis of the current-voltage response confirms that tip-induced, trap-mediated space-charge-limited current and trap-assisted tunneling processes drive the low- and high-resistance states, respectively. Our results demonstrate that both smaller nanocrystals and heavier alkaline earth substitution decrease the onset voltage and improve stability and state retention of monomodal assemblies and bimodal nanocrystal mixtures, thus providing a base correlation that informs fabrication of solution-processed, memristive nanocrystal assemblies.

With an ever increasing scientific, technological, and industrial interest in high surface area, porous nanofiber mats, electrospinning has emerged as a popular method to produce fibrous assemblies for use across biomedical, energy, and environmental applications. However, not all precursor solutions nor complex geometries can be easily fabricated using the traditional single-nozzle apparatus. Therefore, coaxial electrospinning, a modified version of electrospinning that features a concentrically aligned dual nozzle, has been developed. This review will first describe the mechanism of electrospinning two precursor solutions simultaneously and the operational parameters that need to be optimized to fabricate continuous fibers. Modifications that can be made to the coaxial electrospinning process, which enable the fabrication of uniform fibers with improved properties, as well as the fabrication of fibers that are hollow, functionalized, and from "nonspinnable precursors" will be discussed as a means of promoting the advantages of using a coaxial setup. Examples of how coaxially electrospun nanofibers are employed in diverse applications will be provided throughout this review. We conclude with a timely discussion about the current limitations and challenges of coaxial electrospinning.

Changes in the elastic properties of brain tissue have been correlated with injury, cancers, and neurodegenerative diseases. However, discrepancies in the reported elastic moduli of brain tissue are persistent, and spatial inhomogeneities complicate the interpretation of macroscale measurements such as rheology. Here we introduce needle induced cavitation rheology (NICR) and volume-controlled cavity expansion (VCCE) as facile methods to measure the apparent Young's modulus E of minimally manipulated brain tissue, at specific tissue locations and with sub-millimeter spatial resolution. For different porcine brain regions and sections analyzed by NICR, we found E to be 3.7 ± 0.7 kPa and 4.8 ± 1.0 kPa for gray matter, and white matter, respectively. For different porcine brain regions and sections analyzed by VCCE, we found E was 0.76 ± 0.02 kPa for gray matter and 0.92 ± 0.01 kPa for white matter. Measurements from VCCE were more similar to those obtained from macroscale shear rheology (0.75 ± 0.06 kPa) and from instrumented microindentation of white matter (0.97 ± 0.40 kPa) and gray matter (0.86 ± 0.20 kPa). We attributed the higher stiffness reported from NICR to that method's assumption of a cavitation instability due to a neo-Hookean constitutive response, which does not capture the strain-stiffening behavior of brain tissue under large strains, and therefore did not provide appropriate measurements. We demonstrate via both analytical modeling of a spherical cavity and finite element modeling of a needle geometry, that this strain stiffening may prevent a cavitation instability. VCCE measurements take this stiffening behavior into account by employing an incompressible one-term Ogden model to find the nonlinear elastic properties of the tissue. Overall, VCCE afforded rapid and facile measurement of nonlinear mechanical properties of intact, healthy mammalian brain tissue, enabling quantitative comparison among brain tissue regions and also between species. Finally, accurate estimation of elastic properties for this strain stiffening tissue requires methods that include appropriate constitutive models of the brain tissue response, which here are represented by inclusion of the Ogden model in VCCE.

Current strategies to treat chronic wounds offer limited relief to the 7.75 million patients who suffer from burns or chronic skin ulcers. Thus, as long as chronic wounds remain a global healthcare problem, the development of alternate treatments remain desperately needed. This review explores the recent strategies employed to tailor electrospun nanofiber mats towards accelerating the wound healing process. Porous nanofiber mats readily produced by the electrospinning process offer a promising solution to the management of wounds. The matrix chemistry, surface functionality, and mat degradation rate all can be fine-tuned to govern the interactions that occur at the materials-biology interface. In this review, first we briefly discuss the wound healing process and then highlight recent advances in drug release, biologics encapsulation, and antibacterial activity that have been demonstrated via electrospinning. While this versatile biomaterial has shown much progress, commercializing nanofiber mats that fully address the needs of an individual patient remains an ambitious challenge.

