High affinity of 3D spongin scaffold towards Hg(II) in real waters.

This study focuses on the ability of commercial natural bath sponges, which are made from the skeletons of marine sponges, to sorb Hg from natural waters. The main component of these bath sponges is spongin, which is a protein-based material, closely related to collagen, offering a plenitude of reactive sites from the great variety of amino acids in the protein chains, where the Hg ions can sorb. For a dose of 40 mg L-1 and initial concentration of 50 µg L-1 of Hg(II), marine spongin (MS) removed ~90% of Hg from 3 water matrixes (ultrapure, bottled, and seawater), corresponding to a residual concentration of ~5 µg L-1, which tends to the recommend value for drinking water of 1 µg L-1. This value was maintained even by increasing the MS dosage, suggesting the existence of a gradient concentration threshold below which the Hg sorption mechanism halts. Kinetic modelling showed that the Pseudo Second-Order equation was the best fit for all the water matrixes, which indicates that the sorption mechanism relies most probably on chemical interactions between the functional groups of spongin and the Hg ions. This material can also be regenerated in HNO3 and reused for Hg sorption, with marginal losses in efficiency, at least for 3 consecutive cycles.

Enhanced proton conductivity in a layered coordination polymer.

[Gd(H4nmp)(H2O)2]Cl·2H2O (1) converts into [Gd2(H3nmp)2]·xH2O (2) (x = 1 to 4) with a notable increase in proton conductivity. 1 is a charged layered material counter balanced by chloride ions, with proton conductivity values of 1.23 × 10-5 S cm-1 at 98% relative humidity (RH) and 40 °C. At 98% RH and 94 °C the observed conductivity is 0.51 S cm-1, being to date one of the highest values ever reported for a proton-conducting coordination polymer. This increase is observed during a structural transformation into 2 that occurs at high temperature and RH. While this remarkable conductivity is observed only after transformation and by maintaining high humidity conditions, as-synthesized 2 also shows a conductivity value of 3.79 × 10-2 S cm-1 at 94 °C and 98% RH, still ranked as one of the highest reported values. Moreover, it is shown that the key factor for high proton conduction is the unusual dynamic structural transformation with water insertion and release of chloride ions.

Green Graphene-Chitosan Sorbent Materials for Mercury Water Remediation.

The development of new graphene-based nanocomposites able to provide synergistic effects for the adsorption of toxic heavy metals in realistic conditions (environment) is of higher demand for future applications. This work explores the preparation of a green nanocomposite based on the self-assembly of graphene oxide (GO) with chitosan (CH) for the remediation of Hg(II) in different water matrices, including ultrapure and natural waters (tap water, river water, and seawater). Starting at a concentration of 50 µg L-1, the results showed that GO-CH nanocomposite has an excellent adsorption capacity of Hg (II) using very small doses (10 mg L-1) in ultrapure water with a removal percentage (% R) of 97 % R after only two hours of contact time. In the case of tap water, the % R was 81.4% after four hours of contact time. In the case of river and seawater, the GO-CH nanocomposite showed a limited performance due the high complexity of the water matrices, leading to a residual removal of Hg(II). The obtained removal of Hg(II) at equilibrium in river and seawater for GO-CH was 13% R and 7% R, respectively. Our studies conducted with different mimicked sea waters revealed that the removal of mercury is not affected by the presence of NO3- and Na+ (>90% R of Hg(II)); however, in the presence of Cl-, the mercury removal was virtually nonexistent (1% R of Hg(II)), most likely because of the formation of very stable chloro-complexes of Hg(II) with less affinity towards GO-CH.

Efficient Water Self-Diffusion in Diphenylalanine Peptide Nanotubes.

Nanotubes of self-assembled dipeptides exemplified by diphenylalanine (FF) demonstrate a wide range of useful functional properties, such as high Young's moduli, strong photoluminescence, remarkable piezoelectricity and pyroelectricity, optical waveguiding, etc., and became the object of intensive research due to their ability to combine electronic and biological functions in the same material. Two types of nanoconfined water molecules (bound water directly interacting with the peptide backbone and free water located inside nanochannels) are known to play a key role in the self-assembly of FF. Bound water provides its structural integrity, whereas movable free water influences its functional response. However, the intrinsic mechanism of water motion in FF nanotubes remained elusive. In this work, we study the sorption properties of FF nanotubes directly considering them as a microporous material and analyze the free water self-diffusion at different temperatures. We found a change in the regime of free water diffusion, which is attributed to water cluster size in the nanochannels. Small clusters of less than five molecules per unit cell exhibit ballistic diffusion, whereas, for larger clusters, Fickian diffusion occurs. External conditions of around 40% relative humidity at 30 °C enable the formation of such large clusters, for which the diffusion coefficient reaches 1.3 × 10-10 m2 s-1 with an activation energy of 20 kJ mol-1, which increases to attain 3 × 10-10 m2 s-1 at 65 °C. The observed peculiarities of water self-diffusion along the narrow FF nanochannels endow this class of materials with a new functionality. Possible applications of FF nanotubes in nanofluidic devices are discussed.

