Hydrophobic Switching Research Articles

Surface Modification, Topographic Design and Applications of Superhydrophobic Systems.

Superhydrophobic surfaces with expanded wetting behaviors, like tunable adhesion, hybrid surface hydrophobicity and smart hydrophobic switching have attracted increasing attention due to their broad applications. Herein, the construction methods, mechanisms and advanced applications of special superhydrophobicity are reviewed, and hydro/superhydrophobic modifications are categorized and discussed based on their surface chemistry, and topographic design. The formation and maintenance of special superhydrophobicity in the metastable state are also examined and explored. In addition, particular attention is paid to the use of special wettability in various applications, such as membrane distillation, droplet-based electricity generators and anti-fogging surfaces. Finally, the challenges for practical applications and future research directions are discussed.

Titelbild: Solvent‐Influenced Fragmentations in Free‐Standing Three‐Dimensional Covalent Organic Framework Membranes for Hydrophobicity Switching (Angew. Chem. 13/2022)

Die physikochemischen Eigenschaften von freistehenden organischen Membranen können ohne Änderung der Bausteine oder nachträgliche synthetische Modifikationen abgestimmt werden. Der Forschungsartikel (e202200905) von Dinesh Shetty et al. demonstriert eine neuartige, präsynthetisch kontrollierte Gerüstbildungstrategie, um die Hydrophobie von 3D-COF-Membranen abzustimmen. Die hydrophobe 3D-COF-Membran zeigt eine potenzielle Verwendung für die Demulgierung eines Öl-Wasser-Gemischs, ein bedeutendes Umwelt- und Wasserwiederverwendungsproblem.

Solvent‐Influenced Fragmentations in Free‐Standing Three‐Dimensional Covalent Organic Framework Membranes for Hydrophobicity Switching

AbstractThe ordered open organic frameworks membranes are attractive candidates for flow‐assisted molecular separations. The physicochemical properties of such membranes mostly depend on their selectively chosen functional building blocks. In this work, we have introduced a novel concept of functional switchability of three‐dimensional covalent organic framework (3D‐COF) membranes through a simple solvent‐influenced fragmentation method. This room‐temperature interfacial synthesis provides free‐standing 3D‐COF membranes with distinct physicochemical properties from the same building monomers. Notably, the change of solvent from chloroform to ethyl acetate switches the membrane property from hydrophilic (water contact angle 60°) to hydrophobic (water contact angle 142°) nature. The hydrophobic 3D‐COF membrane selectively passes oil molecules from an oil–water emulsion with a gravitational flux of 1536 L m−2 h−1.

Solvent-Influenced Fragmentations in Free-Standing Three-Dimensional Covalent Organic Framework Membranes for Hydrophobicity Switching.

The ordered open organic frameworks membranes are attractive candidates for flow‐assisted molecular separations. The physicochemical properties of such membranes mostly depend on their selectively chosen functional building blocks. In this work, we have introduced a novel concept of functional switchability of three‐dimensional covalent organic framework (3D‐COF) membranes through a simple solvent‐influenced fragmentation method. This room‐temperature interfacial synthesis provides free‐standing 3D‐COF membranes with distinct physicochemical properties from the same building monomers. Notably, the change of solvent from chloroform to ethyl acetate switches the membrane property from hydrophilic (water contact angle 60°) to hydrophobic (water contact angle 142°) nature. The hydrophobic 3D‐COF membrane selectively passes oil molecules from an oil–water emulsion with a gravitational flux of 1536 L m−2 h−1.

Electric Field Driven Surface Ion Transport in Hydrophobic Nanopores†

Main observation and conclusionWater behavior in nanoconfined hydrophobic environment is different from that in the bulk, which greatly influences mass transport. Hydrophobicity switching of nanopores showing great potential for controlled water or ion transport has been realized through several methods, especially the voltage‐triggered wetting/dewetting inspired by biological ion channels. However, in the hydrophobic silanized nanopores, the finite ionic current is still observed and the ion transport mechanism is not yet clear. Here, we explore the ion transport behavior in the hydrophobic silanized anodic aluminum oxide (AAO). Ion transport through this hydrophobic membrane is confirmed, although no aqueous pathway was observed. Results show that ions transport through the cross‐linked silane layer on the inner surface. It is revealed that metal ions, not just the protons or hydroxide ions, are involved in the ion transport driven by external electric field. This study provides a new insight into the ion transport in nanoconfined hydrophobic environment, which is helpful to understand the biological processes and design new nanofluidic devices.