Thermoset coatings have been used extensively to protect and enhance the appearance of substrates for industrial maintenance and architectural applications. Here, we demonstrate that anionic polymerization can be used to first graft hydroxyethyl methacrylate methylene malonate (HEMA-MM) onto a latex particle at ambient conditions, while subsequent ultraviolet (UV) exposure enabled their crosslinking into robust coatings. At room temperature, in the presence of air and water, the polymerization of HEMA-MM was initiated by anionic carboxyl groups present on the MAA latex particles and subsequently grafted onto the surface of particles. The pendent hydroxyethyl methacrylate (HEMA) group enabled UV-curing via free radical polymerization and the formation of a crosslinked network. Systematic investigations were conducted to study the formation and performance of the crosslinked coatings as a function of HEMA-MM incorporation. The incorporation of 10 wt% HEMA-MM into MAA latex yielded crosslinked coatings with decreased swelling, a heightened glass transition temperature (by ~20 °C) and a 2.9-fold improvement in the Young's moduli compared to controls (without HEMA-MM). Here, we demonstrate a facile method that provides a one-step grafting-functionalization approach using functional methylene malonates to produce UV-curable and high-performance coatings at room temperature and under atmospheric environments.

[Image: see text] As demand for clean water increases, there is a growing need for effective sustainable water treatment systems. We used the symbiotic culture of bacteria and yeast (SCOBY) that forms while brewing kombucha tea as a living water filtration membrane (LFM). The LFMs function as ultrafiltration membranes with a permeability of 135 ± 25 L m(–2) h(–1) bar(–1) and a 90% rejection of 30 nm nanoparticles. Because they contain living microorganisms that produce cellulose fibers, the surface of an LFM heals after a puncture or incision. Following punctures or incisions, membrane permeability, after a rapid increase postpuncture, returns to 110–250% of the original flux after 10 days in a growth solution. Additionally, LFMs may be manufactured using readily available materials, increasing membrane production accessibility.

Correction for ‘Encapsulating bacteria in alginate-based electrospun nanofibers’ by Emily Diep et al., Biomater. Sci., 2021, 9, 4364–4373, DOI: 10.1039/D0BM02205E.

Surface-associated transport of flowing bacteria, including cell rolling, is a mechanism for otherwise immobile bacteria to migrate on surfaces and could be associated with biofilm formation or the spread of infection. This work demonstrates how the moduli and/or local polymer concentration play critical roles in sustaining contact, dynamic adhesion, and transport of bacterial cells along a hydrogel or hydrated brush surface. In particular, stiffer more concentrated hydrogels and brushes maintained the greatest dynamic contact, still allowing cells to travel along the surface in flow. This study addressed how the mechanical properties, molecular architectures, and thicknesses of minimally adhesive poly(ethylene glycol) (PEG)-based coatings influence the flow-driven surface motion of Staphylococcus aureus MS2 cells. Three protein-repellant PEG-dimethylacrylate hydrogel films (∼100 μm thick) and two protein-repellant PEG brushes (8-16 nm thick) were sufficiently fouling-resistant to prevent the accumulation of flowing bacteria. However, the rolling or hopping-like motions of gently flowing S. aureus cells along the surfaces were specific to the particular hydrogel or brush, distinguishing these coatings in terms of their mechanical properties (with moduli from 2 to 1300 kPa) or local PEG concentrations (in the range 10-50% PEG). On the stiffer hydrogel coatings having higher PEG concentrations, S. aureus exhibited long runs of surface rolling, 20-50 μm in length, an increased tendency of cells to repeatedly return to some surfaces after rolling and escaping, and relatively long integrated contact times. By contrast, on the softer more dilute hydrogels, bacteria tended to encounter the surface for brief periods before escaping without return. The dynamic adhesion and motion signatures of the cells on the two brushes were bracketed by those on the soft and stiff hydrogels, demonstrating that PEG coating thickness was not important in these studies where the vertically oriented surfaces minimized the impact of gravitational forces. Control studies with similarly sized poly(ethylene oxide)-coated rigid spherical microparticles, that also did not arrest on the PEG coatings, established that the bacterial skipping and rolling signatures were specific to the S. aureus cells and not simply diffusive. Dynamic adhesion of the S. aureus cells on the PEG hydrogel surfaces correlated well with quiescent 24 h adhesion studies in the literature, despite the orientation of the flow studies that eliminated the influence of gravity on bacteria-coating normal forces.

