Simple synthesis of soft, tough, and cytocompatible biohybrid composites.

Collagen is the most abundant component of mammalian extracellular matrices. As such, the development of materials that mimic the biological and mechanical properties of collagenous tissues is an enduring goal of the biomaterials community. Despite the development of molded and 3D printed collagen hydrogel platforms, their use as biomaterials and tissue engineering scaffolds is hindered by either low stiffness and toughness or processing complexity. Here, we demonstrate the development of stiff and tough biohybrid composites by combining collagen with a zwitterionic hydrogel through simple mixing. This combination led to the self-assembly of a nanostructured fibrillar network of collagen that was ionically linked to the surrounding zwitterionic hydrogel matrix, leading to a composite microstructure reminiscent of soft biological tissues. The addition of 5-15 mg mL-1 collagen and the formation of nanostructured fibrils increased the elastic modulus of the composite system by 40% compared to the base zwitterionic matrix. Most notably, the addition of collagen increased the fracture energy nearly 11-fold ([Formula: see text] 180 J m-2) and clearly delayed crack initiation and propagation. These composites exhibit elastic modulus ([Formula: see text] 0.180 MJ) and toughness ([Formula: see text]0.617 MJ m-3) approaching that of biological tissues such as articular cartilage. Maintenance of the fibrillar structure of collagen also greatly enhanced cytocompatibility, improving cell adhesion more than 100-fold with >90% cell viability.

Synthesis of Raspberry-like Nanoparticles via Surface Grafting of Positively Charged Polyelectrolyte Brushes: Colloidal Stability and Surface Properties.

A method to synthesize stable, raspberry-like nanoparticles (NPs), using surface grafting of poly(glycidyl methacrylate) (PGMA) brushes on a polystyrene (PS) core with varying grafting densities, is reported. A two-step functionalization reaction of PGMA epoxide groups comprising an amination step first using ethylene diamine and then followed by a quaternization using glycidyltrimethylammonium chloride generates permanently and positively charged polyelectrolyte brushes, which result in both steric and electrostatic stabilization. The dispersion stability of the brush-bearing NPs is dramatically improved compared to that of the pristine PS core in salt solutions at ambient (25 °C) and elevated temperatures (60 °C). Additionally, the grafted polyelectrolyte chains undergo a reversible swelling in the presence of different ionic strength (IS) salts, which modulate the surface properties, including roughness, stiffness, and adhesion. An atomic force microscope under both dry and wet conditions was used to image conformational changes of the polyelectrolyte chains during the swelling and deswelling transitions as well as to probe the nanomechanical properties by analyzing the corresponding force-sample separation curves. The quaternized polyelectrolyte brushes undergo a conformational transition from a collapsed state to a swelled state in the osmotic brush (OB) regime triggered by the osmotic gradient of mobile ions to the interior of the polymer chain. At IS ∼ 1 M, the brushes contract and the globules reform (salted brush state) as evidenced by an increase in the surface roughness and a reduction in the adhesion of the brushes. Beyond IS ∼ 1 M, quartz crystal microbalance with dissipation monitoring measurements show that salt uptake continues to take place predominantly on the exterior surface of the brush since salt adsorption is not accompanied by a size increase as measured by dynamic light scattering. The study adds new insights into our understanding of the behavior of NPs bearing salt-responsive polyelectrolyte brushes with adaptive swelling thresholds that can ultimately modulate surface properties.

Electrocatalysis in Alkaline Media and Alkaline Membrane-Based Energy Technologies.

