Design of Abrasion-Resistant, Long-Lasting Antifog Coatings.

Fog formation is a common challenge for numerous applications, such as food packaging, mirrors, building windows, and freezer/refrigerator doors. Most notably, fog forms on the inner surfaces of prescription glasses and safety eyewear (particularly when used with a mask), face shields, and helmet lenses. Fogging is caused by the distortion of light from condensed water droplets present on a surface and can typically be prevented if the surface static water contact angle (θ) is less than ∼40°. Such a low contact angle can be readily achieved by either increasing the substrate surface energy or by engineering surface nanotexture. Unfortunately, such nanotexture can be readily damaged with use, while high surface energy substrates get covered with low surface energy foulants over time. Consequently, even with numerous ephemeral antifog coatings, currently there are no commercially available, durable, and permanent antifog coatings. Here we discuss the development of a new class of high-performance antifog coatings that are abrasion-resistant and long-lasting. These polyvinylpyrrolidone-based coatings, designed based on the classical Ratner-Lancaster wear model, dramatically outperform the base polymer, as well as all tested commercially available antifog coatings. Specifically, these coatings exhibit a > 400% increase in fogging time compared to base polymer, a > 50,000% increase in wear resistance, and excellent long-term antifog performance. The developed coatings also significantly outperformed all tested commercially available antifog coatings in terms of their antifog performance, wear resistance, and long-term cyclical performance. Additionally, the key design strategies employed here─incorporation of toughening agents and hydrophilic slip additives─offer a new approach to developing high-performance, durable antifog coatings based on other well-known antifog polymers.

Co-Delivery Polymeric Poly(Lactic-Co-Glycolic Acid) (PLGA) Nanoparticles to Target Cancer Stem-Like Cells.

Nanoparticle drug delivery has been promoted as an effective mode of delivering antineoplastic therapeutics. However, most nanoparticle designs fail to consider the multifaceted tumor microenvironment (TME) that produce pro-tumoral niches, which are often resistant to chemo- and targeted therapies. In order to target the chemoresistant cancer stem-like cells (CSCs) and their supportive TME, in this chapter we describe a nanoparticle-based targeted co-delivery that addresses the paracrine interactions between CSC and non-cancerous mesenchymal stem cells (MSCs) in the TME. Carcinoma-activated MSCs have been shown to increase the chemoresistance and metastasis of CSC. Yet their contributions to protect the CSC TME have not yet been systematically investigated in the design of nanoparticles for drug delivery. Therefore, we describe the fabrication of degradable poly(lactic-co-glycolic acid) (PLGA) nanoparticles (120-200 nm), generated with an electrospraying process that encapsulates both a conventional chemotherapeutic, paclitaxel, and a targeted tyrosine kinase inhibitor, sunitinib, to limit MSC interactions with CSC. In the 3D hetero-spheroid model that comprises both CSCs and MSCs, the delivery of sunitinib as a free drug disrupted the MSC-protected CSC stemness and migration. Therefore, this chapter describes the co-delivery of paclitaxel and sunitinib via PLGA nanoparticles as a potential targeted therapy strategy for targeting CSCs. Overall, nanoparticles can provide an effective delivery platform for targeting CSCs and their TME together. Forthcoming studies can corroborate similar combined therapies with nanoparticles to improve the killing of CSC and chemoresistant cancer cells, thereby improving treatment efficiency.

Polysiloxane-Based Liquid-like Layers for Reducing Polymer and Wax Fouling.

