Hydrophobic Monolayer Research Articles

Graphene Exfoliation in Binary NMP/Water Mixtures by Molecular Dynamics Simulations.

We investigate the molecular mechanism underlying the liquid-phase exfoliation of graphene in aqueous/N-methyl-2-pyrrolidone (NMP) solvent mixtures and calculate the associated free energies, considering different NMP concentrations and exfoliation temperatures. We employ steered molecular dynamics to establish a path for the exfoliation of a graphene sheet from graphite within each solvent environment. Then, we conduct umbrella sampling simulations throughout the created paths to compute the potential of mean force (PMF) of the graphene sheet. As the exfoliated nanosheet disperses into the liquid, it becomes fully covered by an adsorbed solvent monolayer. We analyze the composition of the monolayer by measuring the direct contacts of either NMP or water molecules with the carbon surface. The carbon surface exhibits a preference for adsorbing NMP over water. The NMP molecules form a hydrophobic compact monolayer structure, effectively protecting the carbon interface from unfavorable interactions with water. The creation of the hydrophobic monolayer is a key factor in the exfoliation process, as it effectively inhibits the restacking of exfoliated nanosheets. An adequate level of graphene solubility is achieved through the addition of 20 % to 30 % water by weight to the NMP solvent. This finding holds significant importance for improving production efficiency and reducing dependence on organic solvents in the industrial manufacturing of graphene.

Low-Friction Soft Robots for Targeted Bacterial Infection Treatment in Gastrointestinal Tract.

Untethered and self-transformable miniature robots are capable of performing reconfigurable deformation and on-demand locomotion, which aid the traversal toward various lumens, and bring revolutionary changes for targeted delivery in gastrointestinal (GI) tract. However, the viscous non-Newtonian liquid environment and plicae gastricae obstacles severely hamper high-precision actuation and payload delivery. Here, we developed a low-friction soft robot by assembly of densely arranged cone structures and grafting of hydrophobic monolayers. The magnetic orientation encoded robot can move in multiple modes, with a substantially reduced drag, terrain adaptability, and improved motion velocity across the non-Newtonian liquids. Notably, the robot stiffness can be reversibly controlled with magnetically induced hardening, enabling on-site scratching and destruction of antibiotic-ineradicable polymeric matrix in biofilms with a low-frequency magnetic field. Furthermore, the magnetocaloric effect can be utilized to eradicate the bacteria by magnetocaloric effect under high-frequency alternating field. To verify the potential applications inside the body, the clinical imaging-guided actuation platforms were developed for vision-based control and delivery of the robots. The developed low-friction robots and clinical imaging-guided actuation platforms show their high potential to perform bacterial infection therapy in various lumens inside the body.

Spontaneous bilayer wrapping of virus particles by a phospholipid Langmuir monolayer

We report here the spontaneous formation of lipid-bilayer-wrapped virus particles, following the injection of “naked” virus particles into the subphase of a Langmuir trough with a liquid monolayer of lipids at its air–water interface. The virus particles are those of the well-studied cowpea chlorotic mottle virus, CCMV, which are negatively charged at the pH 6 of the subphase; the lipids are a 9:1 mix of neutral DMPC and cationic CTAB molecules. Before adding CCMV particles to the subphase we establish the mixed lipid monolayer in its liquid-expanded state at a fixed pressure (17.5 mN/m) and average area-per-molecule of (41Å2). Keeping the total area fixed, the surface pressure is observed to decrease at about 15 h after adding the virus particles in the subphase; by 37 h it has dropped to zero, corresponding to essentially all the lipid molecules having been removed from the air–water interface. By collecting particles from the subphase and measuring their sizes by atomic force microscopy, we show that the virus particles have been wrapped by lipid bilayers (or by two lipid bilayers). These results can be understood in terms of thermal fluctuations and electrostatic interactions driving the wrapping of the anionic virus particles by the cationic lipids.Graphical Spontaneous acquisition by a virus particle of, first, a hydrophobic lipid monolayer envelope and, then, a hydrophilic lipid bilayer envelope, as it interacts from the subphase with an oppositely charged Langmuir monolayer

Vapor-etching honeycomb-like zinc plating layer for constructing anti-corrosion lubricant-infused surfaces.

