Synergistic antibacterial effect and mechanism between Cu2O nanoparticles and quaternary ammonium salt in moisture-curable acrylic coatings.

Combining with various antibacterial mechanisms is the preferred strategy to fabricate coatings with effective antibacterial performance. Herein, Cu2O nanoparticles and dimethyloctadecyl [3-(trimethoxysilyl) propyl] ammonium chloride, a kind of quaternary ammonium salt (QAS), were simultaneously incorporated into a moisture-curable acrylic resin in order to achieve both contact-killing and release-killing abilities for antibacterial coatings. The surface morphology, surface composition and basic properties of the coatings were thoroughly characterized. The antibacterial performance of the coatings was determined by in-vitro bacteriostatic test. Under the constant total mass fraction of antibacterial agents, both Cu2O and QAS content possessed the highest value on the coating surface at Cu2O/QAS mass ratio of 1:1, and correspondingly, the coatings reached sterilizing rate above 99 % against both E. coli and S. loihica, indicating the existence of synergistic effect between Cu2O and QAS. The synergistic antibacterial mechanism of the coatings involved two aspects. Firstly, the combination of contact-killing and release-killing biocides resulted in high bactericidal and antibiofilm activity against different bacteria. Further, the grafting of QAS molecules on the surface of Cu2O particles brought about the spontaneous migration of nanoparticles to the coating surface. The interaction between Cu2O and QAS also inhibited the phase separation of QAS and prolonged the release of Cu2+ at the same time. The coatings, therefore, exhibited stable antibacterial performance at varied service conditions.

Sol-gel-derived hard coatings from tetraethoxysilane and organoalkoxysilanes bearing zwitterionic and isothiazolinone groups and their antifouling behaviors.

Current environmentally friendly marine antifouling (AF) coatings are mainly polymeric with a relatively low hardness. Hard sol-gel-derived AF coatings for underwater robot-cleaning are seldom used. In this work, two new organoalkoxysilanes, i.e., (N-methoxyacylethyl)-3-aminopropyltriethoxysilane and 2-(2-hydroxy-3-(3-(trimethoxysilyl)propoxy)propyl)benzo[d]isothiazol-3(2H)-one, were synthesized by a facile method. These two precursors were used with tetraethoxysilane (TEOS) to produce three series of hybrid AF coatings with zwitterionic group (Z-χ), antibacterial group (1,2-benzisothiazolin-3-one) (A-χ) and zwitterionic and antibacterial groups (S-χ) by a sol-gel process. The hardness of the coatings was measured using a pencil hardness tester and the AF behaviors of the coatings were examined by laboratory and field assays. A pencil hardness up to 5 H was achieved and slight deterioration was observed after 9 months of immersion in artificial seawater for the A-χ and S-χ coatings at a sufficiently high TEOS content. A synergistic effect between the zwitterion and antimicrobial agents existed but was not obvious. A higher TEOS content led to a higher hardness and better AF performance regardless of the type of AF group. Even with the same biofilm formation after field assay, coatings with a higher TEOS content exhibited a better resistance to mussel settlement.

Pickering emulsion approach for fabrication of waterborne cross-linkable polydimethylsiloxane coatings with high mechanical performance.

HYPOTHESIS: The Pickering emulsion approach has been frequently employed to fabricate various emulsions. However, the direct formation of cross-linked polymer films from Pickering emulsions and double functions (emulsified and mechanical reinforcement) of Pickering agents have not been sufficiently reported. EXPERIMENTS: Fumed silica was co-modified with vinyltrimethoxysilane (VTMS) and hexamethyl disilylamine (HMDS) and was further adopted to emulsify vinyl or hydrogen dimethicone. The as-obtained Pickering emulsions were mixed with Karstedt catalyst capsules to produce one-component waterborne cross-linkable polydimethylsiloxane (PDMS) coatings that were subsequently transformed into elastic films after drying at ambient temperature. FINDINGS: The co-modification of fumed silica with VTMS/HMDS is shown to balance the Pickering emulsion effect and film-forming ability of the coatings. Greater amounts of grafted VTMS/HMDS or higher modified silica dosages demonstrated better Pickering emulsion effects. Nevertheless, because Pickering agents hinder the coalescence of silicone oil droplets, the appropriate modified silica concentration is crucial for achieving the highest cross-link density and thus the highest mechanical strength. The grafted CC groups can endow the modified silica with hydrosilylation reactivity and can thus additionally contribute to the mechanical performance of PDMS film. In addition, the Pickering emulsion approach is shown to be superior to the traditional emulsion approach for acquiring waterborne coatings with high mechanical performance.