Surface fouling occurs when undesired matter adheres and accumulates on a surface, resulting in a decrease or loss of functionality. Polymer and wax fouling can cause costly blockages to crude oil pipelines, clog jet fuel injectors, foul chemical reaction vessels, and significantly decrease the efficiency of heat exchangers. Fouling occurs in many forms but can be segmented based on adherent size, modulus, and chemical functionality. Depending on the foulant, surface design strategies can vary greatly. Few strategies exist to prevent the buildup of wax and polymers on surfaces. In this report, we investigate the potential of highly disordered, siloxane liquid-like layers as a strategy for reducing wax and polymer deposition. In our tests, it was found that the liquid-like layers developed here were able to reduce postadsorption roughness for polymer and wax by as much as 35- and 47-fold, respectively, when compared to the control. SFG was utilized to investigate the molecular-level interfacial properties for each of the modified surfaces to help understand the antifouling mechanism. The data showed that the likely higher grafting density and a large degree of random conformational freedom at the liquid-surface interface make the developed siloxane-covered surfaces energetically unfavorable for polymer and wax accretion.

Surfaces with instant and persistent antimicrobial efficacy against bacteria and SARS-CoV-2.

Surfaces contaminated with bacteria and viruses contribute to the transmission of infectious diseases and pose a significant threat to global public health. Modern day disinfection either relies on fast-acting (>3-log reduction within a few minutes), yet impermanent, liquid-, vapor-, or radiation-based disinfection techniques, or long-lasting, but slower-acting, passive antimicrobial surfaces based on heavy metal surfaces, or metallic nanoparticles. There is currently no surface that provides instant and persistent antimicrobial efficacy against a broad spectrum of bacteria and viruses. In this work, we describe a class of extremely durable antimicrobial surfaces incorporating different plant secondary metabolites that are capable of rapid disinfection (>4-log reduction) of current and emerging pathogens within minutes, while maintaining persistent efficacy over several months and under significant environmental duress. We also show that these surfaces can be readily applied onto a variety of desired substrates or devices via simple application techniques such as spray, flow, or brush coating.

Durable Liquid- and Solid-Repellent Elastomeric Coatings Infused with Partially Crosslinked Lubricants.

Surfaces that are resistant to both liquid fouling and solid fouling are critical for many industrial and biomedical applications. However, surfaces developed to address these challenges thus far have been generally susceptible to mechanical damage. Herein, we report the design and fabrication of robust solid- and liquid-repellent elastomeric coatings that incorporate partially crosslinked lubricating chains within a durable polymer matrix. In particular, we fabricated partially crosslinked omniphobic polyurethane (omni-PU) coatings that can repel a broad range of liquid and solid foulants. The fabricated coatings are an order of magnitude more resistant to cyclic abrasion than current state-of-the-art slippery surfaces. Further through the integration of classic wetting and tribology models, we introduce a new material design parameter (KAR) for abrasion-resistant polymeric coatings. This combination of mechanical durability and broad antifouling properties enables the implication of such coatings to a wide variety of industrial and medical settings, including biocompatible implants, underwater vehicles, and antifouling robotics.

Continuous Liquid-Liquid Extraction and in-Situ Membrane Separation of Miscible Liquid Mixtures.

Separation operations are critical across a wide variety of manufacturing industries and account for about one-quarter of all in-plant energy consumption in the United States. Conventional liquid-liquid separation operations require either thermal or chemical treatment, both of which have a large environmental impact and carbon footprint. Consequently, there is a great need to develop sustainable, clean methodologies for separation of miscible liquid mixtures. The greatest opportunities to achieve this lie in replacing high-energy separation operations (e.g., distillation) with low-energy alternatives such as liquid-liquid extraction. One of the primary design challenges in liquid-liquid extraction is to maximize the interfacial area between two immiscible (e.g., polar and nonpolar) liquids for efficient mass transfer. However, this often involves energy-intensive methods including ultrasonication, pumping the feed and the extractant through packed columns with high tortuosity, or using a supercritical fluid as an extractant. Emulsifying the feed and the extractant, especially with a surfactant, offers a large interfacial area, but subsequent separation of emulsions can be energy-intensive and expensive. Thus, emulsions are typically avoided in conventional extraction operations. Herein, we discuss a novel, easily scalable, platform separation methodology termed CLEANS (continuous liquid-liquid extraction and in-situ membrane separation). CLEANS integrates emulsion-enhanced extraction with continuous, gravity-driven, membrane-based separation of emulsions into a single unit operation. Our results demonstrate that the addition of a surfactant and emulsification significantly enhance extraction (by >250% in certain cases), even for systems where the best extractants for miscible liquid mixtures are known. Utilizing the CLEANS methodology, we demonstrate continuous separation of a wide range of miscible liquid mixtures, including soluble organic molecules from oils, alcohols from esters, and even azeotropes.