Cryo-EM structure in situ reveals a molecular switch that safeguards virus against genome loss.

The portal protein is a key component of many double-stranded DNA viruses, governing capsid assembly and genome packaging. Twelve subunits of the portal protein define a tunnel, through which DNA is translocated into the capsid. It is unknown how the portal protein functions as a gatekeeper, preventing DNA slippage, whilst allowing its passage into the capsid, and how these processes are controlled. A cryo-EM structure of the portal protein of thermostable virus P23-45, determined in situ in its procapsid-bound state, indicates a mechanism that naturally safeguards the virus against genome loss. This occurs via an inversion of the conformation of the loops that define the constriction in the central tunnel, accompanied by a hydrophilic-hydrophobic switch. The structure also shows how translocation of DNA into the capsid could be modulated by a changing mode of protein-protein interactions between portal and capsid, across a symmetry-mismatched interface.

Active Surface Hydrophobicity Switching and Dynamic Interfacial Trapping of Microbial Cells by Metal Nanoparticles for Preconcentration and In-Plane Optical Detection.

The surface hydrophobicity of a microbial cell is known to be one of the important factors in its adhesion to an interface. To date, such property has been altered by either genetic modification or external pH, temperature, and nutrient control. Here we report a new strategy to engineer a microbial cell surface and discover the unique dynamic trapping of hydrophilic cells at an air/water interface via hydrophobicity switching. We demonstrate the surface transformation and hydrophobicity switching of Escherichia coli (E. coli) by metal nanoparticles. By employing real-time dark-field imaging, we directly observe that hydrophobic gold nanoparticle-coated E. coli, unlike its naked counterpart, is irreversibly trapped at the air/water interface because of elevated hydrophobicity. We show that our surface transformation method and resulting dynamic interfacial trapping can be generally extended to Gram-positive bateria, Gram-negative bacteria, and fungi. As the dynamic interfacial trapping allows the preconcentration of microbial cells, high intensity of scattering light, in-plane focusing, and near-field enhancement, we are able to directly quantify E. coli as low as 1.0 × 103 cells/ml by using a smartphone with an image analyzer. We also establish the identification of different microbial cells by the characteristic Raman transitions directly measured from the interfacially trapped cells.

Thickness Changes in Temperature-Responsive Poly(N-isopropylacrylamide) Ultrathin Films under Ambient Conditions.

In this paper, we report detailed experimental observations of unusual changes in the thickness of solid poly(N-isopropylacrylamide) (PNIPAM) ultrathin films, which are well known to have temperature-responsive hydrophilic–hydrophobic switching properties. To date, a number of studies have been carried out on the bulk and the brush forms of PNIPAM in contact with liquid water, as well as in highly humid environments, and, recently, these ultrathin films have been preliminarily shown to exhibit temperature responses even under low-humidity, ambient conditions. In this work, the thicknesses of ultrathin PNIPAM films in a temperature/moisture-controlled sample stage were monitored continuously using multichannel X-ray reflectometry. At room temperature, the sample thickness showed an unexpected increase after thermal treatment at 70 °C for 3 h. In the temperature cycle between 15 and 60 °C, heating and cooling resulted in some clear differences. During cooling, initially, the thickness was almost constant but began to increase when the temperature exceeded 33 °C, which corresponds to the lower critical solution temperature (LCST). This observation indicates that the PNIPAM ultrathin film is sensitive to the small amounts of water contained in the air, even under ambient, low-humidity conditions. On the other hand, during heating run from 15 to 60 °C, the humidity dependence was monotonic, and no specific changes in the PNIPAM films were observed at around the LCST. By studying the humidity dependence, we found that the hydrophilic and hydrophobic states of the PNIPAM ultrathin film exhibit different temperature dependence behaviors. In addition, we found that swelling takes place even under low-moisture conditions. To understand the difference in the thickness changes observed on cooling and heating further, some models considering the effect of the boundary conditions in the polymer ultrathin film system were considered. In the case of the ultrathin film, the hydrophilic/hydrophobic switching property occurred only in the surface layer, which dominated the absorption of water molecules from air. In contrast, the interface layer was time-stable and provided an escape route for water molecules during heating.