Epoxy-based powder coatings are an attractive alternative to solvent-borne coatings. Here, in-house synthesized low glass transition temperature (Tg) particles containing epoxy resin and polymethyl methacrylate formed coatings at room temperature upon impact with a surface. Suspension polymerization was used to prepare particles as a function of diglycidyl ether of bisphenol A (DGEBA) and methyl methacrylate ratios. Higher incorporation of DGEBA decreased the Tg to below ~20°C and eliminated the need to heat the particles and/or aluminum substrates to form coatings. Using an electrostatic powder coating apparatus, a ~70% particle deposition efficiency was achieved on aluminum substrates heated to 200°C. Whereas, at room temperature, high-speed single particle impact experiments proved that particle bonding occurred at a critical velocity of 438 m/s, comparable to commercial cold spray technologies. The in-house synthesized particles used in this study hold potential in traditional and emerging additive manufacturing applications.

We present the first demonstration of the direct encapsulation of cargo into polyelectrolyte complex (PEC) fiber mats. This approach takes advantage of the intrinsic self-assembly characteristics of complex coacervates to simplify the formulation requirements to electrospin fibers containing a high loading and an even distribution of cargo. Two families of structurally similar fluorescent dyes were used as model cargo of varying hydrophobicity and charge and were encapsulated into coacervates of poly(4-styrenesulfonic acid, sodium salt) and poly(diallyldimethylammonium chloride). The coacervate phase behavior, dye partitioning, and resulting fibers were systematically investigated as a function of dye and salt concentration. Strong partitioning was facilitated by favorable electrostatic and π–π interactions but was adversely affected by increased salt. We further identified that dye and salt interactions can be treated as independent control parameters to modulate the properties and electrospinnability of...

We demonstrate antifouling ultrafiltration membranes with retained selectivity and pure water flux through the controlled deposition of zwitterionic polymers and poly(ethylene glycol) (PEG). Molecules for polymerization were immobilized on the membrane’s surface yet prevented from attaching to the membrane’s pores due to a backflow of nitrogen (N2) gas achieved using an in-house constructed apparatus that we named the polymer prevention apparatus, or “PolyPrev”. First, the operating parameters of the PolyPrev were optimized by investigating the polymerization of dopamine, which was selected due to its versatility in enabling further chemical reactions, published metrics for comparison, and its oxidative self-polymerization. Membrane characterization revealed that the polydopamine-modified membranes exhibited enhanced hydrophilicity; moreover, their size selectivity and pure water flux were statistically the same as those of the unmodified membranes. Because it is well documented that polydopamine coatings do not provide a long-lasting antifouling activity, poly(2-methacryloyloxyethyl phosphorylcholine) (polyMPC, Mn = 30 kDa) and succinimidyl-carboxymethyl-ester-terminated PEG (Mn = 40 kDa) were codeposited while dopamine was polymerizing to generate antifouling membranes. Statistically, the molecular-weight cutoff of the polyMPC- and PEG-functionalized membranes synthesized in the PolyPrev was equivalent to that of the unmodified membranes, and the pure water flux of the PEG membranes was equivalent to that of the unmodified membranes. Notably, membranes prepared in the PolyPrev with polyMPC and PEG decreased bovine serum albumin fouling and Escherichia coli attachment. This study demonstrates that by restricting antifouling chemistries from attaching within the pores of membranes, we can generate high-performance, antifouling membranes appropriate for a wide range of water treatment applications without compromising intrinsic transport properties.