One-component waterborne in vivo cross-linkable polysiloxane coatings for artificial skin.

Polysiloxane-based artificial skins are able to emulate the mechanical and barrier performance of human skin. However, they are usually fabricated in vitro, restricting their diverse applications on human body. Herein, we presented one-component waterborne cross-linkable polysiloxane coatings prepared from emulsified vinyl dimethicone, emulsified hydrogen dimethicone, and Karstedt catalyst capsules that were first synthesized by solvent evaporation method. The coating had good storage stability and meanwhile could form an elastic film quickly through merging of silicone oil droplets and subsequent hydrosilylation reaction. It was found that the mass ratio of vinyl dimethicone emulsion/hydrogen dimethicone emulsion (V/H), and the dosage of Karstedt catalyst capsules (K/(V + H)) were critical to the curing time, morphology, and mechanical properties of the coatings. With appropriate values of V/H and K/(V + H), the polysiloxane film had the mechanical performance comparable to that from solvent-based one. The coating could be topically applied to human skin in vivo and in situ turned into an elastic, invisible thin film with good water resistance. In contrast to those reported polysiloxane materials, the one-component waterborne polysiloxane coating was nontoxic and convenient for in vivo application on human body, making it be a promising candidate as artificial skin in the fields of cosmetics, medical treatment, and E-skin.

Preparation and synergistic antifouling effect of self-renewable coatings containing quaternary ammonium-functionalized SiO2 nanoparticles.

Confronting the complexity of marine biofouling, no single ecofriendly technology has been reported for efficient anti-biofouling. Combination of multiple antifouling factors should be one of the strategies for strengthening the anti-biofouling performance. Here we synthesized quaternary ammonium modified SiO2 nanoparticles (QAS-SiO2) and incorporated them into self-polishing polymer (SP) to get the coatings combining self-renewal ability, micro-nano structured topography, and bactericidal function. The coatings acquired underwater superoleophobic surface after immersion in artificial seawater due to their micro-nano structured surface together with the hydrolyzed SP. In comparison with unmodified SiO2, QAS-SiO2 had better compatibility with SP and caused less increment of self-polishing rate. Synergistic antifouling effect was interestingly observed between self-renewal ability and bactericidal function in both the laboratory assay based on the adhesion of Shewanella loihicas and natural field trial. The micro-nano structured topography contributed to underwater superoleophobicity but did not exhibit its impact on antifouling performance. QAS-SiO2 can also slightly inhibit the adhesion of diatoms and reduce the settlement of plantigrades of the mussel. In addition, we also demonstrated the coatings with lower quantity of biofilm exhibited less settlement of plantigrades of mussel.

Polyurethane, epoxy resin and polydimethylsiloxane altered biofilm formation and mussel settlement.

In many environments, biofilms are a major mode and an emergent form of microbial life. Biofilms play crucial roles in biogeochemical cycling and invertebrate recruitment in marine environments. However, relatively little is known about how marine biofilms form on different substrata and about how these biofilms impact invertebrate recruitment. Here, we performed a comparative analysis of a 28-day-old biofilm community on non-coated (a control glass) and coated substrata (polyurethane (PU), epoxy resin (EP) and polydimethylsiloxane (PDMS)) and examined the settlement of Mytilus coruscus plantigrades on these biofilms. PU, EP and PDMS deterred the development of marine biofilms by reducing the biofilm biomass including the biofilm dry weight, cell density of the bacteria and diatoms and chlorophyll a concentrations. Further analysis of bacterial community revealed that EP altered the bacterial community composition compared with that on the glass substrata by reducing the relative abundance of Ruegeria (Alphaproteobacteria) and by increasing the relative abundance of Methylotenera (Betaproteobacteria) and Cyanobacteria in the biofilms. However, bacterial communities developed on PU and PDMS, as well as glass and PU, EP and PDMS did not exhibit differences from each other. The M. coruscus settlement rates on biofilms on PU, EP and PDMS were reduced by 20-41% compared with those on the glass after 28 days. Thus, the tested coatings impacted the development of marine biofilms by altering the biofilm biomass and/or the bacterial community composition. The mussel settlements decreased in the biofilms that formed on the coatings compared with those on non-coated glass.