Thermoresponsive Polyurethane Bearing Oligo(Ethylene Glycol) as Side Chain Without Polyol at Polymer Backbone Achieved Excellent Hydrophilic and Hydrophobic Switching.

In order to prepare thermoresponsive polyurethane gels, a novel polyurethane bearing oligo(ethylene glycol) (OEG) as the side chain is successfully synthesized with hexamethylene diisocyanate and OEG tartrate ester. The aqueous solution of the polyurethane shows sharp and clear lower critical solution temperature behavior at 34 °C. Furthermore, a hydrogel based on the same polyurethane is also successfully prepared using glycerol as the crosslinker. This polyurethane hydrogel including 10 mol% of glycerol presents a large swelling ratio change between 4 °C and 37 °C from 250% to 40%.

Reversible superhydrophilicity and hydrophobicity switching of V2O5 thin films deposited by magnetron sputtering

V2O5 thin films are well-known “smart” materials due to their reversible wettability under UV irradiation and dark storage. Their surfaces are usually hydrophobic and turn into hydrophilic under UV irradiation. However, the V2O5 thin films deposited by magnetron sputtering in present work are superhydrophilic and turned into hydrophobic after days’ of storage in air. This change can be recovered by heating. The effects of many factors including surface roughness, irradiation from visible light, UV, & X-ray, and storage in air & vacuum on the reversible switching of wettability were investigated. The results show that air absorption is the main factor causing the film surface change from superhydrophilicity to hydrophobicity.

A Voltage-Responsive Free-Blockage Controlled-Release System Based on Hydrophobicity Switching.

Controlled-release systems based on mesoporous silica nanomaterials (MSNs) have drawn great attention owing to their potential biomedical applications. Various switches have been designed to control the release of cargoes through the construction of physical blocking units on the surface of MSNs. However, such physical blockages are limited by poor sealing ability and low biocompatibility, and most of them lack closure ability. Herein, a voltage-responsive controlled-release system was constructed by functionalizing the nanopore of MSNs with ferrocene. The system realized free-blockage controlled release and achieved pulsatile release. The nanopores of the ferrocene-functionalized MSNs were hydrophobic enough to prevent invasion of the solution. Once a suitable voltage was applied, the nanopores became hydrophilic, which was followed by invasion of the solution and the release of the cargos. Moreover, pulsatile release was realized, which avoided unexpected release after the stimulus disappeared. Thus, we believe that our studies provide new insight into highly effective blockage for MSNs. Furthermore, the voltage-responsive release system is expected to find use in electrical stimulation combination therapy and bioelectricity-responsive release.

Voltage-Responsive Controlled Release Film with Cargo Release Self-Monitoring Property Based on Hydrophobicity Switching.

Herein, voltage-responsive controlled release film was constructed by grafting ferrocene on the mesoporous inverse opal photonic crystal (mIOPC). The film achieved free-blockage controlled release and realized the monitoring of cargo release without external indicator. Free-blockage was attributed to the voltage switchable nanovalves which undergo hydrophobic-to-hydrophilic transition when applying voltage. Monitoring of cargo release was attributed to the optical property of mIOPC, the bandgap of mIOPC had a red shift when the solution invaded in. The film was hydrophobic enough to stop solution intrusion. Once the voltage was applied, the film became hydrophilic, leading to invasion of the solution. As a result, the cargos were released and the bandgap of mIOPC was red-shifted. Therefore, in this paper both a free-blockage controlled release film and a release sensing system was prepared. The study provides new insights into highly effective controlled release and release sensing without indicator.

Electrostatic Switch Function in the Mechanism of Protein Kinase A Iα Activation: Results of the Molecular Dynamics Simulation.