By combining antifouling shark-skin patterns with antibacterial titanium dioxide (TiO2) nanoparticles (NPs), we present a simple route toward producing durable multifunctional surfaces that decrease microbial attachment and inactivate attached microorganisms. Norland Optical Adhesive, a UV-crosslinkable adhesive material, was loaded with 0, 10, or 50 wt % TiO2 NPs from which shark-skin microstructures were imprinted using solvent-assisted soft nanoimprint lithography on a poly(ethylene terephthalate) (PET) substrate. To obtain coatings with an exceptional durability and an even higher concentration of TiO2 NPs, a solution containing 90 wt % TiO2 NPs and 10 wt % tetraethyl orthosilicate was prepared. These ceramic shark-skin-patterned surfaces were fabricated on a PET substrate and were quickly cured, requiring only 10 s of near infrared (NIR) irradiation. The water contact angle and the mechanical, antibacterial, and antifouling characteristics of the shark-skin-patterned surfaces were investigated as a function of TiO2 composition. Introducing TiO2 NPs increased the contact angle hysteresis from 30 to 100° on shark-skin surfaces. The hardness and modulus of the films were dramatically increased from 0.28 and 4.8 to 0.49 and 16 GPa, respectively, by creating ceramic shark-skin surfaces with 90 wt % TiO2 NPs. The photocatalytic shark-skin-patterned surfaces reduced the attachment of Escherichia coli by ~70% compared with smooth films with the same chemical composition. By incorporating as low as 10 wt % TiO2 NPs into the chemical matrix, over 95% E. coli and up to 80% Staphylococcus aureus were inactivated within 1 h UV light exposure because of the photocatalytic properties of TiO2. The photocatalytic shark-skin-patterned surfaces presented here were fabricated using a solution-processable and roll-to-roll compatible technique, enabling the production of large-area high-performance coatings that repel and inactivate bacteria.

Luminescent semiconductor nanocrystals or quantum dots (QDs) provide exquisite electro-optical properties that are ideal for biological sensing applications. Unlike traditional fluorescent dyes that lack in long-term stability and the ability to detect multiple signals simultaneously, QDs have overcome these obstacles, and thus, their potential use as in vivo and in vitro fluorophores has greatly advanced since their discovery in the 1980’s. In this review article, we discuss the classic and current protocols used to synthesize QDs, as well as the adaptability of QD surfaces for versatile bioconjugation. Energy transfer mechanisms represent the basis for the strong attraction of QDs to the biosensing community and thus, we examine the parameters that are required for efficient fluorescence resonance energy transfer, bioluminescence resonance energy transfer, and chemiluminescence resonance energy transfer. In addition, the recent advances in the detection of heavy metal ions, pathogens, and cancer biomarkers are also highlighted in this review. While QDs have shown much progress, the materials selection and commercialization of QDs for biological applications remain an ambitious challenge.

Despite lacking visual, auditory, and olfactory perception, bacteria sense and attach to surfaces. Many factors, including the chemistry, topography, and mechanical properties of a surface, are known to alter bacterial attachment, and in this study, using a library of nine protein-resistant poly(ethylene glycol) (PEG) hydrogels immobilized on glass slides, we demonstrate that the thickness or amount of polymer concentration also matters. Hydrated atomic force microscopy and rheological measurements corroborated that thin (15 μm), medium (40 μm), and thick (150 μm) PEG hydrogels possessed Young's moduli in three distinct regimes, soft (20 kPa), intermediate (300 kPa), and stiff (1000 kPa). The attachment of two diverse bacteria, flagellated Gram-negative Escherichia coli and nonmotile Gram-positive Staphylococcus aureus was assessed after a 24 h incubation on the nine PEG hydrogels. On the thickest PEG hydrogels (150 μm), E. coli and S. aureus attachment increased with increasing hydrogel stiffness. However, when the hydrogel's thickness was reduced to 15 μm, a substantially greater adhesion of E. coli and S. aureus was observed. Twelve times fewer S. aureus and eight times fewer E. coli adhered to thin-soft hydrogels than to thick-soft hydrogels. Although a full mechanism to explain this behavior is beyond the scope of this article, we suggest that because the Young's moduli of thin-soft and thick-soft hydrogels were statistically equivalent, potentially, the very stiff underlying glass slide was causing the thin-soft hydrogels to feel stiffer to the bacteria. These findings suggest a key takeaway design rule; to optimize fouling-resistance, hydrogel coatings should be thick and soft.

In this study, we have improved membrane performance by enhancing ultrafiltration membranes with electrospun nanofibers. The high-porosity nanofiber layer provides a tailorable platform that does not affect the base membrane structure. To decouple the effects that nanofiber chemistry and morphology have on membrane performance, two polymers commonly used in the membrane industry, cellulose and polysulfone, were electrospun into a layer that was 50 μm thick and consisted of randomly accumulated 1-μm-diameter fibers. Fouling resistance was improved and selectivity was retained by ultrafiltration membranes enhanced with a layer of either cellulose or polysulfone nanofibers. Potentially because of their better mechanical integrity, the polysulfone nanofiber-membranes demonstrated a higher pure-water permeance across a greater range of transmembrane pressures than the cellulose nanofiber-membranes and control membranes. This work demonstrates that nanofiber-enhanced membranes hold potential as versatile materials platforms for improving the performance of ultrafiltration membranes.