Introduction: Biomimetic lubricant-infused porous surfaces are developed and applied for omniphobicity and corrosion protection, which exhibit great advantages compared to superhydrophobic surfaces. Methods: Herein, superhydrophobic Fe@E-Zn@PFOA was prepared via the electrodeposition of laminated Zinc coating, further vapor etching, and post-modification with perfluoro caprylic acid. The facile, inexpensive, and environment-friendly water vapor etching process can form a porous honeycomb-like structure. Moreover, the perfluoropolyether lubricant was wicked into the porous and superhydrophobic surfaces, obtaining lubricant-infused surfaces of Fe@E-Zn@PFOA@PFPE. Results and discussion: The influences of the textured roughness and chemical composition on the surface wettability were systematically investigated. The Fe@E-Zn@PFOA@PFPE performs omniphobicity with small sliding angles and superior corrosion resistance compared with the superhydrophobic surface, owing to their multiple barriers, including infused lubricant, hydrophobic monolayers, and compact Zn electroplating coating. Thus, the proposed lubricant-infused surface may provide insights into constructing protective coatings for the potential applications of engineering metal materials.

Improving water transport through sub‐nanometer channels by alternating hydrophilic–hydrophobic patterns

AbstractHydrophilicity is key factor to sub‐nanometer channels for water transport. However, how to effectively integrate the respective advantages of hydrophilicity and hydrophobicity to realize ultrafast water transport at the sub‐nanometer scale is still confusing. By using sub‐nanometer channels formed by two‐dimensional covalent organic frameworks as typical models, we herein demonstrate that alternating hydrophilic–hydrophobic patterns in channels are capable of significantly improving water transport. Alternatingly stacking hydrophilic and hydrophobic monolayers is testified to be energetically favorable to directly piling their multilayers. Meanwhile, alternatingly‐stacked hydrophilic–hydrophobic multilayers are able to achieve much higher water permeability than individual hydrophilic or hydrophobic multilayers. The effect of framework flexibility is also investigated. The exceptional performances benefit from the perfect balance between excellent wettability of hydrophilicity and low friction of hydrophobicity. In order to give full play to the synergistic advantages, the thickness of hydrophobic patterns spaced by hydrophilic ones should be less than 1 nm.

Overexpressing an Arabidopsis SEIPIN1 reduces rubber particle size in guayule

A conventional source of natural rubber (NR) is from Hevea (Hevea brasiliensis). NR production from Hevea is limited by its narrow growth region and susceptibility to leaf blight disease. In response to these limitations, and to address NR supply and security, guayule (Parthenium argentatum Gray) has been developed as an alternative crop. NR consists mainly of cis-1,4-polyisoprene synthesized in/on rubber particles (RPs). RPs resemble lipid droplets (LDs) in that both are generated from endoplasmic reticulum (ER) and consist of hydrophobic cores and phospholipid monolayers. A prominent ER-related protein seipin plays an essential role in controlling LD biogenesis from the ER surface. Prior expression of AtSEIPIN1 in Arabidopsis increased LD size and consequently increased its core constituent triacylglycerol content in seed. To investigate if AtSEIPIN1 can similarly impact RPs and production of cis-1,4-polyisoprene, we generated three independent transgenic guayule lines overexpressing AtSEIPIN1 (SEIoe). Compared with wild-type, fewer RPs were observed, and RP size was significantly reduced in all SEIoe lines. Although not always statistically significant, NR quantity and quality were also reduced in SEIoe lines. Resin contents were reduced in mature stems, but not in young plantlets of SEIoe lines. The mechanisms of how AtSEIPIN1 influences RP biogenesis and NR production in guayule are discussed.

Interfacial engineering of hydrophobic octadecanethiol/Pd metallene toward electrocatalytic nitrogen reduction.

In this work, we propose the modification of ultrathin and wrinkled Pd metallene by hydrophobic octadecanethiol (Pdene@C18) via Pd-S bonds for the nitrogen reduction reaction. The hydrophobic self-assembled monolayer C18 can effectively capture more N2 and inhibit the hydrogen evolution reaction. As a result, a high NH3 yield and Faraday efficiency of 27.97 μg h-1 mgcat.-1 and 14.29% are achieved for Pdene@C18 under neutral conditions, respectively, highlighting the modification of hydrophobic monolayers for efficient nitrogen electro-reduction to ammonia.