Mitigating cavitation erosion using biomimetic gas-entrapping microtextured surfaces (GEMS).

Cavitation refers to the formation and collapse of vapor bubbles near solid boundaries in high-speed flows, such as ship propellers and pumps. During this process, cavitation bubbles focus fluid energy on the solid surface by forming high-speed jets, leading to damage and downtime of machinery. In response, numerous surface treatments to counteract this effect have been explored, including perfluorinated coatings and surface hardening, but they all succumb to cavitation erosion eventually. Here, we report on biomimetic gas-entrapping microtextured surfaces (GEMS) that robustly entrap air when immersed in water regardless of the wetting nature of the substrate. Crucially, the entrapment of air inside the cavities repels cavitation bubbles away from the surface, thereby preventing cavitation damage. We provide mechanistic insights by treating the system as a potential flow problem of a multi-bubble system. Our findings present a possible avenue for mitigating cavitation erosion through the application of inexpensive and environmentally friendly materials.

Rendering SiO2/Si Surfaces Omniphobic by Carving Gas-Entrapping Microtextures Comprising Reentrant and Doubly Reentrant Cavities or Pillars.

We present microfabrication protocols for rendering intrinsically wetting materials repellent to liquids (omniphobic) by creating gas-entrapping microtextures (GEMs) on them comprising cavities and pillars with reentrant and doubly reentrant features. Specifically, we use SiO2/Si as the model system and share protocols for two-dimensional (2D) designing, photolithography, isotropic/anisotropic etching techniques, thermal oxide growth, piranha cleaning, and storage towards achieving those microtextures. Even though the conventional wisdom indicates that roughening intrinsically wetting surfaces (θo < 90°) renders them even more wetting (θr < θo < 90°), GEMs demonstrate liquid repellence despite the intrinsic wettability of the substrate. For instance, despite the intrinsic wettability of silica θo ≈ 40° for the water/air system, and θo ≈ 20° for the hexadecane/air system, GEMs comprising cavities entrap air robustly on immersion in those liquids, and the apparent contact angles for the droplets are θr > 90°. The reentrant and doubly reentrant features in the GEMs stabilize the intruding liquid meniscus thereby trapping the liquid-solid-vapor system in metastable air-filled states (Cassie states) and delaying wetting transitions to the thermodynamically-stable fully-filled state (Wenzel state) by, for instance, hours to months. Similarly, SiO2/Si surfaces with arrays of reentrant and doubly reentrant micropillars demonstrate extremely high contact angles (θr ≈ 150°-160°) and low contact angle hysteresis for the probe liquids, thus characterized as superomniphobic. However, on immersion in the same liquids, those surfaces dramatically lose their superomniphobicity and get fully-filled within <1 s. To address this challenge, we present protocols for hybrid designs that comprise arrays of doubly reentrant pillars surrounded by walls with doubly reentrant profiles. Indeed, hybrid microtextures entrap air on immersion in the probe liquids. To summarize, the protocols described here should enable the investigation of GEMs in the context of achieving omniphobicity without chemical coatings, such as perfluorocarbons, which might unlock the scope of inexpensive common materials for applications as omniphobic materials. Silica microtextures could also serve as templates for soft materials.

Conductive polysaccharides-based proton-exchange membranes for fuel cell applications: The case of bacterial cellulose and fucoidan.

Conductive natural-based separators for application in polymer electrolyte fuel cells (PEFCs) were fabricated by combining a bacterial polysaccharide, i.e. bacterial cellulose (BC), and an algae sulphated polysaccharide, i.e. fucoidan (Fuc). The diffusion of fucoidan aqueous solution containing a natural-based cross-linker, viz. tannic acid, into the wet BC nanofibrous three-dimensional network, followed by thermal cross-linking, originated fully bio-based proton exchange membranes (PEMs). The PEMs present thermal-oxidative stability in the range of 180-200 °C and good dynamic mechanical performance (storage modulus ≥ 460 MPa). Additionally, the BC/Fuc membranes exhibit protonic conductivity that increases with increasing relative humidity (RH), which is a typical feature for numerous water-mediated proton conductors. The traditional Arrhenius-type plots demonstrate a linear behaviour with a maximum protonic conductivity of 1.6 mS cm-1 at 94 °C and 98 % RH. The results showed that these fully bio-based conductive membranes have potential as eco-friendly alternatives to other PEMs for application in PEFCs.

Antimicrobial and Conductive Nanocellulose-Based Films for Active and Intelligent Food Packaging.

