A New Class of Polyion Complex Vesicles (PIC-somes) to Improve Antimicrobial Activity of Tobramycin in Pseudomonas Aeruginosa Biofilms.

Pseudomonas aeruginosa (PA) is a major healthcare concern due to its tolerance to antibiotics when enclosed in biofilms. Tobramycin (Tob), an effective cationic aminoglycoside antibiotic against planktonic PA, loses potency within PA biofilms due to hindered diffusion caused by interactions with anionic biofilm components. Loading Tob into nano-carriers can enhance its biofilm efficacy by shielding its charge. Polyion complex vesicles (PIC-somes) are promising nano-carriers for charged drugs, allowing higher drug loadings than liposomes and polymersomes. In this study, a new class of nano-sized PIC-somes, formed by Tob-diblock copolymer complexation is presented. This approach replaces conventional linear PEG with brush-like poly[ethylene glycol (methyl ether methacrylate)] (PEGMA) in the shell-forming block, distinguishing it from past methods. Tob paired with a block copolymer containing hydrophilic PEGMA induces micelle formation (PIC-micelles), while incorporating hydrophobic pyridyldisulfide ethyl methacrylate (PDSMA) monomer into PEGMA chains reduces shell hydrophilicity, leads to the formation of vesicles (PIC-somes). PDSMA unit incorporation enables unprecedented dynamic disulfide bond-based shell cross-linking, significantly enhancing stability under saline conditions. Neither PIC-somes nor PIC-micelles show any relevant cytotoxicity on A549, Calu-3, and dTHP-1 cells. Tob's antimicrobial efficacy against planktonic PA remains unaffected after encapsulation into PIC-somes and PIC-micelles, but its potency within PA biofilms significantly increases.

Single-Polymer Friction Force Microscopy of dsDNA Interacting with a Nanoporous Membrane.

Surface-grafted polymers can reduce friction between solids in liquids by compensating the normal load with osmotic pressure, but they can also contribute to friction when fluctuating polymers entangle with the sliding counter face. We have measured forces acting on a single fluctuating double-stranded DNA polymer, which is attached to the tip of an atomic force microscope and interacts intermittently with nanometer-scale methylated pores of a self-assembled polystyrene-block-poly(4-vinylpyridine) membrane. Rare binding of the polymer into the pores is followed by a stretching of the polymer between the laterally moving tip and the surface and by a force-induced detachment. We present results for the velocity dependence of detachment forces and of attachment frequency and discuss them in terms of rare excursions of the polymer beyond its equilibrium configuration.

Bifunctional Carbanionic Synthesis of Fully Bio-Based Triblock Structures Derived from ß-Farnesene and ll-Dilactide: Thermoplastic Elastomers.

Current environmental challenges and the shrinking fossil-fuel feedstock are important criteria for the next generation of polymer materials. In this context, we present a fully bio-based material, which shows promise as a thermoplastic elastomer (TPE). Due to the use of ß-farnesene and L-lactide as monomers, bio-based feedstocks, namely sugar cane and corn, can be used. A bifunctional initiator for the carbanionic polymerization was employed, to permit an efficient synthesis of ABA-type block structures. In addition, the "green" solvent MTBE (methyl tert-butyl ether) was used for the anionic polymerisation, enabling excellent solubility of the bifunctional anionic initiator. This afforded low dispersity (D=1.07 to 1.10) and telechelic polyfarnesene macroinitiators. These were employed for lactide polymerization to obtain H-shaped triblock copolymers. TEM and SAXS revealed clearly phase-separated morphologies, and tensile tests demonstrated elastic mechanical properties. The materials featured two glass transition temperatures, at - 66 °C and 51 °C as well as gyroid or cylindrical morphologies, resulting in soft elastic materials at room temperature.

Redox- and pH-Responsive Polymersomes with Ferrocene Moieties Exhibiting Peroxidase-like, Chemoenzymatic Activity and H2O2-Responsive Release Behavior.