Hydrogen energy-based electrochemical energy conversion technologies offer the promise of enabling a transition of the global energy landscape from fossil fuels to renewable energy. Here, we present a comprehensive review of the fundamentals of electrocatalysis in alkaline media and applications in alkaline-based energy technologies, particularly alkaline fuel cells and water electrolyzers. Anion exchange (alkaline) membrane fuel cells (AEMFCs) enable the use of nonprecious electrocatalysts for the sluggish oxygen reduction reaction (ORR), relative to proton exchange membrane fuel cells (PEMFCs), which require Pt-based electrocatalysts. However, the hydrogen oxidation reaction (HOR) kinetics is significantly slower in alkaline media than in acidic media. Understanding these phenomena requires applying theoretical and experimental methods to unravel molecular-level thermodynamics and kinetics of hydrogen and oxygen electrocatalysis and, particularly, the proton-coupled electron transfer (PCET) process that takes place in a proton-deficient alkaline media. Extensive electrochemical and spectroscopic studies, on single-crystal Pt and metal oxides, have contributed to the development of activity descriptors, as well as the identification of the nature of active sites, and the rate-determining steps of the HOR and ORR. Among these, the structure and reactivity of interfacial water serve as key potential and pH-dependent kinetic factors that are helping elucidate the origins of the HOR and ORR activity differences in acids and bases. Additionally, deliberately modulating and controlling catalyst-support interactions have provided valuable insights for enhancing catalyst accessibility and durability during operation. The design and synthesis of highly conductive and durable alkaline membranes/ionomers have enabled AEMFCs to reach initial performance metrics equal to or higher than those of PEMFCs. We emphasize the importance of using membrane electrode assemblies (MEAs) to integrate the often separately pursued/optimized electrocatalyst/support and membranes/ionomer components. Operando/in situ methods, at multiscales, and ab initio simulations provide a mechanistic understanding of electron, ion, and mass transport at catalyst/ionomer/membrane interfaces and the necessary guidance to achieve fuel cell operation in air over thousands of hours. We hope that this Review will serve as a roadmap for advancing the scientific understanding of the fundamental factors governing electrochemical energy conversion in alkaline media with the ultimate goal of achieving ultralow Pt or precious-metal-free high-performance and durable alkaline fuel cells and related technologies.

Probing the Interfacial Properties of Oil-Water Interfaces Decorated with Ionizable, pH Responsive Silica Nanoparticles.

Particle-stabilized emulsions (Pickering emulsions) have recently attracted significant attention in scientific studies and for technological applications. The interest stems from the ease of directly assembling the particles at interfaces and modulating the interfacial properties. In this paper, we demonstrate the formation of stable, practical emulsions leveraging the assembly of ionizable, pH responsive silica nanoparticles, surface-functionalized by a mixture of silanes containing amine/ammonium groups, which renders them positively charged. Using pH as the trigger, the assembly and the behavior of the emulsion are controlled by modulating the charges of the functional groups of the nanoparticle and the oil (crude oil). In addition to their tunable charge, the particular combination of silane coupling agents leads to stable particle dispersions, which is critical for practical applications. Atomic force microscopy and interfacial tension (IFT) measurements are used to monitor the assembly, which is controlled by both the electrostatic interactions between the particles and oil and the interparticle interactions, both of which are modulated by pH. Under acidic conditions, when the surfaces of the oil and the nanoparticles (NPs) are positively charged, the NPs are not attracted at the interface and there is no significant reduction in the IFT. In contrast, under basic conditions in which the oil carries a high negative charge and the amine groups on the silica are deprotonated while still positively charged because of the ammonium groups, the NPs assemble at the interface in a closely packed configuration yielding a jammed state with a high dilatational modulus. As a result, two oil droplets do not coalesce even when pushed against each other and the emulsion stability improves significantly. The study provides new insights into the directed assembly of nanoparticles at fluid interfaces relevant to several applications, including environmental remediation, catalysis, drug delivery, food technology, and oil recovery.

S and O Co-Coordinated Mo Single Sites in Hierarchically Porous Tubes from Sulfur-Enamine Copolymerization for Oxygen Reduction and Evolution.

