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A CaO2 peroxide reservoir in polyether sulfone and poly(vinylidene fluoride) polymer beads enables the haloperoxidase reaction of Bi0.2Ce0.8O1.9 enzyme mimics without external addition of H2O2.

Preventing bacterial adhesion on materials surfaces is an important problem in marine, industrial, medical and environmental fields and a topic of major medical and societal importance. A defense strategy of marine organisms against bacterial colonization relies on the biohalogenation of signaling compounds that interfere with bacterial communication. These reactions are catalyzed by haloperoxidases, a class of metal-dependent enzymes, whose activity can be emulated by ceria nanoparticles. The enzyme-like activity of ceria was enhanced by a factor of 3 through bismuth substitution (Ce1−xBixO2−δ). The solubility of Bi3+ in CeO2 is confined to the range 0 < x < 0.25 under quasi-hydrothermal conditions. The Bi3+ cations are located close to the nanoparticle surface because their ionic radii are larger than those of the tetravalent Ce4+ ions. The synthesis of Ce1−xBixO2−δ (0 < x < 0.25) nanoparticles was upscaled to yields of ∼50 g. The halogenation activity of Ce1−xBixO2−δ was demonstrated with phenol red assays. The maximum activity for x ≈ 0.2 is related to the interplay of the ζ-potential of surface-engineered Ce1−xBixO2−δ nanoparticles and their BET surface area. Ce0.80Bi0.20O1.9 nanoparticles with optimized activity were incorporated in polyethersulfone beads, which are typical constituents of water filter membrane supports. Although Ce1−xBixO2−δ nanoparticles are not bactericidal on their own, naked Ce1−xBixO2−δ nanoparticles and polyethersulfone/Ce1−xBixO2−δ nanocomposites showed a strongly reduced bacterial coverage. We attribute the decreased adhesion of the Gram-negative soil bacterium Pseudomonas aeruginosa and of Phaeobacter gallaeciensis, a primary bacterial colonizer in marine biofilms, to the formation of halogenated signaling compounds. No biocides are needed, H2O2 (formed in daylight) and halide are the only substrates required. The haloperoxidase-like activity of Ce1−xBixO2−δ may be a promising starting point for the development of environmentally friendly, “green” nanocomposites, when the use of conventional biocides is prohibited.

Preventing bacteria from adhering to material surfaces is an important technical problem and a major cause of infection. One of nature's defense strategies against bacterial colonization is based on the biohalogenation of signal substances that interfere with bacterial communication. Biohalogenation is catalyzed by haloperoxidases, a class of metal-dependent enzymes whose activity can be mimicked by ceria nanoparticles. Transparent CeO

Functional microgels provide a versatile basis for synthetic in vitro platforms as alternatives to animal experiments. The tuning of the physical, chemical, and biological properties of synthetic microgels can be achieved by blending suitable polymers and formulating them such to reflect the heterogenous and complex nature of biological tissues. Based on this premise, this paper introduces the development of volume-switchable core-shell microgels as 3D templates to enable cell growth for microtissue applications, using a systematic approach to tune the microgel properties based on a deep conceptual and practical understanding. Microscopic microgel design, such as the tailoring of the microgel size and spherical shape, is achieved by droplet-based microfluidics, while on a nanoscopic scale, a thermoresponsive polymer basis, poly(N-isopropylacrylamide) (PNIPAAm), is used to provide the microgel volume switchability. Since PNIPAAm has only limited cell-growth promoting properties, the cell adhesion on the microgel is further improved by surface modification with polydopamine, which only slightly affects the microgel properties, thereby simplifying the system. To further tune the microgel thermoresponsiveness, different amounts of N-hydroxyethylacrylamide are incorporated into the PNIPAAm network. In a final step, cell growth on the microgel surface is investigated, both at a single microgel platform and in spheroidal cell structures.

Modifying the surfaces of metal oxide nanoparticles (NPs) with monolayers of ligands provides a simple and direct method to generate multifunctional coatings by altering their surface properties. T...