In this study, we exploit the excellent fouling resistance of polymer zwitterions and present electrospun nanofiber mats surface functionalized with poly(2-methacryloyloxyethyl phosphorylcholine) (polyMPC). This zwitterionic polymer coating maximizes the accessibility of the zwitterion to effectively limit biofouling on nanofiber membranes. Two facile, scalable methods yielded a coating on cellulose nanofibers: (i) a two-step sequential deposition featuring dopamine polymerization followed by the physioadsorption of polyMPC, and (ii) a one-step codeposition of polydopamine (PDA) with polyMPC. While the sequential and codeposited nanofiber mat assemblies have an equivalent average fiber diameter, hydrophilic contact angle, surface chemistry, and stability, the topography of nanofibers prepared by codeposition were smoother. Protein and microbial antifouling performance of the zwitterion modified nanofiber mats along with two controls, cellulose (unmodified) and PDA coated nanofiber mats were evaluated by dynamic protein fouling and prolonged bacterial exposure. Following 21 days of exposure to bovine serum albumin, the sequential nanofiber mats significantly resisted protein fouling, as indicated by their 95% flux recovery ratio in a water flux experiment, a 300% improvement over the cellulose nanofiber mats. When challenged with two model microbes Escherichia coli and Staphylococcus aureus for 24 h, both zwitterion modifications demonstrated superior fouling resistance by statistically reducing microbial attachment over the two controls. This study demonstrates that, by decorating the surfaces of chemically and mechanically robust cellulose nanofiber mats with polyMPC, we can generate high performance, free-standing nanofiber mats that hold potential in applications where antifouling materials are imperative, such as tissue engineering scaffolds and water purification technologies.

Corrosion causes over $100 billion in damage annually. Cinnamaldehyde, a bioactive agent derived from cinnamon bark, can mitigate the corrosion of metals but has a negative effect on hydration when incorporated in cementitious systems. In order to avoid these negative consequences while harnessing anti-corrosive properties, cinnamaldehyde was incorporated in a cementitious mixture through the use of lightweight aggregate (LWA). The same method was used for penetrating corrosion inhibitors in an attempt to reduce the time required for the inhibitor to reach and protect reinforcing steel. The setting time, compressive strength, heat evolution (via semi-adiabatic calorimetry), and autogenous shrinkage of the experimental mixtures were measured and an accelerated corrosion test (ACT) was used to quantify performance in a corrosive environment. Experimental mortars showed prolonged setting times, reduced compressive strength, heat evolution, and autogenous expansion. However, the experimental mortars showed an increase in time to cracking when exposed to a corrosive environment.

In this study, we exploit the high silver ion exchange capability of Linde Type A (LTA) zeolites and present, for the first time, electrospun nanofiber mats decorated with in-house synthesized silver (Ag(+)) ion exchanged zeolites that function as molecular delivery vehicles. LTA-Large zeolites with a particle size of 6.0 μm were grown on the surface of the cellulose nanofiber mats, whereas LTA-Small zeolites (0.2 μm) and three-dimensionally ordered mesoporous-imprinted (LTA-Meso) zeolites (0.5 μm) were attached to the surface of the cellulose nanofiber mats postsynthesis. After the three zeolite/nanofiber mat assemblies were ion-exchanged with Ag(+) ions, their ion release profiles and ability to inactivate Escherichia coli (E. coli) K12 were evaluated as a function of time. LTA-Large zeolites immobilized on the nanofiber mats displayed more than an 11 times greater E. coli K12 inactivation than the Ag-LTA-Large zeolites that were not immobilized on the nanofiber mats. This study demonstrates that by decorating nanometer to micrometer scale Ag(+) ion-exchanged zeolites on the surface of high porosity, hydrophilic cellulose nanofiber mats, we can achieve a tunable release of Ag(+) ions that inactivate bacteria faster and are more practical to use in applications over powder zeolites.