The highly efficient bifunctional catalyst for the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER) is the key to achieving high-performance rechargeable Zn-air batteries. Non-precious-metal single-atom catalysts (SACs) have attracted intense interest due to their low cost and very high metal atomic utilization; however, high-activity bifunctional non-precious-metal SACs are still rare. Herein, we develop a new nanospace-confined sulfur-enamine copolymerization strategy to prepare a new type of bifunctional Mo SACs with O/S co-coordination (Mo-O2S2-C) supported on the multilayered, hierarchically porous hollow tubes. The as-prepared catalyst can not only expose more active sites and facilitate mass transfer due to their combined micropores, mesopores, and macropores but also have the S/O co-coordination structure for optimizing the adsorption energies of the ORR intermediates. Its ORR activity is among the highest, and it shows a low overpotential of 324 mV for the OER at 10 mA cm-2 in all of the reported Mo-based catalysts. When assembled in a Zn-air battery, it exhibits a high maximal power density of 197.3 mW cm-2 and a long service life of 50 hours, superior to those of Zn-air batteries using commercial Pt/C+IrO2.

Monitoring the Early Stages of Formation of Oil-Water Emulsions Using Flow Cytometry.

Characterization of complex oil emulsions is critical yet challenging both in science and in many industrial applications. Here we demonstrate for the first time the use of flow cytometry as a fast method for characterizing complex, polydisperse oil-water emulsions. Owing to our interest in understanding how the presence of specific ions might affect the properties of oil-water emulsions including size, polydispersity, and complexity, we present a systematic study of oil emulsions in deionized water and various brines of different ionic strength. Forward scatter (FSC) and side scatter (SSC) intensities associated with detailed statistics were judiciously combined to provide a better understanding of these complex systems. We find that the type and concentration profiles of ions around the oil droplets affect significantly the properties of the emulsion. Weakly hydrated cations NH4+ and Ca2+ appear to be more effective in screening the charge of oil droplets compared to the monovalent Na+ and divalent Mg2+ ions, respectively. As a result, coalescence and formation of larger droplets are seen in the case of NH4Cl and CaCl2 compared to NaCl and MgCl2, respectively. In addition, weakly hydrated anions such as Cl- can come closer to the oil surface and, thus, decrease the effective screening that the Na+ ions provide as compared to SO42- ions, which leads to more stable emulsions in NaCl compared to Na2SO4. In addition to these specific findings, the work demonstrates the utility of the technique as a new tool for characterizing oil emulsions in a wide spectrum of fields ranging from food to oil and gas applications.

Scalable Synthesis of Switchable Assemblies of Gold Nanorod Lyotropic Liquid Crystal Nanocomposites.

A new class of solvent free, lyotropic liquid crystal nanocomposites based on gold nanorods (AuNRs) with high nanorod content is reported. Application of shear results in switchable, highly ordered alignment of the nanorods over several centimeters with excellent storage stability for months. For the synthesis, AuNRs are surface functionalized with a charged, covalently tethered corona, which induces fluid-like properties. This honey-like material can be deposited on a substrate and a high orientational order parameter of 0.72 is achieved using a simple shearing protocol. Switching shearing direction results in realignment of the AuNRs. For a film containing 75 wt% of AuNRs the alignment persists for several months. In addition to the lyotropic liquid crystal characteristics, the AuNRs films also exhibit anisotropic electrical conductivity with an order of magnitude difference between the conductivities in direction parallel and perpendicular to the alignment of the AuNRs.

Simple Synthesis of Elastomeric Photomechanical Switches That Self-Heal.

This article introduces a simple two-stage method to synthesize and program a photomechanical elastomer (PME) for light-driven artificial muscle-like actuations in soft robotics. First, photochromic azobenzene molecules are covalently attached to a polyurethane backbone via a two-part step-growth polymerization. Next, mechanical alignment is applied to induce anisotropic deformations in the PME-actuating films. Cross-linked through dynamic hydrogen bonds, the PMEs also possess autonomic self-healing properties without external energy input. This self-healing allows for a single alignment step of the PME film and subsequent "cut and paste" assembly for multi-axis actuation of a self-folded soft-robotic gripper from a single degree of freedom optical input.

Extreme ultraviolet resist materials for sub-7 nm patterning.