Rapid and Robust Surface Treatment for Simultaneous Solid and Liquid Repellency.

A wide range of liquid and solid contaminants can adhere to everyday functional surfaces and dramatically alter their performance. Numerous surface modification strategies have been developed that can reduce the fouling of some solids or repel certain liquids but are generally limited to specific contaminants or class of foulants. This is due to the typically distinct mechanisms that are employed to repel liquids vs solids. Here, we demonstrate a rapid and facile surface modification technique that yields a thin film of linear chain siloxane molecules covalently tethered to a surface. We investigate and characterize the liquid-like morphology of these surfaces in detail as the key contributing factor to their anti-fouling performance. This surface treatment is extremely durable and readily repels a broad range of liquids with varying surface tensions and polarities, including water, oils, organic solvents, and even fluorinated solvents. Additionally, the flexible, liquid-like nature of these surfaces enables interfacial slippage, which dramatically reduces adhesion to various types of solids, including ice, wax, calcined gypsum, and cyanoacrylate adhesives, and also minimizes the nucleation of inorganic scale. The developed surfaces are durable and simple to fabricate, and they minimize fouling by both liquids and solids simultaneously.

Design and applications of surfaces that control the accretion of matter.

Surfaces that provide control over liquid, solid, or vapor accretion provide an evolutionary advantage to numerous plants, insects, and animals. Synthetic surfaces inspired by these natural surfaces can have a substantial impact on diverse commercial applications. Engineered liquid and solid repellent surfaces are often designed to impart control over a single state of matter, phase, or fouling length scale. However, surfaces used in diverse real-world applications need to effectively control the accrual of matter across multiple phases and fouling length scales. We discuss the surface design strategies aimed at controlling the accretion of different states of matter, particularly those that work across multiple length scales and different foulants. We also highlight notable applications, as well as challenges associated with these designer surfaces' scale-up and commercialization.

Novel Omniphobic Platform for Multicellular Spheroid Generation, Drug Screening, and On-Plate Analysis.

Multicellular spheroids are superior to other culture geometries in reproducing critical physiological conditions of tumors, such as the diffusion of oxygen, nutrients, waste, and drugs, leading to a more precise model of in vivo drug sensitivity and resistance. Previously reported spheroid culture platforms are often difficult to use, expensive, single-use, or mechanically unstable. Here, we report a facile, mechanically stable, high-throughput spheroid culture platform based on hierarchically textured omniphobic surfaces. The developed omniphobic surfaces display very high contact angles with a range of different liquids, including the cell-laden culture media, thereby minimizing the cell surface contact area. Additionally, these surfaces maintain these high contact angles for extended periods of time to ensure cell aggregation. Using this novel platform, we demonstrate the generation and maintenance of robust multicellular spheroids, as well as heterogeneous, multicell-type spheroids. The platform is extremely robust, resistant to mechanical shock, allows for on-plate imaging, and is also the first-ever spheroid generation platform that can be reused repeatedly. Finally, the platform is suitable for on-plate drug screening and enables the first-ever, on-plate immunofluorescence staining and imaging of spheroids.

Non-Fluorinated, Superhydrophobic Binder-Filler Coatings on Smooth Surfaces: Controlled Phase Separation of Particles to Enhance Mechanical Durability.