We used molecular dynamics to find the average path of the A-domain H → B conformational transition in protein kinase A Iα. We obtained thirteen productive trajectories and processed them sequentially using factor and cross-correlation analyses. The conformational transition is presented as partly deterministic sequence of six events. Event B represents H → B transition of the phosphate binding cassette. Main participants of this event form electrostatic switch cAMP(O6)–A202(N-H)–G199(C=O). Through this switch, cAMP transmits information about its binding to hydrophobic switch L203–Y229 and thus triggers conformational transition of A-domain. Events C and D consist in N3A-motif displacement towards phosphate binding cassette and B/C-helix rotation. Event E involves an increase in interaction energy between Y229 and β-subdomain. Taken together, events B, E, and D correspond to the hinge movement towards β-barrel. Transition of B/C-helix turn (a.a. 229–234) from α-form to π-form accounts for event F. Event G implies that π-helical turn is replaced by kink. Emerging in the resulting conformation, electrostatic interaction R241–E200 facilitates kink formation. The obtained data on the mechanism of cAMP-dependent activation of PKA Iα may contribute to new approaches to designing pharmaceuticals based on cAMP analogs.

PH-Responsive nano sensing valve with self-monitoring state property based on hydrophobicity switching

pH-Responsive free-blockage nanovalves with self-monitoring state property were constructed based on the hydrophobicity switching of mesoporous photonic crystal.

MD Simulations and FRET Reveal an Environment-Sensitive Conformational Plasticity of Importin-β

The nuclear pore complex mediates nucleocytoplasmic transport of macromolecules in eukaryotic cells. Transport through the pore is restricted by a hydrophobic selectivity filter comprising disordered phenylalanine-glycine-rich repeats of nuclear pore proteins. Exchange through the pore requires specialized transport receptors, called exportins and importins, that interact with cargo proteins in a RanGTP-dependent manner. These receptors are highly flexible superhelical structures composed of HEAT-repeat motifs that adopt various degrees of extension in crystal structures. Here, we performed molecular-dynamics simulations using crystal structures of Importin-β in its free form or in complex with nuclear localization signal peptides as the starting conformation. Our simulations predicted that initially compact structures would adopt extended conformations in hydrophilic buffers, while contracted conformations would dominate in more hydrophobic solutions, mimicking the environment of the nuclear pore. We confirmed this experimentally by Förster resonance energy transfer experiments using dual-fluorophore-labeled Importin-β. These observations explain seemingly contradictory crystal structures and suggest a possible mechanism for cargo protection during passage of the nuclear pore. Such hydrophobic switching may be a general principle for environmental control of protein function.

NMR Studies of Hexaacylated Endotoxin Bound to Wild-type and F126A Mutant MD-2 and MD-2·TLR4 Ectodomain Complexes

Host response to invasion by many gram-negative bacteria depends upon activation of Toll-like receptor 4 (TLR4) by endotoxin presented as a monomer bound to myeloid differentiation factor 2 (MD-2). Metabolic labeling of hexaacylated endotoxin (LOS) from Neisseria meningitidis with [(13)C]acetate allowed the use of NMR to examine structural properties of the fatty acyl chains of LOS present in TLR4-agonistic and -antagonistic binary and ternary complexes with, respectively, wild-type or mutant (F126A) MD-2 ± TLR4 ectodomain. Chemical shift perturbation indicates that Phe(126) affects the environment and/or position of each of the bound fatty acyl chains both in the binary LOS·MD-2 complex and in the ternary LOS·MD-2·TLR4 ectodomain complex. In both wild-type and mutant LOS·MD-2 complexes, one of the six fatty acyl chains of LOS is more susceptible to paramagnetic attenuation, suggesting protrusion of that fatty acyl chain from the hydrophobic pocket of MD-2, independent of association with TLR4. These findings indicate that re-orientation of the aromatic side chain of Phe(126) is induced by binding of hexaacylated E, preceding interaction with TLR4. This re-arrangement of Phe(126) may act as a "hydrophobic switch," driving agonist-dependent contacts needed for TLR4 dimerization and activation.

