Synthesis of robust underwater glues from common proteins via unfolding-aggregating strategy.

Underwater adhesive proteins secreted by organisms greatly inspires the development of underwater glue. However, except for specific proteins such as mussel adhesive protein, barnacle cement proteins, curli protein and their related recombinant proteins, it is believed that abundant common proteins cannot be converted into underwater glue. Here, we demonstrate that unfolded common proteins exhibit high affinity to surfaces and strong internal cohesion via amyloid-like aggregation in water. Using bovine serum albumin (BSA) as a model protein, we obtain a stable unfolded protein by cleaving the disulfide bonds and maintaining the unfolded state by means of stabilizing agents such as trifluoroethanol (TFE) and urea. The diffusion of stabilizing agents into water exposes the hydrophobic residues of an unfolded protein and initiates aggregation of the unfolded protein into a solid block. A robust and stable underwater glue can thus be prepared from tens of common proteins. This strategy deciphers a general code in common proteins to construct robust underwater glue from abundant biomass.

Enhancing Bioavailability of Fertilizer through an Amyloid-Like Protein Coating.

Foliar fertilization acts as a ubiquitous component of conventional crop production, which brings considerable economic and ecological costs. Due to droplets rebounding and splashing during spraying and rain erosion, low bioavailability of fertilizer results in severe environmental pollution. Contrary to conventional fertilizer formulations with polymers, surfactants, and organic reagents, a method of improving fertilizer bioavailability based on a biocompatible protein coating is presented herein. In this system, whey protein concentrate (WPC) can undergo amyloid-like aggregation after the reduction of its disulfide bond by the reducing agent tris(2-carboxyethyl) phosphine (TCEP). Such aggregation affords a fast formation of the optically transparent and colorless phase-transitioned WPC (PTW) coating at the solid/water interface, with robust interfacial adhesion stability. Upon packaging with fertilizers through electrostatic and hydrogen-bonding interactions, such reliable interfacial adhesion thereby facilitates the effective deposition of fertilizers on superhydrophobic and hydrophobic leaf surfaces, with excellent adhesion stability. Based on practical farmland test, this work demonstrates that the application of PTW can significantly boost the bioavailability of fertilizers and decrease at least 30% fertilizer use in large-scale crop planting. This innovative strategy has the great potential to offer a transformative step forward in managing fertilizer contamination and overuse in future agriculture.

Optical Manipulation of Liquids by Thermal Marangoni Flow along the Air-Water Interfaces of a Superhydrophobic Surface.

The control of liquid motion on the micrometer scale is important for many liquid transport and biomedical applications. An efficient way to trigger liquid motion is by introducing surface tension gradients on free liquid interfaces leading to the Marangoni effect. However, a pronounced Marangoni-driven flow generally only occurs at a liquid-air or liquid-liquid interface but not at solid-liquid interfaces. Using superhydrophobic surfaces, the liquid phase stays in the Cassie state (where liquid is only in contact with the tips of the rough surface structure and air is enclosed in the indentations of the roughness) and hence provides the necessary liquid-air interface to trigger evident Marangoni flows. We use light to asymmetrically heat this interface and thereby control liquid motion near superhydrophobic surfaces. By laser scanning confocal microscopy, we determine the velocity distribution evolving through optical excitation. We show that Marangoni flow can be induced optically at structured, air-entrapping superhydrophobic surfaces. Furthermore, by comparison with numerical modeling, we demonstrate that in addition to the Marangoni flow, buoyancy-driven flow occurs. This effect has so far been neglected in similar approaches and models of thermocapillary driven flow at superhydrophobic surfaces. Our work yields insight into the physics of Marangoni flow and can help in designing new contactless, light-driven liquid transport systems, e.g., for liquid pumping or in microfluidic devices.

Control of Droplet Evaporation on Oil-Coated Surfaces for the Synthesis of Asymmetric Supraparticles.

Controlling the droplet evaporation on surfaces is desired to get uniform depositions of materials in many applications, for example, in two- and three-dimensional printing and biosensors. To explore a new route to control droplet evaporation on surfaces and produce asymmetric particles, sessile droplets of aqueous dispersions were allowed to evaporate from surfaces coated with oil films. Here, we applied 1-50 µm thick films of different silicone oils. Two contact lines were observed during droplet evaporation: an apparent liquid-liquid-air contact line and liquid-liquid-solid contact line. Because of the oil meniscus covering part of the rim of the drop, evaporation at the periphery is suppressed. Consequently, the droplet evaporates mainly in the central region of the liquid-air interface rather than at the droplet's edge. Colloidal particles migrate with the generated upward flow inside the droplet and are captured by the receding liquid-air interface. A uniform deposition ultimately forms on the substrate. With this straightforward approach, asymmetric supraparticles have been successfully fabricated independent of particle species.