The development of compartments for the design of cascade reactions in a local space requires a selective spatiotemporal control. The combination of enzyme-loaded polymersomes with enzymelike units shows a great potential in further refining the diffusion barrier and the type of reactions in nanoreactors. Herein, pH-responsive and ferrocene-containing block copolymers were synthesized to realize pH-stable and multiresponsive polymersomes. Permeable membrane, peroxidase-like behavior induced by the redox-responsive ferrocene moieties and release properties were validated using cyclovoltammetry, dye TMB assay, and rupture of host-guest interactions with ß-cyclodextrin, respectively. Due to the incorporation of different block copolymers, the membrane permeability of glucose oxidase-loaded polymersomes was changed by increasing extracellular glucose concentration and in TMB assay, allowing for the chemoenzymatic cascade reaction. This study presents a potent synthetic, multiresponsive nanoreactor platform with tunable (e.g., redox-responsive) membrane properties for potential application in therapeutics.

Nanoporous Block Copolymer Membranes with Enhanced Solvent Resistance Via UV-Mediated Cross-Linking Strategies.

In this work, a block copolymer (BCP) consisting of poly((butyl methacrylate-co-benzophenone methacrylate-co-methyl methacrylate)-block-(2-hydroxyethyl methacrylate)) (P(BMA-co-BPMA-co-MMA)-b-P(HEMA)) is prepared by a two-step atom-transfer radical polymerization (ATRP) procedure. BCP membranes are fabricated applying the self-assembly and nonsolvent induced phase separation (SNIPS) process from a ternary solvent mixture of tetrahydrofuran (THF), 1,4-dioxane, and dimethylformamide (DMF). The presence of a porous top layer of the integral asymmetric membrane featuring pores of about 30 nm is confirmed via scanning electron microscopy (SEM). UV-mediated cross-linking protocols for the nanoporous membrane are adjusted to maintain the open and isoporous top layer. The swelling capability of the noncross-linked and cross-linked BCP membranes is investigated in water, water/ethanol mixture (1:1), and pure ethanol using atomic force microscopy, proving a stabilizing effect of the UV cross-linking on the porous structures. Finally, the influence of the herein described cross-linking protocols on water-flux measurements for the obtained membranes is explored. As a result, an increased swelling resistance for all tested solvents is found, leading to an increased water flux compared to the pristine membrane. The herein established UV-mediated cross-linking protocol is expected to pave the way to a new generation of porous and stabilized membranes within the fields of separation technologies.

Transparent Polymer Opal Thin Films with Intense UV Structural Color.

We report on shear-ordered polymer photonic crystals demonstrating intense structural color with a photonic bandgap at 270 nm. Our work examines this UV structural color, originating from a low refractive index contrast polymer composite system as a function of the viewing angle. We report extensive characterization of the angle-dependent nature of this color in the form of 'scattering cones', which showed strong reflectivity in the 275-315 nm range. The viewing range of the scattering was fully quantified for a number of planes and angles, and we additionally discuss the unique spectral anisotropy observed in these structures. Such films could serve as low-cost UV reflection coatings with applications in photovoltaics due to the fact of their non-photobleaching and robust mechanical behavior in addition to their favorable optical properties.

Dye-Loaded Mechanochromic and pH-Responsive Elastomeric Opal Films.

In this work, the preparation and fabrication of elastomeric opal films revealing reversible mechanochromic and pH-responsive features are reported. The core-interlayer-shell (CIS) particles are synthesized via stepwise emulsion polymerization leading to hard core (polystyrene), crosslinked interlayer (poly(methyl methacrylate-co-allyl methacrylate), and soft poly(ethyl acrylate-co-butyl acrylate-co-(2-hydroxyethyl) methacrylate) shell particles featuring a size of 294.9 ± 14.8 nm. This particle architecture enables the application of the melt-shear organization technique leading to elastomeric opal films with orange, respectively, green brilliant reflection colors dependent on the angle of view. Moreover, the hydroxyl moieties as part of the particle shell are advantageously used for subsequent thermally induced crosslinking reactions enabling the preparation of reversibly tunable mechanochromic structural colors based on Bragg's law of diffraction. Additionally, the CIS particles can be loaded upon extrusion or chemically by a postfunctionalization strategy with organic dyes implying pH-responsive features. This convenient protocol for preparing multi-responsive, reversibly stretch-tunable opal films is expected to enable a new material family for anti-counterfeiting applications based on external triggers.