Continuous ongoing development of dense integrated circuits requires significant advancements in nanoscale patterning technology. As a key process in semiconductor high volume manufacturing (HVM), high resolution lithography is crucial in keeping with Moore's law. Currently, lithography technology for the sub-7 nm node and beyond has been actively investigated approaching atomic level patterning. EUV technology is now considered to be a potential alternative to HVM for replacing in some cases ArF immersion technology combined with multi-patterning. Development of innovative resist materials will be required to improve advanced fabrication strategies. In this article, advancements in novel resist materials are reviewed to identify design criteria for establishment of a next generation resist platform. Development strategies and the challenges in next generation resist materials are summarized and discussed.

Characterization of Sulfur and Nanostructured Sulfur Battery Cathodes in Electron Microscopy Without Sublimation Artifacts.

Lithium sulfur (Li-S) batteries have the potential to provide higher energy storage density at lower cost than conventional lithium ion batteries. A key challenge for Li-S batteries is the loss of sulfur to the electrolyte during cycling. This loss can be mitigated by sequestering the sulfur in nanostructured carbon-sulfur composites. The nanoscale characterization of the sulfur distribution within these complex nanostructured electrodes is normally performed by electron microscopy, but sulfur sublimates and redistributes in the high-vacuum conditions of conventional electron microscopes. The resulting sublimation artifacts render characterization of sulfur in conventional electron microscopes problematic and unreliable. Here, we demonstrate two techniques, cryogenic transmission electron microscopy (cryo-TEM) and scanning electron microscopy in air (airSEM), that enable the reliable characterization of sulfur across multiple length scales by suppressing sulfur sublimation. We use cryo-TEM and airSEM to examine carbon-sulfur composites synthesized for use as Li-S battery cathodes, noting several cases where the commonly employed sulfur melt infusion method is highly inefficient at infiltrating sulfur into porous carbon hosts.

Atomistic molecular dynamics simulations of carbohydrate-calcite interactions in concentrated brine.

We report atomistic molecular dynamics simulations to study the interactions of a model carbohydrate monomer (Glucopyranose) and calcite slabs in brine. We show that the interactions between the sugar molecules and the mineral decrease with increasing salinity. The decrease is due to the formation of salt layers on the calcite surfaces, which screen the carbohydrate-calcite hydrogen bonding. This screening effect depends on the affinities of calcite surface to specific ions as well as to the carbohydrate molecules.

Hierarchical hybrid peroxidase catalysts for remediation of phenol wastewater.

We report a new family of hierarchical hybrid catalysts comprised of horseradish peroxidase (HRP)-magnetic nanoparticles for advanced oxidation processes and demonstrate their utility in the removal of phenol from water. The immobilized HRP catalyzes the oxidation of phenols in the presence of H2 O2 , producing free radicals. The phenoxy radicals react with each other in a non-enzymatic process to form polymers, which can be removed by precipitation with salts or condensation. The hybrid peroxidase catalysts exhibit three times higher activity than free HRP and are able to remove three times more phenol from water compared to free HRP under similar conditions. In addition, the hybrid catalysts reduce substrate inhibition and limit inactivation from reaction products, which are common problems with free or conventionally immobilized enzymes. Reusability is improved when the HRP-magnetic nanoparticle hybrids are supported on micron-scale magnetic particles, and can be retained with a specially designed magnetically driven reactor. The performance of the hybrid catalysts makes them attractive for several industrial and environmental applications and their development might pave the way for practical applications by eliminating most of the limitations that have prevented the use of free or conventionally immobilized enzymes.

Surface functionalization of thin-film composite membranes with copper nanoparticles for antimicrobial surface properties.