Seawater-Induced Healable Underwater Superoleophobic Antifouling Coatings.

Creating an artificial surface, mimicking a live fish scale that repels oil underwater and with self-healing properties, would be significant for the development of nontoxic marine antifouling coatings. Here, we report a seawater-induced strategy to create in situ an underwater superoleophobic surface, starting from the coatings of a self-polishing polymer and seawater-responsive polymer-grafted SiO2 nanoparticles. The coatings' surfaces were able to renew in artificial seawater through the hydrolysis of the superficial self-polishing polymer and its subsequent dissolution. Particularly, the grafted poly(triisopropylsilyl acrylate- co-3-methacryloxypropyltrimethoxysilane) chains could transform into hydrophilic ones via seawater-induced hydrolysis, which additionally strengthened the oil-repellency (zero oil adhesive force) and endowed the surface with excellent antiprotein adsorption characteristics. Because the hydrolysis was limited to the superficial layer of the coatings, it could avoid the water-swelling that instead occurs with conventional underwater superoleophobic coatings, with significant benefits to its durability. We believe that the seawater-induced renewal of underwater superoleophobic surfaces will be useful in extreme marine environments.

Dual-Porosity Hollow Carbon Spheres with Tunable Through-Holes for Multi-Guest Delivery.

Dual-porosity hollow carbon spheres (DPHCs) with small mesopores (2-4 nm) and large through-holes (20-30 nm) in shells were successfully synthesized using colloidal silica as the template, small silica nanoparticles as nanomasks, and nontoxic dopamine as the carbon precursor followed by post-carbonization and etching. The synthesized DPHCs were further oxidized to be hydrophilic and then used to simultaneously deliver the protein bovine serum albumin (21 × 4 × 14 nm3) and the small molecule doxorubicin (<1 nm), which exhibited a high loading capacity of 689.4 and 1421.2 mg/g, respectively. The release of these two guest molecules can be controlled independently under the stimuli of heat and acidity. In vitro and in vivo experiments also proved that the DPHCs are promising for the co-delivery of multiple cargoes of different sizes.

Bioinspired Design of Three-Dimensional Ordered Tribrachia-Post Arrays with Re-entrant Geometry for Omniphobic and Slippery Surfaces.

Hydro- and oleophobic (namely, omniphobic) coatings or surfaces have many important applications, but tremendous challenges in fabrication aspects still remain. Herein, we report a bioinspired design and nanofabrication of three-dimensional (3D) tribrachia-post arrays with re-entrant geometry (3D TPARG) for superhydrophobic and oleophobic polymer films or surfaces. By simply controlling the temperatures and time to treat silica colloidal templates, we can readily fabricate 3D ordered polymer arrays of tribrachia-posts or hexagonal tribrachia-posts with re-entrant geometries that resemble the skin of a springtail insect after the template is removed. These polymer surfaces exhibit excellent and self-healing superhydrophobicity and oleophobicity even against temperature, acids, alkalis, and mechanical damage. Moreover, their liquid-infused nanostructured surfaces still display very good liquid-sliding ability for water and oils. Our 3D TPARG design strategy may help the development of omniphobic polymer coatings or surfaces for practical applications in self-cleaning surfaces, liquid transport, antifouling materials, and many other important fields.

Silver Nanoparticles Impact Biofilm Communities and Mussel Settlement.