There has been a recent drive to develop non-fluorinated superhydrophobic coatings due to the toxicity, cost, and environmental impact of perfluorinated components. One of the main challenges in developing superhydrophobic coatings in general and non-fluorinated superhydrophobic coatings in particular is optimization of mechanical durability, as the rough asperities required for maintaining superhydrophobicity tend to be easily removed by abrasion. Although rough and self-similar hydrophobic surfaces composed of loosely adhered particles or highly porous structures tend to produce excellent superhydrophobicity, they have low inherent mechanical durability and their longevity under real conditions is compromised. To address this issue, this work investigates the addition of a polymeric matrix material (the binder) to hydrophobic nanoparticles (the filler) to produce spray-coated superhydrophobic surfaces with improved inherent mechanical durability. Hansen solubility parameters were used to tune the interactions between the binder, filler, and solvent used to deliver the coating. It was found that lowering the binder/filler miscibility and using a poor solvent mixture generates more surface roughness, thereby lowering the minimum filler load required to achieve superhydrophobicity. This leads to an overall more inherently durable system that remains hydrophobic for thousands of light abrasion cycles.

Lysis and direct detection of coliforms on printed paper-based microfluidic devices.

Coliforms are one of the most common families of bacteria responsible for water contamination. Certain coliform strains can be extremely toxic, and even fatal if consumed. Current technologies for coliform detection are expensive, require multiple complicated steps, and can take up to 24 hours to produce accurate results. Recently, open-channel, paper-based microfluidic devices have become popular for rapid, inexpensive, and accurate bioassays. In this work, we have created an integrated microfluidic coliform lysis and detection device by fabricating customizable omniphilic regions via direct printing of omniphilic channels on an omniphobic, fluorinated paper. This paper-based device is the first of its kind to demonstrate successful cell lysing on-chip, as it can allow for the flow and control of both high and low surface tension liquids, including different cell lysing agents. The fabricated microfluidic device was able to successfully detect E. coli, via the presence of the coliform-specific enzyme, ß-galactosidase, at a concentration as low as ∼104 CFU mL-1. Further, E. coli at an initial concentration of 1 CFU mL-1 could be detected after only 6 hours of incubation. We believe that these devices can be readily utilized for real world E. coli contamination detection in multiple applications, including food and water safety.

Inkjet-printed micro-calibration standards for ultraquantitative Raman spectral cytometry.

Herein we report the development of a cytometric analysis platform for measuring the contents of individual cells in absolute (picogram) scales; this study represents the first report of Raman-based quantitation of the absolute mass - or the total amount - of multiple endogenous biomolecules within single-cells. To enable ultraquantitative calibration, we engineered single-cell-sized micro-calibration standards of known composition by inkjet-printer deposition of biomolecular components in microarrays across the surface of silicon chips. We demonstrate clinical feasibility by characterizing the compositional phenotype of human skin fibroblast and porcine alveolar macrophage cell populations in the respective contexts of Niemann-Pick disease and drug-induced phospholipidosis: two types of lipid storage disorders. We envision this microanalytical platform as the foundation for many future biomedical applications, ranging from diagnostic assays to pathological analysis to advanced pharmaco/toxicokinetic research studies.

Design of surfaces for controlling hard and soft fouling.

In this review, we present a framework to guide the design of surfaces which are resistant to solid fouling, based on the modulus and length scale of the fouling material. Solid fouling is defined as the undesired attachment of solid contaminants including ice, clathrates, waxes, inorganic scale, polymers, proteins, dust and biological materials. We first provide an overview of the surface design approaches typically applied across the scope of solid fouling and explain how these disparate research efforts can be united to an extent under a single framework. We discuss how the elastic modulus and the operating length scale of a foulant determine its ability or inability to elastically deform surfaces. When surface deformation occurs, minimization of the substrate elastic modulus is critical for the facile de-bonding of a solid contaminant. Foulants with low modulus or small deposition sizes cannot deform an elastic bulk material and instead de-bond more readily from surfaces with chemistries that minimize their interfacial free energy or induce a particular repellant interaction with the foulant. Overall, we review reported surface design strategies for the reduction in solid fouling, and provide perspective regarding how our framework, together with the modulus and length scale of a foulant, can guide future antifouling surface designs. This article is part of the theme issue 'Bioinspired materials and surfaces for green science and technology'.