Temperature Variation Enables the Design of Biobased Block Copolymers via One-Step Anionic Copolymerization.

A one-pot approach for the preparation of diblock copolymers consisting of polystyrene and polymyrcene blocks is described via a temperature-induced block copolymer (BCP) formation strategy. A monomer mixture of styrene and myrcene is employed. The unreactive nature of myrcene in a polar solvent (tetrahydrofuran) at -78 °C enables the sole formation of active polystyrene macroinitiators, while an increase of the temperature (-38 °C to room temperature) leads to poly(styrene-block-myrcene) formation due to polymerization of myrcene. Well-defined BCPs featuring molar masses in the range of 44-117.2 kg mol-1 with dispersities, Ð, of 1.09-1.21, and polymyrcene volume fractions of 30-64% are accessible. Matrix assisted laser desorption ionization-time of flight mass spectrometry measurements reveal the temperature-controlled polymyrcene block formation, while both transmission electron microscopy and small-angle X-ray scattering measurements prove the presence of clearly microphase-separated, long range-ordered domains in the block copolymers. The temperature-controlled one-pot anionic block copolymerization approach may be general for other terpene-diene monomers.

Rings and Chains: Synthesis and Characterization of Polyferrocenylmethylene.

The synthesis and characterization of polyferrocenylmethylene (PFM) starting from dilithium 2,2-bis(cyclopentadienide)propane and a Me2 C[1]magnesocenophane is reported. Molecular weights of up to Mw  = 11 700 g mol-1 featuring a dispersity, Ð, of 1.40 can be achieved. The material is studied by different methods comprising nuclear magnetic resonance (NMR) spectroscopy, matrix-assisted laser desorption/ionization time of flight (MALDI-ToF) mass spectrometry, differential scanning calorimetry (DSC), and thermogravimetric analysis (TGA) measurements elucidating the molecular structure and thermal properties of these novel polymers. Moreover, cyclic voltammetry (CV) reveals quasi-reversible oxidation and reduction behavior and communication between the iron centers. Also, the crystal structure of a related cyclic hexamer is presented.

Systematic study of precursor effects on structure and oxygen reduction reaction activity of FeNC catalysts.

In this work, the effect of porphyrin loading and template size is varied systematically to study its impact on the oxygen reduction reaction (ORR) activity and selectivity as followed by rotating ring disc electrode experiments in both acidic and alkaline electrolytes. The structural composition and morphology are investigated by 57Fe Mössbauer spectroscopy, transmission electron microscopy, Raman spectroscopy and Brunauer-Emmett-Teller analysis. It is shown that with decreasing template size, specifically the ORR performance towards fuel cell application gets improved, while at constant area loading of the iron precursor (here expressed in number of porphyrin layers), the iron signature does not change much. Moreover, it is well illustrated that too large area loadings result in the formation of undesired side phases that also cause a decrease in the performance, specifically in acidic electrolyte. Thus, if the impact of morphology is the focus of research it is important to consider the area loading rather than its weight loading. At constant weight loading, beside morphology the structural composition can also change and impact the catalytic performance. This article is part of the theme issue 'Bio-derived and bioinspired sustainable advanced materials for emerging technologies (part 2)'.

The quantitative impact of fluid vs. solid interfaces on the catalytic performance of pickering emulsions.

