Engineering dense tumor constructs via cellular contraction of extracellular matrix hydrogels.

Physical characteristics of solid tumors such as dense internal microarchitectures and pathological stiffness influence cancer progression and treatment. While it is routine to engineer culture substrates and scaffolds with elastic moduli that approximate tumors, these models often fail to capture characteristic internal microarchitectures such as densely compacted concentric ECM fibers at the stromal interface. Contractile mesenchymal cells can solve this engineering challenge by deforming, contracting, and compacting extracellular matrix (ECM) hydrogels to decrease tissue volume and increase tissue density. Here we demonstrate that allowing human fibroblasts of varying origins to freely contract collagen type I-containing hydrogels co-seeded with carcinoma cell spheroids produces a tissue engineered construct with structural features that mimic dense solid tumors in vivo. Morphometry and mechanical testing were conducted in tandem with biochemical analysis of proliferation and viability to confirm that dense carcinoma constructs engineered using this approach capture relevant physical characteristics of solid carcinomas in a tractable format that preserves viability and is amenable to extended culture. The reported method is adaptable to the use of multiple mesenchymal cell types and the inclusion of fibrin in the ECM combined with seeding of endothelial cells to produce prevascularized constructs. The physical dense carcinoma constructs engineered using this approach may provide more clinically relevant venues for studying cancer pathophysiology and the challenges associated with the delivery of macromolecular drugs and cellular immunotherapies to solid tumors.

Lubrication mechanisms of dispersed carbon microspheres in boundary through hydrodynamic lubrication regimes.

HYPOTHESIS: Carbon microspheres have been shown to reduce friction and surface wear at relatively low speeds and high applied loads (i.e., within the boundary lubrication regime). We hypothesize that in dilute colloidal lubricating systems there is an interplay between the size of the carbon microspheres and the lubrication gap size, which determines the dominant lubricating mechanism of the system. EXPERIMENTS: A 60 wt% aqueous glycerol solution was used as the base lubricant and compared to various carbon particle-based lubricant formulations ranging in particle concentrations from 0.05 to 0.30 vol%. The tribological properties of the various lubricant formulations were tested on a pin-on-disk tribometer. A simplified Stribeck plot was produced to understand the changing mechanism of lubrication over a wide range of conditions. FINDINGS: The Stribeck curves show that the carbon microspheres assist lubrication by a rolling mechanism primarily in the boundary lubrication regime. A 0.20 vol% carbon-based lubricant formulation showed the best friction reduction compared to the base lubricant. Increasing speed increases the lubricating gap between the friction pair beyond the size of the particles, thereby nullifying the rolling mechanism of the particles. We introduce a modified specific film thickness parameter to determine the lubrication regime in a particle-lubricant system.

Friction force-based measurements for simultaneous determination of the wetting properties and stability of superhydrophobic surfaces.

HYPOTHESIS: Contact angle and sliding angle measurements are widely used to characterize superhydrophobic surfaces because of the simplicity and accessibility of the technique. We hypothesize that dynamic friction measurements, with increasing pre-loads, between a water drop and a superhydrophobic surface is more accurate because this technique is less influenced by local surface inhomogeneities and temporal surface changes. EXPERIMENTS: A water drop, held by a ring probe which is connected to a dual-axis force sensor, is sheared against a superhydrophobic surface while maintaining a constant preload. From this force-based technique, static and kinetic friction forces measurements are used to characterize the wetting properties of the superhydrophobic surfaces. Furthermore, by applying increased pre-loads to the water drop while shearing, the critical load at which the drop transitions from the Cassie-Baxter to Wenzel state is also measured. FINDINGS: The force-based technique predicts sliding angles with reduced standard deviations (between 56 and 64%) compared to conventional optical-based measurements. Kinetic friction force measurements show a higher accuracy (between 35 and 80%) compared to static friction force measurements in characterizing the wetting properties of superhydrophobic surfaces. The critical loads for the Cassie-Baxter to Wenzel state transition allows for stability characterization between seemingly similar superhydrophobic surfaces.

Force-Based Characterization of the Wetting Properties of LDPE Surfaces Treated with CF4 and H2 Plasmas.