Bacterial nanocellulose (BNC) is becoming an important substrate for engineering multifunctional nanomaterials with singular and tunable properties for application in several domains. Here, antimicrobial conductive nanocomposites composed of poly(sulfobetaine methacrylate) (PSBMA) and BNC were fabricated as freestanding films for application in food packaging. The nanocomposite films were prepared through the one-pot polymerization of sulfobetaine methacrylate (SBMA) inside the BNC nanofibrous network and in the presence of poly(ethylene glycol) diacrylate as cross-linking agent. The ensuing films are macroscopically homogeneous, more transparent than pristine BNC, and present thermal stability up to 265 °C in a nitrogen atmosphere. Furthermore, the films have good mechanical performance (Young's modulus ≥ 3.1 GPa), high water-uptake capacity (450-559%) and UV-blocking properties. The zwitterion film with 62 wt.% cross-linked PSBMA showed bactericidal activity against Staphylococcus aureus (4.3-log CFU mL-1 reduction) and Escherichia coli (1.1-log CFU mL-1 reduction), and proton conductivity ranging between 1.5 × 10-4 mS cm-1 (40 °C, 60% relative humidity (RH)) and 1.5 mS cm-1 (94 °C, 98% RH). Considering the current set of properties, PSBMA/BNC nanocomposites disclose potential as films for active food packaging, due to their UV-barrier properties, moisture scavenging ability, and antimicrobial activity towards pathogenic microorganisms responsible for food spoilage and foodborne illness; and also for intelligent food packaging, due to the proton motion relevant for protonic-conduction humidity sensors that monitor food humidity levels.

Assessing omniphobicity by immersion.

HYPOTHESIS: Coating-free approaches to achieve liquid repellent, or omniphobic, surfaces could exploit inexpensive intrinsically wetting materials, such as polyethylene terephthalate and nylon, for applications such as liquid-vapor extraction and drag reduction. However, it is not clear whether the existing criteria for assessing coating-based omniphobicity, based on contact angles, would be reliable for coating-free approaches, especially considering localized defects/damages during manufacturing and usage. EXPERIMENTS: We assessed the omniphobicity of silica surfaces adorned with arrays of doubly reentrant pillars, cavities, and hybrid designs with sessile drops and on immersion in water and hexadecane through contact angle goniometry and confocal microscopy. FINDINGS: We demonstrate that the assessment of omniphobicity of surfaces derived from intrinsically wetting materials can be misleading, if solely based on the measurement of contact angles. Specifically, localized defects in microtextures consisting of pillars may lead to the spontaneous loss of omniphobicity and detecting them through contact angles can be difficult. We also demonstrate that the immersion of those surfaces into probe liquids may serve as a simple and quick 'litmus' test for omniphobicity. Thus, immersion as the additional criterion for omniphobicity might prove itself useful in the context of large-scale manufacturing.

Biomimetic coating-free surfaces for long-term entrapment of air under wetting liquids.

Trapping air at the solid-liquid interface is a promising strategy for reducing frictional drag and desalting water, although it has thus far remained unachievable without perfluorinated coatings. Here, we report on biomimetic microtextures composed of doubly reentrant cavities (DRCs) and reentrant cavities (RCs) that can enable even intrinsically wetting materials to entrap air for long periods upon immersion in liquids. Using SiO2/Si wafers as the model system, we demonstrate that while the air entrapped in simple cylindrical cavities immersed in hexadecane is lost after 0.2 s, the air entrapped in the DRCs remained intact even after 27 days (~106 s). To understand the factors and mechanisms underlying this ten-million-fold enhancement, we compared the behaviors of DRCs, RCs and simple cavities of circular and non-circular shapes on immersion in liquids of low and high vapor pressures through high-speed imaging, confocal microscopy, and pressure cells. Those results might advance the development of coating-free liquid repellent surfaces.

Doubly Reentrant Cavities Prevent Catastrophic Wetting Transitions on Intrinsically Wetting Surfaces.

Omniphobic surfaces, that is, which repel all known liquids, have proven of value in applications ranging from membrane distillation to underwater drag reduction. A limitation of currently employed omniphobic surfaces is that they rely on perfluorinated coatings, increasing cost and environmental impact and preventing applications in harsh environments. Thus, there is a keen interest in rendering conventional materials, such as plastics, omniphobic by micro/nanotexturing rather than via chemical makeup, with notable success having been achieved for silica surfaces with doubly reentrant micropillars. However, we found a critical limitation of microtextures comprising pillars that they undergo catastrophic wetting transitions (apparent contact angles, θr → 0° from θr > 90°) in the presence of localized physical damages/defects or on immersion in wetting liquids. In response, a doubly reentrant cavity microtexture is introduced, which can prevent catastrophic wetting transitions in the presence of localized structural damage/defects or on immersion in wetting liquids. Remarkably, our silica surfaces with doubly reentrant cavities could exhibit apparent contact angles, θr ≈ 135° for mineral oil, where the intrinsic contact angle, θo ≈ 20°. Further, when immersed in mineral oil or water, doubly reentrant microtextures in silica (θo ≈ 40° for water) were not penetrated even after several days of investigation. Thus, microtextures comprising doubly reentrant cavities might enable applications of conventional materials without chemical modifications, especially in scenarios that are prone to localized damages or immersion in wetting liquids, for example, hydrodynamic drag reduction and membrane distillation.