Pickering emulsions (PEs), i.e. particle stabilized emulsions, are used as reaction environments in biphasic catalysis for the hydroformylation of 1-dodecene into tridecanal using the catalyst rhodium (Rh)-sulfoxantphos (SX). The present study connects the knowledge about particle-catalyst interactions and PE structure with the reaction results. It quantifies the efficiency of the catalytic performance of the catalyst localized in the voids between the particles (liquid-liquid interface) and the catalyst adsorbed on the particle surface (liquid-solid interface) using a new numerical approach. First, it is ensured that the overall packing density and geometry at the droplet interface and the size of the water droplets of the resulting w/o PEs are predictable. Second, it is shown that approximately all particles assemble at the droplet surface after emulsion preparation and neither the packing parameter nor the droplet size change with the particle surface charge or size when the total particle cross section is kept constant. Third, studies on the influence of the catalyst on the emulsion structure reveal that irrespective of the particle charge the surface active and negatively charged catalyst Rh-SX reduces the PE droplet size significantly and decreases the particle packing parameter from s = 0.91 (hexagonal packing in 2D) to s = 0.69 (shattered structure). In this latter case, large voids of the free w/o interface form and become covered with the catalyst. With a deep knowledge about the PE structure the reaction efficiencies of the liquid-liquid vs. the solid-liquid interface are quantified. By excluding any other influence factors, it is shown that the activity of the catalyst is the same at the fluid and solid interface and the performance of the reaction is explained by the geometry of the system. After the reaction, the catalyst retention via membrane filtration is shown to be successfully achieved without damaging the emulsions. This enables the continuous recovery of the catalyst, i.e. the most expensive compound in PE-based catalytic reactions, being a crucial criterion for industrial applications.

Embedding Photoacids into Polymer Opal Structures: Synergistic Effects on Optical and Stimuli-Responsive Features.

Opal films with their vivid structural colors represent a field of tremendous interest and obtained materials offer the possibility for many applications, such as optical sensors or anti-counterfeiting materials. A convenient method for the generation of opal structures relies on the tailored design of core-interlayer-shell (CIS) particles. Within the present study, elastomeric opal films were combined with stimuli-responsive photoacids to further influence the optical properties of structurally colored materials. Starting from cross-linked polystyrene (PS) core particles featuring a hydroxy-rich and polar soft shell, opal films were prepared by application of the melt-shear organization technique. The photoacid tris(2,2,2-trifluoroethyl) 8-hydroxypyrene-1,3,6-trisulfonate (TFEHTS) could be conveniently incorporated during freeze-drying the particle dispersion and prior to the melt-shear organization. Furthermore, the polar opal matrix featuring hydroxylic moieties enabled excited-state proton transfer (ESPT), which is proved by spectroscopic evaluation. Finally, the influence of the photoacid on the optical properties of the 3-dimensional colloidal crystals were investigated within different experimental conditions. The angle dependence of the emission spectra unambiguously shows the selective suppression of the photoacid's fluorescence in its deprotonated state.

The Metallocene Battery: Ultrafast Electron Transfer Self Exchange Rate Accompanied by a Harmonic Height Breathing.

The first all-metallocene rechargeable battery consisting of poly-cobaltocenium/- and poly-ferrocene/reduced graphene oxide composites as anode and cathode was prepared. The intrinsically fast ET self-exchange rate of metallocenes was successfully combined with an efficient ion-percolation achieved by molecular self-assembly. The resulting battery materials show ideal Nernstian behavior, is thickness scalable up to >1.2 C cm-2 , and exhibit high coulombic efficiency at ultrafast rates (200 A g-1 ). Using aqueous LiClO4 , the charge is carried exclusively by the anion. The ClO4 - intercalation is accompanied by a reciprocal height change of the active layers. Principally, volume changes in organic battery materials during charging/discharging are not desirable and represent a major safety issue. However, here, the individual height changes-due to ion breathing-are reciprocal and thus prohibiting any internal pressure build-up in the closed-cell, leading to excellent cycling stability.

Functional Metalloblock Copolymers for the Preparation and In Situ Functionalization of Porous Silica Films.

Stimuli-responsive mesoporous silica films were prepared by evaporation-induced self-assembly through the physical entrapment of a functional metalloblock copolymer structuring agent, which simultaneously served to functionalize the mesopore. After end-functionalization with a silane group, the applied functional metalloblock copolymers were covalently integrated into the silica mesopore wall. In addition, they were partly degraded after the formation of the mesoporous film, which enabled the precise design of accessible mesopores. These polymer-silica hybrid materials exhibited remarkable and gating ionic permselectivity and offer the potential for highly precise pore filling design and combination with high-throughput printing techniques. This in situ functionalization strategy of mesoporous silica using responsive metalloblock copolymers has the potential to improve how we approach the design of complex architectures at the nanoscale for tailored transport. This functionalization strategy paves the way for a variety of technologies based on molecular transport in nanoscale pores, including separation, sensing, catalysis, and energy conversion.