Hydrophobic switching nature of methylcellulose ultra-thin films: thickness and annealing effects

We have studied the thermosensitive property of methylcellulose (MC) thin films supported on Si substrate by static sessile drop contact angle measurements, and their surface properties and thin film structure by x-ray reflectivity (XRR) and atomic force microscopy (AFM) techniques. From the static sessile drop contact angle measurements, the MC thin films showed the characteristic hydrophilic-to-hydrophobic transition at ∼70 °C, which is the lower critical solution temperature of the bulk solution volume phase separation transition. For films with thickness d ≤ Rg, the onset of such a transition is affected by the film thickness while very thick films, d ≫ Rg, yielded higher contact angles. Annealing the MC thin films with thicknesses ∼200 Å (near the radius of gyration, Rg, of the polymer) below the bulk glass transition temperature (Tg ∼ 195 ° C) would not change the hydrophobic switch nature of the film but annealing ‘at’ and above the bulk Tg would change its surface property. From surface topography images by AFM, there were no significant changes in either the roughness or the film texture before and after annealing. With XRR data, we were able to determine that such changes in the surface properties are highly correlated to the film thickness changes after the annealing process. This study, we believe, is the first to examine the thermal annealing affects on the thermal response function of a thermoresponsive polymer and is important for researching how to tailor the hydrophobic switching property of MC thin films for future sensing applications.

PH Valve Based on Hydrophobicity Switching

pH switchable valves were constructed using nanoporous membranes, the surface of which was modified by mixtures of aminopropyl trimethoxy silane and butyl trimethoxy silane. The modified membranes are dry at neutral and basic conditions because of their hydrophobicity but open to flux of aqueous solutions at slightly acidic pH because of protonation of amino groups. The resulting high contrast between the open and the closed states and a high flux in the open state because of large pore size make the approach attractive in applications where pH switching is employed, for example, in drug delivery applications.

Poly(N‐isopropylacrylamide) grafting on aluminium to actively switch its surface drag in water

AbstractActive control of flow over object surfaces achieved by means of mechanical and/or electrical methods has recently been studied. However, there has been no report on actively switching the surface drag of an object by chemical modification of the object's surface. Poly(N‐isopropylacrylamide) (PNIPA) was grafted onto the surface of an aluminium (Al) substrate via (A) surface‐initiated atom transfer radical polymerization and (B) radical polymerization with an azo‐group surface initiator. The grafting density was 0.19 and 0.15 chains nm−2, respectively. The water contact angle of the PNIPA‐grafted Al surface reversibly changed between 55° and 82° for (A) and between 42° and 65° for (B) at temperatures of 25 and 40 °C, which was ascribed to the temperature‐responsive, hydrophilic–hydrophobic switching of the grafted PNIPA surface. The PNIPA grafting was applied on the surface of an ogive‐shaped Al model. The normalized dropping speed of the model in water increased 1.1 times at 42 °C in comparison to that at 22 °C. Switching of the surface drag of PNIPA‐grafted Al in water was demonstrated on the basis of the hydrophilicity and hydrophobicity of the grafted Al surface, the switching occurring with a change in temperature. Copyright © 2010 Society of Chemical Industry

Novel type of Ras effector interaction established between tumour suppressor NORE1A and Ras switch II

A class of putative Ras effectors called Ras association domain family (RASSF) represents non-enzymatic adaptors that were shown to be important in tumour suppression. RASSF5, a member of this family, exists in two splice variants known as NORE1A and RAPL. Both of them are involved in distinct cellular pathways triggered by Ras and Rap, respectively. Here we describe the crystal structure of Ras in complex with the Ras binding domain (RBD) of NORE1A/RAPL. All Ras effectors share a common topology in their RBD creating an interface with the switch I region of Ras, whereas NORE1A/RAPL RBD reveals additional structural elements forming a unique Ras switch II binding site. Consequently, the contact area of NORE1A is extended as compared with other Ras effectors. We demonstrate that the enlarged interface provides a rationale for an exceptionally long lifetime of the complex. This is a specific attribute characterizing the effector function of NORE1A/RAPL as adaptors, in contrast to classical enzymatic effectors such as Raf, RalGDS or PI3K, which are known to form highly dynamic short-lived complexes with Ras.