Biofouling is a major operational challenge in reverse osmosis (RO) desalination, motivating a search for improved biofouling control strategies. Copper, long known for its antibacterial activity and relatively low cost, is an attractive potential biocidal agent. In this paper, we present a method for loading copper nanoparticles (Cu-NPs) on the surface of a thin-film composite (TFC) polyamide RO membrane. Cu-NPs were synthesized using polyethyleneimine (PEI) as a capping agent, resulting in particles with an average radius of 34 nm and a copper content between 39 and 49 wt.%. The positive charge of the Cu-NPs imparted by the PEI allowed a simple electrostatic functionalization of the negatively charged RO membrane. We confirmed functionalization and irreversible binding of the Cu-NPs to the membrane surface with SEM and XPS after exposing the membrane to bath sonication. We also demonstrated that Cu-NP functionalization can be repeated after the Cu-NPs dissolve from the membrane surface. The Cu-NP functionalization had minimal impact on the intrinsic membrane transport parameters. Surface hydrophilicity and surface roughness were also maintained, and the membrane surface charge became positive after functionalization. The functionalized membrane exhibited significant antibacterial activity, leading to an 80-95% reduction in the number of attached live bacteria for three different model bacterial strains. Challenges associated with this functionalization method and its implementation in RO desalination are discussed.

Facile synthesis and application of a carbon foam with large mesopores.

By combining elements of hard- and soft-templating, a facile synthesis method for carbon foams with large mesopores has been demonstrated. A commercial Pluronic surfactant was used as the structure-directing agent as well as the carbon precursor. No micelle swelling agent or post treatment is necessary to enlarge mesopores. As such this method requires fewer synthesis steps and is highly scalable. The as-synthesized meso-carbons showed potential applications in the fields of carbon oxide capture and lithium-sulfur batteries.

Probing the Mechanism of Targeted Delivery of Molecular Surfactants Loaded into Nanoparticles after Their Assembly at Oil-Water Interfaces.

A targeted and controlled delivery of molecular surfactants at oil-water interfaces using the directed assembly of nanoparticles, NPs, is reported. The mechanism of NP assembly at the interface and the release of molecular surfactants is followed by laser scanning confocal microscopy and surface force spectroscopy. The assembly of positively charged polystyrene NPs at the oil-water interface was facilitated by the introduction of carboxylic acid groups in the oil phase (e.g., by adding 1 wt % stearic acid to hexadecane to produce a model oil). The presence of positively charged NPs consistently lowers the stiffness of the water-oil interface. The effect is lessened, when the NPs are present in a solution of NaCl or deionized water at pH 2, consistent with a less dense monolayer of NPs at the interface in the last two systems. In addition, the NPs reduce the interfacial adhesion (i.e., the "stickiness" of the interface or, put differently, the pull-off force experienced by the atomic force microscopy (AFM) tip during retraction). After the assembly, the NPs can release a previously loaded cargo of surfactant molecules, which then facilitate the formation of a much finer oil-water emulsion. As a proof of concept, we demonstrate the release of octadecyl amine, ODA, that has been incorporated into the NPs prior to the assembly. The release of ODA causes the NPs to detach from the interface altering the interfacial properties and leads to finer oil droplets. This approach can be exploited in applications in several fields ranging from pharmaceutical and cosmetics to hydrocarbon recovery and oil-spill remediation, where a targeted and controlled release of surfactants is wanted.

Effects of Mesoporosity and Conductivity of Hierarchically Porous Carbon Supports on the Deposition of Pt Nanoparticles and Their Performance as Electrocatalysts for Oxygen Reduction Reaction in Alkaline Media.

The structural characteristics of supports, such as surface area and type of porosity, affect the deposition of electrocatalysts and greatly influence their electrochemical performance in fuel cells. In this work, we use a series of high surface area hierarchical porous carbons (HPCs) with defined mesoporosity as model supports to study the deposition mechanism of Pt nanoparticles. The resulting electrocatalysts are characterized by several analytical techniques, and their electrochemical performance is compared to a state-of-the-art, commercial Pt/C system. Despite the similar chemical composition and surface area of the supports, as well as similar amounts of Pt precursor used, the size of the deposited Pt nanoparticles varies, and it is inversely proportional to the mesopore size of the system. In addition, we show that an increase in the size of the catalyst particles can increase the specific activity of the oxygen reduction reaction. We also report on our efforts to improve the overall performance of the above electrocatalyst systems and show that increasing the electronic conductivity of the carbon support by the addition of highly conductive graphene sheets improves the overall performance of an alkaline fuel cell.

Formation mechanism of carbogenic nanoparticles with dual photoluminescence emission.