Low-interfacial toughness materials for effective large-scale deicing.

Ice accretion has adverse effects on a range of commercial and residential activities. The force required to remove ice from a surface is typically considered to scale with the iced area. This imparts a scalability limit to the use of icephobic coatings for structures with large surface areas, such as power lines or ship hulls. We describe a class of materials that exhibit a low interfacial toughness with ice, resulting in systems for which the forces required to remove large areas of ice (a few square centimeters or greater) are both low and independent of the iced area. We further demonstrate that coatings made of such materials allow ice to be shed readily from large areas (~1 square meter) merely by self-weight.

Wettability Engendered Templated Self-Assembly (WETS) for the Fabrication of Biocompatible, Polymer-Polyelectrolyte Janus Particles.

Fabrication of charged, multiphasic, polymeric micro- and nanoparticles with precise control over their composition, size, and shape is critical for developing the next generation of drug carriers for combinatorial therapies and theranostics. The addition of charged polyelectrolyte multilayers on the surface of polymeric particles can significantly improve their stability, targeting efficacy, drug-release kinetics, and their ability to encapsulate different drugs within a single particle. Many of the traditional methods for multilayer functionalization of multiphasic polymeric particles are time and energy intensive which significantly limits their scalability, and therefore therapeutic potential. In this work, we combine the bulk layer-by-layer polyelectrolyte application methodology with our previously developed technique of fabricating multiphasic polymeric particles on substrates with patterned wettability to synthesize biocompatible, monodisperse, Janus polymer-polyelectrolyte particles.

Smooth, All-Solid, Low-Hysteresis, Omniphobic Surfaces with Enhanced Mechanical Durability.

The utility of omniphobic surfaces stems from their ability to repel a multitude of liquids, possessing a broad range of surface tensions and polarities, by causing them to bead up and either roll or slide off. These surfaces may be self-cleaning, corrosion-resistant, heat-transfer enhancing, stain-resistant or resistant to mineral- or biofouling. The majority of reported omniphobic surfaces use texture, lubricants, and/or grafted monolayers to engender these repellent properties. Unfortunately, these approaches often produce surfaces with deficiencies in long-term stability, durability, scalability, or applicability to a wide range of substrates. To overcome these limitations, we have fabricated an all-solid, substrate-independent, smooth, omniphobic coating composed of a fluorinated polyurethane and fluorodecyl polyhedral oligomeric silsesquioxane. Liquids of varying surface tension, including water, hexadecane, ethanol, and silicone oil, exhibit low-contact-angle hysteresis (<15°) on these surfaces, allowing liquid droplets to slide off, leaving no residue. Moreover, we demonstrate that these robust surfaces retained their repellent properties more effectively than textured or lubricated omniphobic surfaces after being subjected to mechanical abrasion.

A predictive framework for the design and fabrication of icephobic polymers.

Ice accretion remains a costly, hazardous concern worldwide. Icephobic coatings reduce the adhesion between ice and a surface. However, only a handful of the icephobic systems reported to date reduce the ice adhesion sufficiently for the facile and passive removal of ice, such as under its own weight or by mild winds. Most of these icephobic surfaces have relied on sacrificial lubricants, which may be depleted over time, drastically raising the ice adhesion. In contrast, surfaces that use interfacial slippage to lower their adhesion to ice can remain icephobic indefinitely. However, the mechanism of interfacial slippage, as it relates to ice adhesion, is largely unexplored. We investigate how interfacial slippage reduces the ice adhesion of polymeric materials. We propose a new, universally applicable framework that may be used to predict the reduction in the adhesion of ice to surfaces exhibiting interfacial slippage. This framework allows one to rationally engender icephobicity in essentially any polymeric system, including common thermoplastics. Hence, we present several new, extremely icephobic systems fabricated from a wide range of materials, including everyday engineering plastics and sustainable, natural oils.

Designing Self-Healing Superhydrophobic Surfaces with Exceptional Mechanical Durability.