Microfluidic strategies to enable the growth and subsequent serial crystallographic analysis of micro-crystals have the potential to facilitate both structural characterization and dynamic structural studies of protein targets that have been resistant to single-crystal strategies. However, adapting microfluidic crystallization platforms for micro-crystallography requires a dramatic decrease in the overall device thickness. We report a robust strategy for the straightforward incorporation of single-layer graphene into ultra-thin microfluidic devices. This architecture allows for a total material thickness of only ~1 μm, facilitating on-chip X-ray diffraction analysis while creating a sample environment that is stable against significant water loss over several weeks. We demonstrate excellent signal-to-noise in our X-ray diffraction measurements using a 1.5 μs polychromatic X-ray exposure, and validate our approach via on-chip structure determination using hen egg white lysozyme (HEWL) as a model system. Although this work is focused on the use of graphene for protein crystallography, we anticipate that this technology should find utility in a wide range of both X-ray and other lab on a chip applications.

Nanofiber mats hold potential in numerous applications that interface with microorganisms. However, a fundamental study that quantifies the transport of microorganisms into three-dimensional microenvironments, such as nanofiber mats, has not yet been conducted. Here, we evaluate the microbial uptake capacity of three hydrophilic cellulose sorbents, a high surface area electrospun nanofiber mat, as well as two commercial products, a macrofibrous Fisherbrand fabric and an adsorptive Sartorius membrane. The small average fiber diameter (∼1.0 μm) and large porosity of the nanofiber mats enabled a 21 times greater collection of Escherichia coli K12 per milligram of material than the macrofibrous Fisherbrand controls and 220 times more than the Sartorius controls. In most cases, the exposure time of the nanofiber mats to the microorganisms was sufficient to reach a quasi-equilibrium state of microbial uptake, allowing the calculation of an adsorption coefficient (Keq) that relates the concentration of cells in the sorbent to the concentration of cells remaining in solution. The Keq of the nanofiber mats was 420, compared to 9.2 and 0.67 for the Fisherbrand and Sartorius controls, respectively. In addition to E. coli, we studied the cellulose nanofiber mat uptake of two additional medically relevant and distinct microorganisms, Gram-negative Pseudomonas aeruginosa PA01 and Gram-positive Staphylococcus aureus MW2, to probe whether microorganism removal is bacteria-specific. The high uptake capacity of all three bacteria by the nanofiber mats indicates that microbial uptake is independent of the microorganism's adhesion mechanism. This work suggests that cellulose nanofiber mat “sponges” are a green platform technology that has the potential to remove detrimental microorganisms from wounds, trap bacteria within a protective military textile, or remediate contaminated water.

Biofilm-associated infections stemming from medical devices are increasingly challenging to treat due to the spread of antibiotic resistance. In this study, we present a simple strategy that significantly enhances the antifouling performance of covalently crosslinked poly(ethylene glycol) (PEG) and physically crosslinked agar hydrogels by incorporation of the fouling-resistant polymer zwitterion, poly(2-methacryloyloxyethyl phosphorylcholine) (pMPC). Dopamine polymerization was initiated during swelling of the hydrogels, which provided dopamine and pMPC an osmotic driving force into the hydrogel interior. Both PEG and agar hydrogels were synthesized over a broad range of storage moduli (1.7,1300 kPa), which remained statistically equivalent after being functionalized with pMPC and polydopamine (PDA). When challenged with fibrinogen, a model blood-clotting protein, the pMPC/PDA-functionalized PEG and agar hydrogels displayed a >90% reduction in protein adsorption compared to hydrogel controls. Further, greater than an order-of-magnitude reduction in Escherichia coli and Staphylococcus aureus adherence was observed. This study demonstrates a versatile materials platform to enhance the fouling resistance of hydrogels through a pMPC/PDA incorporation strategy that is independent of the chemical composition and network structure of the original hydrogel.