Adsorption of fluoranthene and phenanthrene by virgin and weathered polyethylene microplastics in freshwaters

Concern exists regarding potential health impacts associated with contaminants of emerging concern (CECs) that adsorb to microplastics (MPs). Previous studies have examined MPs as potential contaminant vectors in marine environments as opposed to freshwaters that represent drinking water sources. This study examined adsorption of two polycyclic aromatic hydrocarbons (PAHs), phenanthrene and fluoranthene, by virgin and weathered polyethylene (PE) in both artificial and natural freshwater matrices. Adsorption kinetics and isotherms conducted in artificial freshwater (AFW) consistently showed higher adsorption onto smaller (200 μm) PE when compared to 1090 μm PE. Adsorption mechanisms were primarily associated with hydrophobic interactions and monolayer chemisorption. As well, environmental factors including dissolved organic matter (DOC), pH, and polymer weathering also impacted adsorption. This work provides new insights regarding the adsorption of organic pollutants to better understand the risk of MPs in drinking water sources.

Liquid-based nanogenerator fabricated by a self-assembled fluoroalkyl monolayer with high charge density for energy harvesting

<h2>Summary</h2> Liquid-based triboelectric nanogenerators (L-TENGs) have been considered as a promising tool to utilize clean energy. Here, we reported a tubular L-TENG (TL-TENG) based on fluoroalkyl monolayer-modified silica. It exhibited excellent electric output with an output voltage of 101.5 V, peak power density of 43.0 mW m⁻², and surface charge density of 500.3 μC m⁻². The electric output could be modulated by the thickness of the dielectric layer, types of liquid, and oscillation frequency, which was reasonably explained by our equivalent capacitor model. The hydrophobic fluoroalkyl monolayer could promote the electron transfer, and the dielectric layer could inhibit the leakage current perpendicular to the surface, both leading to the enhancement of electric output. A wearable TL-TENG was finally demonstrated to harvest body motion energy and power lighting devices efficiently. This kind of TL-TENG possesses great potential in the fields of energy harvesting and self-powered wearable devices in the wild.

Effect of Hydrophobicity and Charge Separation on the Antifouling Properties of Surface-Tethered Zwitterionic Peptides.

Zwitterionic peptides emerge as a class of highly effective antifouling material in a wide range of applications such as biosensors, biomedical devices, and implants. We incorporated neutral amino acid spacers with different hydrophobicities, including serine (Ser), glycine (Gly), and leucine (Leu), into zwitterionic peptides with lysine-glutamic acid repeating units and investigated the structure and antifouling performance of the zwitterionic peptide brushes by surface plasma resonance, surface force apparatus (SFA), and all-atomistic molecular dynamics (MD) simulation techniques. Our results demonstrate that the hydrophilicity of neutral spacers alters the structure and antifouling performance of the peptide-modified surface. Hydrophilic Ser-inserted peptides reduced the interaction between the peptide monolayer and protein foulants, while hydrophobic Leu significantly increased the protein adhesion. SFA force measurements show that the presence of more spacers would increase the adhesion between the peptide monolayer and the modeling foulant lysozyme, especially for the hydrophobic spacers. MD simulations reveal that hydrophilic Ser spacers retain the hydrophilicity of the peptide monolayer and improve the antifouling performance, and Gly spacers give rise to more interchain cross-links. Leu spacers result in a more hydrophobic peptide monolayer, which leads to dehydration of the peptide monolayer and reduces the antifouling performances.

Hydrophobic passivation of ultra-high-Q silica wedge resonators using hexamethyldisilazane.

Dissipative Kerr solitons in ultra-high-Q resonators are extremely sensitive to the thermal behavior of the resonators. Especially for resonators with hydrophilic surfaces, moisture continuously adsorbs on their surfaces and causes additional absorption loss that results in an excessive thermal shift of resonance frequency. This change makes soliton mode locking more challenging or even impossible. Here, we report hydrophobic monolayer passivation using hexamethyldisilazane on ultra-high-Q silica wedge resonators. It was experimentally confirmed that the Q-factor and dispersion were maintained after passivation, and excess thermal shift by moisture was inhibited for more than three days in the atmosphere. Soliton mode locking was successfully performed with the resonator one month after passivation.