Opposing Temperature Dependence of the Stretching Response of Single PEG and PNiPAM Polymers.

The response of switchable polymer blends and coatings to temperature variation is important for the development of high-performance materials. Although this has been well studied for bulk materials, a proper understanding at the molecular level, in particular for high stretching forces, is still lacking. Here we investigate the molecular details of the temperature-dependent elastic response of two widely used water-soluble polymers, namely, polyethylene glycol (PEG) and poly(N-isopropylacrylamide) (PNiPAM) with a combined approach using atomic force microscopy (AFM) based single molecule force spectroscopy (SMFS) experiments and molecular dynamics (MD) simulations. SMFS became possible by the covalent attachment of long and defined single polymers featuring a functional end group. Most interestingly, varying the temperature produces contrasting effects for PEG and PNiPAM. Surprising as these results might occur at first sight, they can be understood with the help of MD simulations in explicit water. We find that hydration is widely underestimated for the mechanics of macromolecules and that a polymer chain has competing energetic and entropic elastic components. We propose to use the temperature dependence to quantify the energetic behavior for high stretching forces. This fundamental understanding of temperature-dependent single polymer stretching response might lead to innovations like fast switchable polymer blends and coatings with polymer chains that act antagonistically.

Fluoropolymer-Containing Opals and Inverse Opals by Melt-Shear Organization.

The preparation of highly ordered colloidal architectures has attracted significant attention and is a rapidly growing field for various applications, e.g., sensors, absorbers, and membranes. A promising technique for the preparation of elastomeric inverse opal films relies on tailored core/shell particle architectures and application of the so-called melt-shear organization technique. Within the present work, a convenient route for the preparation of core/shell particles featuring highly fluorinated shell materials as building blocks is described. As particle core materials, both organic or inorganic (SiO2) particles can be used as a template, followed by a semi-continuous stepwise emulsion polymerization for the synthesis of the soft fluoropolymer shell material. The use of functional monomers as shell-material offers the possibility to create opal and inverse opal films with striking optical properties according to Bragg's law of diffraction. Due to the presence of fluorinated moieties, the chemical resistance of the final opals and inverse opals is increased. The herein developed fluorine-containing particle-based films feature a low surface energy for the matrix material leading to good hydrophobic properties. Moreover, the low refractive index of the fluoropolymer shell compared to the core (or voids) led to excellent optical properties based on structural colors. The herein described fluoropolymer opals and inverse opals are expected to pave the way toward novel functional materials for application in fields of coatings and optical sensors.

Combining Soft Polysilazanes with Melt-Shear Organization of Core-Shell Particles: On the Road to Polymer-Templated Porous Ceramics.

The preparation of ordered macroporous SiCN ceramics has attracted significant interest and is an attractive area for various applications, e.g., in the fields of catalysis, gas adsorption, or membranes. Non-oxidic ceramics, such as SiCN, own a great stability based on the covalent bonds between the containing elements, which leads to interesting properties concerning resistance and stability at high temperature. Their peculiar properties have become more and more important for a manifold of applications, like catalysis or separation processes, at high temperatures. Within this work, a feasible approach for the preparation of ordered porous materials by taking advantage of polymer-derived ceramics is presented. To gain access to free-standing films consisting of porous ceramic materials, the combination of monodisperse organic polymer-based colloids with diameters of 130 nm and 180 nm featuring a processable preceramic polymer is essential. For this purpose, the tailored design of hybrid organic/inorganic particles featuring anchoring sites for a preceramic polymer in the soft shell material is developed. Moreover, polymer-based core particles are used as sacrificial template for the generation of pores, while the preceramic shell polymer can be converted to the ceramic matrix after thermal treatment. Two different routes for the polymer particles, which can be obtained by emulsion polymerization, are followed for covalently linking the preceramic polysilazane Durazane1800 (Merck, Germany): (i) Free radical polymerization and (ii) atom transfer radical polymerization (ATRP) conditions. These hybrid hard core/soft shell particles can be processed via the so-called melt-shear organization for the one-step preparation of free-standing particle films. A major advantage of this technique is the absence of any solvent or dispersion medium, enabling the core particles to merge into ordered particle stacks based on the soft preceramic shell. Subsequent ceramization of the colloidal crystal films leads to core particle degradation and transformation into porous ceramics with ceramic yields of 18-54%.