Published data on the mechanical strength and elasticity of lung tissue is widely variable, primarily due to differences in how testing was conducted across individual studies. This makes it extremely difficult to find a benchmark modulus of lung tissue when designing synthetic extracellular matrices (ECMs). To address this issue, we tested tissues from various areas of the lung using multiple characterization techniques, including micro-indentation, small amplitude oscillatory shear (SAOS), uniaxial tension, and cavitation rheology. We report the sample preparation required and data obtainable across these unique but complimentary methods to quantify the modulus of lung tissue. We highlight cavitation rheology as a new method, which can measure the modulus of intact tissue with precise spatial control, and reports a modulus on the length scale of typical tissue heterogeneities. Shear rheology, uniaxial, and indentation testing require heavy sample manipulation and destruction; however, cavitation rheology can be performed in situ across nearly all areas of the lung with minimal preparation. The Young’s modulus of bulk lung tissue using microindentation (1.9±0.5 kPa), SAOS (3.2±0.6 kPa), uniaxial testing (3.4±0.4 kPa), and cavitation rheology (6.1±1.6 kPa) were within the same order of magnitude, with higher values consistently reported from cavitation, likely due to our ability to keep the tissue intact. Although cavitation rheology does not capture the non-linear strains revealed by uniaxial testing and SAOS, it provides an opportunity to measure mechanical characteristics of lung tissue on a microscale level on intact tissues. Overall, our study demonstrates that each technique has independent benefits, and each technique revealed unique mechanical features of lung tissue that can contribute to a deeper understanding of lung tissue mechanics.

The biocidal properties of gecko skin and cicada wings have inspired the synthesis of synthetic surfaces decorated with high aspect ratio nanostructures that inactivate microorganisms. Here, we investigate the bactericidal activity of oriented zinc phthalocyanine (ZnPc) nanopillars grown using a simple pencil-drawn graphite templating technique. By varying the evaporation time, nanopillars initiated from graphite that was scribbled using a pencil onto silicon substrates were optimized to yield a high inactivation of the Gram-negative bacteria, Escherichia coli. We next adapted the procedure so that analogous nanopillars could be grown from pencil-drawn graphite scribbled onto stainless steel, flexible polyimide foil, and glass substrates. Time-dependent bacterial cytotoxicity studies indicate that the oriented nanopillars grown on all four substrates inactivated up to 97% of the E. coli quickly, in 15 min or less. These results suggest that organic nanostructures, which can be easily grown on a broad range of substrates hold potential as a new class of biocidal surfaces that kill microbes quickly and potentially, without spreading antibiotic-resistance genes.

Clinically, biofilm-associated infections commonly form on intravascular catheters and other hydrogel surfaces. The overuse of antibiotics to treat these infections has led to the spread of antibiotic resistance and underscores the importance of developing alternative strategies that delay the onset of biofilm formation. Previously, it has been reported that during surface contact, bacteria can detect surfaces through subtle changes in the function of their motors. However, how the stiffness of a polymer hydrogel influences the initial attachment of bacteria is unknown. Systematically, we investigated poly(ethylene glycol) dimethacrylate (PEGDMA) and agar hydrogels that were twenty times thicker than the cumulative size of bacterial cell appendages, as a function of Young’s moduli. Soft (44.05 – 308.5 kPa), intermediate (1495 – 2877 kPa), and stiff (5152 – 6489 kPa) hydrogels were synthesized. Escherichia coli and Staphylococcus aureus attachment onto the hydrogels was analyzed using confocal microscopy after 2 and 24 hr incubation periods. Independent of hydrogel chemistry and incubation time, E. coli and S. aureus attachment correlated positively to increasing hydrogel stiffness. For example, after a 24 hr incubation period, there were 52% and 82% less E. coli adhered to soft PEGDMA hydrogels, than to the intermediate and stiff PEGDMA hydrogels, respectively. A 62% and 79% reduction in the area coverage by the Gram-positive microbe S. aureus occurred after 24 hr incubation on the soft versus intermediate and stiff PEGDMA hydrogels. We suggest that hydrogel stiffness is an easily tunable variable that, potentially, could be used synergistically with traditional antimicrobial strategies to reduce early bacterial adhesion, and therefore the occurrence of biofilm-associated infections.

Biopolymer hydrogels are important materials for wound healing and cell culture applications. While current synthetic polymer hydrogels have excellent biocompatibility and are nontoxic, they typically function as a passive matrix that does not supply any additional bioactivity. Chitosan (CS) and pectin (Pec) are natural polymers with active properties that are desirable for wound healing. Unfortunately, the synthesis of CS/Pec materials have previously been limited by harsh acidic synthesis conditions, which further restricted their use in biomedical applications. In this study, a zero-acid hydrogel has been synthesized from a mixture of chitosan and pectin at biologically compatible conditions. For the first time, we demonstrated that salt could be used to suppress long-range electrostatic interactions to generate a thermoreversible biopolymer hydrogel that has temperature-sensitive gelation. Both the hydrogel and the solution phases are highly elastic, with a power law index of close to -1. When dried hydrogels were placed into phosphate buffered saline solution, they rapidly rehydrated and swelled to incorporate 2.7× their weight. As a proof of concept, we removed the salt from our CS/Pec hydrogels, thus, creating thick and easy to cast polyelectrolyte complex hydrogels, which proved to be compatible with human marrow-derived stem cells. We suggest that our development of an acid-free CS/Pec hydrogel system that has excellent exudate uptake, holds potential for wound healing bandages.

