Composition Regulation by Flow Copolymerization of Methyl Methacrylate and Glycidyl Methacrylate with Free Radical Method

It is important to match the feeding ratio of comonomers to the composition ratio in the resulting copolymers as closely as possible in industrial production, where the goal is often to produce more a homogeneous composition in copolymers. In this study, a flow copolymerization system with a conventionally initiated free radical method, together with randomly selected polymerization conditions is investigated. It is succeeded in achieving a closer match between the composition ratio and feeding ratio than previously reported in the copolymerization of styrene with methyl methacrylate and of glycidyl methacrylate with methyl methacrylate, which will widen the range of applications, by precisely controlling the mixing and heating in a flow polymerization apparatus. This is confirmed by the fact that the estimated values of reactivity ratios, r₁ and r₂, which are used in the reaction kinetics of copolymerization, are close to 1.     

Dip Coating of Water-Resistant PEDOT:PSS Films Based on Physical Crosslinking

Water-resistant poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) films are valuable in biomedical applications; however, they typically require crosslinkers to stabilize the films, which can introduce undesired aggregation or phase separation reactions. Herein, a dipping-based process to prepare PEDOT:PSS films on nonplanar surfaces without crosslinker is developed. Sequential soaking of a dip-coated PEDOT:PSS film in ethanol and water imparts water resistance to the film. Microscopic and spectroscopic techniques are used to monitor the process and confirm that the ethanol soaking elutes the excess PSS from the film bulk, which stabilizes the film prior to the water-soaking process. The obtained films act as conductors and semiconductors on curved surfaces, including 3D-printed objects. A film deposited on a curved surface is successfully applied as the channel layer in a neuromorphic organic electrochemical transistor. This approach can enable integrated bioelectronic and neuromorphic applications that can be readily deployed for facile prototyping.     

A DNA-Micropatterned Surface for Propagating Biomolecular Signals by Positional on-off Assembly of Catalytic Nanocompartments

Signal transduction is pivotal for the transfer of information between and within living cells. The composition and spatial organization of specified compartments are key to propagating soluble signals. Here, a high-throughput platform mimicking multistep signal transduction which is based on a geometrically defined array of immobilized catalytic nanocompartments (CNCs) that consist of distinct polymeric nanoassemblies encapsulating enzymes and DNA or enzymes alone is presented. The dual role of single entities or tandem CNCs in providing confined but communicating spaces for complex metabolic reactions and in protecting encapsulated compounds from denaturation is explored. To support a controlled spatial organization of CNCs, CNCs are patterned by means of DNA hybridization to a microprinted glass surface. Specifically, CNC-functionalized DNA microarrays are produced where individual reaction compartments are kept in close proximity by a distinct geometrical arrangement to promote effective communication. Besides a remarkable versatility and robustness, the most prominent feature of this platform is the reversibility of DNA-mediated CNC-anchoring which renders it reusable. Micropatterns of polymer-based nanocompartment assemblies offer an ideal scaffold for the development of the next generation responsive and communicative soft-matter analytical devices for applications in catalysis and medicine.     

PGRP-LB: An Inside View into the Mechanism of the Amidase Reaction

Peptidoglycan recognition proteins (PGRPs) are ubiquitous among animals and play pivotal functions in insect immunity. Non-catalytic PGRPs are involved in the activation of immune pathways by binding to the peptidoglycan (PGN), whereas amidase PGRPs are capable of cleaving the PGN into non-immunogenic compounds. Drosophila PGRP-LB belongs to the amidase PGRPs and downregulates the immune deficiency (IMD) pathway by cleaving meso-2,6-diaminopimelic (meso-DAP or DAP)-type PGN. While the recognition process is well analyzed for the non-catalytic PGRPs, little is known about the enzymatic mechanism for the amidase PGRPs, despite their essential function in immune homeostasis. Here, we analyzed the specific activity of different isoforms of Drosophila PGRP-LB towards various PGN substrates to understand their specificity and role in Drosophila immunity. We show that these isoforms have similar activity towards the different compounds. To analyze the mechanism of the amidase activity, we performed site directed mutagenesis and solved the X-ray structures of wild-type Drosophila PGRP-LB and its mutants, with one of these structures presenting a protein complexed with the tracheal cytotoxin (TCT), a muropeptide derived from the PGN. Only the Y78F mutation abolished the PGN cleavage while other mutations reduced the activity solely. Together, our findings suggest the dynamic role of the residue Y78 in the amidase mechanism by nucleophilic attack through a water molecule to the carbonyl group of the amide function destabilized by Zn²⁺.     