Low-density polyethylene (LDPE) films are widely used in packaging, insulation and many other commodity applications due to their excellent mechanical and chemical properties. However, the water-wetting and water-repellant properties of these films are insufficient for certain applications. In this study, bare LDPE and textured LDPE (T-LDPE) films were subjected to low-pressure plasmas, such as carbon tetrafluoride (CF4) and hydrogen (H2), to see the effect of plasma treatment on the wetting properties of LDPE films. In addition, the surface of the LDPE film was textured to improve the hydrophobicity through the lotus effect. The LDPE and T-LDPE films had contact angle (θ) values of 98.6° ± 0.6 and 143.6° ± 1.0, respectively. After CF4 plasma treatments, the θ values of the surfaces increased for both surfaces, albeit within the standard deviation for the T-LDPE film. On the other hand, the contact angle values after H2 plasma treatment decreased for both surfaces. The surface energy measurements supported the changes in the contact angle values: exposure to H2 plasma decreased the contact angle, while exposure to CF4 plasma increased the contact angle. Kinetic friction force measurements of water drops on LDPE and T-LDPE films showed a decrease in friction after the CF4 plasma treatment, consistent with the contact angle and surface energy measurements. Notably, the kinetic friction force measurements proved to be more sensitive compared to the contact angle measurements in differentiating the wetting properties of the T-LDPE versus 3× CF4-plasma-treated LDPE films. Based on Atomic Force Microscopy (AFM) images of the flat LDPE samples, the 3× CF4 plasma treatment did not significantly change the surface morphology or roughness. However, in the case of the T-LDPE samples, Scanning Electron Microscopy (SEM) images showed noticeable morphological changes, which were more significant at sharp edges of the surface structures.

Advances in the Fabrication and Characterization of Superhydrophobic Surfaces Inspired by the Lotus Leaf.

Nature has proven to be a valuable resource in inspiring the development of novel technologies. The field of biomimetics emerged centuries ago as scientists sought to understand the fundamental science behind the extraordinary properties of organisms in nature and applied the new science to mimic a desired property using various materials. Through evolution, living organisms have developed specialized surface coatings and chemistries with extraordinary properties such as the superhydrophobicity, which has been exploited to maintain structural integrity and for survival in harsh environments. The Lotus leaf is one of many examples which has inspired the fabrication of superhydrophobic surfaces. In this review, the fundamental science, supported by rigorous derivations from a thermodynamic perspective, is presented to explain the origin of superhydrophobicity. Based on theory, the interplay between surface morphology and chemistry is shown to influence surface wetting properties of materials. Various fabrication techniques to create superhydrophobic surfaces are also presented along with the corresponding advantages and/or disadvantages. Recent advances in the characterization techniques used to quantify the superhydrophobicity of surfaces is presented with respect to accuracy and sensitivity of the measurements. Challenges associated with the fabrication and characterization of superhydrophobic surfaces are also discussed.

Determination of the Sliding Angle of Water Drops on Surfaces from Friction Force Measurements.

Superhydrophobic surfaces have attracted considerable attention because of their unique water-repellency and their wide range of applications. The conventional method to characterize the surface wetting properties of surfaces, including superhydrophobic surfaces, relies on measuring static and dynamic contact angles, and sliding angles of water drops. However, because of the inhomogeneities inherently present on surfaces (smooth and textured), such optical methods can result in relatively large variability in sliding angle measurements. In this work, by using a force-based technique with ±1 µN sensitivity, the friction force between water drops and various surfaces is measured. The friction force can then be used to accurately predict the sliding angle of water drops of various sizes with improved consistency. We also show that the measured friction force can be used to determine the critical drop size below which a water drop is not expected to slide even at a tilt angle of 90°. The proposed technique to characterize the wetting properties of surfaces has a higher accuracy (between 15% and 65%, depending on the surface) compared to optical methods.

Tunable Friction Through Stimuli Responsive Hybrid Carbon Microspheres.