Non-covalently embedded oxytocin in alkanethiol monolayer as Zn2+ selective biosensor

Peptides are commonly used as biosensors for analytes such as metal ions as they have natural binding preferences. In our previous peptide-based impedimetric metal ion biosensors, a monolayer of the peptide was anchored covalently to the electrode. Binding of metal ions resulted in a conformational change of the oxytocin peptide in the monolayer, which was measured using electrochemical impedance spectroscopy. Here, we demonstrate that sensing can be achieved also when the oxytocin is non-covalently integrated into an alkanethiol host monolayer. We show that ion-binding cause morphological changes to the dense host layer, which translates into enhanced impedimetric signals compared to direct covalent assembly strategies. This biosensor proved selective and sensitive for Zn2+ ions in the range of nano- to micro-molar concentrations. This strategy offers an approach to utilize peptide flexibility in monitoring their response to the environment while embedded in a hydrophobic monolayer.

Spreading Dynamics of a Precursor Film of Ionic Liquid or Water on a Micropatterned Polyelectrolyte Brush Surface.

Time evolution of the microscopic wetting velocity of 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (EMI-TFSI) or water on a micrometer-scale line-patterned surface with a poly(3-sulfopropyl methacrylate) brush and a hydrophobic perfluoroalkyl monolayer was precisely measured by direct observation using optical microscopy and a selective dyeing method over a long period (178 days). When a liquid droplet was placed on the dyed line-patterned brush surface, the liquid penetrated and spread into the polymer brush layer, forming a precursor thin film that extended beyond the macroscopic contact line. The elongation proceeded in two stages by an adiabatic process followed by a diffusive process. The elongation distance X increased with time in proportion to t2.6 for water and t0.81 for EMI-TFSI during the adiabatic process. In a diffusive process, the advancing velocity of the precursor film was markedly reduced to be expressed as X ∝ t0.66 for water and X ∝ t0.21 for EMI-TFSI, indicating that the diffusive process was affected by the energy dissipation of the wetting system. The high viscosity and the strong molecular interaction of EMI-TFSI with the polymer brush gave a large entropy change during the wetting process to result in a slower spreading velocity.

Migration and Degradation in Composting Environment of Active Polylactic Acid Bilayer Nanocomposites Films: Combined Role of Umbelliferone, Lignin and Cellulose Nanostructures.

This study was dedicated to the functional characterization of innovative poly(lactic acid) (PLA)-based bilayer films containing lignocellulosic nanostructures (cellulose nanocrystals (CNCs) or lignin nanoparticles (LNPs)) and umbelliferone (UMB) as active ingredients (AIs), prepared to be used as active food packaging. Materials proved to have active properties associated with the antioxidant action of UMB and LNPs, as the combination of both ingredients in the bilayer formulations produced a positive synergic effect inducing the highest antioxidant capacity. The results of overall migration for the PLA bilayer systems combining CNCs or LNPs and UMB revealed that none of these samples exceeded the overall migration limit required by the current normative for food packaging materials in both non-polar and polar simulants. Finally, all the hydrophobic monolayer and bilayer films were completely disintegrated in composting conditions in less than 18 days of incubation, providing a good insight on the potential use of these materials for application as active and compostable food packaging.

Electrowetting valves for sweat-based microfluidics

Skin-compatible microfluidic valving systems with on-demand sweat capture are necessary to understand the temporal variation of biomarkers. Here, we demonstrate solution-based electrowetting valves with rapid actuation integrated into a flexible microfluidic sweat collection patch. The valve is produced by inkjet-printing a pair of silver electrodes with spacings of 0.2–2 mm and modifying the downstream electrode with a hydrophobic self-assembled monolayer. To complete the valve, a microfluidic channel is fabricated from laser ablation of adhesive layers and pressed over the silver electrodes. Artificial perspiration is driven by capillary action within the channel until stopped by the electrowetting valve. A low voltage is applied to the electrodes, decreasing the surface energy of the hydrophobic monolayer and allowing the fluid front to continue through the microchannel. Statistical analysis demonstrated that applied voltage, and not electrode spacing, influenced valve actuation time, with 17 ± 8 s for 4 V and 40 ± 16 s for 1 V. Inkjet-printing conditions were also optimized to achieve a valve fluid retention time of 9 h. Using four electrowetting valves, an integrated wearable device is designed for artificial perspiration collection through valve actuation at distinct time points over 40 min. Finally, these inexpensive, user-friendly, and disposable electrowetting valves offer exciting opportunities for non-invasive point-of-care sweat monitoring.