Silver nanoparticles (AgNPs) demonstrating good antimicrobial activity are widely used in many fields. However, the impact of AgNPs on the community structures of marine biofilms that drive biogeochemical cycling processes and the recruitment of marine invertebrate larvae remains unknown. Here, we employed MiSeq sequencing technology to evaluate the bacterial communities of 28-day-old marine biofilms formed on glass, polydimethylsiloxane (PDMS), and PDMS filled with AgNPs and subsequently tested the influence of these marine biofilms on plantigrade settlement by the mussel Mytilus coruscus. AgNP-filled PDMS significantly reduced the dry weight and bacterial density of biofilms compared with the glass and PDMS controls. AgNP incorporation impacted bacterial communities by reducing the relative abundance of Flavobacteriaceae (phylum: Bacteroidetes) and increasing the relative abundance of Vibrionaceae (phylum: Proteobacteria) in 28-day-old biofilms compared to PDMS. The settlement rate of M. coruscus on 28-day-old biofilms developed on AgNPs was lower by >30% compared to settlement on control biofilms. Thus, the incorporation of AgNPs influences biofilm bacterial communities in the marine environment and subsequently inhibits mussel settlement.

Polymer Colloidal Sphere-Based Hybrid Solid Immersion Lens for Optical Super-resolution Imaging.

The optical microscope is a widely used real-time investigation tool, but usually suffers from low resolution due to the Abbe diffraction limit. Herein, we design and successfully synthesize ZrO2/polymer hybrid colloidal microspheres with as high as 47.5 wt % inorganic nanoparticles by suspension polymerization of 9,9'-bis[4-(2-acryloyloxyethyloxy)phenyl]fluorene (BAEPF). Owing to the homogeneous dispersion, high density, and high refractive index of inorganic nanoparticles and deformability of polymers, the obtained ZrO2/poly(BAEPF) hybrid colloidal microspheres have a high refractive index, optical transparency, and controllable curvature and thus can be directly used as a hybrid solid immersion lens (hSIL) for the optical microscope, achieving super-resolution imaging of 50 nm and even 45 nm under a standard white light or blue light optical microscope, which is far beyond the diffraction limit for visible light optical microscopes. Our hSIL design concept and strategy demonstrate efficient, fast, and solid practical potentials for optical super-resolution imaging and may also create another application possibility for polymer colloidal spheres.

Recent Development of Durable and Self-Healing Surfaces with Special Wettability.

Artificial special wetting surfaces have drawn much interest due to their important applications in many fields. Nevertheless, tremendous challenges still remain for the fabrication of wetting surfaces with durable and self-healing properties. Here, recent progress of durable, self-healing wetting surfaces is highlighted by discussing the fabrications of several typical wetting surfaces including superhydrophobic surfaces, superamphiphobic surfaces, underwater superoleophobic surfaces, and high hydrophilic antifouling surfaces based on expertise and related research experience. To conclude, some perspectives on the future research and development of these special wetting surfaces are presented.

Self-Healing Underwater Superoleophobic and Antibiofouling Coatings Based on the Assembly of Hierarchical Microgel Spheres.

Marine biofouling has been plaguing people for thousands of years. While various strategies have been developed for antifouling (including superoleophobic) coatings, none of these exhibits self-healing properties because the bestowal of a zoetic self-repairing function to lifeless artificial water/solid interfacial materials is usually confronted with tremendous challenges. Here, we present a self-repairing underwater superoleophobic and antibiofouling coating through the self-assembly of hydrophilic polymeric chain modified hierarchical microgel spheres. The obtained surface material not only has excellent underwater superoleophobicity but also has very good subaqueous antibiofouling properties. More importantly, this surface material can recover the oil- and biofouling-resistant properties once its surface is mechanically damaged, similar to the skins of some marine organisms such as sharks or whales. This approach is feasible and easily mass-produced and could open a pathway and possibility for the fabrication of other self-healing functional water/solid interfacial materials.

Controllable Synthesis and Surface Wettability of Flower-Shaped Silver Nanocube-Organosilica Hybrid Colloidal Nanoparticles.

Synthesis of hybrid colloidal particles with complex and hierarchical structures is attracting much interest theoretically and technically in recent years, but still remains a tremendous challenge. Here, we present a mild and controllable wet-chemical method for the synthesis of silver nanocube (Ag NC)-organosilica hybrid particles with finely tuned numbers (with one, two, three, four, five, or six) and sizes of organosilica petals, by simply controlling the affinity with Ag NC/nature, amount, and prehydrolysis process of alkoxysilanes. The morphologies of hybrid colloidal particles have an obvious influence on the surface wettability of the hybrid particle-based films. More and larger organosilica petals can increase the surface hydrophobicity of the hybrid particle-based films.