Two dedicated class C radical S-adenosylmethionine methyltransferases concertedly catalyse the synthesis of 7,8-dimethylmenaquinone.

Dimethylmenaquinone (DMMK), a prevalent menaquinone (MK) derivative of uncertain function, is characteristic for members of the class Coriobacteriia. Such bacteria are frequently present in intestinal microbiomes and comprise several pathogenic species. The coriobacterial model organism Adlercreutzia equolifaciens was used to investigate the enzymology of DMMK biosynthesis. A HemN-like class C radical S-adenosylmethionine methyltransferase (MenK2) from A. equolifaciens was produced in Wolinella succinogenes or Escherichia coli cells and found to methylate MK specifically at position C-7. In combination with a previously described MK methyltransferase (MqnK/MenK) dedicated to MK methylation at C-8, 7,8-DMMK6 was produced in W. succinogenes. The position of the two methyl groups was confirmed by two-dimensional NMR and midpoint redox potentials of 7-MMK6, 8-MMK6 and 7,8-DMMK6 were determined by cyclic voltammetry. A phylogenetic tree of MenK, MenK2 and HemN proteins revealed a Coriobacteriia-specific MenK2 clade. Using chimeric A. equolifaciens MenK/MenK2 proteins produced in E. coli it was shown that the combined linker and HemN domains determined the site-specificity of methylation. The results suggest that the use of MenK2 as a biomarker allows predicting the ability of DMMK synthesis in microbial species.

Recent Trends in Metallopolymer Design: Redox-Controlled Surfaces, Porous Membranes, and Switchable Optical Materials Using Ferrocene-Containing Polymers.

Metallopolymers with metal functionalities are a unique class of functional materials. Their redox-mediated optoelectronic and catalytic switching capabilities, their outstanding structure formation and separation capabilities have been reported recently. Within this Minireview, the scope and limitations of intriguing ferrocene-containing systems will be discussed. In the first section recent advances in metallopolymer design will be given leading to a plethora of novel metallopolymer architectures. Discussed synthetic pathways comprise controlled and living polymerization protocols as well as surface immobilization strategies. In the following sections, we focus on recent advances and new applications for side-chain and main-chain ferrocene-containing polymers as (i) remote-switchable materials, (ii) smart surfaces, (iii) redox-responsive membranes, and some recent trends in (iv) photonic structures and (v) other optical applications.

Crossover from semi-dilute to densely packed thin polymer films at the air-water interface and structure formation at thin film breakup.

A series of poly(n-butyl acrylate) (PnBA, 5 to 32 kg mol-1) homopolymers and diblock copolymers with poly(ethylene glycol) (PEG, constant molecular weight of 0.3 kg mol-1) is synthesized for the purpose of the investigation of quasi-2D polymer films at the air-water interface. The presented compression isotherms show a transition from θ solvent behavior for PnBA homopolymers to good solvent conditions when the volume fraction of the PEG in the block copolymers is increased by decreasing the molecular weight of PnBA. A transition from a semi-dilute regime to a densely packed layer is observed in the pressure isotherms for all the polymers. In the densely packed films we found first evidence for thin film breakup of a thin polymer film directly at the air-water interface. Combination of results from Brewster-Angle-Microscopy and Surface X-ray scattering provide a consistent picture of the film breakup. Our results suggest a preferred length scale of 2.5 µm. This scenario is analogous to a spinodal mechanism driven by thermal fluctuations of the film height.