Stabilization of Hydroxide Ions at the Interface of a Hydrophobic Monolayer on Water via Reduced Proton Transfer.

We report a joint study using surface-specific sum-frequency vibrational spectroscopy and abinitio molecular dynamics simulations, respectively, on a pristine hydrophobic (sub)monolayer hexane-water interface, namely, the hexane/water interface with varied vapor pressures of hexane and different pHs in water. We show clear evidence that hexane on water revises the interfacial water structure in a way that stabilizes the hypercoordinated solvation structure and slows down the migration of hydroxide ion (OH^{-}) relative to that in bulk water. This mechanism effectively attracts the OH^{-} to the water-hydrophobic interface with respect to its counterion. The result illustrates the striking difference of proton transfer of hydrated OH^{-} at the interface and in the bulk, which is responsible for the intrinsic charging effect at the hydrophobic interface.

Computational Insights into the Binding of Monolayer-Capped Gold Nanoparticles onto Amyloid-β Fibrils.

Amyloids-β (Aβ) fibrils are involved in several neurodegenerative diseases. In this study, atomistic molecular dynamics simulations have been used to investigate how monolayer-protected gold nanoparticles interact with Aβ(1-40) and Aβ(1-42) fibrils. Our results show that small gold nanoparticles bind with the external side of amyloid-β fibrils that is involved in the fibrillation process. The binding affinity, studied for both kinds of fibrils as a function of the monolayer composition and the nanoparticle diameter, is modulated by hydrophobic interactions and ligand monolayer conformation. Our findings thus show that monolayer-protected nanoparticles are good candidates to prevent fibril aggregation and secondary nucleation or to deliver drugs to specific fibril regions.

Biodiesel flames as a unique pyrolyzing carbon source for the synthesis of hydrophobic carbon films

We report the rapid single-step flame synthesis of hydrophobic carbon layers (C-layers) on the surface of stainless-steel (SS) substrates using vaporized biodiesel as the fuel. A co-flow canola methyl ester/air diffusion flame is used to generate a hydrophobic monolayer on the surface of the metal substrate upon its insertion into the reaction zone. Carbon deposition on the surface of the SS substrates varies by changing the SS disk’s position in the post-flame, and by varying its exposure time. The thickness and mass of the flame-formed monolayer varied depending on the substrate’s insertion point into the flame. However, the variation of mass did not significantly impact the C-layer’s uniformity or hydrophobicity. We hypothesize that a small “inner-cone” of the biodiesel flame along with a high soot propensity can result in an ideal medium to form uniform hydrophobic C-layers of unique hierarchical surface structure. This is supported by introducing SS substrates in methane/air flames formed using the same co-flow burner. The hydrophobic property of the carbon deposits was quantified by measuring the contact angle of water droplets placed on the film’s surface. A water droplet drop test was conducted on the flame-formed hydrophobic layers to study their wettability property.

Mass spectrometric biosensing: Quantitation of multiplex enzymes using single mass probe and fluorous affinity chip

This work presents a concept of “mass spectrometric biosensing” by using a chip to recognize the targets and mass spectrometry to detect the signals switched by the recognition. The chip is prepared on an ITO slide with a hydrophobic fluorous-tag monolayer to self-assemble the mixture of mass probe and fluorous-tagged cysteine as a spacer through fluorous affinity interaction. The presence of spacer provides suitable conditions for recognition reactions on the chip. By designing a single mass probe as the peptide substrates of corresponding target enzymes, a novel quantitative strategy based on the ratio of signal intensities of different species on the chip is developed for MALDI-MS assay of multiplex enzyme activities. Using caspase-3 and protein kinase A as targets, the reactions with designed mass probe produce three mass shifts to act as two “fingerprint” patterns for obtaining the dual enzyme activities. The proposed biosensing method shows the detectable ranges from 0.05 to 50 μU μL−1 and 0.4–40 μU μL−1 with correlation coefficients of 0.990 and 0.989 for PKA and caspase-3, respectively. The biosensing application has been demonstrated by monitoring these enzymes in cell lysates upon anti-cancer drug treatment, indicating the prospect of the novel biosensing protocol in biomedical study.

High-transmittance and focal controllable plano-convex lenses with embedded nanolens bottoms formed by electrowetting on a colloidal monolayer

UV-curable polymer lenses with a nanolens array decorated on the bottom surface via irreversible electrowetting on a hydrophobic colloidal monolayer.