We explore the use of poly(N-isopropylacrylamide) (PNIPAm)-grafted carbon microspheres (CM) dispersed in water as a stimulus-responsive lubricant. A critical concentration between 3 and 5 mg/mL of PNIPAm-grafted CM is needed to achieve low friction (coefficient of friction ∼ 0.04) at room temperature between borosilicate and silicon surfaces. An increase in the temperature of the system above the lower critical solution temperature (LCST) causes the aggregation of PNIPAm-grafted CM which leads to an increase in friction forces. The process is not immediately reversible unless the lubricant is sonicated so as to redisperse the aggregates. This work provides insight into the rolling friction mechanism and demonstrates the importance of particle singlets in achieving effective lubrication through a rolling mechanism.

Anomalous Potential-Dependent Friction on Au(111) Measured by AFM.

We present an exploratory study of the tribological properties between an AFM probe and a Au(111) surface in an aqueous environment while subjected to applied surface potentials. Using a three-electrode setup, the electrical potential and interfacial electric field on a Au(111) working electrode are controlled. Lateral force microscopy is used to measure the friction forces between the AFM probe and the Au surface. As the AFM probe approaches the surface, normal forces are also measured to gain insight into the interfacial forces. When a positive potential is applied to the Au surface, the friction is found to rise sharply at a critical potential and level off at a relatively high value. However, when a negative potential is applied, the friction forces are low, even lower compared to the open circuit potential case. These changes in friction, by a factor of approximately 35, as a function of the applied potential are found to be reversible over multiple cycles. We attribute the origin of the high friction at positive potentials to the formation of a highly confined, ordered icelike water layer at the Au/electrolyte interface that results in effective hydrogen bonding with the AFM probe. At negative potentials, the icelike water layer is disrupted, resulting in the water molecules acting as boundary lubricants and providing low friction. Such friction experiments can provide valuable insight into the structure and properties of water at charged surfaces under various conditions and can potentially impact a variety of technologies relying on molecular-level friction such as MEMs.

Enhanced Adhesion of Mosquitoes to Rough Surfaces.

Insects and small animals capable of adhering reversibly to a variety of surfaces employ the unique design of the distal part of their legs. In the case of mosquitoes, their feet are composed of thousands of micro- and nanoscale protruding structures, which impart superhydrophobic properties. Previous research has shown that the superhydrophobic nature of the feet allows mosquitoes to land on water, which is necessary for their reproduction cycle. Here, we show that van der Waals interactions are the main adhesion mechanism employed by mosquitoes to adhere to various surfaces. We further demonstrate that the judicious creation of surface roughness on an opposing surface can increase the adhesion strength because of the increased number of surface elements interacting with the setae through multiple contact points. Although van der Waals forces are shown to be the predominant mechanism by which mosquitoes adhere to surfaces, capillary forces can also contribute to the total adhesion force when the opposing surface is hydrophilic and under humid conditions. These fundamental properties can potentially be applied in the development of superior Long Lasting Insecticidal Nets (LLINs), which represent one of the most effective methods to mitigate mosquito-transmitted infectious diseases such as Malaria, Filaria, Zika, and Dengue.

Triboelectricity Generation from Vertically Aligned Carbon Nanotube Arrays.

We explore the use of vertically aligned carbon nanotube (VACNT) arrays as an electrode in a triboelectric nanogenerator (TENG) that harvests mechanical energy and converts it to electrical energy. When VACNT arrays 1 cm2 in area are mechanically contacted with PET and PTFE counter electrodes in vertical contact-separation mode, currents up to 0.16 and 0.21 µA and voltages up to 1.42 and 3.20 V are obtained, respectively. The VACNT TENG output remains stable even after more than 20 000 continuous contact cycles. A 0.47 µF capacitor is successfully charged to 4.5 V in 60 s using a VACNT-PTFE triboelectric nanogenerator (TENG) prototype.

Polymer grafted hard carbon microspheres at an oil/water interface.