We present a systematic investigation of the formation mechanism of carbogenic nanoparticles (CNPs), otherwise referred to as C-dots, by following the pyrolysis of citric acid (CA)-ethanolamine (EA) precursor at different temperatures. Pyrolysis at 180 °C leads to a CNP molecular precursor with a strongly intense photoluminescence (PL) spectrum and high quantum yield formed by dehydration of CA-EA. At higher temperatures (230 °C) a carbogenic core starts forming and the PL is due to the presence of both molecular fluorophores and the carbogenic core. CNPs that exhibit mostly or exclusively PL arising from carbogenic cores are obtained at even higher temperatures (300 and 400 °C, respectively). Since the molecular fluorophores predominate at low pyrolysis temperatures while the carbogenic core starts forming at higher temperatures, the PL behavior of CNPs strongly depends on the conditions used for their synthesis.

Superhydrophilic thin-film composite forward osmosis membranes for organic fouling control: fouling behavior and antifouling mechanisms.

This study investigates the fouling behavior and fouling resistance of superhydrophilic thin-film composite forward osmosis membranes functionalized with surface-tailored nanoparticles. Fouling experiments in both forward osmosis and reverse osmosis modes are performed with three model organic foulants: alginate, bovine serum albumin, and Suwannee river natural organic matter. A solution comprising monovalent and divalent salts is employed to simulate the solution chemistry of typical wastewater effluents. Reduced fouling is consistently observed for the superhydrophilic membranes compared to control thin-film composite polyamide membranes, in both reverse and forward osmosis modes. The fouling resistance and cleaning efficiency of the functionalized membranes is particularly outstanding in forward osmosis mode where the driving force for water flux is an osmotic pressure difference. To understand the mechanism of fouling, the intermolecular interactions between the foulants and the membrane surface are analyzed by direct force measurement using atomic force microscopy. Lower adhesion forces are observed for the superhydrophilic membranes compared to the control thin-film composite polyamide membranes. The magnitude and distribution of adhesion forces for the different membrane surfaces suggest that the antifouling properties of the superhydrophilic membranes originate from the barrier provided by the tightly bound hydration layer at their surface, as well as from the neutralization of the native carboxyl groups of thin-film composite polyamide membranes.

Acoustophoretic Liquefaction for 3D Printing Ultrahigh-Viscosity Nanoparticle Suspensions.

An acoustic liquefaction approach to enhance the flow of yield stress fluids during Digital Light Processing (DLP)-based 3D printing is reported. This enhanced flow enables processing of ultrahigh-viscosity resins (µapp  > 3700 Pa s at shear rates γ ˙  = 0.01 s-1 ) based on silica particles in a silicone photopolymer. Numerical simulations of the acousto-mechanical coupling in the DLP resin feed system at different agitation frequencies predict local resin flow velocities exceeding 100 mm s-1 at acoustic transduction frequencies of 110 s-1 . Under these conditions, highly loaded particle suspensions (weight fractions, ϕ = 0.23) can be printed successfully in complex geometries. Such mechanically reinforced composites possess a tensile toughness 2000% greater than the neat photopolymer. Beyond an increase in processible viscosities, acoustophoretic liquefaction DLP (AL-DLP) creates a transient reduction in apparent viscosity that promotes resin recirculation and decreases viscous adhesion. As a result, acoustophoretic liquefaction Digital Light Processing (AL-DLP) improves the printed feature resolution by more than 25%, increases printable object sizes by over 50 times, and can build parts >3 × faster when compared to conventional methodologies.

Multifunctional graphene/platinum/Nafion hybrids via ice templating.

We report the synthesis of multifunctional hybrids in both films and bulk form, combining electrical and ionic conductivity with porosity and catalytic activity. The hybrids are synthesized by a two-step process: (a) ice templation of an aqueous suspension comprised of Nafion, graphite oxide, and chloroplatinic acid to form a microcellular porous network and (b) mild reduction in hydrazine or monosodium citrate which leads to graphene-supported Pt nanoparticles on a Nafion scaffold.