Nanosized‐Layered LiVO2 Prepared from Peroxo‐Polyvanadic Acid and Its Electrochemical Properties

Nanosized‐layered rock‐salt LiVO₂ was prepared by a new method from peroxo‐polyvanadic acid. The X‐ray diffraction pattern was well fitted with the space group R?3m in the Rietveld analysis and the crystallite size was estimated at 47 nm. The electrochemical properties as cathode materials for lithium ion batteries were investigated. The specific capacity of LiVO₂ was greatly improved to 149 mAh/g under the current density of 149 mA/g, in comparison with that of the conventional LiVO₂ below 50 mAh/g prepared by the solid‐state reactions.     

Tight and uniform layer of covalently bound aminoethylophenyl groups perpendicular to gold surface for attachment of biomolecules

Strongly adhered layers of the compound with the primary amino group directed toward the solution were obtained at the gold surface by chronoamperometric electroreduction of 4-aminoethylobenzenodiazonium salt (AEBD) in acetonitrile solution at appropriately selected potential. The used techniques (EQCM, AFM, EIS, PM, IRRAS) showed that the nature and thickness of formed aminoethylophenyl layer strongly depend on the potential applied to the electrode. Electroreduction of AEBD salt at a potential more negative than -0.6 V (vs Ag/AgCl) leads to about monolayer on the gold surface. Additionally, such a layer was very tight and uniform. The electrochemical measurements indicate that the efficient and precise attachment of biomolecules to the aminoethylophenyl layer is only possible when this layer is formed at appropriate potential. This was shown for ss- and dsDNA.     

Dithizone modified gold nanoparticles films for potentiometric sensing

For the first time, application of a membrane composed of gold nanoparticles decorated with complexing ligand for potentiometric sensing is shown. Gold nanoparticles drop cast from a solution form a porous structure on a substrate electrode surface. Sample cations can penetrate the gold nanoparticles layer and interact with ligand acting as a charged ionophore, resulting in Nernstian potentiometric responses. Anchoring of complexing ligand on the gold surface abolishes the necessity of ionophore application. Moreover, it opens the possibility of preparation of potentiometric sensors using chelators of significantly different selectivity patterns further enhanced by the absence of polymeric membrane matrix. This was clearly seen, for example, for gold nanoparticles stabilizing the applied ligand-dithizone-thiol conformation leading to a high potentiometric selectivity toward copper ions, much higher than that of ionophores typically used to induce selectivity for polymeric ion-selective membranes.     

Utilization of a Biodegradable Mulch Sheet Produced from Poly(Lactic Acid)/Ecoflex?/Modified Starch in Mandarin Orange Groves

We have developed a mulch sheet made by inflation molding of PLA, Ecoflex^® and modified starch, which all have different biodegradabilities. A field test of use as an agricultural mulch sheet for mandarin oranges was carried out over two years. The mechanical properties of the mulch sheet were weakened with time during the field test, but the quality of the mandarin oranges increased, a result of the controlled degradation of the sheet. The most degradable modified starch degraded first, allowing control of the moisture on the soil. Accelerator mass spectroscopy was used for evaluation of the biomass carbon ratio. The biomass carbon ratio decreased by degradation of the biobased materials, PLA and modified starch in the mulch sheet.