Pickering emulsions offer an established method of stabilizing oil-in-water emulsions as either an alternative to surfactants or as an additive together with surfactants, providing greater colloidal stability even at low particle concentrations. This work presents a novel experimental approach to study the influence of several system parameters on the effectiveness of Pickering emulsion systems. Specifically, a dodecane oil drop stabilized by hard carbon microspheres in an aqueous saline solution is used as a model system to obtain both quantitative and qualitative information on the effectiveness of the microspheres as a function of their surface wetting properties. The test setup, in which a macroscopic oil drop is brought into contact with a test surface in a controlled motion and environment, allows for several aspects of the test (for e.g., oil drop size, approach velocity, normal force, solution ionic strength, temperature, pH, and presence of surfactants) to be potentially controlled and studied precisely. To demonstrate the capabilities of the experimental set-up, hard carbon microspheres are modified with a poly(styrenesulfonate) shell through ATRP in order to tune the wettability of the particles through choice of polymer, which are then used to stabilize a dodecane oil drop in an aqueous saline solution. The particles effectively form a steric barrier preventing the spreading of an oil drop on hydrophobic surfaces and also preventing the coalescence of stabilized oil drops.

Hydrogel Inverse Replicas of Breath Figures Exhibit Superoleophobicity Due to Patterned Surface Roughness.

The wetting behavior of a surface depends on both its surface chemistry and the characteristics of surface morphology and topography. Adding structure to a flat hydrophobic or oleophobic surface increases the effective contact angle and thus the hydrophobicity or oleophobicity of the surface, as exemplified by the lotus leaf analogy. We describe a simple strategy to introduce micropatterned roughness on surfaces of soft materials, utilizing the template of hexagonally packed pores of breath figures as molds. The generated inverse replicas represent micron scale patterned beadlike protrusions on hydrogel surfaces. This added roughness imparts superoleophobic properties (contact angle of the order of 150° and greater) to an inherently oleophobic flat hydrogel surface, when submerged. The introduced pattern on the hydrogel surface changes morphology as it swells in water to resemble morphologies remarkably analogous to the compound eye. Analysis of the wetting behavior using the Cassie-Baxter approximation leads to estimation of the contact angle in the superoleophobic regime and in agreement with the experimental value.

Load-Induced Hydrodynamic Lubrication of Porous Films.

We present an exploratory study of the tribological properties and mechanisms of porous polymer surfaces under applied loads in aqueous media. We show how it is possible to change the lubrication regime from boundary lubrication to hydrodynamic lubrication even at relatively low shearing velocities by the addition of vertical pores to a compliant polymer. It is hypothesized that the compressed, pressurized liquid in the pores produces a repulsive hydrodynamic force as it extrudes from the pores. The presence of the fluid between two shearing surfaces results in low coefficients of friction (µ ≈ 0.31). The coefficient of friction is reduced further by using a boundary lubricant. The tribological properties are studied for a range of applied loads and shear velocities to demonstrate the potential applications of such materials in total joint replacement devices.

Additive-mediated electrochemical synthesis of platelike copper crystals for methanol electrooxidation.

A room-temperature electrochemical approach to synthesizing anisotropic platelike copper microcrystals and nanocrystals in the presence of potassium bromide is presented. Morphological and elemental characterization was performed using SEM, TEM, and XRD to confirm the anisotropic morphology and crystal structure of the synthesized copper particles. A possible mechanism for explaining the anisotropic crystal growth is proposed on the basis of the preferential adsorption of bromide ions to selective crystal faces. The shape-dependent electrocatalytic property of copper particles is demonstrated by its enhanced catalytic activity for methanol oxidation. Further development of such anisotropic copper particles localized on an electrode surface will lead us to find a suitable alternative for noble metal-based electrocatalysts for the methanol oxidation reaction relevant to fuel cells.

Origin of the contact angle hysteresis of water on chemisorbed and physisorbed self-assembled monolayers.

Self-assembled monolayers (SAMs) are known to form on a variety of substrates either via chemisorption (i.e., through chemical interactions such as a covalent bond) or physisorption (i.e., through physical interactions such as van der Waals forces or "ionic" bonds). We have studied the behavior and effects of water on the structures and surface energies of both chemisorbed octadecanethiol and physisorbed octadecylamine SAMs on GaAs using a number of complementary techniques including "dynamic" contact angle measurements (with important time and rate-dependent effects), AFM, and electron microscopy. We conclude that both molecular overturning and submolecular structural changes occur over different time scales when such SAMs are exposed to water. These results provide new insights into the time-dependent interactions between surfaces and colloids functionalized with SAMs when synthesized in or exposed to high humidity or bulk water or wetted by water. The study has implications for a wide array of phenomena and applications such as adhesion, friction/lubrication and wear (tribology), surfactant-solid surface interactions, the organization of surfactant-coated nanoparticles, etc.