A facile and chemical specific method to synthesize highly reduced graphene oxide (HRG) and Pd (HRG@Pd) nanocomposite is presented. The HRG surfaces are tailored with amine groups using 1-aminopyrene (1-AP) as functionalizing molecules. The aromatic rings of 1-AP sit on the basal planes of HRG through π–π interactions, leaving amino groups outwards (similar like self-assembled monolayer on 2D substrates). The amino groups provide the chemically specific binding sites to the Pd nucleation which subsequently grow into nanoparticles. HRG@Pd nanocomposite demonstrated both uniform distribution of Pd nanoparticles on HRG surface as well as excellent physical stability and dispersibility. The surface functionalization was confirmed using, ultraviolet–visible (UV–Vis), Fourier transform infra-red and Raman spectroscopy. The size and distribution of Pd nanoparticles on the HRG and crystallinity were confirmed using high-resolution transmission electron microscopy and powder X-ray diffraction and X-ray photoelectron spectroscopy. The catalytic efficiency of highly reduced graphene oxide-pyrene-palladium nanocomposite (HRG-Py-Pd) is tested towards the Suzuki coupling reactions of various aryl halides. The kinetics of the catalytic reaction (Suzuki coupling) using HRG-Py-Pd nanocomposite was monitored using gas chromatography (GC).

The Magneli phase V6O11 was synthesized in gram amounts from a powder mixture of V6O11/V7O13 and vanadium metal, using the spark plasma sintering (SPS) technique. Its structure was determined with synchrotron X-ray powder diffraction data from a phase-pure sample synthesized by conventional solid-state synthesis. A special feature of Magneli-type oxides is a combination of crystallographic shear and intrinsic disorder that leads to relatively low lattice thermal conductivities. SPS prepared V6O11 has a relatively low thermal conductivity of κ = 2.72 ± 0.06 W (m K)-1 while being a n-type conductor with an electrical conductivity of σ = 0.039 ± 0.005 (μΩ m)-1, a Seebeck coefficient of α = -(35 ± 2) μV K-1, which leads to a power factor of PF = 4.9 ± 0.8 × 10-5W (m K2)-1 at ∼600 K. Advances in the application of Magneli phases are mostly hindered by synthetic and processing challenges, especially when metastable and nanostructured materials such as V6O11 are involved. This study gives insight into the complications of SPS-assisted synthesis of complex oxide materials, provides new information about the thermal and electrical properties of vanadium oxides at high temperatures, and supports the concept of reducing the thermal conductivity of materials with structural building blocks such as crystallographic shear (CS) planes.

Modifying the surfaces of metal oxide nanoparticles (NPs) with monolayers of ligands provides a simple and direct method to generate multifunctional coatings by altering their surface properties. This works best if the composition of the monolayers can be controlled. Mussel-inspired, noninnocent catecholates stand out from other ligands like carboxylates and amines because they are redox-active and allow for highly efficient surface binding and enhanced electron transfer to the surface. However, a comprehensive understanding of their surface chemistry, including surface coverage and displacement of the native ligand, is still lacking. Here, we unravel the displacement of oleate (OA) ligands on hydrophobic, OA-stabilized TiO

The Magnéli phase V

Transition-metal oxide nanoparticles and molecular coordination compounds are highlighted as functional mimics of halogenating enzymes. These enzymes are involved in halometabolite biosynthesis. Their activity is based upon the formation of hypohalous acids from halides and hydrogen peroxide or oxygen, which form bioactive secondary metabolites of microbial origin with strong antibacterial and antifungal activities in follow-up reactions. Therefore, enzyme mimics and halogenating enzymes may be valuable tools to combat biofilm formation. Here, halogenating enzyme models are briefly described, enzyme mimics are classified according to their catalytic functions, and current knowledge about the settlement chemistry and adhesion of fouling organisms is summarized. Enzyme mimics with the highest potential are showcased. They may find application in antifouling coatings, indoor and outdoor paints, polymer membranes for water desalination, or in aquacultures, but also on surfaces for food packaging, door handles, hand rails, push buttons, keyboards, and other elements made of plastic where biofilms are present. The use of natural compounds, formed in situ with nontoxic and abundant metal oxide enzyme mimics, represents a novel and efficient "green" strategy to emulate and utilize a natural defense system for preventing bacterial colonization and biofilm growth.