The past decade saw a drastic increase in the understanding and applications of superhydrophobic surfaces (SHSs). Water beads up and effortlessly rolls off a SHS due to its combination of low surface energy and texture. Whether being used for drag reduction, stain repellency, self-cleaning, fog harvesting, or heat transfer applications (to name a few), the durability of a SHS is critically important. Although a handful of purportedly durable SHSs have been reported, there are still no criteria available for systematically designing a durable SHS. In the first part of this work, we discuss two new design parameters that can be used to develop mechanically durable SHSs via the spray coating of different binders and fillers. These parameters aid in the rational selection of material components and allow one to predict the capillary resistance to wetting of any SHS from a simple topographical analysis. We show that not all combinations of sprayable components generate SHSs, and mechanically durable components do not necessarily generate mechanically durable SHSs. Moreover, even the most durable SHSs can eventually become damaged. In the second part, utilizing our new parameters, we design and fabricate physically and chemically self-healing SHSs. The most promising surface is fabricated from a fluorinated polyurethane elastomer (FPU) and the extremely hydrophobic small molecule 1H,1H,2H,2H-heptadecafluorodecyl polyhedral oligomeric silsesquioxane (F-POSS). A sprayed FPU/F-POSS surface can recover its superhydrophobicity even after being abraded, scratched, burned, plasma-cleaned, flattened, sonicated, and chemically attacked.

Rational Design of Hyperbranched Nanowire Systems for Tunable Superomniphobic Surfaces Enabled by Atomic Layer Deposition.

Superomniphobic surfaces display contact angles of θ* > 150° and low contact angle hysteresis with virtually all high and low surface tension liquids. The introduction of hierarchical scales of texture can increase the contact angles and decrease the contact angle hysteresis of superomniphobic surfaces by reducing the solid-liquid contact area. Thus far, it has not been possible to fabricate superomniphobic surfaces with three or more hierarchical scales of texture where the size, spacing, and angular orientation of features within each scale of texture can be independently varied and controlled. Here, we report a method for tunable control of geometry in hyperbranched ZnO nanowire (NW) structures, which in turn enables the rational design and fabrication of superomniphobic surfaces. Branched NWs with tunable density and orientation were grown via a sequential hydrothermal process, in which atomic layer deposition was used for NW seeding, disruption of epitaxy, and selective blocking of NW nucleation. This approach allows for the rational design and optimization of three-level hierarchical structures, in which the geometric parameters of each level of hierarchy can be individually controlled. We demonstrate the coupled relationships between geometry and contact angles for a variety of liquids, which is supported by mathematical models. The highest performing superomniphobic surface was designed with three levels of hierarchy and achieved the following advancing/receding contact angles with water 172°/170°, hexadecane 166°/156°, octane 162°/145°, and heptane 160°/130°.

Bioinspired surfaces for turbulent drag reduction.

In this review, we discuss how superhydrophobic surfaces (SHSs) can provide friction drag reduction in turbulent flow. Whereas biomimetic SHSs are known to reduce drag in laminar flow, turbulence adds many new challenges. We first provide an overview on designing SHSs, and how these surfaces can cause slip in the laminar regime. We then discuss recent studies evaluating drag on SHSs in turbulent flow, both computationally and experimentally. The effects of streamwise and spanwise slip for canonical, structured surfaces are well characterized by direct numerical simulations, and several experimental studies have validated these results. However, the complex and hierarchical textures of scalable SHSs that can be applied over large areas generate additional complications. Many studies on such surfaces have measured no drag reduction, or even a drag increase in turbulent flow. We discuss how surface wettability, roughness effects and some newly found scaling laws can help explain these varied results. Overall, we discuss how, to effectively reduce drag in turbulent flow, an SHS should have: preferentially streamwise-aligned features to enhance favourable slip, a capillary resistance of the order of megapascals, and a roughness no larger than 0.5, when non-dimensionalized by the viscous length scale.This article is part of the themed issue 'Bioinspired hierarchically structured surfaces for green science'.