Light diffusing films fabricated by strawberry-like PMMA/SiO2 composite microspheres for LED application.

This paper presents a facile method to fabricate volumetric light diffusing films with high transmittance and haze simultaneously by mimicking the micro- and nanostructure of compound eyes. Strawberry-like polymethyl methacrylate/SiO2 composite microspheres were first prepared via the electrostatic attraction between positively charged PMMA spheres and negatively charged SiO2 nanoparticles, and further blended with polyacrylate latex to produce light diffusing coatings. A novel light diffusing film with hemispherical surface was built by casting the light diffusing coatings on optical-grade PET film. Effects of the sizes of PMMA spheres and SiO2 nanoparticles on the optical properties of light diffusing film were investigated by a haze meter and application on a LED lamp. The best result (transmittance 94.6% and haze 84.2%) was achieved for the strawberry-like composite microspheres based on 1 µm PMMA spheres and 50 nm SiO2 nanoparticles. The light-diffusing mechanism of the strawberry-like microspheres in the film was discussed.

Facile fabrication of carbon spheres with tunable morphologies from novel polymeric carbon precursors.

This study presents a facile and general method for fabrication of carbon spheres with tunable morphologies based on the sol-gel reaction of a novel polymeric carbon precursor. The carbon precursor was fabricated by the synthesis of resole, a low-molecular weight polymer of phenol and formaldehyde, and then the modification with poly(ethylene glycol) monomethyl ether (PEG). By turning the modification degree of resole with different amounts of PEG and the hydrolysis and condensation reactions of this precursor, carbon spheres with various morphologies, including regular spheres, hollow spheres of different pore sizes, and raspberry- and peanut-like spheres, were produced easily. This should be attributed to the condensation, self-assembly, and phase separation of the new polymeric carbon precursors during the sol-gel process.

Facile fabrication of self-repairing superhydrophobic coatings.

A self-repairing superhydrophobic organic coating comprising polystyrene, fluorinated poly(methylsiloxane), fluorinated alkyl silane modified silica nanoparticles and photocatalytic titania nanoparticles shows self-repairing ability after mechanical damage, photocatalytic self-cleaning performance, and thus long-term outdoor durability.

Porous nickel hydroxide-manganese dioxide-reduced graphene oxide ternary hybrid spheres as excellent supercapacitor electrode materials.

This paper reports the first nickel hydroxide-manganese dioxide-reduced graphene oxide (Ni(OH)2-MnO2-RGO) ternary hybrid sphere powders as supercapacitor electrode materials. Due to the abundant porous nanostructure, relatively high specific surface area, well-defined spherical morphology, and the synergetic effect of Ni(OH)2, MnO2, and RGO, the electrodes with the as-obtained Ni(OH)2-MnO2-RGO ternary hybrid spheres as active materials exhibited significantly enhanced specific capacitance (1985 F·g(-1)) and energy density (54.0 Wh·kg(-1)), based on the total mass of active materials. In addition, the Ni(OH)2-MnO2-RGO hybrid spheres-based asymmetric supercapacitor also showed satisfying energy density and electrochemical cycling stability.

Recent advances in applications and performance of inorganic hollow spheres in devices.

Inorganic hollow spheres have wide, important applications due to their unique structure, controllable morphology, and composition. Recent developments in the application and performance of inorganic hollow spheres in solar cells, UV photodectors, gas sensors, and supercapacitors are discussed. For each inorganic hollow sphere based device, a critical comment is given based on knowledge and related research experience. Some perspectives on the future research and development of these inorganic-hollow-sphere devices are given.

Facile synthesis, self-assembly, and photoelectrical performance of SrTiO3 hollow spheres with open holes.

This paper presents a facile method to synthesize monodisperse SrTiO3 hollow spheres with one or two openings through a template-assisted approach. These hollow spheres were further self-assembled into densely packed nanofilms at a "hexane-water" interface. TEM, SEM, HRTEM, XRD, etc., were employed to characterize the morphology and structure of the SrTiO3 hollow spheres as well as the corresponding nanofilms. The nanofilm-based photodevice displayed considerably higher sensitivity to UV than visible light and dark.