Design and fabrication of gecko-inspired adhesives.

Recently, there has been significant interest in developing dry adhesives mimicking the gecko adhesive system, which offers several advantages compared to conventional pressure-sensitive adhesives. Specifically, gecko adhesive pads have anisotropic adhesion properties; the adhesive pads (spatulae) stick strongly when sheared in one direction but are non-adherent when sheared in the opposite direction. This anisotropy property is attributed to the complex topography of the array of fine tilted and curved columnar structures (setae) that bear the spatulae. In this study, we present an easy, scalable method, relying on conventional and unconventional techniques, to incorporate tilt in the fabrication of synthetic polymer-based dry adhesives mimicking the gecko adhesive system, which provides anisotropic adhesion properties. We measured the anisotropic adhesion and friction properties of samples with various tilt angles to test the validity of a nanoscale tape-peeling model of spatular function. Consistent with the peel zone model, samples with lower tilt angles yielded larger adhesion forces. The tribological properties of the synthetic arrays were highly anisotropic, reminiscent of the frictional adhesion behavior of gecko setal arrays. When a 60° tilt sample was actuated in the gripping direction, a static adhesion strength of ~1.4 N/cm(2) and a static friction strength of ~5.4 N/cm(2) were obtained. In contrast, when the dry adhesive was actuated in the releasing direction, we measured an initial repulsive normal force and negligible friction.

Carbon microspheres as ball bearings in aqueous-based lubrication.

We present an exploratory study on a suspension of uniform carbon microspheres as a new class of aqueous-based lubricants. The surfactant-functionalized carbon microspheres (∼0.1 wt %) employ a rolling mechanism similar to ball bearings to provide low friction coefficients (µ ≈ 0.03) and minimize surface wear in shear experiments between various surfaces, even at high loads and high contact pressures. The size range, high monodispersity, and large yield stress of the C(µsphere), as well as the minimal environmental impact, are all desirable characteristics for the use of a C(µsphere)-SDS suspension as an alternative to oil-based lubricants in compatible devices and machinery.

Use of electrochemical deposition to create randomly rough surfaces and roughness gradients.

A novel approach to reproducibly generating randomly rough surfaces over large areas and generating surface roughness gradients is presented. By tuning the electrochemical deposition potential for silver onto an electrode, the island nucleation density can be systematically varied resulting in thin films of different roughness. We find that the potential range that significantly influences the surface roughness also corresponds to a reaction/mixed-controlled deposition regime. The roughness can be replicated onto other moldable materials, thus enabling future studies involving the effect of surface roughness.

Gecko adhesion pad: a smart surface?

Recently, it has been shown that humidity can increase the adhesion of the spatula pads that form the outermost (adhesive) surface of the tokay gecko feet by 50% relative to the main adhesion mechanism (i.e. van der Waals adhesive forces), although the mechanism by which the enhancement is realized is still not well understood. A change in the surface hydrophobicity of a gecko setal array is observed when the array, which supports the spatulae, is exposed to a water drop for more than 20 min, suggesting a change in the hydrophilic-lyophilic balance (HLB), and therefore of the conformation of the surface proteins. A surface force apparatus (SFA) was used to quantify these changes, i.e. in the adhesion and friction forces, while shearing the setal array against a silica surface under (i) dry conditions, (ii) 100% humidity and (iii) when fully immersed in water. The adhesion increased in the humid environment but greatly diminished in water. Although the adhesion forces changed significantly, the friction forces remained unaffected, indicating that the friction between these highly textured surfaces is 'load-controlled' rather than 'adhesion-controlled'. These results demonstrate that the gecko adhesive pads have the ability to exploit environmental conditions to maximize their adhesion and stabilize their friction forces. Future designs of synthetic dry adhesives inspired by the gecko can potentially include similar 'smart' surfaces that adapt to their environment.