Responsive Ionogel Surface with Renewable Antibiofouling Properties.

The synthesis of ionogels with a responsive, self-replenishing surface for combating biofouling is described. Ionogels are prepared by infiltrating poly(vinylidene fluoride-co-hexafluoropropylene) with binary mixtures of ionic liquids (IL): 1-octadecyl-3-methylimidazolium bis(trifluoromethyl sulfonyl)imide ([C18 C1 im][NTf2 ], melting point Tm = 55 °C) and 1-hexyl-3-methylimidazolium bis(trifluoromethyl sulfonyl)imide ([C6 C1 im][NTf2 ], Tm = -9 °C). The IL mixtures release spontaneously from the gel matrix and eventually crystallize on the surface. This leads to self-replenishment of the surface of ionogels even after mechanical damage. The incorporation of [C6 C1 im][NTf2 ] provides the antimicrobial efficacy of ionogels while the crystals of [C18 C1 im][NTf2 ] serve as a skeleton maintaining [C6 C1 im][NTf2 ] on the surface. By heating, the ionogel surface transforms from solid to liquid-infused state-the removal of biofilms/bacteria developed under a long time of colonization is facilitated. The antimicrobial efficacy is maintained even after several cycles of biofilm formation and detachment. This work provides an opportunity to apply ionogels as functional coatings with renewable antibiofouling properties.

A Superhydrophobic Surface Templated by Protein Self-Assembly and Emerging Application toward Protein Crystallization.

A proteinaceous superhydrophobic material for facile protein crystallization is reported. The lysozyme phase transition is rationally manipulated to form a reliable superhydrophobic coating on virtually arbitrary material surfaces with good thermostability and mechanical robustness. Such a surface exhibits a fascinating capability to drive protein crystallization, and the protein crystal array can be facilitated in a large area at an ultralow protein concentration.

Soft landing of cell-sized vesicles on solid surfaces for robust vehicle capture/release.

Based on a concept of a smooth and steady landing of fragile objects without destruction via a soft cushion, we have developed a model for the soft landing of deformable lipid giant unilamellar vesicles (GUVs) on solid surfaces. The foundation for a successful soft landing is a solid substrate with a two-layer coating, including a bottom layer of positively charged lysozymes and an upper lipid membrane layer. We came to a clear conclusion that anionic GUVs when sedimented on a surface, the vesicle rupture occurs upon the direct contact with the positively charged lysozyme layer due to the strong coulombic interactions. In contrast, certain separation distances was achieved by the insertion of a soft lipid membrane cushion between the charged GUVs and the lysozyme layer, which attenuated the coulombic force and created a mild buffer zone, ensuring the robust capture of GUVs on the substrate without their rupture. The non-covalent bonding facilitated a fully reversible stimuli-responsive capture/release of GUVs from the biomimetic solid surface, which has never been demonstrated before due to the extreme fragility of GUVs. Moreover, the controllable capture/release of cells has been proven to be of vital importance in biotechnology, and similarity the present approach to capture/release cells is expected to open the previously inaccessible avenues of research.

Self-assembled monolayer-assisted negative lithography.

Self-assembled monolayers (SAMs) have been widely employed as etching resists in wet lithography systems to form patterns in which the ordered molecular packing of the SAM regions significantly delays the etchant attack. A generally accepted recognition is that the SAMs ability to resist etching is positively correlated to the quality of the surface-assembled structures, and a more ordered molecular packing would correspond to a better etching resistance. Such a classical belief is debated in the present work by providing an alternative SAM-assisted negative lithography where ordered SAM regions are etched more quickly than their disordered counterparts. This method features a unique photoirradiation-imprinted patterning process that simply consists of two steps: (1) UV irradiation on an OH-terminated SAM-modified gold surface through a photomask and (2) the subsequent immersion of the exposed substrate in an aqueous etching solution of N-bromosuccinimide/pyridine to develop a wet lithographic pattern. The entire experimental process reveals a finding from previous work that the etching rate on the UV-exposed regions with disordered molecular packing could be modulated to be slower than that in the unexposed well-defined SAM regions. Longer irradiation times would also revert the patterns from negative to positive. Thus, by merely using one kind of SAM-modified surface to provide both positive and negative micropatterns on gold layers, one could obtain flexible opportunities for high-resolution micro/nanofabrication resembling photolithography.