In this study, we have fabricated robust patterned surfaces that contain biocompatible and antifouling stripes, which cause microorganisms to consolidate into bare silicon spaces. Copolymers of methacryloyloxyethyl phosphorylcholine (MPC) and a methacrylate-substituted dihydrolipoic acid (DHLA) were spin-coated onto silicon substrates. The MPC units contributed biocompatibility and antifouling properties, while the DHLA units enabled crosslinking and the formation of robust thin films. Photolithography enabled the formation of 200 μm wide poly(MPC-DHLA) stripped patterns that were characterized using atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS) and rhodamine 6G staining. Regardless of the spacing between the poly(MPC-DHLA) stripes (10, 50, or 100 μm) Escherichia coli (E. coli) rapidly adhered to the bare silicon gaps that lacked the copolymer, confirming the antifouling nature of MPC. Overall, this work provides a surface modification strategy to generate alternating bio-fouling and non-fouling surface structures that are potentially applicable for researchers studying cell biology, drug screening, and biosensor technology.

Due to the persistent spread of antibiotic resistance, commercial antibiotic treatments are proving ineffective. Cinnamaldehyde (CA), a volatile essential oil, eradicates pathogens non-specifically. However, the ability to incorporate essential oils into nanofiber mats has not yet been demonstrated, and, only six studies have electrospun two immiscible phases. Here, CA (0.5 and 5.0%) was incorporated into chitosan/poly(ethylene oxide) (PEO) solutions that were successfully electrospun into mats with ∼50 nm fiber diameters. Solid-state NMR results corroborated with release studies wherein the 5.0% CA mats released a statistically higher amount of CA-liquid (545% more) and CA-vapor (279% more) than the 0.5% CA mats. In time dependent cytotoxicity studies, the intrinsic antibacterial activity of chitosan along with the quick release of CA enabled high inactivation rates against Escherichia coli and Pseudomonas aeruginosa . For the first time we have demonstrated chitosan/CA/PEO nanofiber mats can serve as CA delivery vehicles that potentially eradicate pseudomonas infections.

To obtain a fundamental understanding of the various factors affecting pressure filtration performance, we developed a coupled computational fluid dynamics (CFD) and discrete element method (DEM) model for simulating the effect of solvent flow through the solid particle cake. The model was validated using data collected by filtering mixtures of spherical glass beads and deionized water through a dead-end cell over a range of applied pressures. Numerical experiments were performed to study the effects of particle properties, liquid properties and operating conditions on filtration performance. The model predicted that the filtrate flow rate could be strongly affected by the mean size of the particles, the presence of small particles (i.e. fines) in the particle distribution, the viscosity of the liquid, and particle deformation leading to cake compression. Our study demonstrated that CFD-DEM modeling is a powerful approach for understanding cake filtration processes and predicting filtration performance.

Electrospinning is a cost effective and facile method to manufacture fiber mats appropriate for biomedical applications. Due to its high molecular weight and charged backbone, hyaluronic acid (HA) fiber mats with consistent fiber morphology have been difficult to electrospin from neutral pH solutions. Here, we present that the electrospinning of HA fibers in aqueous dimethylformamide solutions is facilitated by the addition of three phosphate salts. The salts—glycerol phosphate (GP), sodium phosphate (SP), and tripolyphosphate (TPP)—facilitated electrospinning of the solutions as characterized by conductivity measurements and fiber morphology. From tensile experiments, HA mats electrospun with SP demonstrated improved Young’s modulus (12 MPa) over HA mats spun with either GP or TPP (5 and 3 MPa, respectively). This work demonstrates that a new neutral solvent system can be employed to spin HA fibers, which offers the potential for using the fibers for biomedical applications, such as a bone biomimetic.